JPS6332050B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel method for producing hydroxy compounds. Conventionally, methods for producing alcohol compounds, which are an example of hydroxy compounds, include, for example, a method of reacting an olefin compound with sulfuric acid (hydration of an olefin compound) or hydroboration of an olefin, and the resulting organic compound is A method of oxidizing an elementary compound using hydrogen peroxide is known. However, although the former method described above has the advantage of being economically superior for the synthesis of general alcohol compounds, there are various restrictions on the reaction conditions (reaction conditions are harsh), and the types of olefin compounds that can be applied are limited. The disadvantage is that it is limited. Furthermore, the latter method has the disadvantage that boron hydride, which is the starting material used here, tends to react with water and must be handled with great care. The present inventors previously proposed a method for producing an alcohol compound that eliminates the above-mentioned drawbacks, as shown by the general formula K ₂ [RSiF ₅ ] (where R represents a substituted or unsubstituted monovalent hydrocarbon group). The inventor proposed a method of reacting a silicon compound with 3-chlorobenzoyl peroxide (see Japanese Patent Application Laid-Open No. 112801/1982), but after further intensive research, the present invention was completed. That is, the present invention provides organotrifluorosilane and 3-chlorobenzoyl hydroperoxide in a solvent selected from the group of dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide, or a mixed solvent of tetrahydrofuran and hexamethylphosphoric triamide. The present invention relates to a method for producing a hydroxy compound, characterized in that the reaction is carried out in the presence of one species or two or more species. The reaction according to the method of the present invention proceeds easily at room temperature, and the desired hydroxy compound can be obtained in high yield.
In particular, primary alcohol compounds can be advantageously obtained. Furthermore, the method of the present invention can also be applied to the production of aldehyde and ketone compounds as described below. This is because once an alcohol compound is produced, it undergoes tautomerism according to the following formula, as is generally well known. Conventionally, various methods for producing aldehyde and ketone compounds have been known, but there are few techniques for directly producing them from olefin compounds, and only a few methods using ozone are known. However, in this method, the double bond is broken, resulting in an aldehyde compound with one less carbon atom than the starting material, and in the case of cyclic compounds, a ring-opening reaction occurs, resulting in a final product with a cyclic structure. The problem is that even if you aim for it, you can't get it. On the other hand, in the case of using a compound having a trifluorosilyl group at the end of the molecule used as the starting material in the present invention and a structure in which the organic group has an aliphatic unsaturated bond, the starting material and the carbon atom Aldehyde compounds with the same number are obtained in high yields, and in the case of internal olefins, ketone compounds are obtained, in which the carbon atom to which the trifluorosilyl group is attached is converted into a carbonyl group, and the carbon atom at the other position is Even if there is a double bond in the reaction, the reaction proceeds without being affected. Therefore, the compounds obtained by the present invention are highly selective and are expected to be applied to the synthesis of physiologically active natural products and pharmaceuticals. The method of the present invention will be explained in detail below. First, organotrifluorosilane, which is used as a starting material in the present invention, can be represented by, for example, the general formula R'SiF ₃ (where R' represents a monovalent hydrocarbon group). R' in the formula includes an alkyl group such as a methyl group, an ethyl group, a propyl group, or a butyl group, an alkenyl group such as a vinyl group or an allyl group, an aryl group such as a phenyl group or a tolyl group, and an aralkyl group such as a benzyl group. Examples include groups in which some or all of the hydrogen atoms of these groups are substituted with halogen atoms or organic groups. Such organotrifluorosilane can be obtained, for example, by a method in which a corresponding halogenosilane is treated with a fluoride such as hydrogen fluoride, antimony trifluoride, or zinc fluoride, or by a method in which a chlorosilane and a fluorinated silane, which were previously proposed by the present inventors, are used. It can be easily obtained by a method of reacting with copper. Organotrifluorosilanes that can be used in the present invention include, for example, C ₈ H ₁₇ SiF ₃ PhCH ₂ CH ₂ SiF ₃ PhMe ₂ CCH ₂ SiF ₃ PhSiF ₃ (E)-C ₆ H ₁₃ CH=CHSiF ₃ (E)-PhCH=CHSiF ₃ (However, in the above formula, Me represents a methyl group and Ph represents a phenyl group. The same applies hereinafter). Next, in the present invention, 3-chlorobenzoyl hydroperoxide is used as a starting material together with the above silane.

