JPS6024784B2 - Method for producing 4-[4-(anilino)phenoxy]-2-pentenoic acid derivative - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a 4-[4-(alini/)phenoxy]-2-benthenic acid converter.

The 4-[4-anili/)phenoxy]-2-pentenoic acid derivative of the present invention is a new compound, and has the general formula (wherein R is a chlorine atom, a bromine atom or a trifluoromethyl group, R2
is a chlorine atom, a bromine atom or a nitro group R3 is a hydrogen atom,
It is represented by a lower alkyl group, a lower alkenyl group, and R4 represents a hydrogen atom or a lower alkyl group, and is useful as a pesticide and has high herbicidal activity.

The present invention provides 4-(anilino)phere/fer compounds and 3.4
- Removes dihalobentanoic acid derivatives.

Provided is a method for producing a 41[41(anilino)phenoxy]12-benthenic acid derivative by reaction in the presence of a hydrogen genide teaching agent. The 4-(anilino)phenol compound used in the present invention has the general formula (wherein R is a chlorine atom, a bromine atom, or a trifluoromethyl group, R2 is a chlorine atom, a bromine atom or a nitro group, R3 is a hydrogen atom, a lower alkyl group, (lower alkenyl group).

Further, the 3,4-dihalobentanoic acid derivative is represented by a general formula in which the substituent R4 is a lower alkyl group such as a methyl group, ethyl group, propyl group, butyl group.

In this case, x is a halogen atom such as chlorine or bromine. Next, the present invention will be explained in more detail. Although the present invention can be carried out without a solvent, it is preferable to use a solvent in order to advance the reaction smoothly.

In this case, the solvents used include ketones such as acetone, butanone, and methyl ethyl ketone, lower alcohols such as methanol, ethanol, and propanol, ethers such as tetrahydrofuran, diethyl ether, methoxybutanol, diethylene glycol, ethylene glycol, and dimethyl ether, benzene, and toluene. Examples include aromatic hydrocarbons such as, aliphatic hydrocarbons such as hexane, dimethylformamide, and dimethylsulfoxide. Also,
As mystery dehydrohalogenation agents, hydroxides or salts of alkali metals such as potassium and sodium, magnesium,
Hydroxides or salts of alkali metals such as calcium are used.

Examples include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, magnesium hydroxide, calcium hydroxide, magnesium carbonate, and calcium carbonate. Furthermore, in the present invention, the dihalobentanoic acid derivative is usually 1 to 1.9 sound moles, preferably 1.1 to 1.9 sound moles, relative to the 4-(anili/)phenol compound. Use needle sounds.

The hydroxides or salts of alkali metals or alkali metals used as dehydrohalogenation reagents are those mentioned in 4 above.
The amount used is usually 1 to 3 times the mole of the mono(anilino)phenol compound.

The reaction is usually carried out at a temperature ranging from 0°C to 150°C, preferably from 50 to 100 qo.

In addition, the reaction time varies depending on the reaction temperature and target product, but
Generally, the reaction can be completed in 3 to 6 hours. The present invention will be explained below with reference to Examples, but the present invention is not limited to these Examples.

Example 1 3.2 hours of 4-(2,4-dichloroalinino)phenol, 4 hours of ethyl 3,4-dibromobentanoate, 2.2 hours of anhydrous potassium carbonate, and 30 hours of ethanol were added to a 100-liter round bottom flask. 4. The reaction was carried out by heating under reflux immediately.

After the reaction was completed, the solid was filtered out and the solvent was distilled off.

The product was recrystallized from n-hexane to give white ethyl 4-[4-(2,4-dichloroanilino)phenoxy]-2-pentenoate with a melting point of 72-7yo (yield: 63%). I got it. Infrared absorption spectrum (KBr) -1 $50 (N-H), 2960-2850 (C one day), 1
699 (C=○), 1641 (C=C), 159115
07 (N-H), 1462 (C), 13 spots 128 stops 1041 (C-0) 1257 (C-0), 967 (C one day), 85 stops 80
0(C-H) nuclear magnetic resonance absorption spectrum (CDC13,
Internal standard TMS. Legs) 6 1.31 (t) Group 8 1.51 (d) Navy 6 4.24 (q) 2 days 6 4.93 (p) IH 6 6.06 (d) IH 6 5.93 (s) IH 6 6-75-7-4 (mC) mother's day elemental analysis (C, 9th, as 9CI2N03) The results were as follows.

