CS277114B6 - 1- [4- (3-Alkoxy-3-methyl-2-bromobutoxy) phenyl] -alkyl ester alkanoic acid as biologically active substance and process for its preparation - Google Patents
1- [4- (3-Alkoxy-3-methyl-2-bromobutoxy) phenyl] -alkyl ester alkanoic acid as biologically active substance and process for its preparation Download PDFInfo
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- CS277114B6 CS277114B6 CS903867A CS386790A CS277114B6 CS 277114 B6 CS277114 B6 CS 277114B6 CS 903867 A CS903867 A CS 903867A CS 386790 A CS386790 A CS 386790A CS 277114 B6 CS277114 B6 CS 277114B6
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Abstract
Nová biologicky účinná látka obecného vzorce I (I), (CH3)2C(OR)CHBrCH2O-C6H4-CH(R)OCO(CH2)aCH3 kde symbol R značí alkylskupinu s rovným či rozvětveným řetězcem s maximálně 4 atomy uhlíku, symbol a značí celé číslo v rozmezí 0 až 16. Její pesticidní účinek byl vyzkoušen na roztočích. Způsob přípravy látek obecného vzorce I, spočívá v reakci hydroxysloučeniny obecného vzorce II (CH3)2C(OR)CHBrCH2O-C6H4-CH(R)OH (II), kde symbol P má výše uvedený význam s alkanovou kyselinou obecného vzorce III ch3(ch2)aCOOH (III), kde symbol a má výše uvedený význam za přítomnosti katalytického množství 4-dimethylaminopyridinu a ekvimolárního množství dicyklohexylkarbodiimidu při teplotě 10 až 20 °C nebo s chloridem či anhydridem alkanové kyseliny za přítomnosti bezvodého pyridinu při 20 až 60 °C.A new biologically active substance of the general formula I (I), (CH3)2C(OR)CHBrCH2O-C6H4-CH(R)OCO(CH2)aCH3 where the symbol R denotes a straight or branched chain alkyl group with a maximum of 4 carbon atoms, the symbol a denotes an integer in the range 0 to 16. Its pesticidal effect was tested on mites. The method for preparing compounds of general formula I consists in reacting a hydroxy compound of general formula II (CH3)2C(OR)CHBrCH2O-C6H4-CH(R)OH (II), where the symbol P has the above meaning, with an alkanoic acid of general formula III ch3(ch2)aCOOH (III), where the symbol a has the above meaning, in the presence of a catalytic amount of 4-dimethylaminopyridine and an equimolar amount of dicyclohexylcarbodiimide at a temperature of 10 to 20 °C or with an alkanoic acid chloride or anhydride in the presence of anhydrous pyridine at 20 to 60 °C.
Description
Vynález se týká 1-/4-(3-alkoxy-3-methyl-2-brombutoxy)fenyl/-alkyesteru alkanové kyseliny a způsobu jeho přípravy.The invention relates to a 1- [4- (3-alkoxy-3-methyl-2-bromobutoxy) phenyl] -alkanoic acid ester and a process for its preparation.
V současné době je známa řada látek imitujících, případně naopak zabraňujících v hmyzím organismu působení jednoho z jeho vlastních, tzv. metamorfóžních hormonů. Látky s tímto účinkem, zvané juvenoidy, respektive antijuvenoidy, způsobují poruchy embryonálního vývoje, překotnost, respektive retardaci až inhibici metamorfózy. (Bowers W. S., Ohta Z., Gleers J. S., Marsella F. A., Science 1967, 193, 542; Kahovcová J., Romaňuk M., J. Chem. Eng. Data 1981, 26., 223; Kahovcvoá J. , Sláma K. , Romaňuk M. , AOAt present, a number of substances are known which imitate or, on the contrary, prevent the action of one of its own, so-called metamorphous hormones, in the insect organism. Substances with this effect, called juvenoids and antijuvenoids, respectively, cause disorders of embryonic development, rapid or retardation or even inhibition of metamorphosis. (Bowers WS, Ohta Z., Gleers JS, Marsella FA, Science 1967, 193, 542; Kahovcová J., Romaňuk M., J. Chem. Eng. Data 1981, 26., 223; Kahovcvoá J., Sláma K. , Romanuk M., AO
248922).248922).
Látky popsané v předmětu vynálezu jsou příkladem alifaktickoaromatických sloučenin s vicinální alkoxybromskupinou obsahující v molekule esterovou vazbu, jež mají výše popsané biologické účinky.The compounds described in the present invention are an example of aliphactic-aromatic compounds with a vicinal alkoxybromo group containing an ester bond in the molecule, which have the biological effects described above.