[Formula] is a conventionally known compound, but in the present invention it is essential that the chlorine atom is bonded to the 3-position (m-position). Further, specific examples of the aprotic polar solvent used in the method of the present invention include dimethylformamide, N-methylpyrrolidone, and hexamethylphosphoric acid triamide, but in the present invention, a mixed solvent consisting of two or more of these solvents is used. can also be used. Further, a mixed solution of tetrahydrofuran and hexamethylphosphoric triamide can also be used as the solvent in the present invention in the same manner as above. As mentioned above, in the method of the present invention, organotrifluorosilane and 3-chlorobenzoyl hydroperoxide are reacted in the presence of an aprotic polar solvent, but the ratio of the silane and peroxide used is almost negligible. It may be equimolar. In addition, a wide temperature range can be adopted as the reaction temperature, but for example, when the organic group in the organotrifluorosilane is saturated, 0 to 80
°C, preferably room temperature; if the organic group in the silane has an aliphatic unsaturated bond, a side reaction of oxidation may occur, so it is generally carried out at a low temperature. Specifically, -30 to -70℃ (preferably -
It is recommended that the temperature range be around 50°C. The general formula for the reaction according to the present invention is as follows. In this case, R′ is C ₈ H ₁₇ SiF ₃ , PhSiF ₃ or
When it does not have an aliphatic unsaturated bond such as PhCH ₂ CH ₂ SiF ₃ , it exists as a hydroxy compound as it is, but if R′ is C ₆ H ₁₃ CH=CHSiF ₃ or When the alcohol compound has an aliphatic unsaturated bond organic group such as Isolated as a ketone and alcohol compound. Next, examples of the present invention will be given. Example 1 Octyltrifluorosilane (C ₈ H ₁₇ SiF ₃ ) and 3-chlorobenzoi hydroperoxide

4 at room temperature in the presence of dimethylformamide, N-methylpyrrolidone, hexamethylphosphoric triamide, or a mixture of tetrahydrofuran and hexamethylphosphoric triamide (1:1) as shown in Table 1 below.
After reacting for ~6 hours, octanol (C ₈ H ₁₇ OH) was obtained in the yield shown in the same table. As a comparative example, Table 1 also shows the yield when benzene, nitrobenzene, dioxane, propylene carbonate, diethyl ether, tetrahydrofuran, or a mixture (1:1) of diethyl ether and dimethylformamide was used as the solvent. Example 2 Experiment 1 2-phenylethyltrifluorosilane 580mg
(3.05 mmol) in dimethylformamide (15 ml), 617.3 mg (3.33 mmol) of 3-chlorobenzoyl hydroperoxide (purity 93%) was added as a solid under ice cooling. cloudy). When no heat generation was observed, the mixture was cooled to room temperature, stirred for 4 hours, and then a 1:1 mixture of ether and water was added to carry out a hydrolysis reaction. The aqueous layer was then extracted three times with ether, the ether layers were combined, washed with a sodium thiosulfate solution and a sodium bicarbonate solution, and then dried over sodium sulfate. When the ether was distilled off and distilled using a Kugelrohr, 301 mg of 2-phenylethyl alcohol was obtained.
(2.47 mmol) was obtained (yield 81%). The product was identified by comparison with the standard. ¹ HNMR (100MHz, CCL ₄ , TMS standard), δ2.86 (t, j = 7.5Hz, CH ₂ ), 3.84 (t, j = 7.5
Hz, CH ₂ ), 3.93 (s, OH), 7.4-7.7 (m, C ₆ H ₅ ) Experiments 2-5 The following second organotrifluorosilane
The treatment was almost the same as in Experiment 1 above, except that the types of compounds shown in the table were used and the reaction times were set as shown in the table. Enylpropanol or 2-norbornyl alcohol was synthesized, respectively. The yields of these products were determined and the results are shown in Table 2 below. Experiment 6 (E)-1-octenyltrifluorosilane 796mg
(4.06 mmol) in dimethylformamide (20 ml) was cooled to -50°C in a nitrogen gas atmosphere, and 3-chlorobenzoyl hydroperoxide was added to the solution.
A solution of 778 mg (4.19 mmol) in dimethyl formaldehyde (2 ml) was added dropwise (it became cloudy upon addition). After stirring at -50°C for 1 hour, a 1:1 mixture of water and pentane was added to carry out a hydrolysis reaction at the lowest possible temperature. After extraction with pentane three times, the organic layers were combined, treated in the same manner as in Experiment 1, and distilled to obtain 424 mg (3.32 mmol) of octanal (yield: 82%). The product was identified by comparison with the standard. ¹ HNMR (100MHz, ccl ₄ , TMS) δ0.90 (t,
CH ₃ ), 1.1-1.8 (m, (CH ₂ ) ₅ ), 2.36 (d, t, j
=7 Hz and 2 Hz, CH ₂ CHO), 9.68 (t, J =
2Hz, CHO) Experiments 7-12 Use the following second organotrifluorosilane as the organotrifluorosilane.
Except for using the compounds shown in the table, the same treatment as in Experiment 6 above was carried out to obtain the types of aldehyde compounds or ketone compounds shown in the table. The yields of these compounds were investigated and the results are shown in Table 2 below.

【table】

【table】

【table】

【table】

Claims (1)

[Claims] 1 Organotrifluorosilane and 3-chlorobenzoyl hydroperoxide in one or two solvents selected from the group of dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide, or a mixed solvent of tetrahydrofuran and hexamethylphosphoric triamide. A method for producing a hydroxy compound, characterized by carrying out the reaction in the presence of the above.