Method of producing derivatives of 2-arylpropyl ethers or thio ether

专利摘要:
2-Arylpropyl ether or thioether derivatives represented by the following general formula [I]: <IMAGE> [I] wherein Ar stands for an aryl group, R stands for a methyl or ethyl group, Y stands for an oxygen or sulfur atom, and B stands for a group represented by the following formula [II]: <IMAGE> [II] or the following general formula [III]: <IMAGE> [III] wherein Z stands for an oxygen or sulfur atom or a carbonyl or methylene group, R1 stands for a hydrogen or halogen atom or a lower alkyl group or a lower alkoxy group, and n is an integer of from 1 to 5 with the proviso that when n is 2 or more, the groups R1 may be the same or different, are produced by reacting a compound represented by the following formula (V): <IMAGE> (V) with a compound represented by the following formula (VI): B-CH2-D (VI) wherein Ar, R and B are defined above, A is a halogen atom and D is Y-H in which Y is as defined above, in the presence of a base in dimethylsulfoxide or sulfolane. The compounds thus prepared have excellent insecticidal and acaricidal activities while the toxicity of these compounds are very low.
公开号:SU1442067A3
申请号:SU823520651
申请日:1982-12-09
公开日:1988-11-30
发明作者:Тояма Терухико；Татибана Хадзиме；Удагава Такатоси；Гохбара Масатоси；Накатани Киеси；Нумата Сатоси；Иноуе Цунео；Кодака Кендзи；Исии Цутому
申请人:Мицуи Тоатцу Кемикалз, Инк. (Фирма)；
IPC主号:

专利说明:

The invention relates to a method. for the preparation of new derivatives of 2-aryl-protic ether or thioether of the general formula
SNS
AP-С-СН2-Т-СНг-В
R
de Y is an oxygen or sulfur atom; Ar - biphenyl or unsubstituted
or substituted by lower alkyl-. naphthyl scrap, unsubstituted f- | 5 NIL or phenyl, substituted by one 1-shea several substituents selected from the group containing halogen, shzshiy alkyl-, lower halo
 alkyl-, lower alkoxy, ims- haloalkoxy-, lower alkoxycarbonyl-, lower hapoalkoxycarbonyl-, lower apkylthio-, lower halo- 25 alkylthio-, lower alkenyl-, lower alkenyloxy-, lower haloalkenyl-) and halo
 kenyloxy, lower quinil,
lower alky shloksi-, lower jq
 alkoxyalkyl-, lower alkoxy-alkoxy-, metutenedioxy, nitro, cyano-, acetyl-e phenoxy-, and C. -C-cycloalkoxy-syradic-n;
R is methyl or etSh1,
B is a gross formula:
,, RI C / 40
oxygen or sulfur atom
carbonyl or 1megylene, hydrogen or halogen, lower alkyl, lower alkoxy radical,
A - phenyl, substituted gaR - methyl, B - group of forms
Tgi
"These compounds possess insecticarctic activity." . The purpose of the invention is to find a spa; soba according to new derivatives of arylpropyl ether or
0
50
five
Q
thioether, which have a higher insecto-acaricidal activity.
The invention is illustrated by the examples below.
Example 1. To 20 MP of benzene, 0.5 g of p-toluenesulfonic acid, 3 g of 3-phenoxybenzyl alcohol and 2.5 g of 2- (4-chlorophenyl) -2-methylpropyl alcohol are added and the whole mixture is heated at reflux for 10 hours (water formed during the reaction was distilled off). This mixture is cooled to room temperature, water is added to it, the benzene layer is washed with water and dried. Benzene is isolated under reduced pressure and the crude ether obtained is purified by column chromatography on 150 g of silica gel (1: 1 toluene / n-hexane mixture is used as eluant) and 2.3 g of 3-phenoxybenzyl-2 are obtained. - (4-chlorofensch) -2-methypropyl ether (yield is 51% of the theoretical, calculated from the amount of 2- (4-chlorophenyl) -2-methylpropyl alcohol). 1.5832.
IR
film
(cm): 1600, 1505,
with
0
five
0
1270, 1230, 1120, 1025, 840, 705,
NMR d (CCl4) (ppm): 1.26 (s, 6Fi) i 3.25 (s, 2H) j 4.27 (s, 2H) j 6.6-7.3 (m, 13H ).
Calculated,%: C 75, H 6.32 C1 9.66.
C iiH-iClOi
Found,%: C 75, 18; H 6.51; C1 9.70,
Example 2; K20 ml of toluene was added 1.4 g of anhydrous aluminum chloride and the mixture was stirred at room temperature. Then a solution of 2 g of 3- (4-fluorophenoxy) benzyl alcohol and 2.0 g of 2- (3,4-dichlorophenyl) -2-methylpropyl alcohol in 5 ml of toluene at room temperature are added to the mixture according to keel mile. and heat it with stirring at 100 ° C for 6 hours. Cool the reaction mixture to room temperature, pour into water and extract with toluene. Under pressure, toluene is distilled off and the resulting crude ether is purified by silica gel column chromatography (using an eluent mixture (1 :)
toluene-n-hexane) and obtain 1.2 g of 3- (4-fluorophenoxy) -benzyl-2- (3,4-dichlorophenyl) -2-methylpropyl ether (yield 59% of theory). , 1.5732.
IR (cmO: 1590, 1505, 1490,
1265, 1205, 1100, 1035,695.
NMR with (CC14) (ppm): 1.30 (s, 6Hi 3.34 (s, 2H); 4.38 (s, 2H) 6.7-7.4 (m, 11H).
Calculated,%: C 69.09; H 5.29j C1 8.87i F 4.75.
C 2 Found,%: C 68.88} H 5.34; C1 8.75; F 4.57.
Example 3. To 20 ml of xylene, add 3 MP of phosphoric acid, 15 g of 3- (4-bromophenoxy) benzyl alcohol and 3 g of 2- (4-fluoropensch1) -2-netilpropyl alcohol and heat the mixture at its boiling point 10 hours (the resulting reactionary water is distilled off). The mixture is cooled to room temperature and treated in the same manner as described in Example 1, to obtain 1.8 g of 3- (4-bromophenoxy) -benzyl-2- (4-fluorophenyl) -2-metric 1 ether (yield 55% of theoretical). 5778.
IR (cm-): 1605, 1580, 1510, 1485, 1250, 1165, 1100, 1070, 1010, 830.
NMR .if (CCltf) (ppm): 0.67 (t, 3N, j 7.2 Hz); 1.30 (s, 3N); 1.5-1.9 (m, 2H), 3.39 (s, 2H); 4.39 (s, 2H); 6.7-7.5 (, m, 12H).
Calculated,%: C 65.02; H 5.46, Br 18.02; F 4.29.
Ci4Ha4BrFO
Found,% D C 65.34} H 5.33; Br 18.21i F 4.17.
Example 4. Preparation of 3- (4- -fluorophenoxy) benzyl-2 (4-fluorofensch1) -methyl butyl ether.
To 20 ml of toluene were added 2 ml of concentrated sulfuric acid, 2.7 g of 3- (4-fluorophenoxy) benzyl
sH
chromatographic column with 100 g of silica gel (using eluent mixed solvent g (1: 1) toluene-n-hexane), to
2.2 g of the desired ester (yield is 46% of theoretical). 1.5478.
IR Mahe, cm-Chv film): 1585, 10 1505, 1230, 1195, 1165, 1100, 830, 780, 690.
NMR c / (CCl4). ppm: 0.65 (t, j 7.5 Hz, ЗН) - 1.28 (s, ЗН), 1.5-1.9 (m, 2Н); 3.37 (s, 2H) i 4.35 (s, 15 2H) J 6.7-7.3 (m, 12H).
Calculated,%: C 75.37} H 6.32; F 9.94.
From 2
Found%: C 75.54 H 6.21 20 F 10.01.
Example 5. 2- (4-Chlorophenyl) - -2-methylamine opilic alcohol is reacted with 3- (4-methyphenoxy) - benzyl alcohol in the presence of. 25 sulfuric acid under ordinary conditions for the esterification reaction. Exit 3- (4-methylphenoxy) benzyl-2- (4-chlorophenyl) -2- -methylpropyl ether is 57% of the theoretical. 30 1.5741.
IR about ac cm-Chv film): 1595, 1510, 1455, 1260, 1215, 1110, 1015, 830, 695.
NMR rf (CClp ppm: 1.29 (s, 6l4 2.31 (s, 3H) i 3.32 (s, 2H); 4.35 (s, 2H) i 6.7-7.3 (m, 12H).
Calculated,%: C 75.68 H 6.61-, C1 9.31,
Found,%: C 75.86; H 6.42 C1 9.22. .
35
40
Example 6. 3-Phenoxybenzene-2- (4-chlorofesh1p) -2-ETILEPROPSH1OVY 45 the ester was synthesized according to the procedure described in Synthesis Example 4 (yield is 48% of theoretical). “1.5778.
IR i) „ax cm- (film): 1595, 1505, alcohol and 2.3 g of 2- (4-fluorofensch1) -2-mesa 1265, 1230, 1115, 1025, 835, 700.
NMR sC (CC1,) ppm: 0.65 (t, j - 7.8 Hz, 3N); 1.26 (s, 3N) 1.5-1.7 (m, 2H) V3.30 (s, 2H) i 4.28 (s, 2H) j 6.6-7.3 (m, 1bH) .
The calculated temperature is added to the mixture: 55 Calculated,%: C 75.68 N 6.62i water, separates the toluene layer, about - C 1 9.31. washed with water and dried and evaporated under reduced pressure, and the resulting crude ether is purified on
tilbutyl alcohol and the mixture is boiled for 6 hours under reflux (the water formed in the reaction is removed). The mixture is cooled to rooms Ce4HasC10i
Found,%: C 75.70; H 6.58; C1 9.27.
sH
chromatographic column with 100 g of silica gel (using eluent mixed solvent g (1: 1) toluene-n-hexane), to
2.2 g of the desired ester (yield is 46% of theoretical). 1.5478.
IR Mahe, cm-Chv film): 1585, 0 1505, 1230, 1195, 1165, 1100, 830, 780, 690.
NMR c / (CCl4). ppm: 0.65 (t, j 7.5 Hz, ЗН) - 1.28 (s, ЗН), 1.5-1.9 (m, 2Н); 3.37 (s, 2H) i 4.35 (s, 5 2H) J 6.7-7.3 (m, 12H).
Calculated,%: C 75.37} H 6.32; F 9.94.
From 2
Found%: C 75.54 H 6.21 0 F 10.01.
Example 5. 2- (4-Chlorophenyl) - -2-methylamine opilic alcohol is reacted with 3- (4-methyphenoxy) - benzyl alcohol in the presence of 5 sulfuric acid under normal conditions for the esterification reaction. Exit 3- (4-methylphenoxy) benzyl-2- (4-chlorophenyl) -2- -methylpropyl ether is 57% of the theoretical. 0 1,5741.
IR about ac cm-Chv film): 1595, 1510, 1455, 1260, 1215, 1110, 1015, 830, 695.
NMR rf (CClp ppm: 1.29 (s, 6l4 2.31 (s, 3H) i 3.32 (s, 2H); 4.35 (s, 2H) i 6.7-7.3 (m, 12H).
Calculated,%: C 75.68 H 6.61-, C1 9.31,
Found,%: C 75.86; H 6.42 C1 9.22. .
five
0
 Calculated,%: C 75.68 H 6.62 C1 9.31.
Ce4HasC10i
Found,%: C 75.70; H 6.58; C1 9.27.
Example. To 20 ml of dimethyl sulfoxide were added 2 g of 3-phenoxybenzyl alcohol, 2 g of 2- (4-methylphenyl) -2-methylpropyl alcohol and 2.2 g of N, N-dicyclohexylcarbodiimide and the mixture is heated with stirring for 3 h. The reaction mixture is cooled to room temperature, BbmHBarof in water and extracted with benzene. The benzene extract is washed with water and dried with anhydrous sodium sulphate. Benzene is distilled off under reduced pressure and the resulting crude ether is purified by column chromatography on silica gel (a mixture (1: 1) of toluene — n-hexane is used as eluant), followed by 2.1 g of 3-phenoxybe zyl-2- (4-methylphenyl) -2-methylproduct ether. n | 1.5794.
IR AJMaccCcM) (film): 1590, 1495, 1260, 1220, 1110, 820, 700.
NMR c / (CC1) ppm: 1.28 (s, 6H) 2.26 (s, 3N) 3.32 (s, 2H) J 4.25 (s, 2H); 6.7-7.4 (m, 13H).
Calculated,%: C, 83.20; H, 7.56.
C H
Found,%: C, 83.25; H 7.59.
P R and m r 8. Preparation of 8-phenok sibenzyl-2- (4-difluoromethoxyfensh1) -2- -methylpropyl ether.
To a mixture of 20 ml of xylene and 2.1 g of di-dichexylcarbodiimide there is added dropwise a solution of 2.0 g of 3-phenoxybenzyl alcohol in 10 ml of xylene at room temperature. The mixture was stirred at 50 ° C for 2 hours. Then a solution of 2.2 g (2- (4-difluoromethoxy-lipensch1) -2-methyl-1-propanol in 10 ml of xylene was added dropwise to this mixture while stirring. with stirring, heated to 120 ° C for 5 hours. The mixture is cooled to room temperature and water is added to it, after which the mixture is extracted with xylene. The xylene extract is washed with water and dried over anhydrous sodium sulfate. Xylene is distilled off under reduced pressure and the remaining oil is purified using column chromatography on 150 g of silica gel (as elu that a mixture (1: 1) toluene-n-hexane) to give 1.35 g of the expected product (yield = 34% theory).
n1 ° 1.5490.
IR d1d, o, ks CM (film): 1580, 1485, 1380, 1250, 1215, PZO, 1040, 690.
five
0
five
NMR / (CC1) ppm: 1.32 (s, 6H), 3.36 (s, 2H) i 4.21 (s, 2H), 6.38 (t, 1H j 75Hz); 6.8-7.4 (m, 13H).
The following are examples of compounds prepared according to the method prepared, namely:
3-phenoxybenzyl-2- (4-methoxyphenyl) -2-methylpropyl ether) and thioether.
Ether (see tab. T, Comp. 1)
TIOEFIR (OjS
Calculated,% Found,%.
C76.1576.38
H6,926.80
S8,478,66
3- (4-fluorophenoxy) benzyl-2- (4-) -fluorophenyl) -2-ethylpropyl ether and thioether
Ether (see tab. 1, Comp. 2) Cr4H thioether
Calculated,% Found,%
C72,3372,56
Н6,076,21
F9,549,48
S8,058,32
3-fvnoxybenzyl-2- (4-methoxyphenyl) -2-ethylpropyl ether and thioether
Ether C.sH 2jO 3
Calculated,% С79,75
H7,50
Thioether With 2irH 2 iS

