JPH09151165A - Method for producing carboxylic acid esters - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a method for producing carboxylic acid esters useful for agricultural chemicals, pharmaceuticals and the like. SOLUTION: An organic chloride having at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent is converted into a palladium compound and the following general formula (V), ( A method for producing carboxylic acid esters, which comprises reacting with carbon monoxide and alcohols or phenols in the presence of a base, using one kind of phosphine compound selected from VI) and (VII) as a catalyst. Embedded image [Effect] Aromatic carboxylic acid esters can be synthesized by the reaction of aromatic chloride and carbon monoxide.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a novel method for producing carboxylic esters useful for agricultural chemicals, medicines and the like.

[0002]

2. Description of the Related Art As a method for producing an aromatic or heterocyclic carboxylic amide or ester, an aromatic or heterocyclic halogen compound and a primary or secondary amine are reacted in the presence of palladium / triarylphosphine. A method for reacting with carbon monoxide has been disclosed (US Pat.
No. 588358). However, in these methods, reactions with iodides and bromides are performed as aromatic halides, but no reactions are performed with aromatic chlorides. The phosphine compound used as the catalyst is a triarylphosphine which is completely different from the present invention. JP-A-61-293950 discloses a method for producing a carboxylic acid or an ester thereof using a chloro or bromoallene carbonyl chromium compound, but it is difficult to produce a tricarbonyl chromium complex as a reaction substrate. It is expensive and has toxicity issues.

[0003]

As described above, there is no known method for synthesizing an aromatic carboxylic acid ester by reacting an aromatic chloride with carbon monoxide. In view of the above situation, the present inventors have conducted intensive studies on the reaction between an aromatic or heterocyclic chloride and carbon monoxide, and as a result, established a method for obtaining aromatic or heterocyclic carboxylic esters in good yield. And
The present invention has been completed.

[0004]

DISCLOSURE OF THE INVENTION According to the present invention, an organic chloride having at least one chlorine atom on a ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent is converted into a palladium compound. And a carvone characterized by reacting with carbon monoxide and alcohols or phenols in the presence of a base, using a phosphine compound selected from the following general formulas (V), (VI) and (VII) as a catalyst: The present invention relates to a method for producing acid esters.

More specifically, the general formula (IV):

Embedded image R ¹ · (Cl) m (IV) (In the formula, R ¹ represents an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent, and m represents an integer of 1 or more. .) To a palladium compound and a compound represented by the general formula (V):

Embedded image (R) ₂ -P—X—P— (R) ₂ (V) (wherein R represents an alkyl group or a phenyl group which may have a substituent, and X represents 1 carbon atom). An alkylene group of ~ 6,

Embedded image Or a binaphthyl group. )

General formula (VI):

Embedded image (Wherein R is the same as above) and the general formula (VII):

Embedded image (Wherein n represents an integer of 1 to 5) 1 selected from
Carbonylation catalyst consisting of certain phosphine compounds, and carbon monoxide in the presence of an inorganic or organic base and

General formula (II):

[Image Omitted] R ⁴ OH (II) (wherein R ⁴ may have a substituent and represents an aliphatic hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic hydrocarbon group). General formula (I-2) characterized by reacting with an alcohol represented by the following formula:

Embedded image The present invention relates to a method for producing a carboxylic acid ester represented by R ^1. (COOR ⁴ ) m (I-2) (wherein R ¹ , R ⁴ and m are the same as described above).

The reaction of the present invention can be represented, for example, by the following scheme.

Embedded image (In the formula, R, R ¹ , R ⁴ , m, n and X are the same as above.)

That is, an organic chloride represented by the general formula (IV) is reacted with a palladium compound and a phosphine compound represented by the general formula (V) as a catalyst in the presence of a base, in the presence or absence of a solvent, The desired carboxylic acid ester represented by the general formula (I-2) can be produced by reacting with carbon monoxide and the alcohol represented by the general formula (II).

