JPS59104343A - Production of carboxylic acid and esters thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carbonic acid or its esters by the reaction of formic acid or its Nisdels with melefin, and in this case, formic acid or Nispur formate is added to an olefin to produce a higher carbonic acid. or its ester.

The addition of formic acid esters to olefins has previously been described in U.S. Pat. No. 3,849,456, in which the -C reaction is catalyzed by a peroxide. The reaction is relatively non-selective in that it produces a wide mixture of Nisder carboxylic acids.

Addition of formic acid or its esters to olefins can be catalyzed by noble metals of group V111, such as iridium, which produces a narrower mixture of Nisder carboxylates than in the case of catalysis with peroxides as described above. It has been discovered that there are advantages in that moreover,
By appropriate adjustment of the reaction conditions, high selectivity can be achieved in that, for example, higher carboxylic acids and their ester products can exceed 90% by weight of the liquid beef product.

Thus, according to the present invention, a process for producing a carbonic acid having at least two more carbon atoms than formic acid or a Nisdel thereof comprises adding formic acid or an ester to an olefin and having at least two more carbon atoms than formic acid. In order to produce a large amount of acids or esters, the presence of an effective amount of a noble metal of group ν as a catalyst -C1 high selectivity -C! It consists of an olefin and a reaction port, 5-, which connects l1i1 acid or its ester.

Convenience - The Group VIII noble metal is preferably a compound that is soluble in the reactants and products under the reaction conditions.

No. VIII. Noble metals include rhodium, rhodium, osmium, iridium and platinum.

Preferably, the group viii metal compound is for example [1''(
Schif11λktaj,n)α]1, Na21rα6. Xl
l 20, old rcU [P(Ca It 5) 3]
s, Cf! IrC[](PIEt,a)2,I
RG3. X1120, lrl+, XH20, Nas
Ir(NO2>6.Xl+2 [1.

[:(Cs H5) 21r:] NO3, Ir(CI
)12, IrH3[P(C6It,)3]3,(
[:111112) It is an iridium compound that is a Qu salt or complex of 21rSnα3. Preferred compounds are [
1r(cyclooctadiene)α]2.111CA3. X
112[], Ir[]r3. XlI20, Ir
+3. Xl+20 and iridium tris-r cetyl acetonate.

The symbol X indicates different degrees of hydration and can range from 0 to 12, and metallic iridium can be used.

Preferably, a Ken compound promoter, such as an iodide promoter, is also used in conjunction with the Group V111 noble metal.

Suitable iodides are alkyl iodides, especially methyl iodide &1+
It is a lower alkyl iodide. A suitable concentration of iodide for Group VIII noble metals is 1 to 500 moles per mole of Group VIII noble metal.

When formic acid is the reactant, some of the iodide tends to be converted to the -C carboxylic acid by reaction with the formic acid. For example, methyl iodide is converted to acetic acid. Therefore, it is preferred that the alkyl group of the iodide promoter be the same as that in the acid produced as the reaction product. When producing propionic acid, it is preferred to use ethyl iodide.

The reaction can be carried out in either gas phase or liquid phase. In the latter case, a solvent is usually used for the liquid reactant. A suitable solvent has the formula lIC0211, where R is C1-C
8 aliphatic, C4-C8 alicyclic, C7C12'J'ralkyl, C6-C1o aryl.

Preferably, a strong acid that is compatible with the catalyst is also present as a co-promoter for the catalyst. Compatible means that strong acids must not deactivate the catalyst. The iodide promoter can be omitted when acid is present. By strong acid is meant one that is more acidic than the carbonic acid used as a solvent, for example an acid with an INK less than O (as measured in water). Suitable strong acids are mineral acids and sulfonic acids, such as hap-)luenesulfonic acid, and methanesulfonic acid, for example from 1.5 to 50% by weight.
Use in the amount of The concentration of acid varies widely, typically 10wt.
Liquid sulfonic acids can be used, for example, although concentrations of up to % are advantageous.

