JPH047737B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for producing cinnamic acid esters by reacting styrenes, carbon monoxide, alcohol, and oxygen. Cinnamic acid esters are industrially important compounds such as raw materials for perfumes 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, this method, which uses expensive raw materials, is not an industrially preferred method. There are several methods for producing cinnamic acid esters by reacting inexpensive styrenes with carbon monoxide, alcohol, and oxygen in the presence of a catalyst (for example, JP-A-57-70836 or JP-A-56-15242). Proposed. (Problems to be Solved by the Invention) The above-mentioned methods have not yet reached a stage where they can be industrialized because their reaction results are unsatisfactory and their catalyst activity and reaction rate are low. The object of the present invention is to develop a more advantageous industrial method for producing cinnamic acid esters using styrenes, carbon monoxide, alcohol, and oxygen as raw materials. As a result, (a) platinum group metals or compounds thereof; (b) compounds of iron or copper; Family, 8A Iron family, 1B
and a compound of at least one metal selected from the group consisting of oxides, hydroxides, carbonates, aliphatic carboxylates, aromatic carboxylates, and complex compounds of metals of Group 2B and Group 2B. By reacting styrenes, carbon monoxide, alcohol, and oxygen in the presence of a dehydrating agent, cinnamic acid esters can be obtained with high reaction performance under mild reaction conditions, and the catalyst The present invention was achieved by discovering an extremely industrially advantageous method for producing cinnamic acid esters, which has high activity and high reaction rate. (Means for Solving the Problems) Specifically, the styrenes used in the method of the present invention include styrene, α-methylstyrene, β-methylstyrene, α-ethylstyrene,
β-ethylstyrene, o-methylstyrene, m-
Alkyl derivatives of styrene such as methylstyrene, P-methylstyrene, m-ethylstyrene, P-ethylstyrene, P-tertiarybutylstyrene, β-methyl-P-isopropylstyrene, or P-chlorostyrene, P-methoxystyrene , 3,4-dimethoxystyrene and other styrene derivatives having a substituent on the aromatic ring that does not inhibit the reaction. Alcohols include methanol, ethanol, propanol, butanol, pentanol,
Alcohols such as octanol, cyclopentanol, cyclohexanol, phenol, benzyl alcohol, ethylene glycol, and propylene glycol, or they may have substituents such as halogen or alkoxy groups that do not inhibit the reaction. The amount used is 1 to 50 moles per mole of styrene, and it may be used not only as a reaction raw material but also as a solvent. The partial pressure of carbon monoxide is usually 50 Kg/cm ² G or less, preferably normal pressure to 50 Kg/cm ² G; if the partial pressure is higher than this, the corresponding by-products such as phenylsuccinic acid diesters increase. More preferably, normal pressure ~
It is 40Kg/cm ² G. The partial pressure of oxygen is not particularly limited, but is arbitrarily selected within a range in which the composition of the gas mixture in the reaction system does not fall within the explosive range. These gases should be diluted with an inert gas such as nitrogen or argon to avoid explosion. Therefore, carbon monoxide and oxygen may be used in their pure state, or may be used already diluted with an inert gas. Air may also be used as the oxygen source. In the reaction according to the method of the present invention, alcohol as a raw material can essentially be used as a solvent, but any solvent that does not inhibit the reaction can also be used. The reaction according to the method of the present invention comprises (a) a platinum group metal or its compound as the first component, (b) a compound of iron or copper as the second component, and (c) group 4A of the periodic table as the third component. 7A group, 8A iron group, 1B group and
In the presence of a catalyst comprising at least one metal compound selected from the group consisting of oxides, hydroxides, carbonates, aliphatic carboxylates, aromatic carboxylates, and complex compounds of Group 2B metals. It will be held on. The platinum group metal or its compound as the first component includes metals such as ruthenium, rhodium, palladium, osmium, iridium, or platinum, or halides of these metals, and organic carbonates such as nitrates, sulfates, phosphates, and acetic acid. Examples include acid salts and oxides. Among them, palladium,
Palladium chloride is particularly preferred. Further, complex compounds such as these dibenzylidene acetone complexes, benzonitrile complexes, acetylacetonate complexes, and amine complexes can also be used.
