阅读说明：本技术 用于制备燃料添加剂的方法 (Method for producing a fuel additive ) 是由 S·V·菲利普 M·冈特 于 2018-12-19 设计创作，主要内容包括：提供了用于制备取代的燃料添加剂<I>d</I>的方法。所述方法包括实施以下反应：<Image he="127" wi="438" file="100004_DEST_PATH_IMAGE002.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>各个Y独立地选自卤素基团,并且X选自-O-或-NR<Sub>10</Sub>-。(Provides a method for preparing substituted fuel additives d The method of (1). The method comprises carrying out the following reaction: each Y is independently selected from a halogen group and X is selected from-O-or-NR 10 ‑。)

1. A process for preparing a fuel additive having the formula:

wherein: r₁Is hydrogen;

R₂、R₃、R₄、R₅、R₁₁and R₁₂Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

R₆、R₇、R₈and R₉Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

x is selected from-O-or-NR₁₀-, wherein R₁₀Selected from hydrogen and alkyl; and

n is a number of 0 or 1,

the method comprises carrying out the following reaction:

wherein: each Y is independently selected from halogen groups.

2. The method of claim 1, wherein each Y is independently selected from Br, Cl, and I, and more preferably from Br and Cl.

3. The process according to claim 1 or claim 2, wherein the reaction is carried out in the presence of a metal catalyst, and the metal catalyst is preferably selected from palladium catalysts (e.g. organometallic palladium catalysts) and copper catalysts (e.g. elemental copper, copper (I) halide and copper (I) oxide).

4. The method of claim 3, wherein the reaction is carried out in the presence of a palladium catalyst and a copper catalyst.

5. A process according to claim 3 or claim 4, wherein the catalyst is used in combination with an organic ligand, preferably an organic ligand selected from organophosphorus ligands, alkanolamines, aniline derived ligands and ligands derived from amino acids.

6. The process of any one of claims 3 to 5, wherein the catalyst is present relative to the starting materialaIn particular, 0.02 to 1 molar equivalent, preferably 0.025 to 0.5 molar equivalent and more preferably 0.05 to 0.3 molar equivalent.

7. The process according to any one of claims 1 to 6, wherein the reaction is carried out in the presence of a solvent selected from toluene, tert-amyl alcohol, dimethylformamide, ethanolamine, tetrahydrofuran and dioxane.

8. The process according to any one of claims 1 to 7, wherein the reaction is carried out in the presence of a base, preferably an inorganic base and more preferably an alkali metal base, for example selected from alkali metal carbonates, alkali metal alkoxides, alkali metal hydrides, alkali metal organosilicon compounds and alkali metal phosphates.

9. The method of claim 8, wherein the base is present relative to the starting materialaIn particular, 0.5 to 2 molar equivalents, preferably 0.7 to 1.5 molar equivalents and more preferably 0.8 to 1.25 molar equivalents are used.

10. The method of any one of claims 1 to 9, wherein the reagentbTo relative to the starting materialaIn particular, 0.5 to 4 molar equivalents, preferably 1 to 3 molar equivalents and more preferably 1.5 to 2.5 molar equivalents are used.

11. The process according to any one of claims 1 to 10, wherein the reaction is carried out at a temperature of greater than 60 ℃, preferably greater than 70 ℃ and more preferably greater than 80 ℃, for example 80 to 150 ℃.

12. The method of any one of claims 1 to 11, wherein the reacting comprises the sub-steps of:

。

13. the method of any one of claims 1 to 11, wherein the reacting comprises the sub-steps of:

14. the method of claim 12 or claim 13, wherein the substeps are carried out in the presence of different metal catalysts.

15. The method of any one of claims 12 to 14, wherein the substeps are carried out in the presence of different ligands.

16. The process according to any one of claims 1 to 15, wherein the process is a batch process, wherein the fuel additive is produced in a batch quantity of more than 100kg, preferably more than 150kg, and more preferably more than 200 kg.

