阅读说明：本技术 用于生产含氧化合物的转移加氢甲酰化 (Transfer hydroformylation for producing oxygenates ) 是由 A·卡彭特 A·维尔萨姆 L·玛藤斯 于 2019-08-20 设计创作，主要内容包括：本公开内容提供由烯烃形成含氧化合物的方法,其包括醛作为合成气的甲酰基来源替代的加氢甲酰化。在至少一种实施方案中,加氢甲酰化方法在低温下和在环境压力下或接近环境压力进行用于将烯烃转化为醛,从而降低副产物的形成,例如通过原料的骨架异构化或双键；或通过形成的醛和醇的进一步转化。在至少一种实施方案中,使用气态烯属产物(例如乙烯)代替张紧的烯烃(例如降冰片烯)改进控制转移加氢甲酰化反应中的平衡。(The present disclosure provides a process for forming oxygenates from olefins comprising hydroformylation with aldehyde as a formyl source replacement for syngas. In at least one embodiment, the hydroformylation process is conducted at low temperatures and at or near ambient pressure for the conversion of olefins to aldehydes, thereby reducing the formation of by-products, such as by skeletal isomerization or double bonds of the feedstock; or by further conversion of the aldehyde and alcohol formed. In at least one embodiment, the use of a gaseous olefinic product (e.g., ethylene) in place of a strained olefin (e.g., norbornene) improves the equilibrium in a controlled transfer hydroformylation reaction.)

1. A process for preparing an aldehyde comprising:

in a reaction vessel_xAldehyde, C_yContacting an olefin with a metal catalyst, wherein x is an integer from 3 to 41 and y is an integer from 2 to 40; and

obtaining C_y+1Aldehyde product and C_x-1An olefin product.

2. The process of claim 1 wherein the olefin is an alpha olefin.

3. The method of claim 1, further comprising maintaining a reaction temperature of 80 ℃ to 100 ℃.

4. The method of claim 1, further comprising maintaining a reaction pressure of 150psig or less.

5. The process of claim 1, wherein the process is free of introducing syngas into the reaction vessel.

6. The process of claim 1, wherein the process is free of introducing carbon monoxide into the reaction vessel.

7. The process of claim 1, wherein the olefin product is ethylene.

8. The method of claim 1, wherein the aldehyde is represented by formula (I):

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl, and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

9. The method of claim 8, wherein R¹And R²Is hydrogen.

10. The method of claim 8, wherein R³And R⁴Independently is hydrogen or C₁-C₅An alkyl group.

11. The method of claim 8, wherein R³And R⁴Each of which is hydrogen.

12. The method of claim 1, wherein C₂-C₄₀The olefin is represented by formula (II):

wherein R is⁵、R⁶、R⁷And R⁸Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

13. The process of any one of claims 1 to 12, wherein the metal catalyst is represented by formula (III):

M[L]_n (III)

wherein M is a group 9 metal, L is any suitable ligand capable of coordinating a group 9 metal, and n is an integer from 1 to 10.

14. The method of claim 13, wherein M is Rh or Co.

15. The method of claim 14, wherein the metal catalyst is selected from Rh₄(CO)₁₂、Rh₆(CO)₁₆Rhodium (acetyl acetonate) dicarbonyl, rhodium (I) chlorodicarbonyl dimer, chlorobis (ethylene) rhodium dimer, HRh (CO)₄、HRh(CO)PPh₃、[RhCOD(OMe)]₂、[Rh(CO)₂(acetylacetone)]。

16. The process of claim 14 wherein the metal catalyst is selected from the group consisting of Co (acac)₃、HCo(CO)₄And HRh (CO) (PPh)₃)₃。

17. The process of claim 1, wherein the olefin product is represented by formula (IV):

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl; and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

18. The method of claim 17, wherein R of formula (IV)¹And R²Is hydrogen.

19. The process of claim 1, wherein the aldehyde product is represented by formula (V):

wherein R is⁵And R⁶Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

20. The method of claim 19, wherein R⁵And R⁶At least one of which is C₁-C₃₈An alkyl group.

21. The method of claim 20, wherein R⁵And R⁶At least one of which is C₁-C₁₀An alkyl group.

22. The method of claim 21, wherein R⁵And R⁶At least one of which is C₁-C₅An alkyl group.

23. The method of claim 19, wherein R⁵And R⁶At least one of which is C₁₀-C₃₈An alkyl group.

24. The method of claim 23, wherein R⁵And R⁶At least one of which is C₂₀-C₃₈An alkyl group.

25. The method of claim 24, wherein R⁵And R⁶At least one of which is C₃₀-C₃₈An alkyl group.

26. The method of claim 19, wherein R⁵Is hydrogen and R⁶Is C₁₀-C₃₈An alkyl group.

27. The method of claim 26, wherein R⁶Is C₃₀-C₃₈An alkyl group.

28. The process of claim 1, wherein the aldehyde is propionaldehyde and the aldehyde product is heptaldehyde.

29. The process of claim 1, wherein the aldehyde is propionaldehyde and the aldehyde product is norbornal.

30. The process of claim 1, wherein the aldehyde is propionaldehyde and the aldehyde product is tridecanal.

31. A process for preparing an aldehyde comprising:

1) contacting in a reaction vessel at a reaction temperature of 80 ℃ to 100 ℃ and a reaction pressure of 150psig or less:

a) c represented by the formula (I)_xAn aldehyde, wherein x is an integer from 3 to 41:

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl, and R³And R⁴Each is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group;

b) c represented by the formula (II)_yAn α -olefin, wherein y is an integer from 2 to 40:

wherein R is⁵、R⁶、R⁷And R⁸Each independently is hydrogen, or a substituted or unsubstituted hydrocarbyl group; and

c) a metal catalyst represented by formula (III): m [ L ]]_n(III)

Wherein M is a group 9 metal, preferably Rh or Co, L is any suitable ligand capable of coordinating a group 9 metal, and n is an integer from 1 to 10; and

2) obtaining:

i) c represented by the formula (V)_y+1Aldehyde product:

wherein R is⁵And R⁶Each as defined above; and

ii) C represented by the formula (IV)_x-1Olefin production:

wherein R is¹、R²、R³And R⁴Each as defined above.

32. The process of claim 31, wherein the process is free of introducing syngas and/or carbon monoxide into the reaction vessel.

33. The process of claim 31, wherein the olefin product is ethylene.

34. The method of claim 31, wherein each R¹And R²Is hydrogen, each R³And R⁴Independently is hydrogen or C₁-C₅Alkyl radical, each R⁵And R⁶Is C₁-C₅Alkyl, and M is Rh or Co.

35. The method of claim 31, wherein the metal catalyst is selected from Rh₄(CO)₁₂、Rh₆(CO)₁₆Rhodium (acetyl acetonate) dicarbonyl, rhodium (I) chlorodicarbonyl dimer, chlorobis (ethylene) rhodium dimer, HRh (CO)₄、HRh(CO)PPh₃、[RhCOD(OMe)]₂、[Rh(CO)₂(acetylacetone)]、Co(acac)₃、HCo(CO)₄And HRh (CO) (PPh)₃)₃。

36. The process of claim 31, wherein the aldehyde is propionaldehyde and the aldehyde product is heptaldehyde, norbornanal, tridecanal, or a mixture thereof.

FIELD

The present disclosure relates to a process for producing higher oxygenates (oxygenates) from higher olefins by a transfer hydroformylation (transfer hydroformylation) reaction of an aldehyde as an alternative.

