JPS606641A - Production of chrysanthemumic acid derivative - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as an intermediate of agricultural chemicals and pharmaceuticals, especially as an intermediate of pyrethroid insecticide, in high yield, under mild reaction condition, by reacting a specific ethylene compound with a nitro compound having a specific partial structure. CONSTITUTION:The chrysanthemumic acid derivative of formula III having cis or trans configuration can be produced by reacting the ethylene compound of formula I (R1 and R2 are H, halogen or lower alkyl; R3 is acetyl, arylsulfonyl, nitro, cyano, or lower alkoxycarbonyl; R4 is cyano or lower alkoxycarbonyl) with a nitro compound having the partial structure of formula II in an organic solvent in the presence of an alkali at 0-50 deg.C for 1-several hours. The nitro compound is e.g. the compound of formula IV (R5 and R6 are H, halogen or an organic group free from nitro group or having a tertiary nitro group; R7 is H, halogen or lower alkyl; R8 is H or lower alkyl).

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel production method, and specifically relates to a general formula (wherein R8 and R2 are a hydrogen atom, a halogen atom, or a lower alkyl group, and R3 is an acetyl group, an allynylsulfonyl group, This is a method for producing a thin acid derivative having a partial structure represented by a nitro group, a cyan group, or a lower alkoxycarbonyl group, and R4 represents a cyano group or a lower alkoxycarbonyl group.

The thin acid rust conductor produced according to the present invention is a compound useful as an intermediate for agricultural chemicals, and particularly as an intermediate for pyrethroid insecticides.

Conventionally, the following method is known as an industrial method for producing a dilute acid.

CH3\/CH3 /\C02RCO□R (or CN) However, in these known methods, method (1) requires that the raw material ethyl diazoacetate is unstable, and method (2) uses a Grignard reagent. However, the reaction system had to be maintained in an anhydrous state.

On the other hand, as a laboratory method, there is known a method of the following formula in which a Schiff tetrapropane derivative is produced by reacting an ethylene compound represented by the following general formula [1%') with nitromethane.

(Chem, Ber, 1978 111(9), 3
094-104) In this method, when R1 and R2 of the ethylene compound are lower alkyl groups as in the present invention, the yield of the cyclopropane rust conductor is 10 to 22%.
This is extremely low.

The present inventors utilized this reaction to create a nitro compound (hereinafter referred to as an allyl nitro compound) that has a structure with high yield.
The present invention was completed based on the discovery that the desired cyclopropane ring can be produced in good yield by using the following method, regardless of the type of substituent of the ethylene compound.

That is, the present invention relates to the general formula (wherein R1 and R2 are a hydrogen atom, a halogen atom, or a lower argyl group, R3 is an acetyl group, an arylsulfonyl group, a nitro group, a cyano group, or a lower alkodicarbonyl group, and R4 represents a cyano group or a lower alkoxycarbonyl group, and is characterized by reacting an allylnitro compound with an allyl nitro compound (wherein Ro, R2, R3 and R4 have the same meanings as above). This is a method for producing a dilute acid derivative represented by

The raw allyl nitro compound is a compound that is stable in alkali and has no nitro group other than the nitro group, or if it has a nitro group other than the nitro group, if the nitro group is in the tertiary position. Any compound can be used.

Examples of such allyl nitro compounds include the following.

(In the formula, R5 and R6 each represent a hydrogen atom, a halogen atom, or an organic group that does not have a nitro group or has a nitro group at the tertiary position, and R7 represents a hydrogen atom, a halogen atom, or a lower alkyl group. , R8 represents a hydrogen atom or a lower alkyl group).

R9 is any group (provided that if the substituent is a nitro group,
When the substituent has a nitro group, it is limited to the tertiary position. ), n u O or a positive integer, R7 and R8
has the same meaning as above. ).

R8, R
o and n have the same meanings as above. ).

More specifically, as type (1), HO-CH2(CH2)m CH= C) Summer-CH2N
O2, ArSO2(CH2)mcH=cII CH2N
O2, t ＼ The (2) type and the (3) type of Kasa's compound are obtained.

The reaction of the present invention is carried out in an organic solvent in the presence of an alkali.

As the historical solvent, DMSO, HMPA, DMF, acetonitrile, MIBK, etc. are used. Also benzene,
It is also possible to carry out the reaction in the presence of a phase transfer catalyst using toluene or the like.

As the alkali, common alkalis such as sodium hydroxide, potassium hydroxide, and sodium alkoxide are used.

The reaction temperature is 0 to 50°C, preferably around room temperature, and a reaction time I'i of 1 to several hours is sufficient.

