Method of producing pyrrol derivatives

专利摘要:
The invention relates to heterocyclic compounds, in particular, a process for the preparation of pyrrole derivatives of general formula 1: R 6 -C (O) -X, where the X group of the formula @ R 1 - -CH 2 -C = CH, -CH = C = CH 2 , -CH-CH = CH 2 , -CH-CH = CHCL or -C (O) C 6 H 5 R 2 -H, NO 2 , CF 3 or CN R 3 -H, NO 2 , CF 3 , CN or -C (O) -OCH 3 R 4 -H, CN or CF 3 R 5 -H, CN, CH 3 or -C = CH R 6 -LIBO R 7 -C 6 H004-CH [CH (CH 3 ) 2 ] -, where R 7 -CL or -OCHF 2 , or-CH-C (CH 3 ) 2 -CR 8 R 9 , where R 8 —H or CH 3 , R 9 —CH 3 or —CH = CR 10 R 11 , where R 10 —H, F, CL or BR, R 11 —H, F, BR, CF 3 or —C (O) O- (C 1 -C 4 ) alkyl with insecticidal acaricidal activity, which can be used in agriculture. The goal is to create new active compounds of the specified class. Synthesis is carried out by the reaction of an alcohol of the general formula W: HO-X, where X is above, with an acid of the general formula IV: R 6 -C (O) OH, where R 6 is above, or its acid chloride in methylene chloride in the presence of dicyclohexylcarbodiimide and 4-dimethylaminopyridine at 0-10 ° C. New compounds with insecticidal acaricidal activity outperformed bioallethrin 1.3-12.7 times. 2 tab.
公开号:SU1493103A3
申请号:SU853947352
申请日:1985-08-13
公开日:1989-07-07
发明作者:Тессье Жан；Демут Жан-Пьер；Тальани Лоран
申请人:Руссель Юклаф (Фирма)；
IPC主号:

专利说明:

about with
This invention relates to a process for the preparation of new chemical compounds of the pyrrolic series, namely pyrrole derivatives of the general formula
About RS
VC-CH .RB
p - lo. Hij fg g
R,
where R, - СН.,,
-OH, -CH 2-CH CK-C1 or
Rj is H, N0 ,, CFs or CN;
Rj - Н, NOj, Срз, CN or СООСН ,;
R - H, CN, or CFj,
Rj - H, ON, SNE or,
RJ - either R-YOVCH
CHlCHj) ,,
where R- - Cl or OSIGG,
 LL NZ
either,
.
R:
 3
where R g is H or CH J
I
Sh
Us- SNZ or P
,
where Rfo is H, F, C1 or Br; Rf, - H, F, Br, CF, or
COOAlk (C-C)
jcoTopbie have an intrinsic acaricidal activity and can be used in agriculture.
The aim of the invention is to develop a method for producing new pyrrole derivatives having insecticarctic activity.
Example 1. l- (2-propenyl) -1 -1H-pyrrol-3-yl 1R methyl ester, cis (4Z) -3- (3-methoxy-3-oxo 1-propyl) -2,2-dimethyl -cyclopropane carboxylic acid.
452 mg of 3-Cl- (2-nponeonyl) pyrrolyl methanol, 10 cm of methylene chloride are dissolved, cooling is added until 795 mg of 1K, cis (2,2-dimethyl 3-) 3-oxo, 3-methoxy , 1 (Z) nopenyl cyclopropane carboxylic acid and stirred for 10 minutes. In addition, a solution containing 8 cm of methylene chloride, 835 mg of dicyclohexyl carbodiimide and 5 mg of dimethylaminopyridine is added dropwise, drop by drop. When the addition is complete, allow the temperature of the reaction mixture to rise to room temperature and hold the mixture with stirring for 16 hours. Filter off, concentrate the filtrate to dryness.
Dry extract taken in the air. Filtered to remove insoluble matter. The filtrate is concentrated and 1.112 g of a crude product is obtained, which is chromatographed on silica, eluting with a mixture of hexane-isopropyl ether (55-45) with 2% triethylamine. A product is obtained which is purified again in isopropyl ether. Thus receive 700 mg of the target product.
