前苏联专利SU1549475A3 Method of producing derivatives of 1-(4-substituted phenyl)-1-e-/3-(4-haloidophenoxyphenyl)-prop-1-e

专利PDF首页>>前苏联专利

专利附录

专利说明

权利要求

类似技术

同族专利

引用文献

法律状态

优先权

专利摘要:
Pesticidal compounds of formula I RACR3=CR4CHDRBI in which formula: RA represents a group ArCR1R2-in which Ar represents a phenyl or naphthyl group optionally substituted by one or more halogen, alkoxy, haloalkoxy, methylenedioxy, C1-C6 alkyl or haloalkyl groups; R1 and R2 together with the carbon to which they are attached represent a C3-C6 cycloalkyl group optionally substituted by one or more halogen atoms or C1-C6 alkyl groups. R3 and R4 which may be identical or differ, represent hydrogen halogen or C1-C6 alkyl groups and RB represents the residue of an alcohol RB CHDOH in which D is hydrogen or cyano and of which the [1R, cis]2,2-dimethyl-3-(2,2-dibromovinyl) cyclopropane carboxylic ester is significantly insecticidal, the configuration of RA and CHDRB about the double bond being mutually trans, and processes for the production of compounds I, intermediates, pesticidal compositions comprising I, processes for the production thereof, methods for controlling pests, especially rice pests, in which such compounds are utilized and the use of compounds I for the manufacture of a pesticide.
公开号:SU1549475A3
申请号:SU853995752
申请日:1985-12-06
公开日:1990-03-07
发明作者:Эллиотт Майкл；Франк Джеймс Норман；Пол Сингх Хамбей Бупиндер；Бейдар Ахмет
申请人:Нэшнл Рисерч Дивелопмент Корпорейшн (Фирма)；
IPC主号:

专利说明:

,
From
This invention relates to a process for the preparation of new 1- (4-substituted phenyl) (4-halophenoxyphenyl) -prop-1-en-3-yl-cyclopropane derivatives of the general formula
RACR3 CP4CHDRB,
where R. is AgSR, Pr, where Ar is phenyl, substituted by halogen, lower alkoxy group;
R (and R - together with the carbon atom to which they are attached, mean cyclopropyl; VE, P, D - hydrogen;
PB - halogen-substituted phenoxyphenyl group,
which possess insecticidal activity.
The purpose of the invention is to obtain derivatives of substituted cyclopropane,
s
which have a higher activity.
Example (compound 2), 1- - 4-Chlorophenyl) (4-fluoro-3-pheno-syphenyl) -prop-1-enylT-cyclopropane,
To a stirred solution of 2-methyl-2-butene (0.5 ml) in dry ether (2 ml) in a stream of nitrogen at 0 ° C, borane-methylsulfide complex (1.15 ml of 2M solution in ether) is added and the mixture is stirred in over 1 h. A solution of 1- (4-chloro-phenyl) -1-ethynyl-cyclopropane (0.4 g) in ether (5 ml) is added in one portion, stirred for 10 minutes and then allowed to warm to room temperature. temperatures of about 45 minutes. Then the ether is evaporated under reduced pressure, the residue is dissolved in dry benzene (10 ml) and kept in a stream of aaota.
In another flask, tetrakis triphenyl phosphine palladium (0) (0.1 g) was stirred in a stream of nitrogen in dry benzene (10 ml) and a solution of 4-fluoro-3-phenoxybenzyl bromide (0.6 g) in dry benzene (10 ml about 10 minutes, then the reagent is added to this mixture, followed by the addition of a 2M aqueous solution of sodium hydroxide and the mixture is refluxed for 2 hours.
After cooling, a 3M aqueous solution of sodium hydroxide (1 ml) is added, followed by the addition of 30% HgO (1 mm). After the exothermic reaction is stopped, the reaction mixture is stirred at room temperature for 1.5 hours, poured into water and extracted with ether (three times). - The wounded extracts are washed with water, dried and the solvent is removed under reduced pressure. The product was isolated by thin layer chromatography on ccgel, eluting with pure petroleum ether. T, kip, 40-60 ° C, yield 0.29 g nD 1, 5805.
NMR H: 1.3 (m, 4H, - (CH2) g-); 3.4 (d, 2H, SNgCN); 5.6 (m, 2H,); 6.6-7.4 (m, 12H, Ar).
EXAMPLE 2 (compound 4) 1- (4-Ethoxyphenyl) -1-E-3-4-fluoro-3-phenoxy) prom-1-enyl-cyclopropane.
To a stirred solution of 2-methyl-2-butene (0.5 ml) in dry ether (2 ml) in a stream of nitrogen at 0 ° C are added methyl borane, a sulfide complex (1.15 ml of a 2 M solution in ether) and stirred for 1 h. "Solution of 1- (4-ethoxyphenyl) -1-ethynyl-chi
five
0
five

