阅读说明：本技术 烷烃到烯烃的氧化 (Oxidation of alkanes to alkenes ) 是由 R·A·佩里亚纳 B·G·哈士古驰 M·M·孔尼克 于 2018-05-25 设计创作，主要内容包括：本发明提供了一种将烷烃转化为烯烃的方法。该方法包括(a)在包含含氧酸和任选地一种或多种选自不可氧化的液体、盐添加剂、路易斯酸和水的添加剂的液体介质中使烷烃与(i)包含氧化形式的主族元素的氧化性亲电试剂接触,或与(ii)氧化剂和还原形式的氧化性亲电试剂接触,以提供氧化的中间体和还原形式的氧化性亲电试剂；(b)任选地将氧化的中间体和还原形式的氧化性亲电试剂分离；和(c)对氧化的中间体进行消除反应以提供烯烃和含氧酸。(The present invention provides a process for converting alkanes to alkenes. The method comprises (a) contacting an alkane with (i) an oxidizing electrophile comprising a main group element in an oxidized form, or with (ii) an oxidizing agent and a reduced form of the oxidizing electrophile, in a liquid medium comprising an oxoacid and optionally one or more additives selected from the group consisting of non-oxidizable liquids, salt additives, lewis acids, and water, to provide an oxidized intermediate and a reduced form of the oxidizing electrophile; (b) optionally separating the oxidized intermediate from the reduced form of the oxidizing electrophile; and (c) subjecting the oxidized intermediate to an elimination reaction to provide the olefin and the oxoacid.)

1. A process for converting an alkane to an alkene, the process comprising

(a) Reacting an alkane with an oxygen acid in a liquid medium comprising the oxygen acid and optionally one or more additives selected from the group consisting of non-oxidizable liquids, salt additives, Lewis acids and water

(i) An oxidizing electrophile comprising an oxidized form of a main group element, or

(ii) The oxidizing agent is contacted with a reduced form of an oxidizing electrophile,

to provide an oxidized intermediate and a reduced form of an oxidizing electrophile;

(b) optionally separating the oxidized intermediate from the reduced form of the oxidizing electrophile; and

(c) the oxidized intermediate is subjected to an elimination reaction to provide an olefin and an oxo acid.

2. The method of claim 1, comprising (b) separating the oxidized intermediate and the reduced form of the oxidizing electrophile.

3. The process of claim 1 or claim 2, wherein (c) is carried out in the presence of an acid catalyst.

4. The process of claim 1 or claim 2, wherein (c) is carried out in the presence of a base catalyst.

5. The process of any one of claims 1 to 4, further comprising (d) separating the olefin and the oxoacid.

6. The process of claim 5, wherein the separated oxoacid is recycled for use in step (a).

7. The method of any one of claims 1-6, wherein the alkane is C₂-C₂₀Alkane, C₂-C₂₀Heteroalkane, C₃-C₂₀Cycloalkanes, C₃-C₂₀A heterocyclic alkane, an aryl alkane, a heteroaryl alkane, or a combination thereof.

8. The method of claim 7, wherein the alkane is ethane, propane, butane, or a mixture thereof.

9. The method of any one of claims 1-8, wherein the oxidizing electrophile comprises a main group element.

10. The method of claim 9, wherein the oxidizing electrophile comprises gallium, germanium, arsenic, tin, thallium, lead, antimony, selenium, tellurium, bismuth, or iodine.

11. The method of claim 10, wherein the oxidizing electrophile comprises Sb (V), Te (VI), Te (IV), Bi (V), Se (VI), Se (IV), As (V), I (III), or Sn (IV).

12. The method of any one of claims 1-11, wherein the oxidizing electrophile comprises at least one conjugate anion of an oxoacid.

13. The method of claim 12, wherein the conjugated anion of an oxoacid is an aliphatic carboxylate, heteroaliphatic carboxylate, aromatic carboxylate, heteroaromatic carboxylate, aliphatic sulfonate, heteroaliphatic sulfonate, aromatic sulfonate, heteroaromatic sulfonate, aliphatic phosphate, heteroaliphatic phosphate, aromatic phosphate, heteroaromatic phosphate, aliphatic borate, heteroaliphatic borate, aromatic borate, heteroaromatic borate, or a mixture thereof.

14. The method of claim 13, wherein the conjugate anion of an oxo acid is trifluoroacetate, acetate, alkylsulfonate, phosphate, nitrate, sulfate, triflate, or fluorosulfate.

15. The method of any one of claims 1-14, wherein the oxidizing electrophile is of formula M⁺ⁿX_pL_qWherein M is a cation of a main group element in oxidation state n, X is a conjugate anion of an oxoacid, L is a ligand, n is an integer of 2 to 6, p is an integer of 1 to 6, and q is an integer of 0 to 5.

16. The method of claim 15, wherein M is⁺ⁿX_pL_qWith olefins in a liquid medium to give the reduced form of formula M^+(n-2)X_p-2L_qOr M^+(n-1)X_p-1L_qAn electrophile of (1).

17. The method of any one of claims 1-16, wherein the oxidizing electrophile is present in an at least stoichiometric amount relative to the amount of alkene produced.

18. The method of any one of claims 1-16, wherein the oxidizing electrophile is present in a less than stoichiometric amount relative to the alkane and is used as a catalyst.

19. The method of claim 18, further comprising (e) contacting the reduced form of the oxidizing electrophile with an oxidizing rejuvenating reagent to rejuvenate the oxidizing electrophile.

20. The method of claim 19, wherein the oxidative regeneration reagent is a quinone, molecular oxygen, air, ozone, peroxide, nitric oxide, nitrous oxide, nitric acid, nitroxide, sulfur trioxide, or a combination thereof.

21. The method of claim 19, wherein step (e) is an electrochemical process.

22. The method of any one of claims 19-21, wherein the reduced form of the oxidative electrophile is contacted with the oxidative regeneration reagent in the presence of an oxidative regeneration catalyst to regenerate the oxidative electrophile.

23. The method of claim 22, wherein the oxidative regeneration catalyst comprises copper, silver, iron, cobalt, manganese, nickel, chromium, vanadium, or combinations thereof.

24. The method of any one of claims 19-23, wherein the oxidative regeneration reagent oxidizes the reduced form of an oxidative electrophile to an oxidative electrophile in the liquid medium in the presence of an alkane.

25. The process of any one of claims 19-24, wherein the regenerated oxidizing electrophile is recycled for use in step (a).

26. The method of any one of claims 1-25, wherein the oxoacid is an aliphatic carboxylic acid, heteroaliphatic carboxylic acid, aromatic carboxylic acid, heteroaromatic carboxylic acid, aliphatic sulfonic acid, heteroaliphatic sulfonic acid, aromatic sulfonic acid, heteroaromatic sulfonic acid, aliphatic phosphonic acid, heteroaliphatic phosphonic acid, aromatic phosphonic acid, heteroaromatic phosphonic acid, boric acid, aliphatic boric acid, heteroaliphatic boric acid, aromatic boric acid, heteroaromatic boric acid, or a mixture thereof.

27. The method of any one of claims 1-26, wherein the oxoacid is trifluoroacetic acid, acetic acid, methanesulfonic acid, phosphoric acid, nitric acid, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfuric acid, or a mixture thereof.

28. The process according to any one of claims 1 to 27, wherein all or part of the oxo acid is added as the anhydride of the oxo acid.

29. The process of any one of claims 1-28, wherein the liquid medium comprises a non-oxidizable liquid selected from the group consisting of fluorinated hydrocarbons, sulfones, deactivated aromatics, deactivated aliphatics, deactivated heteroaromatics, deactivated heteroaliphatics, or combinations thereof, wherein the non-oxidizable liquid is substantially inert in the presence of an oxidizing electrophile.

30. The method of any one of claims 1-29, wherein the liquid medium comprises a salt additive.

31. The method of claim 30, wherein the liquid medium comprises formula Q_aZ_bA salt additive, wherein Q is a cation, Z is a conjugate anion bridging an oxide, a terminal oxide, a hydroxide, or an oxyacid, a is an integer from 1 to 5, and b is an integer from 1 to 5, wherein a and b are the same or different and balance the oxidation states of Q and Z.

32. The method of claim 31, wherein Z is a conjugate anion of an oxo acid and is selected from one or more of: aliphatic carboxylates, heteroaliphatic carboxylates, aromatic carboxylates, heteroaromatic carboxylates, aliphatic sulfonates, heteroaliphatic sulfonates, aromatic sulfonates, heteroaromatic sulfonates, aliphatic phosphates, heteroaliphatic phosphates, aromatic phosphates, heteroaromatic phosphates, aliphatic borates, heteroaliphatic borates, aromatic borates, heteroaromatic borates, and mixtures thereof.

33. The method of claim 31 or 32, wherein Q is a proton, an alkali metal cation, an alkaline earth metal cation, a rare earth metal cation, a main group element cation, or a combination thereof.

34. The method of any one of claims 1-33, wherein the liquid medium comprises a lewis acid.

35. The process of any one of claims 1-34, wherein the reaction temperature in (a) is about 50 ℃ to about 300 ℃.

36. The process of any one of claims 1-35, wherein the reaction pressure in (a) is about 2psi (about 13.8kPa) to about 500psi (about 3450 kPa).

Background

Olefins are the largest organic commodity chemicals produced in global quantities and they also play a role in the production of other commodity chemicals in bulk. However, in the chemical industry, efficient and low cost techniques for producing olefins using relatively inert small molecules (e.g., alkanes) are not currently well developed.

The chemical industry typically produces olefins on a commercial scale through variations of cracking technology. For example, as shown in equation 1, more than 90% of the ethylene currently produced is derived from steam cracking of naphtha, ethane, and/or propane.

The reaction is carried out at high temperatures (i.e., about 700 ℃ to about 1000 ℃) and requires a residence time of milliseconds; furthermore, product selectivity will be greatly reduced if the effluent is not quenched immediately. In addition, longer olefins, such as 1-octene, are formed by a completely different process (e.g., oligomerization of ethylene). However, this technique is costly and leaves a large carbon footprint.

Recently, new technologies have emerged to convert light alkanes (e.g., ethane and propane) and oxygen to olefins. These techniques use an oxidative dehydrogenation reaction shown in formula 2

The oxidative dehydrogenation reaction is carried out at a lower temperature (i.e., about 300 ℃ to about 600 ℃) than the reactions used in cracking technology; however, it often suffers from low conversion and it often leads to over-oxidation to CO₂And coke, which deactivates the heterogeneous catalyst. The reaction may also result in low product selectivity.

Thus, current olefin production technologies either require the use of high temperatures or suffer from low conversion and/or low product selectivity. Thus, there is a need in the chemical industry for a low temperature alternative that results in high conversion and/or high selectivity of the desired olefin product. Furthermore, there is a need for a cost effective olefin production process that can reduce the carbon footprint.

Brief description of the invention

The invention provides a process for converting an alkane to an alkene, the process comprising, consisting essentially of, or consisting of: (a) contacting an alkane with (i) an oxidizing electrophile comprising a main group element in an oxidized form, or with (ii) an oxidizing agent and an oxidizing electrophile in a reduced form, in a liquid medium comprising an oxoacid and optionally one or more additives selected from the group consisting of non-oxidizable liquids, salt additives, lewis acids, and water, to provide an oxidized intermediate and the oxidizing electrophile in a reduced form; (b) optionally separating the oxidized intermediate from the reduced form of the oxidizing electrophile; and (c) subjecting the oxidized intermediate to an elimination reaction to provide the olefin and the oxoacid.

Brief description of the drawings

FIG. 1 shows the conversion of R-H to R-X via C-H activation and M-R functionalization.

Fig. 2 is a list of exemplary oxidizing electrophiles.

Fig. 3 shows an exemplary reaction cycle for the oxidation process, which includes the isolation of the oxidized intermediates.

Fig. 4 shows an exemplary reaction cycle for an oxidation process that does not include isolation of oxidized intermediates.

Fig. 5 shows an exemplary reaction cycle for a one-pot oxidation process.

Fig. 6A is a table of exemplary reaction conditions for the steps outlined in example 4. Fig. 6B is a table of exemplary results of the steps outlined in example 4.

Detailed Description

The invention provides a process for converting an alkane to an alkene, the process comprising, consisting essentially of, or consisting of: (a) contacting an alkane with (i) an oxidizing electrophile comprising a main group element in an oxidized form, or (ii) an oxidizing agent and an oxidizing electrophile in a reduced form, in a liquid medium comprising an oxoacid and optionally one or more additives selected from the group consisting of non-oxidizable liquids, salt additives, lewis acids, and water, to provide an oxidized intermediate and the oxidizing electrophile in a reduced form; (b) optionally separating the oxidized intermediate from the reduced form of the oxidizing electrophile; and (c) subjecting the oxidized intermediate to an elimination reaction to provide the olefin and the oxoacid.

The process converts alkanes to alkenes. The effectiveness of the methods described herein is best demonstrated in terms of the ability of the oxidizing electrophile to selectively react with the functionalized or unfunctionalized alkane to form an oxidized intermediate (e.g., R-OY). The oxidized intermediate may then optionally be separated from the reduced form of the oxidizing electrophile before undergoing an elimination reaction to provide the olefin. The product of the direct oxidation of an alkane is less reactive than the corresponding alkane; in addition, the groups in the oxidized intermediate (e.g., -OY) are more electron withdrawing than the hydrogen in the corresponding C-H bond of the functionalized or unfunctionalized alkane (i.e., R-H). This oxidation process is advantageous because it generally produces a product with high selectivity and high alkane conversion.

Alkanes typically require harsh reaction conditions (e.g., radical-based chemical reactions) to carry out chemical conversions, and conventional techniques tend to result in complex product mixtures that include over-oxidized products. In contrast to conventional techniques, the processes described herein do not utilize harsh reaction conditions to form olefins. More particularly, the process does not form olefins by a free radical mechanism. Without wishing to be bound by any theory, it is believed that the mechanism by which this process converts alkanes to oxygenated intermediates and subsequently produces the corresponding alkenes occurs through an electrophilic C-H activation ("CHA") reaction.

An important emerging method for direct oxidation of C-H bonds of alkanes to C-X bonds (where X is a heteroatom containing group) is based on an electrophilic C-H activation reaction as shown in FIG. 1. The reaction involving the substance MX₂Which reacts directly with R-H (i.e., the C-H bond of the alkane) to produce H-X and MX-R intermediates. The key advantage of the C-H activation reaction is that the cleavage of the R-H bond is performed by a coordinated process involving a single transition state (TS1) in which new M-R and H-X bonds are generated as the R-H bond is cleaved. Three important advantages of the concerted lysis are: (i) does not generate reactive species (e.g., radicals, carbenium or carbanions) that can lead to non-selective reactions, (ii) the energy input required to cleave the RH bond can be moderated by the energy released when new MR and HX bonds are formed, so these reactions can be facilitated, and (iii) the nature of M and X can be adjusted to ensure that the product R-X is less reactive than the substrate R-H. Using MX which can subsequently undergo a redox reaction₂A substance that can couple the C-H activation reaction with the M-R functionalization reaction. The resulting M-R functionalization reaction proceeds by involving a single Transition State (TS)₂) The cooperative process of (a) is carried out,the functionalized product (R-X) and the reducing species (M) may be selectively formed. As shown in FIG. 1, reoxidation of M with an oxidizing agent (Ox) allows the bulk reaction of R-H with Ox to form R-X without consuming MX₂。

Previously shown, formula M (OY)₂The electrophilic oxidizing agent is capable of promoting direct oxidation of alkanes to the corresponding alcohols via electrophilic C-H activation ("CHA") reactions. When in the corresponding acidic solvent HOY (e.g. H)₂SO₄、HSO₃CF₃、HCO₂CF₃And HSO₃CH₃) It is particularly effective when carried out in (1). However, it has not been demonstrated that combining selective C-H-functionalization reactions with elimination reactions of oxygenated intermediates can effectively produce alkenes from alkanes. The present invention provides a novel process that produces olefins at lower cost and reduced emissions compared to the prior art.

