JPS61275246A - Production of carboxylic acid ester - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as a solvent, plasticizer, etc., by catalytically reacting an olefin with carbon monoxide, oxygen and alcohol in the presence of a palladium catalyst, copper salt and alkali metal halide under relatively mild conditions. CONSTITUTION:An olefin, e.g. 1-dodecene, is reacted with carbon monoxide, oxygen and an alcohol, e.g. methanol, in the presence of a palladium catalyst, e.g. fine powder of palladium, palladium halide, palladium acetate or palladium carbon, copper salt, e.g. copper acetate, copper chloride or copper iodide, and alkali metal halide, e.g. sodium chloride, lithium chloride or sodium iodide and, as desired, a compound of an iron family metal or cobalt family metal of Group VIII of the periodic table as a cocatalyst added thereto, e.g. iron carbonyl or cobalt carbonyl, to afford the aimed carboxylic acid ester, e.g. methyl 2-methyldodecanoate.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a method for producing a dicarboxylic acid ester by catalytic reaction in the presence of an olefin, carbon monoxide, oxygen and alcohol.

Carboxylic acid esters are important as solvents, plasticizers, and other key industrial substances.

[Conventional technology]

Conventionally, olefin and carbon monoxide*j? A method of producing an ester by reacting alcohol and alcohol in the presence of a catalyst is known, and a typical published technique is disclosed in U.S. Patent No. 4,30
No. 3,589, etc., the conventional method requires high temperature and high pressure and is difficult to implement industrially. JP-A No. 53U040,709 discloses a technique carried out in the presence of oxygen, but the product is a dicarboxylic acid diester. In addition, as a technique to be implemented in the presence of protonic acid, Japanese Association Patent Publication No. 59-501
No. 904 is available, but as it uses an excessive amount of concentrated hydrochloric acid, it is easy for those skilled in the art to understand that corrosion of the equipment is not a problem, and there are restrictions on the types of olefins that can be used, which is not common. It will be. In addition, when the present inventors tried this method again, the yield was lower than that of the present invention (see comparative example below)0 [Problems to be solved by the invention] The present inventors As a result of studies to overcome the shortcomings of the conventional methods, the present invention was completed by discovering a technique that can be carried out under milder conditions than the conventional methods.

A carboxylic acid ester is produced by reacting an olefin, carbon monoxide, oxygen, and alcohol in the presence of a metal herogonide.

The present invention requires that the reaction be carried out in the presence of a palladium catalyst. Palladium catalysts that can be used include palladium metal such as palladium fine powder and palladium salts, palladium salts such as palladium halides, acetates and nitrates, and palladium supported on carriers such as palladium on carbon and palladium alumina. etc. can be exemplified.

The present invention is carried out in the presence of a copper salt, and the copper salt is
Copper or cupric salts can be used. Examples of suitable copper salts include acetate steel, copper acetylacetonate, chloride steel, bromide steel,
Includes iodide steel, nitrate steel, etc. The amount of copper salt used is in the range of 1150 G to 2 molar equivalents based on the olefin.

The present invention must be carried out in the presence of an alkali metal halide, such as sodium chloride, lithium chloride, potassium chloride, cesium heptadide, potassium fluoride,
Sodium bromide, potassium bromide, sodium iodide, potassium iodide, etc. can be used. Furthermore, when a palladium salt is used as a palladium catalyst, it can be first reacted with an alkali metal halide and then used as a palladium ate complex. The amount of the alkali metal halide to be used can be selected from a range of 1,500 to 1 equivalent relative to the olefin.

