CS238949B1 - Processing of aliphatic aldehydes - Google Patents

Abstract

General aliphatic aldehyde derivatives formula I, ^ R1 - CH = N - NH - A ^ J + X_ / 1 / wherein R 1 is unbranched or branched non-cyclic hydrocarbon with from about 7 to about 20 carbon atoms and one to about four double bonds A is a group of formula COCH2N + H / R2 / 2, COCH2N + / R2 / 3 or , N-pyridinioacetyl, where R 2 is alkyl of 1 to 3 carbon atoms, X is a halogen atom and the method of their preparation. Derivatives are used for preparation pheromone release agents. monitoring mass capture or disorientation insect pests.

Description

(54) Derivatives of aliphatic aldehydes and processes for their preparation

Derivatives of aliphatic aldehydes of the formula I ^ R ¹ - CH = N - NH - N J ⁺ X ^_ / 1 / wherein R ¹ is a radical of straight chain or branched non-cyclic hydrocarbon having 7.až 20 carbon atoms and one to four double bonds,

A is a group of formula

C0CH N ₂ ⁺ H / R ^{2/2 +} COCH2 N / R ^2/3 or N-pyridinioacetylová group, wherein R is alkyl ^of 1-3 carbon atoms;

X is a halogen atom and a process for their preparation.

Derivatives are used for the preparation of pheromone release agents for. monitoring, mass capture or disorientation of insect pests.

The invention relates to derivatives of aliphatic aldehydes which release pheromones or substances affecting the behavior of insects and a process for their preparation. Aliphatic aldehydes having 12 to 18 carbon atoms and one or two double bonds form part of a group of insect sex pheromones that are currently increasingly used in integrated plant protection.

A practical way of using these substances is to apply them to determine the population density and flight time of a particular pest, to predict their occurrence or to directly control the pest by mass trapping or disorientation.

For the practical use of pheromones, it is necessary that the effective amount of the active substance be released uniformly and over a long period of time, i.e. for at least one flight of the pest. Aliphatic aldehyde type pheromones are highly reactive and therefore unstable, leading to rapid loss of biological activity.

Various types of evaporators are used for their application, such as rubber evaporators for monitoring, hollow fibers for monitoring and disorientation, and sprayable microencapsulated disorientation preparations, in which the pheromones are optionally stabilized by the addition of various antioxidants.

A second way to counteract the loss of biological activity of these aldehydes is to prepare their derivatives, from which pheromone is released by external factors. To date, aldehyde addition compounds with hydrogen sulphite / BEEVOR P.S. and others,

BULL. Ent. Res. 67, 439 (1977) or acetals with alcohols, degradable by ultraviolet light (PICKETT J. A. et al., 10th International Congress of Plant Protection, Brighton, UK, 1983).

Despite a number of advantages, however, these derivatives are characterized in that the rate of pheromone release is very difficult to influence and, moreover, the preparation is relatively complex.

The subject oředloženého invention are derivatives of aliphatic aldehydes of the formula I ^ R ¹ - CH-N - NH - aJ ⁺ X / 1 / wherein R is a radical of straight chain or branched non-cyclic hydrocarbon having 7 to 20 carbon atoms and jedhou to four double bonds and

A is a group of the formula, _co-CH2 -R / R _2/2,

CO-CH ₂ -S / R _2/3 or

C <= CH ₂ -Q wherein R is alkyl of 1-3 carbon atoms and X is a halogen atom and a process for preparing derivatives of aliphatic aldehydes of the general formula I, which comprises reacting an aldehyde of the formula II

R ¹ -CHO (11) wherein R ¹ is as defined above, is reacted with a compound of formula III,

wherein A is as defined above (in an inert organic solvent, preferably an alcohol) at a temperature of -10 ° C to 50 ° C, preferably at room temperature, whereupon the anion C1 is optionally converted to another anion.

This synthesis is very simple and consists only in mixing the relatively available substances in a solvent. The reaction proceeds at room temperature and can be monitored by thin-layer chromatography in a manner known per se.

Purification of the reaction product is also very simple and consists in simple chromatography of the residue of the reaction mixture to ten times Florisil. The derivatives thus obtained have reduced volatility and are soluble in both polar and non-polar solvents, which greatly facilitates their application.

Due to the pH of the environment they decompose at different speeds and this decomposition is also due to air humidity. The aliphatic aldehyde derivatives of the present invention which release pheromone eliminate some of the disadvantages of preventing the wider practical use of aldehyde-based pheromones. Thus, they extend their practical applicability as a means of integrated plant protection.

The invention is further illustrated by the following non-limiting examples.

Example 1

O

To a solution of acethydrazide-trimethylammonium chloride (Girard T, 0.9 g, 5.4 mmol) in 3 mL of methanol is added a solution of 3,7-dimethyl-6-octenal (0.8 g, 5.2 mmol) in 2 mL The reaction was monitored by thin layer chromatography (silica gel, chloroform, methanol 10: 1).