After the reaction is completed, usual post-treatments such as neutralization, extraction, and water washing are performed to obtain the desired product.

Seika! If necessary, purification can be performed by column chromatography, crystallization, or distillation.

The structure was determined by IR, N11114ASS spectrum, etc.

The starting allyl nitro compound can be obtained by reacting the corresponding bromine compound with a nitrite or by oxidizing the corresponding amine or oxime.

The production method of the present invention is an extremely excellent production method as an industrial production method because the reaction proceeds under mild conditions and the target compound can be obtained in good yield.

In addition, the allyl nitro compound used in the production method of the present invention can be any compound as long as it satisfies the above-mentioned Tokai requirements, and the carbon atoms adjacent to the nitro group react selectively to form the desired cyclopropane ring. can be formed. Therefore, the present invention can be applied to a very wide range of methods for producing dilute acid derivatives.

Furthermore, the production method according to the present invention is an extremely advantageous thin film, since it is possible to arbitrarily produce the trans isomer and the cis isomer by appropriately selecting the types of substituents for R3 and R4 of the compound represented by the general formula (1). This is a method for producing an acid rust conductor.

Next, examples will be given to explain the present invention in more detail.0 Example 1 Synthesis of ethyl 1-cyano-2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate; Compound No. I DM KOI O.15g (2.2m mol)
SO5d dissolves in water 05n1e, l-nitro-3-
After 0.23 F (2 mmot) of methyl-2-butene was added dropwise and stirred for 5 minutes, 0.31 t C2 mmot of ethyl 2-cyano-3,3-dimethylacrylate was added and stirred vigorously at room temperature. After 3 hours, the reaction solution was poured into water (50 mfl) and extracted three times with 20 Td chloroform. The extract was washed three times with saturated brine, dried over anhydrous magnesium sulfate, and then chloroform was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (benzene eluent) to obtain the target product 0.36f (yield 81%) as a pale yellow liquid.

IR(neat) 22210 cm-”,
1 7 20 cm-”NMR (CDC13) δ:
1.10-1.38 (m, 91(), 1.72
(s, 3)1), 1.78 (s, 3H),
2.44 (d, J = 7Hz, 0.211
), 2.64 (d 1J = 7Hz, 0.8H
), 4.22 (m, 21(), 5.0-5.2(
m, 01) Example 2 Synthesis of ethyl 1-cyano-2,2-dimethyl-3-(1-hepranyl)cyclopropanecarboxylate: Compound No. 3 KOHo, 15 f C2,2mmot) was converted to n1805
After dropping 0.34 f (2 m mot) of 1.1-nitro-2-octene dissolved in 0.5 m of water,
Stir for a minute. Ethyl 2-cyano-3,3-dimethylacrylate 031? (2 mmot) was added, and the reaction and post-treatment were performed in the same manner as in Example 1 to obtain the target product 0.354 (yield 67%).

IR (neat): 2210cm-', 1720
cm”NMR (CDC13) δ: 0.88 (m,
3H), 1.30-1.50 (m115H), 2.
10 (m.

2H), 2.34-2.64 (m, IH), 4
．． 24 (m 12H), 5.14-5.40 (m
, IH) , 5.64-6.00 (m, Hi) Example 3 Synthesis of ethyl 1-cyano-2,2-dimethyl-3-(cyclopentylidenemethyl)cyclopronocarboxylate: Compound No. 4 KOH0,15f (2,2 mmot) in DMSO5
The mixture was dissolved in 0.5 mQ of water, and 0.28 f (2 mmot) of 2-nitroethylidenecyclopenkune was added dropwise, followed by stirring for 5 minutes. Ethyl 2-cyano-3,3-dimethylacrylate 0.31 ? (2 mmot) was added, and the reaction and post-treatment were carried out in the same manner as in Example 1.
385' (yield 75%) was obtained.

IR (neat): 2210C+n", 1720
cm-”NMR (CDCta) δ: 1.30
(t, 3H), 1.30 (8°3H), 1.
32 (S 13H), 1.55 (m, 4H),
2.0 (m, 4H), 2.50 (m, IH),
4.25 (q.

2H), 5.1 (m, IH) Table 1 below similarly shows representative examples of compounds produced by the production method of the present invention.

Claims (1)

[Scope of Claims] (R411 acetyl, arylsulfonyl, nitro, cyano, or lower alkodicarbonyl group) and R4 is a cyano group or a nitro compound having a partial structure represented by a lower a. ) A method for producing a thin acid derivative having a partial structure represented by: