JPS6092242A - Manufacturing method of cinnamic acid ester - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for perfume or a raw material for agricultural chemicals inexpensively in high yield, by reacting a styrene with an aliphatic alcohol, carbon monoxide and oxygen in the presence of a specific compound consisting of palladium metal, copper and a rare earth element compound. CONSTITUTION:A styrene, preferably a compound shown by the formula (A<1> is H, halogen, etc.; R<2> is H, or 1-6C alkyl) is reacted with 1-4C aliphatic alcohol, carbon monoxide and oxygen in the presence of a catalyst comprising (A) palladium metal or its compound, (B) a salt of copper or iron, and (C) a rare earth element compound, having a blending ratio of the three component wherein a ratio of the component A to the component B is 1:0.1-500, preferably 1:10-300 calculated as atomic ratio and a ratio of the component B to the component C is 1:0.001-100, preferably 1:0.1-50 calculated as atomic ratio, at normal temperature -200 deg.C, to give the desired compound.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a method for producing a cinnamic acid ester, and particularly relates to a method for producing a cinnamic acid ester by oxidatively cal-nylating styrenes in the presence of an alcohol. It is.

[Prior art]

Cinnamic acid, cinnamaldehyde, cyclamenaldehyde, β
-It is not only used as a raw material for fragrances, such as amyl cinnamaldehyde, but also useful as a raw material for agricultural chemicals.
On a laboratory scale, it can be produced by the Perkin reaction.

Examples of obtaining cinnamic acid esters by oxidative carbonylation reaction of styrene include JP-A-53-40709, JP-A-56-15242, JP-A-56-22749, JP-A-5
6-22760. JP-A-56-71039, JP-A-57
-21342,ll! 1972-21343, 1977 Japanese Patent Publication No. 5
7-70836, etc.0 Among these conventional examples, one that discloses a typical catalyst system is JP-A No. 5
6-15242 and JP-A-57-70836. Q In JP-A-56-15242, (1) platinum group metals or their compounds, (2) copper salts or iron salts, and (3) alkali metals, alkaline earth metals. , a catalyst comprising an organic acid salt of a metal selected from aluminum group metals is disclosed.

Furthermore, in JP-A-57-70836, (1) platinum group metals or their salts, (2) copper or iron salts, and (3) alkali metal or alkaline earth metal hydroxides in an ethylene glycol ether solvent are disclosed. Although it has been disclosed that the reaction is carried out in the presence of a catalyst consisting of one or more compounds selected from O, carbonate, and acetate, the selectivity and yield of the reaction were not satisfactory. Japanese Patent Application Laid-Open No. 1989-1999, which was the earliest application among the above-mentioned conventional examples.
3-40709, it is reported that a trace amount of methyl cinnamate was obtained by oxidative carnylation of styrene in the presence of methanol using a platinum metal or its compound, a copper salt, and a tertiary amine as a catalyst. . However, in this reaction, the selectivity for methyl cinnamate is extremely low.

[Purpose of the invention]

The present invention was made to industrially advantageously produce cinnamic acid ester using inexpensive raw materials, and the purpose is to be able to produce cinnamic acid ester with high selectivity and yield. The purpose of the present invention is to provide a wire made of cinnamic acid ester.

[Structure of the invention]

In order to achieve this objective, the present inventors have conducted intensive research on a method for producing cinnamic acid esters by oxidative carginylation of styrenes, and have found that (a) palladium metal or its compound, (b) ) Copper or iron salts and (C)
The present invention was achieved by discovering the novel fact that cinnamic acid esters can be produced with extremely high selectivity and yield by carrying out the reaction in the presence of a catalyst made of a rare earth compound.

That is, the present invention provides a method for converting styrene into an aliphatic compound having 1 to 4 carbon atoms in the presence of a catalyst consisting of (a) radium metal or a compound thereof, (b) a salt of copper or iron, and (C) a rare earth compound. The gist of this invention is a process for producing cinnamic acid esters, which is characterized by reaction with alcohol, carbon oxide, and oxygen.

The present invention will be explained in detail below.

In the process of the invention, styrenes are reacted with an aliphatic alcohol having 1 to 4 carbon atoms, carbon oxide and oxygen in the presence of a specific catalyst.

The styrenes have the general formula (wherein R1 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and R represents hydrogen or an alkyl group having 1 to 4 carbon atoms. Styrenes represented by 0) representing an alkyl group of 6, specifically styrene, β-methylstyrene, p-methylstyrene, p-methoxystyrene, p-chlorostyrene, β-methyl-p-isoglobil Examples include styrene and β-amylstyrene.

