CS200329B1 - Insecticide based on compounds regulating evolution of insects and method for preparing thereof - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to an insecticidal composition based on substances controlling the development of insects with cyclic acetal bonding in a molecule, to processes for their preparation and use.

A number of synthetic and natural substances having the same physiological effect as the juvenile hormone produced by insects have already been described in the literature. This bioanalog of insect JH (Juvenoids), belonging to various types of organic compounds due to its chemical structure, has so far been a promising, so-called third generation of insecticides. At present, precursors of the aforementioned juvenoids, which have a higher molecular weight than the juvenoids themselves, are already being synthesized and applied. Thus, the persistence in abiotic application conditions can be expected with these substances. (Sláma K., Romaňuk M., J. Insect Biochem.

6, 579 (1976). Examples of both juvenoid and juvenoidogenic agents are the compounds of the present invention.

SUMMARY OF THE INVENTION The present invention provides an insecticidal composition based on insecticide controlling agents, characterized in that it contains as active ingredient Juvenoid juvenoidogenic compounds having a cyclic acetel bond in a molecule of the formula It

LUA LC X ·

R ^X R ² (OR ³ ) C-CH 2) a - C (R ⁴ Z ¹ ) -C (R ⁵ Z ² ) - (CH 2) _b -CH (R ⁶ ) -O - / - -C- OAC ¹ (I) \ _Z ^{0 (CX} (CX ⁵ X ⁶ ))

200 329

200 329 in which

- the symbol a denotes an oil number between 0 and 2

- the symbol b denotes 0 or 1

- the symbols o, d, e denote an integer ranging from 0 to 2

R and R are methyl or ethyl

- the symbol R ³ represents a straight and branched chain carbon alkyl having a total of no more than 6 atoms, alkoxyalkyl and a straight or branched chain having a total of no more than 6 carbon atoms, hydroxyalkyl and a straight or branched chain having a total number of no more than 6 carbon atoms, straight or branched chain having a maximum of 6 carbon atoms, cyanoalkyl and straight or branched chain having a maximum of 6 carbon atoms, straight or branched chain aoyloxyalkyl having a total of no more than 6 carbon atoms, (cycloalkyl) - alkyl having a total of no more than 6 atoms carbon, (oxacycloalkyl) alkyl with a maximum number of carbon atoms, aralkyl and a total of 9 carbon atoms 4 5

R, R are hydrogen, methyl or ethyl

- R is a straight or branched alkyl of up to 6 carbon atoms or a phenyl group

1

- the symbols Z and Z denote hydrogen or together form a double bond or, in the case of a ' Z, also denotes an alkoxy group and a straight or branched chain with a total number of not more than 6 carbon atoms

- the symbols X to X ^ & represent hydrogen, linear or branched substituent of formula Z ³ - (CH) t · I> A Oele where f is a number ranging from 1 to 15; the symbols Z, which are identical to or from each other may llěit, represents hydrogen or straight or branched chain alkyl is 1 to 15 carbon atoms, in which aubstituenteoh X ¹ to X & is Oelke most 30 carbon atoms, straight or branched chain substituent of the formula Z ⁴ - (CH) Z ⁵ wherein the aymbol Z ⁴ has the meaning given above; g denotes an oil number in the range of 0 to 15; symbol c

Z, which is represented in the formula by up to three times, represents chlorine or bromine, -OH, -OZ (R) or phenyl, wherein Z ^ represents straight or branched alkyl of 1 to 15 carbon atoms

the bond -O-C 1 X ² - CX ³ X * -O- in the general formula I represents a group

A process for the preparation of compounds regulating the development of a cyclic insect in a molecule of the formula I is to react with an alkyl halide of the formula II (R ¹ R ² ) C-CH- (CH 2) ft - C (R ⁴ Z ¹ ) -C (R ⁵ Z ² ) - (CH 2) _b -CH (R ⁶ ) -X (Π)

2 wherein R, R

R ⁴ to R ⁶ ,

Z ^A , Z, a, h have the meanings given above and X represents chlorine or bromine with aoylphenol of the formula III

COR ⁷ (III)