Suitable olefins for use in the present invention are:
having 30 carbons, and in its aliphatic, acyclic or alicyclic form (aliphatic heteroaliphatic), I-I 11g2.
1 to 1.174 is independently hydrogen, hydrogen, alkyl, alkenyl, aryl, cyclo-rlkyl, cycloD
AlkenylgB moiety, or in heteroaliphatic compounds nitrogen, phosphorus, sulfur, +1ilt
, H is a ``butene or 1.
k) be done. Suitable compounds having the formula 1 are ethylene, propylene, butene-1; butene-2; pentene;
Hexene: octene; hexadecene; 2-methylpropene: styrene; 1,4-hexy→nodiene; acrolein, methyl vinyl ketone and 2-cyclohexyl butene. If desired, mixtures of the olefins listed in - can also be used.

Suitable esters of formic acid are those having the formula HCO2R, where 5 and 1 are [2, .about.C81I].

Conveniently, the reaction is carried out at 100-250°C, preferably at 17
It is carried out at a temperature within the range of 0 to 215°C.

In the case of casseous olefins, the pressure is autogenous pressure (aut
(1) It is desirable that the pressure be at least 1 Opsi. Convenient pressure is 200
-1200psi range.

To reduce the source of undesirable decomposition of formic acid, the concentration of formic acid is low, e.g. 25 wt% of the reaction solution, and the partial pressure of the melefin is high, e.g. 300 psi in the case of ethylene.
It is preferable to keep it as follows. For reactions involving formic acid esters, for example, methyl formate, the same conditions are known to be catalyzed by iridium activated with iodide. helps reduce losses.

The reaction is conducted in the substantial absence of oxygen, although carbon monoxide or an inert gas such as nitrogen or hydrogen may be present.

The products of the present invention have a wide range of uses, for example, D-vinoic acid is used as an agro-C preservative.

Next, examples of the present invention will be shown.

Example 1 1! In the Reaction Examples of Methyl ifate and Ethylene, all reactants and products are added in liquid phase, except for ethylene in Examples 1-5 and 7-11, and the catalyst is used in solution.

The pressure reached in the reaction vessel was not measured in any case.
15 to R corrosion resistance autoclave? g of methyl formate,
A reaction mixture consisting of 8.1 g of methyl iodide as promoter, 40.5 g of acetic acid as solvent and Irα3 of fl, Ig is charged. The autoclave is sealed, flushed three times with ethylene and then pressurized with 4 ps i ethylene with stirring. The autoclave is then heated and the temperature reaches 20 ps
Hold at t for 25 hours. After cooling and depressurization, the product was collected and analyzed by gas-liquid chromatography (G, 1, C), containing 135% by weight of p[1pimenic acid, ?
The product was found to contain 5% methyl propionate, 2-8% methyl acetate (produced by Nisder exchange) and 63% unreacted methyl formate.

Example 2 Reaction of methyl formate with ethylene In this example, propimenic acid was reacted with methyl formate and ethylene.
C as a solvent to measure the amount of acetic acid produced.

The 3° mate crepe of Example 1 used was 15. (Methyl Jjikate of Ig, 90g methyl iodide as promoter, 40.5
Charge g of propionic acid as solvent, Olg of Irα3. Next, the procedure of Example 1 was carried out. Analysis of the product showed only 0.8% acetic acid, traces of methyl acetate, and 83% unreacted methyl formate.

Propionic acid esters were also produced, but the amount produced was not practically sufficient for the propionic acid solvent used.

This example shows that under the conditions of Example 1, only a small amount of acetic acid
4 shows what will be done.

Example 1? A comparison with Nisdel shows that 135% of the liquid phase reaction product is Nisdel butylvinate (i.e., propimenic acid and Nisdel).