Specific examples of aliphatic alcohols having 1 to 4 carbon atoms include methanol, ethanol, isoglobil alcohol, n-butyl alcohol, t-butyl alcohol, etc., but acetals, ketals, carboxylic acid It is also possible to use compounds that can dissociate within the reaction system to release the above-mentioned alcohols, such as orthoesters, dialkoxy polychloroalkanes, orthoboric acid esters.

In the production method of the present invention, in order to obtain a higher production yield of cinnamic acid ester, the dissolved molar ratio of styrene to the aliphatic alcohol in the reaction system is 0.5 to 1.
5. Carbon oxide and oxygen can be used in a pure state, but they can also be used after being diluted with an inert gas such as nitrogen or argon. In order to obtain a higher yield of cinnamic acid ester, the partial pressure of carbon monoxide in the reaction system should be adjusted to 710 or more 10 kg/c.
It is preferable to maintain the carbon monoxide partial pressure to the oxygen partial pressure in the reaction system at 1.0 to 2.5.

In the method of the invention, the reaction is carried out in the presence of a catalyst consisting of (a)-f radium metal or a compound thereof, (b) a salt of copper or iron and (C) a rare earth compound.

- Mother radium metal or its compounds include - radium black, metal with a carrier - Metals such as mother radium - Zero-valent palladium complexes such as mother radium or tetrakis (triphenylphosphine); Inorganic salts of divalent metals such as palladium acetate, palladium nitrate; Carnates of divalent metals and radium such as palladium acetate, benzoic acid, and radium; Examples include palladium compounds such as divalent palladium complexes such as (triphenylphosphine)cyclobaladium.

When these radium metals or compounds thereof are supported on a carrier, silica, alumina, silica alumina, magnesia, titania, diatomaceous earth, activated carbon, graphite, barium carbonate, calcium carbonate, etc. are used as the carrier.

Examples of copper or iron salts include inorganic salts such as hydrochlorides, nitrates, sulfates, phosphates, borates, and organic acid salts such as acetates and benzoates.

The valence of copper or iron in the salts may be monovalent or divalent.

Examples of rare earth compounds include oxides, composite oxides, or salts of a total of 17 elements, including scandium and yttrium of group 3a, and lanotanoids from lanthanum to lutetium. Specifically, the oxides T-L T-C80t% P
Examples include basic oxides such as r6011s Lat Os, and examples of composite oxides include composite oxides of mixtures of several types of rare earth elements (generally referred to as mitshu metal). In addition, the mixing ratio of the three components (a), (b), and (C) in the catalyst used in the method of the present invention is
(a) z + radium metal or its compound and (b) copper or iron salt in an atomic ratio of 1:o, i ~ 500,
Preferably, the ratio is in the range of 1:10 to 300, and (
b) The ratio of steel or iron salts to (C) rare earth compound is 1:0.01-100 in atomic ratio, preferably 1:0.1-100.
It is preferable to adjust the range to 50.

In the present invention, there is no problem even if no reaction solvent is used, but in some cases, an appropriate inert solvent may be used to facilitate the operation. Examples of solvents include ethers such as diethyl ether, diphenyl ether, dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether; ketones such as acetone, methyl ethyl ketone, sibutyl ketone, and acetophenone; methyl acetate, ethyl acetate, ethyl zolopionate, benzyl benzoate, and phenyl succinate. Aromatic hydrocarbons such as benzene, toluene, p-xylene, and ethylbenzene; Aliphatic or alicyclic hydrocarbons such as n-hexane, n-octane, and cyclohexane; Acetamide, N-methyl Amides such as pyrrolidone; carnates such as ethylene carnate and propylene carnate.

In the production method of the present invention, the yield of cinnamic acid ester can be improved by increasing the reaction temperature;
If the temperature is too high, side reactions such as the production of carbon dioxide will occur, resulting in a decrease in the selectivity of cinnamic acid ester. Therefore, the reaction temperature is usually room temperature to 200°C, preferably 50°C.
It is appropriate that the temperature is within the range of ~150°C.

The desired cinnamic acid ester can be easily separated and obtained from the reaction product liquid obtained by the reaction of the present invention by employing ordinary separation means such as distillation and extraction.

By the method of the present invention, the oxidative reaction of styrenes represented by the general formula (wherein 'u I and R1 are the same as the above definitions) is carried out by the oxidative reaction KIF), the general formula, and 1 (wherein R1 and R' are A cinnamic acid ester represented by 0), which is the same as the above definition and R3 represents an alkyl group having 1 to 4 carbon atoms, is obtained.

[Embodiments of the invention]

EXAMPLES The present invention will be explained in more detail with reference to examples below, but the present invention is not limited to the following examples unless it exceeds the gist thereof.

