JPS6229552A - Production of cinnamic acid ester - Google Patents

Abstract

PURPOSE:To obtain the titled substance, by reacting a styrene with CO, an alcohol and oxygen in the presence of a catalyst consisting of a Pd (compound), copper compound, halogen compound and compound of a metal selected from Groups 4A, 8A, etc., and CO2. CONSTITUTION:A styrene is reacted with CO, an alcohol, e.g. methanol, cyclopentanol or polyethylene glycol,and oxygen to give the corresponding cinnamic acid ester. In the processes, a catalyst consisting of (A) Pd or a compound thereof, e.g. organic acid salt, inorganic acid salt or complex, (B) a copper compound, e.g. inorganic acid salt, carboxylic acid salt or organic anion salt, (C) a halogen compound and (D) a compound of a metal selected from Groups 4A, 5A, 7A, 8A iron family and 2B is used as a catalyst to carry out the reaction in the presence of CO2 at 40-160 deg.C under 1-300atm for 0.05-10hr. EFFECT:The catalyst activity is enhanced by the CO2. USE:A raw material for perfumes, agricultural chemicals, etc.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a method for producing corresponding cinnamon esters by reacting styrenes, carbon oxide, alcohol and oxygen in the presence of a catalyst and carbon dioxide. Regarding.

Cinnamic acid esters are widely used as fragrances or raw materials for fragrances due to their aromatic properties, and are also important compounds as raw materials for agricultural chemicals and photosensitive resins.

(Prior Art) Cinnamic acid has conventionally been produced on a small scale by a reaction using benzaldehyde and acetic acid derivatives as main raw materials.

However, since this method uses expensive raw materials, it is not an industrially preferred method. As a method using cheaper raw materials, there is a method that attempts to produce cinnamic acid esters by reacting styrenes, carbon oxide, alcohol and oxygen in the presence of a catalyst (some proposals have been made (for example, 15242/1983, 2274/1983
9, JP-A-56-22750, JP-A-56-71039
, Japanese Patent Publication No. 57-21342. Japanese Patent Publication No. 57-21343,
JP 57-70836, JP 60-92242, JP 60-92243, JP 60-94940, JP 60-97935, JP 60-109545, etc.]
.

(Problems to be Solved by the Invention) However, in any of the methods, the reaction results and catalytic activity have not reached industrially satisfactory levels.

The purpose of the present invention is to provide a more advantageous industrial production method for cinnamic acid esters using styrenes, carbon oxide, alcohol, and enzymes as raw materials. An object of the present invention is to provide a method for producing cinnamon esters.

(Means for Solving the Problems) In order to achieve the above object, the present inventors have continued intensive studies and found that when producing cinnamic acid esters from styrenes, carbon-mide, alcohol and oxygen, In addition to palladium metal or its compound as a catalyst component,
It was found that copper atoms and halogen atoms play important roles, and if different compounds are used or at least some of them are used as the donor source for copper atoms and the donor source for halogen atoms, both atoms We found that much more favorable results can be obtained than when using only the same compound as the donor source of We found that this can have a significant impact.

There is no precedent for carrying out a reaction by adding carbon dioxide to the reaction system. Several references suggest the possibility of using oxygen simply as a diluent inert gas in specific and limited catalyst systems or reaction systems.

JP-A-56-15242 discloses a method using a platinum group metal or a compound thereof, a copper salt or an iron salt, and an organic acid salt of a metal selected from alkali metals, alkaline earth metals, and aluminum group metals as a catalyst; Showa 56
-22749 and JP-A-56-22750 disclose a method in which a platinum group metal or its compound, a copper salt or an iron salt, and a quaternary amine are used as catalysts to react under restrictions such as a limited partial pressure of carbon monoxide. , in the specification, regarding the raw material oxygen, there is a statement that ``Here, oxygen may be oxygen, air, or an oxygen-containing gas obtained by arbitrarily diluting oxygen with an inert gas such as nitrogen, argon, or carbon dioxide.'' There is. However, with these methods, carbon dioxide gas,
That is, this merely suggests the possibility of using carbon dioxide as an inert gas, and all of the Examples either do not use an inert gas or use only nitrogen. There are no specific examples or descriptions of how to use carbon dioxide. On the other hand, in all the publications cited above other than the above, regarding the dilution of the gas used, they all mention that dilution with "inert gas such as nitrogen" or "inert gas such as nitrogen, argon, etc." Although it is described as being good, there is no mention of carbon dioxide at all. As mentioned above, there are no examples of carbon dioxide producing special effects (which cannot be expected at all from the above-mentioned literature).