Background

Hydroformylation (OXO process) is an important industrial process which involves the preparation of oxygen-containing organic compounds by reaction of carbon monoxide and hydrogen (also known as synthesis gas or syngas) with carbon compounds containing olefinic unsaturation. Both linear and branched aldehydes are formed, which are further converted to alcohols, diols, carboxylic acids, amines, acrolein, acetals, and aldol condensation products. Hydroformylation products are widely used as raw materials for various bulk chemicals (bulk and chemical), mainly in plasticizers (i.e. additives that improve the plasticity or flowability of the material), detergents and in the synthesis of natural products and flavors. The reaction is carried out in the presence of a carbonylation catalyst, such as rhodium (Rh) or cobalt (Co), and results in the formation of a compound, such as an aldehyde, which has one more carbon atom in its molecular structure than the starting olefinic feedstock. Rhodium and cobalt are used commercially, with rhodium generally being more reactive than cobalt. For example, higher alcohols can be produced as follows: by commercial C in the so-called "OXO" process₂-C₄₀Hydroformylation of olefin fractions to carbonylation reaction products containing aldehydes which, upon hydrogenation, yield the corresponding C₃-C₄₁Saturated alcohols. The raw product of the hydroformylation reaction will contain catalyst, aldehydes, alcohols, unreacted feed, synthesis gas and by-products.

In addition, synthesis gas is produced by gasification of carbon-containing fuel to gaseous products and is a mixture of carbon monoxide, hydrogen and carbon dioxide. This gasification is accomplished by partial oxidation and/or reforming reactions in the gasification and reforming unit. Syngas is a mixture of carbon monoxide, carbon dioxide and hydrogen, which can then be converted into hydrocarbons and oxygenates. Syngas can be produced from many sources, including natural gas, coal, biomass, or virtually any hydrocarbon feedstock, by reaction with steam or oxygen to effect partial oxidation. Syngas is an important intermediate resource for the production of hydrogen, ammonia, methanol, and synthetic hydrocarbon fuels.

In addition, the method can be used for producing a composite materialHydroformylation is widely used to produce oxygenates (e.g. aldehydes and alcohols) from olefinic feeds on an industrial scale. Conventional reaction conditions often require elevated temperatures and moderate to high syngas (H)₂/CO) pressure. For example, cobalt catalyzed systems used on branched higher olefins often require synthesis gas pressures in excess of 1000psi and temperatures at or near 150 ℃. Even so-called low pressure processes based on phosphine-containing rhodium or cobalt catalysts operate at pressures greater than 100psi of syngas. Accordingly, there is a need in the art for improved cost and energy efficient processes to convert olefins to higher oxygenates without the use of synthesis gas. There is also a need to provide a methane/carbon dioxide free alternative to conventional hydroformylation technology.

The Rh-Xantphos catalyzed transfer hydroformylation reaction discovered by Dong and coworkers represents a significant breakthrough in syngas replacement hydroformylation technology. Key features of their operation include the use of weakly coordinating anions capable of mediating proton transfer in conjunction with the use of strained (strained) alkenes (e.g., norbornene and norbornadiene) as formyl acceptors. However, Dong and colleagues select strained olefins because the strain energy (about 24kcal/mol) of the bridged, cyclic hydrocarbon is sufficient to drive the transfer hydroformylation reaction to completion. Without ring tension relaxation, transfer hydroformylation reactions involving linear aldehydes and olefins were calculated to be nearly thermally neutral and expected to be challenging to mediate. Thus, there is a need for a transfer hydroformylation process using aldehydes and olefins that involves the synthesis of higher oxygenates using higher olefins (e.g., 1-hexene) whose by-products (e.g., ethylene) will be volatile and easily removed.

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SUMMARY

The present disclosure provides a process for forming higher oxygenates from higher olefins comprising using an aldehyde as a formyl (CHO) source substitute for syngas, an olefin and a catalyst. In at least one embodiment, the method comprises reacting C₃-C₄₁Aldehyde, C₂-C₄₀Contacting an olefin with a metal catalyst and obtaining C₃-C₄₁Aldehyde products and olefins.

In at least one embodiment, the method of making an aldehyde comprises reacting C in a reaction vessel_xAldehyde, C_yContacting an olefin with a metal catalyst, whichWherein x is an integer of 3 to 41 and y is an integer of 2 to 40. The method comprises obtaining C_y+1Aldehyde product and C_x-1An olefin product.

C₃-C₄₁The aldehyde may be represented by formula (I):

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl; and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

C₂-C₄₀The olefin may be represented by formula (II):

wherein R is⁵、R⁶、R⁷And R⁸Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, e.g., a saturated hydrocarbyl group.

Detailed description of the invention

The present disclosure provides a process for forming oxygenates from olefins comprising transfer hydroformylation of aldehydes as a formyl (CHO) source replacement for syngas. The present disclosure also provides a transfer hydroformylation process carried out at low temperatures and at or near ambient pressure for converting higher olefins to higher aldehydes, thereby reducing the formation of by-products, such as by skeletal isomerization or double bonds of the feedstock; or by further conversion of the aldehyde and alcohol formed (i.e. formation of condensation products; decarbonylation; further oxidation).

For example, the present disclosure relates to a transfer hydroformylation process to produce aldehydes, the process comprising contacting a catalyst system comprising one or more catalysts and optionally a support with a low cost aldehyde feed and a C₂-C₄₀Olefins such as C₃-C₁₈Contacting the olefin under mild conditions to provide an aldehyde product andvolatile olefin by-products.

In at least one embodiment, the process uses a linear olefin in place of the strained olefin (e.g., norbornene) and propionaldehyde (propanal) to control the equilibrium in the transfer hydroformylation reaction by producing a gaseous olefinic product (e.g., ethylene) from a propanol starting material. The present disclosure describes the use of transfer hydroformylation on olefins having 6 or more carbon atoms, e.g., 10 or more carbon atoms, and propylene as a feedstock. In a further embodiment, the present disclosure provides a process for producing an aldehyde mixture comprising (contacting) a feed comprising one or more aldehydes with one or more olefins in a single liquid phase in the presence of a catalyst comprising a rhodium complex in combination with an organophosphorus ligand (e.g., comprising a tertiary organophosphine or organophosphite) and under conditions to completely or partially convert the starting aldehyde(s) to olefin(s) and convert the starting olefin(s) to a mixture of higher oxygenates. For example propionaldehyde to ethylene and hexene to heptaldehyde.

The process of the present disclosure provides an attractive alternative to conventional hydroformylation technology, enabling capital cost savings in new plant construction and operating costs savings for existing hydroformylation plants by operating under reaction conditions that enable operation at or near ambient pressure with a mild temperature range (typically 70 ℃ to 120 ℃). The present disclosure relates to hydroformylation processes using transfer hydroformylation technology, wherein a suitable catalyst system (e.g., rhodium phosphine) mediates the apparent transfer of formyl groups from a low cost aldehyde feed (i.e., propionaldehyde) to higher olefins to produce higher oxygenates (e.g., aldehydes and alcohols) under mild conditions.

Without being bound by theory, in a transfer hydroformylation reaction, the donor aldehyde undergoes a transition metal mediated decarbonylation reaction to produce a metal carbonyl hydride intermediate. This intermediate can then be reacted with an acceptor olefin to produce the desired hydroformylation product. A significant feature of using this chemistry is that the decarbonylation of one aldehyde is effectively combined with the hydroformylation of another. In addition, the removal of by-products (e.g., ethylene) facilitates the conversion process of higher olefins, resulting in greater production of the desired higher oxygenates.

