JPS629191B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing homoallylic alcohol or substituted derivatives thereof. Homoallylic alcohol refers to a compound represented by the following formula: CH ₂ = CH—CH ₂ —CH ₂ —OH (A), where “homo” means:
This term refers to having one more methylene group in the same series as a certain compound (Kyoritsu Shuppan "Chemistry Dictionary" Vol. 8, p. 709). Homoallylic alcohol has _a methylene _{group ( -}
The structure corresponds to having a large number of CH ₂ --). Homoallylic alcohol or its carbon-
Homoallylic alcohol substituted derivatives having various substituents on the carbon chain are disclosed, for example, in "Chemistry Letters" published by the Chemical Society of Japan, pages 919-922 (1979) or in Japanese Patent Application Laid-open No. 102828/1983. Homoallylic alcohol is 1,3-diene, 1,
It is useful as an intermediate in the production of 3-diol, 1,4-diketone, and furan derivatives. Conventionally, in the production of homoallylic alcohol, allyl lithium, allyl copper, allyl copper,
A method is known in which an allyl metal compound such as allyl Grignard reagent or allylsilane is reacted.
However, this reaction method requires a stoichiometric amount of allyl metal compound under anhydrous conditions, but this allyl metal compound is not easy to prepare and is expensive, so it cannot be used as an industrial production method. is disadvantageous. On the other hand, it is already known that diallyltin dibromide or diallytin diiodide is produced when tin metal is reacted with allyl bromide or allyl iodide. It is known that substituted derivatives of homoallylic alcohol can be produced in good yields by reacting in tetrahydrofuran (THF) or ethers in the presence of lower alkanols such as methanol and ethanol. It is also known that di-(substituted allyl)tin dihalides having various substituents on the allyl groups of diallyltin dihalides react in a similar manner to produce substituted derivatives of homoallyl alcohol (Chemical Society of Japan). Published "Chemistry Letters" 1527
(See page 1528 (1981) and Japanese Patent Application Laid-open No. 102828/1983). Moreover, in this case, diallytin dibromide or diallytin diiodide is prepared by reacting metallic tin with allyl bromide or iodide in a THF or water-containing ether solvent, and in the same reaction system, further aldehyde or ketone is prepared. It is known that homoallyl alcohol or its substituted derivatives can be produced by a one-step reaction method in which compounds are reacted [see "Chem. Lett." 1527-1528, supra.
Page (1981); JP-A-57-102828 and “Organometallics” 2 , pp. 191-193 (1983)
Year)〕. The above one-step reaction method requires charging more than stoichiometric amount of metal tin, the price of tin is relatively high, and a large amount of tin material needs to be discharged in the post-treatment process. For these reasons, this method is not advantageous as an industrial method for producing homoallylic alcohols. On the other hand, a method is known in which homoallylic alcohols are produced by directly electrolytically reducing allyl bromide to produce the corresponding allyl anion, which is then reacted with a ketone compound [“Bull.Chem.Soc.Jpn .，
" 56 , 1791-1794 (1983)]. However, this method has a low yield and is difficult to be an industrial production method. In the above-mentioned known method, the diallyltin dihalide or di-(substituted allyl)tin dihalide used is Generally written, the following general formula () A compound represented by [wherein R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkynyl group or an aryl group, and X represents a halogen atom] be. In addition, the aldehyde or ketone to be used is generally written as the following general formula () [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkenyl group, or R ¹ and
R ² jointly represents one cycloalkyl group]
This is a carbonyl compound represented by In the above-mentioned known method of producing homoallyl alcohols by reacting the compound of formula () with the carbonyl compound of formula () in the presence of water or lower alkanol, although the detailed reaction mechanism has not yet been elucidated, the following method can be used. It is estimated that the reaction proceeds according to two reaction equations. First reaction formula Second reaction formula However, Y in the compound of formula () is a hydrogen atom when reacting in the presence of water, and is an alkyl group derived from the alkanol when reacting in the presence of a lower alkanol. In addition, when R ³ , R ⁴ , R ⁶ , and R ⁷ in the starting compound of formula () each represent a hydrogen atom, for example, the compound of formula (a) produced through the first reaction formula, The compound of formula (b) produced through the second reaction formula is
