CS241705B1 - Insecticide agent with effect of juvenile hormone and preparation method off effective substances - Google Patents

Description

The invention relates to an insecticidal composition having the action of a juvenile hormone, a process for its preparation and use.

In addition to many juvenoid and juvenogenic oxygen-containing potential pesticides, mainly in the field of terpenic compounds, attention is also paid to physiologically active compounds containing a sulfur atom in the molecule. The compounds described in the application of the invention are exemplary of sulfonic bonded aliphatic-aromatic ethers in the aliphatic part of the molecule having the effect of insect juvenile hormone.

SUMMARY OF THE INVENTION The present invention provides a juvenile hormone insecticidal composition comprising: a compound of formula I as active ingredient;

where symbols

Z ¹ , Z ² represent hydrogen or together form a double bond,

R @ ¹ denotes phenyl, halophenyl, alkylphenyl of up to 3 carbon atoms in straight or branched chain alkyl,

R ² denotes a straight or branched chain alkyl group having 1 to 4 carbon atoms,-COR ³ , -COOR ³ , wherein R ³ denotes a branched or unbranched alkyl group having 1 to 4 carbon atoms.

The process for the preparation of the above-mentioned compounds of the formula (I) consists in reacting an epoxy compound of the formula ( ² ) wherein ² ;

R ^2, Z ^1, Z ² denotes toiéž as in formula I, with compounds of formula III flexible

R ¹ 4-SH (III) where symbol i

R @ ¹ denotes the same as in formula I in a weakly alkali-ethanol environment at a temperature of 15 to 25; ° C to give the product of formula (I);

In the following, the invention is explained in more detail by way of examples, without being limited thereto.

He did

To a solution of 0.3 g (0.001 mol) of 4- (6,7-epoxy-3,7-dimethyloctyloxy) propiophenone in 8 ml of 96% ethanol was added 0.11 g (0.001 mol) of thiophenol in 16 ml of 96% ethanol. and then 33 ml of saturated aqueous sodium bicarbonate solution and allowed to stand at 15-25 ° C overnight. After most of the ethanol was evaporated under reduced pressure, water was added to the reaction mixture and extracted with diethyl ether. The ether layer was further dried over anhydrous. MgSO4, concentrated in vacuo and purified by column chromatography on silica gel with 8 wt. % water (eluent: perol ether containing up to 50 vol% diethyl ether) to give 0.15 g (37%) of chromatic pure 4- (7-hydroxy-6-phenylthio-3,7-dimethyloctyloxy) propiophenone.

Elementary analysis:

calculated:

% C, 72.42;% H, 8.27;

found:

72.21% C, 8.22% H. MS analysis:

414 (C, 2SH34O3S),

399 (C24H31O3S)

386 (C23H19O3S),

356 (C 22 H 25 O 2 S),

327 (C30H2302S),

304 (C19H2aO3),

275 (C17H23O3),

207 (C 13 H 19 S),

155 (C20H19),

151 (C9HhO ₂₎

121 (C 7 H 5 O 2), 11 (C 6 H 5 S);

IC analysis (5%, CCU):

3616 (i »OH)

3530 (vOH bond),

1686 (vC = 0),

1603, 1586, 1576, 1510 (var.),

1380, 1370 (δ _with CH 3) cm -1.

NMR analysis: CDCl 3 TMS, δ (ppm)]:

0.99 (t, 3H);

1.00 (d, 3H, J = 6.0),

1.18, 1.27 (s, 6H);

1.30-1.50 (m, 6H)

1.50-1.90 (m, H),

2.86 (q, 2 H),

2.5-2.9 (m, H);

3.75-4.25 (m, 2H),

6.87, 7.91 (d, 4H, J = 8.5),

7.1-7.5 (m, 5H).

In the same way they were prepared:

8- (4-ethylphenoxy) -3- (4-chlorophenyl) thio-2,6-dimethyl-2-octanol:

MS analysis:

420/2 (C24H33CIO2S)

402/4 (C24H31CIOS)

362/4 (C21H27ClOS),

241/3 (C12H14ClOS),

157 (C10H21O),

144/6 (CeHsCIS),

122 (CaH 10 O),

107 (C 7 H 7 O);

ethyl {4- [7-hydroxy-6- (4-methylphenyl) thlo-3,7-dimethyloctyloxy] benzoate}:

IR analysis (3%, CCU):

3517 (vOH bond),

1719 (vC = 0),

1608, 1582, 1515, 1495 (arom.), 1384, 1369 ( _with CH 3),

1276 (vC-O ester) cm ^-1 ;

NMR analysis [CDCl 3 (TMS, δ ppm)]:

0.94 (m, 3H);

1.23 (s, 3H).