0
five
C AND
S
76.49 7.19 7.6
76.64 7.07 7.21
3- (4-fluorophenoxy) -benzyl-2- (4-fluorophenyl) -2-methylpropyl ether and thioether
Ether (see tab. 1, Com. 45)
Thioether Cj jHj.
0
five
3- (4-fluorophenoxy) -benzyl-2- (4-methylfensch1) -2-methylpropyl ether and
thioether
Ether (see tab, 1, Comp. 3) TFR jFOS
Calculated,% Found,% C 75.75 75.93 H 6,626.74
F 4,994,87
S 8,438,69
3- (4-bromophenoxy) -benz-2- (4-chlorophenyl) -2-methylpropyl ether and
thioether
59
Introductions,% 76.80 7.44 7.89
3.0S2 Calculated,% 73.89 7.15 15.17
ether С Н
thioether
ether (see tab. 1, Tioether
Calculated,% С 74.27 Н 7.39 S 7.34
78
thioether
ether
Calculated%
C 77.39
H 7.89
Tioether Cjj Calculated%
C74,63
H7.61
S7.11
Z-phenoxybenzyl-2- IL) -phenyl -2-methylP1 thioether
Ether (see tab. 1,
Tioether Calculated,%
C 73.42
H 6.16
C1 8.67
S 7,84
3-phenoxybeisyl-yl) -phenyl 3-2-ethylg
Ether, Calculated,%
From 76.74
H 6.69
C1 8.71
Tioether Computed%
C 73.82
H 6.43
C1 8.38
S 7.58
Ether C, .HiN02
C 3-phenoxybenzyl-2- 4- (1-butenyl- -2) phenyl -2-methylpropyl, th ether and thioether
Ether (see tab. 1, compound 110)
Tioefnr
Calculated, Found,% С 80.55 80.64 Н 7.517.47
 S 7.96 "8.01
3-phenoxybenzyl-2- 4- (1-butenyl-2) -phenyl-2-ethylpropyl ether and
thioether
Ether C, NC, 0
Calculated,% Found,%
С83,9684,03
H8,058.01
Tioether
Calculated,% Found,%
С80,7280,82
H7,747,69
S7,707,73
3-phenoxybenzene -1-2- 4- (2-butenyl-2) -phenyl -2-methyl 1-propyl ether and
tioefnr
Ether (see tab. 1, comp. 111) Tioether
Calculated,% Found,% C 80.55 80.63 N 7.517.48
S 7,968,02
3-phenoxybenzyl-2- 4- (2-butenyl-2) -phenyl [-2-ethylpropyl ether and
thioether
Ether SgzNz-gOa
Calculated,% Found,%. C 83.96 84.01 N 8.058.02
Tioether With jH
Calculated,% Found,% C 80.72 80.91 and 7.747.68
S 7,707,74
The following examples describe methods for preparing the starting compounds.
Example 9. The compound of the following formula is synthesized as follows:
R
(RS) J
i-CHjOH (ii),
SNS
where R, R, R see tab. 2 and 3.
1. A mixture of 10 g of arylacetonitrile, 20 g of KOH, 20 g of water and 2 g of triethylbenzylammonium bromide are maintained
at 80-90 ° C and methyl iodide is added dropwise to this mixture in an amount of 1.2 mol / mol aryl trifyl for 1 to 2 hours. 10 g of KOH and 2 g of triethyl benzyl ammonium bromide are then added to the mixture. At the same temperature, the desired is added dropwise to the mixture for 1-4 hours.
amount of alkyl halide
1.2 mol / mol arylacetonitrile.
The mixture is cooled to room temperature and extracted with toluene. The desired dialkyl arylacetonitrile is obtained from a toluene extract.
2. The dialkyl aryl acetonitrile synthesized earlier in step 1 is hydrolyzed at 130-150 ° C with 50% sulfuric acid or water-soluble mixture of diethylene glycol and KOH to obtain 2-aryl-2-alkylpropionic acid having the following formula:
25
SNS
C-COOH (III) R
In tab. 2 and 3 show the properties of 2Q compounds of formula III
3. The 2-aryl-2-alkylpropionic acid synthesized in step 2 is reduced in tetrahydrofuran with lithium aluminum hydride to give 2-aryl-2-alkylpropyl alcohol
Example 10. 2- (4-Chlorophenyl) -2-methylpropyl alcohol is synthesized
by the following methods.
1. To 16.9 g of chlorobenzene, 1J5 g of ferric chloride was added, and hydrogen chloride gas was passed into the mixture for 10 minutes. Then to this
46 g of tertbutyl chloride are added dropwise to the mixture at 30 ° C over 1 hour. The mixture is kept for 2 hours at 30 ° C. The reaction mixture is washed with an aqueous solution of sodium carbonate and then with water and evaporated under reduced pressure, giving 25 g of 4-tert-butyl chlorobenzene (mp. Mm Hg)
Calculated,% C 7l, 21j H 7.7j C1 21.02.
SNS I, (1)
h ..
(2) BN-HC1
2.7 g of magnesium chips and a small amount of iodine as a catalyst are added to 100 ml of dry ether and 17 g of methyl iodide are gradually added to the mixture. The mixture is then refluxed for 30 minutes and, while the temperature rises, 100 ml of benzene is added to the mixture in order to replace the ester with benzene. Then, 18.9 g of the starting nitride is added dropwise to this mixture while boiling.
The mixture is additionally boiled for 3 hours, and then, with cooling for 30 minutes, 20 ml of 6N is added dropwise to this mixture. hydrochloric acid. The temperature is then increased and the mixture is heated to reflux for 7 hours. The mixture is then cooled to room temperature, the benzene layer is separated, washed with water, dried over sodium sulfate and evaporated under reduced pressure to give 19.2 g of 2- ( 3,4-methylenedioxy phenyl) -2-metsh1-2-outanona.
SNS
C-C-CH3
Ikomax (film): 2970, 2890, 1720, 1495, 1250, 1045, 940, 820.
NMR “fCCCl) ppm: 1.38 (s, 6H); 1.85 (s, NN); 5.91 (s, 2H); 6.67 (s, ZN).
Calculated,%: C 69.88; H 6.84.
Found,%: C, 69.99) H, 6.70.
2. At a temperature below 20 ° C, 12.8 g of bromine is added dropwise to a mixture of 7.4 g of sodium hydroxide, 35 ml of water and 10 ml of dioxane. The temperature is then raised to, 10 g of 2- (3,4-methi-lendioxyphenyl) -2-methyl-3-butanone is gradually added to the mixture, and the mixture is refluxed at 90-95 ° C for 2 hours. .
The mixture is cooled to room temperature and the required amount of sodium hydrogen sulfate is added. The mixture is then extracted with toluene. The remaining aqueous solution is acidified with concentrated hydrochloric acid and extracted with toluene. The toluene extract is washed with water, dried
65 14A2067
over sodium sulfate and vacuum under reduced pressure, crawling 7.5 g of 2- (3,4-methylenedioxyphenyl) -2-methylpropionic acid.
NMR cf (CCl) ppm: 1.61 (s, 6H); 6.03 (s, 2E}; 7.04 (s, 3N).
Vyagisleno,%: C 63.45} H 5.81.
66
Found,%: C 65.45; H 5.36, F 20.49.
2. Dissolve in 100 ml of acetone g 8.0 g of 2,4-bis- (4-difluoromethoxyphenyl) -4-methyl-2-pentane and 30 g of KMpO are added to the solution at 30 ° C. A mixture of ne IIh.
stirred for 10 hours while and to the mixture while cooling down, added Found,%: C, 63.2 s; H 5.97. 20 ml of ethyl alcohol, in order to 3. In a solution of tetrahydrofuran 2- to decompose the excess amount- (3, A-methylenedioxyphenyl) -2-methylproduct KMpO ;. The mixture is stirred into citric acid. The 1 h line is reduced, which is formed by reacting aluminum hydride to give 2- (3.4-manganese dioxide, the filter-methylenedioxyphenyl) -2-methylpropyl is removed, it is sufficient. - Alcohol with water and then with acetone. Filter | . 3390, 2960, rat is evaporated under reduced pressure — 1495, 1235, 1040, 940, 810. a mixture of extras-3.39 (s, 2H) j 5.87 (s, 2H); 6.6-6.9 20 RUYUT toluene. A dilute aqueous solution of NaOH is added to the toluene extract, the mixture is shaken thoroughly and the separated aqueous layer is added. the solution is acidified concentrated (m, 3N).
Calculated,%: C 68.02; H 7.27.
S., iH Oz
Found,%: C 68.19; H 7.13.
Example 12. Preparation of 2- (4-25 hydrochloric acid and extracted with α-difluoromethoxyphenyl) -2-methylpropyl-toluene. The toluene extract is washed with water, dried and evaporated under reduced pressure, to obtain 4.2 g of the desired 2- (4-difluoromethoxyphenol alcohol.
1. Dissolve 18.0 g of 2,4-bis- (4-hydroxyphenyl) -2-methyl-2-pentane in 100 MP of adetonitrile, and add to the solution an additive of Znil) -2-methylpropionic acid
10 g of 50% NaOH are added. Then, at 60-70 ° C, the discharge of difluorochloromethane (freon 22) is started. When difluorochloromethane is blown in an amount of about 60% of the start blowing field for approximately 20 minutes (approximately 20 minutes later), 10 g of 50% KOH is added to the reaction mixture and the flow is continued further. The purge is stopped after the amount of difluorochloromethane being blown is 1.5 times greater than the amount necessary for the reaction to proceed. The reaction mixture is cooled to room temperature and drunk in 500 ml of water and the mixture is extracted with toluene. The toluene layer is washed with water, dried over sodium sulfate and evaporated under reduced pressure.
The resulting crude ester is purified on a chromatographic column with 200 g of silica gel (toluene is used as the solvent) to obtain 19.2 g of 2,4-bis- (4-difluoromethoxyphenyl) -4-methyl-2-pentane. The yield is 77%. Fri, 1.5285. Calculated,%: C 65.21 J H 5.47 j F 20.63.
C eHioF Oi
67
66
Found,%: C 65.45; H 5.36, F 20.49.
2. Dissolve 8.0 g of 2,4-bis- (4-difluoromethoxyphenyl) -4-methyl-2-pentane in 100 ml of acetone and add 30 g of KMpO to the solution at 30 ° C. The mixture is stirred for 10 hours at, and 20 ml of ethyl alcohol is added dropwise to the mixture while cooling, in order to decompose the excess amount of KMPO ;. The mixture is stirred for 1 hour, the manganese dioxide formed by the reaction is removed by filtration, rinsed with a sufficient amount of water and then with acetone. Filter5
0
Th.pl. 68.5-69.5 ° C). The yield is 84%.
NMR J (CCl), ppm: 1.58 (s, 6H); 6.42 (t, 1H, J 7.5 Gd) 7.03 (d, 2H, JAB 8.8 Hz) 7.87 (d, 2H, JAB 8.8 Hz); type AB; 11.76 (broad, s, 1H).
Calculated,%: C 57.39 - H 5.25 F 16.51.
S., H j F e
Found,%: 57.55; H 5.14, F 16.58.
3. To a mixture of 20 ml of tetrahydrofuran and 0.5 g of lithium aluminum hydride, drop by drop (- a solution of 2.0 g of 2- (4-difluoromethoxyphenyl) -2-methylpropionic acid in 10 ml of tetrahydrofuran at 40 ° C. The temperature is then raised and the mixture is heated to reflux for 30 minutes. The mixture is cooled to room temperature and ethanol is added dropwise to the mixture to decompose excess lithium aluminum hydride. Water is then added to the mixture to complete this decomposition The precipitate formed is removed by filtration and removed from the filtrate by regonki tetrahydrofuran under reduced pressure. The residue was extracted benzsiyum, 5ei0
five
The ash extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure to obtain 1.8 g of 2- (4-difluoromethoxyphenyl) -2-methylpropyl alcohol. The yield was 96%.%.
HK VMMI C. (film): 3360, 1510, 1380, 1220, 1185, 1130, 1040, 835.
Calculated,%: C, 61.16; H 6.53; F 17.59.
C, H (F 2 O 7
Found%: C 61.29 H 6.60i F 17.43.
Example 13. Preparation of 2- (4-α-fluorophenyl) -2-methybutyl alcohol.
1. A 300-mp flask was charged with 16.6 g of 4-fluorotoluene, 30.0 g of N-bromosuccinimide, 0.5 g of benzoyl peroxide and 150 ml of carbon tetrachloride, and the mixture was heated under reflux for 2 hours. the mixture is cooled to room temperature and the precipitate formed is removed by filtration, and the residual solution of the CC is washed with dilute alkali and then water, dried over sodium sulfate, evaporated under reduced pressure to obtain 28.8 g of 4-fluorobenzyl bromide.
Calculated,%: C, 44.48; H 3.20 Br 42.27; F 10.05.
Found,%: C 44.72; H 3.09-, Br 42.53; F 9.94.
A solution of 28.8 g of the crude bromide thus obtained in 30 ml of ethanol was added dropwise to a mixture of 8.8 g of sodium cyanide and 9.0 g of water at 70-80 ° C over 30 minutes. The mixture was kept for 5 hours and the mixture was cooled to room temperature and poured into water. Celite and benzene are then added to the mixture, stirred and celite removed by filtration. The benzene layer is separated, washed with water, dried over sodium sulfate and extruded under reduced pressure to obtain 13.2 g of crude 4-fluorobenzyl cyanide.
IR ohm к s. Cm: 2270, 1615, 1520, 1430, 1240, 1170, 825.
Calculated,%: C 71.10; H 4.48; F 14.06i N 10.37.
Found,%: C 71.34; H 4.29; F 14.23; N 10.15.
0
five
2. Into the flask, 12.8 g of crude 4-fluorobenzyl cyanide, 40 g of 50% NaOH and 2 g of triethylbenzylammonium bromide are charged, and 14 g of methyl iodide is added dropwise with stirring of the mixture at 15 minutes.
The mixture is stirred for 30 minutes at and then cooled to room temperature. The mixture is drunk in ice water. The mixture is extracted with benzene, the benzene extract is washed with water, dried over sodium sulfate and evaporated under reduced pressure, 5 to obtain 13.4 g in 1-4 methyl fluoride-zilcyanide.
Calculated,%: C, 72.47; H 5.41; . F 12.74; N 9.39. CjHjFN
Found% C 72.28i H 5.29 j iF 12.82; N 9.48.
A flask was charged with 7.0 g of o-methyl-4-fluorobenzyl cyanide, 15 g of KOH, 10 g of water and 2.0 g of triethyl benzylammonium chloride, and 10 were added dropwise to this mixture with stirring at 80 ° C over 1 hour. ml of ethyl bromide. The mixture is kept at this temperature for 2 hours. Subsequent operations are carried out in the same manner as described above, and 7.9 g of crude o (α-ethyl-c (α-methyl-4-fluorobenzyl cyanide) are obtained.
Calculated,%: C, 74.55; H 6.83; F 10.72; N 7.90.
C i, H ,, FN
Found Z: C 74.31; H 6.99; F 10.94-, N 7.73.
A mixture of 7.6 g of crude e / -ethyl-a (a-methyl-4-fluorobenzyl cyanide, 20 ml of water and 20 ml of concentrated sulfuric acid is refluxed for 5.5 hours at 134-137 ° C. Mixture cooled to room temperature and extracted with benzene and the benzene solution is extracted with dilute alkali, the diluted alkali extract is acidified to pH 7.5 with concentrated sulfuric acid and extracted with benzene to remove impurities.The aqueous solution is then acidified to pH 4.6 with concentrated saline acid and extracted with benzene. The ash extract was washed with water, dried over sodium sulfate, and evaporated under reduced pressure to give 3.8 g of 2- (4-fluorofensch1) -2-methyl butanoic acid.
0
five
0
five
0
five
NR (CRClj) ppm: 0.85 (t, 3N, J 7 Hz) 1.55 (s, 3N); 1.8-2.3 (m, 2H); 7.0-7.6 (m, 4H); 11.3 (broad s, 1H).
Calculated,%: C 67.33; H 6.68; F 9.68.
C ,, N - (ZRO
Found,%: C, 67.24; H, 6.78; F, 9.83.
3. A solution of 3.0 g of 2- (4-fluorophenyl) -2-methylbutanoic acid in 10 ml of tetrahydrofuran is added dropwise to a mixture of 20 MP of tetrahydrofuran and 0.5 g of lithium aluminum hydride at 40 ° C. The temperature is then placed and the mixture is refluxed for 30 minutes. The mixture is cooled to room temperature and to the mixture by
ethanol is added dropwise in order to dissolve it in 20 hours for 4 hours in order to
live an excess of lithium aluminum hydride. Water is then added to the mixture to complete this decomposition. The precipitate formed is separated by filtration and the tetrahydrofuran is removed from the filtrate by distillation under reduced pressure. The residue is extracted with benzene, the benzene extract is taken up in water, dried over sodium sulfate and evaporated under reduced pressure to give 2.6 g of 2- (4-α-fluorophenyl) -2-methyl butyl alcohol, PD 1.5035.
IR J atcCM HpLenka): 3360, 1610, 1240, 1175, 1040, 840.
Calculated,%: C 72.50, H 8.30 j F 10.42. C ,, 11,, 7,
Found,%: C, 72.85; H 8.22, F 10.35.
Example 14. Obtaining 2- (4-methylthiophenyl) -2-methylpropyl alcohol.
1. Synthesis of 4-methylthiobenzyl chloride
18.2 g of methylal is added to 200 ml of 1,2-dichloroethane and 61.4 g of anhydrous aluminum chloride is dissolved when the solution is cooled with water. Then, at room temperature, 24.8 g of thioanisole is added dropwise to the mixture, and the mixture is stirred in
for 3 hours to react, drink the reaction mixture in water and add concentrated hydrochloric acid to dissolve the solids. The mixture is then extracted with benzene, the extract is washed with water and a dilute solution of sodium bicarbonate in water and again
washed with water. The extract is then dried over sodium sulfate and evaporated, yielding 30.7 g of an oily residue.
Calculated,%: C 55.64; H 5.25 | C1 20.53i S 18.57.
Found,%: C 55.48; H 5.16; C1 20.75; S 18.74.
2. Synthesis of (4-methylthiophenyl) acetone nitrile.
10.5 g of sodium cyanide are dissolved in 12 g of water and the solution is heated at 60 ° C. A solution of 30.7 g of the oily product obtained earlier in stage 1 in ethyl alcohol is added dropwise to the above solution, the mixture is boiled with a reverse reaction. The reaction mixture is subsequently treated according to a conventional method and purified on a chromatographic column using
5 as benzene as eluent, and 14.7 g of (4-methylthiophenyl) acetonitrile (oily product) are obtained.
IR l) “KS cm- (film): 2200, 1500, 1420, 1105, 800.
0 NM tf (CC14) ppm: 2.37 (s, 3N); 3.56 (s, 2H) 7.16 (s, 4H).
Calculated,%: C, 66.22; H 5.56; N 8.58; S 19.67.
Found,%: C 66.49, H 5.51; N 8.44; B 19.83.
3. Synthesis of 1- (4-methylthiophenyl) -1,1-dimethyl acetonitrile.
Out of 13.1 g of (4-methoxyphenyl) -aceto-0 nitrile Pol5T1, according to a procedure similar to that described in Example 24-1, 13.9 g of the intended product.
Calculated,%: C 69.07-, H 6.85 fN 7.32; S 16.76.
five
With „H, iNS