The present disclosure provides transfer hydroformylation processes that can provide low temperature and low pressure processes for the conversion of higher olefins to higher aldehydes. The use of low severity processes reduces the formation of by-products, such as skeletal isomerization or double bonds of the feedstock; or by further conversion of the aldehyde and alcohol formed (i.e. formation of condensation products; decarbonylation; further oxidation).

Definition of

For the purposes of this disclosure, a numbering scheme of groups of the periodic table as described in Chemical and Engineering News, 63(5), page 27 (1985) is used. Thus, a "group 4 metal" is an element from group 4 of the periodic table, such as Hf, Ti or Zr.

In the present disclosure, the articles "a" or "an" mean at least one unless the context clearly dictates otherwise.

An "isomer" of a first compound is a separate compound in which each molecule contains the same constituent atoms as the first compound, but in which the configuration of these atoms differs three-dimensionally.

When isomers of a given alkyl, alkenyl, alkoxy, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers in the family (e.g., isobutyl, sec-butyl, and tert-butyl). Likewise, reference to an alkyl, alkenyl, alkoxy, or aryl group without specification to a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

The terms "substituent", "group" and "moiety" may be used interchangeably.

As used herein, and unless otherwise specified, the term "C" refers to a compound having a structure that is substantially similar to a structure of a conventional compound_n"means hydrocarbon(s) having n carbon atoms per molecule, where n is a positive integer.

As used herein, and unless otherwise specified, the term "hydrocarbon" means a class of compounds containing hydrogen bonded to carbon, and encompasses mixtures of (i) saturated hydrocarbon compounds, (ii) unsaturated hydrocarbon compounds, and (iii) hydrocarbon compounds (saturated and/or unsaturated), including mixtures of hydrocarbon compounds having different values of n.

The term "alkyl group" or "alkyl" refers interchangeably to a saturated hydrocarbon group consisting of carbon and hydrogen atoms. "Linear alkyl group" refers to a noncyclic alkyl group in which all carbon atoms are covalently bonded to no more than two carbon atoms. "branched alkyl group" refers to a non-cyclic alkyl group in which at least one carbon atom is covalently bonded to more than two carbon atoms. "cycloalkyl group" refers to an alkyl group in which all carbon atoms form a ring structure containing one or more rings.

The term "aryl group" refers to an unsaturated cyclic hydrocarbon group consisting of carbon and hydrogen atoms, wherein the carbon atoms are linked to form a conjugated pi-system. Non-limiting examples of aryl groups include phenyl, 1-naphthyl, 2-naphthyl, 3-naphthyl, and the like.

The term "arylalkyl group" refers to an alkyl group substituted with an aryl group or an alkylaryl group. Non-limiting examples of arylalkyl groups include benzyl, 2-phenylpropyl, 4-phenylbutyl, 3- (3-methylphenyl) propyl, 3- (p-tolyl) propyl, and the like.

The term "alkylaryl group" refers to an aryl group substituted with an alkyl group. Non-limiting examples of alkylaryl groups include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-methyl-1-naphthyl, 6-phenylhexyl, 5-pentylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 7-phenylheptyl, 4-octylphenyl, and the like.

The term "cycloalkylalkyl group" refers to an alkyl group substituted with a cycloalkyl group or an alkylcycloalkyl group. An example of a cycloalkylalkyl group is cyclohexylmethyl.

The term "alkylcycloalkyl group" refers to a cycloalkyl group substituted with an alkyl group. Non-limiting examples of alkylcycloalkyl groups include 2-methylcyclohexyl, 3-methylcyclohexyl, 4-tert-butylcyclohexyl, 4-phenylcyclohexyl, cyclohexylphenyl, and the like.

Substituted hydrocarbyl groups are groups in which at least one hydrogen atom has been replaced by a heteroatom or a heteroatom-containing group, e.g. by at least one functional group such as halogen (Cl, Br, I, F), NR₂、OR*、SeR*、TeR*、PR*₂、AsR*₂、SbR*₂、SR*、BR*₂、SiR*₃、GeR*₃、SnR*₃、PbR*₃Substituted, or wherein at least one heteroatom such as halogen (Cl, Br, I, F), O, S, Se, Te, NR, PR, AsR, SbR, BR, SiR₂、GeR*₂、SnR*₂、PbR*₂Have been inserted into a hydrocarbyl group, wherein R is independently hydrogen or a hydrocarbyl group.

A "Cn" group or compound refers to a group or compound that includes a total number n of carbon atoms. Thus, a "Cm-Cn" or "Cm to Cn" group or compound refers to a group or compound that includes a total number of carbon atoms in the range of m-n. Thus, C₁-C₅₀Alkyl groups refer to alkyl groups that include a total number of carbon atoms in the range of 1 to 50.

The term "carbon backbone" in the context of olefins and alkyl groups refers to the longest straight carbon chain in the molecule of the compound or group in question.

The term "carbon backbone" of an olefin is defined as a straight carbon chain comprising C ═ C functionality and having the largest number of carbon atoms.

The term "olefin" refers to an unsaturated hydrocarbon compound having a hydrocarbon chain containing at least one carbon-carbon double bond in its structure, wherein the carbon-carbon double bond does not form part of an aromatic ring. The olefins may be linear, branched linear or cyclic.

"olefins" (or "olefins"), alternatively referred to as "olefins", are linear, branched or cyclic compounds of carbon and hydrogen having at least one double bond.

The term "terminal olefin" refers to an olefin having a terminal carbon-carbon double bond in its structure ((R)¹R²)-C＝CH₂Wherein R is¹And R²May independently be hydrogenOr any hydrocarbyl group, e.g. R¹Is hydrogen and R²Is an alkyl group). "Linear terminal olefin" is a terminal olefin as defined in this paragraph, wherein R¹Is hydrogen, and R²Is hydrogen or a linear alkyl group.

The term "vinyl olefin" means an olefin having the formula:

wherein R is a hydrocarbyl group, such as a saturated hydrocarbyl group.

The term "vinylidene olefin" means an olefin having the formula:

wherein each instance of R is independently a hydrocarbyl group, such as a saturated hydrocarbyl group.

The term "1, 2-disubstituted vinylidene olefin (vinylene)" means:

(i) an olefin having the formula:

or

(ii) An olefin having the formula:

or

(iii) (ii) mixtures of (i) and (ii) in any ratio,

wherein each instance of R is independently a hydrocarbyl group, such as a saturated hydrocarbyl group.

The term "trisubstituted vinylidene olefin" means an olefin having the formula:

wherein each instance of R is independently a hydrocarbyl group, such as a saturated hydrocarbyl group.

The term "tetra-substituted vinylidene olefin" means an olefin having the formula:

wherein each instance of R is independently a hydrocarbyl group, such as a saturated hydrocarbyl group.

A "substituted alkyl" or "substituted aryl" group is an alkyl or aryl group made from carbon and hydrogen wherein at least one hydrogen is replaced by a heteroatom, a heteroatom-containing group, or a linear, branched, or cyclic substituted or unsubstituted hydrocarbyl group having 1 to 30 carbon atoms. Heterocyclic rings are rings having a heteroatom in the ring structure, as opposed to heteroatom-substituted rings in which a hydrogen atom on the ring is replaced by a heteroatom. For example, Tetrahydrofuran (THF) is a heterocyclic ring and 4-N, N-dimethylamino-phenyl is a heteroatom-substituted ring.

