JPH041187A - Production of furylpropagyl carbinols - Google Patents

Abstract

PURPOSE:To efficiently and safely obtain the title compound useful as an intermediate for pyrethroid chemical by reacting furylhaloallylcarbinols with an alkali metal hydroxide in the presence of polyethylene glycol. CONSTITUTION:Furylhaloallylcarbinols expressed by formula I (R<1> is H or methyl; R<2> is Cl, Br or I) are reacted with a hydroxide (preferably NaOH) of alkali metal or alkoxide (preferably sodium methoxide) of alkali metal in the presence of polyethylene glycol, preferably at 0-70 deg.C to provide the aimed compound expressed by formula II. Furthermore, the compound expressed by formula I is e.g. obtained by reacting corresponding furfurals with a 2,3- dihalopropene in a solvent consisting essentially of water in the presence of zinc.

Description

DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing furylpropargyl carbinols useful as intermediates for agricultural chemicals, medicines, fragrances, etc., particularly as intermediates for pyrethroid epidemic prevention drugs.

<Prior art> As a method for producing furylpropargyl carbinols, for example, a method of obtaining them by Grignard reaction of propargyl bromide or propargyl chloride with furfurals is known (Japanese Patent Application Laid-open No. 118780/1983), However, since propargyl firomide and propargyl chloride have self-degrading properties,
In industrial large-scale use, there are problems such as the need for measures (safety measures) to suppress their self-degradability, and the above-mentioned production methods are not necessarily industrially advantageous.

In addition, as a means to solve the above problems, the present inventors have previously developed propargyl bromide or propal 4'71/
We have developed a method for producing furylpropargyl carbinols by dehydrohalogenating furyl haloallyl carbinols without using chloride (Japanese Patent Application No. 1-55784).
issue).

<Problems to be Solved by the Invention> The present inventors have intensively investigated a method for obtaining furylpropargyl carbinols, which is more advantageous from an industrial perspective, through an efficient dehydrohalogenation reaction of furylhaloallylcarbinols. As a result, the present invention was achieved.

<Means for Solving the Problems> That is, the present invention provides a compound of the general formula (II) (wherein R1 represents a hydrogen atom or a methyl group, and R1
represents a chlorine, bromine or iodine atom. ) and alkali metal hydroxide or alkali metal alkoxide in the presence of polyethylene glycol (wherein R1 is The present invention relates to a method for producing furylpropargyl carbinols represented by the following formula (having the same meaning as above).

The present invention will be explained in detail below.

The polyethylene glycol (PEG) used in the present invention has various molecular weights; for example, PEG
200, PEG300, PEG400, PEG600, etc.

The amount of PEG used is furyl haloallyl carbinol II
It is usually 0.5 to 10 times the mole, preferably 0.5 to 5 times the mole relative to (It).

Examples of alkali metal hydroxides include sodium hydroxide,
Potassium hydroxide, lithium hydroxide, etc. are mentioned, and sodium hydroxide and potassium hydroxide are preferably mentioned.

Examples of alkali metal alkoxides include sodium methoxide, sodium ethoxide, and sodium tert.
-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, lithium methoxide, lithium ethoxide, lithium isopropoxide, etc., preferably sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide and potassium tert-butoxide.

The amount of such base used is furyl haloallyl carbinol! It is usually 1 to 15 times the molar amount of i), preferably 1 to 10 times the molar amount.

There are no particular restrictions on the use of a solvent, and PEG may be used as a solvent.However, due to the relationship between the reaction temperature and the type of PEG, PEG may not dissolve, and in that case, P
It is preferable to add a solvent to dissolve EG, and a mixed solvent of water and other solvents can also be used.

There are no particular restrictions on the type of solvent, and there are no particular restrictions on the amount of solvent used outside the water, but furyl haloallyl carbinols (
It is usually 1 to 10 times the amount by weight. When water is used, the amount used is usually 1 to 4 times the weight of the alkali metal hydroxide or alkali metal alkoxide.

The reaction temperature is 0°C to 70°C, the reaction time is not particularly limited, and the raw material furyl haloallyl carbinols (U)
The point in time when disappears from the reaction system can be defined as the reaction bond point.