Podstatou vynálezu je 1-/4-(3-alkoxy-3-methyl-2-brombutoxy(fenyl/alkylester alkanové kyseliny obecného vzorce I (CH3)2C(OR)CHBrCH20-C6H4-CH(R)OCO(CH2)aCH3 (I), kde symbol R značí alkylskupinu s rovným či rozvětveným řetězcem s maximálně 4 atomy uhlíku, symbol a značí celé číslo v rozmezí 0 až 16.The present invention provides 1- / 4- (3-alkoxy-3-methyl-2-bromobutoxy (phenyl / alkyl ester of an alkanoic acid of formula I (CH 3 ) 2 C (OR) CHBrCH 2 O-C 6 H 4 -CH (R OCO (CH 2 ) and CH 3 (I), where R is a straight or branched chain alkyl group of up to 4 carbon atoms, and is an integer ranging from 0 to 16.
Způsob přípravy l-/4-(3-alkoxy-3-methyl-2-brombutoxy)fenyl/-alkylesteru alkanové kyseliny se povádí tak, že se nechá reagovat hydroxysloučenina obecného vzorce II (CH3)2C(OR)CHBrCH2O-C6H4-CH(R)OH (II), kde symbol R má výše uvedený význam s alkanovou kyselinou obecného vzorce IIIThe process for the preparation of the alkanoic acid 1- [4- (3-alkoxy-3-methyl-2-bromobutoxy) phenyl] alkyl ester is carried out by reacting a hydroxy compound of formula II (CH 3 ) 2 C (OR) CHBrCH 2 OC 6 H 4 -CH (R) OH (II), wherein R is as defined above with an alkanoic acid of formula III
CH3(CH2)aCOOH (III), .CH 3 (CH 2 ) and COOH (III),.
kde symbol a má výše uvedený význam za přítomnosti 4-dimethylaminopyridinu a dicyklohexylkarbodiimidu při teplotě 10 až 20 °C nebo s chloridem či anhydridem alkanové kyseliny za přítomnosti bezvodého pyridinu při 20 až 60 °C.wherein the symbol a has the meaning given above in the presence of 4-dimethylaminopyridine and dicyclohexylcarbodiimide at a temperature of 10 to 20 ° C or with an alkanoic acid chloride or anhydride in the presence of anhydrous pyridine at 20 to 60 ° C.
V dalším je vynález blíže objasněn na příkladu provedení, aniž se na tento výlučně omezuje.In the following, the invention is explained in more detail by means of an exemplary embodiment, without being limited thereto.
PříkladExample
0,15 g (1 mmol' kyseliny děkanové, .0,35 g (1,1 mmol) 1-/4-(3-methoxy-3-methyl-2-brombutoxy)fenyl/-l-propanolu, 0,2 mg (1 mmol) dicyklohexylkarbodiimidu a 0,01 g (0,1 mmol) N.N-dimethylaminopyridinu bylo rozpuštěno a mícháno v 10 ml bezvodého diethyléteru při 15 až 20 °C po dobu 2 hodin. Po zředění reakční směsi diethyléterem a filtraci byla éterická vrstva postupně promyta 5%ním vodným roztokem kyseliny chlorovodíkové a vodou, vysušena a odpařena. Odparek poskytl po dělení na sloupci silikagelu (eluční činidlo petroléter obsahující až 20 obj.% diethyléteru) 0,36 g (70 %) produktu reakce.0.15 g (1 mmol) of decanoic acid, 0.35 g (1.1 mmol) of 1- [4- (3-methoxy-3-methyl-2-bromobutoxy) phenyl] -1-propanol, 0.2 mg (1 mmol) of dicyclohexylcarbodiimide and 0.01 g (0.1 mmol) of N, N-dimethylaminopyridine were dissolved and stirred in 10 ml of anhydrous diethyl ether at 15 to 20 ° C for 2 hours. washed successively with 5% aqueous hydrochloric acid and water, dried and evaporated to give 0.36 g (70%) of the reaction product after separation on a silica gel column (eluent: petroleum ether containing up to 20% by volume of diethyl ether).