The term "heteroaryl" means an aryl group in which a ring carbon atom (or two or three ring carbon atoms) has been replaced with a heteroatom such as N, O or S. As used herein, the term "aromatic" also refers to a pseudo-aromatic heterocycle, which is a heterocyclic substituent having similar properties and structure (nearly planar) as an aromatic heterocyclic ligand, but by definition is not aromatic; also the term aromatic refers to substituted aromatic compounds.

The term "hydrocarbyloxy" or "hydrocarbyloxy" means a hydrocarbyl (alkyl) ether or aryl ether group, wherein the term hydrocarbyl is as defined above. Examples of suitable hydrocarbyl ether groups can include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, phenoxy, and the like.

When isomers of a given alkyl, alkenyl, alkoxy, or aryl group (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl) are present, reference to one member of the group (e.g., n-butyl) shall expressly disclose the remaining isomers in the family (e.g., isobutyl, sec-butyl, and tert-butyl). Likewise, reference to an alkyl, alkenyl, alkoxy, or aryl group without specification to a particular isomer (e.g., butyl) explicitly discloses all isomers (e.g., n-butyl, isobutyl, sec-butyl, and tert-butyl).

The term "ring atom" means an atom that is part of a cyclic ring structure. By this definition, a benzyl group has six ring atoms and tetrahydrofuran has 5 ring atoms.

For the purposes of this disclosure and the claims thereto, the term "substituted" means that a hydrogen group has been replaced by a heteroatom or heteroatom-containing group. For example, a "substituted hydrocarbyl group" is a group made from carbon and hydrogen (as described above) in which at least one hydrogen is replaced by a heteroatom or heteroatom-containing group.

As used herein, Mw is the weight average molecular weight, weight% is weight percent and mol% is mole percent. Unless otherwise indicated, all molecular weight units (e.g., Mw) are g/mol.

For the sake of brevity, certain abbreviations may be used, including but not limited to: me is methyl, Ph is phenyl, Et is ethyl, Pr is propyl, iPr is isopropyl, n-Pr is n-propyl, Bu is butyl, cPR is cyclopropyl, iBu is isobutyl, tBu is tert-butyl, p-tBu is p-tert-butyl, nBu is n-butyl, sBu is sec-butyl, p-Me is p-methyl, Ph is phenyl, Bn is benzyl (i.e., CH₂Ph), COD is cyclooctadiene, THF (also known as THF) is tetrahydrofuran, acac is acetylacetone, RT is room temperature (and is 23 ℃, unless otherwise indicated), tol is toluene, EtOAc is ethyl acetate and Cy is cyclohexyl, inHg is in inches of mercury, psi is pounds force per square inch.

Oxygen-containing compound and preparation method thereof

Overview

In at least one embodiment, the present disclosure relates to a process for forming oxygenates from olefins comprising the hydroformylation of olefins and the use of aldehydes (as a formyl (CHO) source alternative to syngas). The method may comprise reacting an aldehyde (e.g., C)₃-C₄₁Aldehydes), olefins (e.g. C)₂-C₄₀Olefin) and a metal catalyst and obtaining an aldehyde product (e.g., C)₃-C₄₁Aldehyde products) and olefin products (e.g., ethylene).

Aldehydes

Any suitable aldehyde may be used in the methods of the present disclosure. In at least one embodiment, the aldehyde is C represented by formula (I)₃-C₄₁Aldehyde:

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl, and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group. In at least one embodiment, R¹And R²Is hydrogen. R³And R⁴Can independently be hydrogen or C₁-C₃₈Alkyl radicals, e.g. C₁-C₂₀Alkyl radicals, e.g. C₁-C₁₀Alkyl radicals, e.g. C₁-C₅An alkyl group. In at least one embodiment, R³And R⁴Each of which is hydrogen.

In at least one embodiment, the aldehyde can be one or more of propionaldehyde, butyraldehyde, pentanal (valeraldehyde), hexanal, heptanal, octanal, nonanal, decanal, undecanal, dodecanal, tridecanal, tetradecanal, pentadecanal, 3-methylbutyraldehyde, 3-methylpropanal (isovaleraldehyde), 4-methylpropanal, unsubstituted and substituted cyclohexanecarboxaldehyde. The use of an aldehyde to be converted to a gaseous olefinic product, for example propionaldehyde and ethylene, respectively, provides control over the hydroformylation reaction equilibrium due to the volatility (and ease of removal) of the gaseous olefinic product from the reaction vessel. In addition, the use of inexpensive propionaldehyde as a feedstock for higher olefins results in the formation of higher oxygenates. Propionaldehyde is also a starting material that is readily formed by the hydroformylation of ethylene, and ethylene, which is a byproduct of the process of this disclosure, may be recycled to form additional propionaldehyde.

In at least one embodiment, the molar ratio of aldehyde to olefin is from 20:1 to 1:1, such as from 15:1 to 1:1, for example from 10:1 to 2:1, such as from 5:1 to 2: 1.

Olefins

The olefin used in the process of the present disclosure may be an alpha-olefin, a 1, 2-disubstituted vinylidene olefin, or a trisubstituted vinylidene olefin.

Any suitable olefin may be used in the process of the present disclosure. In at least one embodiment, the olefin is C represented by formula (II)₂-C₄₀Olefin (b):

wherein R is⁵、R⁶、R⁷And R⁸Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, e.g., a saturated hydrocarbyl group. In at least one embodiment, the olefin is an alpha-olefin, wherein R⁷And R⁸Is hydrogen.

In at least one embodiment, R⁵、R⁶And R⁷Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group. In at least one embodiment, R⁵、R⁶And R⁷Independently is hydrogen or C₁-C₃₈Alkyl radicals, e.g. C₁-C₂₀Alkyl radicals, e.g. C₁-C₁₀Alkyl radicals, e.g. C₁-C₅An alkyl group. In at least one embodiment, R⁵、R⁶And R⁷One or more of which is C₁-C₃₈Alkyl radical, C₁-C₂₀Alkyl radicals, e.g. C₁-C₁₀Alkyl radicals, e.g. C₁-C₅An alkyl group.

In at least one embodiment, R⁵And R⁶One or more of which is C₁₀-C₃₈Alkyl radicals, e.g. C₂₀-C₃₈Alkyl radicals, e.g. C₃₀-C₃₈An alkyl group. At least oneIn one embodiment, R⁵Is hydrogen and R⁶Is C₁₀-C₃₈Alkyl radicals, e.g. C₂₀-C₃₈Alkyl radicals, e.g. C₃₀-C₃₈An alkyl group.

In at least one embodiment, suitable olefins include substituted or unsubstituted C₂-C₄₀Olefins, e.g. C₂-C₂₀Olefins, e.g. C₂-C₁₂Olefins such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, and isomers thereof. C₂-C₄₀The olefin monomers may be linear, branched or cyclic. C₂-C₄₀The cyclic olefin may be strained or unstrained (monocyclic) or polycyclic, and may optionally include heteroatoms and/or one or more functional groups.

In at least one embodiment, suitable olefins include C₂-C₄₀Olefins, e.g. C₂-C₂₀Olefins, e.g. C₂-C₁₂Olefins, such as ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene. In at least one embodiment, C₃-C₄₀The olefin monomer may be linear and may optionally include heteroatoms and/or one or more functional groups.