The process comprises converting an alkane to an alkene. As used herein, the term "alkane" is meant to comprise at least two adjacent sp³Organic molecules that hybridize carbon atoms (i.e., alkane-containing moieties; also known as alkyl-containing compounds). Adjacent sp³The hybridized carbon atom may be methine, methylene, methyl, or a combination thereof. The alkane can be substituted, unsubstituted, branched, linear, cyclic, or combinations thereof, and can be fully saturated or include unsaturated or aromatic moieties, provided that the alkane has at least one sp³Hybridization of carbon atoms, at least one C-H bond (e.g. 1,2 or 3) with a second sp having at least one C-H bond (e.g. 1,2 or 3)³The hybridized carbon atoms are adjacent. For example, an alkane may comprise one or more alkene moieties such that when the alkane is converted to an alkene, the alkene is a diene, triene, or the like. In some embodiments, the alkane is C₂-C₂₀Alkane, C₂-C₂₀Heteroalkane, C₃-C₂₀Cycloalkanes, C₃-C₂₀A heterocycloalkane, an arylalkane, a heteroarylalkane, or a combination thereof. In other embodiments, the alkane is ethane, propane, butane, or a mixture thereof.

The term "C₂-C₂₀By alkane "is meant a substituted or unsubstituted C of 2 to 20 (i.e., 2,3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, or 20) carbon atoms in length₂-C₂₀Alkyl carbon chains. In some embodiments, C₂-C₂₀The alkane can be saturated, unsaturated, branched, linear, cyclic, or combinations thereof, provided that C is₂-C₂₀The alkane has at least two adjacent sp³Hybridized methine, methylene, and/or methyl. C₂-C₂₀An illustrative, but non-limiting list of alkanes includes ethane, propane, n-butane, 1-butene, isobutane, 1-pentene, pentane, isopentane, neopentane; and structural isomers of hexane, heptane, octane, nonane, decane, or combinations thereof.

As used herein, "C" is₂-C₂₀Heteroalkane "means substituted or unsubstituted C₂-C₂₀Alkanes that contain at least 1 heteroatom (e.g., O, S, N and/or P) in the core of the molecule (i.e., any portion of the molecule other than the alkane-containing portion). Thus, at least 1 heteroatom may be a pendant substituent or part of the carbon chain. In some cases, C₂-C₂₀Heteroalkanes have at least 2 heteroatoms in the core of the molecule (e.g., at least 3, 4, 5, or 6 heteroatoms in the core of the molecule). In some embodiments, C₂-C₂₀The heteroalkane compound comprises a moiety selected from an ether, an ester, a carbonate, an amide, an amine, a carbamate, a thioether, a thioester, a phosphate, a heterocycloalkane, a haloalkane, an acetyl, an alcohol, a ketone, an aldehyde, a carboxylate, a carboxylic acid, a hemiacetal, an acetal, a ketal, an imine, an imide, a thiol, a disulfide, a sulfoxide, a thioketone, or a combination thereof. The heteroalkanes can be substituted, unsubstituted, branched, linear, cyclic, or combinations thereof.

As used herein, the term "C₃-C₂₀Cycloalkane "refers to a substituted or unsubstituted C comprising a cyclic alkane moiety containing, for example, 3 to 6 carbon atoms or 5 to 6 carbon atoms₃-C₂₀An alkane. In some embodiments, C₃-C₂₀The cycloalkane is cyclopropane, cyclobutane, cyclopentane or cyclohexane. In some embodiments, C₃-C₂₀The cycloalkane may be a cycloalkene, provided that the cycloalkene comprises an alkane-containing moiety. The term "cycloalkene" refers to a cycloalkane having at least one C-C double bond in the ring, as described herein. The cycloalkene can be, for example, cyclopentene or cyclohexene. In some embodiments, C₃-C₂₀The term "arene" refers to an unsubstituted or substituted aromatic carbocyclic moiety that is planar and contains 4n +2 pi electrons, where n is 1,2, or 3, as is commonly understood in the art, according to H ü ckel's rule.

As used herein, the term "C₃-C₂₀Heterocyclanes "means C containing a cycloalkane moiety₃-C₂₀Alkanes, the cycloalkane moiety comprising, for example, 3 to 6 carbon atoms or 5 to 6 carbon atoms, and which comprise at least 1 heteroatom (e.g., O, S, N and/or P) in the core of the molecule (i.e., any portion of the molecule other than the alkane-containing moiety). Thus, at least 1 heteroatom may be a pendant substituent or contained in a cyclic chain. In some cases, C₃-C₂₀The heterocycloalkane has at least 2 heteroatoms in the core of the molecule (e.g., at least 3, 4, 5, or 6 heteroatoms in the core of the molecule). In some embodiments, C₃-C₂₀The heterocyclic alkane compound comprises a moiety selected from the group consisting of an ether, an ester, a carbonate, an amide, an amine, a carbamate, a thioether, a thioester, a phosphate, a halogenated alkane, an acetyl, an alcohol, a ketone, an aldehyde, a carboxylate, a carboxylic acid, a hemiacetal, an acetal, a ketal, an imine, an imide, a thiol, a disulfide, a sulfoxide, a thioketone, or a combination thereof. C₃-C₂₀An exemplary but non-limiting list of heterocyclic alkanes includes tetrahydrofuran, piperazine, morpholine, cyclohexanone, and 2-cyclohexylethanol.

As used herein, "arylalkane" refers to a substrate comprising a substituted or unsubstituted monocyclic or polycyclic aromatic substrate(e.g., phenyl, xylyl, naphthyl, biphenyl, anthracenyl, or combinations thereof) C₆-C₂₀An alkane. An exemplary arylalkane is ethylbenzene.

As used herein, "heteroarylalkane" refers to a C comprising at least 1 heteroatom (e.g., O, S, N and/or P) in the core of the molecule (i.e., any portion of the molecule other than the alkane-containing portion)₆-C₂₀An aryl alkane. Thus, at least 1 heteroatom may be a pendant substituent or contained in a monocyclic or polycyclic heteroaromatic substituent. In certain instances, the heteroarylalkane has at least 2 heteroatoms in the core of the molecule (e.g., at least 3, 4, 5, or 6 heteroatoms in the core of the molecule).

In some embodiments, the heteroarylalkane comprises a monocyclic or polycyclic heteroaromatic substrate. The term "heteroaromatic substrate" refers to an aromatic compound having at least one heteroatom (O, S or N) in at least one ring. In certain embodiments, the heteroaromatic substrate is polycyclic and has 2,3, or 4 aromatic rings. The heteroaromatic substrates containing heteroatoms may contain one or two oxygen and/or sulfur atoms and/or 1-4 nitrogen atoms per ring, provided that the total number of heteroatoms in each ring is four or less and each ring has at least one carbon atom. The fused rings completing the polycyclic groups may contain only carbon atoms and may be saturated, partially saturated, or unsaturated. The nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen atoms may optionally be quaternized. A heteroaromatic substrate that is polycyclic must include at least one fully aromatic ring, but the other fused ring or rings may be aromatic or non-aromatic. In some embodiments, the heteroaromatic substrate is pyrrolyl, isoindolyl, indolizinyl, indolyl, furanyl, benzofuranyl, benzothienyl, thienyl, pyridyl, acridinyl, naphthyridinyl, quinolinyl, isoquinolinyl, isoxazolyl, oxazolyl, benzoxazolyl, isothiazolyl, thiazolyl, benzothiazolyl, imidazolyl, thiadiazolyl, tetrazolyl, triazolyl, oxadiazolyl, benzimidazolyl, purinyl, pyrazolyl, pyrazinyl, pteridinyl, quinoxalinyl, phthalazinyl, quinazolinyl, triazinyl, phenazinyl, cinnolinyl, pyrimidinyl, pyridazinyl, or a combination thereof.

As used herein, the term "substituted," in the context of any moiety, may mean that one or more hydrogens on the designated atom or group is replaced with another group, provided that the designated atom's normal valence is not exceeded. For example, when the substituent is oxo (i.e., ═ O), two hydrogens on the atom are substituted. In certain embodiments, the substituent is halo (e.g., fluoro, chloro, bromo, iodo), hydroxy, cyano, nitro, alkoxy, amino, aryl, heteroaryl, alkyl, heteroalkyl, oxo, or combinations thereof. Combinations of substituents and/or variables are permissible only if such substitutions do not materially adversely affect synthesis or use of the compound. A substituted moiety typically contains at least one (e.g., 1,2,3, 4, 5, 6, etc.) substituent in any suitable position (e.g., 1,2,3, 4, 5, or 6, etc.).

The oxidized intermediate produced in step (a) may be any suitable oxidized intermediate. Typically, an oxidized intermediate is any compound formed by the process of an oxidation step, an oxygenation step, or a combination thereof. In some embodiments, the oxygenated intermediates are alcohols, carboxylic acids, esters, or combinations thereof. In certain embodiments, the oxidized intermediate has been displaced with an oxo acid and/or dehydrated to produce a modified product, such as an ester. In certain embodiments, the oxidized intermediate has undergone a hydration reaction to produce a modified product, such as an alcohol. In some cases, the oxidized intermediate is oxidized at least one position, e.g., the oxidized intermediate can be oxidized at two different positions or more, three different positions or more, four different positions or more, or five different positions or more. In some embodiments, the oxidized intermediates are oxidized at two or more (e.g., 3 or more, 4 or more, or 5 or more) different positions having the same functional group. In other embodiments, the oxidized intermediate is oxidized at two or more (e.g., 3 or more, 4 or more, or 5 or more) different positions having at least two different functional groups.

In some embodiments, the oxidized intermediate is an alkyl electrophilic intermediate. As used herein, the term "alkyl electrophilic intermediate" refers to an intermediate in which the oxidizing electrophile has undergone an electrophilic C-H activation ("CHA") reaction to produce a metal-carbon bond. Without wishing to be bound by any particular theory, it is believed that according to aspects of the invention described herein, the alkyl electrophilic intermediate may continue to form an oxidized intermediate, or an elimination reaction may be performed to produce an olefin.

As used herein, the term "alkene" refers to a compound comprising at least two adjacent sp's having a carbon-carbon double bond therebetween²Any organic molecule of hybridized carbon atoms (i.e., an alkenyl-containing compound). Adjacent sp²The hybridized carbon atom can be derived from two adjacent sp which have been oxidized³A hybridized carbon atom. For example, the alkene can be substituted, unsubstituted, branched, linear, cyclic, or a combination thereof, and can be fully unsaturated or include a saturated or aromatic moiety, provided that the alkene has at least one and a second sp²Sp adjacent to hybridized carbon atom²A hybridized carbon atom. Thus, the olefin may be C₂-C₂₀Olefin, C₂-C₂₀Heteroolefins, C₃-C₂₀Cycloolefin, C₃-C₂₀A heterocyclic alkene, an aryl alkene, a heteroaryl alkene, or a combination thereof. In other embodiments, the olefin is ethylene, propylene, butylene, or a mixture thereof. Thus, as described herein, C₂-C₂₀Alkane, C₂-C₂₀Heteroalkane, C₃-C₂₀Cycloalkanes, C₃-C₂₀The definition of heterocycloalkanes, arylalkanes, heteroarylalkanes applies to C₂-C₂₀Heteroolefins, C₃-C₂₀Cycloolefin, C₃-C₂₀Heterocyclic alkene, aryl alkene, heteroaryl alkene, provided that C₂-C₂₀Alkane, C₂-C₂₀Heteroalkane, C₃-C₂₀Cycloalkanes, C₃-C₂₀The heterocyclic alkane, aryl alkane or heteroaryl alkane comprises at least one alkene moiety.

The oxidizing electrophile comprises a main group element. The main group elements (M) generally include elements in the late transition metals and non-metal groups of the periodic table, and include, for example, elements having atomic numbers 31, 32, 33, 34, 35, 49, 50, 51, 52, 53, 81, 82, and 83. In one embodiment, the term "main group element" generally refers to any element having a filled 4d or 5d orbital, which undergoes a net one-or two-electron change in the oxidation state. Suitable main group elements include thallium, indium, lead, antimony, mercury, tin, selenium, tellurium, arsenic, cadmium, iodine and bismuth. In some embodiments, the main group element is antimony, tellurium, bismuth, or arsenic. In some embodiments, the oxidizing electrophile comprises iodine. In other embodiments, the oxidizing electrophile comprises sb (v), te (vi), te (iv), bi (v), se (vi), se (iv), as (v), i (iii), or sn (iv).

The method comprises contacting an alkane with an oxidizing electrophile comprising an oxidized form of a main group element. As described herein, the oxidized form of the main group element can be any suitable main group element in any suitable oxidation state. For example, the main group element may have an oxidation state of +7, +6, +5, +4, +3, +2, or +1, particularly an oxidation state of +6, +5, +4, +3, or + 2. In preferred embodiments, the main group element in oxidized form has any oxidation state suitable for one-or two-electron reduction/oxidation processes.

In some embodiments, the method comprises contacting the alkane with an oxidizing agent and a reduced form of an oxidizing electrophile. As used herein, "reduced form of an oxidizing electrophile" refers to any reduced form of an oxidizing electrophile comprising a main group element. In general, the reduced form of the oxidizing electrophile comprises a main group element having one or two electronic differences in oxidation state relative to an oxidizing electrophile comprising a main group element in oxidized form. For example, the reduced form of the oxidizing electrophile will have a main group element in an oxidation state or neutral oxidation state of +6, +5, +4, +3, +2, or + 1. In certain embodiments, the reduced form of the oxidizing electrophile comprises a main group element in an oxidation state or neutral oxidation state of +4, +3, +2, or + 1. In some embodiments, the reduced form of the oxidizing electrophile can be any suitable chemical variant of the oxidizing electrophile that results in the reduction of the main group element by one or two electrons, preferably two electrons.

In embodiments where the process comprises contacting an alkane with an oxidizing agent and a reduced form of an oxidizing electrophile, the oxidizing agent can be any suitable oxidizing agent capable of producing an oxidized form of the main group element. For example, the oxidizing agent (e.g., an oxidative regeneration agent) can be molecular oxygen, air, peroxide, nitric oxide, nitrous oxide, nitric acid, sulfur trioxide, ozone, or a combination thereof. The oxidizing agent may be used under an inert atmosphere or in combination with air. The peroxide may be, for example, an organic peroxide, an inorganic peroxide, hydrogen peroxide, or a combination thereof. In some embodiments, the oxidizing agent may be an organic oxidizing agent. For example, the oxidizing agent may be a quinone or a nitroxide. In certain embodiments, the oxidizing agent is molecular oxygen, air, ozone, hydrogen peroxide, organic peroxides, nitric acid, or combinations thereof.