0
Found,%: C 69.34; H 6.79, - N 7.23; S 16.88.
NMR f (CCl) ppm: 1.66 (s, 6H), 2.45 (s, 3N); 7.2-7.6 (m, 4H).
4. Synthesis of 1- (4-methylthiophenyl) -1- -methylpropionic acid.
3.8 g of 1- (4-methylthiophenyl) -1-1-dimethylacetonitrile was added to a mixture of 5.0 g of potassium hydroxide, 5 g of water and 20 ml of diethylene glycol, and the reaction was carried out at 130-140 ° C for 7 hours. The reaction mixture is cooled and drunk into water. The mixture is extracted with benzene, the remaining aqueous solution under 71
acidified with concentrated hydrochloric acid in order to precipitate a precipitate. The mixture is extracted with ether, the extract is rinsed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate and reduced, yielding 1.9 g of solid 1- (4-methylthiophenyl) -1-methylpropionic acid.
NMR tf (acetone-df), ppm, 1.54 (s, 6H) i 2.43 (s. ZN) - 7.0-7.5 (m, 4H).
Calculated,%: C, 62.83; H 6.71; S 15.25.




 11 tT -iS
Found,%: C 62.57 N 6.79j
S 15.43.
5. Synthesis of 2- (4-methylthiophenyl) -1-m-methylpropyl alcohol.
In accordance with the conventional method, lithium aluminum hydride is reduced to 1.9 g of 1- (4-methylthiophene-1) -1-methy1-propionic acid to obtain 1.5 g of the desired product.
NMR f (CCl4) ppm: 1.26 (s, 5H) j 2.39 (s, 3N); 3.38 (s, 2H); 7.0-7.4 (m, 4H).
Calculated,%: C, 67.30; H, 8.22; S, 16.33.
C ,, N ,, OS
The 15 extracts are washed with water and dried over sodium sulfate and extruded under reduced pressure to obtain 7.9 g of an oily residue. The oily residue is purified on a chromatography column with silica gel, using benzene-hexane mixed solvent (1: 3) as the diluent, to obtain 5.3 g of the intended product (oily product).
25 IR l; “Ak with cm- (film): 2950, 1500, 1410, 1395, 1380, 1120, 1105, 1020, 830, 755.
NMR / (CClt) ppm: 1.31 (s, 6H); 2.81 (s, 2H) i 7.18 (d, 4H).
30 Calculated,%: C 60.17 H 6.01f S 16.06; Cl 17.76. C 2 (iH.j4Cli 5g
Found,%: C 59.06; H 6.07; S 16.55, Cl 17.56.
3. Synthesis of 2- (4-chlorophenyl) -2-methylpropylthiol.
Suspended in 25 ml of dry diethyl ether 0.095 mg lithium gum
Found,%: C 67.56; H 8.09; S 16.21.
Example 15. 2- (4-Chlorophenyl) -2 -2-methylproshtiol synthesized by 35
following method.
1. Synthesis of 2- (4-chlorophenyl) -2-methylpropyltseilate.
To a mixture of 10.0 F 2- (4-chlorophenyl) -2-. methyl propyl alcohol and 20 ml of pyri-40 hydrochloride and to this suspension 10.8 g of chloride are added dropwise a solution of 1.0 g of bis- 2- (4-chlorophenyl) -2-methylpropyl 2 disulfide in 10 ml of diethyl 45 NICOM for 2 hours. The reaction mixture is poured into water and 15% dilute sulfuric acid is added, the mixture is extracted with benzene. The benzene extract is washed with a saturated
p-Toluenesulfonyl, the mixture is reacted for 1 hour at 50-55 ° C. The reaction mixture is poured into ice-cold water, and the mixture is acidified with dilute hydrochloric acid and extracted with benzene. The benzene extract is washed with a saturated aqueous solution of sodium chloride, dried over sodium sulfate, and evaporated under reduced pressure with an aqueous solution of sodium chloride, then obtained, to obtain 19.3 g of white solid-dried over sodium sulfate and
Stretch under reduced pressure to obtain 1.0 g of an oily residue.
go residue (so pl. 69-71,5 C).
IR h) „„ “cm-ChKVg): 1595, 1480, 1355, 1175, 970, 825.
IK l „“ KS cm - Chplenka): 2965, 2570,
C NMR (CC14) ppm: 1.31 (s, 6H) i 55 1 1370, 1105, 1020,
2.44 (s, 3H) j 3.89 (s, 2H); 7.13 (s, 4H); 7.18-7.60 (m, 4H / AB-type /).
Calculated,%: C 60.26; H 5.65; C1 10.46; S 9.46.
890.
NMR e / (CCl4) ppm: 0.80 (t, 1H) 1.33 (s, 6H); 2.68 (d, 2H) i 7.23 (s, 4H).
72
C, -, H, 9C10., S
Found,%: C 60.08; H 5.56; C1 10.67; S 9,7.4.
2. Synthesis of bis-C.2- (4-chlorophenyl) -2- -methylpropyl disulfide.
A mixture of the obtained in step 1, 13 g of tovilate, 20.0 g of sodium hydrosulfate (70% purity) and 100 ml of 90% ethanol is stirred and refluxed for 3 hours to allow the reaction to take place. The reaction mixture is poured into water and the mixture is extracted with benzene, benzene.
the extract is washed with water and dried over sodium sulfate and extruded under reduced pressure to obtain 7.9 g of an oily residue. The oily residue is purified on a silica gel column chromatography using benzene-hexane mixed solvent (1: 3) as the diluent, to obtain 5.3 g of the intended product (oily product).
IR l; “Ak with cm- (film): 2950, 1500, 1410, 1395, 1380, 1120, 1105, 1020, 830, 755.
NMR / (CClt) ppm: 1.31 (s, 6H); 2.81 (s, 2H) i 7.18 (d, 4H).
Calculated,%: C 60.17 H, 6.01f S, 16.06; Cl 17.76. C 2 (iH.j4Cli 5g
Found,%: C 59.06; H 6.07; S 16.55, Cl 17.56.
3. Synthesis of 2- (4-chlorophenyl) -2-methylpropylthiol.
Suspended in 25 ml of dry diethyl ether 0.095 mg lithium gum
of the hydride and to this suspension is added dropwise a solution of 1.0 g of BISIC "KS cm - Chlenum"): 2965, 2570,
1 1370, 1105, 1020,
890.
NMR e / (CCl4) ppm: 0.80 (t, 1H); 1.33 (s, 6H); 2.68 (d, 2H) i 7.23 (s, 4H).
73 C 59.83, H 6.53;
Calculated,%: C1 17.66; S 15, .97.
Found,% t C 59.64 H 6.45; C1 17.94 S 15.87.
Scientific name
Nephotettix cincticeps Uhler Sogata furcifera Horvath-White
 Stephanitis pyrioides Scott Psylla pyrisuga Foster
Tsyila mari Schmidberger Aleurolobus taonabae Kuvana Dialeurodes citri Ashmead Trialeurodes vaporariorum Westw Aphis gossypii Glover. Brevicoryne brassicae linne
Myzus persicae Sulzer Rhopalosiphum maidis Fitch Icerya purchas Maskell Planococcus citri Risso Unaspis yanonensis Kuwana
Canephora asiatica Staudinger Acrocercops astaurota Meyrick Lithocolletis ringoniella Metsiraiur Plutella maculipennis Curtis Promalactis inopisema Butler Adoxophyes orana
Cinaphalocrocis medinalis Guenee-grass leaf roller roll Etiella zinckenella Treitschke Ostrinia furnacalis Hubner Syllepte derogata Fabricius Hypertrophia cunea Drury Trimeresia miranda Butler
Agrotis fucosa Butler Heliothis obsoleta Fablicius Leucania separata Walker
144206774
The insect parasites are described below in relation to which the obtained compounds can be used as an active substance in insecticidal and acaricidal compositions, namely:
Common name
1. Hemiptera
Green rice Tsitkad White-backed delfatsid. Brown delfatsid Small brown delfatsid Cabbage bug White-faced bug The brown-marble bug bedboard Rice bug bedder Southern green bug bedder Thin rice bug Japanese pear bugle Pear pearl lacer Pearstepster
Whitefly striped Whitegrass citrus Whitefly greenhouse Hlopkova tl: Cabbage tl
Green peach tl
T Corn Leaf
Redback Australian gutter
Citrus Worm
East Citrus Shchitovka
2. Lepidoptera
Mulberry bagworm
Pear moth
Moth blond leaf
Moth cabbage seed cotton caterpillar
Mala China Leafworm Cane Mat Worm
Soy bean grinder
Herbs on the Maker
Bean Grinder Lima Bean
Corn moth
Cotton Moth
merianska bela butterfly P deniza gooseberry Neparny silkworm d
Cherna is marked crested
Common scoop Hlopkova scoop
75
Mamestera brassicae Linne Plusia nigrisigna Walker Spodoptera litura Fablicius Patnara guttata Bremer et Gray Pieris rapae crucivora Boi.sduval Chilo suppressalis Walker
Malanotus caudex cande ze
Anthrenus verbasci Linne Tenebroides mauritanicus Linne Lyctus brunneus Stephens-Lyctus powder
Epilachna vigintioctimaculata Fablcius beetle
Monochamus alternatus Waterhouse Xylotrechus pyrrhoderus Bates Aulacophora femoralis Motschulsky Oulema oryzae Kuwaymama Phyllotreta striolata Fablicius Callosobruchus chinensis Linsech
4. Hymenoptera
Athalia japonica Rohwer Arge similis Vollenhoven Arge pagana Panzer
5. Diptera
Tipula aino Alexander
Culex pipiens fatigans Wiede
Aedes aegypti Linne-Yellow
Asphondylia sp.
Hylemya antiqua meigen
Hylemya platura meigen
Musca domestica vicina Macqu
Dacus cucurbitae Coquillett
Chlorops oryzae matsumuraagromyza oryzae munakata
Pulex irritans Linne Xenopsylla cheopis Rothschil Ctenocephalides canis Curtis
7. Thysomoptera
Scirtothrips dorsalis Hood Thrips tabaci Lindeman Chloethrips oryzae Williams
1442067
76
Cabbage worms
-Beetroot caterpillar
-Tabacna scoop
- Crow of rice plant
- Ordinary cabbage caterpillar
- Rice stalker grinder
 Coleoptera
Sweet Potato Wire
Kozheed collection
- Larva Moorish goats vki
- Liktus Hoodboy
Ladybird with 28 spots
-Japanese black barbel
- Grape Grinder
- Pumpkin leaf
-Listoed draw
-Block beetle striped
- Dolphonosik bean, Asuki
-Dragonist rice plant
-Small rice weevil
- Small black dolgonayake leaf cutter
-Dolgonosik peach Khrushche kupreyyny
-Japanese bug
- Cabbage sawfly
- Azalea sawfly
- Sickling roses
Dolphin rice
Mosquito home
Mosquito yellow feverish
Gallitsa pod bean
Onion Fly Larva
Sprout fly larva
House fly
Fly dyonna
Larva of a rice steal fly
Moth rice
-Bloch human
- Tropical rat flea
- flea dog
-Trype yellow cha
-Trip onion
-Trip rice
8, Ahoplura
Pediculus humanus corporis De Geer Phthirus pubis Linne Haematopinus Eurysternus Nitzsh
9. Psocoptera
Trogium pulsatorium Linne Liposcelis bostrychophilus Badonnel
10. Orthoptera
Gryllotalpa africara palisot de
Beauvois
Locusta migratoria danica linne
CTxya japonica Willemse-Short
eleven,
Blattella germanica Linne PeriplanetS fuliginosa Servillo
Boophilus Unicroplus Canesfrini Hemitarsonemuslatus Banks Panonychus citri Me Gregor Tetranychus lelarius Linne Tetranychus urticae Koch-Two Rhizoglyphus ech inophus Fumouze Robin
In the insecticidal and acaricidal composition of the aforementioned 2-arylpropyl ether or thioether derivative is contained in an amount of 0.001 to 95% by weight, preferably 0.01 to 50% by weight.
All parts shown in the following description are parts by weight, and the proposed compounds are indicated by the numbers given in Table. one.
An example of a recipe is 1 A mixture of 20 parts of a compound selected from compounds 1-111, 2 hours of Sorpol (a mixture of neonic surfactants and anionic surfactants) and 60 parts of xylene are mixed and an emulsion is prepared.
In the actual use of the inventive compound as an active ingredient, it is usually applied with a dosage of 1-300 g, preferably 2-100 g, particularly preferably 5-20 g, per 10 ap. ;
- Your pussy
-Osh pubis
- shortcone louse cattle
Book louse flour ploka book louse
 African Bear Locust migrant Short-rice rice sara cha
Dictyoptera
Red-haired cockroach
- Smoky brown cockroach Acarina
-Buck tick
- wide tick
-Red citrus mite carmine mite
-Dupy spiny web spider mite
- Root mite
The following tests illustrate insect acaricidal activity.
Samples. To the mixture of 20 parts, we offer my compound and 20 parts of the product Sorpor M-20B (a mixture of neonic surfactants and anionic surfactants) are added 60 parts of xylene and the mixture is thoroughly mixed. The resulting emulsifiable concentrate is diluted to a predetermined concentration with distilled water and used
the resulting diluted product. I
In fish toxicity testing, the test compound is dissolved in acetone to obtain a 1% solution, and the calculated amount of this solution is used.
As comparative compounds under the same conditions as the proposed compound, the compounds described below were tested:
sn-so-sl // h
I I L (f СН О CN /
SNS SNZ
b)
CH-SNG-O-SNG
SN, SNZ
c) pyrethrin
d) Ofunak Go, 0-diethyl-0- (3-oxo--2-phenyl-2H-pyridazin-6-yl) -thiophosphate
d) MTMK (m-tolyl-N-methylcarbamate)
e) Mesomyl (N- - (methylcarbamoyloxy) -thioamidoacetic acid S-methyl ester)
g) DCVF (0,0-dimethyl-0- (2,2-dichlorophenyl) phosphate)
h) Ortoran (o, 8-dimethyl-H-acetiophosphoramidothiolate)
i) Permethrin