The present inventors further investigated the use of carbon dioxide and found that when the reaction was carried out in the presence of carbon dioxide under conditions using a specific catalyst system, surprisingly, The present invention was achieved by discovering that cinnamic acid esters have higher catalyst activity and higher reaction performance.

That is, the present invention provides for the production of corresponding cinnamic acid esters by reacting styrenes, -carbon oxides, alcohols, and oxygen, using (1) palladium metal or its compound, (2) a copper compound, (2) a halogen compound, and (2) as a catalyst. At least one member selected from the group consisting of Groups 4A, 5A, 7A, 8A of the periodic table according to the International Union of Pure and Applied Chemistry (hereinafter simply referred to as the periodic table), iron group 8A, and group 2B.
This is a method for producing cinnamic acid esters, which is characterized by reacting compounds of at least one metal in the presence of carbon dioxide.

Styrenes used in the method of the present invention include:
Specifically, styrene, α-)f-rustyrene, β-methylstyrene, α-ethylstyrene, β-ethylstyrene, 0-methylstyrene, m-methylstyrene, p-methylstyrene, 1η-ethylstyrene, p- Ethylstyrene, p-tert-butylstyrene, β-methyl-p
Examples include alkyl derivatives of styrene such as -isopropylstyrene, and derivatives of styrene having a substituent in the aromatic cap that does not inhibit the reaction, such as p-chlorostyrene, p-methoxystyrene, and 3,4-dimethoxystyrene.

Alcohols include methanol, ethanol, propatool, butanol, pentanol, octatool, cyclopentanol, cyclopentanol, phenol,
These are alcohols such as benzyl alcohol, ethylene glycol, polyethylene glycol, and propylene glycol, and they may have a substituent such as a halogen or an alkoxy group that does not inhibit the reaction. The amount of these alcohols used is 1 to 100 per mole of styrene.
It is expressed in molar parts and can be used not only as a reaction raw material but also as a solvent.

In the reaction according to the method of the present invention, the alcohol as a raw material can essentially be used as a solvent, but any solvent can also be used as long as it does not inhibit the reaction. Examples of such solvents include ethers such as diethyl ether, dipropyl ether, methyl ethyl ether, phenylethyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethylene glycol diethyl ether, and tetraethylene glycol dimethyl ether, and ketones such as acetone, methyl ethyl ketone, and acetophenone. esters such as methyl acetate, ethyl acetate, and methyl propionate, aromatic hydrocarbons such as benzene, toluene, p-xylene, ethylbenzene, chlorobenzene, and dichlorobenzene, or their substituted compounds, n-hexane, n-pentane, Aliphatic or alicyclic hydrocarbons such as cyclohexane, carbonates such as propylene carbonate and dimethyl carbonate, nitriles such as acetonitrile and benzonitrile, aromatic nitro compounds such as nitrobenzene, amide compounds such as dimethylformamide, Examples include sulfone compounds such as sulfolane.

The first component of the catalyst of the present invention, palladium metal or its compound, includes palladium black, metal palladium supported on a substrate such as activated carbon, asbestos, or silica alumina, dibenzylidene acetone complex, or tetrakis(triphenylphosphine). Zero-valent palladium complexes such as palladium, zero-valent palladium metals or compounds, palladium chloride, inorganic acid salts of palladium such as palladium nitrate, organic acid salts such as palladium acetate or palladium benzoate, bis(acetylacetate), Examples include divalent palladium compounds such as palladium complexes such as nato)palladium, cyclooctadienecyclovaladium, and palladium chloride benzonitrile complex.

The amount of palladium metal or its compound used is 0.1 gram atom or less, preferably 5 x 10 to 1 mol of styrene as a palladium metal atom.
In the range of 1×10 gram atoms.

Copper compounds that are the second component of the catalyst include copper carbonate, steel chloride, copper inorganic acid salts such as copper nitrate or silver phosphate, copper acetate, copper propionate, copper stearate, copper cinnamate, and benzoic acid. Examples include salts of aliphatic or aromatic carboxylic acids of copper such as copper, and salts of organic anions of copper such as copper acetylacetonate. These copper compounds can be used alone or in combination of two or more. These copper compounds are preferably dissolved in the reaction mixture, but
There is no problem even if a portion remains insoluble. The amount of these copper compounds used is 0.004 to 0.4 gram atoms as copper atoms per liter of reaction mixture. however,
When halogenated steel is used as the halogen compound of the third catalyst component, the range includes the copper atom of this compound. Preferably, o, o o per reaction mixture 1
s~0.6 gram atom.