C₂-C₄₀Olefins such as C₂-C₁₈The olefin may be ethylene, propylene, butene, pentene, hexene, heptene, octene, nonene, decene, undecene, dodecene, norbornene, norbornadiene, dicyclopentadiene, cyclopentene, cycloheptene, cyclooctene, cyclooctadiene, cyclododecene, 7-oxanorbornene, 7-oxanorbornadiene, substituted derivatives thereof, and isomers thereof, such as hexene, heptene, octene, nonene, decene, dodecene, cyclooctene, 1, 5-cyclooctadiene, 1-hydroxy-4-cyclooctene, 1-acetoxy-4-cyclooctene, 5-methylcyclopentene, cyclopentene, dicyclopentadiene, norbornene, norbornadiene, and isomers, homologs, and derivatives thereof, such as norbomadieneBornylene, norbornadiene, and dicyclopentadiene.

For purposes of this disclosure, ethylene should be considered an alpha-olefin.

In at least one embodiment, the olefin is a gaseous olefin, the olefin pressure in the reaction vessel is greater than about 5psig (34.5kPa), such as greater than about 10psig (68.9kPa), for example greater than about 45psig (310kPa), and the pressure in the reaction vessel is less than 150 psig. When a diluent is used together with the gaseous olefin, the aforementioned pressure range may also be suitably used as the total pressure of the olefin and the diluent. Also, when the process is carried out using a liquid olefin under an inert gaseous atmosphere, the aforementioned pressure range can be suitably used for the inert gas pressure.

Metal catalyst

The "catalyst system" includes any suitable rhodium precursor, at least one organophosphorus ligand, and a suitable carboxylic acid. The catalyst system may be produced by combining the catalyst components in a suitable manner to provide an active catalyst complex. Combinations of organophosphorus ligands and metal precursors can be used to provide unactivated catalyst complexes (procatalysts), which can be isolated or generated in situ. When "catalyst system" is used to describe the catalyst compound prior to activation, it is meant the metal precursor along with the organophosphorus ligand. When used to describe the combination after activation, it is meant to refer to the combination of transition metal precursor/organophosphorus ligand and carboxylic acid. The transition metal compound may be neutral (as in the procatalyst), or a charged species. For purposes of this disclosure, when the catalyst system is described as comprising a neutral stable form of the components, one of ordinary skill in the art will fully appreciate that ionic forms are also available. For example, the carboxylate anion may combine with the transition metal to provide a neutral species or separate to provide the transition metal cation and the carboxylate anion.

The catalyst system and/or components thereof may be oxygen and/or moisture sensitive and, thus, its preparation and/or storage and/or use during the hydroformylation process may be carried out in the substantial absence of oxygen and/or moisture. In at least one embodiment of the present disclosure, the preparation of the catalyst and/or the hydroformylation reaction is carried out in an inert atmosphere, such as a nitrogen or helium atmosphere or an argon atmosphere. In at least one embodiment, the preparation of the catalyst and/or the hydroformylation reaction is carried out in an inert gas filled environment, such as a glove box.

Various rhodium precursors and organophosphorus ligands can be used in the present disclosure. The hydroformylation of lower olefins such as ethylene, propylene and butenes typically uses a rhodium catalyst stabilized by a phosphorus-containing ligand, which operates in a technology known as low pressure oxo (lpo). The present disclosure provides a method of operating at near ambient pressure. In another embodiment, a catalyst containing cobalt is used and the process is run at higher pressure. In a similar manner to cobalt, rhodium catalyzed hydroformylation can also be run at higher pressures, and in some embodiments, without the use of stable ligands other than carbon monoxide or with weak ligands such as triphenylphosphine oxide (TPPO). The present disclosure provides Rh-or Co-mediated hydroformylation processes operating at near ambient pressure.

In the description herein, catalyst M [ L ]]_nCan be described as catalyst precursor, procatalyst compound, M [ L ]]_nA catalyst compound or a transition metal compound, and these terms are used interchangeably (where M is rhodium, L is any suitable ligand capable of coordinating a group 9 metal, such as a phosphine, and n is a positive integer such as 1,2, 3, 4, 5 or 6). An "anionic ligand" is a negatively charged ligand that donates one or more pairs of electrons to a metal ion. A "neutral donor ligand" is an electrically neutral ligand that donates one or more pairs of electrons to a metal ion.

The metal catalyst may be represented by formula (III):

M[L]_nX (III)

wherein M is rhodium, L is any suitable ligand capable of coordinating a group 9 metal, for example a phosphine, n is a positive integer such as 1,2, 3, 4, 5 or 6, and X is a weakly coordinating anionic ligand such as an alkyl or arylcarboxylate.

The catalyst contained in the reaction mixture may be any suitable rhodium metal complex having a ligand. It is to be understood that while the complex is characterized as comprising a metal and an organic ligand, without being limited by theory, the active catalyst that actually functions is an organophosphorus-stabilized metal carboxylate. The ligands may comprise a monodentate or polydentate triorganophosphine, triorganarsine or triorganosilaharmontine (triorganosilbine), with phosphines and phosphites of particular industrial importance. For example, simple monodentate phosphines and phosphites may be used, such as exemplified by triphenylphosphine and triphenyl phosphite. However, the advantage of polydentate ligands is the large excess of ligands that are often used, unlike when monodentate ligands are used. Carboxylate anions may include, but are not limited to, arylcarboxylates such as 3, 5-dimethylbenzoate, and alkylcarboxylates such as stearate or hexanoate or naphthenate (napthenate).

Any suitable concentration of catalyst can be used in the hydroformylation reaction medium of the present disclosure. For example, when the catalyst metal is rhodium and when the ligand is Xantphos, the liquid reaction medium may contain from about 0.01 mol% to 20 mol% rhodium and up to about 50 mol% Xantphos.

Examples of rhodium precursors include, but are not limited to, the following rhodium in any suitable oxidation state (e.g., (I), (II), or (III)), and mixtures thereof: an oxide; inorganic salts such as rhodium fluoride, rhodium chloride, rhodium bromide, rhodium iodide and rhodium sulfate; rhodium salts of carboxylic acids such as rhodium acetate; rhodium tetraacetate, rhodium acetylacetonate, rhodium (II) isobutyrate, rhodium (II) 2-ethylhexanoate, rhodium carbonyl compounds such as Rh₄(CO)₁₂、Rh₆(CO)₁₆(acetylacetonatodicarbonylrhodium (I); and other common rhodium species such as chlorodicarbonylrhodium dimer, [ RhCoD (OMe)]₂、[Rh(CO)₂(acetylacetone)]And the like.

If a catalyst support is used, the catalyst compound may be loaded onto the catalyst support in any amount, provided that the process proceeds to the desired product. For example, the catalyst compound may be loaded onto the support in an amount greater than about 0.01 wt% of the group 9 metal, such as greater than about 0.05 wt% of the group 9 metal, based on the total weight of the catalyst compound plus the support. For example, the catalyst compound may be loaded onto the support in an amount of less than about 20 wt.% of the group 9 metal, such as less than about 10 wt.% of the group 9 metal, based on the total weight of the catalyst compound and the support.