Test 1 (impact on tobacco moth),
The emulsifiable concentrate of the test compound is prepared according to the method described in Example 1 of formulation 1 and diluted to a concentration of 20 or 100 parts per million ppm). The leaves of sweet potatoes are immersed in a diluted solution for 10 s, dried in air and placed in a plastic cup having a diameter of 10 cm. Then, a caterpillar of a second-age tobacco scoop is freely placed in this cup. The cup is left in the thermostat chamber at. After 24 hours, the number of dead and living caterpillars is counted and the mortality rate is calculated. The result obtained is expressed as the average value obtained from the mortality data obtained in the three test cups.
The results are shown in Table. four..
Test 2 (immersion test
caterpillars of tobacco scoops).
Dilutions having a concentration of a substance of 20 or 100 ppm are prepared in the same manner as described in Test 1.
In diluted solutions for 5 seconds, the caterpillars of the tobacco scoop of the second and fifth age stages are immersed and excess liquid is removed with filter paper. Then the caterpillars are freely placed in a plastic cup and fed artificial food there. The cups are then placed on incubation in a thermostat chamber at 25 C. After 24 hours, the number of dead and living caterpillars is calculated and the mortality rate is calculated. This test was carried out on three plates, the result being presented as an average over all tests.
The results are shown in Table. five.
As can be seen from the table. 5, compared with fenvalerate (a) and permerin (i), which have a strong effect on insect pest insect pests, the proposed compounds are more effective and also more effective than the compound (b), which is a structural analog of the proposed compounds.
Test 3 (impact on sustainable green rice cyclists and sensitive green rice cyclops). ; Rice seedlings are cultivated in hydroponic pots having a diameter of 5 cm. Chemical dilutions of a compound with a concentration of 20 or 100 ppm are prepared in this way; as described in test 1, and applied with a sprayer in an amount of 3 ml per pot. The treated seedlings are swept in air and covered with a metal mesh cylinder. In each pot, 10 adult females of stable green tsikadok (collected in the area of Nikagavar) and sensitive green rice tsadok (collected in
Chigasaki). After 24 hours, the numbers of live animals are killed and the degree of mortality is calculated. These tests were carried out on three pots and the average mortality was calculated.
The results are shown in Table. 6
Test 4 (effect on a diamond with a diamond back).
Cover the leaves of cabbage with a plastic cup and place 10 larvae of the third stage of the moth with a rum of a fish-like back in it.
Chemical dilution is applied from the applicator with a dose of 3 ml per dish, the dilution concentration of 100 and 20 ppm is prepared in the same manner as described in test 1.
After chemical dilution was sprayed, the dish was closed and after 24 hours the number of dead and living larvae was counted and the mortality was calculated. The test was performed on three plates and the average value was calculated.
The results are presented in Table. 7
Test 5 (effect on green peach aphids).
Sprouts (having 3-4 leaves) eggplant grown in a pot infect with green peach aphids and give the insects to grow. Count the number of insects. Chemical dilution having a concentration of 100 ppm, prepared as described in test 1, is applied using a sprayer at a dose of 10 ml per pot. The pot is then placed in a glass greenhouse. After 24 hours, the number of live insects is counted and the mortality is calculated.
The test is carried out on three pots and an average value is calculated.
The results are presented below (sign A means mortality above 95%, sign B means mortality of 80-95%, sign C means mortality of 50-80%, and sign D means mortality less than 50%).
connect
Insecticidal activity
B A A
6 7 8 9 11 12 14 15 18 20 24 29 39 41 48 49 50 52 53 55 57
59
62
, 64
69
73
78
86
93
95
96
103
105
b
Well
3
A A B A A B A B A A A A B A A A A A A A B A A A
A B A A A A B A A B A B D D S
As can be seen from the data, the proposed compounds exhibit higher activity with both the standard for the intended purpose and the analogue in structure.
Test 6 (effect on adult double-spotted spider mites).
Place on a cotton absorbent (2 cm 2 cm) impregnated with water a kidney-shaped bean leaf perforated with a cork (15 mm in diameter) and produce 100 adult individuals of a two-spotted spider mite. A 3 ml chemical dilution is applied from a nebulizer, having a concentration of 100 pph, and prepared in the same manner as in Test 1.
The disk of the sheet placed on the cotton adsorbent is placed in a thermostat chamber maintained at 25 C. After 24 hours, the number of dead individuals is counted and the mortality is calculated.
831A42067
The test was performed on three leaf discs and the mean value was measured.
The results are presented below:
tested connection
one
2
3
four
five
6
7
eight
9
10 11 12 13 14 15 16 17 18 19 20 21
22 23 24 25 26 27 -28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Mortality,%
100 100
90
80 100 100 100
60,100
90,100
80
80 100
70
90,100,100
60,100
80
50,100,100
90
80
60,100
60,100
90,100
95
80
85,100
70
90,100
60,100
90,100
80 100
95 100 100 100 100 100
8 A
80
90
100
100
80
90
100
100
60
100
100
90
100
100
80
90
100
60
100
90
100
100
90
100
100
100
100
100
90
60
90
90
80
100
100
80
100
90
100
100
100
100
80
100
80
80
100
100
100
90
80
70
100
100
100
90
100
90

70
100
20
ABOUT
40
Test 7 (effect on German Prussian cockroaches).
The bottom of a high Petri dish, having a diameter of 9 cm and a height of 9 cm, processes 50 or 10 mg / cm of the test compound, taken as an aqueous solution of an emulsifiable concentrate prepared using the method described in test 1, and give the cup to air dry. In order for the adult individuals not to get out of the cup, the inner wall of the cup is treated with oil. Then 10 male cockroaches are put out into each cup and the cup is placed
From now on, the number of agonizing and dead individuals is calculated. The test is carried out in two plates and an average value is calculated. The results are presented in Table. eight.
into the thermostat chamber, at 25 ° C. After 24 h
Test 8 (fish toxicity)
A water tank, with a depth of 60 cm, a height of 40 cm, and a length of 30 cm, is filled with water and released into the tank of 10 carp fry, having a body length of about 5 allowing them to adapt to the environment in the tank. Test compound is applied in such a way that its concentration in water is 10.1 or 0.1 ppm. After 48 h, calculate. the number of dead and living carp and explore the effects on fish.
The results are shown below (BCM chemical concentration, in which 1/2 of the tested fish die 48 hours): Test compound
e
fish, high speed h / mpn
Bbmie
Bbmie
Above
Above
Above
0.01-0.05
Above 10
Vs1e 10
Bbmie 10
ten
one
ten
ten
ten
ten
five
0
five