The olefin that is the raw material of the present invention has a molecular weight of 2 to 3.
Acyclic olefins with 0 carbon atoms or cyclic olefins with #) 4 to 30 carbon atoms per molecule may be mentioned. Olefins may have D', 2 or 3 olefinic carbon-carbon double bonds per molecule, with the double bonds being either internal or terminal. It can be represented by the formula % (2), in which W and - are independently hydrogen atoms, or alkyl, alkenyl, alkagenyl, cycloalkyl, aryl, aral, which may have a substituent that does not participate in the reaction. , fuchloroalkenyl or cycloalkagenyl groups, or together with at and! can also form a ring system. Examples of suitable olefins include, for example, ethylene, propylene, l-
Butene, 2-butene, 1-pentene, 2-pentene, 1
-hexene, 2-hexene, 3-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene, 2-
octene, 3-octene, 4-octene, 1-nonene,
1-decene, 1-undecene, 1-dodecene, 1-tridecene, 3-tridecene, ]-hebutadecene, 1-eicosene, cyclopentene, cyclohexene, cyclooctene, cyclododecene, styrene, allylbenzene, p
- Methylstyrene, p-isobutylstyrene, p-methoxysterene, p-chlorostyrene, m-chlorostyrene, p-fluorostyrene, pentafluorostyrene,
1.5-hexadiene, 1゜6-hebutadiene, l, 9
-decadiene, 1.5゜9-7 clododecatriene, vinyl fluoride, 3゜3.3-trifluoropropene, 4
-Methyl pentenoate, 3.3-dimethyl-4-methyl pentenoate, methyl 10-undecenoate, 5-hemocene-
2-on etc. can be exemplified.

In carrying out the present invention, the presence of carbon monoxide and oxygen is an essential requirement. The carbon monoxide and oxygen partial pressures can be their own pressures at the reaction temperature used, or they may be diluted with an inert gas that does not participate in the reaction. It can also be carried out under increased pressure, in which case a range of 0.1 to 30 atmospheres above the autogenous pressure is preferred from the viewpoint of safety, but a higher pressure can be used if desired. The partial pressure ratio of carbon monoxide and oxygen is 0.1
A range from 1 to 10 can be selected. As the alcohol which is the raw material of the present invention, monohydric and polyhydric alcohols can be used. Suitable alcohols can be represented by the general formula %, where t is independently a hydrogen atom, an alkyl, aryl or a hydroxyl group, or two t's taken together form a ring system. It can also be formed.

Examples of suitable alcohols include, for example, methanol, ethanol, linear or cyclic propanes which may be branched, butanols, pentanols or alcohols, pumendiol, benzyl alcohol. etc. are included. The amount of alcohol used is preferably a stoichiometric amount or more, and an excess amount can also be used to serve as a diluent.

When carrying out the present invention, it is also possible to add a group of iron or cobalt metal compounds as co-catalysts. These cocatalysts are preferable because they can improve the product yield, but they tend to reduce selectivity, so they may be added if desired. As promoters, iron, ruthenium, osmium,
Cobalt, rhodium and iridium metals, metal salts,
Metal complex compounds and organometallic complexes can be used. Suitable promoters include iron carbonyl, ruthenium carbonyl, osmium carbonyl, cobalt carbonyl, rhodium carbonyl, iron chloride, cobalt chloride, ruthenium chloride, rhodium chloride, hepterocene, and the like. In practicing the cocatalyst invention, additional solvents that do not participate in the reaction can be used if desired.

The individual solvents used can form a single phase.

Alternatively, a solvent capable of forming a second liquid phase may be used. Examples of these include ether solvents such as diethyl ether, tetrahydrochloride, dioxane, hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, and xylene, dichloromethane, chloroform, and chlorobenzene. Examples include halogenated hydrocarbon solvents.

The reaction temperature can be carried out at ambient temperature, but elevated temperatures, for example in the range from 20 to 150°C or even higher temperatures, can also be used.

A more detailed explanation will be given below using examples and comparative examples.

Example 1 n-C1゜H21CH==CH2+ ■ + MeOH
-1→tet2hydro7rane (4d), methanol (4m
) into a mixed solvent of palladium chloride (34.3m9°0) while blowing a mixed gas of carbon monoxide and oxygen under normal pressure.
．． 19 mmol), sodium chloride! (944,1,6
0 mmol) and cupric chloride (0.20 g, 1.
52 mmol 1 ) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. 1-dodecey (
0.5au, 2.25mm01) was added thereto, and the mixture was reacted for 6 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and then dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified using a chromatograph.
- A mixture of methyl methyldodecanoate and methyl n-tridecanoate (93 near) was prepared in an isolated yield of 51-0 (conversion yield 7).
3).

Methyl 2-methyldodecanoate 'H-NMR (CDCIg): JU, 85 (3H,
bt), 1.10 (3H, d, J=6.6Hz)
, 1.23 (16H.

bs), 1.50 (2H, br), 2.35 (IH.

m), 3.63 (3H, s).

