CS252584B1 - Mixed ester of succinic acid with 1-(2,2-dimethyl-2h-chroman-6-yl)-1-alkonol and 5,9,12-trimethyl-4-6-tetradecadien-3-ol or its 13-hydroxy-,13-aloxy-and 13-aralcoxcarbonylalkylcarboxyderivative and method of its preparation - Google Patents

Abstract

The essence of the solution is a mixed acid ester succinic with 1- (2,2-dimethyl-2H-chromem-6-yl) -1- -alkanol and 5,9,13-trimethyl-4-6-tetradecadiene- -3-ol, and its 13-hydroxy-, 13-alkoxy, respectively 13-aralkoxycarbonylalkylcarboxy derivative WHAT , ch3 ch3 R 1 -CH 2 -CO-CH 2 -CH 2 -CO-O-R 2 Process for preparing a mixed acid ester succinic is the reaction of a monoester derivative in reaction with alcohol in the presence catalytic amount of 4-dimethylaminopyridine and dicyclohexylcarbodiimide in an anhydrous medium diethyl ether at 15-25 ° C.

Description

The present invention relates to a mixed succinic ester with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-alkanol and 5,9,13-trimethyl-4,6-tetradecadien-3-ol, respectively 13-hydroxy-, 13-alkoxy- and 13-aralkoxycarbonylalkylcarboxy derivative as a biologically active substance and a process for its preparation.

Substances which cause developmental deviation in their final effect on insects include the compounds of the invention. Their specificity is that they contain in the molecule a portion responsible for developmental deviation caused by the effect typical of juvenile hormone analogs and a portion responsible for developmental deviation caused by the effect typical for precocene-type analogs.

The present invention provides a mixed succinic ester with 1- (2,2-dimethyl-2H-dimethyl-2H-chromen-6-yl) -1-alkanol and 5,9,13-trimethyl-4,6-tetradecadiene-3 -ol, respectively its 13-hydroxy-, 13-alkoxy- and 13-aralkoxycarbonylalkylcarboxy derivative of the general formula X

o -co -ch ₂ -ch ₂ -co-o -r ² where R ¹ denotes a straight or branched chain alkyl group having a maximum of 3 carbon atoms, 2 R denotes a group

CH-CH-CH-CH _K 3, 3.25

R -C- (CH ₂ ) ₃ -CH-CH ₂ -CH = CH-C = CH-CH ^CH 3 wherein R represents hydrogen or a straight or branched-chain alkoxy group having a maximum of 3 carbon atoms or -OR ⁴ wherein R ⁴ denotes a group

-CO - (CH _{2) 2} -CO ₂ -O-CH

CH ·,

CH,

2

A process for preparing a mixed succinic ester of formula I (R, R is as defined above, R is hydrogen or a hydroxyl group or a straight or branched chain alkoxy group of up to 3 carbon atoms) is characterized by reacting a monoester derivative of the formula II

o-co-ch ₂ -ch ₂ -cooh wherein R ¹ is as defined above with an alcohol of formula III? ^H 3 CH, C, H _{c 3} 1 i ³ i ^{2 5} RC- (CH ² ), - CH-CH, -CH = CH-C = CH-CH-OH ^{2 3} I ²

CH ₃ CH ₃ (III) wherein R is as defined above in the presence of an equimolar amount of dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine in anhydrous diethyl ether at 15-25 ° C.

A process for preparing a mixed succinic ester of formula I (R, R is as defined above, R is OR, wherein R is as defined above) is characterized by reacting twice the molar amount of the monoester derivative of formula XI, where R ¹ is as defined above, with an alcohol of formula III wherein R ³ is hydroxyl, in the presence dvojnásovného molar amount of dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine in an anhydrous diethyl ether at a temperature of 15-25 ° C.

The invention is further illustrated by the following examples without being limited thereto.

He did

Reaction mixture of 64 mg (0.2 mmol) of monoester of succinic acid with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-propanol, 56 mg (0.2 mmol) trimethyl-13-methoxy-4,6-tetradecadien-3-ol and 41 mg (0.2 mmol) of dicyclohexylcarbodiimide in 5 mL of anhydrous diethyl ether were stirred at 15-25 ° C for 2 hours in the presence of a catalytic amount of 4-dimethylaminopyridine and then left to stand overnight.