19 20 21 22 23 24 29 30 31 33 35 37 41 45 46 47 48 49 50 51 52 53 55 62 69 73 105 107 and
10 10 10 10
one
10 10
one
10 10 10 10 10
one
10 10 10 10 10
one
10 10 0.1
eleven
ten
one
one
Above
Above
Above
Above
Above
Above
Above
Above
Bbmie
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Above
Below 0,005
Below 0,005
As can be seen from the data, known compounds a and m exhibit higher toxicity to carp.
Test 9 (toxicity test).
A predetermined amount of a solution or suspension of the test compound in corn oil is administered orally to males weighing 19-23 g (0.2 MP per 10 g body weight). After 7 days, the number of dead mice is counted and the effects on the mice are examined. The results obtained are the following LD-50 - the amount of the chemical, affecting 1/2 of the test animals):
Test compound
1-111 a in e
Acute toxicity after oral administration of LD-50, mg / kg
Bbmie 500
260
340
220
28
From the results presented above, it can be seen that the proposed compounds are safer compared to pirate 871442067
rinom (b) and fenvalerate (a), exhibiting low toxicity to warm-blooded animals.
 From the results obtained in the above tests, it can be seen that the proposed compounds, respectively, have a higher activity compared with lime compounds and compounds of similar structure, their use is safe, since their toxicity to warm-blooded animals is lower than toxic - comparing compounds. Compared with fenvalerate (a) and g permitrin (i), which has a broad spectrum of insecticidal activity and exhibits high insecticidal activity, and this is obviously the proposed compounds are more useful, because they are safer with the same or greater activity. to warm-blooded animals and aquatic dwellers and as a result, can be applied more widely.J5
w s and h
Formulation Example 2.
In 10 parts of acetone, 1 part of the proposed Compound is dissolved and 99 parts of dust clay are added to this solution, and the mixture is obtained by evaporation of the mixture.
Test 10 (the experiment was carried out in accordance with prescription example 2).
Rice seedlings (12–13 cm high) were transplanted into a growing vessel (10 cm in diameter, 8 cm in height). The seedlings were crushed with a metal mesh cylinder (4 cm in diameter, 15 cm high, and the number of holes was 16 mesh, or about 6.4 holes over a length of 1 cm), in the upper part of which was a sponge. Twenty females (of recurrent origin) of rice cyclops were placed in a vessel. Dust was prepared in a manner similar to that described in Formulation Example 2, and used in an amount of 2 kg / 10 ares (or 20 kg / ha). processing from the sprayer in the case of each of the compounds. After 48 h, the number of dead and residual 3-phenoxybenzyl-2- (4-methoxyphenyl) -2-methyl methyl ether and thioether were calculated (comp. 1, -) 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-fluorophenyl) -2-ethyl 1 -propyl ether and thioether (comp. 2, -) 100/100
3-phenoxybenzyl-2- (4-methoxyphenyl) -2-ethylpropyl ether and thioether 100/100
7
88
The death tolls were lost and the death rate was estimated. The experiments were repeated twice and the average value determined. The results obtained follow;
Test 11. Conducted in the same way as for the above-mentioned proposed compounds, and the results are presented in the following form, the numerator shows the mortality (%) of a sustained green rice cattle in the case of ether, the denominator is the mortality (%) of a sustained green rice cycts in thioether applications:
89144206790
3- (4-fluorophenoxy) -benzyl-2- (4-fluorophenyl) -2-methylpropyl ether and thioether comp. 45, -) 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-methylphenyl) -2-methylpropyl ether and thioether (comp. 3, -) 100/100
3- (4-6 chromophenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpro1Ball ether and thioether (comp. 4 and 37) 100/100
3- (4-bromophenoxy) -benzyl-2- (4-chlorophenyl) -2-ethyl 1 Propyl ether and thioether (comp. 46, -) 100/100
3-phenoxybenzyl-2-fenSh1-2-methylpropyl ether and thioether (comp. 5, -) 100/90
3-phenoxybenzyl-2-phenyl-2-ethylpropyl ether and thioether 100/90
3- (4-fluorophenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 6 and 9) 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-chlorophenyl) -2-ethylp1 opyl ether and thioether. 100/100
3- (4-fluorophenoxy) -benzyl-2- (3,4-dimethylphenyl) -2-metr-propyl ether and thioether 100/100
3-phenoxybenzene1-2- (3,4-methylenedioxyphenyl) -2-methylpropyl 10th ether and thioether (comp. 7, -) 100/100
3-Phenoxbenz1-1- (3,4-methylenedioxyphenyl) -2-ethyl 1 -propyl ether and thioether 100/100
3- (4-methoxyphenoxy) -benzyl-2- (4-methylthiophenyl) -2-methylpropyl ether and thioether (comp. 8, -). 80/80
3- (3-chlorophenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 10, -) 100/90
3- (3-chlorophenoxy) -benzyl-2- (4-chlorophenyl) -2-ethylpropyl ether and thioether 100/90
3- (3-fluorophenoxy) -benzyl-2- (4-fluorophenyl) -2-methylpropyl ether and thioether 100/100
3- (3-fluorophenoxy) benzyl-2- (4-chlorophenyl) -2-ethylpropyl ether and thioether 100/100
3- (4-fluorophenoxy) -benzsh1-2- (4-difluoromethoxyphenyl) -2-methylpropyl ether and thioether (comp. 11, -) 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-difluoromethoxyphenyl) -2-ethylpropyl ether and thioether 100/100
5-6enzyl-3-furylmethyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 12, -) 100/90
5-benzyl-3-furylmethyl-2- (4-chlorophenyl) -2-ethylpropyl ether and thioether 100/80
3- (4-methoxyphenoxy) -benzyl-2-phenyl-2-methylpropyl ether and thioether (comp. 13, -) 100/90
3- (4-methoxyphenoxy) -benzyl-2-phenyl-2-ethylproduct ether and thioether 100/90
3- (2-fluorophenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 14, -) 100/100
3- (4-fluorophenoxy) -benzyl-2- (3-chloro-4-methylphenyl) -2-methyl 11-propyl ether and thio ether 100/100
3-phenylthiobenzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 15, -) 100/90
3-phenoxybenzyl-2- (4-trifluoromethylthiophenyl) -2-methylpropyl ether and thioether (comp. 104, -) 100/100
3- (4-bromophenoxy) -benzyl-2- (4-fluorophenyl) -2-ethylpropyl
ether and thioether (comp. 16, -) 100/100
3- (4-bromophenoxy) -benzsh1-2- (4-fluorophenyl) -2-methylpropyl
ether and thioether 100/100
3-phenoxybenzyl-2- (4-trifluoromethylphenyl) -2-ethylpropyl
ether and thioether 100/100
91144206792
3-phenoxybenzyl-2- (4-trifluoromethylthiophenyl) -2-ethylpropyl ether and thioether 100/100
3- (4-fluorophenoxy) -benzyl-2- (3,4-dichlorophenyl) -2-methylpropyl ester and thioether (comp. 17, -) 100/100
3- (4-fluorophenoxy) -benzip-2- (3,4-dichlorophenyl) -2-ethylpro-11Sch1 ether and thioether 100/100
3-phenoxybenzyl-2- (4-difluoro1-methoxyphenyl) -2-methylpropyl ether and thioether (comp. 18, -) .100 / 100
3- (4-fluorophenoxy) -beisyl-2- (4-difluoromethylthiophenyl) -2-methylpropyl ester and thioether 100/100
3-phenoxybenzyl-2- (4-difluoromethoxyphenyl) -2-ethylpro1Slide ester and thioether100 / 100
3-phenoxybeneyl-2- (3,4-dimethoxyphenyl) -2-methyl globular ether and thioether (comp. 88, -) 100/100
3- (4-chlorophenoxy) -benzyl-2- (4-cyanophenyl) -2-methyl 1 propyl ether and thioether 100/100
3- (3-fluorophenoxy) -benzyl-2- (3,4-difluorophenyl) -2-ethyl 1-propyl ether and thioether 100/100
3- (4-methylphenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp., 19, -) 100/80
3- (4-methylphenoxy) -benzyl-2- (4-chlorophenyl) -2-ethyl 1 -propyl ether and thioether 100/80
3-phenoxybenzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 49 and 20) 100 / 3- (2-bromophenoxy) -benzyl-2- (3,4-dibro1 enyl) -2- methylpropyl ether and thioether 100/100
3- (2-chlorophenoxy) -benzyl-2- (4-trifluoromethoxyphenyl) -2-methylpropyl ether and thioether 100/100
3- (3-methoxyphenoxy) -benzyl-2- (4-ethylfensch1) -2-methylpropyl ether and thioether 100/100
3- (2-methylphenoxy) -benzyl-2- (4-isopropylphensh1) -2-methylpropyl ether and thioether 100/100
3- (4-bromophenoxy) -benzyl-2- (3,4-dichlorophenyl) -2-methylpropyl ether and thioether (comp. 21, -) 100/100
3- (A-fluorophenoxy) -benzyl-2- (4-trifluoromethylthiophenyl) -2-methylpropyl ether and thioether 100/100
3- (4-bromophenoxy) -benzyl-2- (3,4-dichlorophenyl) -2-ethyl hydrochloride and thioether 100/100
3- (3-bromophenoxy) -benzyl-2- (1,2,3,4-tetrahydronaphthalen-7-yl) -2-methylpropyl ether and thioether 100/90
3- (4-chlorobenzyl) -benzyl-2- (4-ethoxyphenyl) -2-metsh1Pro11Il ester and thioether 100/100
3- (3,5-dichlorophenoxy) -benzip-2- (indian-5-yl) -3-methylpropsh10-ester and thioether 100/90
3-phenoxybenzyl-2- (4-difluoromethylthiophenyl) -2-methylpropyl ether and thioether, 100/100
3-phenoxybenzene -1- (4-difluoromethylthiophenyl) -2-ethylpropyl ether and thioether 100/100
3-benzoylbenzyl-2- (4-chlorofensh1) -2-methylpropyl ether and thioether (comp. 22, -) 100/90
3-benzoylbenzyl-2- (4-chlorophenyl) -2-eth1pro11Lyl ester and thioether 100/80
3- (4-fluorophenoxy) -benzip-2- (3-trifluoromethylphensh1) -2-metsh1-propyl ether and thioether (comp. 23, -) 100/100
3- (3-fluorophenylthio) -benzyl-2- (3-methyl-feshsh) -2-methylglovether and thioether.90 / 80
3-phenoxybenzyl-2- (4-methylthiophenyl) -2-methylpropyl ether and thioether (comp. 24, -) 100/100
93144206794
3-phenoxybenzyl-2- (4-methylthiophenyl) -2-ethylpropyl ether and thioether. 100/100
3-phenoxybenzyl-2- (4-pentafluoroethoxyphenyl) -2-methylpropyl ether and thioether 100/100
3-phenoxybenzyl-2- (3,4-difluoromethylenedioxyphenyl) -2-methylpropyl ether and thioether 100/100
3- (4-Fluorophenoxy) -benzyl-2- (4-Pentafluoroethoxyphenyl) -2-methyl shspropyl ether and thioether 100/100
3- (3-chlorophenoxy) -benzsh1-2- (4-difluoromethoxyphenyl) -2-methylpropyl ether and thioether (comp. 25, -) 100/100
3- (3-chlorophenoxy) -benzsh-1- 2- (4-difluoromethoxyphenyl) -2-ethylpropyl ether and thioether 100/100
3- (4-chloro-2-methylphenoxy) benzyl-2- (4-allylphenyl) -2-methylpropyl ether and thioether 100/100
3- (3,5-dichlorobenzoyl) -benzsh1-2- (4-tert-butylphenyl) -2-metsh1-propyl ether and thioether. 100/100
3- (4-chlorophenoxy) -benzyl-2- (3-chloro-4-fluorophenyl) -2-methylpropyl ether and thioether 100/100
3- (3-methylphenoxy) -benzyl-2- (4-chlorophenyl) -2-methylproduct of the ether and thiozfir (comp. 26, -) 100/90
3- (3-methylphenoxy) -benzyl-2- (4-chlorophenyl) -2-ethylproggal ether and thioether 100/90
3- (2-methoxyphenoxy) -benzyl-2- (4-methoxymethylphenyl) -2-methylpropyl ether and thioether 100/90
3- (4-methoxyphenoxy) -benzyl-2- (4-methoxyphenyl) -2-methylpropyl ether and thioether 100/90
((3- (3-bromophenoxy) -benzyl-2- (3-methoxy-4-methylphenyl) -2-methylpropyl ether and thioether (, Cope 27u -) 100/100
3- (4-fluorobenzyl) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether 100/100
3- (3,4-dichlorophenoxy) -benzyl-2- (4-isobutyrylphenyl) -2-methylpropyl ether and thioether 100/90
3- (4-fluorophenoxy) -benzsh1-2-phenyl-2-methylpropyl ether and thioether (comp. 28) 100/100
3- (4-fluorophenoxy) -benzsh1-2-phenyl-2-ethylpropyl ether and thioether-100/100
3- (3-chloro-5-methoxyphenoxy) -benzyl-2- (3,4-di-tert-butsh1phenyl) -2-methylpropyl ether and thioether 100/100
3- (3-chlorophenoxy) -benzyl-2- (3-methylphenyl) -2-methylpropyl ether and thioether 100/100
3- (4-fluorophenylthio) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether. 100/80
3- (4-, bromophenoxy) -benznp-2- (4-difluoromethoxyphensh1) -2-methylpropyl ether and thioether (comp. 30, -) 100/100
3- (4-bromophenoxy) -benzy -2- (4-difluoromethoxyphenyl) -2-ethylpro-saw-ether and ester100 / 100
3- (4-fluorophenoxy) -benzyl-2- (4-tert-butylfeNIL) -2-methyl propyl ether and thioether 100/100
3-phenoxybenzyl-2- (2-naphthyl) -2-methylpropyl ether and thioether (comp. 31, -) 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-isopropylphenyl) -2-methylpropyl ether and thioether 100/90
3-phenoxybenzyl-2- (2-naphsh1) -2-ethylpropyl ether and thioether100 / 100
3- (4-fluorophenoxy) -benzip-2- (4-methoxyphenyl) -2-methylpropyl ether and thioether 100/100
3- (4-fluorophepoxy) -benzl-2- (4-methoxyphensh1) -2-ethylpropyl ether and thioether 100/100
95144206796
3- (4-fluorophenoxy) -benzyl-2- (4-chloro-3-methylphenyl) -2-methyl propyl ether and thioether
3-Phenoxybenz1-2-3, (trifluoromethoxy) -phenyl j-2-methyl-proglyl ester and thioether
3-phenoxybenzyl-2- (4-methoxy-3, 3-dimethylphenyl) -2-methylpropyl ether and thioether
. 3- (4-bromophenoxy) -benzyl-2- (4-methylphenyl) -2-metsh1propyl ether and tiafer (comp. 33, -)
3-phenoxy enzyl-2-C4- (2,2-dichlorovinyloxy) -phenyl -2-methyl-propyl ether and thioether
3- (4-methoxyphenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 34, -)
3-phenoxybenzyl-2-G4- (1,1,2,2-tetraphetoethoxy) -fenleJ-2-me- thi propyl ether and thioether
3-benzylbenzyl-2- (4-chlorophenyl) -2-methyl ether and thioether (comp., 35, -)
3-phenoxybenzyl-2- 4- (1,1,2,2-tetrafluoroethoxy) -phenyl1-2-ethylpropyl ether and thioether
3- (4-fluorophenoxy) -benznl-2- (Z-methylphenyl) -2-methylpropyl ether and thioether (comp. 36, -)
3-phenoxybenzyl-2- (4-chlorophenyl) -2-ethylpropyl ether and thio ether (comp. 50, -)
3-phenoxybenzyl-2- (3,4-dichlorophenyl) -2-methylpropyl ether and thioether (comp. 48)
3-phenoxybenzyl-2- (3,4-dichlorophenyl) -2-ethylpro1 8-cycle ether and thioether (comp. 52, -).
3-phenoxybenzyl-2- (4-chloro-3-bromophenyl) -2-methylpropyl ether and thioether
3- (3-chlorophenyl) benzsh1-2- (3,4-dichlorophensh1) -2-methylpropyl ether and thioether (comp. 38, -)
3- (3-chlorophenoxy) -benzyl-2- (3,4-dichlorophenyl) -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- (4-chloro-3-bromophenyl) -2-ethylpropyl ether and thioether
3-Fenwxybenzyl-2- 14- (2,2,2-trifluoroethoxy) -phenyl -2-methyl 1-propyl ether and thioether
3-phenoxybenzyl-2- 4- (2,2,2-trifluoroethoxy) phenyl} -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- (3-trifluoromethylphensh1) -2-methyl 1-propyl ether and thiosulfur (comp. 39, -)
3-phenoxybenzyl-2- (3-chloro-4-methoxyphenyl) -2-methylpropyl ether and thioether
3- (4-methoxyphenoxy) -benzyl-2- (4-bromophenyl) -2-methylpropyl ether and thioether (comp. 40, -)
3- (4-methoxyphenoxy) -benzyl-2- (3,4-dichlorophenyl) -2-methylpropyl ether and thioether (comp. 41, -)
3-phenoxybenzyl-2- (6-methyl-2-naphtsh1) -2-methylpropyl ether and thioether (comp. 71, -)
3- (4-fluorophenoxy) -benzyl-2- (3-bromo-4-chlorophenyl) -2-methylpropi; 1st ester and thioether,.
z -phenoxybenzyl-2-G4- (2,2-dichlorovinip) phenyl -2-methylpropyl-)
