CS200428B1 - Process for preparing amidine or hydrazidine derivatives of 1-aza-1-cycloheptene - Google Patents

Description

The present invention relates to a process for the preparation of formula I, amidine or hydrazidine derivatives of 1-aza-1-cyCH,

I ²

CH,

AND

CH ₂ v

wherein R and R are hydrogen, amino, C 1 -C 3 alkoxyanilino, (o-, p-dinitro) -aniline.

and tautomeric forms thereof when R ' ^- is hydrogen.

The compounds of the formula I are prepared according to the process of the invention, which is characterized in that 1-azacycloheptan-2-thione of the formula

0¾ - HH / j3H _2/3

CHg - C = S

CHCHg N

- C-SH reacts with the compound of formula II, nn 428

200 420

HN

(II), "v," wherein R and R are as previously defined, at room temperature in the presence of a solvent or melt under a nitrogen atmosphere.

If the compounds obtained have a hydrogen atom on the non-cyclic nitrogen atom, they can be represented by the mesomeric structures of the formula Ia,

CIL · / <? H _2/3

CH "

CH _q

R | - / CH _2/3

CH ,,

C = -N

NH (1 a), p

wherein R is as defined above.

It is to be understood that in the absence of this, i.e., when hydrogen is not present at the non-cyclically bonded nitrogen atom of formula (Ia), only one ----------------- of the abovementioned molded structures, represented by the structure on the left side of ob, of formula la.

The compounds prepared according to the invention can be used as active ingredients of fungicidal agents in the control of plant diseases. They are also active against the most harmful fungi from agricultural crops such as phycomyoets, and since they have a systemic effect in addition to their curative effect, they can be used to treat foliage, stalks or fruit in addition to the reproductive parts of plants or soil. In addition, they can be used for their unique synergistic action with fungitoxic compounds of the series

2,4-dihloro-6- (o-chloroanilino) -1,3,3,5-triazine, n-dodeeylguanidine salts of, e.g., alkylsulfonic acids,

3,5-diphenyl-1-methyl-4 (1H) -pyridone, alpha- (2-chlorophenyl) -alpha- (4-fluorophenyl) -5-pyimidinemethanol, 3- (4-chlorophenyl) -1,1-dimethylurea; and lead arsenate.

Preferred amounts of the compounds according to the invention are in the treatment of soil preferably 0.05 to 500 ppm by weight of soil, in the treatment of leaves, stems, fruits preferably in the range of 0.1 to 5 kg per hectare and in the treatment of grain, tubers, bulbs or other reproductive parts of plants preferably in the range of 0.5 to 100 g per kg of treated plant material.

The preparation of the compounds of formula I, Ia is carried out by mixing 1 mol of 1-aza-2-thiocycloheptane with an excess of an amine or hydrazine derivative, preferably with 3 mol. If a liquid amine or hydrazine derivative is used, it is operated without a solvent. However, it is also possible to react the relevant components in the melt or to use a non-polar diluent such as carbon tetrachloride. For the preparation of the compounds of the formula, ammonia gas or a freshly prepared fresh solution are added to a 1-cycloheptan-2-thion solution ammonia in these diluents. The reaction is conducted at an elevated temperature of about 200 ⁰ C, preferably at 80 to 180 ⁰ 0, suitably at a temperature at which the reaction homogeneously mixing slořek, for conducting a nitrogen stream freed of traces of oxygen passage

200 420 with an alkaline solution of pyrocateohin or pyrogallol.

The isolation of the reaction product, if not eliminated during the reaction, is carried out after distilling off the excess of the amine or hydrazine components or solvent, in the free base form, or after the addition of the mineral acid or p-toluenesulfonic acid in the form of salts.

The following examples illustrate the preparation of the compounds of the invention in more detail. Example 1 o

Preparation of a compound of formula (Ia) wherein R = CH _g O. . NH.

2.6 g of 1-azacyclohepton-2-thione, 2.6 g of p-anisidine and 25 ml of dimethylformamide were introduced into a two-necked flask equipped with nitrogen inlet and reflux condenser. Under a gentle stream of nitrogen, the mixture was heated to boiling for 3 hours. After distilling off the solvent, the solid residue was crystallized from a mixture of petroleum ether and ether. The product was identified as 2- (p-anisidino) -1-aza-1-cycloheptene mp 86-87 ^° C.

Example 2

Preparation of a compound of formula (Ia) wherein R = NHg ·

The procedure and procedure were as described in Example 1 with 12.9 g of 1-azacycloheptan-2-thione and 8 ml of 90% hydrazine hydrate. After heating was complete, a stream of nitrogen was introduced until the contents of the flask had cooled. The crystallized product had mp after recrystallization from benzene 102 ⁰ C. It has been identified as 2-hydrazino-laza-1-cycloheptene. It gives crystalline sulfate very well soluble in water.

Example 3

2

Preparation of a compound of formula I wherein R = R = H.

To 2 mol of ammonium chloride NH 4 Cl in 500 mL of absolute ethanol was added 1 mol of 1-azacycloheptane-2-thione over 1 hour. After complete addition, the reaction was heated to boiling and allowed to stand overnight. After evaporation of 300 ml of ethanol and cooling, the crystals of cyclic amidine hydrochloride precipitated, which after recrystallization from a mixture of absolute ethanol and ether had a melting point of 160 ^° C.