They are the same and cannot be distinguished from each other. The present inventors produced homoallyl alcohols of formulas (a) and (b) by reacting diallyltin dihalide or di-(substituted allyl)tin dihalide of formula () with a carbonyl compound of formula (). Regarding the above-mentioned known method, the production of homoallyl alcohols of formulas (a) and (b) was devised so that the tin compound represented by the estimated formula (), which is produced as a by-product during the reaction for producing homoallyl alcohols, could be reused. Research was conducted with the intention of improving overall manufacturing efficiency and reducing costs. As a result, the tetravalent tin compound of the estimated formula (), which was produced as a by-product in the homoallylic alcoholization reaction of the raw material carbonyl compound (), remains in the reaction system or is removed from the reaction system and then subjected to electrolytic reduction. and the following formula () The compound of divalent tin, which is estimated to be represented by By reacting with allyl halide shown by the formula ()
It has been shown that the reactant tin compound can be recycled and reused by converting it into diallyltin dihalide or its substituted product, that is, regenerating the compound of formula () and reacting it again with the carbonyl compound of formula (). This finding led to the completion of the present invention. That is, the gist of the present invention is that water or a lower alkanol represented by the formula () R ⁸ OH () [in the formula, R ⁸ represents an alkyl group having 1 to 5 carbon atoms] or the formula () R ⁹ COOH () [In the formula, R ⁹ represents an alkyl group having 1 to 5 carbon atoms or hydrogen] In the presence of a proton donor which is a lower alkanoic acid represented by the general formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkynyl group or an aryl group, and X represents a halogen atom] Diallyltin dihalide or di-(substituted allyl)tin dihalide and general formula () [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkenyl group, or R ¹ and
R ² jointly represents one cycloalkyl group]
By reacting with the ketone or aldehyde represented by the general formulas (a) and (b) [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the above-mentioned meanings] or a substituted derivative thereof is produced, and the above-mentioned Diaryltin dihalide or di- of formula ()
(Substituted allyl)tin dihalide is consumed in the reaction to produce homoallylic alcohols represented by formulas (a) and (b) or substituted derivatives thereof; a tin compound produced when the above reaction is completed; That is, the following formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X have the same meanings as above, and Y is a hydrogen atom when water is used as the above proton donor; When used, it is the same alkyl group as R ⁸ , and when a lower alkanoic acid is used, it is an alkanoyl group (OCR ⁹ )].A tin compound is electrolytically reduced in a solvent containing a proton donor. By doing so, the following formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X have the same meanings as above] and metal tin, and then General formula for tin compounds and metal tin () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X have the above-mentioned meanings] are reacted to form the general formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and Diallyltin dihalide or di-(substituted allyl)tin dihalide of the general formula () has the general formula () By reacting a ketone or aldehyde represented by [wherein R ¹ and R ² have the above-mentioned meanings], formulas (a) and (b) can be obtained. [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the above-mentioned meanings] or a substituted derivative thereof is produced. The above general formulas (a) and (
b) A method for producing homoallylic alcohol or a substituted derivative thereof. Examples of aldehyde or ketone compounds of the general formula () used in the method of the invention include alkyl aldehydes such as acetaldehyde, propyl aldehyde, isopropyl aldehyde, hexyl aldehyde, etc.; alkenyl aldehydes such as crotonaldehyde, acrylic aldehyde, methacryl aldehyde, citral; Cyclohexanone; 2-
Methylcyclohexanone; Benzylaldehyde;
Benzaldehyde; examples include acetone, butyl methyl ketone, acetyl pyropionic acid, benzyl methyl ketone, phenethyl methyl ketone, and the like. Diallyltin dihalide or di-(substituted allyl)tin dihalide of the general formula () used in the method of the present invention
Dihalides generally have β, γ-
It can be a dihalide derived from a diorganotin with an unsaturated hydrocarbon residue, more particularly a dihalide with various substituents (R ³ , R 4 , R ⁴ ,
R ⁵ , R ⁶ , R ⁷ ). The dihalide can be in the form of dichloride, dibromide or diiodide. Formula in the compound of general formula ()

Preferred examples of the moiety represented by the formula include alkenyl groups such as allyl group, methallyl group, crotyl group, prenyl group, α,α-dimethylallyl group, and cinnamyl group. In the method of the present invention, the proton donor to be present during the reaction between the compound of the general formula () and the compound of the general formula () includes water; or a lower alkanol of the formula (), such as methanol and ethanol. Also, lower alkanoic acids, such as acetic acid,
Alkanoic acids of the general formula () R ⁹ COOH () [in the formula, R ⁹ is an alkyl group having 1 to 5 carbon atoms or hydrogen] such as propionic acid and butyric acid can also be used as proton donors; When an acid is present, the by-produced tetravalent tin compound is expressed by the following formula: It is estimated that it is a compound represented by Inorganic acids such as sulfuric acid, hydrochloric acid, and hydrobromic acid can also be used as proton donors. Any compound may be used as long as it functions to donate protons to the carbonyl group of the aldehyde or ketone compound of general formula () in the reaction with the compound of general formula (). In the method of the present invention, the solvent used as a reaction medium in the reaction step between the compound of general formula () and the compound of general formula () may be any organic solvent that does not inhibit the electrolytic reduction reaction in the next step. Often, an organic solvent may be used alone, a mixture of two or more kinds, or a mixed solvent of water and an organic solvent may be used. Examples of organic solvents that can be used include methanol, ethanol, propanol,
Lower alkanols such as tertiary butanol, other aliphatic alcohols, lower alkanoic acids such as acetic acid, propionic acid, butyric acid and other fatty acids, ethers such as tetrahydrofuran, diethyl ether, monoglyme, diglyme, dioxane, acetone, methyl ethyl ketone , ketones such as diethyl ketone, esters such as ethyl acetate, ethyl formate, and diethyl carbonate, aliphatic nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, and methylene chloride, dichloroethane, chloroform, etc. and halogenated hydrocarbons. The amount of the solvent to be used is not particularly limited, but is generally 0.1 to 10, preferably 0.2 to 1, per mole of the compound of general formula (). Adding an acid to a reaction mixture consisting of a compound of general formula (), a compound of general formula (), and a reaction medium,
It is also possible to activate carbonyl compounds of general formula () that have low reactivity. The acids used for this activation include inorganic acids such as sulfuric acid, hydrochloric acid, hydrobromic acid, and nitric acid, or organic acids such as formic acid, acetic acid, propionic acid, and paratoluenesulfonic acid, as well as aluminum chloride, boron trifluoride, etc. Lewis acids, etc. The amount of acid used is in the range of 0.01 to 10 mol equivalent per 1 mol of carbonyl compound (),
Particularly preferred is an amount equivalent to 0.05 to 5 moles. The reaction between a compound of general formula () and a compound of general formula () can be carried out over a relatively wide range of temperatures from 10 to 100°C, but usually at room temperature, and if necessary under heating or cooling. It can be carried out. In the method of the present invention, from the beginning, diallyltin dihalide or di-(substituted allyl)tin halide of formula () prepared in advance is used to convert it into a carbonyl compound of formula () in the presence of a proton donor. However, in advance, in the reaction vessel in which the method of the present invention is to be carried out, the allyl halide or Diallyltin dihalide or di-(substituted allyl) of the formula () can be obtained by adding a precursor tin compound as described below to the substituted allyl halide and reacting it.
It is also possible to prepare tin dihalide on-site and allow it to act on the coexisting carbonyl compound of formula () to carry out the reaction for producing homoallylic alcohols of formula (a) and formula (b). Such precursor tin compounds include metal tin, divalent tin compounds such as stannous tin halides such as stannous chloride and stannous bromide, and stannous tin compounds such as tin tetrachloride and tin tetrabromide. Tin halide or tetravalent tin compounds such as diallyl-diphenyl tin can be used alone or in combination. The amount used is 0.01 to 1 mol, preferably 0.1 to 0.5 mol, per 1 mol of the carbonyl compound of formula (). As described above, the carbonyl compound of formula () and diallytin dihalide or di-
Homoallylic alcohols of formulas (a) and (b) or substituted derivatives thereof are produced in the step of reacting the (substituted allyl)tin dihalide with the proton donor compound. In the above reaction, the tin compound of the formula () undergoes chemical conversion and a tetravalent tin compound presumed to be represented by the formula () is produced as a by-product. In the conventional method, this by-produced tetravalent tin compound was simply disposed of, but in the method of the present invention, it is then electrolytically reduced and reacted with the compound of formula () to form the compound of formula (). The tin compound is regenerated and used again for reaction with the carbonyl compound of formula (). In order to recycle the above-mentioned by-produced tetravalent tin compound, the intended homoallyl alcohol products can be obtained by a conventional method from the reaction solution containing the homoallyl alcohol products of formulas (a) and (b). Collect the
At the same time, the by-produced tetravalent tin compound estimated to be represented by the above formula () is once separated, and this by-produced tetravalent tin compound is electrolytically reduced, after which the compound of formula () is produced. may be subjected to a process consisting of producing and regenerating a tin compound of formula () by the reaction of However, if the unreacted carbonyl compound of formula () remains in the above reaction solution, the reaction solution can be used as is, or if necessary, the carbonyl compound of formula () can be added to the reaction solution. Further, the reaction solution containing the by-product tetravalent tin compound can be subjected to an electrolytic reduction reaction while adding the allyl halide or substituted allyl halide of formula (). The latter operating means is simpler. Once the by-product tetravalent tin compound estimated to be represented by formula () is separated from the reaction solution,
The above electrolytic reduction step is performed by placing an organic solution of the separated and recovered by-product tetravalent tin compound between a pair of cathode and anode. In order for the electrolytic reduction to proceed, a proton donor must be present in the electrolytic reaction system, which can be water, an organic acid such as a lower alkanoic acid, or an inorganic acid, or a mixture thereof, and may be added as necessary. added or added. In order to capture the active halogenating agent generated at the anode due to the electrolytic reaction, olefins such as ethylene, propene, and cyclohexene can be used together, and the amount of this scavenger used is equal to the amount of the carbonyl compound of formula () used. The amount is equivalent to 0.1 to 100 moles per mole, preferably 1 to 5 moles. The electrodes used in the electrolytic reduction step in the method of the present invention are those commonly used in electrolytic reactions, such as gold, platinum, gold or platinum-plated titanium, nickel, tin, carbon, titanium, nickel, stainless steel, lead, etc. However, platinum, tin, stainless steel, and carbon are preferred as materials that give better results. Current density is 1~100mA/
cm ² , but from the viewpoint of current efficiency and reaction rate, 3 to 20 mA/cm ² is preferable. The theoretical amount of electricity in this electrolytic reaction is 2 faradays/mol, but in reality it is 1 to 20 faradays/mol, especially 2 to 20 faradays/mol.
A current application of 10 faradays/mole is preferred. The electrolytic reduction reaction can be carried out over a relatively wide range of temperatures from 10 to 100°C. The electrolytic tank can be used as either a single tank or an anode/cathode separated tank, and the electrolytic reaction method is as follows:
When subjected to an electrolytic reduction reaction in both continuous and batch processes, 4 of the by-products are estimated to be shown in equation ().
The valent tin compound is converted into a divalent tin compound estimated to be represented by the formula () and zero-valent tin (ie, metal tin). On the other hand, when the by-product tetravalent tin compound estimated to be represented by formula () is subjected to an electrolytic reduction reaction without separating it from the reaction solution, this reaction liquid to a pair of cathodes,
It is placed between the anodes. In this case as well, electrolytic reduction can be carried out in exactly the same manner as in the above case, but at the start of electrolytic reduction, allyl halide or substituted allyl halide of formula () can be added in advance to the reaction solution. The divalent tin compound estimated to be represented by the formula () and metal tin produced by electrolytic reduction are the allyl and metal tin of the formula () that coexist.
It immediately reacts with a halide or substituted allyl halide to re-form diallyltin dihalide or di-(substituted allyl)tin dihalide of formula (). This diallyltin dihalide or di-(substituted allyl)tin dihalide is further reacted with the carbonyl compound of formula () remaining in the reaction solution or added to form the target homoallyl of formula (a) and formula (b). Produces alcohol. In addition, the allyl halide or substituted allyl halide of the formula () above can be obtained by the reaction of the diallyltin dihalide or di-(substituted allyl)tin dihalide of the formula () with the carbonyl compound of the formula (a). The compound of formula () is added in advance to the solution in which the compound of formula () is reacted with the compound of formula () because it does not interfere with the production reaction of the homoallylic alcohol of formula (b). be able to. If added in advance in this way, the compound of formula () needs to be added later for the reaction between the divalent tin compound of formula () produced in the subsequent electrolytic reduction step and metal tin. There isn't. If desired, the process of the invention may contain a precursor tin compound as described above, such as tin metal or stannous chloride, and an allyl halide or substituted allyl halide of formula () to form a carbonyl compound of formula (). preparing a diaryltin dihalide of formula () by reacting a precursor tin compound with a compound of formula () in this solution; An operation for producing homoallylic alcohols of formulas (a) and (b) by reaction with a carbonyl compound of formula () that was previously present in a solution, and a process of producing homoallyl alcohols of formula () by-produced by this process. The operation of electrolytically reducing a tetravalent tin compound estimated to have a divalent tin compound estimated to have the formula () as an electrolytic reduction product and the allyl halide of the formula () with respect to metallic tin. An operation for regeneratively producing diallytin dihalides of the formula () through a reaction;