In certain embodiments, the oxidizing electrophile comprises at least one conjugate anion of an oxoacid. For example, the oxidizing electrophile may comprise 1,2,3, 4, 5, or 6 conjugate anions of an oxo acid. As used herein, "oxo acid" refers to any organic or inorganic acid containing hydrogen, oxygen, and at least one other element, wherein the protic hydrogen is attached to oxygen. Typically, the conjugate anion of an oxo acid is selected from the group consisting of sulfite, sulfate, bisulfate, thiosulfate, nitrite, nitrate, phosphate, phosphite, hydrogenphosphate, dihydrogenphosphate, carbonate, hydrogencarbonate, oxalate, cyanate, isocyanate, chromate, dichromate, permanganate, carboxylate, sulfonate, borate, and any combination thereof.

In some embodiments, the conjugated anion of the oxoacid is an electron deficient alkoxylate, an aryl oxide, or a combination thereof. As used herein, the term "electron deficient alkoxylate" refers to any alkoxylate having at least one electron withdrawing substituent as described herein. For example, the electron deficient alkoxylate may be a trifluoroethoxylate. The term "aryloxide," as used herein, refers to any oxide having an optionally substituted aryl group, as described herein. For example, the electron deficient aryl oxide may be a phenoxide having an electron withdrawing group on the ring.

In some embodiments, the conjugate anion of an oxyacid is a carboxylate, sulfate, sulfonate, phosphate, borate, or a combination thereof, each of which is optionally substituted. Typically, the carboxylate salt can be an aliphatic carboxylate salt (e.g., acetate), an aromatic carboxylate salt, or a fluorinated carboxylate salt (e.g., Trifluoroacetate (TFA)). Similarly, the sulfonate may be an aliphatic sulfonate (e.g., a mesylate), an aromatic sulfonate, or a fluorinated sulfonate (e.g., a triflate). The conjugated anion of the oxoacid can be an aliphatic carboxylate, heteroaliphatic carboxylate, aromatic carboxylate, heteroaromatic carboxylate, aliphatic sulfonate, heteroaliphatic sulfonate, aromatic sulfonate, heteroaromatic sulfonate, aliphatic phosphate, heteroaliphatic phosphate, aromatic phosphate, heteroaromatic phosphate, aliphatic borate, heteroaliphatic borate, aromatic borate, heteroaromatic borate, or mixtures thereof. In some embodiments, the conjugate anion of an oxyacid is trifluoroacetate, acetate, alkylsulfonate, phosphate, nitrate, sulfate, triflate, or fluorosulfate.

As used herein, "aliphatic group" refers to a substituted or unsubstituted C₁-C₉Alkyl substituents, wherein "C₁-C₉Alkyl "refers to an alkyl carbon chain of 1 to 9 (i.e., 1,2,3, 4, 5, 6, 7, 8, or 9) carbon atoms in length. In some embodiments, C₁-C₉The alkyl group can be saturated, unsaturated, branched, linear, cyclic, or combinations thereof. C₁-C₉An illustrative, but non-limiting list of alkylaliphatic radicals includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl or combinations thereof. In certain embodiments, the aliphatic group is perfluorinated.

As used herein, "heteroaliphatic" refers to a compound that is present in a moleculeContaining at least 1 heteroatom (e.g., O, S, N and/or P) in the core (i.e., the carbon skeleton) of (a)₁-C₉An alkyl substituent. C₁-C₉The alkyl substituents may be saturated, unsaturated, branched, linear, cyclic, or combinations thereof. In certain instances, heteroaliphatic substituents have at least 2 heteroatoms in the core of the molecule (e.g., at least 3, 4, 5, or 6 heteroatoms in the core of the molecule). In some embodiments, the heteroaliphatic compound is an ether, ester, carbonate, amide, amine, carbamate, thioether, thioester, phosphate, heterocyclic alkane, or a combination thereof. In certain embodiments, the heteroaliphatic group is perfluorinated.

As used herein, "aromatic group" refers to a substituted or unsubstituted monocyclic or polycyclic aromatic substituent. An exemplary but non-limiting list of aromatic substituents includes phenyl, xylyl, naphthyl, biphenyl, anthracyl, or combinations thereof. In certain embodiments, the aromatic group is perfluorinated.

As used herein, "heteroaromatic group" refers to a substituted or unsubstituted monocyclic or polycyclic aromatic compound having at least one heteroatom (e.g., O, S or N) in at least one ring. In certain embodiments, the heteroaromatic substituent is polycyclic and has 2,3, or 4 aromatic rings. Heteroaromatic substituents containing heteroatoms may contain one or two oxygen and/or sulfur atoms and/or 1-4 nitrogen atoms per ring, provided that the total number of heteroatoms in each ring is 4 or less, and each ring has at least one carbon atom. The fused rings completing the polycyclic groups may contain only carbon atoms and may be saturated, partially saturated, or unsaturated. The nitrogen and sulfur atoms may optionally be oxidized, and the nitrogen atoms may optionally be quaternized. Heteroaromatic substituents as polycyclic must include at least one fully aromatic ring, but other fused rings may be aromatic or non-aromatic. In some embodiments, the heteroaromatic substituent is pyrrolyl, isoindolyl, indolizinyl, indolyl, furanyl, benzofuranyl, benzothienyl, thienyl, pyridyl, acridinyl, naphthyridinyl, quinolinyl, isoquinolinyl, isoxazolyl, oxazolyl, benzoxazolyl, isothiazolyl, thiazolyl, benzothiazolyl, imidazolyl, thiadiazolyl, tetrazolyl, triazolyl, oxadiazolyl, benzimidazolyl, purinyl, pyrazolyl, pyrazinyl, pteridinyl, quinoxalinyl, phthalazinyl, quinazolinyl, triazinyl, phenazinyl, cinnolinyl, pyrimidinyl, pyridazinyl, or a combination thereof. In certain embodiments, the heteroaromatic group is perfluorinated.

In some embodiments, the oxidizing electrophile has formula M⁺ⁿX_pL_qWherein M is a cation of a main group element in an oxidation state n, X is a conjugate anion of an oxoacid, L is a ligand, n is an integer from 2 to 6 (i.e., 2,3, 4, 5, or 6), p is an integer from 1 to 6 (i.e., 1,2,3, 4, 5, or 6), and q is an integer from 0 to 5 (i.e., 0, 1,2,3, 4, or 5). Formula M⁺ⁿX_pL_qThe oxidizing electrophile of (a) can have any suitable net charge. For example, M⁺ⁿX_pL_qThe oxidizing electrophile of (a) can have a net charge of +5, +4, +3, +2, or +1, or a neutral net charge. In certain embodiments, formula M⁺ⁿX_pL_qThe oxidizing electrophile of (a) is a neutral species. Without wishing to be bound by any particular theory, the reactive species [ M⁺ⁿX_p]May have up to q number of ligands (L) to balance [ M [⁺ⁿX_p]Net charge and/or solvation [ M ] of⁺ⁿX_p]The remaining charge of. In some embodiments, M⁺ⁿX_pL_qWith an alkane in a liquid medium to produce formula M^+(n-2)X_p-2L_qOr M^+(n-1)X_p-1L_qA reduced form of the oxidizing electrophile of (a). In certain embodiments, n and p are the same or different and are each an integer from 2 to 6 (i.e., 2,3, 4, 5, 6) and q is an integer from 0 to 4 (i.e., 0, 1,2,3, or 4).

X of any of the foregoing formulae can be any suitable conjugate anion of an oxo acid described herein in any suitable oxidation state. Typically, X is one or more selected from the group consisting of aliphatic carboxylates, heteroaliphatic carboxylates, aromatic carboxylates, heteroaromatic carboxylates, aliphatic sulfonates, heteroaliphatic sulfonates, aromatic sulfonates, heteroaromatic sulfonates, aliphatic phosphates, heteroaliphatic phosphates, aromatic phosphates, heteroaromatic phosphates, aliphatic borates, heteroaliphatic borates, aromatic borates, and heteroaromatic borates. As used herein, a carboxylate may be an alkylated variant (e.g., acetate), a fluorinated variant (e.g., Trifluoroacetate (TFA)), or an arylated variant (e.g., benzoate or benzoic acid). As used herein, "alkylated variants" and "arylated variants" refer to carboxylic acids comprising an alkyl or aryl group, respectively, as defined herein. Similarly, the sulfonate can be an alkylated variant (e.g., methanesulfonate) or a fluorinated variant (e.g., trifluoromethanesulfonate). In certain embodiments, X is one or more selected from the group consisting of trifluoroacetate, acetate, benzoate, sulfate, methanesulfonate, and trifluoromethanesulfonate. Typically, X has an oxidation state of-4, -3, -2, or-1.

The ligand (L) may be any ligand which is suitably coordinated to the main group element (M). Typically, each ligand is the same or different, and each may be anionic or neutral. In some embodiments, each ligand (L) is independently an oxide (e.g., a bridging oxide (bridging oxy) or a terminal oxide (terminal oxy)), a hydroxide, or a combination thereof. In certain embodiments, the ligand is anionic and helps balance the charge of the oxidizing electrophile. In certain embodiments, the ligand is neutral and contributes to the charge of the solvated oxidizing electrophile. In some embodiments, the ligand is a non-oxidizable liquid (e.g., solvent), an olefin molecule, an olefin oxidation product, or a combination thereof.

In some embodiments, the ligand is at least one aliphatic-based or aromatic-based monodentate or bidentate ligand and comprises at least one oxy, amino, thiol, sulfonyl, or carboxyl group, and optionally comprises one or more electron withdrawing groups as described herein. In certain embodiments, the ligand comprises at least one carboxyl group. As used herein, "aliphatic-based" or "aromatic-based" refers to the entire ligand, and the ligand may be bound directly to an aliphatic or aromatic moiety, or indirectly to an aliphatic or aromatic moiety via at least one oxy, amino, thiol, sulfonyl, or carboxyl group. The terms "aliphatic" and "aromatic" are as described herein.

In certain embodiments, the ligand is aromatic-based. In embodiments where the ligand is aromatic-based, the ligand may comprise at least one carboxyl group and/or at least one nitro group.

In certain embodiments, the ligand is selected from the following moieties:

wherein R, R 'and R' are the same or different and are each optionally substituted alkyl; ar is an optionally substituted aryl group, and n is 0 or an integer of 1 to 6.

The ligand may also have the formula-Ar-EWG, wherein Ar is an optionally substituted aryl group and EWG is at least one electron withdrawing group, as described herein. For example, the electron withdrawing group may be selected from-NO₂fluorine-C_1-8Alkyl, -F, -OOCR, -COOH, -OH₂ ⁺，-CONH₂，-COOR，-NR₃ ⁺、-CN、-SO₃H、-SO₃R、-SO₃W, and combinations thereof. In the context of electron withdrawing groups, R is hydrogen or any aliphatic group (e.g., C)_1-8Alkyl, fluoro-C_1-8Alkyl), a heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted, and W is a cation comprising a metal selected from: boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, alkali metals or alkaline earth metals.

For example, the ligand may be:

in some embodiments, the oxidizing electrophile has any one of the structural formulas shown in figure 2.

Any suitable method may be used to prepare the oxidizing electrophile. For example, the oxidizing electrophile can be prepared separately as a stable and isolatable compound, or the oxidizing electrophile can be generated in situ from a reduced form of the oxidizing electrophile, by a substitution reaction, or by a dehydration reaction. Combinations of any of these methods may also be used.

The ligand may be present in the mixture in less than stoichiometric amounts relative to the main group element, in stoichiometric amounts relative to the main group element, or in at least stoichiometric amounts relative to the main group element.

In certain embodiments, the oxidized or reduced form of the oxidizing electrophile is present in an amount that is at least stoichiometric with respect to the amount of alkene produced (e.g., with respect to the amount of alkane reacted). Typically, when the oxidative electrophile is present in at least a stoichiometric amount relative to the olefin, no oxidative regenerant is present in the reaction. In other embodiments, the oxidized or reduced form of the electrophile is present in a substoichiometric amount relative to the alkane. Typically, when the oxidizing electrophile is present in a substoichiometric amount, the oxidative regeneration reagent and optionally the oxidative regeneration catalyst are present to regenerate the oxidative electrophile from the reduced form of the oxidative electrophile. In some preferred embodiments, the oxidative electrophile in oxidized or reduced form is present in at least a stoichiometric amount relative to the olefin produced, and no oxidative regeneration reagent and optional oxidative regeneration catalyst are required, but it may be present in a liquid medium. In other preferred embodiments, the oxidative electrophile is present in a substoichiometric amount relative to the olefin produced, and the oxidative regeneration reagent or oxidative regeneration catalyst is present. In some embodiments, the oxidizing electrophile is present in a substoichiometric amount relative to the olefin produced and acts as a catalyst.

In this process, the reduced form of the oxidizing electrophile is generated in situ from the reduction of the oxidizing electrophile as the olefin is formed. If desired, the reduced form of the oxidizing electrophile can be used to regenerate the oxidizing electrophile. In some embodiments, the reduced form of the oxidizing electrophile is provided directly to a process for converting an alkane to an alkene. In these cases, the reduced form of the oxidizing electrophile is used to produce the oxidizing electrophile. Thus, when the reduced form of the oxidizing electrophile is provided directly to the process in at least a stoichiometric or sub-stoichiometric amount, the oxidizing agent is present in the reaction mixture to generate the oxidizing electrophile.

Thus, a process for converting an alkane to an alkene can include an oxidizing electrophile or a reduced form of an oxidizing electrophile or both an oxidizing electrophile and a reduced form of an oxidizing electrophile. The amount of oxidizing electrophile and/or reduced form of oxidizing electrophile is not particularly limited, such that a sufficient amount of oxidizing electrophile is present to convert the alkane to the alkene.

Thus, the oxidizing electrophile and/or reduced form of the oxidizing electrophile can be present in an amount of about 0.1 mol% or more (e.g., about 0.2 mol% or more, about 0.3 mol% or more, about 0.4 mol% or more, about 0.5 mol% or more, about 1 mol% or more, about 2 mol% or more, about 3 mol% or more, about 5 mol% or more, about 10 mol% or more, about 20 mol% or more, about 50 mol% or more, or about 100 mol% or more) of the alkane. Alternatively or additionally, the oxidizing electrophile and/or reduced form of the oxidizing electrophile can be present in an amount of about 2000 mol% or less (e.g., about 1500 mol% or less, about 1000 mol% or less, about 900 mol% or less, about 800 mol% or less, about 700 mol% or less, about 600 mol% or less, about 500 mol% or less, about 400 mol% or less, about 300 mol% or less, about 200 mol% or less, about 100 mol% or less) of the alkane. Any two of the foregoing endpoints can be used to define a closed range, or any single endpoint can be used alone to define an open range. For example, the oxidizing electrophile and/or reduced form of the oxidizing electrophile may be present in an amount from about 0.1 mol% to about 2000 mol% of the alkane, e.g., from about 0.1 mol% to about 1500 mol%, from about 0.1 mol% to about 1000 mol%, from about 0.1 mol% to about 900 mol%, from about 0.1 mol% to about 800 mol%, from about 0.1 mol% to about 700 mol%, from about 0.1 mol% to about 600 mol%, from about 0.1 mol% to about 500 mol%, from about 0.1 mol% to about 400 mol%, from about 0.1 mol% to about 300 mol%, from about 0.1 mol% to about 200 mol%, from about 0.1 mol% to about 100 mol%, from about 0.2 mol% to about 100 mol%, from about 0.3 mol% to about 100 mol%, from about 0.4 mol% to about 100 mol%, from about 0.5 mol% to about 100 mol%, from about 1 mol% to about 100 mol%, from about 2 mol% to about 100 mol%, from about 3 mol% to about 100 mol%, from about 10 mol%, from about 100 mol%, from about 10 mol% to about 100 mol%, from about 100 mol%, or a mixture of the alkane, From about 50 mol% to about 100 mol%, from about 100 mol% to about 1000 mol%, or from about 100 mol% to about 600 mol%.

