CS270729B1 - Alkyl-4- (3-alkoxy-3-alkyl-2-halobutoxy) phenylketones as Biologically Active Substances and Processes for their Preparation - Google Patents

Abstract

The subject of the solution are new biologically active substances of the general formula X ch3/r3/c/or1/-chx-ch2o-(c6h4>-cor2 (I), where the symbol X. denotes halogen (chlorine, bromine), the symbol R denotes a straight-chain or branched alkyl group with a maximum of 5 carbon atoms, the symbol Rz denotes an alkyl with 1 to 3 carbon atoms with a straight-chain or branched chain. the symbol R3 denotes a methyl or ethylI group. Their pesticidal effects were tested, for example, on insects and mites. Another part of the solution is a method of preparing substances of the general formula I, consisting in the reaction of a ketone of the general formula II CH3/R3/C=CH-CH_O-(CgH4)-COR2 (II), where the symbols R2, R3 have the above-mentioned meaning with a straight-chain or branched alkanol with a maximum of 5 carbon atoms and N-halogen succinimide at a temperature of 0 to 5 C.

Description

The invention relates to alkyl-4- (3-alkoxy-3-alkyl-2-halobutoxy) -phenyl ketones as biologically active substances and to a process for their preparation.

The essence of the present invention are alkyl-4- / 3-alkoxy-3-alkyl-2-halogenbutoxy / phenyl ketone of the general formula I CH ₃ / R ³ / C / ¹ or / ₂ -CHX-CH ² O- -C0R (I) wherein X represents halogen (chlorine, bromine); R ¹ represents a straight-chain or branched alkyl group having at most 5 carbon atoms, R ² represents alkyl having 1 to 3 straight-chain or branched carbon atoms.

chain, R represents a methyl or ethyl group.

Process for preparing alkyl-4- / 3-alkoxy-3-alkyl-2-halogenbutoxy / -fenylketonů is characterized by reacting a ketone of the formula II CH ₃ / R ³ / C = CHCH ₂ O-Ζθ) - COR ² (II),

3 'f wherein R, R are as defined above, with a straight-chain or branched alkanol having at most 5 carbon atoms and N-halosuccinimide at a temperature of 0 to 5 ° C.

The invention is further elucidated by means of an exemplary embodiment, without being limited thereto.

Example 1

To 2.2 g (10 mmol) of 4- (3-methyl-2-butenoxy) propiophenone dissolved in 20 ml of anhydrous ethanol under a nitrogen atmosphere was added 3.0 g (17 mmol) of n-bromosuccinimide at 0-5 ° C. After stirring the reaction mixture for 15 hours at 0-5 ° C, the mixture was diluted with water and extracted with diethyl ether. The separated and washed ether layer was dried, evaporated and the residue was then chromatographed on silica gel with 8% by weight of water (eluent containing up to 20% by volume of diethyl ether). Chromatographically uniform fractions gave 2.5 g (73%) of 4- (2-bromo-3-ethoxy-3-methylbutoxy) propiophenone after evaporation of the elution solvent.

IC analysis / CCI _4, 6% /: 1688 / P 0 = C /, 1605, 1582, 1514 / U arom./, 1392, 1383, 1368 / / £ Γ ₃ 0Η ₃ / σω ^_1.

MS analysis: 342/4 / M ^+, C _c H _o, br0 /, 217 / C..H .. 0- /, 164/6 / CH "BrO / 87 / C _c H .O /. · * Lo 23 3 14 1/2 3 1U 3 11 ³ H NMR analysis / 200 MHz /: 1.18 / t, 3 H, J = 7.0 /, 1.21 / t, 3 H, J = 7.0 /, 1.38 and 1.42 / s, 6H /, 2.95 (q, 2H, J = 7.0), 3.48 (q, 2 H, J = 7.0), 4.27 (m, 2 H), 4.65 (m, H), 6.94 and 7.94 (arom.), 4H, J = 9.0 / ¹³ NMR analysis (200 MHz): 8.38 (CH, CH, CO), 15.94 (0CH, CH 2), 22.26 and 24.59 (CH-JC, χ λ 33 -

31.39 / CH ₃ CH ₂ CO /, 57.55 / OCH ₂ CH ₃ /, 58.61 / CHBr /, 69.88 / CH ₂ O /, 76.07 / C / CH _3/2 /, 114.37, 130.16, 130.32, 161.98 / benzene nucleus / , 199.35 / CO /.

Example 2

4- [2-Bromo-3-methoxy-3-methylbutoxy] -propiophenone was prepared in the same manner.

¹³ C NMR analysis (200 MHz): 8.37 (CH ₃ CH ₂ ), 21.96 and 23.76 (CH 2 -C), 31.39 (CH ₃ CH ₂ ), 50.00 (CHBr),

58.44 / _OCH3 /, 69.75 / CH ₂ O /, 76.21 / _C / CH _3/2 /, 114.35, 130.16, 130.35, 161.91 / benzene nucleus /, 199.35 / CO /. __ ..

MS analysis: 328/30 / ^M, C H_.BrO _lc, / 299/301 / C, H ,, Bro, /, 179/81 / C, H, BrO / 121 / C HO /

21 o 1J 10 3 o 12 .41 / ^ 7115 ^ 2 / '

Biological effects have been studied, for example, in the mite Tetranychus urticae and the termite Prorhinotermes simplex. In the tested termite Prorhinotermes simplex, the compounds according to the invention affect the development of soldiers and white soldiers, the representation of castes, so that in addition to the retardation of development they cause insecurity and extinction of colonies.

CS 270 729 Bl

For example, for 4- (2-bromo-3-methoxy-3-methylbutoxy) propiophenone was found (concentration 0.2% by weight: after 12 days 0/0, after 14 days 0/0, after 16 days 0/0 (in the numerator% of fully developed white soldiers, in the denominator% of created intercast).

In the mite Tetranychus urticae, the compounds of the invention affect oogenesis and hatchability.

Thus, 4- (2-bromo-3-ethoxy-3-methylbutoxy) propiophenone at a concentration of 10% by volume in acetone (contact application to bean leaves) caused 10 spider mites Tetranychus urticae to lay only 10 eggs. Compared to the parallel experiment with acetone alone, when the same number of mites laid 100 eggs, of which they hatched after 7 days of the next generation of mites, oogenesis and hatchability were strongly affected.

Similarly, 4- (2-bromo-3-methoxy-3-methylbutoxy) propiophenone (10% v / v in acetone): 6 mites laid 1 egg.

Claims (2)

OBJECT OF THE INVENTION 1 i CH ₃ / R ° / C / OR / -CHX-CH ₂ O- -COR dke X denotes galogen (chlorine, bromine), R denotes a straight-chain or branched alkyl group 2 having a maximum of 5 carbon atoms, R denotes a straight-chain or branched alkyl group having 1 to 3 carbon atoms, R ³ denotes a methyl or ethyl group as biologically active substances. 2. A process for the preparation of the compounds according to item 1, characterized in that a ketone of the general formula II is reacted with ch ₃ / r ³ / c = ch-ch ₂ o- (O) -COR ² (II), Alkyl-4- (3-alkoxy-3-alkyl-2-halobutoxy) phenyl ketones of the general formula I Wherein R, R are as defined above, with a straight or branched chain alkanol having up to 5 carbon atoms and N-halosuccinimide at a temperature of 0 to 5 ° C.