0
five
0
50
55
lopropane (0.42 g) in ether (5 ml) is added in one portion, stirred for 10 minutes and then allowed to warm to room temperature for about 1 hour. The ether is then evaporated under reduced pressure, the residue is dissolved in dry benzene ( 10 ml) and stored under a stream of nitrogen.
In another flask, tetrakis (triphenylphosphine) palladium (O) was mixed with 0.1 g in a stream of nitrogen in dry benzene (10 ml) and a solution of 4-fluoro-3-phenoxybenzyl bromide (0.62 g) in dry benzene was added over 10 min. To this mixture is then added the reagent obtained followed by the addition of 2M aqueous sodium hydroxide (2.3 ml) and the mixture is refluxed for 2 hours. After cooling, an ZM aqueous solution of sodium hydroxide (1 ml) is added followed by 30 % (1 ml). After the exothermic reaction is complete, the reaction mixture is stirred at room temperature for 1.5 hours, poured into water and extracted with ether (three times). The collected extracts are washed with water, dried and the solvent is removed under reduced pressure. The product was isolated by thin layer chromatography on silica gel, eluting with pure petroleum ether. B.p. 40-60 ° C, yield 0.43 g, n0 1.5799.
NMR H: 0.9 (m, 4H, - (CHg) g); 1.4 (m, 3N, CH9); 3.1 (d, 2H, CH2CH) 3.9 (q, 2H, OCH2); 4.9-5.5 (m, 2H,); 6.5-7.4 (m, 12H, Ar).
Example3 (compound 8). 1- (4-Ethoxyphenyl-1 - E-3-3- (3-fenok, syphenyl) -prop-1-enyl1-2,2-difluoro-cyclopropane,
To a stirred solution of 2-methyl-2-butene (0.5 ml) in dry ether (3 ml) in a stream of nitrogen at 0 ° C, methyl borane sulfide complex (0.23 ml of a 10 M solution in ether) and a mixture of stirred for 1 hour. A solution of 1- (4-ethoxyphenyl) -1-ethynyl-2,2-difluorocyclopropane (0.51 g) in ether (3 ml) was added in one portion, stirred for 10 minutes and then left The mixture is heated to room temperature for about 1.5 hours. The ether is evaporated under reduced pressure, the residue is dissolved in dry benzene (10 ml) and kept in a stream of nitrogen.
In another flask, tetrakis (triphenylphosphine) palladium (O) is stirred.
51549
(0.1 g) in a stream of nitrogen in dry benzene 1 (10 ml) and a solution of 3-phenoxybenzyl bromide (0.63 g) in dry benzene (5 ml) is added for about 10 minutes, then the mixture is added to the mixture prepared with the subsequent addition of a 2K aqueous solution of sodium hydroxide (2.3 ml) and the mixture refluxed for 2.5 hours. After cooling, add ZM aqueous solution of sodium hydroxide (1 ml) followed by addition of 30% (1 ml). After cessation of the exothermic reaction, the reaction mixture is stirred at room temperature for 1.5 hours, poured into water and extracted with ether three times. The selected extracts are washed with water, dried and the solvent is removed under reduced pressure. The product is isolated by thin layer chromatography on silica gel, eluting with pure petroleum
by ether. TKPI 40-60 C, yield 0.13 g,
The relative strength of the housefly and horseradish leaf beetle (biosmethrin 100) is shown in the table, respectively, in the columns
pd 1.5689.
NMR 1H: 1.4 (t, 3N, CH3); 1.0-2.025 HF and MB. Examine the compound form (m, 2H, CHZCP2); 3.3 (d, 2H, CH2CH); 4.0 (q, 2H, OSI); 5.0-5.8 (m, 2H,); 6.6-7.5 (m, 12H, Ar).
Pesticide activity is assessed in relation to domestic fly and horseradish leaf beetle-babanuhi using the following methods.
Domestic fly (Musca domestica), Female flies are treated in the thoracic region with a drop (1 μl) of an insecticide dissolved in acetone. For testing, duplication of a sample of 15 flies for each dosage rate is used, and one compound is tested for six dosages. After treatment, the flies are kept at a temperature of 20 + 1 ° C and the mortality is determined after 24 and 48 hours after treatment. LD5Q values are calculated in micrograms of insecticide per fly, and relative toxicity is calculated by the reciprocal of LDp0.
Horseradish leaf beetle-babanuha (Phac- don cockledriae Fou) 0
Acetone solutions of the test compound are applied windally on adult horseradish leaf beetles using a micro droplet. Treated insects are kept for 48 hours, after which mortality is assessed. For each dosage, duplicate samples of 40-50 horseradish leaf beetles are used, and for each dose, CR4CHDRB (EROV-3-phenoxybenzyl; 4RZROV-4-fluoro-3-phenoxybenzyl),
3QAlso, compared with the known compound of the formula
35
Compound 2 has a relative activity in tests (HF), (MB) 54 and 12, and the known, respectively, 6 and 9c
The thus obtained proposed compounds have a higher akvimnost compared with the known, without exerting a toxic effect on the environment and fish.
50
55