In at least one embodiment, the reaction mixture includes about 10 mol% or less of catalyst M [ L ] relative to the olefin]_n(wherein M is rhodium, L is any suitable ligand capable of coordinating a group 9 metal, e.g., a phosphine, and n is a positive integer, e.g., 1,2, 3, 4, 5, or 6). In at least one embodiment, the catalyst M [ L ] in the hydroformylation reaction]_nThe loading amount of (a) is from about 0.0005 mol% to about 8 mol%, for example from about 0.001 mol% to about 4 mol%, for example from 0.005 mol% to about 2 mol%, for example from about 0.01 mol% to about 1.5 mol%, for example from about 0.02 mol% to about 1 mol%, for example from about 0.03 mol% to about 0.5 mol%.

In at least one embodiment, suitable transition metal complexes may include Rh-based complexes. In addition, such transition metal complexes may be bridged by bidentate ligands. Suitable bidentate ligands include, but are not limited to, bidentate phosphorus ligands such as xanthphos.

Phosphine compounds

The term "phosphine compound" refers to compounds having the formula PR₃Wherein each R is independently a hydrocarbyl group such as an aryl group, an alkylaryl group, an alkyl group, or an arylalkyl group, or each R group is the same.

Non-limiting examples of phosphines include P (OMe)₃、P(OPh)₃Triphenylphosphine, tri (n-butyl) phosphine, tri (tert-butyl) phosphine, tri (n-pentyl) phosphine, tri (n-hexyl) phosphine, tri (n-heptyl) phosphine, tri (n-octyl) phosphine, tri (n-nonyl) phosphine, tri (n-decyl) phosphine, mixtures of any two or more thereof, and the like.

The term "alkyl phosphite" is a subset of phosphites in which each R is independently an alkoxy group, alternatively each R group is the same. Similarly, the term "aryl phosphite" is a subset of phosphites in which each R is independently an aryloxy group, alternatively each R group is the same. When used without the modifier "substituted", the term "diphosphorous acidBy ester "is meant having the formula R₂Compound of (1) -Danu₂Wherein each R is independently alkoxy, aryloxy, and aralkoxy (as those terms are defined above), and wherein L is alkoxydiyl or aryloxydiyl. When any of these terms is used with the modifier "substituted", one or more hydrogen atoms have been replaced independently by-OH, -F, -Cl, -Br, -I, -NH₂、—NO₂、—CO₂H、—CO₂CH₃、—CN、—SH、—OCH₃、—OCH₂CH₃、—C(O)CH₃、—NHCH₃、—NHCH₂CH₃、—N(CH₃)₂、—C(O)NH₂、—OC(O)CH₃or-S (O)₂NH₂Instead.

In a further embodiment, the rhodium complex is [ RhCO (OMe)]₂A complex or a variant thereof, which is soluble in the reaction solvent and does not contain a strong phosphine ligand. While not wishing to be bound by any particular theory, it is believed that phosphines are better sigma donors than phosphites and may enhance the selectivity of the catalyst system to the desired aldehyde.

Product of

Olefin products

The process of the present disclosure produces olefins. The olefin may be represented by formula (IV):

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl; and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group. In at least one embodiment, R¹And R²Each of which is hydrogen.

Oxygen-containing compound: aldehyde products

The process of the present disclosure also produces an aldehyde product (also referred to as oxygenate). In at least one embodiment, the aldehyde product is C represented by formula (V)₃-C₄₁Aldehyde product:

wherein R is⁵And R⁶Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group, e.g., a saturated hydrocarbyl group.

In at least one embodiment, R⁵And R⁶Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group. In at least one embodiment, R⁵And R⁶Independently is hydrogen or C₁-C₃₈Alkyl radicals, e.g. C₁-C₂₀Alkyl radicals, e.g. C₁-C₁₀Alkyl radicals, e.g. C₁-C₅An alkyl group. In at least one embodiment, R⁵And R⁶One or more of which is C₁-C₃₈Alkyl radicals, e.g. C₁-C₂₀Alkyl radicals, e.g. C₁-C₁₀Alkyl radicals, e.g. C₁-C₅An alkyl group.

In at least one embodiment, R⁵And R⁶One or more of which is C₁₀-C₃₈Alkyl radicals, e.g. C₂₀-C₃₈Alkyl radicals, e.g. C₃₀-C₃₈An alkyl group. In at least one embodiment, R⁵Is hydrogen and R⁶Is C₁₀-C₃₈Alkyl radicals, e.g. C₂₀-C₃₈Alkyl radicals, e.g. C₃₀-C₃₈An alkyl group.

Carrier

In at least one embodiment, the catalyst compound used in the methods of the present disclosure may be combined with or deposited on a solid catalyst support. The solid catalyst support will cause the catalyst compound to be heterogeneous. The catalyst support can improve the strength and abrasion resistance of the catalyst. Catalyst supports include silica, alumina, silica-alumina, aluminosilicates, including zeolites and other crystalline porous aluminosilicates, as well as titania, zirconia, magnesia, carbon and crosslinked network polymer resins, such as functionalized crosslinked polystyrene, for example chloromethyl-functionalized crosslinked polystyrene. The catalyst compound may be deposited on the support by any method known to those skilled in the art including, for example, impregnation, ion exchange, precipitation by deposition, and vapor deposition. Alternatively, the catalyst compound may be chemically bound to the support by one or more covalent chemical bonds, for example, the catalyst compound may be immobilized by one or more covalent bonds to one or more substituents of the catalyst ligand.

Activating agent

The terms "cocatalyst" and "activator" are used interchangeably herein and are defined as any compound that can activate any of the catalyst compounds described above by converting a neutral catalyst compound into a catalytically active catalyst compound cation.

After the complexes described above have been synthesized, the catalyst system may be formed by combining them with an activator, such as a non-coordinating anion, in any suitable manner. For example, the noncoordinating anion can be benzoic acid or a hindered carboxylate. Examples include aryl carboxylates such as 3, 5-dimethylbenzoate, and alkyl carboxylates such as stearate or hexanoate or naphthenate.

Hydroformylation conditions

In at least one embodiment, the method of making an aldehyde comprises reacting C in a reaction vessel_xAldehyde, C_yAn olefin is contacted with a metal catalyst, wherein x is an integer from 3 to 41 and y is an integer from 2 to 40. The method comprises obtaining C_y+1Aldehyde product and C_x-1An olefin product.

The temperature of the reaction mixture during hydroformylation may be maintained at any suitable temperature using standard heating and/or cooling means. The reaction temperature may range from about 0 ℃ to about 120 ℃, e.g., from about 10 ℃ to about 90 ℃, e.g., from about 25 ℃ to about 75 ℃, e.g., room temperature (e.g., 23 ℃, unless otherwise specified), optionally from 25 ℃ to 70 ℃, or from 30 ℃ to 65 ℃. Optionally, the reaction temperature is less than 70 ℃. Preferably, the reaction is maintained at a reaction temperature of from 80 ℃ to 100 ℃. The reaction can be carried out (e.g., stirring and/or heating the reaction mixture) for any suitable amount of time, e.g., until the reaction is complete. In at least one embodiment of the present disclosure, the reaction temperature is about 90 ℃. In at least one embodiment, the reaction time is from about 5 hours to about 100 hours, such as from about 15 hours to about 75 hours, for example, about 24 hours or about 96 hours. The reaction pressure can be 150psig or less.

The type of inert solvent (identity) that can be used in the reaction system is flexible as long as it is miscible with the catalyst system and with the reactants and reaction products, has low volatility to facilitate stripping of reaction products and byproducts therefrom, and is, of course, chemically inert in the hydroformylation reaction system, or forms an inherently inert derivative in the system. Molecular weight can be a factor in the reaction solvent because it is related to volatility, and of course, a relatively high molecular weight is desirable in order to facilitate retention of the inert solvent as heavies when stripping the reaction product from the reaction solvent.