new ether and thioether
3- (4-bromophenoxy) -benzsh1-2- (3-trifluoromethylphensh1) -2-methylpropyl ether and thioether (comp. 42, -)
3-phenoxybenzyl-2- (4-nitrofensh1) -2-metsh1propyl ether and
thioether
3-phenoxybenzyl-2- (4-nitrophenyl) -2-ethylpropane 10th ether and thioether (comp. 43)
100/100 100/100 100/100 100/100 100/90 100/100 100/100 100/80 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100 / 100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/90 100/100 100/100 100/100
97144206798
f
3- (4-fluorophenoxy) -benzyl-2-TZ-fluoro-4-methylphenyl) -2-methylpropyl ester and thioether
3- (4-methoxyphenoxy) -benzyl-2- (4-methylphenyl) -2-methylpropyl ether and thioether (comp. 44)
3-phenoxybenzyl- 2- (4-dichlorofluoromethoxyphenyl) -2-methylpropyl ether and thioether
3- (4-fluorophenoxy) -benzyl-2- (3,4-diethylphenyl) -2-methylpropyl ether and thioether
3-phenoxybenzene -1- (4-dichlorofluoromethoxyphenyl) -2-ethylpropyl ether and thioether
3-phenoxybeneyl-2- (4-methylfensh1) -2-methylpropyl ether and thioether (comp. 47)
3-phenoxybenzyl-2- (4-bromophenyl) -2-ethylpropane 1 and thioether
3-phenoxybenzyl-2- (3-chloro-4-methylphenyl) -2-methylpropyl ether and thioether
3-phenoxybeneyl-2- (3,4 dibromophene1) -2-methylpropyl ether and thioether cone. 73, -
3-phenoxybenzyl-2- (4-tert-butsh1phenyl) -2-methylpropyl ether and thioether (Lead. 105, -)
3-phenoxybenzyl-2- (4-fluorophenyl) -2-methylpropyl ether and thioether (comp. 51, -)
3-phenoxybenzip-2- (4-bromophenyl) -2-methylpropyl ether and thioether (comp. 107, -)
3-phenoxybenzene -1- (4-fluorophenyl) -2-ethylpropyl ether and thioether
3-phenoxy-6-benzyl-2- (4-ethynyl-phenyl) -2-methylpropyl and thioether
3-phenoxybenzyl-2- (3-zchor-4-fluorophenyl) -2-ethylpropanoyl ether and thiospir
3-phenoxybenzyl-2- (4-ethylphenyl) -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- (4-chloro-3-methylphenyl) -2-methylpropyl ether and thioether
3-phenoxy-8-nsyl-2-C4-tert-butyl-phenyl) -2-ethylpropanoyl ether and thioether
i 3-phenoxybenzyl-2- (3,4-dimethylphenyl) -2-methylpropyl ether and thioether
3-phenoxybenzyl-2- (3-chloro-4-metshphenyl) -2-ethylpropyl ether and thioether.
3-phenoxybenzyl-2- (3,4-dibromophenyl) -2-ethylproduct ether and thioether
3-phenoxybenzyl-2- (4-chloro-3-methylphenyl) -2-ethylpropyl ether
and thioether
3-phenoxybenzate -2 (3,4-dimethylphenyl) -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- (4-methylphenyl) 2-ethylproduct and thioether (comp. 53, -)
3-phenoxybenzyl-2- (3-chloro-4-fluorophenyl) -2-methylpropyl ether
and thioether
3-phenoxybenzyl-2- (3,4-difluorophenyl) -2-methylpropyl ether and thioether (comp. 75, -)
3-phenoxybenzyl-2- (3,4-difluorophenyl) -2-ethylpropyl ether and
thioether
3-phenoxybenzyl-2- (3-bromo-4-fluorophenyl) -2-methylpropyl ether
and thioether
3-phenoxybenzyl-2- (3-bromo-4-fluorophenyl) -2-ethylpropyl ether
and thioether
100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100
90/85 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/80 100/100 100/100 100/100 100/100 100/100 100/100 100/100 100 / 100 100/100
100/100
99
3-phenoxy6enzyl-2 and thioether
Z-phenoxybenzyl-2 and thioether
Z-phenoxybenzyl-2 and thioether
., Z-phenoxybenzyl-2 and thioether
3-phenoxybenzyl-2-ether and thioether
3-phenoxybenzene -1-2- and thioether
3-phenoxybenzyl-2-ether and thioether
Z-phenoxybenzyl-2- and thioether
Z-phenoxybenzyl-2- and tiafer
Z-phenoxybenzyl-2- and thioether
Z-phenoxybenzyl-2- and thioether
1442067100
(3-fluoro-4-bromophenyl) -2-methylpro1Bd
Z-phenoxybenzyl-2-thioether
3-phenoxybenzene -1-2- and thioether
Z-phenoxybenzyl-2- and thioether
3-phenoxybenzyl-2-ether and thioether
3-phenoxy-bensht-2 and thiosulfate
3-phenoxybenzyl-2-ether and thiozofir
3 phenoxybenzyl-3-ether and thioether
Z-phenoxybenzyl-2- and thioether
Z-phenoxybenzyl-2- and thioether
Z-phenoxybenzyl-2- and thiozofir
Z-phenoxybenzyl-2- and thioether
3-phenoxybenzyl-2- ether and thioether
3-phenoxybenzyl-2-ester and thioether
3-phenoxybenzyl-2-ester and thioether
Zgphenoxybenzyl-2-ether and thioether
Z-phenoxybenzyl-2- ether (comp. 54, -)
Z-phenoxybenzyl-2ether
Z-phenoxybenzyl-2-ether (comp. 55 and 95)
- (3-fluoro-4-bromophenyl) -2-ethyl 1propyl ether - (4-bromo-3-chlorophenyl) -2-methylpropyl ether - (4-bromo-3-chlorophenyl) -2-ethylpropyl ether - (4-fluoro -3-methylphenyl) -2-methyl 1-propyl - (4-fluoro-3-methylphenyl) -2-ethylpropyl ether - (3-fluoro-4-methylphenyl) -2-methyl 1-propyl - (3-fluoro-4-methylphenyl) -2 -ethylpropyl ether - (3-bromo-4-methylphenyl) -2-methyl 1-propyl ether - (3-bromo-4-methylphenyl) -2-ethyl-1-3-methyl ether (3,4-diethylphenyl) -2-methylpropyl ether
(3,4-diethylphenyl) -2-ethylpropyl ether and (4-isopropylphenyl) -2-methylpropyl ether
(4-Isopropylphenyl) -2-ethyl 1-Propyl ester , 4-di-tert-butsh1phenyl) -2-ethylpropyl (3-ethyl-4-metsh1phenyl) -2-methylpropyl ether (3-methyl-4-metshphenyl) -2-ethylpropyl ether (4-ethyl-3-methylphenyl) (4-Ethyl-3-methylphenyl) -2-methylpropyl ester (4-tert-butyl-3-methylphenyl) -2-methylpropyl ether; 2-methyl-3-methyl-phenyl; 4-methyl-3-methylphenyl 2-methylpropyl; - (4-isopropyl-3-methylfeshsh) -2-methylshp) oshsho- (4-isopropsh1-3-metshphenyl) -2-etsh1propyl (4-cyanophenyl) -2-methylpropyl eff p and thio (4-tsianofensh1) -2-etsh1propilovy ether and thio (4-etoksifensh1) -2-methylpropyl ester and tio100 / 100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/100
100/80
100/85
90/85
90/80.
100/100
100/100
100/100
100/100
90/90
90/85
95/90
90/90
100/90
100/85
100/100
3-fenubeibenzsh1- (4-ethoxyphenyl) -2-ethylpropyl ether and thioether
3-phenoxybeneyl-2- (3,5-dichlorophenyl) -2-methylpropyl ether and thioether (s. 56, -)
3-phenoxybenzyl-2- (3,5-dichlorophenyl) -2-ethylpropyl ether and thioether
3-phenoxyben Ech-2- (4- (n-propoxy) -phenyl -2-methylpropyl ether and thioether (comp. 57, -),
3-phenoxybenzyl-2-G4- (n-propoxy) -phenyl -2-ethyl 1 Propyl ether and thioether
3-G4-fluorophenoxy- (benzyl-2) -3-chloro-4-fluorophenyl -2-methyl 1-propyl ether and thioether (comp. 58, -)
3-C4-fluorophenoxy- (benzyl-2) -3-chloro-4-fluorophenyl -2-ethyl propyl ether and thioether
3-phenoxybenzene -1-2- (4-isopropoxyphene1) -2-methylpropyl ether and thioether (seod. 59, -)
3-phenoxybenzene -1- (4-isopropoxyphenyl) -2-ethyl 1 -propyl ether and thioether
3-phenoxybenzyl-2- (4-acetylphenyl) -2-methylpropyl ether and thioether (comp. 60, -)
3-phenoxybenzyl-2- (4-acetylfensh1) -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- (4-cyclopentyloxyfensh1) -2-metsh1propyl ether and thioether (comp. 61, -)
3-phenoxybenzyl-2- (4-cyclopentyloxy-1) -2-ethylproggal ester and thioether
Z-phenyloxybenzyl-2- G4- (n-pentyloxy) -phenyl -2-methylpropyl ether and thioether (comp. 62, -)
Z-phenoxybenzyl-2- G4- (n, pentyloxy) -phenyl -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- (4-isobutyloxyphenyl) -2-methylpropyl ether and thioether (comp. 64, -)
 3 enoksibenzu1-2- (4-isobutyloxyphenyl) -2-eth1prrpyl ether and thioether
3-phenoxybenzene -1- (4-iodophenyl) -2-metsh1propyl ether and thioether (comp. 65, -)
3-phenoxybenz1-2- (4-iodophenyl) -2-ethylpropyl ether and thioether
3- (4-bromophenoxy) -benzyl-2- (4-ethoxyphensh1) -2-methylpropyl
ether and thioether (Comp. 66, -)
3- (4-bromophenoxy) -bvnzil-2- (4-ethoxyfensh1) -2-eth1propyl
ether and thioether
3-phenoxybenzyl-2- (4-vinsh1bxyphenyl) -2-methylpropsh1 Ovine ether
and thioether (Comp. 67, -)
Z-phenoxybenzyl-2- (4-vinyloxyfensh1) -2-ethylpropyl and
thioether
3-phenoxybenz1-2- (4-biphenyl) -2-methylpropyl ether and thioether (comp. 68, -)
3-phenoxybenzyl-2- (4-biphenyl) -2-eth1propyl ether and thioether
3-phenoxybenzyl-2-14- (n-butoxy) -phenyl -2-methylpropyl ether and thioether (comp. 69, -)
3-phenoxybenzyl-2-C4- (n-butoxy) -phenyl -2-ethylpropyl ether
and thioether
3-fen6ksibenzSh1-2- G4- (sec-butoxy) -phenyl1-2-methylpropyl ether and thioether (comp. 70, -)
3-phenoxybenzH1-2- t4- (sec-butoxy) -phenyl -2-ethylproduct ether and thioether
100/100 100/100 100/100 100/95 100/100 100/100 100/100 100/100 100/100 100/95 100/100 100/100 100/100 100/90 100/90 100/100 100 / 100 100/100 100/100 100/100 100/100 100/90 100/95
100/100 100/95
100/100 100/100 100/100 100/100
1031442067104
3-phenoxybenzyl-2- (4-phenoxyphenyl) -2-methylpropyl ether and thioether (comp. 76, -) 100/100
3-phenoxybenzyl-2- (4-phenoxyphenyl) -2-ethylpro. 11Nyl ester and thio-ester 100/100
3-phenoxybenzyl-2- (4-cyclohexyloxyphenyl) -2-methylpropyl ether and thioether (comp. 72, -) 100/100
"3-phenoxybenzyl-2- (4-cyclohexyl-1-oxy-phenyl) -2-ethyl-1-Pro 11-ethyl ester and thio-ether 100/100
3-phenoxybenzyl-2- 4- (1,1-difluoro-2-iodoethoxy) -phenyl -2-methyl-propyl ether and thioether (comp. 74, -) 100/100
3-phenoxybenzene -1-2- 4- (1,1-difluoro-2-iodoxy) -phenyl -2-ethyl-propyl ether and thioether 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-isopropylphenyl) -2-methylpropyl ether and thioether 100/100
3- (4-fluorophenoxy) -benzyl-2- (4-isopropylphenyl) -2-ethyl 1 Proyl ester and thioether 100/100
3-phenoxybenzyl-2- (3-chloro-4-ethoxyphenyl) -2-methylpropyl ether and thioether (comp. 78, -) 100/100
3-phenoxybenzyl-2- (3-chloro-4-ethoxyphenyl) -2-ethylpropyl ether and thioether. 100/100
3-phenoxybenzyl-2-G4- (1,1-difluoroethoxy) -phenyl -2-methylpropyl ether and thioether (comp. 79, -) 100/100
3-phenoxybenzyl-2-C4- (1,1-difluoroethoxy) -phenyl -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzene -1- 2- (4-methoxymethyl-1) -2-methylpropyl ether and thioether (comp. 80, -) 100/100
3-phenoxybenzyl-2- (4-methoxymethylphenyl) -2-ethyl 1 -propyl ether and 100/100 thioether
3-phenoxybenzyl-2- (4-ethoxymethoxyphenyl) -2-methylpropyl ether and thioether (comp. 81) 100/100
3-phenoxybenzene-2- (4-ethoxymethoxyphenyl) -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzyl-2- (4-ethoxymethylphenyl) -2-methylpropyl ether and thioether (comp. 82, -) 100/80
 3-phenoxybenzene -1- 2- (4-ethoxymethylphenyl) -2-ethylpropyl ether and thioether 100/853-phenoxybenzyl-2- (4-methoxymethoxyphenyl) -2-methylpropyl ether and thioether (comp. 83, -) 100/100
3-phenoxybenzene -1- (4-methoxymethoxyphenyl) -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzyl-2- 4- (1-ethoxyethyl) -phenyl -2-methylphenyl ether and thioether (comp. 84, -) 100/100
3-phenoxybenzene -1-2- 4- (1-ethoxyphenyl) -phenyl -2-ethyl 1 -propyl ether and thioether. 100/100
3-phenoxybenzyl-2- (4-carbethoxyphenyl) -2-methylpropyl ether and thioether (comp. 85, -) 100/80
3-phenoxybenzyl-2- (4-carbethoxyphenyl) -2-ethylpropyl ether and thioether 100/80
3-phenoxybenzyl-2- 4- (1-methoxyethyl) -phenyl -2-methylpropyl ether and thioether (comp. 86, -) 90/85
Z-phenoxybenzyl-2- 4- (1-methoxyethyl) -phene 1 -2-ethylpropyl ether and thioether90 / 85
3-phenoxybenzene -1- (4-isopropenylphenyl) -2-methylpropyl ether and thioether (cone, 87, -) 70/70
3-phenoxybenzyl-2- (4-isopropenylphenyl) -2-ethylpropane ester and thioether 70/70
3-phenoxybenzyl-2- 4- (2-ethoxyethoxy) -fench1 -2-methylpropyl ether and thioether (comp. 89, -) 100/95
1051442067 06
3-phenoxybenzyl-2- 4- (2-ethoxyethoxy) -phenyl -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzyl-2- (4-ethoxy-3-methylfensch1) -2-methylglovether and thioether (comp. 90, -) 100/100
3-phenoxybenzyl-2- (4-ethoxy-3-met1shphenyl) -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzene -1-2- 4- (2-methyl-1-propensh1) -phenyl -2-methylpropyl ether and thioether (comp. 91) 100/80
3-phenoxybenzyl-2-C4- (2-methyl-1-propenyl) -phenyl -2-ethyl 1-propyl ether and thioether 100/80
3-phenoxybenzyl-2- (1,2,2-trichlorovinyloxy) -phenyl -2-methylpropyl ether and thioether (comp. 92, -) 100/90
3-phenoxybenzyl-2-G (1,2,2-trifluoro-vinyloxy) -phenyl -2-ethylpropyl ether and thioether 100/95
3-phenoxybenzyl-2- (3, A-diethoxyphenyl) -2-methylpropyl ether and thioether (comp. 93, -) 100/100
3-phenoxybenzyl-2- (3,4-diethoxyphenyl) -2-ethylpropanoyl ether and thioether 100/100
3- (4-ethoxyphenoxy) -benzyl-2- (4-chlorophenyl) -2-methylpropyl ether and thioether (comp. 94, -) 100/90
3- (4-ethoxyphenoxy) -benzyl-2- (4-chlorophenyl) -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzyl-2- (4-ethynylfecyl) -2-methylpropyl ether and thioether (comp. 96, -) 100/100
3-phenoxybenzyl-2- (4-ethynylphenyl) -2-ethylpropyl ether and thioether 100/90
3-phenoxybenzyl-2- (4-ethoxy-3,5-dimethylphenyl) -2-methylpropyl ether and thioether (comp. 97, -) 100/100
3-phenoxybenzyl-2- (4-ethoxy-3,5-dimethylphenyl) -2-ethyl 1 -propyl ether and thioether 100/100
3-phenoxybenzyl-2- (4-propargyloxyphenyl) -2-methylpropyl ether and thioether (comp. 98, -) 100/100
Z-phenoxybenzyl-2- (4-propargyloxypheNIL) -2-ethyl 1 Protic ester and thioether 100/100
3-phenoxybenzyl-2- (4-ethoxy-3-methoxyphenyl) -2-methylpropyl ether and thioether (comp. 99, -) 100/100
3-phenoxybenzyl-2- (4-ethoxy-3-methoxyphenyl) -2-ethylpropyl ether and thioether 100/100
3-phenoxybenzyl-2- (4-ethylthiophenyl) -2-methylpropyl ether
and thioether (Comp. 100, -). 100/90
3-phenoxybenzyl-2- (4-ethylthiophenyl) -2-ethylpropyl ether and thioether 100/90
3- (4-ethoxyphenoxy) -benzyl-2- (4-ethoxyphenyl) -2-methylpropyl ether and thioether (comp. 10.1, -) 100/100
3- (4-ethoxyphenoxy) -benzyl-2- (4-ethoxyphenyl) -2-ethylpropyl ether and thioether. 100/100
Z-phenoxybenzyl-2- t4- (1-chlorovinyl) -phene1 -2-methylpropyl ether and thioether (comp. 102, -) 100/80
3-phenoxybenzyl-2- 4- (1-vinyl chloride) -phenyl J-2-ethylpropyl ether and thioether 100/80
3-phenoxybenzyl-2- (4-vinylphenyl) -2-methylpropyl ether and thioether 100/85
3-phenoxybenzene -1-2- 4- (2,2,2-trifluoroethoxycarbonyl) -phenyl} -2- -methyl stitched ester and thioether (comp. 106) 100/80
3-phenoxybenzyl-2- 4- (2,2,2-trifluoroethoxycarbonyl) -phenyl -2-ethyl propyl ether, 100/75
3-phenoxybenzyl-2- 4- (2-chloroethoxy) -phenyl -2-methylprotetra ester and thioether (comp. 108, -) 100/100
107UA2067i08
3-phenoxene1-2- / 4- (2-chloroethoxy) -feiyl -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2-HA- (1-buten-2-yl) -phenyl -2-methylpropyl ether and thioether (comp. 110, -)
3-phenoxybenzyl-2-G.4- (1-buten-2-yl) -phenyl -2-ethylpropyl ether and thioether
3-phenoxybenzyl-2- 4- (2-buten-2-yl) -phenyl -2-methylpropyl ether and thioether (comp., 111, -)
3-phenoxybenzyl-2- 4- (2-buten-2-yl.) - phenyl 1-2-ethylpropyl ether and thioether
Compound b for comparison
Thus, as can be seen from the above examples, the compounds obtained by the proposed method are