Hydrogen halides such as hydrogen hydride, solutions thereof, and tertiary compounds as halogen compounds that are the third component of the catalyst
Contains 6-class alkyl halides such as butyl chloride and tert-butyl bromide, organic halides that tend to generate halogen ions such as acid halides such as acetyl chloride and benzoyl bromide, phosgene, methyl chloroformate, etc. Carbonic acid derivatives, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide, phosphorus chloride such as phosphorus pentabromide, phosphorus oxyhalides such as phosphoryl trichloride and phosphoryl tribromide, thionyl chloride, thionyl bromide, etc. thionyl rhodanides, tellurium halides such as tellurium tetrachloride and tellurium tetrabromide, group 4A such as titanium and zirconium, group 5A such as vanadium and tantalum, group 6A such as chromium and molybdenum, manganese, etc. 7
Valency of metals of group A, iron group to 8 of iron, cobalt and nickel, group 1B such as copper, group 2B such as zinc, cadmium, group 4B such as germanium, tin and group 5B such as antimony, bismuth Examples include oxyno-logenides and oxyno-logenides.

Among these, chlorine, hydrogen chloride, hydrogen bromide, phosphorus pentachloride,
Preferred are phosphoryl trichloride, vanadium oxytrichloride, chromium trichloride, manganese chloride, iron chloride, iron bromide, copper chloride, copper bromide, zinc chloride, tin chloride, field-grown bismuth, and the like. These halogen compounds alone are 2f! A mixture of i or more may be used.

Among the halogen compounds, copper halide can serve as a part of the copper compound which is the second catalyst component, but it does not serve as all of the copper compound if other catalyst components are missing halogen atoms. The amount of the halogen compound used as the sixth component of the catalyst is 0.0 halogen atom per 1 reaction mixture.
04-0.8 gram atom. However, when a compound containing a halogen atom is used as another catalyst component, the range includes the halogen atom. Preferably, it is from o,ooa to 0.6 gram atoms per reaction mixture.

Group 4A, Group 5A, and Group 7A of the periodic table, which is the fourth component of the catalyst.
Examples of compounds of metals selected from group 8A, iron group 8A, and group 2B include titanium, zirconium, and hafnium.
Oxides and hydroxides of metals of group A, group 5A such as vanadium, niobium, and tantalum, group 7A such as manganese and rhenium, iron group 8A such as iron, cobalt, and nickel, and group 2B metals such as zinc, cadmium, and mercury; Examples include inorganic compounds such as hydrogen chlorides and carbonates, or complex compounds with propionic acid acetate, salts of stearic or aromatic carboxylic acids, acetylacetonate complexes, cyclopentagenyl complexes, or carbonyl complexes. Two or more of these compounds can also be used simultaneously. It is preferable that these compounds be dissolved in the reaction mixture, but there is no problem even if some of them are insoluble.

The amount of the compound used as the fourth component of the catalyst is inclusive.

Of these compounds as the fourth catalyst component, the chloride compound can also serve as part or all of the chloride compound as the third catalyst component.

In the method of the present invention, a dehydrating agent may be present in the reaction system in order to remove generated water. These dehydrating agents include molecular sieves, silica gel, methyl orthoformate, and the like.

The gaseous components in the method of the invention are carbon monoxide, oxygen and carbon dioxide, but these gases may be further diluted with an inert gas such as nitrogen or argon.

The partial pressure of carbon monoxide is 50 atm (absolute pressure, the same applies hereinafter) or less, preferably in the range of 0.005 to 40 atm. The partial pressure of oxygen is 50 atmospheres or less, preferably 0.0
02 to 50 atmospheres. Air can also be used as the oxygen source. - The partial pressure ratio of carbon oxide and oxygen is theoretically i:o, s, or usually in the range of 1:0.2 to 1.2, preferably in the range of 1:0.3 to 1.0. It is.

The partial pressure of carbon dioxide is 500 atm or less, preferably 0.1 to 300 atm, but the partial pressure of carbon dioxide with respect to the total pressure of the reaction is 10% or more (pressure ratio), that is, the carbon dioxide in the reaction mixture gas The concentration of carbon is 10% by volume or more,
Preferably it is in the range of 10% to 98%. If it is less than 10%, the effect of carbon dioxide will not be expressed, and if it exceeds 98%, carbon monoxide and oxygen will be diluted and the reaction will be slowed down.More preferably, it is in the range of 15% to 95%.