These metals or their compounds can also be used in a supported manner. Such carriers include activated carbon, graphite, alumina, silica, silica alumina, magnesia, zeolite, molecular sieves or ion exchange resins. The amount of these used is in the range of 0.00001 to 1.0 gram atom, more preferably 0.00005 to 0.1 gram atom per mole of styrene as a raw material, in terms of metal atoms.
It is a gram atom. Examples of the iron or copper compound as the second component include iron or copper chlorides, nitrates, sulfates, phosphates, and organic acid salts such as acetic acid. Particularly preferred are chlorides. Two or more of these compounds can also be used at the same time. The amount of these compounds used is calculated in terms of metal atoms, and the amount of styrene used as raw material is 1
0.0001 to 20 gram atoms per mole, more preferably 0.001 to 1.0 gram atoms. The third component of the periodic table is group 4A, group 7A, iron group 8A,
Metals as compounds of metals selected from the group consisting of Groups 1B and 2B include titanium, zirconium,
Manganese, technetium, rhenium, iron, cobalt, nickel, copper, silver, gold, zinc, cadmium,
Examples of compounds of these metals include oxides, hydroxides, carbonates, or aliphatic carboxylates such as acetic acid, propionic acid, stearic acid, and succinic acid, and aromatic carboxylates such as benzoic acid or phthalic acid. Examples include acid salts, complex compounds such as acetylacetonate complexes, and cyclopentadienyl complexes. Furthermore, combinations of compounds that can produce these compounds in the reaction system may be used. The second component compound and the third component compound may have the same metal, but the compounds must be different. The amount of these compounds used is 0.0001 to 20 gram atoms, preferably 0.001 to 2.0 gram atoms, per mole of styrene as a raw material, in terms of metal atoms contained. The total reaction pressure of the reaction according to the method of the present invention is normal pressure ~ 500
Kg/cm ² G, preferably normal pressure to 300 Kg/cm ² G,
The reaction temperature is room temperature to 200℃, preferably 40 to 160℃, and the reaction time is 0.01 to 10 hours, preferably 0.05
~3 hours. Cinnamic acid esters can be separated from the reaction product liquid obtained by carrying out the method of the present invention by a conventional separation method such as distillation or extraction. (Operation and Effects of the Invention) According to the method of the present invention, although the reaction proceeds under relatively mild conditions, it gives high reaction results and the turn of the main catalyst exhibiting catalytic activity and reaction rate. Over (1 for 1 gram atom of first component metal)
(indicating the number of moles of cinnamic acid esters produced per hour) gives considerably higher values than in the prior art. That is, the present invention is an extremely industrially advantageous method for producing cinnamic acid esters. (Examples) Hereinafter, the present invention will be explained in detail with reference to Examples and Comparative Examples. Example 1 200 where the part that comes into contact with the reaction solution was protected with glass
50 mg of palladium chloride (0.28 ml autoclaved)
mmol), cupric chloride 700 mg (5.2 mmol), zinc acetate dihydrate 2.8 g (12.7 mmol), styrene
10.4g (100mmol) and 32g methanol
(1.00 mol) and carbon monoxide at 22.5Kg/cm ²
After G was pressurized, a mixed gas of oxygen and nitrogen diluted to an oxygen content of 6% by volume so that the oxygen partial pressure was 11.3 Kg/cm ² G was further pressurized at 188 Kg/cm ² G. The temperature was raised while stirring and maintained at 120-130°C for 30 minutes. After the reaction is completed, the autoclave is cooled, the pressure is released, and the reaction solution is taken out.
The composition of the filtrate was analyzed by high performance liquid chromatography. 38.8 mmol styrene, 52.2 mmol methyl cinnamate and dimethyl phenylsuccinate
It contained 3.7 mmol. Styrene conversion rate
The yield of methyl cinnamate was 85.3% based on the consumed styrene, and the yield of dimethyl phenylsuccinate was 6.0%. The number of moles of methyl cinnamate produced per gram atom of palladium used was 373 moles/(gram atom/hr) per hour (PD turnover). Example 2 Palladium chloride was made into 100 mg and heated at 100 to 120°C for 10
When the same procedure as in Example 1 was carried out except that the reaction was carried out for a minute, the conversion rate of styrene was 63.1%, and the yield of methyl cinnamate based on the consumed styrene was 87.2%.
