JPS62454A - Production of beta-imidated chlorophenylhydrazine based compound - Google Patents

Abstract

PURPOSE:To obtain the titled compound useful as a raw material for herbicides, insecticides and photographic couplers in high yield, by chlorinating at least one hydrogen atom of the phenyl nucleus of a beta-imidated chlorophenylhydrazine based compound. CONSTITUTION:A beta-imidated phenylhydrazine based compound is dissolved in a solvent, e.g. chloroform or benzene, and chlorine atom is introduced into the phenyl group with a chlorinating agent, e.g. chlorine gas or sulfuryl chloride. The resultant beta-imidated chlorophenylhydrazine based compound can be used as a useful intermediate for herbicides or photographic couplers, etc., and starting material for chlorophenylhydrazine without separating from the reaction system.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a β-imidized chlorphenylhydrazine compound from a β-imidized phenylhydrazine compound, and more specifically to a method for producing a weed killer using a β-imidized phenylhydrazine compound as a starting material. The present invention relates to a method for producing in high yield a β-imidized chlorphenylhydrazine compound useful as a raw material for pharmaceuticals, insecticides, and photographic couplers.

C Background of the Invention] Herbicides [e.g. propionyl chloride (2°4.6-
trichlorophenyl) hydrazone, isobutyryl (2,
Phenylhydrazine compounds having a chloro atom in the phenyl nucleus (for example, 2,4,6-trichlorohydrazine) are used as intermediates for 4-dichlorophenyl)hydrazino groups, photographic pyrazolone type magenta couplers, and the like.

When introducing a chlor atom into the phenyl nucleus, the β-position of the hydrazino group is completely protected in advance, for example, J, l-1umph1-1u, H.

)jumble R, Evans%J, Chen+
, 3oc, Yue, pp. 1304-1307 (1925)
To protect the β-amine group of phenylhydrazine with an aldehyde or ketone, the phenyl group is chlorinated,
Next, reduction was performed using zinc or the like. However, this method has the disadvantage that since the zinc used in the reduction usually contains cadmium as an impurity, disposal of the reaction residue poses a pollution problem and the processing cost is high. Furthermore, when aldehydes and ketones used as protective groups for the nitrogen atom at the β-position of phenylhydrazine are removed by reduction, they are released as compounds in which the bond with the nitrogen atom at the β-position becomes a methyl group or a medilene group. It is difficult to reuse it as a protecting group, and it has the disadvantage of increasing costs.

[Object of the Invention] The present invention has been made in view of the above circumstances, and its purpose is to use a β-imidized phenylhydrazine compound as a starting material and to chlorinate the phenyl group of this compound to obtain a high It is an object of the present invention to provide a manufacturing method for obtaining a β-imidized chlorophenylhydrazine compound in high yield and at low cost.

Another object of the present invention is to remove the protective group of the nitrogen atom at the β position of phenylhydrazine compounds under extremely mild conditions, and to efficiently reuse the protective group as a protective group. An object of the present invention is to provide a method for producing a phenylhydrazine compound.

[Structure of the Invention] The above object of the present invention is to produce a β-imidized chlorphenylhydrazine compound by chlorinating at least one hydrogen atom of the nucleus of the β-imidized phenylhydrazine compound. achieved.

[Specific Structure of the Invention] In the present invention, the β-imidized phenylhydrazine compound used as a starting material is preferably represented by the following general formula.

General formula O +1 In the formula, R is a monovalent atom such as a halogen atom or an alkyl group.
u represents a ring, and Z represents an atomic group necessary to form a ring, preferably a 4- to 6-membered ring, to which another ring such as a benzene ring may be further fused. n represents an integer of 0 to 4, and when n is 2 to 4, each may be the same or different.

The monovalent organic group represented by R above is preferably a halogen atom or an alkyl group, more preferably a halogen atom, and particularly preferably a chlorine atom.

Next, specific examples of β-imidized phenylhydrazine compounds preferably used in the present invention will be shown, but the present invention is not limited thereto.