The organic chloride represented by the general formula (IV) that can be used in the present invention includes at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent. And any condensed cyclic hydrocarbon and condensed heterocyclic hydrocarbon. Examples thereof include, for example, chlorobenzene, dichlorobenzene, trichlorobenzene, tetrachlorobenzene, and pentachlorobenzene. Chlorobenzene, hexachlorobenzene, chlorofluorobenzene, chlorodifluorobenzene, chlorotrifluorobenzene, chlorotetrafluorobenzene, chloropentafluorobenzene, trifluoromethylchlorobenzene, chlorotoluene, dichlorotoluene, trichlorotoluene, tetrachlorotoluene, pentachlorotoluene , Ethyl chlorobenzene, chlorocumene, chloromesitylene, dichloromesitylene, chloroxylene, dichloroxylene, trichloroxylene, tetrachloroxylene, chlorophenol, dichlorophenol, trichlorophenol, chloroanisole, dichloroanisole, trichloroanisole, chlorodimethoxybenzene, chlorotrimethoxybenzene , Chloromethylenedioxybenzene, chlorophenoxyphenol, chlorobenzezoylphenol, chlorobenzenesulfonylphenol, chloronitrobenzene, dichloronitrobenzene, chlorocyanobenzene, chlorophenylacetic acid ester, N-acetylchloroaniline, chlorophenoxyaniline, chlorobenzoylaniline, chlorobenzenesulfonyl Aniline, chloro Setophenone, chlorobenzophenone, chloromethylthiobenzene, chlorobenzoic acid ester, chlorodiphenyl ether, benzyloxychlorobenzene, chlorophenylbutoxybenzene, dichlorodiphenyl ether, dichlorobenzophenone, dichlorodiphenylmethane, dichlorodiphenyldifluoromethane, dichlorodiphenylhexafluoropropane, dichlorodiphenylsulfide, dichloro Diphenylsulfoxide, dichlorodiphenylsulfone, dichlorobiphenyl, tetrachlorodiphenylether, tetrachlorobenzophenone, tetrachlorodiphenylmethane, tetrachlorodiphenyldifluoromethane, tetrachlorodiphenylhexafluoropropane, tetrachlorodiphenylsulfide, tetrachloro Phenyl sulfoxide, tetrachloro diphenyl sulfone, tetrachlorobiphenyl, chloronaphthalene, dichloronaphthalene, trichloronaphthalene,
Aromatic organic chlorides such as chloromethylnaphthalene and chloroanthraquinone;

Chlorothiophene, dichlorothiophene,
Heterocyclic organic chlorides such as chlorofuran, chloroindole, dichloroindole, chloropyridine, dichloropyridine, chlorotrifluoromethylpyridine, chloropicoline, dichloropicoline, chloroquinoline, trichloroquinoline, chloroquinoxaline, and dichloroquinoxaline. it can. The organic chloride may be used in a predetermined amount, or may be used in excess to be used as a solvent.

The alcohol represented by the general formula (II) used in the present invention includes, for example, methanol, ethanol,
Aliphatic alcohols such as propanol and butanol, phenol, halophenol, cresol, xylenol,
Examples include aromatic alcohols such as benzyl alcohol and cinnamyl alcohol, and heterocyclic hydroxyls such as furfuryl alcohol and thienyl alcohol. Alcohols may be used in a predetermined amount as they are, or may be prepared in advance as an alkali metal alcoholate and used. The alcohol represented by the general formula (II) is present in the reaction system in an amount ranging from equimolar to 1 mole of the organic chloride to the number of moles corresponding to the number of chloro atoms on the ring of the organic chloride to an excess. Good.

The palladium compound used as a catalyst in the present invention may be used in combination with a phosphine compound. Examples of the palladium compound include palladium metal, palladium carbon, palladium alumina, palladium chloride, palladium bromide, palladium acetate, and the like. Examples thereof include dichlorobiscyanophenylpalladium, dichlorobistriphenylphosphinepalladium, and tetrakistriphenylphosphinepalladium.

Examples of the phosphine compound represented by the general formula (V) which can be used in combination with the palladium compound in the present invention include 1,1-bis (dimethylphosphino) methane and 1,1-bis (diethylphosphino) methane. , 1,
Bis (dialkyl) such as 2-bis (dimethylphosphino) ethane, 1,2-bis (diethylphosphino) ethane, 1,3-bis (dimethylphosphino) propane, and 1,4-bis (dimethylphosphino) butane Phosphino) alkanes, 1,1-bis (diphenylphosphino) methane, 1,2-bis (diphenylphosphino) ethane,
1,3-bis (diphenylphosphino) propane, 1,
4-bis (diphenylphosphino) butane, 1,5-bis (diphenylphosphino) pentane, 1,6-bis (diphenylphosphino) hexane, 2,3-O-isopropylidene-2,3-dihydroxy-1 , 4-bis (diphenylphosphino) butane, bis (diphenylphosphino) ferrocene, bis (diphenylphosphino)
Binaphthyl and 1,2-bis (diphenylphosphino)
Benzene,

Examples of the phosphine compound represented by the general formula (VI) include methyldibenzophosphole, ethyldibenzophosphole, propyldibenzophosphole, butyldibenzophosphole, pentyldibenzophosphole and phenyldibenzophosphole. Examples of the phosphine compound represented by the formula (VII) include 1,1-bis (dibenzophosphoryl) methane, 1,2-bis (dibenzophosphoryl) ethane, 1,3-bis (dibenzophosphoryl) propane, 1,4- Examples thereof include bis (dibenzophosphoryl) butane and 1,5-bis (dibenzophosphoryl) pentane, but the present invention is not limited thereto.

The phosphine compound may be added in an amount of 0.01 to 10.000 moles, preferably 0.1 to 100 moles, relative to the palladium compound. In the present invention, the palladium compound and the phosphine compound represented by the general formula (V), (VI) or (VII) may be used in combination, and may be used alone in the reaction system, or may be prepared in the form of a complex in advance. You may use it. The amount of addition is not particularly limited, but the amount of the palladium compound and the phosphine compound added to the reaction system is 0.0001 times to 0.5 times mol based on 1 mol of the organic chloride represented by the general formula (IV). It may be selected from the range of 0.001 times to 0.1 times the molar amount.

The base that can be used in the present invention may be selected from inorganic bases and organic bases, such as inorganic bases such as sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide, triethylamine, tributylamine, and the like.
Organic bases such as diisopropylethylamine, triisooctylamine, pyridine, N-methylpyrrolidine, N-methylmorpholine, N-ethylmorpholine and the like can be mentioned. As the amount of the base to be used, it is preferable to use an amount necessary for neutralizing the produced hydrogen chloride, but of course it may be at least better or larger than this. The reaction in the present invention can be carried out in the presence or absence of a solvent, and any solvent that can be used may be any solvent that does not significantly inhibit the reaction, such as hexane, benzene, ether, tetrahydrofuran,
Organic solvents such as acetonitrile, dimethylformamide, hexamethylphosphottriamide, acetone and the like can be mentioned.

The reaction of the present invention is carried out under normal pressure to under pressure,
The pressure of carbon monoxide is appropriately selected in the range of 1 to 200 atm, and preferably in the range of 1 to 50 atm. In the present invention, the reaction temperature is usually in the range of 100 ° C to 300 ° C, preferably in the range of 150 ° C to 250 ° C. The reaction vessel used in the present invention may be a commonly used reaction vessel. In the case of a pressurized reaction, any reaction vessel capable of withstanding the reaction pressure may be used, and usually a metal or glass vessel is used.
The reaction time is not constant depending on the amount of the reaction reagent and the reaction temperature, but may be selected from the range of several minutes to 48 hours.
After completion of the reaction, the desired compound can be obtained by treating the product by a conventional method.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION As embodiments of the present invention, examples and comparative examples of the present invention will be shown below, but the present invention is not limited to these.

