Patent Grant
10544079
The invention relates to a process for the direct conversion of diisobutene to a carboxylic acid.
Carboxylic acids are used in the preparation of polymers, pharmaceuticals, solvents and food additives. The routes leading to carboxylic acids generally include the oxidation of hydrocarbons, alcohols or aldehydes, the oxidative cleavage of olefins by ozonolysis, the hydrolysis of triglycerides, nitriles, esters or amides, the carboxylation of Grignard or organolithium reagents, and the halogenation and subsequent hydrolysis of methyl ketones in the haloform reaction.
The object of the invention was to provide a process with which diisobutene (DIBN) can be directly converted to a carboxylic acid.
In the context of this application, “direct conversion” is intended to mean that the reaction takes place in one step, i.e. without separation or work-up or similar of an intermediate product.
This does not exclude, in the course of the reaction, intermediates forming which are directly converted onward.
The object is achieved by a process according to Claim 1.
Process comprising the process steps of:
a) addition of diisobutene;
b) addition of a complex, comprising a compound of general formula (I) and also Pd, or a compound according to general formula (I) and a substance comprising Pd
wherein
R1, R2, R3, R4 are each independently selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl, —(C3-C20)-heteroaryl;
at least one of the R1, R2, R3, R4 radicals is a —(C6-C20)-heteroaryl radical having at least six ring atoms;
and
R1, R2, R3, R4, if they are —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl, —(C3-C20)-heteroaryl or —(C6-C20)-heteroaryl,
may each independently be substituted by one or more substituents selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —O—(C1-C12)-alkyl, —O—(C1-C12)-alkyl-(C6-C20)-aryl, —O—(C3-C12)-cycloalkyl, —S—(C1-C12)-alkyl, —S—(C3-C12)-cycloalkyl, —COO—(C1-C12)-alkyl, —COO—(C3-C12)-cycloalkyl, —CONH—(C1-C12)-alkyl, —CONH—(C3-C12)-cycloalkyl, —CO—(C1-C12)-alkyl, —CO—(C3-C12)-cycloalkyl, —N—[(C1-C12)-alkyl]2, —(C6-C20)-aryl, —(C6-C20)-aryl-(C1-C12)-alkyl, —(C6-C20)-aryl-O—(C1-C12)-alkyl, —(C3-C20)-heteroaryl, —(C3-C20)-heteroaryl-(C1-C12)- alkyl, —(C3-C20)-heteroaryl-O—(C1-C12)-alkyl, —COOH, —OH, —SO3H, —NH2, halogen;
c) feeding in CO;
d) heating the reaction mixture such that the diisobutene is converted to a carboxylic acid, wherein the diisobutene is directly converted to the carboxylic acid.
In a variant of the process, at least two of the R1, R2; R3, R4 radicals are a —(C6-C20)-heteroaryl radical having at least six ring atoms.
In a variant of the process, the R1 and R3 radicals are each a —(C6-C20)-heteroaryl radical having at least six ring atoms,
In a variant of the process, the R1 and R3 radicals are each a —(C6-C20)-heteroaryl radical having at least six ring atoms;
R2 is —(C6-C20)-heteroaryl having at least six ring atoms or is selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl;
and R4 is selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C8-C20)-aryl.
In a variant of the process, the R1 and R3 radicals are each a —(C6-C20)-heteroaryl radical having at least six ring atoms.
and R2 and R4 are selected from —(C1-C12)-alkyl, —(C3-C12)-cycloalkyl, —(C3-C12)-heterocycloalkyl, —(C6-C20)-aryl.
In a variant of the process, the R1 and R3 radicals are each a —(C6-C20)-heteroaryl radical having at least six ring atoms;
and R2 and R4 are —(C1-C12)-alkyl.
In a variant of the process, R1, R2, R3, R4, if they are a heteroaryl radical, are each independently selected from pyridyl, pyridazinyl, pyrimidyl, pyrazinyl, benzofuranyl, indolyl, isoindolyl, benzimidazolyl, quinolyl, isoquinolyl.