It was hot. PD turnover was 590 mol/(gram atom/hr). Example 3 Methanol was added to a 200ml Teflon-coated autoclave equipped with a water-cooled condenser.
The preparation was exactly the same as in Example 1 except that 48 g was used, and a mixed gas of carbon monoxide, oxygen, and nitrogen with a volume ratio of 12:6:94 was added to the mixture so that the total pressure was always maintained during the reaction.
Adjust to 150Kg/cm ² G, 500ml/min
(standard condition). When reacted at 100℃ for 30 minutes, the conversion rate of styrene was 68.3%, and the yield of methyl cinnamate was 82.6% based on the consumed styrene.
It was hot. PD turnover was 403 mol/(gram atom/hr). Example 4 11.0 mg (0.062 mmol) of palladium chloride, 73.4 mg (0.55 mmol) of cupric chloride, and manganese () were placed in a 50 ml autoclave fitted with a Teflon cup.
217 mg (0.75 mmol) of acetylacetonate dihydrate, 1.15 g (11.0 mmol) of styrene, and 10.0 g (312 mmol) of methanol were charged, 13.5 kg/cm ² G of carbon monoxide was introduced under pressure, and the partial pressure of oxygen was increased.
A mixed gas of oxygen and nitrogen containing 6% by volume of oxygen was further pressurized at 112Kg/ ^cm2G so that the pressure was 6.7Kg/ ^cm2G , and the mixture was heated at 100℃.
The reaction was allowed to proceed for 30 minutes. As a result of the same post-treatment and analysis as in Example 1, the conversion rate of styrene was 73%, and the yield of methyl cinnamate based on the consumed styrene was 65%.
It was %. PD turnover was 168 mol/(gram atom/hr). Examples 5 to 19 and Comparative Examples 1 and 2 The reaction was carried out in exactly the same manner as in Example 4, except that the compounds listed in Table 1 and their amounts were used instead of manganese () acetylacetonate dihydrate in Example 4. I went. The results are shown in Table-1. Comparative Example 3 The same procedure as in Example 10 was carried out except that cupric chloride was not used. The conversion rate of styrene was 1.1% and no methyl cinnamate was produced.

[Table] Example 20 In Example 4, 5 was used instead of palladium chloride.
%pd/C (5% by weight of palladium supported on activated carbon) was used in terms of palladium amount of 0.062 milligram atoms, and manganese acetate tetrahydrate was used in place of manganese () acetylacetonate dihydrate, which was 0.56 millimoles. When the reaction was carried out in the same manner as in Example 4, the conversion of styrene was 70%, and the yield of methyl cinnamate based on the consumed styrene was 63%. Example 21 In Example 1, 100 mg of palladium chloride
(0.56 mmol), 3.26 g (20 mmol) of ferric chloride was used instead of cupric chloride, and the reaction time was 17 minutes. The yield of methyl cinnamate was 45% based on the consumed styrene. Examples 22, 23 In Example 4, the same weight of ethanol was used instead of methanol, and zinc acetate dihydrate was used instead of manganese () acetylacetonate dihydrate.
0.56 mmol was used (Example 22) and α-methylstyrene was used instead of styrene (Example 22).
23), otherwise the reaction was carried out in the same manner as in Example 4, and the yield of cinnamic acid esters based on the consumed styrene was 82% (Example 22).
and 66%.

Claims (1)

[Claims] 1 (a) platinum group metals or compounds thereof; (b) compounds of copper or iron; and (c) iron groups of groups 4A, 7A, and 8A of the Periodic Table of the International Union of Pure and Applied Chemistry;
Presence of a catalyst comprising at least one compound selected from the group consisting of oxides, hydroxides, carbonates, aliphatic carboxylates, aromatic carboxylates, and complex compounds of Group 1B and Group 2B metals. under,
In the absence of a dehydrating agent, styrenes, carbon monoxide,
A method for producing the corresponding cinnamic acid esters by reacting alcohol and oxygen.