17. The process of any one of claims 1 to 15, wherein the process is a continuous process.

18. The process according to any one of claims 1 to 17, wherein the reaction is carried out in a reactor or, where the reaction comprises sub-steps (i) and (ii) or (i ') and (ii'), the reactor has a volume of at least 500L, preferably at least 750L, and more preferably at least 1000L.

19. A fuel additive having the formula:

wherein: r₁Is hydrogen;

R₂、R₃、R₄、R₅、R₁₁and R₁₂Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

R₆、R₇、R₈and R₉Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

x is selectedfrom-O-or-NR₁₀-, wherein R₁₀Selected from hydrogen and alkyl; and

n is a number of 0 or 1,

wherein the fuel additive is obtainable by a process according to any one of claims 1 to 18.

20. A method for preparing a fuel for a spark-ignition internal combustion engine, the method comprising:

preparing a fuel additive using the method of any one of claims 1 to 18; and

blending the fuel additive with a base fuel.

21. A fuel for a spark-ignition internal combustion engine, the fuel comprising a fuel additive according to claim 19 and a base fuel.

Technical Field

The present invention relates to a method for preparing an octane boosting additive for use in a fuel for a spark-ignition internal combustion engine. In particular, the present invention relates to a process for the preparation of octane boosting fuel additives which are derivatives of benzo [1,4] oxazines and 1, 5-benzoxazepinones. The invention also relates to a method for preparing a fuel for a spark-ignition internal combustion engine comprising said fuel additive.

Background

Spark ignition internal combustion engines are widely used for domestic and industrial power. For example, spark ignition internal combustion engines are commonly used in the automotive industry for powering vehicles such as passenger cars.

Fuels for spark-ignition internal combustion engines, typically gasoline fuels, typically contain a number of additives to improve fuel properties.

One class of fuel additives is octane improving additives. These additives increase octane number for the fuel, which is desirable to combat problems associated with pre-ignition, such as knock. When the base fuel octane is too low, the addition of an octane improver to the fuel can be performed by a refinery or other supply (suppier), such as a fuel terminal or a bulk fuel mixer, so that the fuel meets the appropriate fuel specifications.

Organometallic compounds containing, for example, iron, lead or manganese are well known octane improvers, of which Tetraethyllead (TEL) has been widely used as a high-efficiency octane improver. However, TEL and other organometallic compounds (if present) are currently commonly used in fuels only in small amounts because they can be toxic, damaging to the engine and damaging to the environment.

Octane improvers that are not metal-based include oxygenates (e.g., ethers and alcohols) and aromatic amines. However, these additives also have various disadvantages. For example, N-methylaniline (NMA) (aromatic amine) must be used at relatively high treat rates (1.5 to 2% additive weight/base fuel weight) to have a significant effect on the octane number of the fuel. NMA may also be toxic. Oxygenates reduce the energy density in the fuel and can cause compatibility problems in fuel storage, fuel lines, seals and other engine components when it comes with NMA that must be added at high processing rates.

Recently, a new class of octane boosting additives has been discovered. These octane boosting additives are derivatives of benzo [1,4] oxazines and 1, 5-benzoxazepinones and show great promise due to their non-metallic nature, their low oxygenate content and their efficacy at low treat rates (see WO 2017/137518). Preferred octane boosting additives of this class are substituted on one or more carbons that form part of an aromatic or heterocyclic ring.

The synthetic routes currently reported in the literature provide various descriptions of how benzoxazines can be prepared on a relatively small scale (from a few hundred mg to a scale of up to 100 kg). For example, US 2008/064871, which relates to compounds for the treatment or prevention of uric acid related diseases such as gout, discloses the preparation of benzoxazine-derived compounds.

However, due to the high cost of specialized raw materials (e.g. methylaminophenols) and reagents (e.g. lithium aluminium hydride and dibromoethane), which are required in stoichiometric amounts, such synthetic methods are not useful for preparing new types of octane boosting additives on an industrial scale (e.g. from 50 up to 20,000 tons/year).

Thus, there is a need for a process for the synthesis of a new class of octane boosting additives that can be implemented on a large scale and that alleviates at least some of the problems highlighted above (e.g., by avoiding the use of expensive aminophenol starting materials).

Summary of The Invention

The invention provides a process for preparing a fuel additive having the formuladThe method of (1):

wherein: r₁Is hydrogen;

R₂、R₃、R₄、R₅、R₁₁and R₁₂Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine anda tertiary amine group;

R₆、R₇、R₈and R₉Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

x is selected from-O-or-NR₁₀-, wherein R₁₀Selected from hydrogen and alkyl; and

n is 0 or 1.

The method comprises carrying out the following reactions:

wherein: each Y is independently selected from halogen groups (halides).

Also provided is a fuel additive obtainable by the process of the inventiond。

The present invention also provides a method for preparing a fuel for a spark-ignition internal combustion engine, the method comprising:

preparation of Fuel additives Using the Process of the inventiond(ii) a And

blending the fuel additive with a base fuel.

Fuel for a spark-ignited internal combustion engine is also provided. The fuel comprises the fuel additive of the inventiondAnd a base fuel.

Detailed description of the invention

Preparation method

The invention provides a method for preparing fuel additivedThe method of (1). According to this method, a fuel additive is prepared by carrying out the following reactiond：

Starting materialaComprising the group Y. Each Y is independently selected from halogen groups, preferably Br, Cl and I, and more preferably Br and Cl.

The reaction is preferably carried out in the presence of a metal catalyst. Preferred metal catalysts are selected from palladium catalysts(e.g., an organometallic palladium catalyst such as tris (dibenzylideneacetone) dipalladium (0) (also known as Pd)₂(dba)₃) And [1, 1' -bis (di-tert-butylphosphino) ferrocene]Palladium (II) dichloride (also known as PdCl)₂(dtbpf))) and a copper catalyst (e.g., elemental copper, copper (I) halide (e.g., copper (I) bromide or copper (I) iodide) and copper (I) oxide), and more preferably a copper catalyst.

In some embodiments, the reaction is carried out in the presence of a combination of catalysts, for example a combination of palladium and copper catalysts, such as those described above.

The catalyst may be used in combination with an organic ligand, preferably selected from organophosphorus ligands (for example selected from 2-dicyclohexylphosphino-2 ', 4', 6 '-triisopropylbiphenyl (also known as XPhos), 2- (dicyclohexylphosphino) 3, 6-dimethoxy-2', 4 ', 6' -triisopropyl-1, 1 '-biphenyl (also known as BrettPhos), 2-di-tert-butylphosphino-2', 4 ', 6' -triisopropylbiphenyl (also known as BrettPhos)tBuXPhos), 2-dicyclohexylphosphino-2 ', 6' -diisopropoxybiphenyl (also known as RuPhos)), alkanolamines (e.g., ethanolamine), aniline-derived ligands (e.g., di (methylamino) benzenes), and ligands derived from amino acids (e.g., proline, hydroxyproline, and N, N-dimethylglycine).

For example, organophosphorus ligands, particularly XPhos, may be used in combination with palladium catalysts, particularly Pd₂(dba)₃Are used together. Alkanolamines (e.g., ethanolamine), aniline-derived ligands (e.g., di (methylamino) benzenes), and amino acid-derived ligands (e.g., proline, hydroxyproline, and N, N-dimethylglycine) may be used with copper catalysts, such as copper halides.

In the case of using the ligand, it may be used in an amount of 1 to 10 molar equivalents, preferably 2 to 8 molar equivalents and more preferably 3 to 6 molar equivalents with respect to the catalyst.

Suitable solvents for carrying out the reaction include toluene, t-amyl alcohol, dimethylformamide, ethanolamine, tetrahydrofuran and dioxane.