In a variant of the process, the compound (I) has the structure (1):
In a variant of the process, the substance in process step b) is selected from: PdCl2, PdBr2, Pd(acac)2, Pd(dba)2 (dba=dibenzylideneacetone), PdCl2(CH3CN)2.
In a variant of the process, the substance in process step b) is Pd(acac)2.
In a variant of the process, the process comprises the additional process step e) e) addition of acetic acid.
In a variant of the process, the process comprises the additional process step f) f) addition of water.
In a variant of the process, the process comprises the additional process step g) g) addition of p-toluenesulfonic acid (PTSA).
In a variant of the process, the reaction mixture is heated to a temperature in the range from 80° C. to 160° C. in process step d).
In a preferred variant of the process, the reaction mixture is heated to a temperature in the range from 100° C. to 140° C. in process step d).
In a variant of the process, the CO is fed in in process step c) such that the reaction proceeds under a CO pressure in the range from 20 bar to 60 bar.
In a preferred variant of the process, the CO is fed in in process step c) such that the reaction proceeds under a CO pressure in the range from 30 bar to 50 bar.
In a variant of the process, the diisobutene is converted to the compound P1:
The invention is elucidated in more detail by means of a working example below.
A 4 ml vial was charged with [Pd(acac)2] (3.05 mg, 0.25 mol %), ligand (X) (20.64 mg, 1.0 mol %), p-toluenesulfonic acid (28.5 mg, 3.75 mol %) and an oven-dried stirrer bar. The vial was then sealed with septa (PTFE-coated styrene-butadiene rubber) and a phenol resin cap. The vial was evacuated and refilled with argon three times. H2O (0.5 ml), acetic acid (1.5 ml) and diisobutene (DIBN) (4.0 mmol) were added to the vial with a syringe. The vial was placed in an alloy plate, which was transferred to an autoclave (300 ml) of the 4560 series from Parr Instruments under argon atmosphere. After flushing the autoclave three times with CO, the pressure of CO was increased to 40 bar at room temperature. The reaction was conducted at 120° C. for 20 h. On conclusion of the reaction, the autoclave was cooled down to room temperature and cautiously decompressed. Isooctane (100 μl) was then added as internal standard. Conversion was measured by GC analysis.
The above-described experiment was carried out with variation of the ligand (X), with X=1 to 8.
The results are compiled in the following table.
As the experimental results show, the object is achieved by a process according to the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 17209336 | Dec 2017 | EP | regional |
| Number | Name | Date | Kind |
|---|---|---|---|
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| 3641074 | Fenton | Feb 1972 | A |
| 3968133 | Knifton | Jul 1976 | A |
| 20070282124 | Eastham | Dec 2007 | A1 |
| 20180022773 | Dong | Jan 2018 | A1 |
| 20190194108 | Sang | Jun 2019 | A1 |
| 20190194110 | Sang | Jun 2019 | A1 |
| 20190194111 | Sang | Jun 2019 | A1 |
| 20190194112 | Sang | Jun 2019 | A1 |
| 20190194113 | Sang | Jun 2019 | A1 |
| 20190194114 | Sang | Jun 2019 | A1 |
| Number | Date | Country |
|---|---|---|
| 887644 | Aug 1953 | DE |
| 1595037 | Aug 1981 | GB |
| 2014005854 | Jan 2014 | WO |
| Entry |
|---|
| U.S. Appl. No. 16/188,995, filed Nov. 13, 2018, Sang et al. |
| U.S. Appl. No. 16/215,991, filed Dec. 11, 2018, Sang et al. |
| U.S. Appl. No. 16/216,004, filed Dec. 11, 2018, Sang et al. |
| U.S. Appl. No. 16/216,020, filed Dec. 11, 2018, Sang et al. |
| U.S. Appl. No. 16/216,037, filed Dec. 11, 2018, Sang et al. |
| U.S. Appl. No. 16/216,053, filed Dec. 11, 2018, Sang et al. |
| European Search Report dated Jun. 21, 2018 in EP 17 20 9336 (5 pages). |
| Number | Date | Country | |
|---|---|---|---|
| 20190194109 A1 | Jun 2019 | US |