The β-imidized phenylhydrazine compound used in the present invention can be obtained, for example, by reacting a phenylhydrazine compound and an acid anhydride in the presence of an acid.

The β-imidized phenylhydrazine compound used in the present invention is used after being dissolved in a solvent during the reaction. Preferred solvents that can be used include, for example, chloroform, carbon tetrachloride, benzene, acetic acid, and the like.

In the present invention, the chlorinating agent used in the reaction system together with the β-imidized phenylhydrazine compound is not particularly limited as long as it is commonly used, but examples include chlorine gas, sulfuryl chloride, hypochlorous acid and its salts ( For example, sodium salt, calcium salt, etc.) may be used, and salashi powder (a mixture containing calcium hypochlorite) may be used.

This sulfuryl chloride can also be used as a solvent.

The chlorinating agent varies depending on the number of chlorine atoms to be introduced into the phenyl group of the β-imidized phenylhydrazine compound, but preferably 1 to 1 chlorinating agent per chlorine atom to be introduced.
．． It is 1 mole. The instruction manual for this chlorinating agent is also related to the reaction temperature. For example, even when using 6 moles of sulfuryl chloride, if the chlorination is carried out at a reaction temperature of about 10°C or less, the 2-position of the phenyl group of the compound is and a chlorine atom is introduced at the 4th position. Furthermore, if chlorination is carried out at a reaction temperature of about 15° C. or higher, chlorine atoms are introduced into the 2.4 and 6 positions of the compound.

The chlorination reaction of the β-imidized phenylhydrazine compound of the present invention is preferably carried out at a temperature in the range of 0 to 100°C. Further, a reaction time of about 3 hours is sufficient.

Next, a typical reaction route for chlorination of the β-imidized phenylhydrazine compound of the present invention is shown below.

In the case where the phenyl nucleus of the raw material β-imidized phenylhydrazine is unsubstituted, the β-imidized chlorphenylhydrazine compound obtained by the method of the present invention has a chloro atom at the 2-position of the phenyl group. , 4-position and 6-position, preferably 2-position and 4-position, more preferably 2-position, 4-position and 6-position.

The method of the invention is particularly useful when introducing chlorine atoms at both the 2- and 6-positions of the phenyl nucleus.

The β-imidized chlorphenylhydrazine compound of the present invention can be used as a starting material for the production of useful intermediates such as herbicides and photographic couplers, and chlorphenylhydrazine without separating it from the reaction system. can.

The β-imidized chlorphenylhydrazine compound obtained by the method of the present invention can be easily converted to chlorphenylhydrazine by hydrolysis.

This hydrolysis uses water and water-miscible organic solvents (e.g. methanol, ethanol) as solvents, and acids (
The reaction is carried out in the presence of a reagent such as hydrochloric acid, sulfuric acid, etc.) or an alkaline agent (eg, sodium hydroxide, potassium hydroxide, etc.). The hydrolysis reaction is preferably carried out at a temperature of 50 to 120°C, and the time required for hydrolysis varies depending on the raw materials used and the reaction temperature, but is preferably 3 to 20 hours.

The amount of the reagent used is preferably 1 mol or more, more preferably 2 mol or more, and about 10 mol is sufficient per 1 mol of the β-imidized chlorphenylhydrazine compound.

[Effects of the Invention] According to the method of the present invention, a β-imidized chlorphenylhydrazine compound in which a chlor atom is introduced into a phenyl group by chlorinating the phenyl group of the β-imidized phenylhydrazine compound has a high This compound can be used in the production of β-imidized chlorphenylhydrazine compounds useful as intermediates for herbicides, photographic couplers, etc., without separating it from the reaction system.

Furthermore, according to the method of the present invention, the 2- and 6-positions of the phenyl nucleus
β-imidized chlorophenylhydrazine compounds having chlorine atoms in both positions can also be produced with good yield and at low cost.