Example 1 Preparation of ortho-α, α, α-trifluoromethylbenzoic acid methyl ester

Embedded image Orthodichlorobenzene trifluoride (18.0 g), sodium methoxide (1.19 g), palladium chloride (3.5 m) in a glass autoclave with an electromagnetic induction stirrer
g), bisdiphenylphosphinobutan (85.3 mg) was added, replaced several times with carbon monoxide, and then filled with 30 kg / cm ² .
React for 1.5 hours with stirring in a salt bath at an internal temperature of 210 ° C. After completion of the reaction, the mixture was cooled to room temperature, washed with water, and then the organic layer was separated.
The concentrate was purified by column chromatography to obtain 1.2 g of methyl o-α-α, α-α-trifluoromethylbenzoate, which was the desired product. NMR: δ (TMS, CDCl ₃ ) (ppm) 3.96 (3H, s) 7.3-7.9 (4H, m) Yield 1.2 g

Example 2 Preparation of ethyl ortho-α, α, α-trifluoromethylbenzoate

Embedded image Orthochlorobenzotrifluoride (18.0 g), ethanol (4.6 g), palladium chloride (17.5 mg), bisdiphenylphosphinobutane (8
5.3 mg) and sodium carbonate (2.3 g), replace with carbon monoxide several times, fill at 30 kg / cm ² , and heat in a salt bath.
The reaction is performed at 00 ° C. for 5 hours with stirring. After completion of the reaction, the mixture was cooled to room temperature, washed with water, the organic layer was separated, and concentrated to obtain 1.9 g of the desired product, ortho-α, α, α-trifluoromethylbenzoic acid methyl ester. NMR: δ (TMS, CDCl ₃ ) (ppm) 1.36 (3H,
t), 4.32 (2H, q), 7.37-7.80 (4H, m) Yield 1.9 g

Example 3 Preparation of 4-methoxyphenyl 2-trifluoromethylbenzoate

Embedded image Ortho-chlorobenzotrifluoride (45.13 g) and para-methoxyphenol (6.
2 g), palladium chloride (88.5 mg), 1,4-bisdiphenylphosphinobutan (213 mg), sodium carbonate (5.3 g), and after several substitutions with carbon monoxide, 30 kg / cm
^The mixture is filled with ² , and the reaction is carried out for 5 hours while stirring at an internal temperature of 190 ° C in a salt bath. After the reaction, the mixture was cooled to room temperature and washed with water, then, the organic layer was separated and concentrated. 10.5 g of the desired ester was obtained. Melting point 62 ~ 63.5 ℃

Example 4 4-isopropylphenyl 2
-Production of trifluoromethyl-benzoate

Embedded image In a metal autoclave, ortho-chlorobenzotrifluoride (45.13 g), para-isopropylphenol (6.8 g), palladium chloride (88.5 mg), 1,4-bisdiphenylphosphinobutan (213 mg), sodium carbonate (5.3 g) ) And replaced several times with carbon monoxide, then 30kg /
The mixture was filled with cm ² , and the reaction was allowed to proceed for 4 hours while stirring at an internal temperature of 190 ° C. After the reaction, the mixture was cooled to room temperature and washed with water, then, the organic layer was separated and concentrated. 11.1 g of the desired ester was obtained. Melting point 82.5-84.5 ℃

Example 5 Production of 1,2,4-triethoxycarbonylbenzene

Embedded image 1,2,2 in glass autoclave with electromagnetic induction type stirrer
4-trichlorobenzene (3.6 g), ethanol (4.6 g)
g), benzene (5 ml), palladium chloride (17.8 mg), bisdiphenylphosphinobutan (85.3 mg) and sodium carbonate (2.3 g), and after several replacement with carbon monoxide, 50 kg
/ Cm ² , and the reaction is carried out for 3 hours with stirring at an internal temperature of 200 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, separated into organic layers, concentrated, and purified by column chromatography to obtain 1.62 g of 1,2,4-triethoxycarbonylbenzene, which was a target substance. NMR: δ (TMS, CDCl ₃ ) (ppm) 1.20 to 1.51 (9H, m) 4.13 to 4.53 (6H, m) 7.57 to 8.25 (3H, m) Yield 1.62 g