200 329 wherein R 'is as defined above at a temperature in the range of from 20 to 80 ° C in an anhydrous aprotic solvent environment preferably in dimethylformamide and in the presence of an alkaline reagent, preferably anhydrous KgCO 4, KOH, CH 2 OH or NaH e to form a cotoether of formula (IV) - (RMc-CH- (CH ₂ ) _and -C (R ⁵ 2 ² ) - (CH ₂ ) _{b -} CH (R ⁶ ) -O-R ⁶ -COR ⁷ ( IV), i 2 A 7 ί 2 V ·· * wherein R, R, R ** to R ', Z, Z, a, b have the meaning given above, which is reacted with compounds of the general formula Vi

HO- (CX ¹ , ² ) ,, - (CX ³ , ⁴ ) ⁿ <CT ⁵ X ⁶ ) -OH (V), c α e where X ¹ to X ⁶ , c, d, e denotes tCkv * co in the presence of a catalyst, preferably p-TsOH, boiling, preferably benzene, toluenes, while removing the reaction water by azeotropic distillation and said solvents, to convert the cyclic acetal of formula VIi (R ¹ R ² ) C-CH- (CH 2); -C (R ⁴ 2 ¹ ) -C (CH 2 ' _ts -CH (R ⁶ ) -O-

(VI),

-C-O-IC ¹ ! ² ! The ^Xs / \ CX ³ X ⁴⁾ ₄

W) _e where symbols r} R? R ⁴ to R? 2 ^ Z ^2, X ¹ to X ^6, a, b, c, d and e are as defined in the cutout, followed by reaction of the cyclic aoetalu of formula VI at a temperature of 15-25 ° C in the presence of a mercuric salt and preferably acetate rfcutnatého ae compounds of the cast iron

R ³ - OH (VII) \

wherein R is as defined above, to form the reaction intermediate in situ with NaBH4.

Said reaction processes may also be carried out in reverse order, i.e. the alkyl halide of formula (11) reacts with an acylphenol of formula (III) to form a cotoether of formula (IV) and reacts at 15-25 in the presence of a mercury salt. VII to form an in situ reacting intermediate and NaBH 4, wherein the reaction product of formula VIII:

R ¹ R ² (OR ³ ) C-CH 2 - (CH 2) a C (R ⁴ 2 ¹ ) -C (R ⁵ 2 ² ) - (CH ² ) _b -CH (R ⁶ ) -O, J _b -CH (R ") ) -O- / Q \ -COR '(VII),

Wherein R @ 1 to R @ 2 @ 2, a, b are as defined above, then react with compounds of formula (V) for a longer time while removing the reaction water by azeotropic distillation and said solvents to form the product of formula (I).

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

Example 1

4- (7- $ ropoxy-3,7-dimethyl-2-octenyloxy) propiophenone ethylene acetal

Preparation of (3,7-dimethyl-2,6-octadienylX4-propionylphenyl) ether:

To a solution of 1.5 g of p-hydroxypropiophenone in anhydrous dimethylformamide was added first

0.56 g of finely dusted KOH and after dissolution 2.17 g of geranyl bromide. The reaction mixture was heated to 60-70 ° C for 2 hours and then allowed to stand at room temperature over the nose. It was then diluted with water and extracted with diethyl ether. Ether layer

200,329 was washed with 10% aqueous KOH and water, dried over anhydrous MgSO. and evaporated under reduced pressure. The residue was chromatographed on 60-120 µm Al gel and 8% w / w water (eluent: petroleum ether containing up to 20% by volume of diethyl ether). Chromatography gave 1.71 g (60%) of (3,7-dimethyl 1-2,6-octadienyl) - (4-propyonyl) ether (tt 160-162 ° C / 13 ° C, mp 29-31 ° C). Elemental analysis for C 19 H 26 N 2 O 2 S: C, 79.67; H, 9.15; Found: 79.8%; 9.06%. MS spectrum (70 eV) t 286 (1 ( +), 151 (C ₈ ^H 10 O 2), 150 ^(C 9 ^H 10 ° 2 ^{) 121}

Preparation of 4- (3,7-dimethyl-2,6-octadienyloxy) propiophenone ethylenaetal 1

A mixture of 630 mg of (3,7-dimethyl-2,6-octadienyl) - (4-propionylphenyl) ether, 160 mg of distilled ethylene glycol and 1 mg of p-toluene sulfonic acid was heated to reflux for 1 hour using a reflux adapter. azeotropic distillation and anhydrous benzene as solvent. After most of the solvent was evaporated under reduced pressure, the residue was partitioned between diethyl ether and saturated NH4CO3 solution and the residue of the dried ethereal layer was further chromatographed on a silica gel column (8% w / w, eluent PE containing up to 20% by volume of diethyl ether). Combination of homogeneous fraction chromatographs gave 350 mg (48%) of 4- (3,7-dimethyl-2,6-octadienyloxy) propiophenone ethylenaetal (m.p. 180-182 ° C / 13 Pa). Elemental analysis for C ₂₁ H ₂₅ O 3 (300)! calculated 76.33% C, 9.15% Found 76.25% Hj 0,9,03% H. Mass spectrum (70 eV) 330 (M +), 301 IWÍOjHjOj), 121 (C ₇ H ₅ O ₂₎ .

Preparation of 4- (7-propoxy-3,7-dimethyl-2-octenyloxy) propiophenone ethylenaetal!

A mixture of 330 mg of 4- (3,7-dimethyl-2,6-octadienyloxy) propiophenone ethylenaetal and 320 mg of mercuric acetate in 7 ml of anhydrous n-propanol was stirred at room temperature for 90 minutes. The reaction mixture was then ice-cooled and treated with 1.4 ml of 3 M NaOH and a solution of 28 mg of β-β in 1 ml of NaOH. ⁱⁿ that it was further stirred at room temperature for 3 hours. ** shaking the reaction mixture between petroleum ether and water, the organic layer obtained after drying over anhydrous MgSO 4 and evaporating the petroleum ether under reduced pressure was chromatographed on silica gel with 8 wt. water (eluent PE containing up to 20% by volume of diethyl ether). 170 mg (43%) of chromatographically pure 4- (7-propoxy-3,7-dimethyl-2-octenyloxy) propiophenone ethyl tenoetal (tm 207-209 ° C / 13 Pa) were chromatographically pure. Elemental analysis for ^C 24®38 ° 4 (390) and calculated 73.80% C, 9.80% H Found $ 73.77% C, 9.49% H.

Example 2

4- (7-Ethoxy-3,7-dimethyl-2-octenyloxy) propiophenone ethylene acetal!

A mixture of 5.15 g of (3,7-dimethyl-2,6-octadienyl) - (4-propionylphenyl) ether and 5.7 g of mercuric acetate in 90 ml of anhydrous ethanol was stirred at room temperature for 90 minutes. After cooling the reaction mixture with ice and adding 13 ml of 3 M NaOH and a solution of 0.34 mg of NaBH in 14 ml of 3 M NaOH 4, the mixture was stirred at room temperature for 3 hours. It was then diluted with water and extracted with petroleum ether. The tract was washed with water, dried over anhydrous MgSO 4 and evaporated under reduced pressure. The residue was separated on silica gel with 8 wt. % water (binder: petroleum ether containing up to 50% by volume of diethyl ether). Chromatographically pure fractions yielded 2.5 g (42%).

4- (7-ethoxy-3,7-dimethyl-2-oktenyloxy) propiophenone (tvl6 _{^B, and} 70 C / 13 mbar).

200 329

Elemental analysis for θ21 ^Η 32 ° 3 (332): calculated 75.86% C, 9.70% H; found 75.59% C, 9.84% H. MS spectrum (70 eV): 332 (M +), 317 (Ο2θΗ29-3), 303 (C C BB OpOp, 287 (C ^ BB ^O O)), 151 (09) ^Η 110 ₂ ), ¹ 21 (Ογ Η ₅ Ο ₂ ), 87 (C ^ O), 59 (C ^ O).

Preparation of ethylene acetal 4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) -propiophenones

A mixture of 731 mg of 4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) propiophenone, 160 mg of distilled ethylene glycol and 1 mg of p-toluenesulfonic acid was heated to reflux using an azeotropic distillation head and anhydrous benzene. as solvents.

After refluxing for one hour, the vast majority of the benzene was evaporated under reduced pressure and the residue was shaken between diethyl ether ® saturated NaHCO 3 solution. The residue of the dried ether layer was chromatographed on silica gel with &gt; water eluent: PE containing up to 20% by volume diethyl ether. Chromatographically pure fractions gave 520 mg (63%) of 4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) propiophenone ethylene acetal (tl 205-227 ° C / 13Pa). Elemental analysis for ^C 23 ^H 36 ° 4 (376): calculated 73.37% C, 9.64% H, found 73.55% C, 9.60% H. MS spectrum (70eV): 37 <4M ⁺ ), 361 ( C, H, O, 347 (C, H, P, 87): IR (5% CCl3) t 927 and 1052 cm &lt; -1 &gt;.