Carbon monoxide, oxygen and carbon dioxide, and inert gases used as necessary, may be charged into the reactor all at once, or the necessary gases may be added continuously or intermittently; Alternatively, a method of continuously or intermittently circulating a mixture of these gases may be used. Among these methods, the method of adding and the method of distributing are more preferable.

The gas mixture used for the reaction may be freshly prepared each time, but once the concentration of each component gas is adjusted using the residual gas used in the reaction or the exhaust gas from the distribution method, In this reaction, carbon dioxide may be produced from carbon monoxide and oxygen as a side reaction, or in the method of the present invention, when the reaction mixture gas is repeatedly used, the carbon dioxide may be produced in a special manner. There is no need to separate and remove it using any other method.

The method of the present invention may be carried out using either a batch method or a continuous flow method.

The total pressure of the reaction in the method of the present invention depends on the partial pressure of carbon monoxide, oxygen and carbon dioxide, or inert gas used, but is usually 500 atmospheres or less, preferably 1 to
The pressure is 500 atm. The reaction temperature is room temperature to 200°C, preferably 40 to 160°C. The reaction time varies depending on the reaction conditions, but is usually 0.01 to 24 hours, preferably 0.05
~10 hours.

After completion of the reaction, the cinnamic acid esters can be separated from the reaction product liquid by a commonly used separation method such as distillation or extraction.

(Operation and Effects of the Invention) According to the method of the present invention, the catalytic activity is increased by carbon dioxide, which can be used extremely easily, and the cinnamate ester is produced with high reaction performance compared to the conventional method (using a small amount of palladium catalyst). In addition, when the reaction mixture gas is recycled, there is no need to separate and remove the by-product carbon dioxide by a special method, making it an industrially extremely advantageous method for producing cinnamic acid esters.

(Example) Hereinafter, the present invention will be explained in detail with reference to Examples.

Example 1 In a glass cylindrical container, 4.5 ■ palladium chloride (0,
025 mmol), cupric acetate monohydrate 1.87 f(
9,37 mmol), cupric chloride 0.419F (3,1
2 mmol), manganous acetate @ tetrahydrate 5.82 f
(15,6 mmol), and styrene 26.04f (
250.0 mmol) was added, methanol was added, and the total amount was concentrated to 125. The amounts of copper atoms and chlorine atoms are o, ioo and 0.050 gram atoms per reaction mixture, respectively. This glass container was inserted into a 500-liter autoclave. The autoclave's stirring blades are made of glass, and the temperature measuring tube is also protected by glass.

The total pressure in the autoclave was maintained at 10 atm, and the partial pressure ratio of -carbon oxide:carbon dioxide was 8.3:5.4:
86.3 at the outlet at 1.2 liters/min (
Continue stirring to reach standard condition) at 100°C.
The mixture was allowed to react for 6 hours. During this time, the outlet gas was vented through a water-cooled reflux condenser. After the reaction was completed, the reaction solution was cooled and taken out and analyzed by high performance liquid chromatography, and it was found that styrene was 20.0 mmol and methyl cinnamate was 21 mmol.
0.8 mmol, dimethyl phenylconophosphate 5.1
It contained mmol. Styrene conversion rate 92.0%,
The selectivity of methyl cinnamate (yield based on consumed styrene) was 91.6%, and the yield of methyl cinnamate (yield based on charged styrene) was 84.6%. The number of moles of cinnamic acid ester produced per gram atom of palladium as one component at catalyst temperature (hereinafter abbreviated as Pd turnover rate) was 8,460.

Comparative Example 1 All the same procedures were carried out except that the mixed gas in Example 1 was changed to a mixed gas that did not contain carbon dioxide and had a partial pressure ratio of -e carbon: oxygen: nitrogen of 8.3: 5.4: 86.3. When the reaction was carried out in the same manner as in Example 1, the conversion rate of styrene was 67.
1%, selectivity and yield of methyl cinnamate were 93, respectively.
．． 4% and 62.7%, and the Pd rotation rate is 6270
Met. Carbon dioxide was detected when a portion of the exhaust gas was analyzed. Shows the production of carbon dioxide due to side reactions.

Examples 2 and 6 and Comparative Example 2 The same procedures as in Example 1 were carried out except that the mixed gas shown in Table 1 was used. The results are shown in Table 1 along with Example 1 and Comparative Example 1.
Shown below.