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining derivatives of 2-arylpropyl ether or thioether of the formula
SNZ AJ-C-CHj-Y-CHx-B
R
where Y is an oxygen or sulfur atom Ar is biphenyl or unsubstituted
or substituted by lower alkyl, unsubstituted phenyl or phenyl substituted by one or more substituents selected from the group including halogen, lower alkyl, lower haloalkyl, lower alkoxy, lower haloalkoxy, lower alkoxycarbonyl, lower haloalkoxycarbonyl , lower alkylthio, lower haloalkylthio, lower alkenyl, lower alkenyloxy, lower haloalkenyl, lower haloalkenyloxy, lower alkynyl, lower alkynyloxy, lower alkoxyalkyl, lower
alkoxyalkoxy, methylenedio si, nitro, cyano-, acetyl-, phenoxy, and C j-C j -cycloalko- with IR adical-,
is methyl or ethyl;
-group of the formula
g G100 / 100 100/100 100/100 100/80
100/75 35
where Z is an oxygen or sulfur atom,
carbonyl or methylene, R is a hydrogen atom hn halogen, lower alkyl, lower alkoxy radical,
or when Ar is phenyl substituted by halogen, and
R is methyl, B is a group of formula
T1
thirty
40
45
50
55
35
characterized in that the compound of formula
SNS
Ag-C-SNg-A
I r
where Ar and R have the indicated meanings:
A - hydroxy group
subjected to interaction with the compound of the formula
B-CH n-D
where B have the specified value
D is a hydroxy group
in the presence of an acid catalyst, in an organic solvent at reflux or in the presence of a dehydrating agent such as N, -dicyclohexylcarbodiimide, in an organic solvent under dehydration conditions.
The priority signs are 02.05.80 with Y 0, Ar is phenyl, substituted by halogen, lower alkyl, R Н, 02.05.80 with Y S, Ar is phenyl, biphenyl, naphthyl, R i is halogen, lower alkyl, lower alkoysykrug.
 1 iA2067
Continuation of table.8
100 100 100 100 100 100 100
100 100
100
90 100 100 100
90,100,100
70 90
100
ten
15
20
25