C day N Analytical value 60.1 4.9 3.8 Theoretical value 60.015.04 3. Satoshi Example 2 4-(4-bromo-2nitroanilino)phenol 3
5 days, butyl 3,4-dipromobentanoate 4.2 times, anhydrous potassium carbonate 1.8 times, and tetrahydrofuran 3 times.
0M was placed in a 100 m' round-bottomed flask, and a flow reaction was carried out for 6 hours.

After the reaction was completed, the solid was molded and the solvent was removed.

The residue was purified by column chromatography (silica gel, developed with benzene) to obtain a deep red viscous oily product, 4-[4-(4-bromo-2-nitroanili/)phenoxy]-2.
-2.3 g of butyl pentenoate (yield 44%) was obtained. Infrared absorption spectrum (NaCI) -1 spot 50 (N day), 3 females 5-3036 (C day), 2950-2850
(C one day), 1717 (C; 0), 16 spots (C ni C),
16131562, 1 spot 9 (1 NQ), 1500 (C-H), 1250, 1050 (C
-0-C), 970 (C one day), 89 stop 852, 839
809 nuclear magnetic resonance absorption spectrum (CC14, internal standard TMS. chest) 6 0. Scale (t) Group 6 1.13-1. General (mc), 1.48 (d) 7 days 6
3,94 (t) Plaque 6 4.85 (p) IH 8 5.86 (dd) IH 6 66-7.4 (mc) 7 days 6 812 (d) IH 69. Matsu (s) IH Examples 3 to 19 The corresponding 4-[4-(anili/)phenoxy] was produced by the reaction of a 4-(anili/)phenol compound and a 3,4-dihalobentanoic acid derivative using the same machine as in Example 1. A 12-pentenoic acid derivative was prepared.

The results are shown in Table 1. Furthermore, the compound of the present invention has a characteristic nuclear magnetic resonance absorption spectrum, and can be immobilized by nuclear magnetic resonance absorption spectrum. Table 2 shows the spectral data of the products of representative compounds Examples 5, 9, and 16 in Table 1.

■ Ship table 1 2 Product of Example 5 (CDC13, internal standard TMS, skin) 6 1.23 (t), 1.44 (d) thin 6 319 (s) 9 days 6 4.20 (q) 28 6 4.81 (p) IH 6 604 (d) IH 6645-7.6 (mc) Group Example 9 product (CDC13, internal standard TMS, breast) 6 1.36 (t), 1.41 ( d) Thin 6 4.15 (q) 2 days 6 4. Matsu (p) IH 3 6.00 (d), 5.87 (s) 2 days 6 6.65
-7.3 (mc) 7 days 6 7.38 (d) IH Product of Example 16 (CC14, internal standard TMS, leg) 6 1.52 (d) Group 6 3.72 (s) 9 days 6 4.95 (p) IH 6 5.96 (d, d) IH 6 6.7-7.7 (mc) 7 days 6 8.50 (s) IH 6 9.64 (s) IH

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼
_3 represents a hydrogen atom, a lower alkyl group, or a lower alkenyl group) 4-(anilino)phenol compound and the general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_4 represents a hydrogen atom or a lower alkyl group, General formula ▲ characterized by reacting a 3,4-dihalopentanoic acid derivative represented by (X_1 represents a halogen atom) in the presence of a dehydrohalogenating agent with or without a solvent
There are mathematical formulas, chemical formulas, tables, etc. ▼ A method for producing a 4-[4-(anilino)phenoxy]-2-pentenoic acid derivative represented by (in the formula, R_1 to R_4 have the same meanings as above).