■Neat: yc=o 1742011.

Mass m/z (rel, int,): 228 (3)
, 101(33), 88(10G), 57(12), 5
5(13), 43(18), 41(17).

Methyl n-tridecanoate 'H-NMEL (CDCl2): δo, 88 (3H,
bt), l, 27 (18H, bs), l, 65 (2H
, br), 2.28 (2H, t, J=6.6Hz), 3
．． 63 (3H.

S).

IR (neat): yc=o l 742C11
'.

Mass m/z (rel, int,): 229 (1)
, 22g (7), 143 (12), 87 (63), 74
(100), 57 (12), 55 (20), 43 (24
), 41(25).

Comparative Example 1 n-C1gH21CH=CH2+ω+MeOH-1 → Tet2 human a7t7 (4sd), metal/-l (4
While blowing a mixed gas of carbon monoxide and oxygen under normal pressure into the mixed solvent of
zg.

0.19 mmol), concentrated hydrochloric acid (L), 2 sRl, 3
mmo 1 ), and cupric chloride (0,211 g
, 1.56 mmol) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. ] - Add dodecene (0.5 m, 2.25 mmol) and heat at room temperature for 6 hours while continuing to blow in a mixed gas of carbon monoxide and oxygen.
Allowed time to react. The reaction mixture was extracted with n-hexane,
After washing with water, it was dried with magnesium sulfate. After distilling off the solvent,
As a result of isolating and purifying the residue by chromatography,
A mixture of methyl 2-methyldodecanoate and methyl n-tridecanoate (95:5) was obtained in an isolated yield of 18% (conversion yield 56%).

Example 2 n-C. Palladium chloride (32.8 mg.

0.18mm01), sodium chloride A (93,1i
ip, 1.59 m-mol), and chlorinated steel (0
, 194g, 1.44mmol) in this order,
The mixture was stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. Dicobalt octacarbonyl (43,4#, 0.12m
mol) and 1-dodecene (0.5 ml, 2.2
5 mmol 1 ) was added thereto, and the mixture was reacted for 6 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After evaporating the solvent, the residue was isolated and purified by chromatography, resulting in a mixture of methyl 2-methyldodecanoate and n-)lysocan methyl (92:
8) was obtained in an isolated yield of 62 cm (conversion yield 91 cm).

Example 3 n-C. H2, CH=CH2+■+MeOH Tet2
While blowing a mixed gas of carbon monoxide and oxygen into a mixed solvent of hydrophne (4-resistant) and methanol (4-) under normal pressure, palladium chloride (33.5 mm) was added.

U, ] 8 mmoj ), sodium chloride (92,31
19,1,57 m-mol), and chlorinated steel (0,
198 g, 1.47 mmol) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. Medium Sadeka Carpo to Hexarodium = /I/ (0,10g
, 0.09 mmo 1 ), and 1-dodece7
(0.5+wj, 2.25 mmol) was added, and the mixture was reacted for 6 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by column chromatography. As a result, a mixture of methyl 2-methyldodecanoate and methyl n-)lysocanoate (92:8) was obtained with an isolated yield of 70%.
The conversion yield was 88 cm).

Example 4 n-C1oH2, CH=CH2+CO+MeOH-1→
Palladium chloride (33.61%F) was added to a mixed solvent of tetrahedron (4-) and methanol (4d) while blowing a mixed gas of carbon monoxide and oxygen under normal pressure.

0.19 mmol), sodium chloride (96,6j19
．． 1.65 m-mol), and cupric chloride (0,2
04g, 1.51mmol) write32.2ap, 0
．． 09 mmol), and l-dodecene (0.5 m,
2.25 mm01 ) was added thereto, and the mixture was reacted for 6 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and then dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by column chromatography. As a result, a mixture of methyl 2-methyldodecanoate and methyl n-toIJ decanoate (89:11) was obtained with a conversion yield of 73%. Obtained.