After filtering out the N, N- ¹ -dicyclohexylurea, the filtrate was washed successively with 5% aqueous hydrochloric acid, saturated sodium chloride solution. The ether layer was dried over anhydrous sodium sulfate and evaporated under reduced pressure. The residue was separated by column chromatography on silica gel with 8% water by weight (eluent: petroleum ether containing up to 20% diethyl ether). 55 mg (47%) of the reaction product was obtained.

MS analysis: 582 (M ^+, C ^ H ^ Og), 567 (C ^ H ^ Og), 535 (C ^ H ^ Og), 346 (C _2Q H ₂ GOG), 331 (C ₁₉ H ₂₃ O ₅ I, 303 (C ₁₇ H ₁₉ O ₅ ), 201 (C ₁₄ H ₁₀ O), 185 (C ₁₄ H 16 O);

IR analysis (CC1 _4): 2830 (ífgCHj of OCH), 1740, 1729 (l / C = O), 1652, 1643 (VC = C), 1615, 1494 ((Zaro.), 1392, 1378, 1365 «^ Cm ^-1 .

In the same manner, a mixed ester of succinic acid with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-propanol and 5,9,13-trimethyl-4,6-tetradecadien-3-ol was prepared.

MS analysis: 552 346

185 (M ^+, C ₃₅ H ₅₂ O _5), 486 (C _3Q H ₄ Go _5), 471 (C ^ H ^ Og), 457 (C ^ H ^ Og), ^(C 20 ^H 26 ° ^O5) ' ^{331 (C} 19 ^H 23 ° 5 ⁾ ' ^{318 <C} 18 ^H 22 ° 5 ⁾ ' ^{303 <C} 17 ^H 19 ^O 5>' ^{201 (C} 14 ^H 17 °>' ^(C 13 ^H 13 ^O) ' ¹⁰¹ < ^C 4 ^H 5 ° 3 '

IR analysis (CCl ₄ ): 1738 (γΟ = Ο), 1652, 1643 (RC = C) (J ” _with CH ₃ ), 1265 (^ C-O ester.) Cm ³ .

1615, 1494 (Var.), 1393, 1382, 1362,

Example 2

Reaction mixture of 64 mg (0.2 mmol) of monoester of succinic acid with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-propanol, 27 mg (0.1 mmol) trimethyl-4,6-tetradecadiene-3,13-ol and 41 mg (0.2 mmol) of dicyclohexylcarbodiimide in 5 ml of anhydrous diethyl ether were stirred at 15-25 ° C for 2 hours in the presence of a catalytic amount of 4-dimethylaminopyridine and then was allowed to stand overnight. After filtering off the N, N'-dicyclohexylurea, the filtrate was washed successively with 5% aqueous hydrochloric acid, saturated sodium chloride solution. The ether layer was dried over anhydrous sodium sulfate and then evaporated under reduced pressure. The residue was separated by column chromatography on silica gel with 8 wt. water (eluting with petroleum ether containing up to 20 vol. diethyl ether). 42 mg (48%) of the reaction product was obtained.

MS analysis: 652 (CjgH ^ Og), 597 (C ₃₅ H _{4 g} O _g), 581 (C ₃₅ H _{49 O?),} 346 (C ₂₀ H _{2 g} O _5), 331 (C _g H ₂₃ O _5); 303 (C ₁₇ H ₁₉ O ₅ ), 201 (C ₁₄ H ₁₀ O), 185 (C ₁₄ H ₁₅ O ₃ ), 101 (C ₄ H ₅ O ₃ );

IR analysis (CC1 _4): 1742, 1729 (vc = O), 1651, 1643 (YC = C), 1614, 1494 (^ arom.), 1375 <C? ^CH 3> · 1266 (YC-0 COOR) cm ^-1 .

Biological effects were monitored.

for termites:

I. affected by the development of soldiers and white soldiers, the overall slowdown in development. Prorhinotermes simplex (application to Whatman # 1 chromatography paper, in acetone) was used as the test organism. To monitor the antijuvenilizing effect, a high degree of developmental determination on the military caste was first induced using the juvenilizing agent methoprene. Influence, ie reduction of the number of soldiers or their prevention, their formation, eventually the emergence of transient individuals between soldiers and larvae known as interkastú is then given as a fraction, where the numerator indicates the percentage of fully developed white soldiers, the denominator of the resulting Ínterkastú.

