CS200330B1 - Process for preparing alkoxyderivatives of aliphatic-aromatic ethers with cyclic acetal bonds in molecule with effect of juvenile hormone - Google Patents

Description

The present invention relates to a process for the preparation of alkoxy derivatives of aliphatic-aromatic ethers having a cyclic acetal bond in a molecule with the action of a juvenile hormone. These insect control agents are described in Czechoslovak author's certificate No. 20C 329.

It has now been found that these substances can also be prepared from other substance benefits.

The present invention relates to a process for the preparation of these compounds of formula (I)

e wherein the symbol a denotes an integer ranging from 0 to 2, the symbol b denotes 0 or 1, • the symbols c, d, e, denote an integer ranging from 0 to 2, 1 2 R and R denote a methyl or ethyl group R znamena

200 330

200 330 straight or branched chain alkyl of up to 6 carbon atoms, straight or branched chain alkyl of up to 6 carbon atoms, (cycloalkyl) alkyl with a total of up to 6 carbon atoms, aralkyl, and a total of up to 9 carbon atoms ,

- the symbols R ⁴ , R 6 _q κθ represent hydrogen, methyl or ethyl, γ

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

2

- the symbols 2 and Z denote hydrogen or together form a double bond,

- X ¹ to X ⁶ represent

- hydrogen _from 4

- a straight or branched substituent of the formula - (CH) 2 - wherein i is an integer ranging from 1 to 15; Z ³ , Z ⁴ , which may be the same or different from each other, denote hydrogen or straight or branched alkyl and from 1 to 15 carbon atoms, in which the total number of carbon atoms in which X is more than 30 ethers is not more than 30 ethers;

- a straight or branched substituent of the formula Z ⁴ - (§H) - wherein the symbol Z ⁴ is as defined above

said; g is an integer ranging from 0 to 15; Z ³ , which is represented by up to three times in the formula, represents chlorine or bromine, -ΟΖ, -ΟΖ fenyl or phenyl, where R < 2 > is straight or branched (C s-C alkyl) alkyl is an alkoxyalkyl halide of formula IX

R-bt ² (OR ³ ) C-CH 2 - (CH 2) a C (R ⁴ 2 ¹ ) -C (R ⁵ Z ² ) - (CH 2) ₁₎ -CH (R ⁶ ) -X (IX),

2. 6 1 2 wherein R to R, 2, Z, a, b, denote the same as in formula 1 and X denotes chlorine or thunder, with the acylphenol of the general formula III ___

HIM

O

- (III), wherein R is as described above, at a temperature in the range of from 20 to 60 ° C in an aprotic solvent environment, preferably in dimethylformamide, and in the presence of an alkaline reagent, preferably anhydrous KgCO 3, KOH. to form a cotoether of formula VIII

R ¹ R ² (OR ³ ) C-CH 6 - (CH 2) and -C (R ⁴ Z ¹ ) -C (R ⁵ Z ² ) - (CH 2) _b -CH (R ⁶ ) -O (VIII),

-COR

Wherein R @ 1 to R @ 2, Z, Z, a, b are as defined above, which is further reacted with compounds of formula V h - (cxM. - (CX ³ X ⁴ ), - (CX ⁵ X ⁶⁾ OH - C 19 (V), wherein X ^ to X až ', c, d, e denotes the same as in formula I, in the presence of a catalyst preferably p-XsOH at boiling point preferably benzene, toluene with removing the reaction water by azeotropic distillation with said solvents to the desired product of formula I.

200 330

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

Example 1 λ of a solution of ISO mg of p-hydroxypropiophenone in 5 ml of anhydrous dimethylformamide was first added 56 mg of powdered KOH and, after dissolution, 280 mg of 1-bromo-3,7-dimethyl-7-propoxyoctane. The reaction mixture was heated for 6 ^U to 70 ° C for 2 hours and then allowed to stand at room temperature over noo. It was then diluted with water and extracted with diethyl ether. The residue of the ether layer dried over anhydrous MgSO 4 was separated by chromatography on a silica gel column (60-120 / ton) with 8 wt. water. A blend of petroleum ether-diethyl ether with a maximum of 20% by volume diethyl ether was used as the eluent. Chromatography gave 174 mg (50%) of 4- (7-propoxy-3,7-dimethyloctyloxy) propiophenone (t at 178-180 ° C / 13Pa). Elemental analysis for C 18 H 16 O 3 (348): calculated 75.81% C, 10.41% H; found 75.51% C,

10.64% H.

A mixture of 140 mg of 4- (7-propoxy-3,7-dimethylokyloxy) propiophenone, 40 mg of distilled 1,2-propylene glycol and 1 mg of p-toluenesulfonic acid was heated under reflux for 1 hour using an azeotropic adapter. distillation and anhydrous benzene as solvent. After benzene was distilled off under reduced pressure, the residue was diluted with saturated UaHCO 3 solution and extracted with diethyl ether. Chromatography of the residue of the dried ether layer on a silica gel column with 8 wt. water (eluent: petiol ether containing up to 20 7 vol. diethyl ether) yielded 68 mg (42%) of 4- (7-propoxy-3,7-dimethyloctyloxy) propiophenone 1,2-propylene acetal (t00 to 205 ° C). 13 Pa). Elemental Analysis Found: C, 73.84; H, 10.41; Found C 73.65%, H 10.56 IR (5% solution in CCl ^): 1367.1368 (d ^ _S CH gem.dimethyl) 1612,1586,1513 cm "^ (J'aromatika) .