Example 5 ne. H21CH=CH2+ Co+MaOH
--1 → Tet 2 Hydrofuran (4d), methanol (4
1R1) mixed solvent, carbon monoxide,! ! Palladium chloride (33,9
II9゜0.19 mmol), sodium chloride (94
, 541, 1, 61m-m01), cupric chloride (
0,207g, 1.54mmol) K;≠51
．． 3rR9,0,10mmo 1 ) and ]-dodecene (0.5m, 2.25mtno 1 ) were added, and the mixture was allowed to react at room temperature for 6 hours while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by column chromatography to obtain a mixture of methyl 2-methyldodecanoate and methyl n-tridecanoate (90:10) with a conversion yield of 78.

Example 6 n-C1oH2,Ct(=C112+ Co + Me
OH-m-→・tetrahuman c! 7:yy (4m), II
Palladium chloride (
33.6 mg.

0.19 mmol), sodium chloride b (0.106 g,
], 81 m-mol), and cupric chloride (0,212
g, 1.57 mmol) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. Ferric chloride (38,5■.

0.23 mmol), and 1-dodecene (0.5 m,
2.25 mmol) was added thereto, and the mixture was reacted for 6 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen.

The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After evaporating the solvent, the residue was isolated and purified by chromatography. As a result, a mixture of methyl 2-methyldodecanoate and n-)lysocan methyl (8
7:13) in an isolated yield of 79 h (conversion yield 93 h).

Example 7 n -C, oH2, CH=CH2+ :CO+ MeO
H-〉Tetrahydro72-(''), methanol (4-
) into the mixed solvent of palladium chloride (34.3 da.) while blowing a mixed gas of carbon monoxide and oxygen under normal pressure.

0.19 mmol), sodium chloride A (L), 10
g, 1.72 m-mol), and cupric chloride (0
, 21 g, 1.56 mmol) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase.

7 Erosene (38,211g, 0,20mmo 1 )
and l-dodecene (0,511Ll, 2.25mm
ol) was added thereto, and the mixture was reacted at room temperature for 6 hours while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by column chromatography. As a result, a mixture of methyl 2-methyldodecanoate and methyl n-tridecanoate (80:20) was obtained with an isolation yield of 80% (conversion yield: 93%). %).

Example 8 n-01°) 121cH=cH2+ Co + MeO
H methanol (81E/) K% Palladium chloride (34
, 6IIg, 0.19 mmol), sodium chloride (
96.5q.

1.65 mmol), and cupric chloride (0,205 g
, 1.52 mmol) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. Add l-dodecene (0.5m, 2.25mm01), carbon monoxide,
The reaction was carried out at room temperature for 6 hours while continuing to blow in the oxygen mixed gas. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by column chromatography. As a result, a mixture of methyl 2-methyldodecanoate and n-)methyl lysocanoate (75:25) was obtained with an isolated yield of 73-(conversion yield). 8
7).

Comparative example 2 n-C1°H2, CH=CH2+ Co + MeQH
--While blowing a mixed gas of carbon monoxide and oxygen into timeethanol (8sd) under normal pressure, palladium chloride (3sd)
0.9ii5+, 0.17 mmol), concentrated hydrochloric acid (0
, 25 m, 3 mmol), and cupric chloride (0,2
02 g, 1.50 mmol) were added in this order and stirred at room temperature for about 10 minutes until the system became a yellow homogeneous phase. 1-dodecene (0.5m, 2.25mmol
) was added thereto, and the mixture was reacted for 6 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified using a column chromatogram 2-fi, and as a result, methyl 2-methyldodecanoate and n
-) 61-
was obtained in an isolated yield (conversion yield of 86-).

Example 9 n-C1°H2,Q (=CH2+ CO+ MeOH-
11 → Tetrahydro 7 run (6 shi), methanol (2 m
/) into a mixed solvent of palladium chloride (34,9~) while blowing a mixed gas of carbon monoxide and oxygen under normal pressure.

0.19 mmol), lithium chloride A (79,5In9
．． 1.87 mmol), and cupric chloride (0,217
g, 1.61 mmol) were added in this order, and the mixture was stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. The reaction was allowed to proceed at room temperature for 6 hours while continuing to blow in oxygen mixed gas.The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate.After distilling off the solvent, the residue was purified using a As a result, a mixture (93%) of methyl 2-methyldodecanoate and methyl n-)lysocanoate was obtained in an isolated yield of 40% (conversion yield 70%).

