JPS6045544A - Production of alpha,beta-unsaturated carbonyl compound - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as an intermediate of perfumery and pharmaceuticals, etc. from an alkenyl silyl ether and an aryl carbonate compound, by using a platinum-group metal compound singly as the essential component of the catalyst. CONSTITUTION:The objective compound of formula II is produced economically using an easily available compound as a catalyst, by contacting the alkenyl silyl ether of formula I (R1-R4 are H or chain hydrocarbon residue which may together form a ring by arbitrary combination; X is trihydrocarbylsilyl) with an aryl carbonate compound in the presence of a catalyst composed essentially of a platinum-group metal compound (salt or complex of Pd, Pt, Rh, Ir or Lu) or a combination of said compound and a unidentate ligand (an electron-donative compound having the atom of the V-group element, i.e. N, P, As a or Sb as the coordination atom). The combined use of the unidentate ligand further improves the activity and the stability of the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing α, β-, β-carbonyl compounds, and more specifically, the present invention relates to a novel method for preparing α, β-, β-carbonyl compounds, and more specifically, α, β- This invention relates to a method for producing unsaturated unsaturated nylbonyl compounds.

Unsaturated ketones such as cyclobentenone derivatives, cyclohexenone derivatives, fuclodobucenone derivatives, etc. are useful chemicals in the fields of perfumery, medicine, chemicals, etc.

As a new method for synthesizing such unsaturated carbonyl compounds,
Recently, a method has been reported in which alkenylsilylnitertoallyl carbonate is treated with a catalyst consisting essentially of palladium and α1oJ-alkylene di(disubstituted)phosphine (Organic Synthetic Chemistry, Vol. 41, No. 7). No. 61
9-632, published in 1983).

However, in this report, the ligands constituting the catalyst were limited to expensive compounds with a special structure, and the results were not necessarily satisfactory from an economic point of view.

Therefore, the present inventors conducted intensive studies to improve the drawbacks of the prior art, and surprisingly, they did not use α,ω-alkylene di(disubstituted) phosphine, which was considered to be an essential catalyst component in the above report. The present inventors have discovered that it is effective to use a palladium compound alone, and that when a monodentate ligand is used in combination, the activity and stability of the catalyst are further improved, and have completed the present invention.

Thus, according to the present invention, an alkenylsilyl ether represented by the following general formula [E] and an allyl carbonate ester are brought into contact with each other in the presence of a woody catalyst consisting of a platinum group metal compound and optionally a monodentate ligand. α represented by the following general formula [1r] characterized by:

A method of making a β-unsaturated carbonyl compound is provided.

formula! (In the above formula, R, , R, , R, and R4 represent hydrogen or a hydrocarbon residue, or a trihydrocar and a lucilyl group, and R1r, R1* R8* R4 may each be arbitrary, ) In the present invention, as the first starting material, the general formula C
I] is used. In the formula, R1 is not only a hydrogen atom but also a methyl group, an ethyl group,
Alkyl group b R such as propyl group or pentyl group
s * Rs t Refers to an alkylene group or an aryl group such as a phenyl group, a trityl group, etc., which is combined with IdR4 to form a ring such as a cyclopentane ring, a cyclohexane ring, a cyclododecane ring, etc., and also refers to R, R,
and R4 means a hydrogen atom or an alkyl group, an alkylene group, or an aryl group similar to R1, and further means a Xa) rehydrocarbylsilyl group. Among the above-mentioned substituents, R+, Rt #, R3 and R4 may each form a ring in any combination.

Specific examples of such compounds include l-L'1-cyclohenyltrimenalsilyl ether, 1-cyclohentenyl, TI/)limethylsilyl ether, etc. A/, 2-methyl-1-cyclohexenyltrimethylsilyl ether, 6-methyl-1-cyclohexenyltrimenalsilyl ether, 1-cyclododecenyltrimethylsilyl ether, 1-cyclohexenyltriethylsilyl ether, 1-cyclododecenyl trimethylsilyl ether, 2
-Pentenyl-1-cyclohexenyltrimethylsilyl ether, 2-propyl-1-cyclohexenyltrimethylsilyl ether, 2-pentyl-1-cyclohexenyltrimethylsilyl ether, 2-pentyl-1-7
Clopentenyl trimethylsilyl ether, 2-pentenyl-1-cyclopentenyl trimethyl silyl ether% 2-pentynyl-1-cyclopentenyl trimethylsilyl ether, 1-phenyl-1-butenyl trisilyl ether f k, 1-7 o henyl trimethylsilyl ether , 1-hexenyltrimethylsilyl ether, 2-
Ethyl 1 7'tenyltrimethylsilyl ether, 3-
Methyl-1-butenyltrimethylsilyl ether, 3-
Examples include phenyl-1-10benyltrimethylsilyl ether.