Example 4 The amount of cupric acetate monohydrate used in Example 1 was reduced to 2.5
Of (12,5 mmol) and instead of cupric chloride,
5.0 methanol solution of hydrogen chloride (concentration 1.25N)
The same procedure as in Example 1 was carried out except that the amount of hydrogen chloride was 6.25 mmol. The amounts of copper atoms and chlorine atoms are o, ioo and 0.050 gram atoms per reaction mixture, respectively. When the reaction was carried out in the same manner as in Example 1, the conversion rate of styrene was 90.5%, the selectivity and yield of methyl cinnamate were 91.1% and 82.4%, respectively, and the Pd turnover rate was 90.5%. was 8240.

Comparative Example 3 The mixed gas in Example 4 and Example 1 was modified so that the partial pressure ratio of carbon:oxygen:nitrogen was 8.3:5.4:86.
When the reaction was carried out in the same manner as in Example 4 except that the mixed gas containing no carbon dioxide was changed, the conversion of styrene was 68.8%, and the selectivity and yield of methyl cinnamate were 94. , 5% and 65.0%, and Pd
The rotation rate was 6500.

Example 5 The reaction was carried out in the same manner as in Example 4 except that the total pressure of the reaction in Example 4 was changed to 6 atm. The conversion of styrene was 87.2%, and the selectivity and yield of methyl cinnamate were excellent. The ratios were 90.3% and 78.7%, respectively, and the Pd rotation ratio was 787o.

Example 6 The amount of palladium chloride used in Example 4 was reduced to 71
, 040 mmol), cupric acetate monohydrate at 1.2°f (6.01 mmol), hydrogen chloride methanol solution (concentration 1.25N) for 10.5 hours, hydrogen chloride 1
Everything was the same as in Example 4 except that the amount was adjusted to 3.1 mmol. The amounts of copper and chlorine atoms are D 48 and 0.105 gram atoms per 1 reaction mixture, respectively. When reacted in the same manner as in Example 4,
The conversion rate of styrene was 84.8%, and the selectivity and yield of methyl cinnamate were 894% and 75.8%, respectively.

Example 7 5% Pd/C (5% by weight of palladium supported on activated carbon) 170■, vanadium oxytrichloride 380■
(2.2 mmol), cupric acetate monohydrate 250F (1
2.5 mmol), manganous acetate tetrahydrate 3.82
F (15,6 mmol) and styrene 26.04 f
(250 mmol) and dilute the total amount to 125 mmol with methanol.
fnt. The reaction was carried out in the same manner as in Example 1 except that the reaction time was 3.5 hours. The styrene conversion rate was 88.6%, and the selectivity and yield of methyl cinnamate were 91.1% and 80.9%, respectively. It was 4%.

Comparative Example 4 All the same procedures as in Example 7 except that the mixed gas in Example 7 was changed to a mixed gas that did not contain carbon dioxide and had a carbon monoxide:oxygen:nitrogen partial pressure ratio of 8.4:5.4:86.2.
When the reaction was carried out in the same manner as above, the yield of methyl cinnamate was 70
．． It was 2%.

Example 8 5.6η (0,025 mmol) of palladium acetate was added in place of palladium chloride in Example 1.
Cobaltous acetate tetrahydrate 3.74 instead of tetrahydrate? (
The reaction was carried out in the same manner as in Example 1 except that 15.0 mmol) was used and the reaction time was 3.5 hours.
The styrene conversion rate was 84.8%, the selectivity and yield of methyl cinnamate were 91.6% and 77.4%, respectively.
The Pd rotation rate was 7740.

Comparative Example 5 The amount of palladium used in Example 8 was 11.23.
■ (o, oso mmol), and the reaction mixture gas was changed to carbon monoxide: cumulative: nitrogen partial pressure ratio of 8.5: 5.3:
The reaction was carried out in the same manner as in Example 8 except that the mixed gas was changed to 86.2, which did not contain carbon dioxide. The conversion of styrene was 86.4%, the selectivity and yield of methyl cinnamate were 90.9% and 78.5%, respectively, and the Pd turnover was 3930.

Example 9 In Example 1, 9.0 μg (0,040 mmol) of palladium in vinegar was used instead of palladium chloride, and 697 mg (3,12 mmol) of cupric bromide was used instead of cupric chloride.
was used, and the partial pressure ratio of -m carbon to oxygen dicarbon dioxide was 8.
The reaction was carried out in the same manner as in Example 1 except that a mixed gas of 7:5.7:85.6 was used. The conversion rate of styrene was 90.7%, and the selectivity and yield of methyl cinnamate were respectively 93.0% and 84.6%, and the Pd rotation rate was 5270.