The solvent includes any suitable organic solvent which is inert under the hydroformylation conditions. The solvent comprises an aromatic hydrocarbon, a chlorinated hydrocarbon, an ether, an aliphatic hydrocarbon, an alcohol, or mixtures thereof. Suitable solvents include THF, acetone, Dimethylformamide (DMF), pentane, isohexane, hexane, octane, benzene, xylene, toluene, methylcyclohexane, fluorobenzene, diethyl ether, dichloromethane, chloroform, and Dimethylsulfoxide (DMSO). In at least one embodiment of the present disclosure, the solvent is THF.

Alternatively, the hydroformylation is carried out "neat", for example in the absence of solvent in the reaction mixture. In such embodiments, the reaction mixture includes only the catalyst, aldehyde, and olefin. Aldehydes and olefins may be diluents for the catalyst and products.

In at least one embodiment, the conversion of the feed material is about 50 mol% or greater, such as about 60 mol% or greater, for example about 70 mol% or greater, such as about 80 mol% or greater, for example about 95 mol% or greater, such as about 99% or greater.

In at least one embodiment, the hydroformylation reaction may occur at near ambient pressure or at ambient pressure (atmospheric pressure), for example, from about 28inHg (13.7psi, 94.8KPa) to about 31inHg (15.2psi, 105KPa), for example, from about 29inHg (14.2psi) to about 30inHg (14.7 psi).

The liquid reaction medium or catalyst solution used comprises (a) the catalyst complex, (b) an excess of the organic ligand used to form the complex over and above the amount of the metal component of the complex catalyst, (c) the hydroformylation reaction product along with by-products resulting from the undesired condensation of the hydroformylation product aldehyde with itself, (d) an amount of hydroformylated olefin which varies with the molecular weight of the olefin (the proportion of liquid olefin in the reaction medium is generally greater when using high molecular weight olefins than when using lower olefins such as ethylene), and (e) in most systems involving processing low to medium molecular weight olefins, an inert reaction solvent. With higher molecular weight olefins such as octene, the olefin itself may act as the reaction solvent in the liquid phase.

In at least one embodiment, sterically hindered acids such as 3, 5-dimethylbenzoic acid may be used in order to reduce or prevent coordination of benzoate groups to the rhodium catalyst. Without wishing to be bound by theory, it is believed that the acid acts as a non-coordinating anion.

A particular advantage of this process is that it can be operated in the absence of synthesis gas, e.g. the process does not involve introducing synthesis gas into the reaction vessel.

A particular advantage of this process is that it can be operated in the absence of carbon monoxide, for example the process does not involve the introduction of carbon monoxide into the reaction vessel.

A particular advantage of this process is that it can be operated in the absence of synthesis gas and carbon monoxide, for example the process does not involve the introduction of synthesis gas and carbon monoxide into the reaction vessel.

The invention also relates to:

1. a process for preparing an aldehyde comprising: in a reaction vessel_xAldehyde, C_yContacting an olefin with a metal catalyst, wherein x is an integer from 3 to 41 and y is an integer from 2 to 40; and obtaining C_y+1Aldehyde product and C_x-1An olefin product.

2. The process of paragraph 1 wherein the olefin is an alpha olefin.

3. The method of paragraph 1 or 2, further comprising maintaining a reaction temperature of 80 ℃ to 100 ℃.

4. The method of any of paragraphs 1 to 3, further comprising maintaining a reaction pressure of 150psig or less.

5. The process of any of paragraphs 1 to 4, wherein the process is free of introducing syngas into the reaction vessel.

6. The process of any of paragraphs 1 to 5, wherein the process is free of introducing carbon monoxide into the reaction vessel.

7. The process of any of paragraphs 1 to 6, wherein the olefin product is ethylene.

8. The method of any of paragraphs 1 to 7, wherein the aldehyde is represented by formula (I):

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl, and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

9. The method of paragraph 8, wherein R¹And R²Is hydrogen.

10. The method of paragraph 8 or 9, wherein R³And R⁴Independently is hydrogen or C₁-C₅An alkyl group.

11. The method of any one of paragraphs 8 to 10, wherein R³And R⁴Each of which is hydrogen.

12. The method of any one of claims 1 to 11, wherein C₂-C₄₀The olefin is represented by formula (II):

wherein R is⁵、R⁶、R⁷And R⁸Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

13. The method of any of paragraphs 1 to 12, wherein the metal catalyst is represented by formula (III):

M[L]_n (III)

wherein M is a group 9 metal, L is any suitable ligand capable of coordinating a group 9 metal, and n is an integer from 1 to 10.

14. The method of paragraph 13, wherein M is Rh or Co.

15. The method of paragraph 14 wherein the metal catalyst is selected from Rh₄(CO)₁₂、Rh₆(CO)₁₆Rhodium (acetyl acetonate) dicarbonyl, rhodium (I) chlorodicarbonyl dimer, chlorobis (ethylene) rhodium dimer, HRh (CO)₄、HRh(CO)PPh₃And [ RhCod (OMe)]₂、[Rh(CO)₂(acetylacetone)]。

16. The method of paragraph 14 wherein the metal catalyst is selected from the group consisting of Co (acac)₃、HCo(CO)₄And HRh (CO) (PPh)₃)₃。

17. The process of any of paragraphs 1 to 16, wherein the olefin product is represented by formula (IV):

wherein R is¹And R²Each is independently hydrogen, alkoxy, or substituted or unsubstituted hydrocarbyl; and R³And R⁴Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

18. The method of paragraph 17, wherein R of formula (IV)¹And R²Is hydrogen.

19. The method of any of paragraphs 1 to 18, wherein the aldehyde product is represented by formula (V):

wherein R is⁵And R⁶Each of which is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group.

20. The method of paragraph 19, wherein R⁵And R⁶At least one of which is C₁-C₃₈An alkyl group.

21. The method of paragraph 20, wherein R⁵And R⁶At least one of which is C₁-C₁₀An alkyl group.

22. The method of paragraph 21, wherein R⁵And R⁶At least one of which is C₁-C₅An alkyl group.

23. The method of paragraph 19, wherein R⁵And R⁶At least one of which is C₁₀-C₃₈An alkyl group.

24. The method of paragraph 23, wherein R⁵And R⁶At least one of which is C₂₀-C₃₈An alkyl group.

25. The method of paragraph 24, wherein R⁵And R⁶At least one of which is C₃₀-C₃₈An alkyl group.

26. The method of paragraph 19, wherein R⁵Is hydrogen and R⁶Is C₁₀-C₃₈An alkyl group.

27. The method of paragraph 26, wherein R⁶Is C₃₀-C₃₈An alkyl group.

28. The process of paragraph 1 wherein the aldehyde is propionaldehyde and the aldehyde product is heptaldehyde.

29. The process of paragraph 1 wherein the aldehyde is propionaldehyde and the aldehyde product is norbornal.

30. The process of paragraph 1 wherein the aldehyde is propionaldehyde and the aldehyde product is tridecanal.

31. A process for preparing an aldehyde comprising:

1) contacting in a reaction vessel at a reaction temperature of 80 ℃ to 100 ℃ and a reaction pressure of 150psig or less:

a) c represented by the formula (I)_xAn aldehyde, wherein x is an integer from 3 to 41:

wherein R is¹And R²Each independently of the other is hydrogen,Alkoxy, or substituted or unsubstituted hydrocarbyl, and R³And R⁴Each is independently hydrogen, or a substituted or unsubstituted hydrocarbyl group;

b) c represented by the formula (II)_yAn alpha olefin, wherein y is an integer from 2 to 40:

wherein R is⁵、R⁶、R⁷And R⁸Each independently is hydrogen, or a substituted or unsubstituted hydrocarbyl group; and

c) a metal catalyst represented by formula (III): m [ L ]]_n (III)

Wherein M is a group 9 metal, preferably Rh or Co, L is any suitable ligand capable of coordinating a group 9 metal, and n is an integer from 1 to 10; and

2) obtaining:

i) c represented by the formula (V)_y+1Aldehyde product:

wherein R is⁵And R⁶Each as defined above; and

ii) C represented by the formula (IV)_x-1Olefin production:

wherein R is¹、R²、R³And R⁴Each of which is as defined above, and,

wherein optionally the process is free of introducing syngas and/or carbon monoxide into the reaction vessel.