Example 2

In the manner described in Example 1, the following were prepared:

4- (6-Methoxy-6-methyl-2-heptyloxy) propiophenone ethylene acetal; n £ = 1.4894,

2-Ethyl-2- [4- (7-ethoxy-3,7-dimethyl-2-octenyloxy) phenyl] -4-hydroxymethyl-1,3-dioxolane;

IR (5% solution in CCl ^): 1363.1388 cm "^ (<Γθ gem.dimethyl), 3605 cm ^- ^ (*, · 'OH), * 20 Rthylenacetal 4-C7 (2-Chloro) ethoxy -3,7-dimethyloctyloxy-propiophenone; n = 1.4920, 4- (7-benziloxy-3,7-dimethyloctyloxy) propiophenone ethylenecetal;

Mass spectrum (70 eV): 411 (M ⁺ -C ₂ H ₅₎ 24γ (0 _{ι7 Η 2γ} 0), 169 (CGH ^)

2-Phenyl-2- [4- (7-ethoxy-3,7-dimethyloctyloxy) phenyl] -4-chloroethyl-1,3-dioxolane; [eta] &lt; 1 &gt; = 1, 5127, 2-Ethyl-2- [4- ( 7-ethoxy-3,7-dimethyloctyloxy) phenyl] -4-chloromethyl-1,3-dioxolane; IR (3% solution in CCl ^) l6ll, 1564.1512 cm ^- ^ (fy aroma ticks), 1364.1361 cm "^ (gem.dimethyl _s) 1172. cm" l (^ asym., Dioxol.kruh ), 1075.1056 cm ^- ((sy 4 -sym, dioxol ring),

2-Ethyl-2- [4- (7-ethoxy-3,7-dimethyloctyloxy) phenyl] -4-methoxymethyl-1,3-dioxolane; IR (6% solution in CCl ^): 1611,1585,1509,1497 cm ^- * · · (JP aromatic), 1369.1380 cm "l (d _with gem.dimethyl), 1160 cm ^- * · · ( J asym., Dioxol ring), 1048 (J-sym., Dioxol ring), 1247 (JJ / CO), 1459 (C ^ es., ΟΗ ^ οπΓ ¹ ,

200 330

2-Ethyl-2- C4- (7-cyclopropylmethoxy-3,7-dimethyloctyloxy) phenyl] -4-chloromethyl-1,3-dioxolane; n ^ ^{0 5} - 1.4985.

The biological activity of the compounds of the invention has been tested on the basis of insect juvenile hormone activity and is described in U.S. Pat. copyright certificate (PV 2219-77).

Claims (1)

SUBJECT OF THE INVENTION A process for the preparation of alkoxy derivatives of aliphatic-eromatic ethers having a cyclic acetal bond in a molecule having the action of a juvenile hormone of the formula I? Λ ² (OR ³ ) C-GH 5) (GH 2) -C (R ⁴ Z ¹ ) -C (R ⁵ Z ² ) - (CH 9) - CH (R ⁶ ) -O- <0} -C- <\ d (I) in which - the symbol a denotes an integer between 0 and 2, - the symbol b denotes 0 or 1, - c, d, e are an integer between 0 and 2, 1 2 - R and R are methyl or ethyl, - R is straight and branched chain alkyl of up to 6 carbon atoms, haloalkyl and straight or branched chain of up to 6 carbon atoms, (cycloalkyl) alkyl with up to 6 carbon atoms, aralkyl and up to 9 carbon atoms, £ c £ - R, R ³ and R are hydrogen, methyl or ethyl, - the symbol R represents straight or branched alkyl having a total of at most 6 carbon atoms or a phenyl group, 1 2 - Z and Z denote hydrogen or together form a double bond, the symbols X ^ to X ^ represent - hydrogen, ^ 4 3 ’ - a straight or branched substituent of the formula Z - (CH) - - wherein f is an integer ranging from 1 to 15; the symbols Z ³ , Z ⁴ which are the same or may differ i denotes hydrogen or straight or branched alkyl β of 1 to 15 carbon atoms, with a total of not more than 3θ of carbon atoms in the substituents X ^ to X ^, ς - a straight or branched substituent of formula Z E ⁴ - (CH ₂ ) _g -, wherein Z ⁴ is as defined above; g is an integer ranging from 0 to c 15; the symbol 2>, which is represented in the formula up to three times, means chlorine or Bromo, -OH, OZ or phenyl, wherein Z is straight or branched (C 1 -C 15) alkyl, as defined by reacting an alkoxyalkyl halide of formula (IX) 200 330 R 2 R ² (O ³ ) C-CH 2 - (CH 2) and -C (R ⁴ 2 ¹ ) -C (R ⁵ 2 ² ) - (CH 2) _b -CH (R ⁶ ) -X (IX), Wherein R to R, 2, 2, a, b, denote the same in formula 1 and X is chlorine or bromine, and the acylphenol of formula III HO (III) wherein R 'is as defined in the formula. Even at a temperature in the range of from 20 to 80 ° C in an anhydrous aprotic solvent, preferably in dimethylformamide, and in the presence of an alkaline reagent, preferably anhydrous K 2 CO 2, KOH, CH 2 OR a or aH, to form a cotoether of formula Vlil R ¹ R ² (OR ³ ) C-CH 2 - (CH 2) and -C (R ⁴ 2 ¹ ) -C (R ⁵ 2 ² ) - (CH 2) _b -CH (R ⁶ ) -O- ^ Q ^ OOR ⁷ (VIII), 1 712. wherein R, and R, 2, 2, a, b are as defined in Formula I, which is further reacted with compounds of Formula V HO- (CX ¹ X ² ) 0- (CX ³ X ⁴ ) d.- (CX ⁵ X ⁶ ) _e -OH (V), where X ¹ to X ¹ , c, d, e mean the same as in the formula I, in the presence of a catalyst preferably p-TsOH at boiling point, preferably benzene, toluene, while removing the reaction water by azeotropic distillation with said solvents to the desired product of the general formula I.