EXAMPLE 3 2-Propyl-2-ethyl-4- (7-ethoxy-3,7-dimethyloctyloxy) -propiophene:

Preparation of (3,7-dimethyl-6-octaayl) - (4-propionylphenyl) ether:

* A solution of 750 mg of p-hydroxypropiophenone and 260 mg of finely refined KOH in 10 ml of anhydrous dimethylformamide was added with 1.1 g of oitronellyl bromide. The mixture was heated at 60-70 ° C for 2 hours and was allowed to stand overnight after cooling to room temperature. After dilution with water by extraction with diethyl ether The ethereal layer was washed with 10% aqueous KOH and water, dried over anhydrous MgSO ^ and evaporated under reduced pressure, the residue ^w Elenia column chromatography on silica with 8% by weight. of water (eluent Pe, containing up to 20% by volume of dimethyl ether) gave 940 mg (64%) of chromatographically pure (3,7-dimethyl-6-octenyl) - (4-propionylphenyl) ether (m.p. 177-179 ° C). ). Elemental analysis for O ₁₉ Η ₂ θ _{0 2} (288): calculated 79.11% C, 9.78% H; % H, 9.66%; Preparation of 4- (3,7-dimethyl-6-octenyloxy) propiophenone 1,2-propylene acetal:

Using the same procedure as in Examples 1 and 2, 553 mg (50%) of 4- (3,7-dimethyl-6-octenyloxy) -propiophenone, 552 mg (50%), were prepared from 920 mg of 4- (3,7-dimethyl-6-octenyloxy) propiophenone. (mp 190-193 ° C / 13Pa) Elemental analysis for ^C 22 ^H 34 ° 3 (346): calculated 76.25% C, 9.89% H 3 found 76.35% C, 10.21% H,

Preparation of 4- (7-ethoxy-3,7-dimethyloctyloxy) propiophenone 2-propylene acetal:

In the manner described in detail in Examples 1 and 2, 4- (3,7-dimethyl-6-octenyloxy) proplophenone was obtained from 540 mg of 4- (3,7-dimethyl-6-octenyloxy) proplophenone 230 mg (40%) of 1,2-propylene acetal of 4- (7- ethoxy (3,7-dimethyloctyloxy) propiophenone (mp 215-221 ° C / 13Pa). Elemental analysis for ^C 24 ^H 40 O 4 (3θ ² ) «calculated 73.42% C, 10.27% H ₅ found 73.47% C, 10.38% H.

Example 4: 4- (6-Ethoxy-6-methyl-2-heptyloxy) propiophenone ethylene acetal:

200 329

Preparation of (6-methyl-5-hepten-2-yl) - (4-proplonylphenyl) ether:

The reaction mixture of 750 mg of p-hydroxypropiophenone, 280 mg of KOH and 955 mg of 2-bromo-6-methyl-5-heptene in 10 ml of anhydrous dimethylformamide was heated at 60-70 ° C for 2 hours and then allowed to stand overnight at room temperature. temperature. After dilution with water, extraction with diethyl ether, drying of the ethereal layer with anhydrous MgSO 4 and evaporation of the solvent under reduced pressure, the residue was separated on a silica gel column and 8% by weight. water (eluent: PE containing up to 20% by volume diethyl ether. Chromatography gave 749 mg (57.6%) of (6-methyl-5-hepten-2-yl) - (4-propyonylphenyl) ether (t 130-132 ° C). Elemental analysis for 9χγ ^Η 24 ^Ο 2 (260): calculated 78.41% C, 9.29% H, found 78.19% C, 9.26% H.

Preparation of 4- (6-methyl-5-hepten-2-yl) propiophenone ethylene acetal:

From the procedure described in Example 1, 367 mg (45%) of 4- (6-methyl-5-hepten-2-yl) -ethylene acetal was obtained from 700 mg of (6-methyl-5-hepten-2-yl) - (4-propionylphenyl) ether. yloxy) propiophenone (tl 143-146 ° C / 13Pa). Elemental analysis for ^ο χθ ^Η 28 ^Ο 3 (304): Calculated: C, 74.96; H, 9.27; Found: C, 75.12; H, 9.47.

Preparation of 4- (6-ethoxy-6-methyl-2-heptyloxy) propiophenone ethylene acetal:

A mixture of 304 mog of 4- (6-methyl-5-hepten-2-yloxy) propiophenone ethylene acetal and 300 mg of mercuric acetate in 5 mL of anhydrous ethanol was stirred at room temperature for 90 minutes. After cooling the reaction mixture with ice and adding 1 ml of 3 KaOH and a solution of 20 mg of NaBH4 in 0.8 ml of 3 M NaOH, the mixture was stirred at room temperature for 3 hours. It was then diluted with water and extracted with petroleum ether. The dried extract residue was separated on silica gel with 8 wt. water (eluent: PE containing up to 50% by volume diethyl ether). The combined chromatographically pure fractions gave 110 mg (31.4%) of 4- (6-ethoxy-6-methyl-2-heptyloxy) propiophenone ethylene acetal (t 153-155 ° C / 13Pa). Elemental analysis for ^2χ Η ° 34 ° 4 (350): Calculated: 71.96% C 9.77% 72.25% started up Hj 0, 9 _of 47% H

Example 5

The following compounds were prepared as described in Examples 1 and 2:

2-Ethyl-2- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) ienyl] -4-hydroxymethyl-1,3-dioxolane, η 4, 1.51-9; IR (5'ní solution in CCl ^): 3605 cm ^"1 (y OH) 30

4- [7- (2-ethoxy) ethoxy-3,7-dimethyl-2-octenyloxy] -propiophenone ethylene acetal, np »1,490, Ethyleneacetal 4-7- (2-acetyloxy) ethoxy-3,7-diE) afhyX ~ 2-octenyloxyr] -propiophenone, n ^{5 5} 1,4 1.4898,

2-Ethyl-2- [4- (7- (2-tetrahydrofuryl) methoxy-3,7-dimethyl-2-octenyloxy) phenyl] -4-hydroxy-90 methyl-1,3-dioxolene, Hp-1,4922, ^x 90

4- [7- (2-Chloro) ethoxy-3,7-dimethyl-2-octenyloxy] propiophenone ethylene acetal, m.p. 21 5

4- C7- (2-Cyano) ethoxy-3,7-dimethyl-2-octenyloxy] propiophenone ethylene acetal, n _D 'sl, 5100,

Mass spectrum (70 eV): 372 (CggH-NO), 208 (C ₁₃ H ₂₂ NO), 165 (C _g H _g O _g). IR spectrum (4% solution in CC1 _4): 2259 cm ^"1 (FCN)

4- (7-Sthoxy-3,7-dimethyl-2-octenyloxy) propiophenone 2,2-dimethyl-1,3-propyleneacetal, MS spectrum (70 eV): 418 (M ⁺ ), 403 (C 8 H 11), 389 ( 024 ^Η 37 ^θ 4), 207 (0 _{2 2} ^Η χ 5 ^ο 3) · 143 (C ₈ H ₉ Og), (C ₅ H _n O),

200 329

4,5-Dibutyl-2-ethyl-2- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] -1,3-dioxolane.

KS spectrumu®. (70 eV) with 442 (CggH ^ op, 413 (C ₂ ^H 7 41 ° ^{277 (C} 17 ^H 25 3> · ⁸⁷ ^ 0).

2-Ethyl-2-C4- (7-ethoxy-3,7-diethyl-2-octenyloxy) phenyl] -4-heptyl-1,3-dioxane. MS (70 ° C) 48488 (M ⁺ ), 473 (C CH ^O op), 459 (C ^H HO ^), 413 (CgH ^Oj), 277 (C ^ HH H ^), (C ^ HHg ^),

4- (7-Benzyloxy-3,7-dimethyl-2-octenyloxy) benzophenone ethylene acetal, n _D = 1.5160,

2-ethyl-2- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] -4-chloromethyl-1,3-dioxolane. Spectrum (3% solution in CCl3) $ 1O75.1O56cto ³ (ydioxolane ring, syni), 1172 (γ dioxolane ring, asym.), 1364.1381 (efs gem.CH,), 1512.1584.16llcss ”* ^ (In aroma ticking). Mass spectrum (70 eV): 424 J ih (M ⁺⁾ 395/7 (C ₂₂ H ₃₂ C 10 _4), 349/51 _{(26 Ο} 2θ Η «.Ο _3), 213 ^ 5 VJ B _{1O 1O} C1O ₃₎ , 149/51 ( ^C 8 ^H 10 ClO 6), 183 ^(C 12 ^H 23 ^{O) 137 (C} 11 ^H ) Ethyl-2- (4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl) ^ ~ methoxy-4-methyl-l, 3-dioxolane, n ²⁴ = 1.5072. Mass spectrum (70 eV): 374 (C ₂ ^H 3 34 ° 4) · ³⁴⁵ ^ ^^ 21¼ ^{329 (C} 21 ^H 29 ° 3 '- 2-Ethyl-2- [4- (7- (2-hydroxy) ethoxy-3,7-dimethyl-2-octenyloxy) phenyl) 4-chloromethyl-1,3-dioxolane, np ⁴ ' = 1.4816 ,

2-Ethyl-2- [(7-ethoxy-3,7-dimethyl-2-oktenyloxy) phenyl] -l, 3-benzodioxole, »p ⁴ = 1.5112, 2-ethyl-2-4- (7 ~ cyclopropylmethoxy-3,7-dimethyl-2-oktenyloxy) phenyl-l, 3-dioxolane, N ²⁴ - 1.5043.

The biological activity of the compounds prepared according to the invention was tested on the activity of insect juvenile hormone, the tissues 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 (Pyrrhovoridae and Pentatomidse). stripped beetles (family Tenebrionidae). The activity of the test substances was evaluated by inhibition of metamorphosis. Egiiter results obtained from the above testing are shown in Table 1 and are expressed in standard units of ID 50, which indicates the amount of the substance in micrograms per insect that induces intermediate forms between larvae and adult (for bugs) from the above experimental conditions. pupa and adult (beetles).

Table 1

Dysdercus Graphosoma ^A enebrio clngulatus italiciun molitor methyl ester of cis-10,11-epoxy-3,7,11-trimethyltrans, trana-2,6-tridecadienic acid (reference substance)

Ethyleneacetal-4 (7-ethoxy-3,7-dimethyl-2-octenyloxy) propiophenone 1

4- (7-Ethoxy-3,7-dimethyl-2-octenyloxy) propiophenone 1,2-propylene acetal 5

4- (7-Propoxy-3,7-dimethyl-2-octenyloxy) propiophenone ethylene acetal 5, 4- (7-ethoxy-3,7-dimethyl-octyloxy) propiophenone 5-propylene acetate 5

Ethylenac etal of 4- (6-methoxy-6-methyl-2-heptyloxy) propiophenone 1

3 '

0.06

200 329 4- (7-Propoxy-3,7-dimethyloctyloxy) proplophenone 4-naphthyleneacetal

4- (6-Ethoxy-methyl-2-heptyloxy) proplophenone ethyl ethylate 10

2-Ethyl-2- (4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl) -4-heptyl-1,3-dioxane 5

4,5-Dibutyl-2-ethyl-2- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] -1,3-dioxolane 8

Ethyleneacetal-4- [7- (2-chloro) ethoxy-3,7-dimethyl-2-octenyloxy] proplophenone 0.5

Claims (2)