Formula (a), (
It is possible to carry out the operation of b) to further produce homoallylic alcohol in the same reaction vessel. In the method of the present invention, the tetravalent tin compound produced as a by-product during the reaction of the carbonyl compound of formula () with the diallyltin dihalide of formula () varies depending on the type of reaction medium, the type of reagent present, etc. Although it is difficult to accurately identify it because it is presumed to be a mixture of various tetravalent tin compounds, the compound presumed to be represented by the formula () is the main component, and this compound is However, after electrolytic reduction, it becomes a divalent tin compound and metal tin, which is estimated to be shown by the formula (),
When these are further reacted with allyl halides of formula (), diallytin dihalides of formula () can be produced regeneratively. Although the entire reaction mechanism in the method of the present invention has not been fully elucidated, in order to facilitate understanding of the method of the present invention, in the same reaction system, diallyltin, which is an example of diallytin dihalides of formula (), Examples will be used to explain how to carry out the process of the invention, including the operation of the reaction for preparing dibromide from tin metal and allyl bromide. First, a solution containing metal tin, an excess amount of allyl bromide, and an excess amount of a carbonyl compound (2) is prepared, and the solution is stirred to cause a reaction. In this case, metal tin first reacts with allyl bromide in the reaction system (at this stage, the carbonyl compound () does not participate in the reaction) to form diallyltin dibromide, which then reacts with the carbonyl compound () in solution. ) to give the desired homoallylic alcohols (a) and (b) in the reaction solution. 4 that was produced as a byproduct at this time
When a reaction solution containing a valent tin compound () and a homoallylic alcohol is subjected to an electrolytic reduction operation,
The tetravalent tin compound ( ) is reduced to a divalent tin compound ( ) and metal tin. Divalent tin compound ()
and metal tin immediately react with unreacted residual allyl bromide in the same reaction solution to regenerate diallytin dibromide.
A cyclic preparation system for dibromide is established, and this regenerated diallyltin dibromide reacts with the remaining carbonyl compound () in the same solution to produce homoallyl alcohols (a) and (b) again.
will be generated. As is clear from the above explanation, the present invention enables the production of homoallylic alcohols by electrolytically reducing the tetravalent tin compound () produced in the reaction to produce homoallylic alcohols in the same reaction system without discharging it outside the reaction system. We have established a technology to regenerate the reactant tin compound () by reacting it with a tin compound () and metal tin, and then reacting it with allyl halides of the formula (), and recycling and using the tin to convert homoallyl from carbonyl compounds. This invention makes it possible to produce alcohols, and is an extremely significant invention industrially. EXAMPLES The present invention will be explained below using Examples, but the present invention is not limited by the Examples. Example 1 (a) Metal tin powder (0.089g,
0.75 mmol), allyl bromide CH ₂ =CHCH ₂ Br
(3.628 g, 30 mmol) and methanol (3.628 g, 30 mmol)
ml) and glacial acetic acid (0.75 ml).
The mixture is stirred at room temperature for 2 hours until the metal tin powder is dissolved to prepare diallyltin dibromide. (b) The reaction solution containing diallytin dibromide and unreacted allyl bromide thus produced was transferred to a 30 ml branched test tube, and benzaldehyde (0.796
g, 7.5 mmol) and cyclohexene (as scavenger for the active halogenating agent) (2.481 g, 30
1-phenyl-3-buten-1-ol is produced by the reaction between diallytin dibromide and benzaldehyde. After attaching a pair of platinum electrodes (2 cm x 1.5 cm) inside the reaction solution without separating this compound, 50 mA was applied while keeping the temperature at 50 °C.
Electrolysis is carried out for 21 hours at a constant current density of (16.7 mA/cm ² ). This electrolytic operation causes an electrolytic reduction reaction that produces a divalent tin compound and metal tin. Also, during this electrolytic operation, diallyltin is produced by the reaction of divalent tin compounds and metal tin with allyl bromide.