In some embodiments of the method, the liquid medium comprises an oxyacid, such as an aliphatic carboxylic acid, heteroaliphatic carboxylic acid, aromatic carboxylic acid, heteroaromatic carboxylic acid, aliphatic sulfonic acid, heteroaliphatic sulfonic acid, aromatic sulfonic acid, heteroaromatic sulfonic acid, aliphatic phosphonic acid, heteroaliphatic phosphonic acid, aromatic phosphonic acid, heteroaromatic phosphonic acid, boric acid, aliphatic boric acid, heteroaliphatic boric acid, aromatic boric acid, heteroaromatic boric acid, or mixtures thereof. In certain embodiments, the oxo acid is trifluoroacetic acid, acetic acid, methanesulfonic acid, phosphoric acid, nitric acid, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfonic acid, or a mixture thereof.

In some embodiments, the oxo acid is an electron deficient alcohol, an aryl alcohol, or a combination thereof. As used herein, the term "electron deficient alcohol" refers to any alcohol having at least one electron withdrawing substituent as described herein. For example, the electron deficient alcohol may be trifluoroethanol. As used herein, the term "aryl alcohol" refers to any alcohol having an aryl group as described herein. For example, the aryl alcohol may be phenol.

In other embodiments, all or a portion of the oxoacid is added in the form of the anhydride of the oxoacid. In a preferred embodiment, a portion of the oxo acids is added in the form of anhydrides. Without wishing to be bound by any particular theory, it is believed that the anhydride may act as a water scavenger, resulting in a reduction in the amount of water in the liquid medium, which in turn causes two molecules of the oxo acid to be produced per one molecule of water and anhydride.

The oxoacid can be present in an amount of about 0.1 mol% or more (e.g., about 0.2 mol% or more, about 0.3 mol% or more, about 0.4 mol% or more, about 0.5 mol% or more, about 1 mol% or more, about 2 mol% or more, about 3 mol% or more, about 5 mol% or more, about 10 mol% or more, about 20 mol% or more, about 50 mol% or more, or about 100 mol% or more) of the oxidizing electrophile. Alternatively or additionally, the oxoacid can be present in an amount of about 2000 mol% or less (e.g., about 1500 mol% or less, about 1000 mol% or less, about 900 mol% or less, about 800 mol% or less, about 700 mol% or less, about 600 mol% or less, about 500 mol% or less, about 400 mol% or less, about 300 mol% or less, about 200 mol% or less, about 100 mol% or less) of the oxidizing electrophile. Any two of the foregoing endpoints can be used to define a closed range, or can be used alone to define an open range. Thus, the oxoacid may be present in an amount of from about 0.1 mol% to about 2000 mol% of the oxidizing electrophile, for example, an amount of about 0.1 mol% to about 1500 mol%, about 0.1 mol% to about 1000 mol%, about 0.1 mol% to about 900 mol%, about 0.1 mol% to about 800 mol%, about 0.1 mol% to about 700 mol%, about 0.1 mol% to about 600 mol%, about 0.1 mol% to about 500 mol%, about 0.1 mol% to about 400 mol%, about 0.1 mol% to about 300 mol%, about 0.1 mol% to about 200 mol%, about 0.1 mol% to about 100 mol%, about 0.2 mol% to about 100 mol%, about 0.3 mol% to about 100 mol%, about 0.4 mol% to about 100 mol%, about 0.5 mol% to about 100 mol%, about 1 mol% to about 100 mol%, about 2 mol% to about 100 mol%, about 3 mol% to about 100 mol%, about 5 mol% to about 100 mol%, about 10 mol% to about 100 mol%, about 20 mol% to about 100 mol%, about 50 mol% to about 100 mol%, or about 1000 mol% is present.

Depending on the embodiment, the liquid medium may comprise one or more additives, such as non-oxidizable liquids, salt additives, lewis acids, and water. Desirably, the additives can be used to provide functional benefits to the reaction mixture (e.g., liquid medium), such as solvation, solubilization, viscosity change, and/or charge transfer.

The amount of the additive is not particularly limited as long as the additive is used in such an amount that a part of the amount of the oxidizing electrophile or in an amount greatly exceeding the amount of the oxidizing electrophile. The one or more additives can be present in an amount of about 0.1 mol% or more (e.g., about 0.2 mol% or more, about 0.3 mol% or more, about 0.4 mol% or more, about 0.5 mol% or more, about 1 mol% or more, about 2 mol% or more, about 3 mol% or more, about 5 mol% or more, about 10 mol% or more, about 20 mol% or more, about 50 mol% or more, or about 100 mol% or more) of the oxidizing electrophile. Alternatively or additionally, the one or more additives can be present in an amount of about 2000 mol% or less (e.g., about 1500 mol% or less, about 1000 mol% or less, about 900 mol% or less, about 800 mol% or less, about 700 mol% or less, about 600 mol% or less, about 500 mol% or less, about 400 mol% or less, about 300 mol% or less, about 200 mol% or less, about 100 mol% or less) of the oxidizing electrophile. Any two of the foregoing endpoints can be used to define a closed range, or a single endpoint can be used alone to define an open range. Thus, the one or more additives may be present in an amount from about 0 mol% to about 2000 mol%, for example, from about 0 mol% to about 1500 mol%, from about 0 mol% to about 1000 mol%, from about 0 mol% to about 900 mol%, from about 0 mol% to about 800 mol%, from about 0 mol% to about 700 mol%, from about 0 mol% to about 600 mol%, from about 0 mol% to about 500 mol%, from about 0 mol% to about 400 mol%, from about 0 mol% to about 300 mol%, from about 0 mol% to about 200 mol%, from about 0 mol% to about 100 mol%, from about 0.1 mol% to about 100 mol%, from about 0.2 mol% to about 100 mol%, from about 0.3 mol% to about 100 mol%, from about 0.4 mol% to about 100 mol%, from about 0.5 mol% to about 100 mol%, from about 1 mol% to about 100 mol%, from about 2 mol% to about 100 mol%, from about 3 mol% to about 100 mol%, from about 5 mol% to about 100 mol%, from about 10 mol% to about 20 mol%, from about 100 mol%, from about 50 mol% to about 100 mol%, from about 0 mol% to about 100 mol%, or more of the oxidizing electrophile, From about 100 mol% to about 1000 mol% or from about 100 mol% to about 600 mol%. In some embodiments, no additives are present in the liquid medium (i.e., about 0 mol% or below detection levels).

In some embodiments, the liquid medium comprises at least one non-oxidizable liquid. The non-oxidizable liquid can be any suitable liquid (e.g., a fluid or solvent) such that the liquid does not interfere with the process of converting alkanes to alkenes. In some embodiments, the oxidized intermediate is a non-oxidizable liquid (e.g., a fluid or solvent). In certain embodiments, the liquid may be considered to be substantially inert under the reaction conditions. In some embodiments, the liquid is substantially inert in the presence of an oxidizing electrophile.

As used herein, "substantially inert" refers to a liquid (e.g., fluid or solvent) that retains greater than about 80% stability in the presence of an oxidizing electrophile, e.g., as measured against a standard non-oxidizable liquid¹Retention of peaks in H Nuclear Magnetic Resonance (NMR) spectra. In certain embodiments, the liquid can retain greater than about 85% stability in the presence of an oxidizing electrophile, such as greater than about 90% stability in the presence of an oxidizing electrophile, greater than about 92% stability in the presence of an oxidizing electrophile, greater than about 94% stability in the presence of an oxidizing electrophile, greater than about 95% stability in the presence of an oxidizing electrophile, greater than about 98% stability in the presence of an oxidizing electrophile, or greater than about 99% stability in the presence of an oxidizing electrophile. Ideally, the liquid is completely inert to the oxidation conditions, but with strong oxidants, it is anticipated that small amounts of liquid may be consumed or lost in subsequent recycle steps.

As used herein, the term "liquid" or "liquid medium" refers to any medium that comprises a liquid. For example, the liquid or liquid medium may be in the form of a liquid-solid medium, a liquid-gas medium, a liquid-liquid medium, a liquid-gas-solid medium, or the like. Thus, the liquid or liquid medium may be, for example, a solution, a gas-sparged liquid, a gel, a colloid, a slurry, a dispersion, an emulsion, or combinations thereof.

In some embodiments, the non-oxidizable liquid is selected from the group consisting of fluorinated hydrocarbons, sulfones, deactivated aromatics, deactivated aliphatics, deactivated heteroaromatics, deactivated heteroaliphatics, carbonates, or combinations thereof.

In some embodiments, the non-oxidizable liquid is one or more suitable fluorinated hydrocarbons. The fluorinated hydrocarbon may be at least one fluorinated or perfluorinated linear aliphatic compound comprising at least 2 carbons, for example at least 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbons. Preferably, the fluorinated hydrocarbon is at least one fluorinated or perfluorinated cyclic aliphatic compound comprising at least 3 carbons, for example at least 4, 5, 6, 7, 8, 9 or 10 carbons. In some embodiments, the fluorinated or perfluorinated cyclic aliphatic compound may be monocyclic, bicyclic, or tricyclic. The fluorinated hydrocarbons may be perfluorinated and branched or straight chain, and may be substituted or unsubstituted. Preferably, the fluorinated or perfluorinated linear aliphatic compound and/or the fluorinated or perfluorinated cyclic aliphatic compound is substituted with one or more aliphatic substituents. More preferably, the fluorinated hydrocarbon is perfluorinated.

Specific examples include perfluoropentane, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorononane, perfluorodecane, perfluorocyclohexane, perfluorocycloheptane, perfluorocyclooctane, perfluorodecalin, perfluoromethylcyclohexane, perfluorodimethylcyclohexane, perfluorotrimethylcyclohexane, perfluoroethylcyclohexane, perfluorodiethylcyclohexane, perfluorotriethylcyclohexane, perfluoroethylmethylcyclohexane, and perfluoro-2, 2,3, 3-tetramethylbutane.

In some embodiments, the non-oxidizable liquid is one or more sulfones of the formula:

wherein R is¹And R²Independently selected from aryl and alkyl, each optionally substituted, the dashed lines represent optional bonds and atoms (e.g., C, N, O, S or P), and x is an integer from 0 to 3 (i.e., 0, 1,2, or 3). In certain embodiments, R¹And R²Linked by a chain to produce a cyclic sulfone.

In some embodiments, the sulfone is at least one alkyl sulfone, wherein R is¹And R²Are each independently selected from alkyl groups. The alkyl group can be any suitable linear, branched, or cyclic alkyl group (e.g., C)_1-9Alkyl groups). In certain embodiments, the alkyl group is substituted with at least 1 electron-withdrawing substituent (e.g., at least 2,3, or 4 electron-withdrawing substituents), such as those described herein. In certain embodiments, the alkyl groups are linked through an alkylene chain to produce cyclic alkyl sulfones, such as sulfolane.

As used herein, "alkyl" refers to an aliphatic substituent, which may be substituted, unsubstituted, branched, straight-chain, cyclic, or a combination thereof, and may be fully saturated or include unsaturated or aromatic moieties. In some embodiments, alkyl is C₁-C₉Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-pentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl or combinations thereof.

In some embodiments, the alkyl group is heteroalkyl, cycloalkyl, or heterocycloalkyl.

As used herein, "heteroalkyl" refers to a substituted or unsubstituted alkyl group that contains at least 1 heteroatom (e.g., O, S, N and/or P) in the core of the molecule (i.e., any portion of the molecule other than the alkane-containing moiety). Thus, at least 1 heteroatom may be a pendant substituent or part of the carbon chain. In certain instances, a heteroalkyl group has at least 2 heteroatoms in the core of the molecule (e.g., at least 3, 4, 5, or 6 heteroatoms in the core of the molecule). In some embodiments, the heteroalkyl comprises a moiety selected from an ether, ester, carbonate, amide, amine, carbamate, thioether, thioester, phosphate, heterocycloalkane, haloalkane, acetyl, alcohol, ketone, aldehyde, carboxylate, carboxylic acid, hemiacetal, acetal, ketal, imine, imide, thiol, disulfide, sulfoxide, thioketone, or a combination thereof.

As used herein, the term "cycloalkyl" refers to a substituted or unsubstituted alkane comprising a cyclic alkane moiety containing, for example, 3 to 6 carbon atoms or 5 to 6 carbon atoms. In some embodiments, the cycloalkyl group is cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl. In some embodiments, the cycloalkyl can be cycloalkenyl, so long as the cycloalkenyl comprises an alkane-containing moiety. The term "cycloalkenyl" refers to cycloalkanes having at least one C-C double bond in the ring, as described herein. For example, cycloalkenyl can be cyclopentenyl or cyclohexenyl.

As used herein, the term "heterocycloalkyl" refers to an alkyl group comprising a cycloalkane moiety comprising, for example, 3 to 6 carbon atoms or 5 to 6 carbon atoms, which contains at least 1 heteroatom (e.g., O, S, N and/or P) in the core of the molecule (i.e., any portion of the molecule other than the alkane-containing moiety). Thus, at least 1 heteroatom may be a pendant substituent or contained in a cyclic chain. In some cases, the heterocycloalkyl group has at least 2 heteroatoms in the core of the molecule (e.g., at least 3, 4, 5, or 6 heteroatoms in the core of the molecule). In some embodiments, the heterocycloalkyl group comprises a moiety selected from an ether, an ester, a carbonate, an amide, an amine, a carbamate, a thioether, a thioester, a phosphate ester, a haloalkane, an acetyl, an alcohol, a ketone, an aldehyde, a carboxylate, a carboxylic acid, a hemiacetal, an acetal, a ketal, an imine, an imide, a thiol, a disulfide, a sulfoxide, a thioketone, or a combination thereof. An exemplary but non-limiting list of heterocycloalkyl groups includes tetrahydrofuranyl, piperazinyl, morpholinyl, cyclohexanonyl, and 2-cyclohexylethanolyl groups.

As used herein, "aryl" refers to any suitable substituted or unsubstituted aromatic or heteroaromatic group as described herein. In some embodiments of the non-oxidizable liquid, the aryl group is deactivated, meaning that the aryl group is substituted with at least 1 (e.g., at least 2,3, or 4 electron-withdrawing substituents) electron-withdrawing substituent such as those described herein.

In some embodiments, the sulfone is a non-oxidizable liquid comprising a sulfonyl group (-SO)₂) Functional groups, e.g. (methylsulfonyl) benzene, (ethylsulfonyl) benzene, (propylsulfonyl) benzene,(isopropylsulfonyl) benzene, (butylsulfonyl) benzene, (methylsulfonyl) pyridine, (ethylsulfonyl) pyridine, (propylsulfonyl) pyridine, (isopropylsulfonyl) pyridine, (butylsulfonyl) pyridine, (cyclohexylsulfonyl) benzene, sulfonyldiphenyl, dibenzothiophene 5, 5-dioxide, 2, 3-dihydrobenzothiophene 1, 1-dioxide, or thiochromane 1, 1-dioxide, each of which is substituted or unsubstituted.