Example 6 Production of 1,2,4,5-tetraethoxycarbonylbenzene

Embedded image 1,2,4,5-Tetrachlorobenzene (1.08 g), ethanol (4.6 g), palladium chloride (88 mg), 1,4-bisdiphenylphosphinobutan (106 mg), sodium carbonate (4.2 g) were placed in a metal autoclave. ), Benzene (15ml), 50kg / cm after several replacement with carbon monoxide
^The mixture is filled with ² , and the internal temperature is set to 200 ° C in a salt bath, and the mixture is reacted for 3 hours with stirring. After the reaction, the mixture was cooled to room temperature, washed with water, concentrated, and purified by column chromatography to obtain 0.87 g of 1,2,4,5-tetraethoxycarbonylbenzene.

Example 7 Preparation of 4,4'-bis (ethoxycarbonyl) benzophenone

Embedded image In a metal autoclave, 4,4'-dichlorobenzophenone (2.51 g), ethanol (4.61 g), palladium chloride (8.7 mg), 1,4-bisdiphenylphosphinobutan (213 mg), sodium carbonate (2.33 g), Add benzene (30 ml) and replace with carbon monoxide several times, then 50 kg / cm
^The mixture was filled with ² , and the mixture was reacted at an external temperature of 230 ° C. for 5 hours while stirring with a salt bath. After the reaction, the mixture was cooled to room temperature and washed with water, then, the organic layer was separated and concentrated. 2.33 g of the target ester was obtained. 74-76 ° C

Example 8 Preparation of 4,4'-bis (ethoxycarbonyl) diphenyl sulfone

Embedded image In a metal autoclave, 4,4'-dichlorodiphenylsulfone (2.87 g), ethanol (4.61 g), palladium chloride (8.8 mg), 1,4-bisdiphenylphosphinobutan (213 mg), sodium carbonate (2.33 g) , Benzene (30 ml), and after several substitutions with carbon monoxide, 50 kg /
The mixture was filled with cm ² and the mixture was reacted at an external temperature of 220 ° C. for 3 hours while stirring with a salt bath. After the reaction, the mixture was cooled to room temperature and washed with water, then, the organic layer was separated and concentrated. 1.96 g of the desired ester was obtained. Melting point 153-6 ℃

Example 9 Preparation of 2-thiophenecarboxylic acid ethyl ester

Embedded image 2-chlorothiophenyl (2.4
g), ethanol (4.6 g), benzene (5 ml), palladium chloride (17.8 mg), bisdiphenylphosphinobutane (85.3 mg), sodium carbonate 2.3 g, and after several substitutions with carbon monoxide, 50 kg / cm Fill with ² and use salt bath for internal temperature 2
React for 3 hours with stirring at 50 ° C. After completion of the reaction, the mixture was cooled to room temperature, washed with water, the organic layer was separated, concentrated, and purified by column chromatography to obtain 1.0 g of a desired product, 2-thiophenecarboxylic acid ethyl ester. NMR: δ (TMS, CDCl ₃ ) (ppm) 1.35 (3H, t) 4.27 (2H, q) 6.88 to 7.73 (3H, m) Yield 1.0 g

Example 10 Preparation of nicotinic acid ethyl ester

Embedded image 3-Chloropyridine (2.3
g), ethanol (4.6 g), benzene (5 ml), palladium chloride (17.8 mg), bisdiphenylphosphinobutan (85.3 mg), and sodium carbonate (2.3 g), and after replacing several times with carbon monoxide, 50 kg / Cm ² , and the reaction is carried out for 3 hours with stirring at an internal temperature of 250 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, separated into organic layers, concentrated and purified by column chromatography to obtain 0.46 g of nicotinic acid ethyl ester as a target. NMR: δ (TMS, CDCl ₃ ) (ppm) 1.41 (3H, t) 4.38 (2H, q) 7.18 to 7.40 (1H, m), 8.12 to 8.28 (1H, m), 8.60 to 8.72 (1H, m) , 9.08-9.13 (1H, m), Yield 0.46g