The regeneration reaction of dibromide and the reaction of 1-phenyl-3-buten-1-ol by reaction of the regenerated diallyltin dibromide with benzaldehyde also proceed. After the electrolysis is completed, the reaction solution is neutralized with a saturated NaHCO ₃ aqueous solution, and the precipitate is removed by suction. After distilling off the solvent under reduced pressure, the solution is extracted three times with a mixed solvent of hexane and acetic acid (3:1), washed once with a saturated aqueous NaCl solution, and then dried over anhydrous Na ₂ SO ₄ . Subsequently, the solvent was distilled off under reduced pressure and the crude product was purified by silica gel column chromatography, resulting in the target compound corresponding to the target homoallylic alcohols of formula (a) and formula (b) of the method of the present invention as shown below. 1-phenyl-3-buten-1-ol represented by is obtained in a yield of 90.7% (0.968 g). For comparison, when the above electrolysis was omitted, the yield of the target compound decreased to 10% or less. Example 2 Benzaldehyde (0.796
g, 7.5 mmol), allyl bromide (3.628 g, 30 mmol), tin metal powder (0.089 g, 0.75 mmol) and cyclohexene (2.481 g, 30 mmol) in distilled methanol (3 ml) and glacial acetic acid (0.75 mmol).
ml) of mixed solvent and stir at room temperature for 2 hours. At this time, a reaction for preparing diallytin dibromide occurs in the same manner as in Example 1, and a reaction for producing 1-phenyl-3-buten-1-ol by the reaction of the produced diallytin dibromide with benzaldehyde. It also happens. Next, without separating the produced 1-phenyl-3-buten-1-ol, a pair of platinum electrodes was attached to the above-mentioned branched test tube containing the reaction solution containing this compound, and the temperature was heated to 50 to 55 °C. Electrolyze by applying current at a constant current of 50mA for 21 hours (5.2F/mol). During this electrolytic operation, as in Example 1, electrolytic reduction reaction and regeneration reaction of diallytin dibromide, and reaction of regenerated diallytin dibromide with benzaldehyde to produce 1-phenyl-3-butene. An additional production reaction of -1-ol proceeds. After the electrolysis was completed, the reaction solution was neutralized with saturated NaHCO ₃ aqueous solution, and the precipitate was removed by suction.
Concentrate the liquid under reduced pressure. The residual liquid was extracted three times with a mixed solvent of hexane-ethyl acetate (1:1), and the organic layer was washed once with saturated brine, and then extracted with anhydrous Na ₂ SO ₄
Dry with. The solvent was distilled off under reduced pressure and the product was purified using a silica gel column to produce 1-phenyl-3-buten-1-ol as a colorless oil.
Obtain 0.968 g (yield 91%). Example 3 Benzaldehyde (0.796
methanol (3 ml) and glacial acetic acid (0.75 ml). Dissolve in mixed solution. Then, stir at room temperature for 2 hours. At this time, as in Examples 1 and 2, a reaction for producing diallytin dibromide and a reaction for producing 1-phenyl-3-buten-1-ol also occur. Next, the generated 1-phenyl-3-butene-1
- Attach a pair of platinum electrodes (2 cm x 1.5 cm) to the test tube containing the reaction solution containing ol and conduct electrolysis at a constant current density of 50 mA (16.7 mA/cm ² ) for 26 hours while maintaining the temperature at 50°C. (Electricity 6.5F/mol). During this electrolytic operation, reactions similar to those in Example 2 proceed. After the electrolysis is completed, the reaction solution is neutralized with a saturated NaHCO ₃ aqueous solution, and the precipitate is removed by suction. After distilling off the solvent under reduced pressure, the solution is extracted three times with a mixed solvent of hexane and ethyl acetate (3:1), washed once with a saturated aqueous NaCl solution, and then dried over anhydrous Na ₂ SO ₄ . Subsequently, the solvent was distilled off under reduced pressure, and the crude product was purified by silica gel column chromatography.
Yield of 1-phenyl-3-buten-1-ol: 95
% (1.05g). Example 4 Benzaldehyde (0.796
methanol (3 ml) and water (0.5 ml). Dissolve in solution. Then, stir at room temperature for 2 hours. At this time, as in Examples 1 and 2, a reaction for producing diallytin dibromide and a reaction for producing 1-phenyl-3-buten-1-ol occur. Next, the generated 1-phenyl-3-butene-1
-A pair of platinum electrodes (2 cm x 1.5 cm) were attached to the test tube containing the skin reaction solution containing ol, and electrolysis was carried out at a constant current density of 50 mA (16.7 mA/cm ² ) while maintaining the temperature at 50°C. Runs for 22.3 hours (electricity consumption 5.6F/
mole). During this electrolytic operation, reactions similar to those in Examples 1 and 2 proceed. After the electrolysis is completed, the reaction solution is neutralized with a saturated NaHCO ₃ aqueous solution, and the precipitate is removed by suction. After distilling off the solvent under reduced pressure, hexane-ethyl acetate (3:
1) Extract three times with a mixed solvent, wash once with a saturated NaCl aqueous solution, and dry with anhydrous Na ₂ SO ₄ . Subsequently, the solvent was distilled off under reduced pressure and the crude product was purified by silica gel column chromatography.
