SU577993A3 - Method of preparing oxadiazole derivatives - Google Patents

Description

(54) METHOD FOR PRODUCING DERIVATIVES

OXADIAZOLE

The invention relates to methods for the distribution of oxadnazop derivatives, which can be used as optical signals for various synthetic, popu-genetic and natural high molecular weight materials.

The patent describes a method piterature popucheni symmetrical 2,5-bis- metokcbenzofypip 6-2, 3,4-oksadiazopa reacting 6-methoxy-benzofuran-2-karboksigidrazida with 6-methoxy-benzofuran-2-karbokskhporidom rastvoritep in the medium and in the presence of pyridine pospeduyuschey cyclization popuchennogo bis- (6-methoxy-benzufuran-2-carboxy) hydrazide in a solvent medium in the presence of POCl I J.

The aim of the invention is to obtain new derivatives of OK JelDiazopa.

A method for the preparation of oxadiazole derivatives of general formup is proposed.

BS

2

where and

A ,, B .. B,

BUT.

AT.

4 "f

 identical epi different and mean hydrogen. Hpor, lower apcnp npi lower apkoksip or A and AJ, respectively, B,

B, together denote the attached

benzene ring;

A | and B is hydrogen ngsh hpsr;

D - 1,4-fet1len or group - CH "CH-,

the fact that

general formupa

h

subject to the interaction of the common formupa

Be Wh

where Au and B-8 have the indicated meanings; one of the three Z values and the hapoid, and aru goy. WH NHj is a group in an inert organic solvent environment in the presence of an acceptor of the hydrogen hapoid followed by cycpyation of the accumulated diaciphydraine of the general formula “Ai Ai. X, AIv. : Nffi - NHU B-B and D have the indicated meanings, in the solvent medium in the presence of% "opoop-superphosphorous with the removal of iM water. The closure of an oxadiazop ring, resulting from water splitting, can be carried out using such water-removing devices as thionyl chloride, phosphorus proporic, loli phosphoric acid, at a temperature of between 50-220 C or by heating diacyl hydrazide in an inert solvent or in a mixture of such solvents in the presence of an acidic catalyst, for example organic sulfonic acids, Lewis acids or mineral acids, predominantly golu-sulfonic acids, boric acid or ZitCtj. Highly boiling aromatic or aliphatic hydrocarbons which may be halogenated can be used as an inert solvent, for example trichlorobenzene, dihporbenol or high boiling aromatic carboxylic esters, for example methyl benzoate. Typically, the loop closure reaction is carried out at temperatures of the order of 15O-25O C. Example 1, 21.9 g of 2-ti-cyanophenylbenzofuran (m.p. 141-143 ° C), shifted from 600 ml glycol and after adding 12 g of potassium hydroxide is stirred for 15 hours with heating to 165-170. Then the mixture is allowed to cool to 12 ° C and 250 ml of 2N, Ng 04 are added dropwise. Then the mixture is poured into 12OO ml of water, sediment. filtered off under vacuum, they are incubated with water, dried in vacuo at 6 °. By recrystallization from o-dichlorobenzene, 22.6 g of 4-benzofuryl (2) benzoic acid are obtained as colorless scales, t, pl. 301-ЗО2 С, 11.8 g of 4-benzofuryl- (2) 1 benzoic acid are suspended in 500 MP chloro-chlorine and with stirring, treated with 2 ml of thionyl chloride and 5 ml of dimetyphoramid. The reaction mixture is kept for 3 hours at which time 5 g of activated carbon is added, heated to 115-120 ° C, elt, and the filtrate is cooled. Then, while stirring, they are placed in an ice bath and the light yellow crystals which have precipitated are filtered off under vacuum, which are washed with benzene and dried under vacuum. Output 4-benzszh)) uryl- (2) 1 benzoyl chloride 97.5 g, so pl. 1VZ-165, 25.6 g 4 benzofuryl-. (2) Ibenzoyl chloride, 17.6 g of bvnzofuran-2-carbono hydrazide. acid and 13 gM, N -dimethylaniline in 40 ml of chlorobenzene are heated to boiling for 6 minutes. Then the mixture is stirred. 30 minutes at 0 C, the floor is filtered off with vacuum, the residue is washed with chlorobenzene, suspended in water and the chlorobenzene entrained in the product is evaporated with water vapor. Then the precipitate is filtered off again under vacuum, the resulting white powder is washed with water and the yield is dried at 39.4 g, i.e. under vacuum at shukt) 258-260 ° C (crude product). The compound has the following structure: / NH-NH 9.9 g of diacylhydrazide 0.5 g of p of toluenesulfonic acid in 150 ml of trichlorobenzene are heated 9O minutes to 210-220 0, while 50 ml of a mixture of trichlorobenzene and water are simultaneously distilled off. After cooling to room temperature under vacuum, the crystalline slurry is filtered off, washed with benzene and methanol and dried under vacuum at 60 ° C, yield 5.2, t. Pl. 231-261 C. The compound has the following structure; In a similar way, the compounds listed in Table 2 can be obtained. 1B table. 2 shows the characteristics of some of the source compounds.

9

ten

eleven

12

13

577993

14 Tabpia2

H

n

H

CH,

H

H

H

H

H tert SdN

H

H

6

H

H

H

eight

Claims (1)

H Compounds whose beisofuran groups are listed in Table. 2, is obtained by reacting the hapano-anhydrides or the corresponding acid anhydrides with carboxylic hydrazides. In the interaction of compound 1 of 4 (see table 2) with hporanhydride fi - (2-benzo) urip) of creep acid, compounds of the following formula are obtained: (i.e. 180-181.5 ° C) 60 „1t. pi 24I-246 C) .55 Claim of the invention Method of obtaining derivatives, oxadiazopa of the general formula 172-174 H n 141-142 H H n159,163 H H171-172 SI, 137-139 H H 129-13О OSI, H Ct 2O5-212 H 248-251 H H where A, AJ, A, A, B, B.BjHB are the same or different and mean hydrogen, hpor, lower alkyl or lower apkoxyp or AJ and A, cooTBercrBeHHoiBj and B together mean a fused benzene ring; A, and B is hydrogen or chpor; D -1,4-pheniphenyl group - consisting in the fact that the compound of the general formula subjected to vaimodis1-viyu with the connection of the general formupa r x ". . -. from d to t Bs where B - B and D have ukё & angde A - B IM8UGH are given & significant values values of the solvent medium in the presence of the / -one of the values of X and it -hapoid and other phosphospot with 1 mol of roe-NH-NHjf group, water. in an inert organic solution; Sources of information taken to the university in the presence of an acdeptor of hapoid in the examination; genus with iospedukmdey tsikaizashi obtained-1. Application of Germany J 2031774 kp. 12 p 9, diacylhydraanum of general formupa published, 1971. hShG-KD