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining derivatives of 1- (4-substituted phenic) - -E-Ј3- (4-halo-idophenoxyphenyl) -prop-1-ene-3-nl-cyclopropane of the general formula
RACR, - CR4CHD R6,
where RA is ArCR1R2, where Ar is phenyl,
substituted by halogen, lower alcock signal;
Five compound dosage levels are used for the compound.
LP performance
50
and accordingly
but the relative strength of action is calculated in the same way as in the case of a home fly.
For both insect species, the relative potency is calculated by comparing with 5-benzyl-3-furylmethyl (lO-trans-chrysanthemate (biosimeter)), which is one of the most toxic known chrysanthemic esters on domestic flies and horse beetle leaves, moreover, its toxicity is 24 times higher than that of alleletrin for a homefly, and 65 times higher than that of alleletrin with respect to the horseradish leaf beetle.
The relative strength of the housefly and horseradish leaf beetle (biosmethrin 100) is shown in the table, respectively, in the columns
HF and MB. Examine compounds of form 25 HF and MB. Compounds of the formula CR4CHDRB (EROV-3-phenoxybenzyl; 4RZROV-4-fluoro-3-phenoxybenzyl) are examined,
3QAlso, compared with the known compound of the formula
35
Compound 2 has a relative activity in tests (HF), (MB) 54 and 12, and the known, respectively, 6 and 9c
The thus obtained proposed compounds have a higher akvimnost compared with the known, without exerting a toxic effect on the environment and fish.
Invention Formula
The method of obtaining derivatives of 1- (4-substituted phenic) - -E-Ј3- (4-halo-idophenoxyphenyl) -prop-1-ene-3-nl-cyclopropane of the general formula
RACR, - CR4CHD R6,
where RA is ArCR1R2, where Ar is phenyl,
substituted by halogen, lower alcock signal;
RBR and R - together with a carbon atom,
to which they are attached, mean cyclopropyl; R, R4, D is hydrogen;
a halogen substituted phenoxyphenyl group, characterized in that the reaction product of a complex of boranmethyl sulfide with 2-methyl-2-butene is reacted with a compound of the general formula
RAC n CH,
where R has the indicated meanings, the resulting product is reacted with a compound of the general formula
RftCHDX, where X is a halogen;
Re, D have the indicated meanings, in the presence of tetrakis triphenylphosphine palladium (O), followed by addition of sodium hydroxide, the reaction mixture thus obtained is treated with an alkaline solution of hydrogen peroxide.