These compounds can be synthesized according to conventional methods. For example, taking ttfl-cyclohexenyltrimethylsilyl ether as an example, it can be easily synthesized by a method in which cyclohexanone and trimethylsilyl chloride are reacted in the presence of a base.

The allyl carbonate ester used as the second starting material is a carbonate ester having at least one allyl residue, and is usually a compound represented by the following general formula [■].

(In the formula, R6 represents a hydrocarbon residue and s R6+ R9
#R8 and R1 represent hydrogen or hydrocarbon residues. )
Specific examples of such compounds include diallyl carbonate,
Dicrotyl carbonate, dimethallyl carbonate, methylallyl carbonate, ethylallyl carbonate, propylallyl carbonate, butylallyl carbonate, pentylallyl carbonate, methylcrotyl carbonate, ethylmethallyl carbonate, etc. In the present invention, a platinum group metal compound or a catalyst consisting essentially of the compound and a monodentate ligand is used in the reaction. . Platinum group metal compounds are salts or complexes of palladium, platinum, rhodium, iridium, and ruthenium;
Specific examples include tris(dibenzylideneacetone)nipalladium(01,) tris(tribenzylideneacetylacetone)tribaodium(0), palladium acetate, palladium propionate, palladium butyrate, palladium benzoate, palladium acetylacetonate, palladium nitrate. , palladium sulfate, palladium chloride.

Examples include platinum acetate and platinum acetylacetonate. When using a strong inorganic acid salt among these compounds, it is desirable to coexist a base such as potassium acetate, sodium alcoholade, or tertiary amine. Further, among the platinum group metals, palladium is preferable in terms of reactivity, and among them, it is preferable to use a zero-valent olefin complex or a divalent organic compound.

In addition, the monodentate ligand used is an electron-donating compound having a Group V element of the periodic table, that is, nitrogen, phosphorus, violet, or antimony, as a coordination atom. Specific examples thereof include pyridine, quinoline, trimethylamine, and triethylamine. , nitrogen-containing compounds such as tributylamine, nitriethylphosphine, tri-n-butylphosphine,
tri-n-dodecylphosphine, triphenylphosphine, tri-n-dodecylphosphine, tri-n-butylphosphine, )+7-p-biphenylsphosphine, tri-methoxyphenylphosphine, phenyldiphenoxyphosphine, triethylphosphite, tri-n-butylphosphine Arsenic-containing compounds such as tri-n-hexyl phosphite, triphenyl phosphite, tri-n-hexyl phosphite, triphenyl thiophosphite, etc.: Arsenic-containing compounds such as triethyl arsenic, tributyl arsenic, triphenyl arsenic, etc. Examples include antimony-containing compounds such as nitripropylantimony and triphenylantimono. Among them, nitrogen-containing compounds and phosphorus-containing compounds are preferable from the viewpoints of reaction activity selectivity and economical efficiency.

Although it is not necessarily essential as such a monodentate ligand beam catalyst component, by using it in an appropriate amount, the stability of the catalyst can be greatly improved and the amount of catalyst used can be reduced. However, if the amount used is too large, the known allylation reaction becomes the main reaction, so the amount is preferably 2.5 mol or less per 1 mol of the metal compound, especially α1 to 2.0 mol, Furthermore, 0.5 to 15
It is appropriate to express it in moles.

The amount of catalyst to be used in the present invention is appropriately selected, but usually 0.01 platinum group metal compound per 100 moles of raw material.
-10 mol, preferably 0.1-5 mol. Although the platinum group metal compound and the monodentate ligand may be reacted in advance, the catalyst is usually prepared by bringing both components into contact in a reaction system.

The reaction of the present invention proceeds easily by bringing two starting materials into contact with a catalyst. For example, 1-
The reaction formula when using cyclohexenyltrimethylsilyl ether and diallyl carbonate is as follows.

The ratio of raw materials used is usually 0.8 to 5 mol, preferably 1 to 2 mol of allyl carbonate per mol of alkenylsilyl ether, reaction temperature is usually 50C or more, preferably 60 to 150C, and reaction time is Usually 10 minutes to 10 hours.