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同族专利:

---

公开号 | 公开日

---

PH18418A|1985-06-26|

---

RU2045511C1|1995-10-10|

---

DE3117510C2|1990-02-15|

---

SE460666B|1989-11-06|

---

US4397864A|1983-08-09|

---

SU1416052A3|1988-08-07|

---

NL188991C|1992-12-01|

---

NL8102070A|1981-12-01|

---

PH18777A|1985-09-25|

---

AU6973681A|1981-11-05|

---

SU1477230A3|1989-04-30|

---

NZ196901A|1983-09-30|

---

FR2481695B1|1984-07-20|

---

GB2118167A|1983-10-26|

---

SE8102420L|1981-11-03|

---

RU2010523C1|1994-04-15|

---

SU1612983A3|1990-12-07|

---

CH651817A5|1985-10-15|

---

FR2481695A1|1981-11-06|

---

HU189506B|1986-07-28|

---

CA1210406A|1986-08-26|

---

DE3117510A1|1982-02-04|

---

IT8148383D0|1981-04-30|

---

BR8102676A|1982-01-26|

---

US4570005A|1986-02-11|

---

AU537884B2|1984-07-19|

---

IT1170937B|1987-06-03|

---

GB2118167B|1984-08-08|

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法律状态:

优先权:

---

申请号 | 申请日 | 专利标题

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JP5787280A|JPS6313412B2|1980-05-02|1980-05-02|

---

JP55148279A|JPS5772928A|1980-10-24|1980-10-24|Novel 2-arylpropyl ether derivtive and thioether derviative, their preparations, insecticide, and acaricide|

---