In some embodiments, the sulfone is (methylsulfonyl) methane ("dimethylsulfone"), (methylsulfonyl) ethane, tetrahydrothiophene 1, 1-dioxide ("sulfolane"), tetrahydro-2H-thiopyran 1, 1-dioxide, thietane 1, 1-dioxide, (ethylsulfonyl) ethane, 1- (ethylsulfonyl) propane, 1- (propylsulfonyl) butane, 1- (butylsulfonyl) butane, 2- (ethylsulfonyl) propane, 2- (isopropylsulfonyl) propane, 1- (ethylsulfonyl) -2-methylpropane, 1- (methylsulfonyl) butane, 1- (ethylsulfonyl) butane, 1- (isopropylsulfonyl) -2-methylpropane, 1- (methylsulfonyl) butane, 1- (isopropylsulfonyl) butane, or mixtures thereof, 1- (ethylsulfonyl) -2-methylpropane, 2-methyl-1- (methylsulfonyl) propane, 1- (isobutylsulfonyl) -2-methylpropane, 2- (tert-butylsulfonyl) -2-methylpropane, perfluoro (methylsulfonyl) methane, perfluoro (methylsulfonyl) ethane, perfluorinated tetrahydrothiophene 1, 1-dioxide, perfluorinated tetrahydro-2H-thiopyran 1, 1-dioxide, perfluorinated thietane 1, 1-dioxide, perfluoro (ethylsulfonyl) ethane, perfluorinated 1- (ethylsulfonyl) propane, perfluorinated 1- (propylsulfonyl) butane, perfluorinated 1- (butylsulfonyl) butane, perfluoropropane, propane, perfluoropropane, perfluorinated 2- (ethylsulfonyl) propane, perfluorinated 2- (isopropylsulfonyl) propane, perfluorinated 1- (ethylsulfonyl) -2-methylpropane, perfluorinated 1- (methylsulfonyl) butane, perfluorinated 1- (ethylsulfonyl) butane, perfluorinated 1- (isopropylsulfonyl) -2-methylpropane, perfluorinated 1- (ethylsulfonyl) -2-methylpropane, perfluorinated 2-methyl-1- (methylsulfonyl) propane, perfluorinated l- (isobutylsulfonyl) -2-methylpropane or perfluorinated 2- (tert-butylsulfonyl) -2-methylpropane, each of which is substituted or unsubstituted.

In other embodiments, the sulfone is (methylsulfonyl) methane ("dimethylsulfone"), (methylsulfonyl) ethane, tetrahydrothiophene 1, 1-dioxide ("sulfolane"), tetrahydro-2H-thiopyran 1, 1-dioxide, thietane 1, 1-dioxide, perfluorinated (methylsulfonyl) methane, perfluorinated (methylsulfonyl) ethane, perfluorinated tetrahydrothiophene 1, 1-dioxide, perfluorinated tetrahydro-2H-thiopyran 1, 1-dioxide, or perfluorinated thietane 1, 1-dioxide.

In some embodiments, the non-oxidizable liquid is one or more deactivated aromatics. As used herein, "deactivated aromatic hydrocarbon" refers to at least one monocyclic or polycyclic aromatic compound having 1 or more electron-withdrawing substituents as described herein. In some embodiments, the aromatic hydrocarbon compound has 2 or more electron-withdrawing substituents, such as 3 or more, 4 or more, 5 or more, or 6 or more electron-withdrawing substituents. In some embodiments, the deactivated aromatics have at least one electron-withdrawing substituent per carbon. In certain embodiments, the deactivated aromatic hydrocarbon is polycyclic and has 2,3, or 4 aromatic rings, and includes, for example, benzene, toluene, xylene, naphthalene, biphenyl, and anthracene. The electron-withdrawing substituent may be any suitable electron-withdrawing substituent, such as those described herein.

An exemplary but non-limiting list of deactivated aromatic hydrocarbons, e.g. deactivated benzenes including C₆H₅(NO₂),C₆H₅(CF₃),C₆H₅F,C₆H₅(COOH),C₆H₅(CONH₂),C₆H₅(COOCF₃),C₆H₅(OOCCF₃),C₆H₅(CN),C₆H₅(SO₃H),C₆H₅(SO₃R),C₆H₅(SO₃Q),m-C₆H₄(NO₂)₂,o-C₆H₄(NO₂)₂,p-C₆H₄(NO₂)₂,m-C₆H₄(CF₃)₂,o-C₆H₄(CF₃)₂,p-C₆H₄(CF₃)₂,m-C₆H₄F₂,o-C₆H₄F₂,p-C₆H₄F₂,m-C₆H₄(COOH)₂,o-C₆H₄(COOH)₂,p-C₆H₄(COOH)₂,m-C₆H₄(CONH₂)₂,o-C₆H₄(CONH₂)₂,p-C₆H₄(CONH₂)₂,m-C₆H₄(COOCF₃)₂,o-C₆H₄(COOCF₃)₂,p-C₆H₄(COOCF₃)₂,m-C₆H₄(OOCCF₃)₂,o-C₆H₄(OOCCF₃)₂,p-C₆H₄(OOCCF₃)₂,m-C₆H₄(CN)₂,o-C₆H₄(CN)₂,p-C₆H₄(CN)₂,m-C₆H₄(SO₃H)₂,o-C₆H₄(SO₃H)₂,p-C₆H₄(SO₃H)₂,m-C₆H₄(SO₃R)₂,o-C₆H₄(SO₃R)₂,p-C₆H₄(SO₃R)₂,m-C₆H₄(SO₃Q)₂,o-C₆H₄(SO₃Q)₂,p-C₆H₄(SO₃Q)₂,m-C₆H₄(CF₃)(NO₂),o-C₆H₄(CF₃)(NO₂),p-C₆H₄(CF₃)(NO₂),m-C₆H₄(CF₃)(F),o-C₆H₄(CF₃)(F),p-C₆H₄(CF₃)(F),m-C₆H₄(CF₃)(COOH),o-C₆H₄(CF₃)(COOH),p-C₆H₄(CF₃)(COOH),m-C₆H₄(CF₃)(CONH₂),o-C₆H₄(CF₃)(CONH₂),p-C₆H₄(CF₃)(CONH₂),m-C₆H₄(CF₃)(CN),o-C₆H₄(CF₃)(CN),p-C₆H₄(CF₃)(CN),m-C₆H₄(CF₃)(SO₃H),o-C₆H₄(CF₃)(SO₃H),p-C₆H₄(CF₃)(SO₃H),m-C₆H₄(CF₃)(SO₃R),o-C₆H₄(CF₃)(SO₃R),p-C₆H₄(CF₃)(SO₃R),m-C₆H₄(CF₃)(SO₃Q),o-C₆H₄(CF₃)(SO₃Q),p-C₆H₄(CF₃)(SO₃Q),m-C₆H₄(F)(NO₂),o-C₆H₄(F)(NO₂),p-C₆H₄(F)(NO₂),m-C₆H₄(COOH)(NO₂),o-C₆H₄(COOH)(NO₂),p-C₆H₄(COOH)(NO₂),m-C₆H₄(CONH₂)(NO₂),o-C₆H₄(CONH₂)(NO₂),p-C₆H₄(CONH₂)(NO₂),m-C₆H₄(COOCF₃)(NO₂),o-C₆H₄(COOCF₃)(NO₂),p-C₆H₄(COOCF₃)(NO₂),m-C₆H₄(OOCCF₃)(NO₂),o-C₆H₄(OOCCF₃)(NO₂),p-C₆H₄(OOCCF₃)(NO₂),m-C₆H₄(CN)(NO₂),o-C₆H₄(CN)(NO₂),p-C₆H₄(CN)(NO₂),m-C₆H₄(SO₃H)(NO₂),o-C₆H₄(SO₃H)(NO₂),p-C₆H₄(SO₃H)(NO₂),m-C₆H₄(SO₃R)(NO₂),o-C₆H₄(SO₃R)(NO₂),p-C₆H₄(SO₃R)(NO₂),m-C₆H₄(SO₃Q)(NO₂),o-C₆H₄(SO₃Q)(NO₂),p-C₆H₄(SO₃Q)(NO₂),1,2,3-C₆H₃(CF₃)₂(NO₂),1,3,4-C₆H₃(CF₃)₂(NO₂),1,3,5-C₆H₃(CF₃)₂(NO₂),1,2,3-C₆H₃(CF₃)(NO₂)₂,1,3,4-C₆H₃(CF₃)(NO₂)₂,1,3,5-C₆H₃(CF₃)(NO₂)₂,1,2,3-C₆H₃F₂(NO₂),1,3,4-C₆H₃F₂(NO₂),1,3,5-C₆H₃F₂(NO₂),1,2,3-C₆H₃(CF₃)F₂,1,3,4-C₆H₃(CF₃)F₂,1,3,5-C₆H₃(CF₃)F₂,1,2,3-C₆H₃(COOH)₂(NO₂),1,3,4-C₆H₃(COOH)₂(NO₂),1,3,5-C₆H₃(COOH)₂(NO₂),1,2,3-C₆H₃(CF₃)(COOH)₂,1,3,4-C₆H₃(CF₃)(COOH)₂,1,3,5-C₆H₃(CF₃)(COOH)₂,1,2,3-C₆H₃(CONH₂)₂(NO₂),1,3,4-C₆H₃(CONH₂)₂(NO₂),1,3,5-C₆H₃(CONH₂)₂(NO₂),1,2,3-C₆H₃(CF₃)(CONH₂)₂,1,3,4-C₆H₃(CF₃)(CONH₂)₂,1,3,5-C₆H₃(CF₃)(CONH₂)₂,1,2,3-C₆H₃(COOCF₃)₂(NO₂),1,3,4-C₆H₃(COOCF₃)₂(NO₂),1,3,5-C₆H₃(COOCF₃)₂(NO₂),1,2,3-C₆H₃(CF₃)(COOCF₃)₂,1,3,4-C₆H₃(CF₃)(COOCF₃)₂,1,3,5-C₆H₃(CF₃)(COOCF₃)₂,1,2,3-C₆H₃(OOCCF₃)₂(NO₂),1,3,4-C₆H₃(OOCCF₃)₂(NO₂),1,3,5-C₆H₃(OOCCF₃)₂(NO₂),1,2,3-C₆H₃(CF₃)(OOCCF₃)₂,1,3,4-C₆H₃(CF₃)(OOCCF₃)₂,1,3,5-C₆H₃(CF₃)(OOCCF₃)₂,1,2,3-C₆H₃(CN)₂(NO₂),1,3,4-C₆H₃(CN)₂(NO₂),1,3,5-C₆H₃(CN)₂(NO₂),1,2,3-C₆H₃(SO₃H)(CN)₂,1,3,4-C₆H₃(SO₃H)(CN)₂,1,3,5-C₆H₃(SO₃H)(CN)₂,1,2,3-C₆H₃(SO₃R)(CN)₂,1,3,4-C₆H₃(SO₃R)(CN)₂,1,3,5-C₆H₃(SO₃R)(CN)₂,1,2,3-C₆H₃(SO₃Q)(CN)₂,1,3,4-C₆H₃(SO₃Q)(CN)₂,1,3,5-C₆H₃(SO₃Q)(CN)₂,1,2,3-C₆H₃(CF₃)₂(SO₃H),1,3,4-C₆H₃(CF₃)₂(SO₃H),1,3,5-C₆H₃(CF₃)₂(SO₃H),1,2,3-C₆H₃(CF₃)₂(SO₃R),1,3,4-C₆H₃(CF₃)₂(SO₃R),1,3,5-C₆H₃(CF₃)₂(SO₃R),1,2,3-C₆H₃(CF₃)₂(SO₃Q),1,3,4-C₆H₃(CF₃)₂(SO₃Q),1,3,5-C₆H₃(CF₃)₂(SO₃Q),1,2,3-C₆H₃(CF₃)₃,1,3,4-C₆H₃(CF₃)₃,1,3,5-C₆H₃(CF₃)₃,1,2,3-C₆H₃(NO₂)₃,1,3,4-C₆H₃(NO₂)₃,1,3,5-C₆H₃(NO₂)₃,1,2,3-C₆H₃F₃,1,3,4-C₆H₃F₃,1,3,5-C₆H₃F₃,1,2,3-C₆H₃(COOH)₃,1,3,4-C₆H₃(COOH)₃,1,3,5-C₆H₃(COOH)₃,1,2,3-C₆H₃(COOCF₃)₃,1,3,4-C₆H₃(COOCF₃)₃,1,3,5-C₆H₃(COOCF₃)₃,1,2,3-C₆H₃(OOCCF₃)₃,1,3,4-C₆H₃(OOCCF₃)₃,1,3,5-C₆H₃(OOCCF₃)₃,1,2,3-C₆H₃(CN)₃,1,3,4-C₆H₃(CN)₃,1,3,5-C₆H₃(CN)₃,1,2,3-C₆H₃(SO₃H)₃,1,3,4-C₆H₃(SO₃H)₃,1,3,5-C₆H₃(SO₃H)₃,1,2,3-C₆H₃(SO₃R)₃,1,3,4-C₆H₃(SO₃R)₃,1,3,5-C₆H₃(SO₃R)₃,1,2,3-C₆H₃(SO₃Q)₃,1,3,4-C₆H₃(SO₃Q)₃,1,3,5-C₆H₃(SO₃Q)₃,1,2,3-C₆H₃(CONH₂)₃,1,3,4-C₆H₃(CONH₂)₃And 1,3,5-C₆H₃(CONH₂)₃. As used herein, R is any aliphatic (e.g., C)_1-8Alkyl, fluoro-C_1-8Alkyl), heteroaliphatic, aromatic or heteroaromatic moieties, each of which is optionally substituted, and Q represents a cation.

In certain embodiments, the non-oxidizable liquid is a nitroarene. As used herein, "nitroarene" refers to any deactivated arene comprising at least one nitro group. For example, the nitroarene may be nitro-substituted benzene, nitro-substituted toluene, nitro-substituted xylene, nitro-substituted naphthalene, nitro-substituted biphenyl, or nitro-substituted anthracene.

In some embodiments, the non-oxidizable liquid is one or more deactivated aliphatic compounds. As used herein, "deactivated aliphatic compound" refers to at least one aliphatic group having 1 or more electron-withdrawing substituents as described herein (e.g., 2 or more, 3 or more, 4 or more, or 5 or more electron-withdrawing substituents).

In some embodiments, the deactivated aliphatic non-oxidizable liquid is at least one saturated, unsaturated, branched, straight chain, or cyclic C₁-C₉An alkyl aliphatic group substituted with at least one electron withdrawing substituent (e.g., 2 or more, 3 or more, 4 or more, or 5 or more electron withdrawing substituents). Deactivated C₁-C₉An illustrative but non-limiting list of alkylaliphatic radicals is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, cyclopentyl, cyclohexyl, propenyl, 2-butenyl, 3-butenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl or combinations thereof, wherein the C is₁-C₉The alkyl group is substituted with 1 or more electron-withdrawing substituents such as those described herein.

In certain instances, the deactivated aliphatic group is methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, or neopentyl, wherein the methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, or neopentyl is substituted with one or more electron withdrawing substituents. In certain embodiments, the deactivated aliphatic group is a methyl, ethyl, n-propyl, or isopropyl group, wherein the methyl, ethyl, n-propane, or isopropyl group is substituted with 1 or more electron withdrawing substituents such as those described herein.