In some embodiments, the methods of the invention comprise the steps of: combining the catalyst, organic ligand and solvent and heating the mixture to a temperature, for example, above 30 ℃, preferably above 40 ℃ and more preferably above 50 ℃, then combining the mixture and starting materiala. Preferably, the starting materialsaPrior to combining, the composition is allowed to cool to room temperature (e.g., to a temperature of 15 to 25 ℃).

The catalyst may be present in relation to the starting materialaIn particular, 0.01 to 1 molar equivalent, preferably 0.02 to 0.5 molar equivalent and more preferably 0.03 to 0.3 molar equivalent is used.

The reaction is preferably carried out in the presence of a base, preferably an inorganic base and more preferably an alkali metal base. For example, the base may be selected from alkali metal carbonates (e.g. sodium carbonate, potassium carbonate or cesium carbonate), alkali metal alkoxides (e.g. alkali metal tert-butoxide such as sodium tert-butoxide or potassium tert-butoxide), alkali metal hydrides (e.g. sodium hydride or potassium hydride), alkali metal organosilicon compounds (e.g. lithium bis (trimethylsilyl) amide) and alkali metal phosphates (e.g. trialkali metal phosphates such as tripotassium phosphate).

The base may be present in relation to the starting materialaIn particular, 0.5 to 2 molar equivalents, preferably 0.7 to 1.5 molar equivalents, and more preferably 0.8 to 1.25 molar equivalents are used.

ReagentbMay be relative to the starting materialaIn particular, 0.5 to 4 molar equivalents, preferably 1 to 3 molar equivalents, and more preferably 1.5 to 2.5 molar equivalents are used.

The reaction is preferably carried out at a temperature above 60 ℃, preferably above 70 ℃ and more preferably above 80 ℃, for example from 80 to 150 ℃. In case the catalyst is a palladium catalyst, the temperature is even more preferably from 80 to 100 ℃. In case the catalyst is a copper catalyst, the temperature is even more preferably from 100 to 120 ℃.

The reaction is usually carried out at ambient pressure, i.e. at a pressure of about 1 bar.

The reaction may be carried out for a period of at least 2 hours, for example, a period of 4 to 24 hours.

Catalyst and ligand, base, solvent andreagentbThe preferred combinations of (a) and (b) are as follows:

● Pd₂dba₃catalysts using XPhos ligands, NaOtBu base, toluene solvent, two L = Cl

● Pd₂dba₃Catalysts using XPhos ligands, K₂CO₃Base, t-amyl alcohol solvent, two L = Cl

● Pd(dtbpf)Cl₂Catalyst, no ligand, NaOtBu base, toluene solvent, two L = Cl

● Pd(dtbpf)Cl₂Catalyst, no ligand, K₂CO₃Base, t-amyl alcohol solvent, two L = Cl

● Pd₂dba₃Catalysts using XPhos ligands, NaOtBu base, toluene solvent, two L = Br

● Pd₂dba₃Catalysts using XPhos ligands, K₂CO₃Base, t-amyl alcohol solvent, two L = Br

● Pd(dtbpf)Cl₂Catalyst, no ligand, NaOtBu base, toluene solvent, two L = Br

● Pd(dtbpf)Cl₂Catalyst, no ligand, K₂CO₃Base, t-amyl alcohol solvent, two L = Br

● CuCl catalyst, no ligand, NaH base, toluene solvent, two L = Cl

● CuCl catalyst, no ligand, NaH base, dimethylformamide solvent, two L = Cl

● CuCl catalyst, no ligand, Cs₂CO₃Base, dimethylformamide solvent, two L = Cl

● CuCl catalyst, ethanolamine ligand, Cs₂CO₃Base, dimethylformamide solvent, two L = Cl

● CuCl catalyst (MeNH)₂C₆H₄Ligand, Cs₂CO₃Base, dimethylformamide solvent, two L = Cl

● CuCl catalyst, no ligand, Cs₂CO₃Alkali, ethanolAmine solvent, two L = Cl.