l-/4-(3-Methoxy-3-methyl-2-brombutoxy)fenyl/-l-propanol: MS analýza: C15H23BrO3(330/332, M+),312/4(C15H21BrO2,M+-H2O),301/3 (c13H18BrO3,M+-C2H5)1- [4- (3-Methoxy-3-methyl-2-bromobutoxy) phenyl] -1-propanol: MS analysis: C 15 H 23 BrO 3 (330/332, M + ), 312/4 (C 15 H 21 BrO 2, M + -H 2 O), 301/3 ( c 13 H 18 BrO 3, M + -C 2 H 5)
NMR analýza(13C,CDC13,200MHz): 10.15(CH3CH2),22.18,23.76((CH3 )..2), 31.76(CH3CH2),49.90(CHBr),58.88(0CH3),69.80(CH2O),75.55(CHOH), 76.20((CH3)2c),114.70,127.21,137.33,157.65(aromatika) 1-/4-(3-Methoxy-3-methyl-2-brombutoxy)fenyl/-l-propylester kyseliny děkanové:NMR analysis ( 13 C, CDCl 3 , 200MHz): 10.15 (CH 3 CH 2 ), 22.18.23.76 ((CH 3 ) .. 2 ), 31.76 (CH 3 CH 2 ), 49.90 (CHBr), 58.88 (0CH 3) ), 69.80 (CH 2 O), 75.55 (CHOH), 76.20 ((CH 3 ) 2 c), 114.70,127.21,137.33,157.65 (aromatic) 1- / 4- (3-Methoxy-3-methyl-2- bromobutoxy) phenyl / -1-propyl decanoate:
Elementární analýza pro C25H41BrO4 (484,58):61,95%,8,50%H.Elemental analysis for C 25 H 41 BrO 4 (484.58): 61.95%, 8.50% H.
NMR analýza (13C,CDCl3,200MHz):9.98(CH3CH2),22.17,23.77((CH3)2C), 31.84(CH3CH2),49.91(CHBr),58.82(OCH3),76.22((CH3)2C),76.75(CHO), 114.60,127.96,133.40 ,'157.82 (aromatika) ,173.23 (0C0) , 14.09 (CH3CH2 CH2),22.64(CH3CH2CH2),29.39(CH3CH2CH2),29.16((CH3(CH2)2CH2),29.23 (CH3(CH2)3CH2CH2),29.10(CH3(CH2)5CH2),25.00(CH3(CH2)6CH2),34.63 (ococh2).NMR analysis ( 13 C, CDCl 3 , 200MHz): 9.98 (CH 3 CH 2 ), 22.17.23.77 ((CH 3 ) 2 C), 31.84 (CH 3 CH 2 ), 49.91 (CHBr), 58.82 (OCH 3 ) , 76.22 ((CH 3 ) 2 C), 76.75 (CHO), 114.60,127.96,133.40, '157.82 (aromatics), 173.23 (0C0), 14.09 (CH 3 CH 2 CH 2 ), 22.64 (CH 3 CH 2 CH 2 ), 29.39 (CH 3 CH 2 CH 2 ), 29.16 ((CH 3 (CH 2 ) 2 CH 2 ), 29.23 (CH 3 (CH 2 ) 3 CH 2 CH 2 ), 29.10 (CH 3 (CH 2 ) 5 CH 2 ), 25.00 (CH 3 (CH 2 ) 6 CH 2 ), 34.63 (eyes 2 ).
Biologický účinek byl zkoušen' na roztoči Tetranychus urticae, škůdci na chmelnicích, v sadech a sklenících (kontaktní aplikace acetonového roztoku na fazolích, disky listů φ 15 mm, 25 až 27 °C). Během pokusu byla sledována akaricidní aktivita (48 hodin). (Viz Tabulka).The biological effect was tested on Tetranychus urticae mites, pests on hop gardens, orchards and greenhouses (contact application of acetone solution on beans, leaf disks φ 15 mm, 25-27 ° C). Acaricidal activity was monitored during the experiment (48 hours). (See Table).
Tabulka. Akaricidní účinek na Tetranychus urticae (chov Plzeň)Table. Acaricidal effect on Tetranychus urticae (breeding Pilsen)
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| Application Number | Priority Date | Filing Date | Title |
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| CS903867A CS277114B6 (en) | 1990-08-06 | 1990-08-06 | 1- [4- (3-Alkoxy-3-methyl-2-bromobutoxy) phenyl] -alkyl ester alkanoic acid as biologically active substance and process for its preparation |
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| CS903867A CS277114B6 (en) | 1990-08-06 | 1990-08-06 | 1- [4- (3-Alkoxy-3-methyl-2-bromobutoxy) phenyl] -alkyl ester alkanoic acid as biologically active substance and process for its preparation |
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| Publication Number | Publication Date |
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| CS386790A3 CS386790A3 (en) | 1992-03-18 |
| CS277114B6 true CS277114B6 (en) | 1992-11-18 |
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| CS903867A CS277114B6 (en) | 1990-08-06 | 1990-08-06 | 1- [4- (3-Alkoxy-3-methyl-2-bromobutoxy) phenyl] -alkyl ester alkanoic acid as biologically active substance and process for its preparation |
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| CS386790A3 (en) | 1992-03-18 |
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