An insecticidal composition based on insecticide regulating agents, characterized in that it contains juvenoid and juvenoldogeamine as an active ingredient. Sausages β by a cyclic acetal bond in the molecule of both formulas IR ¹ R ² (OR ³ ) C-CH ₂ - (CH ₂₎ ) _g -C (R ⁴ Z ^X ) -C (R ⁵ Z ² ) - (CH 2 -CH 2 CH ² ) -O- wherein t ¹ - the symbol a denotes an integer between 0 and 2, - the symbol b denotes 0 or 1, - the symbols c, d, e indicate an integer between 0 and 2, 1 2 - B and R are methyl or ethyl, - R @ 1 represents straight or branched chain alkyl of up to 6 carbon atoms, straight or branched alkoxyalkyl of up to 6 carbon atoms, straight or branched chain hydroxy of up to 6 carbon atoms, or a branched chain having a total number of up to 6 carbon atoms, cyanoalkyl straight or branched having a total number of up to 6 carbon atoms, aoyloxyalkyl of a straight or branched chain having a total number of up to 6 carbon atoms, (oycloalkyl) alkyl and a total number of up to 6 carbon atoms , (oxaoykloalkyl) alkyl with a maximum of 6 carbon atoms, aralkyl with a maximum of 9 carbon atoms, - the symbols R ^ R ^ and představujíθ are hydrogen, methyl or ethyl, - symbol R? denotes straight or branched alkyl having at most 6, carbon atoms or phenylalkyl, 1 2 the symbols Z and Z denote hydrogen or together form a double bond, or in the case where α2 denotes the same straight-chain or branched alkoxy group with a total of at most 6 carbon atoms. 200 329 the symbols X * ιϊ / represent a hydrogen straight or branched substituent of the formula 2 ³ - (CH) _f wherein R f is Oele number ranging from 1 to 15; Z ³ , which may be the same or different, may be hydrogen or a straight or branched alkyl and 1 to 15 carbon atoms, with no more than 3 ^uhlíku carbon atoms in the substituents X * to Χθ, a straight or branched substituent From ⁴ - (CH) k * Z ² wherein Z ¹ is as defined above; g is an integer ranging from 0 to 15; Z ³ , which is represented in and at most three times by chlorine or bromine, -OH, ΟΖθ or phenyl, wherein Z ^ represents straight or branched alkyl of 1 to 15 carbon atoms, the bond -O-C 1 -X ² -CX ³ X ⁴ -O- in formula 1 represents a group 2 _t Process for preparing compounds according to claim 1 characterized by reacting an alkyl halide of the formula 11, 6 (R ¹ R ²⁾ C-CH (CH) C ^(R4 ^ ¹⁾ »C (R ⁵ Z ²⁾ - (CH 2) _b -CH (R ⁶ ) -X (II), in which the symbols H ¹ , R ² , R 2 to R ^{2 to} R ² , R ² , a, b are as defined above and X represents chlorine or bromine, and an acylphenol of formula III (III), γ wherein R is as defined above at a temperature in the range of from 20 to 80 ° C in an anhydrous aprotic solvent environment preferably in dimethylformamide and with an alkali metal reagent and preferably anhydrous KgCO 4, KOH, CH 2 ORa or HaH to form a cotoether (IV), (V), e (x ³ x ⁴ ). (VI), (Customs ⁶ ). (R ¹ R ² ) C - CH - (CH 2) a C (R ⁴ Z ¹ ) -C (R ⁵ Z ² ) - (CH 2) _{b -} CH (R ⁶ ) - compounds of formula (V) HO- (CX ¹ X ² ) o- (CX ³ X ⁴ ) d- (CX ⁵ X ⁶ ) _e -OH wherein X ¹ to X ⁶ , e, d, e denote the same as in formula I 'in the presence of a catalyst and preferably p-TaOH at the boiling point of benzene, toluene, while removing the water by azeotropic distillation and said solvents, converts to the cyclic acetal of formula VI p} (R ¹ R ² ) C-CH- (CH 2) j -C (R ⁴ Z) ¹ ) -C (R ⁵ Si ² ) - (CH 2) _b -CH (R ⁶ ) -OZ 2 -L- (C ¹ x 5 ₍ 1 - / xx ³⁾ : 200 329 wherein R ¹ , R ² , R ^{4 through} R ⁷ through X ⁷ , a, b, c, d, e are as defined above, followed by the reaction of the cyclic aetal of formula VI at a temperature of 15 to 25 ° C at mercuric salts and preferably mercuric acetate and compounds of the formula VII R ³ - OH (VII), wherein R ³ is as defined above to form an in situ reactive with NaBH 4, said reaction processes also being carried out in an altered order, i.e. the alkyl halide veoree II reacts together with the aoylphenol of formula III to blame kotoetheru obeoného formula IV and tan reacted at 15-25 ° C in the presence of a mercuric salt and preferably ootan mercuric aa compounds of the pattern VII to form reakěního reactive intermediate in-situ and Kabhi ^, the product by the reaction pattern VIII R ^X R ² (OR ³ ) C-CH 2 - (CH 2) and -C (R ⁴ Z ¹ ) -C (R ⁵ Z ² ) - (CH 2) _b -CH (R ⁶ ) -O 2 -COR ⁷ (VIII), wherein R ¹ to R ⁷ , Z 2, Z ² , a, b are as defined above and then reacted further with compounds of formula (V) while removing the reaction water by azeotropic deacetillation and said solvents to form the product of formula (I).