 2312 (, 3% toluene). Analogously to example 1, pyrrole derivatives were obtained according to examples 20
five
0
65. In Examples 13, 15, 19, 22, 29, 30, 31, 32, 34, 41, 64 and 65, the acid HID of the corresponding acid was used as the starting material, and the corresponding acid was used in the other examples.
Example 2, C1- (2-propynyl) -1 -1H-pyrrol-3-ylJ methyl ester
o 1R, cis (E) -2,2-dimethyl-3- (3-ethoxy-3-oxo-2-fluoroporn-1-propynyl) -cyclopropane carboxylic acid. Yield 56%. 4-5 ° (With 0.3% toluene). Example 3. 1- (2-propynyl) 5 -1H-pyrrol-3-11l-1R methyl ester, cis (g) -2,2-dimethyl-3- (3-tert-butyloxy-3-oxo-1- propyl) cyclopropane carboxylic acid. Yield 55%. j) +23 (C 0.3% toluene).
Example 4. 1- (2-propynyl) -1 -1H-pyrrol-3-yl 1R methyl ester, cis (E) -2,2-dimethyl-3- (3-methoxy-3-oxo-2-fluoro) -1-propenyl) -cyclopropane carboxylic acid. Yield 34%, s / + 15 ° (with 0.3% toluene).
Pr and measures 5. 1- (2-propynyl) - - 1H-pyrrol-3-yl-methyl 1R ester, cis (E) -2,2-dimstil-3- (3-tertbutoxy-3-oxo- P is fluoro-1-propenyl) -cyclopropane carboxylic acid. Yield 43%. j) 19.5 (C. 1% —Hi.ni toluene).
Example 6. (-propynyl) -1P pyrrol-3. t-methyl 1R ester, 5 cis-2,2-dimethyl 3- (dibromoethenyl) -cyclopropane carboxylic acid. The output of 31%, df -15,5 ° (With 0.5% toluene).
Example 7 C1- (2-propynyl) -1H-0-pyrrol-3-yl} -methyl ester 1R, ic (Z) -2,2-d 1methyl-3- (3-ethoxy-3- -oxo-1-propenyl ) -cyclopropane carboxylic acid. Yield 45%. + 23 ° (With 1% toluene).
five
Example 8. 1R, trans-2,2-dimethyl 3- (2,2-difluoroethenyl) -cyclopropane carboxylic acid (2-propyn-1sh) -lH-pyrrop-3-yl) methyl ester. Q Yield 58%. tijj -34 ° (With 1.5% toluene).
Example 9. 1-C1- (2-propynyl) -1 -1H pyrrol-3-yl} methyl 1R ester, cis-2,2-dimethyl 3- (2,2-difluoroethenyl) -5-cyclopropane carboxylic acid. Yield 45%. o (j, -27 ° (C 0.5% toluene).
Example 10. 1- (2-propinol) -1 H pyrrol-3-yl methyl ester
2,2-dimethyl-3, 3-dimethyl-cycloprocarboxylic acid.
Example 11. 1- (2-propynyl) -1 -1H-pnrrol-3-nl-methyl ester (25) -2- (4-fluoromethoxy phenyl) -3-methyl; m; hydrochloric acid. Yield 62%, / d + 5 ° (C 0.3% -Ht.ni toluene),
Example 12. G1 (2-propinyl) - -1H-pyrrol-3-yl / 1-methyl ester 1R, trans- (LZ) and (LU) 2,2-dimethyl-3- - (3,3,3-trifluoro -2-chloro-1-propenyl) - cyclopropane carboxylic acid, 2) +6.5 (C 0.3% toluene).
Example 13, (K, 5) -cyano-H1 - - (2-propynyl) -1H Pyrrol-3-yl-1R methyl ester, cis-2, 2-d-methyl-3- - (2,2- dibromoethenyl) -cyclopropane carboxylic acid, which is divided into two isomers, A and B. Yield: A 23%; Yield: B 22%.
Example 14. (K, 5) -cyano 1 (2- -propinyl) -1H-pyrrol-3-yl J-methyl ester 1R, cis- (L7.) 2,2-D1shetil-3- (3- -methoxy -3-ox0-1-propenyl) -cyclopropane carboxylic acid. o (rt +24 (C 0.5% -np 1 toluene).