Mixed succinic ester with 1- (2,2-dimethyl-2H-hromen-6-yl) -1-propanol and 5,9,13-trimethyl-4,6-tetradecadiene-3,13-diol (0,2 0/0 after 11 days, 0/0 after 13 days, 0/0 after 15 days, 0/0 after 17 days, 0/0 after 19 days, 0/0 after 21 days.

Effect of methoprene (0.1 wt% in acetone): 10/0 after 11 days, 30/0 after 13 days, 40/0 after 15 days, 60/0 after 17 days, 80/0 after 19 days, 80 / 0 after 21 days.

II. antifeedant effect.

Coptotermes formosanum (application to Whatman # 2 chromatographic paper, in acetone) was used as the test organism. For mixed succinic ester with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-propanol and 5,9,13-trimethyl-4,6-tetradecadien-3-ol (1% w / w) in acetone): there is a 84% reduction in termites in termites compared to termite control groups. For mixed succinic ester with 1- (2,2-dimethyl-2H-hromen-6-yl) -1-propanol and 5,9,13-trimethyl-13-methoxy-4,6-tetradecadien-3-ol ( 0.01 wt.% In acetone) there is a 67% reduction in voracity against the termite control groups.

For a mixed succinic ester with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-propanol with an alcohol of formula III, where R ³ is -OR ⁴ (R ³ , R ⁴ have the above (0.1% by weight in acetone), there is a 52% reduction in voracity compared to termite control groups.

Biological effects have also been studied in Tenebrio molltor. Activity was assessed by inhibition of metamorphosis, and is expressed in quantity in mlkrogramech on the insect individual, which triggers when topically applied form an intermediate forms: ID - _n sample smi1 3 ^ου gust succinic acid ester of this invention (R = ethyl, R = methoxy ) =. 34 = 0.03: 1Dq of the mixed ester sample of the invention (R = ethyl, R = OR, where R is as defined above) = 1.

Claims (3)

SUBJECT OF THE INVENTION 1 2 A process for the preparation of a mixed succinic ester of the general formula I, wherein R and R 2 1 2 1. Mixed succinic ester with 1- (2,2-dimethyl-2H-chromen-6-yl) -1-alkanol and 5,9,13-trimethyl-4,6-tetradecadiene-3-ol or its 13-hydroxy-13-alkoxy and 13-aralkoxykarbonylalkylderivátem formula I, -O-CO-CH ₂ -CH ₂ -CO-OR ^of where R ¹ denotes a straight or branched chain alkyl group having a maximum of 3 carbon atoms, 2 R denotes a group CH CH CH CH _c 3 | 3 3 J2 5 R ₃ -C- (CH ₂ ) ₃ -CH-CH ₂ -CH = CH-C = CH-CHCH Where R is hydrogen or a hydroxy or straight or branched alkoxy group having a maximum of 3 carbon atoms or an -R (R) group, wherein R is (II) - CO - (CH ₂ ) ₂ - CO - O - CH C2 ^h 5 2. A process for the preparation of a mixed succinic ester of the formula I, wherein R and R are as defined above, R @ 1 denotes hydrogen or a hydroxyl group or a straight or branched chain alkoxy group of up to 3 carbon atoms, characterized by reacting the monoester a derivative of the general formula II o-co-ch ₂ -ch ₂ -co-oh wherein R ^d is as defined above with an alcohol of the general formula III CH, CH, CH, C H, _c 3,3 i ³ i ^{2 5} R -C- (CH ₂ ) ₃ -CH-CH ₂ -CH = CH-C-CH-CH-OH-CH ₃ wherein R is as defined above in the presence of an equimolar amount of dicyclohexylcarbodiimide and a catalytic amount of 4-dimethylaminopyridine at a temperature of 15 to 25 ° C. R &lt; 4 &gt; is as defined above, R is -ORR, wherein R is as defined above; characterized in that a double molar amount of a monoester derivative of formula (II), wherein R is as defined above, is reacted with an alcohol of formula III, wherein R is hydroxy in the presence of double molar amount of dicyclohexylcarbodiimide and catalytic amount of 4-dimethylaminopyridine in anhydrous diethyl ether at 15 to 25 ° C.