Further, during the reaction, a diluent may be present, specific examples of which include nitriles such as acetonitrile, propionitrile, butyronitrile, benzonitrile, etc.; dimethylformamide, diethylformamide, dimethylacetamide, dimethylprobioamide.

Amides such as N-methylbilidone; ethers such as but-2-hydrofuran, dioxane, dibutyl ether, ethylene glycol dimethyl ether;
Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; Esters such as methyl acetate, ethyl acetate, propyl acetate, ethyl propionate, etc.; ethanol, propatool, t
Alcohols such as θr-butanol, ethylene glycol, diethylene glycol monoethyl ether, etc.; throat sulfoxides such as dimethyl sulfoxide, diethyl sulfoxide; hard hydrocarbons such as n-hexane, cyclohexane, benzene, toluene, xylene, etc. Among them, non-flotic polar solvents, especially nitriles, amides, ethers, ketones, and esters are particularly prized.

These diluents typically have a starting material concentration of 1 to 50 h
%, and its use can improve the reaction activity, selectivity, and stability of the catalyst. In particular, when the catalyst component does not contain a monodentate ligand, the catalyst becomes unstable, so it is appropriate to use a diluent, and among them, it is preferable to use a nitrile.

After completion of the reaction, a highly purified α,β-unsaturated carbonyl compound, that is, an α,β-unsaturated ketone or an α,β-unsaturated aldehyde, is obtained by separating the target product from the reaction solution according to a conventional method. Such unsaturated carbonyl compounds are used as intermediates for the synthesis of various useful compounds, particularly for perfumes, medicines, and the like.

Thus, according to the present invention, easily available compounds can be used as catalysts, and the desired α.

β-unsaturated carbonyl compounds can be produced economically.

The present invention will be explained in more detail below with reference to Examples.

Example 1 2 moles of diallyl carbonate per mole of 1-cyclohexynyltrimethylsilyl ether in a container.

8 moles of acetonitrile and 0.5 moles of palladium acetate were charged, and after stirring rapidly at room temperature, the temperature was raised to the boiling point of the solution, and the reaction was carried out under reflux under an atmosphere of argon Wlffl for 1 hour. After the reaction was completed, the product was vaporized under reduced pressure according to a conventional method. As a result, 2-cyclohexen-1-one was 76
% yield. In addition, the identification of these compounds was carried out using MR, NMR, and mass spectra.

In addition, when observing the internal state of the system during and after the reaction,
Palladium precipitation began to occur during the course of the reaction, and more severe precipitation was observed after one reaction was completed.

Example 2 An experiment was conducted in the same manner as in Example 1 except that an equimolar amount of triphenylphosphine was used in addition to palladium acetate. As a result, the yield of 2-cyclohexen-1-one was 85%. Incidentally, precipitation of palladium was hardly observed during the reaction.

Example 3 A reaction was carried out in the same manner as in Example 2 except that the compounds shown in Table 1 were used as starting materials. Results first
Shown in the table.

Example 4 A reaction was carried out according to Example 2 except that palladium acetylacetonate was used in place of palladium acetate, and almost the same results as in Example 2 were obtained.

Example 5 A reaction was carried out according to Example 2 except that tris(dibenzyriteneacetone) dipalladium (0) was used in place of palladium acetate, and almost the same results as Example 2 were obtained.

Patent applicant Nippon Shichion Co., Ltd.

Claims (1)

[Claims] 1 General formula [0 (wherein R, , R, , R, and R4 are hydrogen or hydrocarbon residues, X represents a trihydrocarbylsilyl group,
R, , R, , R, and R6 may be chain-like or each may form a ring in any combination) and an allyl type carbonate ester of a platinum group metal compound. A method for using an α,β-unsaturated unsaturated nilbonyl compound represented by the general formula [II] (wherein R, , R, , R′, and R4 are the same as above), which is characterized in that the compound is brought into contact with the α,β-unsaturated unsaturated nilbonyl compound in the presence of 2. The above-mentioned general method, characterized in that the alkenylsilyl ether represented by the general formula [I] and the allyl carbonate ester are brought into contact with a catalyst consisting essentially of (, 1, a platinum group metal compound, and a (bl monodentate ligand). A method for producing an α, β-, β-carbonyl compound represented by formula (II).