After completion of the reaction, the reaction mixture is neutralized, filtered, concentrated, and then the residue is distilled to obtain furylpropargyl carbinols (1) in an excellent yield.

Also, the raw material for this reaction (furyl haloallyl carhi)
-tel (II) is the corresponding furfural and 2
．． It can be obtained by reacting 3-dihalopropene in a solvent mainly composed of water in the presence of zinc (Japanese Patent Application No. 63-2
No. 76849, Japanese Patent Application No. 1-55784).

<Effects of the Invention> According to the present invention, it is possible to improve the volumetric efficiency (amount of target product produced per unit volume) compared to the conventional method, and it is also possible to obtain reaction results equivalent to or better without using expensive reagents. The furylpropargyl carbinols shown in (1) above, which are useful as intermediates for agricultural chemicals, medicines, fragrances, etc., can be produced industrially advantageously and safely.

<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 2”-chloroallyl-5-methylfurylcarbinol 2
0. 32.61 g of PEG300 and 8.58 g of flaky sodium hydroxide were added to OOg, and the reaction mixture was kept at 30°C for 24 hours. After neutralization with 10x hydrochloric acid,
Toluene was added and the mixture was separated. The toluene layer was concentrated under reduced pressure, and the obtained oil was purified by distillation to obtain 14.46 g of 5-methylfurylpropargyl carbinol (1).

Yield 89.8χ bp 74°C10,7m+mH
g edition - NMR data (CDCl2. Internal standard TMS.

δ value) 2.03 (t, 18. J=2.6Hz
)2.25 (d, 3HJ=1.0Hz
)2.70 (dd, 2HJ=6.6.2
．． 6Hz) 2.89 (brs, IH) 4.76 (t, LH, J=6.6Hz
)5.88 (dq, LH, J=3.3,1
．． 0Hz)6.17 (d, IHJ=3
．． 3Hz) Example 2 2“-chloroallyl-5-methylfurylcarbinol 1
After dissolving 8.66g in 18.66g of toluene, 64% of a 50x sodium hydroxide aqueous solution. OOg and PEG200
20, OOg was added and kept at 40°C for 24 hours. After adding toluene and water to separate the layers, the toluene layer was washed with 5x hydrochloric acid and then with 7% aqueous sodium carbonate, and the organic layer was concentrated under reduced pressure. The residue was distilled to obtain 13.35 g of 5-methylfurylpropargyl carbinol.

Yield 88.9χ Comparative Example 1 2'-chloroallyl-5-methylfurylcarbinol 12.30g, 50χ aqueous sodium hydroxide solution 42.3
g,) A mixture of 37 g of toluene and 21.3 g of tetra-n-butylammonium bromide was stirred at 40°C for 8 hours. After neutralizing the reaction mass with II 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 obtain 7.94 g of 5-methylfurylpropargyl carbinol.

Yield 80.0χ Example 3 2°-bromoallyl-5-methylfurylcarbinol 3
5゜28g toluene 70.56g% PEG6006
1.08. and flaked potassium hydroxide 12.8
The reaction mixture was kept at 40° C. for 12 hours, neutralized with 1° hydrochloric acid, and then separated. After washing the toluene layer with water, the resulting oil was concentrated under reduced pressure and purified by distillation to obtain 20.68 g of 5-methylfurylpropargylcarbinol.

Yield 90.2χ Example 4 P in 20.56 g of 2-chloroallylfurylcarbinol
30039, 30 g and 7.15 g of flaked sodium hydroxide were added and kept at 30°C for 30 hours. The reaction mixture was subjected to the same post-treatment as in Example 1, and 14.76 g of furylpropargyl carbinol was added. Obtained.

Yield 91.0χ bp 76°C10.8mmHg
'HNMR de l (CDCIs, internal standard TMS.