After the starting aldehyde had been reacted, the solvent was removed by rotary evaporation, the residue was diluted with 1 ml of chloroform and then chromatographed on 15 g of Florisil (100-200 mesh) using the mobile phase described above.

0.45 g of product (28.5% yield) can be obtained. @ 1 H-NMR / Varian XL-200.

D ₂ 0 + DSS ppm / MS: 3.37 / s, 9H / _CH3 / ₃ / 7.48, 7.68 / t _J? θ = J _{? g} - 6.0; t, J = 5.6,

1H, -CH = N ', 0.92 (d, 3H, CH ₃ , J = 6.6), 1.61 (br s), 3H, CH ₃ -CH-, 1.67 (br s, 3H), CH ₃ -CH =.

IR (IR 20, KBr): 1550, 1566, 1635, 1651, 1696 cm ^-1 .

NH f

N ^^ NH (CH ₃₎ C ²

The procedure of Example 1 was followed except that a solution of acethvrazide-dimethylammonium hydrochloride (Girard D) was used as the starting material. 0.34 g of product (23% yield) was obtained as a low-setting oil.

¹ H-NMR (Varian 100, CDCl ₃ , TMS): 2.33 (s, 6H, (CH ₃ ) ₂ , 1.60, 1.67 (s, 2x3H, CH ₃ -CH =).

EXAMPLE 3 _+% Mn ^ ^{NH (CH 3)} 2 ^{C _}

The procedure of Example 1 was followed except that a solution of acethvrazide-dimethylammonium hydrochloride (Girard D) in methanol and 5- (Z) -hexadecenal in methanol was used as starting materials.

0.43 g of product is obtained (22% yield) as a low-solid oil, ¹ H-NMR / Varian XL-200, D ₂ O + DSS, ppm (spectrum: 2.32 / s, 6H, Ν / ΟΗ). Δ /, 3.07 (s, 2H, CO-CH ₂ N),

7.44 (t, 1H, J = 5.6, CH-N), 5.35 (brt, 2H, -5.0, CH-CH).

Example 4 '

The procedure of Example 3 was followed except that the acethydrazide-pyridinium chloride solution (Girard P) was used as the starting material. 0.53 g of product (25% yield) was obtained as a low-setting oil.

¹ H-NMR / Varian XL-200, 7.417f61 / s, 1H, Jy. θ - J ₇ θ *

CDgOD + TMS, ppm (: 5.34) (brt, 2H, = 5.4, = 1.6, -CH-CH-), = 5.3, J = 5.6, -N-CH-), 8.15 8.67 8.93 (m, 5H, proton arons).

Example 5

JL ^ z N (CH ₃₎ Cl

The procedure of Example 3 was followed except that the acethydrazide-trimethylammonium chloride solution (Girard T) was used as the starting material. 0.5 g of product (22% yield) is obtained as a low-setting oil.

/ ^X H-NMR / Varian XL-200, CDjOD + TMS, ppm / 3.37 / s, 9H, -N / _CH3 / ₃ / 5.34 / br t, 2H, = 5.0, CH -CH- /, 7.33 / t, IH, J = J _{7 7j8>} G - 5.5, -N-CH- /.

Example 6. NH 4 γ'Χ nh (ch ₃ ) ₂ Cl -

O

The procedure of Example 1 was followed, except that a solution of acethydrazide-trimethylammonium chloride (Giral D) in methanol and (E, E) - (8,10) dodecadienal in methanol was used as starting materials. \

0.39 g of product (24% yield) is obtained as a low-setting oil. ¹ H-NMR (Varian XL-2PO, CD 3 OD + TMS, ppm)! 2.32 / s, 6H, N / CH _3/3 5.53 5.98 / br m, 4H, -CH-CH-CH-CH- / 7.29 7.54 / t, lH, J-5.8 (J-6.0, -N-CH-).

Claims (2)

SUBJECT OF THE INVENTION An aliphatic aldehyde derivative of the general formula I, Jr ¹ -CH-N-NH-aJ (1) wherein R ^X is a straight or branched non-cyclic hydrocarbon radical having 7 to 20 carbon atoms and one to four double bonds, A is a group of formula (I), CO - _CH2 - Sh / ² R / _2, CO - CH ₂ - S / R _^2/3 or wherein R is alkyl of 1-3 carbon atoms; X is halogen. 2. A process for the preparation of aliphatic hydrocarbon derivatives of the aforementioned general formula (X), characterized in that the aldehyde of the general formula (II): R ¹ - CHO (11) wherein R ¹ is as defined above, is reacted with a compound of formula III, + Wherein A is as defined above, in an inert organic solvent at a temperature of -10 ° C to 50 ° C, preferably at room temperature, whereupon the anion C1 is optionally converted to another anion.