1.31 (s, 3H);

1.36 (t, 3H, J = 7.0),

1.55-2.0 (m, 6H).

2.30 (s, 3H);

2.5-3.1 (m, 2H);

4.0 (m, 2H).

4.35 (q, 2H, J = 7.0),

6.90, 8.00 (d, 4H, J = 9.0),

7.22, 7.38 (d, 4H, J = 9.0);

MS analysis:

444 (C26H36SO4)

426 (C2SH34SO3)

399 (C24H51SO3)

386 (C23H3SO3)

339 (C21H23SO2)

261 C17H23S

221 C13H17OS

137 (C10H17)

124 C7-H8S

121 (C 7 H 5 O 2), (C 3 H 7 O);

4- [7-hydroxy-6- (4-chlorophenyl) thio-3,7-dimethyl-2-octenyloxy] propiophenone: MS analysis:

446/8 (C25H31CIO3S),

388/90 (C22H25GIO2S),

297/9 (C16H22Cl1OS),

286 (C19H28O2)

240/2 (C12H13ClOS),

150 (C9H10O2)

121 (C 7 H 5 O 2), (C 3 H 7 O);

NMR analysis:

1.21 (t, 3H, J = 7.0),

1.24 and 1.32 (s, 6H),

1.5-2.0 (m, 2H);

1.72 (s, 3H).

2.0-2.50 (m, 2H);

2.94 (q, 2H).

3.0 (m, H);

4.52 (d, 2H, J = 6.5);

5.34 (m, H);

6.89 and 7.92 (d, J = 8.5) 4H,

7.38 and 7.18 (d, J = 8.5) 4H.

The biological activity of the compounds prepared according to the invention was tested on the basis of insect juvenile hormone activity. The activity of the test substances was evaluated by inhibition of metamorphosis and expressed in standard units ID 50, amount of the substance in micrograms per insect, which induced the formation of intermediate forms between pupae and adult in beetles and between larvae and adult (in bugs). The substances were applied topically in 1 microliter of acetone at a 1:10, 1: 100 'dilution etc. to freshly stripped larvae of the last bug instar or freshly stripped beetle pupae.

Examples of activities of the compounds of the invention:

Tenebrlo molitor:

8- (4-ethylphenoxy) -3- (4-chlorophenyl) thio-2,6-dimethyl-2-octanol Graphosoma italicum:

Dysdercus cingulatus 4- [7-hydroxy-6- (4-chlorophenyl) thio-3,7-dimethyl-2-octenyloxy] propiophenone:

4- (7-hydroxy-6-phenylthio-3,7-dimethyloctyloxy) propiophenone 0.1 Pyrrhocoris apterus:

ethyl [4- (7-hydroxy-6- (4-methylphenyl) thio-3,7-dimethyloctyloxy) benzoate] 1

4- [7-Hydroxy-6- (4-chlorophenyl) thio-3,7-dimethyl-2-octenyloxy] propiophenone 0.05

Claims (2)

.Subject An insecticidal composition having the action of a juvenile hormone, characterized in that: Y N A L E Z U contains, as an active substance, compounds of the general formula I (¾ C (OH ₁ -CH _{2 -} ) SR ¹ Z ¹ Z ^Z 2. where symbols ZA, Z ² represents hydrogen or together form a double bond, R @ ¹ denotes phenyl, halophenyl, alkylphenyl having a maximum of 3 atoms. straight or branched chain carbon in alkyl, R ² denotes a straight or branched chain alkyl group having 1 to 4 carbon atoms, -COR ³ , -COOR ³ wherein R ³ denotes a branched or unbranched alkyl group having 1 to 4 carbon atoms. 2. A process for the preparation of the compounds according to claim 1, which comprises reacting an epoxy compound of the formula II O of ^{1 ?} (llø where symbols R ^2, Z ^1, Z ² have the same meaning as in formula I, with compounds of formula III R ¹ —SH (III) where symbol R ¹ has the same meaning as in formula I, in a weakly alkaline ethanol at 15-25 ° C.