32. The process of paragraph 31 wherein the olefin product is ethylene.

33. The method of paragraph 31, wherein each R¹And R²Is hydrogen, each R³And R⁴Independently is hydrogen or C₁-C₅Alkyl radical, each R⁵And R⁶Is C₁-C₅Alkyl, and M is Rh or Co.

35. The method of paragraph 31, wherein the metal catalyst is selected from Rh₄(CO)₁₂、Rh₆(CO)₁₆Rhodium (acetyl acetonate) dicarbonyl, rhodium (I) chlorodicarbonyl dimer, chlorobis (ethylene) rhodium dimer, HRh (CO)₄、HRh(CO)PPh₃、[RhCOD(OMe)]₂、[Rh(CO)₂(acetylacetone)]、Co(acac)₃、HCo(CO)₄And HRh (CO) (PPh)₃)₃。

35. The method of paragraph 31, wherein the aldehyde is propionaldehyde and the aldehyde product is heptaldehyde, norbornanal, tridecanal, or a mixture thereof.

Experiment of

All reactions were carried out under an inert atmosphere. Anhydrous solvents were purchased from commercial sources and degassed and dried over molecular sieves prior to use. Deuterated solvents were purchased from commercial sources, degassed prior to use and dried over molecular sieves. Norbornene, propionaldehyde, heptaldehyde, 3, 5-dimethylbenzoic acid, Xantphos and [ RhCod (OMe)]₂Purchased from a commercial source and used in the as received state. Hexene(s), octene(s), and dodecene(s) are obtained from refinery feedstocks and degassed and dried using Na/K.

Running Topspin with deuterated solvents at Room Temperature (RT) for all materials^TM3.0 software all collected on a Bruker AVANCE III 400MHz Spectrophotometer¹H NMR data.

GC-MS analysis: from Agilent as described below^TM6890 the yield of the hydroformylation product and the number of catalyst conversions (turnover number) were calculated from the data recorded on the GC spectrophotometer. Use of¹H NMR or GC-MS determines the conversion by the relative integration of area product/(area starting material + area product).

All reactions were carried out under an inert atmosphere at 90 ℃ with THF as solvent. Using propionaldehyde as a donor aldehyde along with various acceptor olefins such as 1-hexene and commercial C₆(Linear), C₈(mixing) and C₁₂(linear) feeding to obtain experimental validation. A 20-fold excess of propionaldehyde was used with a relatively high catalyst loading in an attempt to increase the conversion values. Propionaldehyde is relatively inexpensive and the ethylene by-product formed during the transfer hydroformylation process is volatile and therefore can be easily separated. Furthermore, the ability to evolve ethylene gas provides an alternative to driving the transfer hydroformylation reaction to high conversion. In commercial processes, continuous ethylene removal in the gas phase can be used to increase the conversion values. Table 1 illustrates the results obtained under the conditions described above. The experiment was carried out under an inert atmosphere at 90 ℃ with THF as solvent. Catalyst loading in [ RhCod (OMe) ]]₂Is taken as a basis. For each equivalent of [ RhCod (OMe)]₂2 equivalents of 3, 5-dimethylbenzoic acid and Xantphos were used. All mol% values are calculated based on the theoretical molecular weight of the acceptor olefin. Entry 5 represents a feed containing C₈Conditions for highly complex mixtures of isomers. For linear C₆(item 3) and C₁₂The olefin (entry 6) obtained clear evidence of transfer hydroformylation using propionaldehyde as the source of formyl groups. For C-rich containing large amount of internal olefins₈C of (A)₇-C₉The conversion values are low for the feed. Various C's were detected in GC-MS analysis (entry 5)₉Trace evidence of the presence of oxygenates. Without wishing to be bound by theory, it is believed that the highly branched internal olefins interfere with the ability or rate of transfer hydroformylation using the Rh-Xantphos system. It was found that the 1, 5-Cyclooctadiene (COD) precursor underwent isomerization to provide 1,3 and 1,4 cyclooctadiene. The ethylene concentration (based on GC integration) was found to be higher than the expected transferred OXO product in all experiments using propionaldehyde. This finding is consistent with syngas decarbonylation as a competing reaction pathway. The process may benefit from the presence of a low partial pressure of the synthesis gas.

TABLE 1

TABLE 1 continuation

In general, the aldehydes, catalysts, catalyst systems, and methods of the present disclosure can provide oxygenates from olefins. The hydroformylation may be a transfer hydroformylation involving the formation of oxygenates from olefins, which involves the hydroformylation of aldehydes as a replacement for the formyl source of the synthesis gas. The transfer hydroformylation process of the present invention can be carried out at low temperatures and at or near ambient pressure for the conversion of higher olefins to higher aldehydes, thereby reducing the formation of by-products, for example by skeletal isomerization or double bonds of the feedstock; or by further conversion of the aldehyde and alcohol formed (i.e. formation of condensation products; decarbonylation; further oxidation). The use of gaseous olefinic products (e.g., ethylene) in place of strained olefins (e.g., norbornene) improves the equilibrium in a controlled transfer hydroformylation reaction. The present disclosure demonstrates that transfer hydroformylation can be used on higher olefins, for example when propionaldehyde (propanal) is used as a feedstock, resulting in the formation of oxygenates.

Unless otherwise specified, the terms "consisting essentially of and" consisting essentially of do not exclude the presence of other steps, elements or materials, whether or not specifically mentioned in the present specification, as long as such steps, elements or materials do not affect the basic and novel characteristics of the present disclosure, and in addition, they do not exclude impurities and variations that are usually associated with the elements and materials used.

For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, and ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, and ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited in the same manner. Additionally, each point or individual value between its endpoints is included in the range even if not explicitly recited. Thus, each point or individual value may serve as its own lower or upper limit, in combination with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.

All documents described herein are incorporated by reference herein, including any priority documents and/or test procedures, as long as they are not inconsistent herewith. While the form of the disclosure has been illustrated and described, it will be apparent from the foregoing general description and specific embodiments that various changes may be made without departing from the spirit and scope of the disclosure. Accordingly, the disclosure is not intended to be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including". Likewise, whenever a component, element, or group of elements is preceded by the conjunction "comprising," it is to be understood that we also contemplate that the same component or group of elements is preceded by the conjunction "consisting essentially of," "consisting of," "selected from," or "being," and vice versa, in the recitation of said component, element, or elements.

While the disclosure has been described in terms of various embodiments and examples, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments can be devised which do not depart from the scope and spirit of the disclosure.