Furthermore, when obtaining a chlorphenylhydrazine compound from the object of the present invention, the protecting group is removed in the form of a dibasic compound during hydrolysis, so it can be easily converted into an acid anhydride by means such as thermal dehydration, and the main compound can be converted into an acid anhydride. It can also be used repeatedly as an imidizing agent to obtain starting materials for the invention.

[Example] Example 1 Synthesis of β, β-succinyl-2.4.6-dolychlorophenylhydrazine 190 g of β, β-succinyl-phenylhydrazine was gradually added to 810 g of sulfuryl chloride with stirring and cooling with water. It reacted violently and dissolved while generating HCl and SO2 gas. The mixture was then stirred at room temperature (25±5°C) for 1 hour to complete the chlorination reaction.

Subsequently, the excess remaining sulfuryl chloride is recovered by distillation under normal pressure, and further recovered by distillation under reduced pressure, leaving a brown candy-like substance.

After dissolving this in ethyl acetate and washing with a 3% aqueous sodium carbonate solution, the ethyl acetate solution was concentrated, the residue was recrystallized with ligroin, and elemental analysis (C, H.

N), each magnetic resonance spectrum confirmed that it was the desired product. (rli point 12 °C - 125 °C) 282 g (yield 96%) Example 2 Production of N-phthalimino-2,4,6-trichloroaniline N-phthalimino aniline 238Q, carbon tetrachloride, 1
800 g of sulfuryl chloride was added to 1, and the reaction was gradually heated. After boiling and refluxing for 2 hours, the solvent was recovered at normal pressure and further removed under reduced pressure to obtain the target product 333Q (yield 98%).
) was obtained. Melting point: 187°C to 189°C.

Example 3 N-(α,α′-dichlorosuccinimino)-2,4,
6-)-Production of dichloroaniline N-(α,α′-dichlorosuccinimino)aniline was prepared in the same manner as in Example 1, except that 169 g of α,α′-dichlorosuccinic anhydride was used instead of succinic anhydride. 210 g (yield 81%) was obtained.

The target product was confirmed by elemental analysis (C, H, N) magnetic resonance spectra.

Example 4 Production of N-phthalimino-2,4-dichloroaniline The same procedure as in Example 2 was carried out except that the amount of sulfuryl chloride was changed to 2 moles per 1 mole of N-phthalimino-aniline. , target product (melting point 203℃~205℃)
℃) 298 g was obtained.

In addition, the same procedure as in Example 2 was carried out except that the reaction temperature was kept at 0°C to 5°C after adding sulfuryl chloride. As a result, the target product (melting point 204°C to 205°C) was 297°C.
g was obtained.

Example 5 Example 2 except that N-phthalimino-2-chloroaniline and N-7thalimino-4-chloroaniline were used instead of N-phthalimino-aniline in Example 2.
In the same manner as above, the target product N-phthalimino-2
,4,6-)-dichloroaniline was obtained.

Reference Example 2. Production of 4.6-)-lichlorphenylhydrazine To 288 g of β,β-succinyl-2.4°6-trichlorophenylhydrazine obtained in Example 1, 11 methanol,
Add 330% of concentrated hydrochloric acid, and heat and boil under reflux for 5 hours while stirring to complete the hydrolysis reaction. Next, methanol was recovered by distillation under normal pressure and further recovered by distillation under reduced pressure. Immediately add alkaline water (a solution of 215 g of caustic soda and 600 g of water) to the obtained brown powder residue, stir vigorously at 60° C.±10° C. for 20 minutes, and then cool with water. When a large amount of precipitated target crystals are filtered, washed with water, and dried,
185 g of 2°4.6-trichlorophenylhydrazine was obtained as a Seifuku white powder (melting point: 140°C to 141°C). (yield 89%)

Claims (1)

[Claims] A method for producing a β-imidized chlorphenylhydrazine compound, which comprises chlorinating at least one hydrogen atom of a phenyl nucleus of the β-imidized phenylhydrazine compound.