In other embodiments, the deactivated aliphatic group is trifluoromethanol, trifluoromethyl 2,2, 2-trifluoroacetate, 2,2, 2-trifluoroethane-1-ol, 2,2, 2- trifluoroethyl 2,2, 2-trifluoroacetate, perfluoroethyl 2,2, 2-trifluoroacetate, 1,2,2, 2-pentafluoroethane-1-ol, nitromethane, trifluoro (nitro) methane, 1,2, 2-tetrafluoroethane-1, 2-diol, 1,2, 2-tetrafluoro-2- hydroxyethyl 2,2, 2-trifluoroacetate, perfluoroethane-1, 2-diylbis (2,2, 2-trifluoroacetate), ethane-1, 2-dibutylbis (2,2, 2-trifluoroacetate), 1,1,2,2,3, 3-hexafluoropropane-1, 3-diol, propane-1, 2, 3-triyltris (2,2, 2-trifluoroacetate), oxalic acid, 1,1,1,4,4, 4-hexafluorobutane-2, 3-dione, methyl 2,2, 2-trifluoroacetate, methyl 2,2,3,3, 3-pentafluoropropionate or trifluoromethyl 2,2,3,3, 3-pentafluoropropionate.

In other embodiments, the deactivated aliphatic group is trifluoromethyl acetate, ethyl 1, 1-difluoroacetate, ethyl 2,2, 2-trifluoroacetate, ethyl perfluoroacetate, perfluoropropan-2-ylacetate, l, l,3,3, 3-hexafluoropropan-2-yl acetate, 1,2, 2-tetrafluoro-2-hydroxyethyl acetate, perfluoroethane-1, 2-diyl diacetate, ethane-1, 2-diyl diacetate, propane 1,2, 3-triyl triacetate, perfluoropropane-1, 2, 3-triyl triacetate, 1,3, 3-tetrafluoropropane-1, 2, 3-triyl triacetate or 1, 1-difluoroethane-1, 2-diyl diacetate.

In some embodiments, the non-oxidizable liquid is one or more deactivated heteroarenes. As used herein, "deactivated heteroarenes" refers to at least one monocyclic or polycyclic heteroaromatic compound having at least one heteroatom (O, S or N) in at least one ring. The term "heteroaromatic" is as described herein.

In some embodiments, the deactivated heteroarene is isoxazole, oxazole, isothiazole, thiazole, imidazole, thiadiazole, tetrazole, triazole, oxadiazole, pyrazole, pyrazine, pyrimidine, or triazine, each of which is substituted or unsubstituted. In other preferred embodiments, the deactivated heteroarene is pyrrole, furan, thiophene or pyridine, each of which is substituted with at least one substituent that is an electron-withdrawing substituent.

In other embodiments, the deactivated heteroarene is perfluoroisoxazole, perfluorooxazole, perfluoroisothiazole, perfluorothiazole, perfluoroimidazole, perfluorothiadiazole, perfluorotetrazole, perfluorotriazole, perfluorooxadiazole, perfluoropyrazole, perfluoropyrazine, perfluorotriazine, perfluoropyrrole, perfluorofuran, perfluorothiophene, perfluoropyridine, nitropyrrole, nitrofuran, nitrothiophene, nitropyridine, cyanopyrrole, cyanofuran, cyanothiophene, cyanopyridine, picolinic acid, nicotinic acid, isonicotinic acid, pyridinesulfonic acid, pyrrolesulfonic acid, furansulfonic acid, thiophenesulfonic acid, pyridinecarboxylic acid, pyrrolecarboxylic acid, furancarboxylic acid, thiophenecarboxylic acid, trifluoromethylpyridine, trifluoromethylpyrrole, trifluoromethylfuran, or trifluoromethylthiophene.

In some embodiments, the non-oxidizable liquid is one or more deactivated heteroaliphatic compounds. The term "heteroaliphatic" is as described herein. In some embodiments, the heteroaliphatic compound is an ether, ester, carbonate, amide, amine, carbamate, thioether, thioester, phosphate ester, or heterocyclic alkane. The term "heterocycloalkane" refers to a cycloalkane as described herein, wherein at least one heteroatom (e.g., O, S, N and/or P) replaces at least one carbon in the ring system. In one aspect, the heterocycloalkane is a 5-, 6-or 7-membered monocyclic ring and contains one, two or three heteroatoms selected from nitrogen, oxygen and sulfur. Examples of such heterocycloalkyl rings are pyrrolidine, pyrroline, pyran, piperidine, quinuclidine, imidazoline, dioxane, dioxolane, morpholine, thiomorpholine, trithiane, dithiane, pyrazoline, pyrazolidine, piperazine, or combinations thereof.

In certain embodiments, the deactivated heteroaliphatic compound has at least 1 electron-withdrawing substituent. In some embodiments, the deactivated heteroaliphatic compound has at least 2 electron-withdrawing substituent substitutions, such as those described herein (e.g., at least 3, 4, 5, or 6 electron-withdrawing substituents).

In other embodiments, the deactivated heteroaliphatic compound is trifluoro (trifluoromethoxy) methane, 1,1,1,2, 2-pentafluoro-2- (trifluoromethoxy) ethane, 1,1,1,2, 2-pentafluoro-2- (perfluoroethoxy) ethane, tris (trifluoromethyl) amine, 1,1,2,2, 2-pentafluoro-N- (perfluoroethyl) -N- (trifluoromethyl) ethan-1-amine, tris (perfluoroethyl) amine, 2,2, 2-trifluoro-N, N-bis (trifluoromethyl) acetamide, N-bis (trifluoromethyl) formamide, 2,2, 2-trifluoroacetamide, perfluoropyrrolidine, perfluoropyrroline, perfluoropyran, perfluoropiperidine, perfluorodioxane, perfluoromorpholine, Perfluoropiperazine, nitropyrrolidine, nitropyrroline, nitropyran, nitropiperidine, nitrodioxane, nitromorpholine, nitropiperazine, cyanopyrrolidine, cyanopyrroline, cyanopyran, cyanopiperidine, cyanopyridine, cyanopiperazine, pyrrolidinecarboxylic acid, pyrrolinocarboxylic acid, pyranecarboxylic acid, piperidinecarboxylic acid, dioxanecarboxylic acid, morpholinecarboxylic acid, piperazinecarboxylic acid, pyrrolidinesulfonic acid, pyrrolinesulfonic acid, pyranesulfonic acid, piperidinesulfonic acid, dioxanesulfonic acid, morpholinesulfonic acid, or piperazinesulfonic acid.

In some embodiments, the non-oxidizable liquid is one or more carbonates. The carbonate may be a compound comprising at least one carbonate moiety (e.g., a 1 carbon acid ester, a 2 carbon acid ester, a 3 carbon acid ester, or a 4 carbon acid ester). For example, the carbonate may be an alkyl carbonate, a heteroalkyl carbonate, a cycloalkyl carbonate, a heterocycloalkyl carbonate, an aryl carbonate, a bicarbonate, or a combination thereof.

In any of the embodiments described herein, the electron-withdrawing substituent may be any suitable electron-withdrawing group, such as-NO₂fluoro-C_1-8Alkyl, -F, -OOCR, -COOH, -OH₂ ⁺、-CONH₂、-COOR、-NR₃ ⁺、-CN、-SO₃H、-SO₃R、-SO₃W or a combination thereof, wherein R is hydrogen or any aliphatic group (e.g., C)_1-8Alkyl, fluoro-C_1-8Alkyl), a heteroaliphatic, aromatic, or heteroaromatic moiety, each of which is optionally substituted, and W is a cation comprising a metal selected from: boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, alkali metals or alkaline earth metals. In certain embodiments, R is-CF₃。

In some embodiments, the non-oxidizable liquid is the same as the product of the reaction described herein. For example, the non-oxidizable liquid can be an oxidized intermediate (e.g., the oxidation product of propane can be l, 2-propane (trifluoroacetate), which is a deactivated heteroaliphatic compound).

In some embodiments, the liquid medium comprises a salt additive.

Typically, the salt additive is one or more of formula Q_aZ_bWherein Q is a cation, Z is an anion of a bridging oxide, terminal oxide, hydroxide or oxyacid, a is an integer from 1 to 5 (i.e., 1,2,3, 4 or 5), b is an integer from 1 to 5 (i.e., 1,2,3, 4 or 5), and wherein a and b are the same or different and balance the oxidation states of Q and Z.

Q may be any suitable cation in any suitable oxidation state. In some embodiments, Q can be a proton, ammonium, alkali metal cation, alkaline earth metal cation, rare earth metal cation, main group element cation, or combinations thereof. In some embodiments, Q is hydrogen or a cation of lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, or radium. Typically, Q has an oxidation state of +5, +4, +3, +2, or + 1.

Z may be any suitable oxide (e.g., bridging oxide or terminal oxide), hydroxide, or anion of an oxo acid in any suitable oxidation state as described herein. In some embodiments, Z is an anion of an oxyacid that is one or more selected from the group consisting of aliphatic carboxylates, heteroaliphatic carboxylates, aromatic carboxylates, heteroaromatic carboxylates, aliphatic sulfonates, heteroaliphatic sulfonates, aromatic sulfonates, heteroaromatic sulfonates, aliphatic phosphates, heteroaliphatic phosphates, aromatic phosphates, heteroaromatic phosphates, aliphatic borates, heteroaliphatic borates, aromatic borates, and heteroaromatic borates. In certain embodiments, Z is selected from the group consisting of bridging oxides, terminal oxides, hydroxides, sulfites, sulfates, bisulfates, thiosulfates, nitrites, nitrates, phosphites, phosphates, hydrogenphosphates, dihydrogenphosphates, carbonates, hydrogencarbonates, oxalates, cyanates, isocyanates, thiocyanates, carboxylates, sulfonates, and combinations thereof. As used herein, a carboxylate may be an alkylated variant (e.g., acetate), a fluorinated variant (e.g., trifluoroacetate), or an arylated variant (e.g., benzoate or benzoic acid). As used herein, "alkylated variants" and "arylated variants" refer to carboxylic acids comprising an alkyl or aryl group, respectively, as defined herein. Similarly, the sulfonate can be an alkylated variant (e.g., methanesulfonate) or a fluorinated variant (e.g., trifluoromethanesulfonate). In certain embodiments, Z is one or more selected from the group consisting of trifluoroacetate, acetate, benzoate, sulfate, methanesulfonate, and trifluoromethanesulfonate. Typically, Z has an oxidation state of-4, -3, -2, or-1.

The oxoacid in the context of the oxidizing electrophile and the oxoacid in the context of the additive are each independently selected. Thus, the oxoacid in the context of the oxidizing electrophile and the oxoacid in the context of the additive may be the same or different. Typically, the oxoacid in the context of the oxidizing electrophile and the oxoacid in the context of the additive are the same.

In a preferred embodiment, the liquid medium and/or the oxidizing composition comprises a salt of an oxyacid.

In certain embodiments, the oxidizing electrophilic reagent is of formula M⁺ⁿX_pL_qX of (A) is the same as Z of the additive.

In certain embodiments, the oxidizing electrophilic reagent is of formula M⁺ⁿX_pL_qX of (b) is different from Z of the additive.

In some embodiments, Q_aZ_bIs a bronsted acid, salt or combination thereof. In some cases, Q_aZ_bIs acetic acid, ammonium acetate, lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, francium acetate, beryllium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, radium acetate, benzoic acid, ammonium benzoate, lithium benzoate, sodium benzoate, potassium benzoate, rubidium benzoate, cesium benzoate, francium benzoate, beryllium benzoate, magnesium benzoate, calcium benzoate, strontium benzoate, barium benzoate, radium benzoate, trifluoroacetic acid, ammonium trifluoroacetate, lithium trifluoroacetate, sodium trifluoroacetate, potassium trifluoroacetate, rubidium trifluoroacetate, cesium trifluoroacetate, francium trifluoroacetate, beryllium trifluoroacetate, magnesium trifluoroacetate, calcium trifluoroacetate, strontium trifluoroacetate, barium trifluoroacetate, radium trifluoroacetate, sulfuric acid, ammonium sulfate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, francium trifluoroacetate, magnesium trifluoroacetate, lithium trifluoroacetate, sodium sulfate, potassium sulfate, strontium trifluoroacetate, barium trifluoroacetate, Cesium sulfate, francium sulfate, beryllium sulfate, magnesium sulfate, calcium sulfate, strontium sulfate, barium sulfate, radium sulfate, phosphoric acid, methanesulfonic acid, ammonium methanesulfonate, lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, rubidium methanesulfonate, cesium methanesulfonate, francium methanesulfonate, beryllium methanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, strontium methanesulfonate, barium methanesulfonate, radium methanesulfonate, trifluoromethanesulfonic acid, ammonium trifluoromethanesulfonate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, rubidium trifluoromethanesulfonate, cesium trifluoromethanesulfonate, francium trifluoromethanesulfonate, beryllium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, strontium trifluoromethanesulfonate, barium trifluoromethanesulfonate, or radium trifluoromethanesulfonate. In a preferred embodiment, Q_aZ_bIs trifluoroacetic acid, acetic acid, benzoic acid, methanesulfonic acid, or a combination thereof, each of which may be substituted or unsubstituted.

In some embodiments, the liquid medium and/or the oxidizing composition comprises a lewis acid. Typically, the Lewis acid has the formula Q_aZ_bWherein Q is_aZ_bIs any suitable non-halide containing lewis acid that is a strong electron pair acceptor. In which Q is_aZ_bIn embodiments where the Lewis acid is a non-halide containing Lewis acid, Q may be perTransition metal cations, rare earth metal cations, main group element cations, or combinations thereof. In some embodiments, Q is a cation of boron, bismuth, antimony, arsenic, lanthanum, cerium, scandium, yttrium, titanium, zirconium, hafnium, silver, zinc, cadmium, aluminum, gallium, indium, germanium, tin, phosphorus, or a combination thereof. Typically, Q has an oxidation state of +5, +4, +3, +2, or + 1. In certain embodiments, Q is in (III), Sc (III), Zn (II), Ti (IV), Al (III), Ga (III), B (III), Sb (III), Bi (III), or As (III). It will be appreciated that any one or more Q may be combined with one or more Z to satisfy the basic chemical rules to form a non-halide containing Lewis acid (e.g., Ce (OAc))₃、Ce(OTf)₃、Zn(OAc)₂、Zn(OTf)₂、ZnO、In(OAc)₃、In(OTf)₃、In₂O₃、Sb(OAc)₃、Sb(OTf)₃、Sb₂O₃，Bi(OAc)₃、Bi(OTf)₃、Bi₂O₃、Al(OTf)₃、Ga(OTf)₃、Sc(OAc)₃、Sc(OTf)₃Or Sc (OMs)₃). As used herein, "OTf" refers to the triflate, "OMs" refers to the mesylate salt, and "OAc" refers to the acetate salt.

In some embodiments, the liquid medium does not contain halide ions (e.g., Cl)^-、Br^-Or I^-). As used herein, the term "halide ion" is considered to be different from the term halogen atom. In particular, the term halide ion does not include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom) attached to an aliphatic or aromatic substituent (i.e., a substituent that does not decompose under reaction conditions to form a free ion). For example, iodine may be present in aromatic iodine species because this form of iodine is not considered to be a halide ion. In contrast, the term "halide ion" refers to an ion of a salt additive, such as an alkali halide compound (e.g., NaI, KCl, etc.). Thus, the halide ion can be present in the liquid medium in an amount of less than 0.1 mol% (e.g., less than 0.05 mol%, less than 0.01 mol%, less than 0.005 mol%, less than 0.001 mol%) or about 0 mol% of the main group element.

In some embodiments, the liquid medium contains trace amounts of halide ions (e.g., Cl-, Br-, I)^-Or a combination thereof). Impurities in the starting materials or impurities from reactor corrosion may be responsible for the presence of trace halide ions. Thus, the halide ion can be present in an amount of about 0.00001 mol% or greater (e.g., about 0.0001 mol% or greater, about 0.001 mol% or greater, 0.01 mol% or greater, or about 0.1 mol% or greater, or about 1 mol% or greater) of the main group element. Alternatively or additionally, the halide ion may be present in an amount of about 5 mol% or less (e.g., about 4 mol% or less, about 3 mol% or less, about 2 mol% or less, or about 1 mol% or less, or about 0.1 mol% or less) of the main group element. Any two of the foregoing endpoints can be used to define a closed range, or any single endpoint can be used alone to define an open range.

In some embodiments, the additive is water.

In some embodiments, the method comprises separating one or more components from the liquid medium. One or more components may be separated by any suitable means, for example by filtration, distillation, flash evaporation, rectification, stripping, evaporation, absorption, adsorption, column chromatography, crystallization, centrifugation, extraction, recrystallization, membrane separation, or any combination thereof.

Distillation may be used to separate the components of the liquid medium based on differences in the volatility of the components of the mixture. The distillation process may optionally include a chemical reaction. An example of distillation is the removal of water and glycol products from a mixture of higher boiling components comprising oxidizing electrophiles in solution.

Flash evaporation may be used to remove one or more light components from the liquid medium. Flashing is the partial vaporization that occurs when the pressure of a liquid stream is reduced. A typical flash process includes a flow restrictor, such as a control valve, followed by a vessel (i.e., a flash drum) to allow for the de-entrainment of liquid from the gas stream. Additional heating or cooling is optional. The flashing operation may be combined with a chemical reaction. In the flash, the vapor phase is richer in the more volatile components than the remaining liquid phase. The adiabatic flash process results in a lower temperature of the outlet stream compared to the inlet feed. An example of flashing is the removal of light hydrocarbons, dissolved gases and a portion of light components from a liquid mixture that includes metals in solution (e.g., thallium).

Rectification may be used to remove one or more heavier components from a vapor stream by contact with a liquid stream. The less volatile components are concentrated in the liquid stream. The two streams may be contacted by using a packed column, a tray column, a bubble column or a centrifugal contactor. The flow may be co-current or counter-current. Rectification may optionally be combined with chemical reactions. One example of rectification is the removal of ester reaction products from a vapor stream by contact with a liquid stream.

Stripping can be used to remove one or more lighter components from a liquid stream by contact with a vapor stream. The volatile components are concentrated in the vapor stream. The two streams may be contacted by using a packed column, a tray column, a bubble column or a centrifugal contactor. The flow may be co-current or counter-current. The steam stream used for stripping can include steam, air, nitrogen, process streams, and/or other suitable materials to achieve the desired separation. Stripping may optionally be combined with chemical reactions. An example of stripping is the removal of lighter reaction products from the liquid phase by contact with a gas stream.

Evaporation may be used to remove the lighter components by evaporation at the liquid/vapor interface. Evaporator designs may include falling film, rising film, wiped film, plate, and multiple effect evaporators. The evaporation process may optionally be combined with a chemical reaction. One example of an evaporation process is the removal of acetic acid and water from a mixture of heavier liquid components, including antimony species in solution.

Absorption (scrubbing) may be used to selectively dissolve one or more components of the gas mixture into the liquid phase. The two streams may be contacted by using a packed column, a tray column, a bubble column or a centrifugal contactor. If a chemical reaction occurs, the process is called chemisorption. The liquid is selected to achieve the desired separation effect. One example of absorption is the removal of water from a vapor recycle stream by contact with a glycol mixture.

Adsorption can be used to selectively remove one or more components in a stream based on physical or chemical interaction with a solid surface. If a chemical reaction occurs, the process is called chemisorption. The solids are selected to achieve the desired separation effect. One example of adsorption is the use of narrow pore silica to remove water from a liquid recycle stream.

Extraction (partitioning) can be used to selectively remove one or more components from a liquid phase by contact with a second liquid. Due to the different solubility of the two liquid phases, there is a net transfer of material from one phase to the other. The extraction process may optionally be combined with a chemical reaction. One example of extraction is contacting the reactor effluent with a second phase that selectively dissolves the particular reaction products.

Membrane separation can be used to selectively remove one or more components from a fluid stream that includes gases and liquids. For example, pervaporation is a process for separating one or more components from a liquid stream by partial vaporization of a porous or non-porous membrane. Vapor permeation is a process of separating one or more components from a vapor stream by utilizing a porous or non-porous membrane. The membrane material is selected based on its different permeabilities to different components. Membrane separation may optionally be combined with chemical reactions. One example of membrane separation is the use of selective ceramic membranes to remove water from organic reaction mixtures.

The above processes, such as membrane distillation or extractive distillation, may be combined to separate the components of the liquid medium.

In some embodiments, the method comprises (b) separating the oxidized intermediate and the reduced form of the oxidizing electrophile. The separation step may be any suitable method, such as the methods described herein. For example, the oxidized intermediate and the reduced form of the electrophile can be separated by distillation.

The present invention further comprises a process comprising subjecting the oxidized intermediate to an elimination reaction to provide an olefin and to reform the oxoacid. As used herein, the term "elimination reaction" refers to a class of organic chemical reactions in which a pair of atoms or groups of atoms are removed from a molecule, typically by the action of an acid, base, metal, heat (e.g., to an elevated temperature), or a combination thereof. Typically, the elimination reaction removes the hydrogen atom and the conjugate anion of the oxoacid to produce the olefin and the corresponding oxoacid.

In some embodiments, the elimination reaction is carried out in the presence of an acid catalyst capable of promoting the elimination reaction. As used herein, the phrase "facilitating an elimination reaction" refers to reducing the activation energy necessary for elimination. In some embodiments, the acid catalyst is an acid (e.g., an oxyacid), including those described herein.

In some embodiments, the elimination reaction is carried out in the presence of a base catalyst capable of promoting the elimination reaction. In some embodiments, the base catalyst is a conjugate anion of an oxo acid as described herein. In certain embodiments, a stronger base, such as an alkali metal hydroxide or alkaline earth metal hydroxide, is required to facilitate the elimination reaction.

In some embodiments, the elimination reaction is performed by heating the reaction mixture. Generally, the process of conducting the elimination reaction requires a higher temperature than that required to produce the oxidized intermediate from the oxidizing electrophile and alkane. However, in some embodiments (e.g., via acid or base-promoted elimination reactions), the elimination reaction may occur at a temperature similar to that required to produce an oxidized intermediate from the oxidizing electrophile and alkane.

In further embodiments, the process comprises separating the alkene and the oxoacid by any suitable method, such as those described herein. Preferably, the olefin and the oxo acid are separated by distillation. In some embodiments, the separated oxoacids are recycled for use in step (a), as described herein.

In some embodiments, the method further comprises (e) contacting the reduced form of the oxidizing electrophile with a suitable oxidizing rejuvenating reagent to rejuvenate the oxidizing electrophile. Generally, the term "oxidant" is used in the context of generating an oxidizing electrophile, and the phrase "oxidative regenerant" is used in the context of regenerating an oxidizing electrophile. However, the oxidizing agent and the oxidative regeneration agent may be used interchangeably and refer to the chemical moiety used to convert the reduced form of the oxidative electrophile to the oxidative electrophile. The oxidative regeneration reagent may be the same or different from the oxidizing agent. For example, the oxidative regeneration agent can be a quinone, molecular oxygen, air, ozone, peroxide, nitric oxide, nitrous oxide, nitric acid, nitroxide, sulfur trioxide, or combinations thereof. The peroxide may be an organic peroxide, an inorganic peroxide, hydrogen peroxide, or a combination thereof. In some embodiments, the oxidative regeneration reagent may be an organic oxidizer, such as a quinone or a nitroxide. In certain preferred embodiments, the oxidative regeneration agent is molecular oxygen, air, ozone, hydrogen peroxide, organic peroxides, nitric acid, or combinations thereof.

In some embodiments, step (e) is an electrochemical process. As used herein, "electrochemical process" refers to a process that includes the transfer of electrons to or from molecules or ions using, for example, an electrical current and/or an external voltage.

Thus, a process for converting alkanes to alkenes may include an oxidative rejuvenating agent or an oxidant or both an oxidative rejuvenating agent and an oxidant, or neither an oxidative rejuvenating agent nor an oxidant.

In some embodiments, the process for converting alkanes to alkenes comprises neither an oxidative regeneration reagent nor an oxidant. Thus, the oxidative regeneration reagent and the oxidizing agent may be present in an amount of 0 mol% (e.g., below detection levels) of the main group element.

In some embodiments, an oxidative regeneration reagent and/or an oxidizing agent is present in the liquid medium. The amount of oxidative regenerant and/or oxidant is not particularly limited as long as a sufficient amount of oxidative electrophile is maintained in the liquid medium to convert a portion of the alkane to alkene. Thus, the oxidative regeneration reagent and/or oxidant may be present in an amount of about 0.1 mol% or more (e.g., about 0.2 mol% or more, about 0.3 mol% or more, about 0.4 mol% or more, about 0.5 mol% or more, about 1 mol% or more, about 2 mol% or more, about 3 mol% or more, about 5 mol% or more, about 10 mol% or more, about 20 mol% or more, about 50 mol% or more, or about 100 mol% or more) of the alkane. Alternatively or additionally, the oxidative regeneration reagent and/or oxidant may be present in an amount of about 2000 mol% or less (e.g., about 1500 mol% or less, about 1000 mol% or less, about 900 mol% or less, about 800 mol% or less, about 700 mol% or less, about 600 mol% or less, about 500 mol% or less, about 400 mol% or less, about 300 mol% or less, about 200 mol% or less, about 100 mol% or less) of the alkane. Any two of the foregoing endpoints can be used to define a closed range, or any single endpoint can be used alone to define an open range.

In some embodiments, the reduced form of the oxidative electrophile is contacted with the oxidative regeneration reagent in the presence of the oxidative regeneration catalyst to regenerate the oxidative electrophile. The oxidative regeneration catalyst may be any suitable catalyst, such as an oxidative regeneration catalyst comprising copper, silver, iron, cobalt, manganese, nickel, chromium, vanadium, or combinations thereof.

In certain embodiments, the oxidative regenerant oxidizes a reduced form of an oxidative electrophile to an oxidative electrophile in a liquid medium in the presence of an alkane. In certain embodiments, the oxidative regeneration reagent oxidizes the reduced form of the oxidative electrophile to an oxidative electrophile in a separate reactor and added back to the liquid medium. Thus, as described herein, the regenerated oxidizing electrophile can be recycled for use in step (a).

The process for converting alkanes to alkenes may further comprise recycling any components not consumed in the process for reuse in the process (e.g., for reuse in the liquid medium and/or the oxidizing composition). For example, the substrate, oxidizing electrophile, non-oxidizable liquid, additive, or any combination thereof can be recycled and reused in the process.

In some embodiments, a method of converting an alkane to an alkene comprises an oxidizing electrophile and/or a reduced form of an oxidizing electrophile, and a liquid medium that is a heterogeneous mixture or a homogeneous mixture.

As used herein, the phrase "homogeneous mixture" refers to a homogeneous composition comprising one or more phases (e.g., liquid/liquid, liquid/solid, liquid/gas, solid/gas, or liquid/solid/gas). Thus, a homogeneous mixture comprising a liquid may also comprise a gas and/or a solid only if the gas and/or solid is soluble in the liquid to form a homogeneous composition. In embodiments where the liquid medium is a homogeneous mixture, the oxidizing electrophile and/or the reduced form of the oxidizing electrophile is soluble in the liquid medium.

In a preferred embodiment, the liquid medium is a homogeneous mixture. In other preferred embodiments, the liquid medium is a heterogeneous mixture in which any component may be insoluble in the liquid medium, so long as the oxidizing electrophile maintains a level of solubility. Without wishing to be bound by any particular theory, it is believed that the reaction is more efficient when at least the oxidizing electrophile is soluble in the liquid medium. In some embodiments, the liquid medium may transition from a homogeneous mixture to a heterogeneous mixture, or from a heterogeneous mixture to a homogeneous mixture.

In some embodiments, the oxidizing electrophile maintains a solubility such that about 25% or less of the total mass of the oxidizing electrophile is undissolved solids in the mixture (e.g., about 20% or less, about 15% or less, about 12% or less, about 10% or less, about 5% or less, or about 1% or less). Alternatively, the oxidizing electrophile can be completely soluble in the liquid medium (e.g., about 0% of the total mass of the oxidizing electrophile is insoluble solids in the mixture). Thus, the oxidizing electrophile maintains a level of solubility such that about 0% to about 25% of the total mass of the oxidizing electrophile is insoluble solids in the mixture (e.g., about 0% to about 20%, about 0% to about 15%, about 0% to about 12%, about 0% to about 10%, about 0% to about 5%, or about 0% to about 1%).

As used herein, the phrase "insoluble solid" refers to any solid that does not readily dissolve in a liquid medium to form a homogeneous (e.g., homogeneous) composition. The amount of undissolved solids can be determined by any suitable means. For example, microfiltration (i.e., a filter ranging from about 0.1 microns to about 1.0 microns) can be used to filter out an amount of insoluble solids from the liquid medium. Thus, the percentage of the total mass of oxidizing electrophile present as an insoluble solid in the mixture can be determined by dividing the mass of insoluble oxidizing electrophile filtered from the liquid medium using microfiltration by the theoretical total mass of oxidizing electrophile in the mixture.

In some embodiments, the reduced and oxidized forms of the main group element-containing electrophile are soluble in the liquid medium, regardless of whether the mixture is heterogeneous or homogeneous. Thus, the mixture is substantially free (e.g., about 0% by mass and/or below detection levels) of solids comprising oxidizing electrophiles.

The process for converting alkanes to alkenes may be carried out in a single reactor or in at least 2 reactors (e.g., at least 3 or at least 4 reactors). When the process is carried out in a single reactor and the oxidizing electrophile is present in at least a stoichiometric amount, the process for converting an alkane to an alkene does not require regeneration of the oxidizing electrophile. In this embodiment, the process for converting alkanes to alkenes may be carried out under a single set of conditions in a single reactor.

Alternatively, the process may be carried out in a single reactor, wherein the reactor is operated under conditions suitable for converting an alkane to an alkene using an oxidative electrophile and simultaneously regenerating the oxidative electrophile by contacting the electrophile reduction product with an oxidative regeneration reagent. For example, when the oxidizing electrophile is depleted, the oxidizing regenerator is present in the liquid dielectric medium, optionally in the presence of an oxidizing regeneration catalyst, to regenerate the oxidizing electrophile.

In some embodiments, the process may be carried out in a sequential manner in a single reactor. For example, the reactor may be operated first under conditions suitable for converting an alkane to an oxygenated intermediate using an oxidizing electrophile, followed by an elimination reaction, and then subsequently operated under conditions suitable for regenerating the oxidizing electrophile by contacting the electrophile reduction product with an oxidizing regenerant. For example, the oxidizing electrophile may be immobilized within a reactor, wherein the mixture comprising the alkane is first recycled, and then the mixture comprising the oxidizing rejuvenating agent is recycled to rejuvenate the oxidizing electrophile, optionally in the presence of an oxidative regeneration catalyst, upon depletion of the oxidizing electrophile and/or separation of the alkene.

Optionally, the process may be carried out in a two-reactor circulating liquid phase system, wherein the alkane to alkene reaction is carried out in a first reactor and the electrophile reduction product for regenerating the oxidative electrophile and the oxidative regenerant reaction are carried out in a second reactor.

Alternatively, the process may be carried out in a three reactor circulating liquid phase system, wherein the reaction of the alkane to the oxidized intermediate is carried out in a first reactor, the elimination reaction of the oxidized intermediate to the alkene is carried out in a second reactor, and the reaction of the electrophile reduction product for regenerating the oxidizing electrophile and the oxidizing regenerant is carried out in a third reactor.

The process of the present invention may be carried out at any temperature suitable for forming an oxygenated intermediate and ultimately an olefin. In some embodiments, the process for oxidizing alkanes can be carried out at less than about 300 ℃, e.g., less than about 285 ℃, less than about 275 ℃, less than about 260 ℃, less than about 250 ℃, less than about 225 ℃, less than about 200 ℃, less than about 150 ℃, or less than about 140 ℃. Alternatively or additionally, the process for oxidizing alkanes may be carried out at greater than about 50 ℃, such as greater than about 70 ℃, greater than about 80 ℃, greater than about 100 ℃, greater than about 120 ℃, greater than about 140 ℃, greater than about 150 ℃, greater than about 160 ℃, greater than about 170 ℃, greater than about 180 ℃, greater than about 190 ℃ or greater than about 200 ℃. Any two of the foregoing endpoints can be used to define a closed range, or one endpoint can be used alone to define an open range. Thus, the process may be carried out at a temperature of from about 50 ℃ to about 300 ℃, e.g., from about 50 ℃ to about 275 ℃, from about 50 ℃ to about 250 ℃, from about 50 ℃ to about 225 ℃, from about 50 ℃ to about 200 ℃, from about 70 ℃ to about 200 ℃, from about 80 ℃ to about 200 ℃, from about 70 ℃ to about 140 ℃, from about 100 ℃ to about 200 ℃, from about 120 ℃ to about 200 ℃, from about 140 ℃ to about 200 ℃, from about 150 ℃ to about 200 ℃, from about 160 ℃ to about 200 ℃, from about 170 ℃ to about 200 ℃, from about 180 ℃ to about 200 ℃, from about 190 ℃ to about 200 ℃, from about 200 ℃ to about 300 ℃, from about 200 ℃ to about 350 ℃, from about 100 ℃ to about 300 ℃, or from about 150 ℃ to about 250 ℃. In some embodiments, the temperature is from about 50 ℃ to about 300 ℃, and more preferably from about 70 ℃ to about 140 ℃.

The process of the present invention may be carried out at any pressure suitable for forming an oxygenated intermediate and ultimately an olefin. In some embodiments, the process for oxidizing alkanes may be carried out at less than about 2000psi (about 13800kPa), for example, less than about 1500psi (about 10300kPa), less than about 1000psi (about 6900kPa), less than about 500psi (about 3450kPa), less than about 400psi (about 2800kPa), less than about 300psi (about 2100kPa), or less than about 200psi (about 1400 kPa). Alternatively or additionally, the process for oxidizing alkanes may be carried out at greater than about 0psi (about 0kPa), for example, greater than about 1psi (about 6.9kPa), greater than about 2psi (about 13.8kPa), greater than about 3psi (about 20.7kPa), greater than about 4psi (about 27.6kPa), greater than about 5psi (about 34.5kPa), greater than about 10psi (about 69kPa), or greater than about 20psi (about 138 kPa). Any two of the foregoing endpoints can be used to define a closed range, or one endpoint can be used alone to define an open range. Thus, the process may be at about 0psi (about 0kPa) to about 2000psi (about 13800kPa), such as about 0psi (about 0kPa) to about 1500psi (about 10300kPa), about 0psi (about 0kPa) to about 1000psi (about 6900kPa), about 0psi (about 0kPa) to about 500psi (about 3450kPa), about 0psi (about 0kPa) to about 400psi (about 2800kPa), about 0psi (about 0kPa) to about 300psi (about 2100kPa), about 0psi (about 0kPa) to about 200psi (about 1400kPa), about 2psi (about 13.8kPa) to about 1500psi (about 00kPa), about 2psi (about 13.8kPa) to about 1000psi (about 6900kPa), about 2psi (about 13.8kPa) to about 500psi (about 50kPa), about 2psi (about 13.8kPa) to about 400kPa (about 2800kPa), about 2psi (about 13.8kPa) to about 300kPa), about 2psi (about 13.8kPa) to about 500 kPa (about 200 kPa), about 2psi (about 2.8 kPa) to about 200 kPa (about 200 kPa), about 2.10 kPa (about 2800kPa), about 2psi (about 13.8kPa), about 200 kPa) to about 200 kPa (about 200 kPa), about 2.8 kPa (about 10 kPa), about 2psi (about 280, From about 5psi (about 34.5kPa) to about 1000psi (about 6900kPa), from about 5psi (about 34.5kPa) to about 500psi (about 3450kPa), from about 5psi (about 34.5kPa) to about 400psi (about 2800kPa), from about 5psi (about 34.5kPa) to about 300psi (about 2100kPa), or from about 5psi (about 34.5kPa) to about 200psi (about 1400kPa), in some embodiments from about 2psi (about 13.8kPa) to about 500psi (about 3450kPa), and more preferably from about 5psi (about 34.5kPa) to about 200psi (about 1400 kPa).

The invention is further illustrated by the following examples.

(1) A process for converting an alkane to an alkene comprising (a) contacting an alkane with (i) an oxidizing electrophile comprising an oxidized form of a main group element, or with (ii) an oxidizing agent and a reduced form of an oxidizing electrophile, in a liquid medium comprising an oxoacid and optionally one or more additives selected from the group consisting of non-oxidizable liquids, salt additives, lewis acids, and water, to provide an oxidized intermediate and a reduced form of the oxidizing electrophile; (b) optionally separating the oxidized intermediate from the reduced form of the oxidizing electrophile; and (c) subjecting the oxidized intermediate to an elimination reaction to provide the olefin and the oxoacid.

(2) The method of embodiment (1), comprising (b) separating the oxidized intermediate and the reduced form of the oxidizing electrophile.

(3) The method of embodiment (1) or embodiment (2), wherein (c) is carried out in the presence of an acid catalyst.

(4) The method of embodiment (1) or embodiment (2), wherein (c) is carried out in the presence of a base catalyst.

(5) The process of any one of embodiments (l) - (4), further comprising (d) separating the olefin and the oxoacid.

(6) The process of embodiment (5), wherein the separated oxoacid is recycled for use in step (a).

(7) The method of any of embodiments (l) - (6), wherein the alkane is C₂-C₂₀Alkane, C₂-C₂₀Heteroalkane, C₃-C₂₀Cycloalkanes, C₃-C₂₀A heterocyclic alkane, an aryl alkane, a heteroaryl alkane, or a combination thereof.

(8) The process of embodiment (7), wherein the alkane is ethane, propane, butane, or a mixture thereof.

(9) The method of any of embodiments (l) - (8), wherein the oxidizing electrophile comprises a main group element.

(10) The method of embodiment (9), wherein the oxidizing electrophile comprises gallium, germanium, arsenic, tin, thallium, lead, antimony, selenium, tellurium, bismuth, or iodine.

(11) The method of embodiment (10), wherein the oxidizing electrophile comprises sb (v), te (vi), te (iv), bi (v), se (vi), se (iv), as (v), i (iii), or sn (iv).

(12) The method of any of embodiments (l) - (11), wherein the oxidizing electrophile comprises at least one conjugate anion of an oxoacid.

(13) The method of embodiment (l2), wherein the conjugated anion of the oxoacid is an aliphatic carboxylate, heteroaliphatic carboxylate, aromatic carboxylate, heteroaromatic carboxylate, aliphatic sulfonate, heteroaliphatic sulfonate, aromatic sulfonate, heteroaromatic sulfonate, aliphatic phosphate, heteroaliphatic phosphate, aromatic phosphate, heteroaromatic phosphate, aliphatic borate, heteroaliphatic borate, aromatic borate, heteroaromatic borate, or a mixture thereof.

(14) The method of embodiment (l2), wherein the conjugate anion of an oxo acid is trifluoroacetate, acetate, alkylsulfonate, phosphate, nitrate, sulfate, trifluoromethanesulfonate or fluorosulfate.

(15) The method of any of embodiments (1-l4), wherein the oxidizing electrophile is of formula M^{+ n}X_pL_qWherein M is a cation of a main group element in oxidation state n, X is a conjugate anion of an oxoacid, L is a ligand, n is an integer of 2 to 6, p is an integer of 1 to 6, and q is an integer of 0 to 5.

(16) The method of embodiment (15), wherein M⁺ⁿX_pL_qWith alkanes in a liquid medium to give a reduced form of formula M^+(n-2)X_p-2L_qOr M^+(n-1)X_p-1L_qOxidizing electrophiles.

(17) The process of any of embodiments (1) - (16), wherein the oxidizing electrophile is present in an at least stoichiometric amount relative to the amount of olefin produced.

(18) The process of any of embodiments (1) - (17), wherein the oxidizing electrophile is present in a less than stoichiometric amount relative to the alkane and is used as a catalyst.

(19) The method of embodiment (18), further comprising (e) contacting the reduced form of the oxidative electrophile with an oxidative regeneration reagent to regenerate the oxidative electrophile.

(20) The method of embodiment (19), wherein the oxidative regeneration reagent is a quinone, molecular oxygen, air, ozone, peroxide, nitric oxide, nitrous oxide, nitric acid, nitroxide, sulfur trioxide, or a combination thereof.

(21) The method of embodiment (19), wherein step (e) is an electrochemical process.

(22) The process of any one of embodiments (19) - (21), wherein the reduced form of the oxidative electrophile is contacted with the oxidative regeneration reagent in the presence of an oxidative regeneration catalyst to regenerate the oxidative electrophile.

(23) The method of embodiment (22), wherein the oxidative regeneration catalyst comprises copper, silver, iron, cobalt, manganese, nickel, chromium, vanadium, or combinations thereof.

(24) The process of any one of embodiments (19) - (23), wherein the oxidative regeneration reagent oxidizes the reduced form of an oxidative electrophile to the oxidative electrophile in the liquid medium in the presence of an alkane.

(25) The process of any one of embodiments (19) - (24), wherein the regenerated oxidizing electrophile is recycled for use in step (a).

(26) The method of any one of embodiments (1) - (25), wherein the oxoacid is an aliphatic carboxylic acid, heteroaliphatic carboxylic acid, aromatic carboxylic acid, heteroaromatic carboxylic acid, aliphatic sulfonic acid, heteroaliphatic sulfonic acid, aromatic sulfonic acid, heteroaromatic sulfonic acid, aliphatic phosphonic acid, heteroaliphatic phosphonic acid, aromatic phosphonic acid, heteroaromatic phosphonic acid, boronic acid, aliphatic boronic acid, heteroaliphatic boronic acid, aromatic boronic acid, heteroaromatic boronic acid, or a mixture thereof.

(27) The method of any one of embodiments (l) - (26), wherein the oxoacid is trifluoroacetic acid, acetic acid, methanesulfonic acid, phosphoric acid, nitric acid, sulfuric acid, trifluoromethanesulfonic acid, fluorosulfuric acid, or a mixture thereof.

(28) The process of any of embodiments (l) - (27), wherein all or a portion of the oxo acid is added as the anhydride of the oxo acid.

(29) The process of any of embodiments (l) - (28), wherein the liquid medium comprises a non-oxidizable liquid selected from a fluorinated hydrocarbon, a sulfone, a deactivated aromatic hydrocarbon, a deactivated aliphatic compound, a deactivated heteroarene, a deactivated heteroaliphatic compound, or a combination thereof, wherein the liquid is substantially inert in the presence of an oxidizing electrophile.

(30) The method of any one of embodiments (l) - (29), wherein the liquid medium comprises a salt additive.

(31) The method of embodiment (30), wherein the liquid medium comprises formula Q_aZ_bA salt additive wherein Q is a cation, Z is a conjugate anion bridging an oxide, a terminal oxide, a hydroxide, or an oxyacid, a is an integer from 1 to 5, and b is an integer from 1 to 5, wherein a and b are the same or different and balance the oxidation states of Q and Z.

(32) The method of embodiment (31), wherein Z is a conjugated anion of an oxyacid and is one or more selected from aliphatic carboxylate, heteroaliphatic carboxylate, aromatic carboxylate, heteroaromatic carboxylate, aliphatic sulfonate, heteroaliphatic sulfonate, aromatic sulfonate, heteroaromatic sulfonate, aliphatic phosphate, heteroaliphatic phosphate, aromatic phosphate, heteroaromatic phosphate, aliphatic borate, heteroaliphatic borate, aromatic borate, heteroaromatic borate, or mixtures thereof.

(33) The method of embodiment (31) or (32), wherein Q is a proton, an alkali metal cation, an alkaline earth metal cation, a rare earth metal cation, a main group element cation, or a combination thereof.

(34) The method of any one of embodiments (l) - (33), wherein the liquid medium comprises a lewis acid.

(35) The process of any one of embodiments (l) - (34), wherein the reaction temperature in (a) is from about 50 ℃ to about 300 ℃.

(36) The process of any one of embodiments (l) - (35), wherein the reaction pressure in (a) is about 2psi (about 13.8kPa) to about 500psi (about 3450 kPa).

The following examples further illustrate the invention but, of course, should not be construed as in any way limiting its scope.

Example 1

This example shows the proposed addition of an alkane (R-CH) in a reactor₂-CH₂-H) to olefins (R-CH ═ CH)₂) The process steps of (1). The process comprises isolating the oxygenated intermediate (R-CH)₂-CH₂-OY) and a reduced form of an oxidizing electrophile (M). Fig. 3 is a schematic diagram depicting the method.

The process involves an oxidizing electrophile (M (OY)₂) The electrophile reacting with the alkane to produce an oxidized intermediate, a reduced form of the oxidizing electrophile, and an oxoacid (HOY). Here, M is a reduced form of an oxidizing electrophile and OY is a conjugate anion of an oxo acid. OY groups allowed in M (OY)₂Electrophilic M-centers are generated in the substance and protect the oxidized intermediates from further electrophilic reactions.

The oxidized intermediate is separated from the reduced form of the oxidizing electrophile and oxoacid and then eliminated to yield the desired olefin. The elimination step may occur at elevated temperatures and/or be facilitated by a catalyst (e.g., an acid or base). The integral part of the process involves the elimination of the alkyl ester in a separate step forming an oxidized intermediate.

The oxidizing electrophilic M-center (M) can be formed from O in the presence of an acid (HOY)₂Or other suitable oxidant regeneration to produceOxidized electrophilic M-centers (M (OY)₂). Although the process is demonstrated on a primary carbon, the reaction can also occur on any alkane where two adjacent carbons both have a hydrogen atom.

As shown in fig. 3, the process may be "ring-closed" in which the desired olefin is removed from the reactor and the oxidative electrophile is regenerated to begin the process again.