-Phenyl-3-buten-1-ol yield 96%
(1.078g). Example 5 Hexyl methyl ketone CH ₃ in a 30 ml test tube
(CH ₂ ) ₅ COCH ₃ (0.962 g, 7.5 mmol), tin powder (0.178 g, 1.5 mmol), allyl bromide (3.628
g, 30 mmol), cyclohexene (1.24 g, 15
mmol) and dissolve it in a mixed solution of methanol (3 ml) and acetic acid (1.5 ml). Then, stir at room temperature for 2 hours. At this time, the production reaction of diallyltin dibromide occurs as in Examples 1 and 2. The reaction between the produced diallyltin dibromide and hexyl methyl ketone also causes a reaction to produce a homoallyl alcohol derivative represented by the following formula. Next, the following formula generated as the desired product A pair of platinum electrodes (2 cm x 1.5
cm) installed at 50mA while keeping the temperature at 50℃
Electrolysis is carried out for 44.7 hours at a constant current density of (16.7 mA/cm ² ) (electricity 11.2 F/mol). During this electrolytic operation,
Reactions proceed in the same manner as in Examples 1-2. After the electrolysis is completed, the reaction solution is neutralized with saturated NaHCO ₃ aqueous solution, and the precipitate is removed by suction. After distilling off the solvent under reduced pressure, the solution is extracted three times with a mixed solvent of hexane and ethyl acetate (3:1), washed once with a saturated aqueous NaCl solution, and then dried over anhydrous Na ₂ SO ₄ . Subsequently, the solvent was distilled off under reduced pressure and the crude product was purified by silica gel column chromatography to obtain the target compound in a yield of 67% (0.855 g). Example 6 Benzaldehyde (0.796
g, 7.5 mmol), tin powder (0.089 g, 0.75 mmol), crotyl bromide CH ₃ --CH ₂ =CH ₂ --CH ₂ Br
(1.519 g, 11.25 mmol) and cyclohexene (0.930 g, 11.25 mmol) were dissolved in a mixed solution of methanol (3 ml) and acetic acid (0.75 ml).
Then, stir at room temperature for 2 hours. At this time, a reaction occurs to produce dicrotyltin dibromide,
Also, a compound represented by the following formula obtained by the reaction of dicrotyltin dibromide and benzaldehyde
A reaction that produces (a) and compound (b) also occurs. Next, the generated formula Compound (a) represented by 1-phenyl-2-
Methyl-3-buten-1-ol (corresponding to the homoallyl alcohol represented by formula (b) among the target products of the method of the present invention) and the following formula Compound (b) represented by 1-phenyl-3-
Contains a reaction solution containing penten-1-ol (corresponding to the homoallyl alcohol represented by formula (a)) (the production ratio of compound (a) and compound (b) is approximately 1:1). A pair of platinum electrodes (2 cm
x 1.5cm) while maintaining the temperature at 50℃.