In some embodiments, the reaction is carried out as a single reaction (i.e., using a set of reagents and under a set of conditions). However, in some embodiments, the reaction includes the following sub-steps:

in other embodiments, the reaction includes the following sub-steps:

it will be appreciated that in some cases, the intermediates arecStep (ii) will occur spontaneously upon formation and in intermediatesc’Step (ii') will occur spontaneously upon formation. For the purposes of the present invention, these cases are considered as embodiments in which the reaction is carried out in the form of a single reaction.

In a preferred embodiment, the substep is carried out in the presence of a different metal catalyst (i.e., substep (i) is carried out in the presence of a different metal catalyst than substep (ii), and substep (i ') is carried out in the presence of a different metal catalyst than substep (ii').

The substeps may be carried out in the presence of different ligands.

The substeps may be carried out under different conditions.

The process of the invention is preferably carried out on an industrial scale. For example, in the preparation of fuel additivesdIn case the process of (a) is a batch process, the fuel additive is preferably produced in a batch quantity of more than 100kg, preferably more than 150kg, and more preferably more than 200 kg. The process can also be carried out as a continuous process.

For the production of the fuel additive on an industrial scale, it is preferred to carry out the reaction in a reactor or, in case the reaction comprises sub-steps (i) and (ii) or (i ') and (ii'), the reactor has a volume of at least 500L, preferably at least 750L and more preferably at least 1000L. It will be appreciated that where the reaction comprises sub-steps, more than one (e.g. each) sub-step may be carried out in the same reactor.

dOctane enhancing fuel additive

Fuel additives prepared using the process of the inventiondHaving the formula:

wherein: r₁Is hydrogen;

R₂、R₃、R₄、R₅、R₁₁and R₁₂Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

R₆、R₇、R₈and R₉Each independently selected from hydrogen, alkyl, alkoxy-alkyl, secondary amine, and tertiary amine groups;

x is selected from-O-or NR₁₀-, wherein R₁₀Selected from hydrogen and alkyl; and

n is a number of 0 or 1,

provided that R is₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂At least one of which is selected from groups other than hydrogen.

Preferred substituents for fuel additives are described below. It will be appreciated that the preferred substitution patterns also apply to the preparation of fuel additives therefromdStarting material ofaReagent for the preparation of the samebAnd intermediatescAndc'。

in some embodiments, R₂、R₃、R₄、R₅、R₁₁And R₁₂Each independently selected from hydrogen and alkyl, and preferably from hydrogen, methyl, ethyl, propyl and butyl. More preferably, R₂、R₃、R₄、R₅、R₁₁And R₁₂Each independently selected from hydrogen, methyl and ethyl, and even more preferably from hydrogen and methyl.

In some embodiments R₆、R₇、R₈And R₉Each independently selected from hydrogen, alkyl and alkoxy and preferably from hydrogen, methyl, ethyl, propyl, butyl, methoxy, ethoxy and propoxy. More preferably, R₆、R₇、R₈And R₉Each independently selected from hydrogen, methyl, ethyl and methoxy and even more preferably from hydrogen, methyl and methoxy.

R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂And preferably R₆、R₇、R₈And R₉At least one of which is selected from groups other than hydrogen. More preferably, R₇And R₈At least one of which is selected from groups other than hydrogen. In other words, the octane enhancing additive consists of R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂At least one of the positions represented, preferably at the position represented by R₆、R₇、R₈And R₉At least one of the positions represented, and more preferably at R₇And R₈At least one of the represented positions is substituted. It is believed that the presence of at least one group other than hydrogen may improve the solubility of the octane boosting additive in the fuel.

Also advantageously, R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂No more than five of (a), preferably no more than three, and more preferably no more than two, are selected from groups other than hydrogen. Preferably, R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂One or both of which are selected from groups other than hydrogen. In some embodiments, R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂Only one of which is selected from groups other than hydrogen.