Comparative Example 6 All the same as in Example 9 except that the mixed gas in Example 9 was replaced with a carbon dioxide-free mixed gas with a carbon monoxide:oxygen:nitrogen partial pressure ratio of 8.5:5.3:86.2. When the reaction was carried out in the same manner as in 9, the conversion rate of styrene was 73.
．． 0%, selectivity and yield of methyl cinnamate are 6, respectively.
9.5% and 50.7%, and the Pd rotation rate is 317
It was 0.

Examples 10 to 21 and Comparative Examples 7 and 8 The reaction was carried out in the same manner as in Example 1, except that the type and amount of the catalyst acid and the reaction conditions were changed as shown in Table 2. The partial pressure ratio of the mixed gas varies slightly with each preparation, but the ratio is approximately 8.0 to 9.0:5.
0-6.0: range of 85-87.

The results are shown in Table 2 together with Example 9. Comparative examples 7 and 8
In all cases, the Pd turnover rate,
The reaction yield is significantly reduced.

Comparative Example 9 Cupric acetate monohydrate in Example 1 was heated to 299η(o,
i s mmol), cupric chloride from 16.4 to (0,1
The same procedure as in Example 1 was carried out except that the concentration was changed to 0 mmol).

The amounts of copper atoms and chlorine atoms in the reaction mixture 1 are the same (0,002 gram atoms).When the reaction was carried out in the same manner as in Example 1, the styrene conversion rate was 6.2%, and the styrene conversion rate was 6.2%. The yield was less than 0.1%.

Comparative Example 10 Cupric acetate monohydrate in Example 1 was added to 1.20 f(
s, oi mmol), cupric chloride at 8.07 F (6
The same procedure as in Example 1 was carried out except that the concentration was changed to 0.0 mmol).

The amounts of copper atoms and chlorine atoms are 0.528 and 0.960 gram atoms per reaction mixture, respectively.

When the reaction was carried out in the same manner as in Example 1, the conversion of styrene was 53.2%, and the selectivity and yield of methyl cinnamate were 8.4% and 4.5%.

Example 22 The preparation was the same as in Example 1, but the total pressure of the reaction was 51 atm, and the partial pressure ratio of -carbon oxide:acid dicarbon dioxide was 8.
The mixed gas of 6:5.4:86.0 was adjusted so that the flow rate of the exhaust gas at the outlet of the reflux condenser was 1.2 liters/min (standard condition), and the exhaust gas was passed through a dry ice trap. The procedure was the same as in Example 1, except that the mixture was stored in a pressure-resistant container of approximately 10 tons, which had been replaced once with the raw material mixed gas. The conversion rate of styrene was 94.6%, and the selectivity and yield of methyl cinnamate were 92.2% and 872%, respectively.

The gas stored in the pressure container was analyzed, and carbon oxide and oxygen were added to adjust the partial pressure ratio of carbon oxide:Iy:carbon dioxide to 8.7:5.5:84.6.

A small amount (partial pressure ratio 1.2%) of nitrogen was mixed in. The pressure inside the pressure vessel was approximately 25 atmospheres. This adjusted mixed gas was used in the next reaction. In a glass-slit cylindrical container for a 20D fnt autoclave, 1.8 μ (0,010 mmol) of palladium chloride, 748 μ (3,75 mmol) of cupric acetate monohydrate, and 168 ~ (1,25 mmol) cupric chloride were added. ), 1.53 F (6.24 mmol) of manganous acetate tetrahydrate, and 10.42 F (100.0 mmol) of styrene were made into a 50-carbon solution with methanol. Insert this glass container into a 200-cm autoclave and reduce the total pressure to 1
Maintaining the pressure at 0 atmospheric pressure, the adjusted mixed gas is heated at 50[]d/
The reaction was carried out in the same manner as in Example 1 so that the reaction time was 10 minutes (standard condition). Styrene conversion was 90.6%, methyl cinnamate selectivity and yield were 93.1% and 84.1, respectively.
%Met.

Claims (1)

[Claims] 1) In producing the corresponding cinnamic acid esters by reacting styrenes, carbon monoxide, alcohol and oxygen, (1) palladium metal or its compound, (
2) copper compounds, (3) halogen compounds, and (4)
It is characterized by using a compound of at least one metal selected from the group consisting of Group 4A, Group 5A, Group 7A, Iron group 8A, and Group 2B of the periodic table, and reacting in the presence of carbon dioxide. Method for producing cinnamic acid esters.