Příkltfd 4

Preparation of 2- (p-anisidino) -1-aza-1-cycloheptene (R 1 = H, R ² = C 8 H ⁴ OCH 2 -O). 0.3 mol of p-anisidine was heated at 175 ^° C for 1 hour with 0.15 mol of 1-azacycloheptane-2-trione. When the hydrogen sulfide evolution had ceased after this time, the reaction mixture was cooled to and the crystals recrystallized from a mixture of hexane and ether. The melting point of the obtained 2- (p-anisidine) derivative was 86 ^° C.

SUBJECT OF THE INVENTION

A process for the preparation of amidine or hydrazidine derivatives of 1-aza-1-cycloheptene of the general formula I, _η

CH ~

N:

(CHg).

R

R ²

CH ₀ '

where R m and R are hydrogen, amino, C 1 -C 3 alkoxyanilino, or / o-, β-dinitro- / anilino and their tautomeric forms

200 420 of formula la

CHg - (0¾ _{) 3}

CHg NH η

in the case where R and its admixtures are defined as being hydrogen, and where R ² is as defined above, salts with inorganic acids or p-toluenesulfonic acid are treated with 1-azaoyklohentan-2-thione by a compound of the general formula formula II,

R ¹ ₂ (II)

VR

Wherein R and R are as defined above, at room temperature in the presence of a solvent or in a melt under a nitrogen atmosphere.

2. A method of preparing derivatives of the formula I or Ia according to claim 1, wherein the reaction is conducted at 70 to 180 ⁰ C.

Claims (2)

With an alkaline solution of pyrocatechin or pyrogallol. The isolation of the reaction product, if not eliminated during the reaction, is carried out by distilling off excess amine or hydrazine components or solvent, in the form of the free base, or after addition of mineral acid or p-toluenesulfonic acid in the form of salts. The following examples illustrate the preparation of the compounds of the invention in more detail. EXAMPLE 1 Preparation of compounds of formula Ia wherein R = CH 2 O. CgH4. NH. 2.6 g of 1-azacyclohepton-2-thione, 2.6 g of p-anisidine and 25 ml of dimethylformamide were introduced into a two-necked flask equipped with a nitrogen inlet and reflux condenser. With gentle nitrogen flow, the mixture was heated to reflux for 3 hours. After distilling off the solvent, the solid residue was crystallized from petroleum ether / ether. The product was identified as 2- (p-anisidino) -1-aza-1-cycloheptene of m.p. 86 to 87 0 0. EXAMPLE 2 Preparation of Compound of Formula (Ia) wherein R @ 1 NHg @ was run in the same manner as in Example 1 with 12.9 g of 1-aza-cycloheptan-2-thione and 8 ml of 90% hydrazine hydrate. After the heating was complete, a stream of nitrogen was introduced until the contents of the flask were cooled. The crystallized product had a m.p. after recrystallization from benzene 102 ° C. It was identified as 2-hydrazino-laza-1-cycloheptene. The crystalline sulfate is very soluble in water. Example 3 Preparation of a compound of formula I wherein R = R = H. To 2 mol of ammonium chloride NH4 Cl in 500 ml of absolute ethanol was added 1 mol of 1-aza-cycloheptane-2-thione over 1 hour. After the addition was complete, the reaction mixture was heated to quench and allowed to stand overnight. After evaporation of 300 ml of ethanol and upon cooling, the crystals of cyclic amidine hydrochloride, which after recrystallization from an absolute ethanol / ether mixture, had a m.p. 160 0 C. Example 4 Preparation of 2- (p-anisidino) -1-aza-1-cycloheptene (R 6 = H, R 2 = C 8 H 11 OCH 3 (-o), 0.3 mol of p-anisidine was heated at 175 ° C for 1 hour) with 0.15 mol of 1-azacyclo-heptane-2-trione, after which hydrogen sulfide evolution ceased, the reaction mixture was cooled and the crystals recrystallized from hexane / ether. ) of the derivative was 86 ° C. OBJECT OF THE INVENTION A process for the addition of amidine or hydrazidine derivatives of 1-aza-1-cycloheptene of general formula I, η CH-N: (0¾). R 2 R 2 O 2 wherein R m R is hydrogen, amino, alkoxyanilino having 1 to 3 carbon atoms in the alkoxy group, or o-, p-dinitro / anilino and their tautomeric forms 4,200,420 of general formula la Cit, - (0¾ 3 CHg - KH (Ia), η when R a is their addition characterized by being hydrogen, and wherein R 1 is as defined above, salts with inorganic acids or with p-toluenesulfonic acid, at 1- azacyclohentan-2-thione is treated with a compound of formula II, R 12 (II), VR 11 wherein R and R are as defined above, at room temperature in the presence of a solvent or in a melt under nitrogen. 2. A process for preparing derivatives of the formula I or Ia according to claim 1, wherein the reaction is carried out at 70 to 180 DEG. Price 2.40 Kčs TZ 6/70