Example 11 Preparation of 4,7-diethoxycarbonylquinoline

Embedded image In a metal autoclave, 4,7-dichloroquinoline (1.
98 g), ethanol (4.6 g), palladium chloride (8.8
mg), 1,4-bisdiphenylphosphinobutan (106
mg), sodium carbonate (4.2 g), and 15 ml of benzene, and after several replacement with carbon monoxide, filling at 50 kg / cm ² ,
The internal temperature is 200 ° C in a salt bath, and the reaction is carried out for 3 hours with stirring. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, concentrated and purified by column chromatography to obtain 0.87 g of the target compound, 4,7-diethoxycarbonylquinoline. NMR: δ (TMS, CDCl ₃ ) (ppm) 1.31 to 1.58 (6H, m) 4.26 to 4.67 (4H, m) 7.87 to 9.07 (5H, m), yield 0.87 g

Example 12 Preparation of 2,3-diethoxycarbonylpyridine

Embedded image In a metal autoclave, 2,3-dichloropyridine (1.
5 g), palladium chloride (8.8 mg), 1,4-bisdiphenylphosphinobutan (106 mg), sodium carbonate (4.2 g), ethanol (4.6 g) and benzene (15 m
l), replace with carbon monoxide several times, fill with 50 kg / cm ² , raise the internal temperature to 250 ° C in a salt bath, and react with stirring for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, washed with water, concentrated, and purified by column chromatography to obtain 0.04 g of the desired product, 2,3-diethoxycarbonylpyridine. NMR: δ (TMS, CDCl ₃ ) (ppm) 1.27 to 1.57 (6H, m) 4.16 to 4.62 (4H, q) 6.73 to 6.97 (1H, q) 7.98 to 8.30 (2H, m)

Embodiment 13

Embedded image In a 200 ml stainless steel autoclave, 4,4'-dichlorobenzophenone (12.5 g, 0.05 mol), 5% Pd-C
(53 mg), 1,4-bis (diphenylphosphino) butane (426 mg), sodium carbonate (5.8 g, 0.055 mol),
Methanol (16 g) and toluene (30 ml) are added, carbon monoxide is sealed at 30 kg / cm ² , and the mixture is reacted at 200 ° C. for 3 hours. After cooling, toluene (100 ml) and water (100 ml) were added to carry out liquid separation, and the organic layer was concentrated and reconstituted with ethyl acetate to obtain the desired compound. Yield 6.5 g (44% yield)

Embodiment 14

Embedded image In a 200 ml stainless steel autoclave, 3,4-dichlorobenzotrifluoride (4.3 g, 0.02 mol), 2% Pd-
C (106 mg), 1,4-bis (diphenylphosphino)
Butane (341 mg), sodium carbonate (2.1 g, 0.02 mo
l), methanol (4.6 g) and benzene (10 ml) are charged, carbon monoxide is sealed at 30 kg / cm ² , and the reaction is performed at 200 ° C. for 3 hours. After standing to cool, toluene (100 ml), water (100 m
l) was added thereto for liquid separation, and the organic layer was concentrated and then distilled to obtain the target compound. Boiling point 107 ° C (2 mmHg) Yield 4.8 g (91% yield)

Embodiment 15

Embedded image In a 100 ml stainless steel autoclave, 4-chloroacetophenone (7.7 g, 0.05 mol), 5% Pd-C (106 m
g), 1,4-bis (diphenylphosphino) butane (4
26 mg), sodium carbonate (2.9 g, 0.028 mol), ethanol (4.6 g), and toluene (15 ml) were added, carbon monoxide was sealed at 20 kg / cm ² , and the mixture was reacted at 200 ° C. for 3 hours. After cooling, toluene (50 ml) and water (50 ml) were added to carry out liquid separation. The organic layer was concentrated and then recrystallized from ethyl acetate-hexane to obtain the desired compound. Melting point 51-52 ° C Yield 6.1 g (64% yield)