Also preferred is R₂And R₃Is hydrogen, and more preferably R₂And R₃Both are hydrogen.

In a preferred embodiment, R₄、R₅、R₇And R₈At least one of which is selected from methyl, ethyl, propyl and butyl and R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂The remainder of (a) is hydrogen. More preferably, R₇And R₈Is selected from methyl, ethyl, propyl and butyl, and R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂The remainder of (a) is hydrogen.

In a further preferred embodiment, R₄、R₅、R₇And R₈Is methyl, and R is₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂The remainder of (a) is hydrogen. More preferably, R₇And R₈At least one of which is methyl and R₂、R₃、R₄、R₅、R₆、R₇、R₈、R₉、R₁₁And R₁₂The remainder of (a) is hydrogen.

Preferably, X is-O-or-NR₁₀-, wherein R₁₀Selected from hydrogen, methyl, ethyl, propyl and butyl, and preferably from hydrogen, methyl and ethyl. More preferably, R₁₀Is hydrogen. In a preferred embodiment, X is-O-.

n may be 0 or 1, although preferably n is 0.

Octane boosting additives that may be used in the present invention include:

。

preferred octane boosting additives include:

。

particularly preferred are octane boosting additives:

。

mixtures of additives may be used in the fuel composition. For example, the fuel composition may comprise a mixture of:

。

it is understood that reference to alkyl groups includes the different isomers of alkyl groups. For example, reference to propyl includes n-propyl and isopropyl, and reference to butyl includes n-butyl, isobutyl, sec-butyl and tert-butyl.

Additive and fuel composition

The present invention provides a fuel additive obtainable by the process of the inventiond. Preferably, the fuel additive is obtained by the method according to the invention.

The present invention also provides a method for preparing a fuel for a spark-ignition internal combustion engine, the method comprising:

preparation of Fuel additives Using the Process of the inventiond(ii) a And

the fuel additive is blended with a base fuel.

Fuel for a spark-ignited internal combustion engine is also provided. The fuel comprises a fuel additive obtainable and preferably obtained by the process of the inventiondAnd a base fuel.

Gasoline fuels (including those containing oxygenates) are commonly used in spark-ignited internal combustion engines. Accordingly, the fuel composition that may be prepared according to the process of the present invention may be a gasoline fuel composition.

The fuel composition may comprise a major amount (i.e. more than 50 wt%) of a liquid fuel ("base fuel") and a minor amount (i.e. less than 50 wt%) of an additive composition of the invention. Examples of suitable liquid fuels include hydrocarbon fuels, oxygenate fuels, and combinations thereof.

The fuel composition may contain an octane boosting fuel additive in an amount up to 20%, preferably from 0.1% to 10% and more preferably from 0.2% to 5% of the additive weight per weight of base fueld. Even more preferably, the fuel composition contains the fuel additive in an amount of from 0.25% to 2% and even more preferably still from 0.3% to 1% additive weight/base fuel weight. It should be understood that when more than one octane boosting fuel additive is useddWhen these values refer to fuel additives in the fueleThe total amount of (a).

The fuel composition may comprise at least one other fuel additive. Examples of such other additives that may be present in the fuel composition include detergents, friction modifiers/antiwear additives, corrosion inhibitors, combustion modifiers, antioxidants, valve seat recession additives, dehazers/demulsifiers, dyes, markers, fragrances, antistatic agents, biocides, and lubricity improvers. It is also possible to use additional octane improvers in the fuel composition, i.e. without octane boosting fuel additivesdThe octane improver of (1).

The fuel composition is used in a spark-ignition internal combustion engine. Examples of the spark ignition internal combustion engine include a direct injection spark ignition engine and a port fuel injection spark ignition engine. Spark ignition internal combustion engines may be used in automotive applications, such as in vehicles such as passenger cars.

The invention will now be described with reference to the following non-limiting examples.

Examples