Example 10 n -C10H21CH"CH2+■+MeOH--→
', -5cA7 24 (5g, 9iy, 0.20m
mol), and cupric chloride (0,277 g, 2.
05 mmol) and stirred at room temperature for about 30 minutes until the system turned into a yellow homogeneous phase. 1-dob 4t: / (0,44i
1.1.98 mmol) was added thereto, and the mixture was reacted at room temperature for 9 hours while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-chloride, washed with water, dried over magnesium sulfate, and the solvent was distilled off. As a result, methyl 2-methyldodecanoate and methyl n-tridecanoate were obtained with an isolated yield of 71%. A mixture of (87:13) was obtained.

Example 11 n -C1oH2, CH=CH2+ CO+ MeOH
-1 → Tetrahydro72in (4d), methanol (4d
) into the mixed solvent of palladium chloride (39.9 Da) while blowing a mixed gas of carbon monoxide and oxygen under normal pressure.

0.22 mmol), sodium chloride A (0,114
g, 1.95 m-mol), and cupric chloride (0,2
65g, 1.96mmof) in this order,
The mixture was stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. Stop blowing the carbon monoxide and oxygen mixture, attach a balloon containing the carbon monoxide and oxygen mixture (approximately 2/1 v, v,
9. mol) was added and reacted at room temperature for 19 hours. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by chromatography, and as a result, a mixture of methyl 2-methyldodecanoate and El-methyl decanoate (
75:25) was obtained with a conversion yield of 94 h.

Example 12 n-C1゜H21CH=(12+ (,'O+ BtO
Palladium chloride (34.8 Ing.

0.19 mmol), sodium chloride A (0.103 g
, 1.76 m-mol), and cupric chloride (0,
208 g, 1.54 mmol) were added in this order and stirred at room temperature for about 30 minutes until the system became a yellow homogeneous phase. 1-
Dodesen (0.5m.

2.25 mmol) was added thereto, and the mixture was reacted for 8 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and then dried over magnesium sulfate. After evaporating the solvent, the residue was isolated and purified by chromatography, resulting in a mixture of ethyl 2-methyldodecanoate and n-)ethyl lysocanoate (86
:14) was obtained with a conversion yield of 71%.

2-methyldodeca/ethyl acid 'H-NMR (CDC1s): a 0088 (3H,
b t )'t 1,13(3H,d, J=6.6
Hz), 1.25 (3H.

t, J=6.6Hz), 1.30(]6H, bs).

1.60 (2H, br), 2.35 (IH, m).

4.11 (2H, q, J=6.6Hz).

IR (neat): vc=o 1740cst
.

Mass m/z (rel, int+): 243 (2)
, 242(3), 115(22), 102(100),
74 (25), 57 (18), 43 (24), 41 (2
2), 29(18).

n-)ethyl lysocanoate')I-NMR (C1)C13): δ0,8B(3H
, b t ), 1.25 (3H, t , J=6.
6Hz), 1.30 (18H.

bs), 1.65 (2H, br), 2.27 (2H.

t, J=6.6Hz), 4.11(2H,q, J=6.
6Hz).

IR (neat):yc=o 1740cm.

Mass m/z (rel, int,): 242 (7)
, 101(49), 88(100), 73(19),
57 (19), 55 (25), 43 (35), 4] (3
3), 29(30).

Example 13 n -C2H1,C)1:CH2+■+MeOH-> A mixed gas of carbon monoxide and oxygen (normal mol) in a mixed solvent of tetrahtomifuran (4M) and methanol (4 ml),
and cupric chloride (0,224 g, 1.66 mmol
) in this order and stirred at room temperature for about 1 hour until the system turned into a yellow homogeneous phase. 1-Undecene (0,47WLt.

2.28 mmol) was added thereto, and the mixture was reacted for 8 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen.

The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After evaporating the solvent, the residue was isolated and purified by Kakum chromatography, resulting in a mixture of methyl 2-methylundecanoate and methyl n-dodecanoate (9
1.:9) was obtained with a conversion yield of 70%.

