JPH02188577A - Production of propargylfurancarbinols - Google Patents

Abstract

PURPOSE:To advantageously obtain the title compound useful as an intermediate for agricultural chemicals, drugs, etc., without using propargyl bromide, etc., having self decomposition properties and requiring policy of safety by using a haloallylfurancarbinol as a raw material and reacting the haloallylfurancarbinol with a base in a solvent. CONSTITUTION:A haloallylfurancarbinol shown by formula I (R1 is H or methyl; R2 is Cl, Br or I) as a raw material is reacted with a base such as n-butyllithium or sodium methoxide in a solvent at -70 deg.C-120 deg.C to give a compound shown by formula II. The amount of the base used is usually 1-15 equivalent, especially 1-10 equivalent based on the compound shown by formula I. The solvent differs according to the base used. When an organic lithiun or an alkali metal amide is used, tetrahydrofuran or n-pentane is used as the solvent and when alkali metal is used, ethyl ether or methanol is used as the solvent. The amount of the solvent (except water) used is 1-20 pts.wt. based on 1 pt.wt. of the raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing propargylfurancarbinols useful as intermediates for agricultural chemicals, medicines, and the like.

<Prior art> As a method for producing propargyl furan carbinols represented by the general formula (I) H (wherein R1 represents a hydrogen atom or a methyl group), for example, propargyl bromide or propargyl chloride and furfural are used. A method for obtaining it by Grignard reaction is known (Japanese Patent Application Laid-Open No. 118780/1983).

However, since propargyl bromide and propargyl chloride have self-degrading properties, measures to suppress their self-degrading properties (
The above production method was not necessarily an industrially advantageous method, as there were problems such as the need for safety measures.

<Problems to be Solved by the Invention> In view of the above, the present inventors have intensively investigated a method for producing propargylfurancarbinols (I) that does not use propargyl bromide or propargyl chloride, and as a result, have arrived at the present invention. Ta.

Means for Solving the Problems> The present invention provides a haloallylfurancarbinol represented by the general formula (wherein, R1 has the same meaning as above, and R represents a chlorine, bromine, or iodine atom). This is a method for producing propargylfurancarbinols (I), which is characterized by dehydrohalogenating propargyl furancarbinols by reacting them with a base in a solvent.

The present invention will be explained in detail below.

The base used in the present invention is n-butyllithium, S-
Organolithiums such as butyllithium, t-butyllithium-benzyllithium, allyllithium, vinyllithium, phenyllithium, methyllithium, sodium amide, lithium bisdo, lithium diisopropylamide, lithium dicyclohexylamide, lithium bis(trimethylsilyl)amide, etc. alkali metal amides, alkali metals such as lithium, sodium, and potassium; alkali metal alcolades such as sodium methoxide and potassium t-butoxide; lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, and calcium hydroxide. , alkali metal or alkaline earth metal hydroxides such as barium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, magnesium carbonate, calcium carbonate, barium carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, bicarbonate Examples include carbonates of alkali metals or alkaline earth metals such as magnesium, calcium hydrogen carbonate, barium hydrogen carbonate, and mu.

The amount of the base used is usually 1 to 15 times the amount of haloallylfurancarbinol, more preferably 1 to 10 times the amount of haloallylfurancarbinol.

The reaction solvent varies depending on the base used. When using organolithiums or alkali metal amides, a hydrophilic aprotic solvent such as tetrahydrofuran or dioxane or a hydrophobic solvent such as n-pentane, n-hexane, n-hebutane, benzene, toluene or xylene. A single solvent or a mixture of solvents which are inert to the reaction may be used. When using alkali metals, liquid ammonia is used. When using alkali metal alcoholades, hydrophobic or hydrophilic ethers such as ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, diglyme, triglyme, etc.
-pentane, n-hexane, n-hefuran, benzene,
Hydrophobic hydrocarbons such as toluene and xylene, alcohols such as methanol, ethanol, propatool and butanol, hydrophobic halogenated hydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, chlorobenzene and dichlorobenzene, pyridine, A main group such as triethylamine, a hydrophilic aprotic solvent such as acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N-methylpyrrolidone, and mixtures thereof are used. Furthermore, ketones such as a7tone, methyl ethyl ketone, and methyl isobutyl ketone, and mixtures thereof may also be used as long as the solvent does not participate in the reaction.

When using an alkali metal or alkaline earth metal hydroxide or an alkali metal or alkaline earth metal carbonate, the reaction solvent is water or water in addition to the solvents exemplified for alkali metal alcoholades. Mixtures of these exemplary solvents are used, preferably water and hydrophobic hydrocarbon hot media such as toluene, xylene, pentane or hexane or water and hydrophobic halogenated hydrocarbon solvents such as monochlorobenzene or dichlorobenzene. used.

The amount of the solvent other than water to be used is not particularly limited, but is usually 1 to 20 times the weight of the haloallylfurancarbinol. When water is used as a solvent, the amount of water used is 1 to 4 times the weight of the alkali metal or alkaline earth metal hydroxide or carbonate.