Example 3 A rotary stirrer (+tfi) was added to 500 m of corrosion-resistant two-clave with a reaction mixture consisting of 1:12 [1 g of methyl formate, 120 g of solvent, -C of acetic acid, 18 g of methyl iodide as accelerator;
0.4 g of ilicium pentachloride l- and 12 g of co-promoter -C) p-)luenesulfonic acid. The autoclave is sealed, flushed with ethylene : ) times, and then pressurized with 4 (l 0 psi) ethylene without stirring.

The clave is then heated to 200 DEG C. and held at this temperature for 30 minutes. After cooling and depressurization, the product is collected,
G, l, (゛-C analyzed. The analysis is as follows: 10% propimenic acid, 12.7% methyl propymenate, 24.
Contains 9% methyl acetate, 105% unreacted methyl formate.

Example 4 Methyl Formate Reaction with Old Ethylene Example 3 is repeated except that there is no co-promoter of p-toluenesulfonic acid. The product is only 4.0% propionic acid, 14% methyl propylanate and 18.7%
was found to contain methyl acetate and unreacted methyl formate.

A comparison of Examples 3 and 4 shows that high yields of pyropimenic acid and its esters are produced when a strong acid is impregnated into the reaction mixture.

Example 5 Reaction of methyl formate and ethylene In the mate crepe of Example 1, 3 (], (] g
methyl formate, 25. Acetic acid as solvent for (]g, 12
．． Charge 6 g of methyl iodide as promoter, 3.0 g of p-)luenesulfonic acid as co-promoter and (],] 1 of ruthenium. O-1-crepe is flushed with ethylene;) times 1. Closed and stirred
If] (pressurized with lpsi ethylene. The reactor is heated to 2()0° C. for 111 hours and removed after cooling. Analysis by G, L, (: shows that the product is 0,
fi 5wt% methyl b[]pionate, 0.4wt
% ButTJ Pimenic Acid 4 Contains 1 Z, - and 4 Small -C Color 11 Example 6 Reaction of Methyl Formate with Hexene-1 Example: 3 Mate Clay 7 to 6 + 1.0 g Hexene 1.60. 0 g of methyl formate, 120.0 g of propynic acid as solvent, 47.9 g of methyl iodide as promoter, 120 g of 1)-toluenesulfonic acid as co-promoter and (1) , 395 g of irisium dichloride are charged. The autoclave is flushed three times with nitrogen, sealed and then heated to 200° C. After 6 hours at this temperature, the reactor is cooled and the product is placed at t, +: The product was 4.5191% methyl hebutanoate, 6.
Contains 5wt% heflic acid. - was discovered.

Example 7 Reaction of Formic Acid with Ethylene In a 500 mβ quadrilateral autoclave, 5 [ ]9 g of formic acid solution (90 W (%) in water, ]9.5 g of promoter Yoshi-C methyl iodide, 0.417 g of Ilisium trichloride and 15 [1,7 g of Q] as a solvent are charged. The autoclay 7 is sealed, flushed three times with ethylene and then pressurized with 65 (1 (Iq i) ethylene without stirring. The reactor is heated to 200 γ and 1′/A before cooling.
It is kept at this temperature for an hour.

GLC analysis showed that the product contained 2.6 wt% propimenic acid.

Example 8 Reaction of formic acid with ethylene In the autoclave of Example 7, 50.0 g of formic acid solution (90 wt% in water), 29.5 g of ethyl iodide as promoter, O, /104 g of irinium trichloride, 149 .8
g of acetic acid as solvent and 12.3 g of methanesulfonic acid as co-promoter. Autoclave is 3
The reactor is heated once, flushed with ethylene, sealed, and then pressurized with 600 psi ethylene while stirring and held at 200 °C for 30 min before cooling. Product C'; 1. C analysis is 22. /Iw showed that it contained 1% propionic acid.

In this example, the alkyl group of the co-promoter was the same as that in the propionic acid product.

Example 1] Reaction of 11 acids with ethylene in the absence of carboxylic acid solvent In a corrosion-resistant autoclave of 100 m R, 40.5 g
of formic acid solution (IJ()v+1% in water), 7.6 g of methyl iodide and [) as promoter, 103 g of iridium trichloride are charged. The mate clef was sealed, flanneled with ethylene three times, and stirred for 4 (]Oρs1).
Pressurized with ethylene. The reactor is heated and held at 200° C. for an hour at 1+A before cooling.