Methyl 2-methylundecanoate'f(-Nla(CDCI, ):a O,8B(3f(
, bt), 1.14 (3H, d, J=6.6Hz), 1
．． 28 (14H.

bs), 1.60 (2H, br), 1.38 (IH.

m), 3.65 (3H, s).

IR (neat) Niji c=o 1742m.

Ma@s m/z (rel, int,): 2] 4
(3), ] 01 (34), 88 (IOL)),
57(13), 55(19), 43(21), 4](2
5).

Methyl n-dodecanoate 1H-Tachibana Kuu C 13): δ0,88 (3H, b t )
, 1.28(16H,br), ], 60(2H,b
r), 2.27 (2H, m), 3.65 (3H, s).

IR (neat): yc=o l 742C11.

Mass m/z (rel, int,): 214 (5
), 87 (56).

? 4 (100), 57 (10), 55 (19).

43(23), 41(26).

Example 14 Radium chloride (32.6 m9°0.1
8 mmol), sodium chloride (0,105 g, 1
．． 78 mmol), and chlorinated steel (0,228 g,
1.69 mmol) were added in this order and stirred at room temperature for about 1 hour until the system became a yellow homogeneous phase. Cyclododecene (
0,43ia/.

2.25 mmol) was added thereto, and the mixture was reacted for 9 hours at room temperature while continuing to blow in a mixed gas of carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was isolated and purified by column chromatography, and as a result, methyl cyclododecanecarboxylate was detected by 74'I-NMR (CDC13).
: δ1.2-1.8 (22f(, br).

2.50 (] 11. quintat, J=6
．． (OHz).

3.64 (3f(・S)・ 1R (neat): uc=o 1739c+a.

Mass m/z (rel, int,): 226 (3)
, 87 (100), 74 (3L)), 69 (33), 5
5 (69), 43 (26), 41 (82).

Example] 5 CH2=CH(a(2)8CO2Me+CO+MeOH
---→Tet2hydrophine (8-), methanol (8-)
Palladium chloride (65.1η.

0.36 mmol), sodium chloride (0,209 g,
3.52 mmol), and cupric chloride (0,49
5g, 3.68mmo 1) were added in this order,
The mixture was stirred at room temperature for 50 minutes until the system became a yellow homogeneous phase. ]
Methyl 0-cundecenoate (1.2 ml, 5.39
mmol) was added thereto, and the mixture was reacted for 8 hours at room temperature while continuing to blow in a mixed gas of -carbon monoxide and oxygen. The reaction mixture was extracted with n-hexane, washed with water, and dried over magnesium sulfate. After the solvent was distilled off, the 'H-NMR spectrum of the residue showed that dimethyl 2-methyl-1,11-cundecanedicarboxylate and dimethyl 1,12-dodecanedicarboxylate were produced with a conversion yield of 94%. . The product was isolated and purified by preparative GLC.

Dimethyl 2-methyl-1,11-cundecanedicarboxylate'H-NMR (CDCI, ): δ1.13 (3H,
d, J:=7.5Hz), 1.2-1.8 (14H
,br), 2.28 (2H,t, J=7.5Hz)
, 2.4(If(,q.

J=7.5Hz), 3.67 (6H, s).

IR (neat): vc=o 1740cm+
.

Mass m/z (rel, int,): 227 (5)
, 199(12), 17](13), 139(15),
112 (32), 98 (27), 88 (10G), 83
(2t)), 74(20), 69(38), 59(26
), 55 (50), 43 (18), 4] (46).

1.12-Dodecanedicarboxylic acid dimethyl')I-QC
DCI 3): δ1.1-1.8 (18H, b r
).

2.28 (4H, t, J = 7.5Hz), 3.67 (6
H1 easy).

IR (neat): 1740m.

Mass m/z (rel, int,): 227 (21
), 185(23), 153(22), 135(11)
.

112(20), 98(57), 87(21).

84(33), 74(53), 69(35).

59 (22), 55 (46), 43 (27).

4] (40).

Claims (2)

[Claims] (1) A method for producing a carboxylic acid ester, which comprises reacting an olefin, carbon monoxide, oxygen, and alcohol in the presence of a palladium catalyst, a copper salt, and an alkali metal halide. (2) Claim No. 1 comprising the addition of a Group VIII iron or cobalt metal compound as a cocatalyst.
).