The reaction temperature is usually -70°C to 120''C, and the reaction time is not particularly limited, and the end point of the reaction can be taken as the point at which the raw material haloallylfurancarbinol (2) disappears from the reaction system.

A phase transfer catalyst can be added if necessary, and the amount used is usually 0 for haloallylfurancarbinol blood.
．． 01 to 5 times the equivalent.

Such phase transfer catalysts include tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-pentylammonium bromide, tetra-n-pentylammonium iodide, benzyltriethylammonium chloride, benzyltriethylammonium bromide. , organic quaternary ammonium salts such as benzyltripropylammonium chloride, benzyltripropylammonium iodide, cetyltrimethylammonium chloride, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, benzyltriphenylphosphonium chloride, etc. Organic quaternary phosphonium salt, 18-crown-6,15-crown-5,12-
Examples include macrocyclic ethers such as Crown-4.

After completion of the reaction, propargylfurancarbinols (I) can be removed from the reaction mixture by, for example, water injection, extraction, liquid separation, etc., and then distillation of the organic layer.

Haloallylfurancarbinols (■), which are raw material compounds, are combined with furfurals represented by the general formula (wherein, R1 has the same meaning as above) and general formula (X-CH2-C=CHg 1) (formula Wherein, X represents a chlorine, bromine or iodine atom.R
1 has the same meaning as above. ) can be produced by reacting the dihalides shown in the following in the presence of zinc in a reaction solvent containing water as the main solvent.

As for dihalides, 2.8-dichloro-1-propene, 2.8-dibromo-1-propene, 2.8-short-1-propene, 2-chloro-8-bromo-1-
Propene, 2-chloro-8-iodo-1-propene, 2
-bromo-8-chloro-1-propene, 2-bromo-8
-iodo-1-propene, 2-iodo-8-chloro-1
-propene, 2-yo)'-8-bromo-1-propene.

The amount of these dihalides ((t)) used is usually 1 to 8 times the equivalent of the furfural.

Zinc can be used in various commercially available forms, preferably in the form of powder or fine particles, and particularly preferably in the form of powder.

The amount of zinc used is from 0.8 to furfural (2)
It is 8 times by weight, more preferably 1.1 to 1.5 times by weight.

Ammonium halides such as ammonium chloride, ammonium bromide, ammonium iodide, etc. are used as necessary, and the amount used is 0.15% based on the furfurals (2).
~65~6 weight.

As the reaction solvent, a mixture of water, tetrahydrofuran, dioxane, toluene, benzene, monochlorobenzene, ethylene dichloride, etc., or water alone is used, and in the case of a mixture, water must be the main solvent.
More preferably, the composition of water in the mixture is 50% by weight or more.

The absolute amount of water in the reaction solvent is usually 8 to 24 times the weight of the furfural (2), more preferably 4 to 19 times the weight of the furfural (2).
It is twice the weight.

In this reaction, a phase transfer catalyst can be added if necessary, and the amount used is usually 0.05 to 0.4 times the weight of furfural.

Specific examples of such phase transfer catalysts include the above-mentioned organic quaternary ammonium salts.

The reaction temperature is 0°C to 100°C, more preferably 1
The temperature is 5°C to 50°C.

The reaction time is usually 1 to 8 hours, but can be shortened by adding a small amount of acid. Such acids include acetic acid,
Examples include hydrochloric acid and sulfuric acid.

The amount of acid added is 5% by weight or less for acetic acid, and 0% for hydrochloric acid or sulfuric acid, expressed as a concentration relative to water Iζ in the reaction solvent.
．． A suitable amount is 1% by weight or less.

After completion of the reaction, the haloallylfuran carbinols 0 can be removed from the reaction mixture by, for example, filtration, separation, and then distillation of the organic layer.

<Effects of the Invention> Thus, according to the present invention, propargylfurancarbinols represented by the general formula (I) can be produced safely and industrially advantageously.

<Example> The present invention will be explained below with reference to Examples.

Example 1 5-Methylfurfural20. Of, Wed 88f.

Prepare toluene 881 and zinc powder 26f 88-85
2,8-dichloro-1-propene 4 under stirring, kept at °C.
4.4F was added dropwise over 20 minutes and kept at 88-85°C for 4 hours. After the reaction is completed, the crystals derived from the zinc dust are separated from P, 66f of toluene is added to the P solution, and the toluene layer is separated. 7%
After washing with 80F sodium carbonate water and 50F water,
Toluene is distilled off at a temperature below 60°C. Perform simple distillation,
5-Methyl-furyl 2'-chloroallylcarbinol of 80.5F was obtained.

Boiling point 84-b Yield 90% NMR data (CDC1 Karasu, internal standard TMS, δ value)
2.27 (8,8H) 2.75-2.92 (m, 2H) 4.9 5
(dd, IH) 5.25 and 5.26 (S, 2H) 5.8 9 (d, IH) 6.18 (d, IH) 5-Methyl-furyl 2'-chloroallylcarbinol obtained above ! 2. Jll, 50% sodium hydroxide42.
A mixture of 8F, 87f of toluene and 15.1y of benzyltriethylammonium chloride was stirred at 40°C for 8 hours. After extraction by adding 100 f of toluene and 100 f of water, the mixture is separated. After washing the organic layer with 5% hydrochloric acid and then with 7% aqueous sodium carbonate, the organic layer was concentrated under reduced pressure.