Embodiment 16

Embedded image 2-chlorobenzonitrile (2.8 g, 0.02 mol), 2% Pd-C (32 mg) in a 100 ml stainless steel autoclave,
1,4-bis (diphenylphosphino) butane (171 m
g), sodium carbonate (3 g, 0.024 mol), ethanol (4.6 g), and benzene (10 ml) were added, carbon monoxide was sealed at 20 kg / cm ² , and the mixture was reacted at 200 ° C. for 3 hours. After cooling, toluene (50 ml) and water (50 ml) were added to carry out liquid separation. The organic layer was concentrated and then recrystallized from ethyl acetate-hexane to obtain the desired compound. Melting point 62-64 ° C Yield 1.4 g (40% yield)

Embodiment 17

Embedded image In a 200 ml stainless steel autoclave, p-chlorobenzophenone (10 g, 0.046 mol), 5% Pd-C (30 mg),
1,4-bis (diphenylphosphino) butane (590 m
g), sodium carbonate (2.5 g, 0.024 mol), ethanol (21 g), and benzene (10 ml) were charged, carbon monoxide was sealed at 20 kg / cm ² , and the mixture was reacted at 200 ° C. for 3 hours. After cooling, toluene (50 ml) and water (50 ml) were added to carry out liquid separation. The organic layer was concentrated and then recrystallized from ethyl acetate-hexane to obtain the desired compound. Melting point 46-47 ° C Yield 5.6 g (46% yield)

Embodiment 18

Embedded image In a 200 ml stainless steel autoclave, 4-chlorobenzophenone (21.7 g, 0.1 mol), 5% Pd-C (105 mg),
1,4-bis (diphenylphosphino) butane (850 m
g), sodium carbonate (8.0 g, 0.075 mol), 2-ethylhexanol (130 g), and benzene (20 ml) were charged, carbon monoxide was sealed at 20 kg / cm ² and reacted at 200 ° C. for 3 hours. After allowing to cool, toluene (50 ml) and water (50 ml) were added to carry out liquid separation. The organic layer was concentrated and then distilled with a molecular still to obtain the target compound. Boiling point 176 ℃ / 0.1mmHg, Yield 25
g (73% yield)

Embodiment 19

Embedded image In a 100 ml stainless steel autoclave, 4-chlorobenzaldehyde (4.2 g, 0.03 mol), 5% Pd-C (64 m
g), 1,4-bis (diphenylphosphino) butane (2
56 mg), sodium carbonate (1.75 g, 0.016 mol), methanol (4.8 g), and toluene (20 ml) were charged, carbon monoxide was sealed at 20 kg / cm ² , and the mixture was reacted at 200 ° C. for 3 hours. After allowing to cool, toluene (50 ml) and water (50 ml) were added to carry out liquid separation. The organic layer was concentrated and then distilled to obtain the target compound.
Boiling point 170-180 ° C / 2 mmHg, Yield 4.1 g (Yield
87%)

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical display location C07C 317/44 7419-4H C07C 317/44 C07D 213/55 C07D 213/55 213/80 213/80 213/803 213/803 215/50 215/50 333/38 333/38 // C07B 61/00 300 C07B 61/00 300

Claims (4)

[Claims] 1. An organic chloride having at least one chlorine atom on the ring of an aromatic hydrocarbon or a heterocyclic hydrocarbon which may have a substituent, a palladium compound and the following general formula (V): A method for producing carboxylic acid esters, which comprises reacting with carbon monoxide and alcohols or phenols in the presence of a base, using a phosphine compound selected from (VI) and (VII) as a catalyst. General formula (V): embedded image (R) ₂ -P—X—P— (R) ₂ (V) (In the formula, R represents an alkyl group or a phenyl group which may have a substituent, X is an alkylene group having 1 to 6 carbon atoms, and Or a binaphthyl group. ) General formula (VI): (In the formula, R is the same as above.) General formula (VII): (In the formula, n represents an integer of 1 to 5.) 2. The method for producing carboxylic acid esters according to claim 1, wherein the palladium compound is a palladium metal or a zero-, di- or tetra-valent complex supported on a solid. 3. The palladium compound is palladium-carbon, palladium chloride or palladium acetate.
A method for producing the carboxylic acid esters according to the above. 4. The method according to claim 1, wherein the base is an inorganic base or an organic base.