Product G 1. Ci minutes i''7Jqj now,
20. ! Example 10 35.0 g of formic acid was added to the crepe of Example 1.
5.6 g of methyl iodide as promoter, 4 g of p-)luenesulfonic acid as co-promoter, O, ], g of iridium trichloride. The mateclave was flushed three times with ethylene and pressurized to 400 psia;
After sealing, the autoclave is heated to 2°C for 1 hour. During this period, the pressure does not rise above 700 psia. The autoclave is then cooled and the product is collected and heated to G L
Be analyzed in C. The analysis is ], 7.8 wL% methyl propionate, 78 wt% methyl propionate, ], 5 w
A sample containing L% propionic acid and 1.1wL% acetic acid was developed.

This example, along with Examples 11.12 below, illustrates that carboxylic acid solvents are not necessary when strong acids are used.

Example 11 Reaction between methyl formate and ethylene 35.0 g of methyl formate was placed in the Zutclave of Example 1,
5.5 g of methyl iodide as promoter, 4.0 g of methanesulfonic acid as co-promoter, 0.139 g of ilinum trisacetylacetonate-14, the treatment of Example 10 was then carried out. Except for the reaction time in 20072, which was 2 hours, the products were 216% pro-r-+ methyl pionate, 7.8% propimenic acid, 118% methyl acetate by weight. , was found to contain 5.0% acetic acid. .

Example 12 Reaction of methyl formate and hexene-1 in the absence of solvent 1.5.0 g of methyl formate and 25 (1.5.0 g of hexene-1 of Example 1 as promoter) - (θ) methyl iodide, /1.0 g of methanesulfonoic acid as co-promoter, 0.]06 g of iris trichloride. The autoclave is then flushed several times with nitrogen and at 300 psia of nitrogen. The reaction mixture was then heated to 200 t and maintained at this temperature for 3 hours during which time the pressure did not exceed 650 psi. The autoclave was then cooled and the product was analyzed in GLC and weighed. (% It was discovered that it contains 1-heptanoic acid.

Priority claim @ January 13, 1983 ■ United Kingdom (GB
)■888 0 Inventor Peter Sefton Williams 192 King Street, Kotthirangam, North Humberside, Hull, UK

Claims (9)

[Claims] (1) Acid or ester is added to trefin to produce an acid or ester having at least two more carbon atoms than formic acid, and a self-effective amount of Part VII is added to the catalyst.
A method for producing carboxylic acids or esters thereof that yields at least 62 more carbon atoms than formic acid, which comprises reacting formic acid or its esters with an olefin at high temperatures in the presence of a Group I noble metal. . (2) Claim 11jC of group viii is iridium (D. Horn Law of the Book of Jr.). (3) Process 3 according to claim (1) or (2), wherein the halide promoter is present together with the noble metal of group vIll; (4) The method according to claim 5'1, Q11, wherein the saponified product promoter is an alkyl iodide. (5) Is it less auspicious than formic acid? Acids with a high number of carbon atoms have the formula RC02H, and halokenide promoters have the formula 1
1X, and 12 groups of the acid and the halide are the same H. The method according to claim (3) or (4). (6) A method according to each of claims (1) to (5), wherein a strong acid is present in the reaction mixture as a co-promoter. (7) The strong acid is sulfonic acid.
) Method described in section. (8) A method as claimed in each of the preceding claims, wherein the reaction is carried out at a temperature within the range of 1.00 to 250°C and a pressure within the range of 200-12 psi. (9) The method according to each item of claim [1j], wherein the reaction is operated in a liquid phase and a solvent for liquid reactants and products is used. αQ Solvent is carbonic acid Claim No. (S)
) Method described in section. :jdenjmo et al.), 1',,',,i! ,'・・jl;
, J/