类似技术:

公开号 | 公开日 | 专利标题

RU2010523C1|1994-04-15|Insecticide aerosol composition

US4220591A|1980-09-02|Insecticidal esters

EP0111105B1|1990-12-05|Unsaturated aromatic amides as pesticides

US3766218A|1973-10-16|Novel substituted chrysanthemates

US5763700A|1998-06-09|Pesticidal fluoroolefins

SU1549475A3|1990-03-07|Method of producing derivatives of 1-|-1-e-/3-|-prop-1-ene-3-yl/-cyclopropane

US3567743A|1971-03-02|Novel epoxy organic acids and derivatives

RO108522B1|1994-06-30|Derivates of di|-cyclopropyl, its substitutes and intermediaries thereof

HU185330B|1985-01-28|Process for preparing /+/-4-substituted-2-indazoles

EP0004754A2|1979-10-17|Ketoximinoether insecticides

US4339458A|1982-07-13|Insecticidal esters

US4473709A|1984-09-25|Pyrethroid intermediates and process

US4215138A|1980-07-29|Insecticidal compounds of phenylcyclopropane carboxylic acid esters

CA1058623A|1979-07-17|Insecticides

US4567265A|1986-01-28|Cyclopropanoid cyanoesters and method of making same

US4179446A|1979-12-18|Sex pheromone produced by the female Japanese beetle: specificity of male response to enantiomers

EP0043187B1|1986-05-14|Pesticidal cyclobutyl carboxylic ester comprising compositions

US4391823A|1983-07-05|Novel polycyclic insecticidal esters

US3857858A|1974-12-31|Cyclopropane carboxylic acid esters

US4255447A|1981-03-10|Acaricidal compounds of cyclopropane carboxylic acid derivatives

US4778822A|1988-10-18|Insecticidally active ester

CN110642856B|2020-10-02|Dihydroquinidine compounds, preparation method and application thereof, and botanical pesticide

CN110759905B|2021-05-11|9S-acyloxy cinchonine derivative, preparation method and application thereof, and botanical pesticide

US4925985A|1990-05-15|Novel process for the production of 4,6-dimethyl-7-hydroxynonan-3-one

WO1996024573A1|1996-08-15|Novel carboxylic ester derivatives, process for producing the same, and insecticide or insectifuge containing the same

同族专利:

公开号 | 公开日

AR240041A1|1990-01-31|

TW202379B|1993-03-21|

ES551381A0|1987-10-16|

PT80230A|1985-05-01|

JPH0629200B2|1994-04-20|

EP0179788B1|1991-06-12|

DK69892D0|1992-05-26|

EP0179788A1|1986-05-07|

AU3936489A|1989-11-23|

CZ281414B6|1996-09-11|

MX160841A|1990-05-30|

DK69892A|1992-05-26|

HUT38296A|1986-05-28|

DK172479B1|1998-09-21|

HU201219B|1990-10-28|

PT80230B|1987-09-30|

TR25297A|1992-12-16|

BR8506438A|1986-04-15|

GB8528482D0|1985-12-24|

SK256785A3|1997-04-09|

US4777185A|1988-10-11|

JPS61501778A|1986-08-21|

GB8409195D0|1984-05-16|

PL252847A1|1985-12-17|

DK172189B1|1997-12-22|

PL146599B1|1989-02-28|

AU611822B2|1991-06-20|

DK566985D0|1985-12-06|

OA07988A|1987-01-31|

PH22357A|1988-08-12|

AU611579B2|1991-06-13|

GR850875B|1985-11-25|

GB2167749A|1986-06-04|

IE850860L|1985-10-09|

AU3936289A|1989-11-23|

AU584084B2|1989-05-18|

KR920002126B1|1992-03-12|

AU614654B2|1991-09-05|

BE902147A|1985-07-31|

SK278410B6|1997-04-09|

RO93563A|1988-05-30|

DE3583205D1|1991-07-18|

DK566985A|1985-12-06|

ZW6885A1|1986-10-22|

CA1337430C|1995-10-24|

AU3936389A|1989-11-23|

AU613220B2|1991-07-25|

ES551379A0|1987-05-01|

IE58692B1|1993-11-03|

ES8800127A1|1987-10-16|

ES551380A0|1987-05-01|

RO93563B|1987-11-22|

EG17870A|1991-06-30|

KR860700031A|1986-01-31|

ES8705195A1|1987-05-01|

IL74721A|1992-08-18|

CZ256785A3|1996-06-12|

AU4212785A|1985-11-01|

BG46742A3|1990-02-15|

GB2167749B|1988-02-10|

DD238789A5|1986-09-03|

WO1985004651A1|1985-10-24|

ES8705196A1|1987-05-01|

ZA852481B|1985-11-27|

AU3935989A|1989-12-14|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

GB1570982A|1976-03-05|1980-07-09|Shell Int Research|Substituted benzyl ethers and thioethers|

US4242357A|1976-04-09|1980-12-30|Bayer Aktiengesellschaft|Carboxylic acid esters for combating pests|

US4152455A|1977-02-02|1979-05-01|Fmc Corporation|Insecticidal α-trifluoromethyl-3-phenoxybenzyl carboxylates|

JPS6355500B2|1980-10-09|1988-11-02|Mitsui Toatsu Chemicals|

US4562213A|1982-05-12|1985-12-31|Sumitomo Chemical Company, Limited|Certain phenoxy-benzyloxy ether derivatives and an insecticidal and/or acaricidal composition containing the same and methods of use|

AU576307B2|1982-09-24|1988-08-25|Commonwealth Scientific And Industrial Research Organisation|Arthropodicidal compounds|

IL69796A|1982-09-24|1986-10-31|Commw Scient Ind Res Org|Phenylcycloalkylalkane derivatives,their preparation and arthropodicidal compositions containing them|

EP0125204A1|1983-04-12|1984-11-14|Ciba-Geigy Ag|3-Phenoxybenzyl ethers, process for their preparation and their use as pesticides|

AU2827884A|1983-04-25|1984-11-19|Cheminova A/S|Arylcycloalkyl ether derivatives their use and preparation|

DK181683A|1983-04-25|1984-10-26|Cheminova As|ARYLCYCLOALKYLETHER DERIVATIVES, THEIR USE AND PREPARATION|

GB8409195D0|1984-04-09|1984-05-16|Elliott M|Pesticides|US5248834A|1984-04-09|1993-09-28|British Technology Group Limited|Pesticides|

GB8409195D0|1984-04-09|1984-05-16|Elliott M|Pesticides|

US5283371A|1986-03-13|1994-02-01|National Research Development Corporation|Intermediates useful in the production of pesticides|

AT80604T|1987-04-23|1992-10-15|Fmc Corp|INSECTICIDAL CYCLOPROPYL-SUBSTITUTED DICOMPOUNDS.|

GB9219612D0|1992-09-16|1992-10-28|Khambay Bhupinder P S|Pesticidal fluoroolefins|

GB9408605D0|1994-04-29|1994-06-22|British Tech Group|Pesticidal fluoroolefins|

US7932410B2|2008-10-31|2011-04-26|Bedoukian Research, Inc.|Production of pheromones and fragrances from substituted and unsubstituted 1-alken-3yl alkylates|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

GB848409195A|GB8409195D0|1984-04-09|1984-04-09|Pesticides|

[返回顶部]