Electrolysis is carried out for 31 hours at a constant current density of 50 mA (16.7 mA cm ² ). During this electrolytic operation, various reactions proceed in the same manner as in Example 1. After the electrolysis is completed, the reaction solution is neutralized with a saturated NaHCO ₃ aqueous solution, and the precipitate is removed by suction. After distilling off the solvent under reduced pressure, hexane-ethyl acetate (3:
1) Extract three times with a mixed solvent, wash once with a saturated NaCl aqueous solution, and then dry with anhydrous Na ₂ SO ₄ . Subsequently, the solvent was distilled off under reduced pressure and the crude product was purified by silica gel column chromatography to obtain compounds (a) and (b) in a total yield of 42.6% (0.520 g). Example 7 The procedure of Example 2 was repeated using cyclohexanone (7.5 mmol) instead of benzaldehyde. However, the amount of electricity applied during the electrolytic operation was 6.0F/mol. The following formula 1-hydroxy-1-allyl-cyclohexane was obtained in a yield of 68%. Example 8 Crotonaldehyde in a 30ml test tube with a branch
CH ₃ CH=CH—CHO (0.5257 g, 7.5 mmol)
(For stability, a commercial product containing 10% water was used), tin powder (0.089 g, 0.75 mmol), allyl bromide (1.814 g, 15 mmol), and cyclohexene (0.930 g, 11.25 mmol). and dissolve in a mixed solution of methanol (3 ml) and glacial acetic acid (0.75 ml). Then, stir at room temperature for 2 hours. On this occasion,
As in Example 2, the reaction for producing diallytin dibromide occurs. Furthermore, the reaction between the produced diallyltin dibromide and crotonaldehyde causes a reaction to produce homoallyl alcohols represented by the following formula. Next, the generated following formula CH ₃ -CH=CH-CH(OH)-CH ₂ -CH=
A pair of platinum electrodes (2 cm x 1.5 cm) were attached to the test tube containing the reaction solution containing α-propenyl homoallyl alcohol represented by CH ₂ and the temperature was adjusted to room temperature (approx.
Electrolysis is carried out for 18 hours at a constant current density of 50 mA (16.7 mA/cm ² ) while maintaining the temperature (electricity: 4.5 F/mol). During this electrolytic operation, various reactions proceed as in Example 2. After the electrolysis is completed, the reaction solution is neutralized with a saturated NaHCO ₃ aqueous solution, and the precipitate is removed by suction. After distilling off the solvent under reduced pressure, hexane-ethyl acetate (5:
1) Extract three times with a mixed solvent, wash once with a saturated aqueous NaCl solution, and then dry with anhydrous Na ₂ SO ₄ . Subsequently, the solvent is distilled off under reduced pressure and the crude product is purified by silica gel column chromatography to obtain the desired homoaryl alcohol derivative of the above formula in a yield of 42.2% (0.357 g).

Claims (1)

[Scope of Claims] 1. Water or a lower alkanol represented by the formula () R ⁸ OH () [in the formula, R ⁸ represents an alkyl group having 1 to 5 carbon atoms] or the formula () R ⁹ in an organic solvent. In the presence of a proton donor which is a lower alkanoic acid represented by COOH () [wherein R ⁹ represents an alkyl group having 1 to 5 carbon atoms or hydrogen], the general formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkynyl group or an aryl group, and X represents a halogen atom]・Dihalide or di-(substituted allyl)tin dihalide and general formula () [In the formula, R ¹ and R ² each represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an aryl group, or an alkenyl group, or R ¹ and
R ² jointly represents one cycloalkyl group]
By reacting with the ketone or aldehyde represented by the general formulas (a) and (b) [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the above-mentioned meanings] or a substituted derivative thereof is produced, and the above-mentioned Diaryltin dihalide or di- of formula ()
(Substituted allyl)tin dihalide is consumed in the reaction to produce homoallylic alcohols represented by formulas (a) and (b) or substituted derivatives thereof; a tin compound produced when the above reaction is completed; That is, the following formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X have the same meanings as above, and Y is a hydrogen atom when water is used as the above proton donor; When used, it is the same alkyl group as R ⁸ , and when a lower alkanoic acid is used, it is an alkanoyl group (OCR ⁹ )].A tin compound is electrolytically reduced in a solvent containing a proton donor. By doing so, the following formula () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X have the same meanings as above] and metal tin, and then General formula for tin compounds and metal tin () [In the formula, R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and X have the above-mentioned meanings] are reacted to form the general formula () The diallyltin dihalide or di-(substituted allyl)tin dihalide represented by [wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and Diallyltin dihalide or di-(substituted allyl)tin dihalide of the general formula () has the general formula () By reacting a ketone or aldehyde represented by [wherein R ¹ and R ² have the above-mentioned meanings], formulas (a) and (b) can be obtained. [In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ⁷ each have the above-mentioned meanings] or a substituted derivative thereof is produced. The above general formulas (a) and (
A method for producing homoallylic alcohol or a substituted derivative thereof shown in b). 2 General formula () A ketone or aldehyde represented by [wherein R ¹ and R ² have the above meanings] and the general formula () The reaction with diallyltin dihalide or di-(substituted allyl)tin dihalide represented by [wherein R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and The method according to claim 1, wherein the method is carried out either in the same electrolytic cell as the one in which the electrolytic reduction reaction of the tin compound (2) is carried out or in a separate reaction tank.