Example 1 Styrene 7d, methanol 3d 15% P were placed in a spinner-stirred Hastelloy C autoclave with an internal volume of 90 ttrl.
d/mu, c, (5 weight i% + 7)-4 lasium supported on activated carbon) 0.2 s mol (Pa conversion), cupric chloride 0.5 mol, lanthanum oxide (La 20 m
) After charging 1.5ml0Ar and sealing, -carbon oxide 8
9/cmG was press-fitted into. Then 6% oz/Nt
(Nitrogen containing 6 volumes of oxygen) was injected to bring the total pressure to 102
kg/m. After that, autoclave at 100℃.
and the reaction was carried out for 1 hour. After the reaction was completed, the autoclave was water-cooled and depressurized, and the compositions of the reaction gas and product liquid obtained were analyzed by gas chromatography, and the amount and selectivity of methyl cinnamate produced and the amount of carbon dioxide produced were determined.

The results are shown in Table 1.The selectivity of methyl cinnamate was calculated using the following formula.

Methyl cinnamate selectivity = (methyl cinnamate) ÷ (methyl cinnamate + methyl 2 and 3 gropionate + acetophthalne + phenyl succinate m-)) x 00 Examples 2 to 10 In Example I, rare earth compounds and their The reaction and analysis were carried out in the same manner as in Example 1, except that the amounts added were as shown in Table 1, and the amount and selectivity of methyl cinnamate produced and the amount of carbon dioxide produced were determined. The results are shown in Table 1.

Example 11 In Example 1, 5 cm Pa/A, C, was set to 0.
05a+m0J (converted to pa), 10 g of cupric chloride
tnol, and the charging pressure of carbon oxide to 15kll/
The reaction and analysis were carried out in the same manner as in Example 1, except that cmG was used, and the production amount and selectivity of methyl cinnamate and the production needle of carbon dioxide were determined. The results are shown in Table 1.

Table 1 @ 1-・-In, 0.3%, N12o, 71
%, Pre Ott 25 Ssam, 0 including 031 arrogance [Effects of the Invention] According to the method for producing cinnamic acid ester of the present invention detailed above,
Cinnamate esters with high selectivity and yield by oxidative carbonylation of styrenes in the presence of a catalyst consisting of (a) −+ radium metal or its compound, (b) salts of copper or iron, and (e) rare earth compounds. can be manufactured. Furthermore, the method of the present invention allows the production of cinnamic acid esters using inexpensive raw materials and catalyst systems, which is extremely advantageous industrially.

Agent Patent attorney Tsuyoshi Shigeno 1 Procedural support device 1 Indication of the case 1982 Patent application No. 198818 2 Name of the invention Process for producing cinnamic acid ester 3 Relationship with the case of the person making the amendment Name of the patent applicant (596) Mitsubishi Kasei Kogyo Co., Ltd. 4 Agent address 502-6 Akasaka Omotemachi Building 107, 4-8-19 Akasaka, Minato-ku, Tokyo Column for detailed explanation of the invention in the specification to be amended.

7. Contents of the amendment (1) On the bottom line of page 8 of the specification, the phrase “salts may be used” has been changed to “the valence of copper in salts may be monovalent or divalent.”
The valence of iron may be either divalent or trivalent.

” he corrected.

that's all

Claims (1)

[Claims] (1) (a)-f radium metal or its compound, (b)
) A cinnamic acid characterized by reacting styrene with an aliphatic alcohol having 1 to 4 carbon atoms, carbon oxide, and oxygen in the presence of a catalyst consisting of copper or iron salts and (C) a rare earth compound. Production method of ester. (2. In the method for producing a cinnamic acid ester according to claim 1, the styrene compound has a general formula (wherein R' is hydrogen, . (3) A method for producing a cinnamic acid ester according to claim 2, characterized in that the styrene is styrene. 4) A method for producing a cinnamic acid ester according to any one of claims 1 to 3, characterized in that the rare earth compound is a rare earth oxide. (5) Scope of claims Any one of paragraphs 1 to 3
2. The method for producing a cinnamic acid ester according to item 1, wherein the rare earth compound is an organic acid salt of a rare earth element. (6) Any one of claims 1 to 5
In the method for producing cinnamic acid ester described in Section 1, (-')-
A manufacturing method characterized in that the ratio of 4-razoum metal or its compound to (bO) copper or iron salts is 1:0, i~500 in atomic ratio. Any 1 of item 6
In the method for producing a cinnamic acid ester described in paragraph 1, the ratio of (b) steel or iron salts to (C) rare earth compound is 1 in atomic ratio.
A manufacturing method characterized by a ratio of 0.01 to 100.