The residue was subjected to simple distillation to obtain 5-methyl-furylpropargylcarbinol 7,861.

Boiling point 74℃/0.7 mHj Yield 79.2% NMR data (CDC4m, internal standard TMS, δ value)
2.08 (t, IH, J=2.6Hz)2.2
5 (d, 3)1. J=1. OHz)2.70
(dd, 2H, J=6.6.2.6H2)2.89(b
r8. IH) 4.76 (t, IH, J=6.6Hz) 5.8
8 (dq, IH, J = 8.8.1.0Hz) 6.17 (
d, LH, J = 8.8 Hz) Example 2 Furylpropargyl carbyl can be obtained by carrying out the reaction, post-treatment, and purification in the same manner as in Example 1 except for using furfural 17.5 f instead of 5-methylfurfural 20.0 y. Nol is obtained.

Example 8 A mixture of 12.8 F of 5-methyl-furyl 2'-chloroallyl carbinol, 42.8 F of 50% sodium hydroxide, 871 F of toluene and 21.8 F of tetra-n-butylammonium bromide was prepared at 40°C. Stir for hours.

Thereafter, the same operation as in Example 1 was performed to obtain 7.941 of 5-methyl-furylpropargyl carbinol. yield
80.0% Example 4 Frill 2' chloroallyl carbinol 20.011
40% potassium hydroxide 9'r, 4f, hexane 409 and trioctylmethylammonium bromide 2B, 1
The mixture of f was stirred at room temperature for 24 hours.

Thereafter, the same operation as in Example 1 was performed to obtain furylpropargyl carbinol 1B-Of.

Yield 82.8% Example 5 A mixture of 5-methyl-furyl 2'-chloroallyl carbinol 42, 9F and toluene 10F is stirred at 80°C for 5 hours. The organic layer is separated, washed with water, and concentrated under reduced pressure.

Simple distillation of the resulting residue yields 5-methyl-furylpropargyl carbinol.

Example 6 5-methylfurfural 2 2. Of, 1 2.
5% ammonium chloride water 2 6 5 f. 2.8 fI of tetrabutylammonium bromide, 889 toluene and 26fI of zinc powder at 88-85°C.
-Dichloro-1-propene 44.4F was added dropwise over 1 hour, and the mixture was stirred at the same temperature for 8 hours. After the reaction is completed, the crystals derived from zinc dust are separated from P, toluene 66F is added to F[, and the toluene layer is separated.

After washing with 16% sodium bisulfite water at 60F and water at 50F in this order, toluene is distilled off at below 60'C. 82. Simple distillation of the concentrated residue. Oj' 5-methyl-furyl 2
'-Chloroallyl carbinol was obtained.

Boiling point 84-85°C / 0. 8 w Ml yield 86% 18.6 y of 5-methyl-furyl 2'-chloroallylcarbinol obtained above was dissolved in 100 id of methyl ethyl ketone and 276 y of potassium carbonate were added. After raising the temperature to 80°C, it was kept at that temperature for 62 hours. After cooling, insoluble matters were removed by P, and the P solution was washed with saturated brine and dried over zeolite. After removing the desiccant and concentrating under reduced pressure, the residue was purified by distillation to obtain 5-methyl-furyl propargyl carbinol.

Example 7 5-Methyl-furyl 2'-chloroallyl carbinol 10. Dissolve Of in 100 g of dimethylformamide,
6.48 f of sodium hydroxide was added and kept at 40°C for 8 hours. After neutralizing the reaction mass with 10% hydrochloric acid, the solvent was distilled off under reduced pressure, and the residue was dissolved in toluene and water. After separation,
The organic layer was concentrated under reduced pressure and then purified by distillation to 5-methyl-furyl propargyl carbinol6.
Obtained 92F.

Yield: 86.0% (Margin below)

Claims (5)

[Claims] (1) Haloallylfurancarbinols represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a hydrogen atom or a methyl group, and R_2 represents a chlorine, bromine or iodine atom, respectively.) Propargyl represented by the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a hydrogen atom or a methyl group.) Process for producing furancarbinols. (2) The method for producing propargylfurancarbinols according to claim 1, wherein the base is an alkali metal or alkaline earth metal hydroxide. (3) The method for producing propargylfurancarbinols according to claim 1 or 2, wherein the solvent is a mixture of water and a hydrophobic hydrocarbon or a hydrophobic halogenated hydrocarbon solvent. (4) The method for producing propargylfurancarbinols according to any one of claims 1, 2, or 3, which is carried out in the presence of a phase transfer catalyst. (5) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 represents a hydrogen atom or a methyl group.) Furfurals and general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (Formula, R_1 represents a hydrogen atom or a methyl group.) (where R_2 and The propargylfurancarbinol according to claim 1, which obtains a haloallylfurancarbinol represented by ▼ (wherein R_1 represents a hydrogen atom or a methyl group, and R_2 represents a chlorine, bromine or iodine atom, respectively). manufacturing method of types.