δ A direct) 2.06 (t, LH, J=2.6Hz
)2.72 (brs, LH) 2.75 (dd, 2H, J=6.3.
2.6Hz) 4.9 (brt, IH
) 6.3 (m, 2H) 7.4 (m, 1B) Example 5 2'-Chloroallyl-5-methylfurylcarbyl/-lO,og 20053.6 g and powdered sodium methoxy Add 5.79g of
The reaction mixture kept warm at C for 24 hours was subjected to the same post-treatment as in Example 1 to obtain 7.11 g of 5-methylfurylpropargyl carbinol. Yield 88.4χ Example 6 2°-chloroallyl-5-methylfurylcarbinol 1
0.0g of PEG300 20. Add Og and 12.02 g of powdered potassium tert-butoxide, and
The reaction mixture that had been kept at room temperature for 24 hours was subjected to the same post-treatment as in Example 1 to obtain 7.32 g of 5-methylfurylpropargyl carbinol.

Yield 91.0χ Reference example 1 5-methylfurfural 20.0g, water 88g1
Prepare 33g of toluene and 26g of zinc powder 33-35
It was kept at °C. 44 2,3-dichloropropene under stirring
4 g of the mixture was added dropwise over 20 minutes and kept at 33 to 35° C. for 4 hours.

After the reaction was completed, crystals derived from zinc dust were filtered off, 66 g of toluene was added to the filtrate, and the toluene layer was separated. After washing with 30 g of 7χ sodium carbonate water and 50 g of water, toluene was distilled off at 60° C. or lower. Simple distillation was performed to obtain 30.5 g of 2°-chloroallyl-5-methylfurylcarbinol.

bP 84-85°C10,8sn+Hg嘱-NMR
Data (CDCIff, internal standard TMS.

δ value) 2.27 (S, 3H) 2.75-2.92 (TIA, 2B) 4.95
(dd, 18) 5.26 (s, 2H) 5.89 (d, IH) 6.13 (d, IH) Reference example 2 5-methylfurfural 11.0g, 3χ vinegar *3B,
-4g.

Prepare 43.2g of toluene and 13.1g of zinc powder,
38.1 g of 2,3-dibromopropene was added dropwise over 20 minutes while stirring while maintaining the temperature at 30-35°C.
After the reaction was completed by keeping the temperature at C for 2 hours, the insoluble matter was filtered off and washed with 86 g of toluene. The filtrate and washing liquid were mixed, and the toluene layer was separated. The toluene layer was washed with 30 g of 7χ sodium carbonate water, then washed with 50 g of water, and the toluene was distilled off under reduced pressure at 60°C or below. The obtained oil was purified by silica gel column chromatography to obtain 2°-bromoallyl-5-methyl. 11.13 g of furyl carbinol was obtained.

The boiling point could not be measured because the compound decomposed during heating.

NMR data (CDC1, internal standard TMS δ value) 2.08 (brs, IH) 2.28 (d, 3) 1. J-1,0Hz)2
．． 93 (m, 2H) 4.98 (dd, IH, J-5, 1, 8, 4Hz
)5.54 (d, IH, J-1,7Hz)5.
72 (d, LH, J-1, 7Hz) 5.91
(w, 1M) 6.16 (d, 18.J-3,3Hz) Reference Example 3 While stirring a mixture of 18g of furfural, 33g of toluene, 88g of 3χ aqueous acetic acid and 26g of zinc powder,
The temperature was kept at 3-35°C. At the same temperature, 44.4 g of 2,3-dichloropropene was added dropwise over 20 minutes, and then the temperature was kept at the same temperature for 2 hours. After the reaction, the crystals derived from zinc dust were filtered off, and 66 g of toluene was added to the filtrate. In addition, the toluene layer was separated. Wash with 30g of 7χ sodium carbonate water, and add 5g of water.
After washing with 0g, toluene was distilled off at 60°C or lower. Simple distillation was performed to obtain 29.4 g of 2°-chloroallylfurylcarbinol.

bp 74°C10,7mmHg Publication-NMR data (CDC1, internal standard TMS.

δ value) 2.68 (d, IH, J=4.3Hz) 2.8
3 (s, 21) 5.00 (wa, IH) 5.24 (11,2H)

Claims (1)

[Claims] General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1 represents a hydrogen atom or a methyl group, and R
^2 represents a chlorine, bromine or iodine atom. ) is a general formula characterized by reacting a furyl haloallyl carbinol with an alkali metal hydroxide or an alkali metal alkoxide in the presence of polyethylene glycol ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 represents the same meaning as above.) A method for producing furylpropargyl carbinols.