Example 15. Piano l- (2- -propynyl) -1H-pyrrol-3-ylJ-methyl Ether 1R, cis- (AE) 2,2-dimethyl-3- (3- -3 toxy-3-oxo-2- fluoro-1-propenyl) -2,2-dimethyl-cyclopropane carboxylic acid (isomers A and B). Isomer A yield 28%. c / .jj -4.3 ° (C 0.3% toluene). The output of the isomer In 30%. +42 (With 0.5% toluene).
Example 16. (R, 5) -cyano 1- - (2-propynyl) -1H-pyrrol-3-yl} -methyl isopropyl-4-chlorophenyl acetic acid ester. Yield 64%. -20.5 ° (With 0.5% toluene).
EXAMPLE 17 (2-propynyl) pyrrolyl 1R J-methyl ester, cis-3- (2,2-dibromovinyl) -2,2-dimethyl-cyclopropane carboxylic acid. Yield 40%, /.r -12 ° (C 1% toluene).
Example 18. 2-cyano-C (2-propynyl) -1H-pyrrol-4-yl} -methyl 1R ester, cis- (4E) 2,2-dimethyl-3- 3-β-ethoxy 3-oxo-2- fluoro-1-propenyl 3-cyclopropane carboxylic acid. Yield 70%. toluene).
Example 19. 2-cyano-1- (2- -propinsh1) -1H pyrral-4-yl J-methyl ester 1R, cis 2,2-dimethyl-3- (2,2-dibromoethenll) -cyclopropane carbon
 +30 (With 0.5%
acid. Byhg1d 8 t%. with/. -3 (C 0.5% -11, G11 toluene).
Example 20. 2-iutaHo- l- (2- -propin1x) -i1-pyrrole-D-; l methyl ester 1R, Sh1C 2,2-Limet) w 3- (3-methoxy-3-oxo-1-propenyl) -2,2-dimethylcyclopropyl carboxylic acid. dQ - +55.5 (C 0.5% toluene), Example 21. 2-cyano Cl- (2- -propinyl) -1H-pyrrol-4-yl3-methyl 1R ester, cis (/ 1E) 2 , 2-dimethyl-3- (3- -terbuty-3-3-oco-2-fluorop-1-propenyl) cyclopropane carboxylic acid. 5 Yield 51%. yr +35 (With 0.5% toluene).
Example 22. 1- (2-propynyl) -2 -2 cyano-1H-pyrrol-3-yl 1-methyl ester 1R, cis 2,2-dimethyl 3- (2,2-0-dibromoethenyl) -cyclopropane carboxylic acid. Yield 55%. d- - -5,5 (With 1% toluene).
Example 23. f1- (2-propinyl) -. -1H-Pyrrole 3-yl-meth1Syl ester 5 1R, cis- (4E) -2,2-d1shetil-3- (3-ethoxy-3-oxo-2-fluoro-1-propenyl) -cyclopropane carboxylic acid. Exit 47%. o / d +30 (C 0.5% toluene).
0 Example 24. Cl- (2-propynyl) -2 -2 nitro-1H-pyrrol-4-yl J-methyl ester 1R, cis 2,2-dimethyl-3- (2,2-dibromentenyl) -cyclopropane carboxylic acid. Yield 81%. Сз (-1,5 ° 5 (С 1% toluene).
Example 25, C2-nitro 1- (2- -propinyl) -1H-pyrrole 4-yl} -methyl | 1R ester, cis (Z) -2,2-dimethyl-3- (3- - tetoxy-3-oco-1-propylene) -cyclo-0 propane carboxylic acid. Yield 39%, cLy + 57 ° (C 0.5% toluene).
Example 26, C2-nitro-1- (2- -propinyl) -1H-pyrrol-4-yl-methyl ester 1R, or (E) -2,2-dimethyl-3- (3- 5 -tbutoxy-3) -oxo-2-fluoro-1-propenyl) -cyclopropane carboxylic acid. Yield 52%, o (. P (C 0.5% toluene),
Example 27. (R, S) cyano -2- 0 -nitro-1- (2-propynyl) -1-H-pyrrole-4-yl} methyl 1R ester, cis-2,2-dimethyl- 3- (2,2-dibromoethenyl) -cyclopropane carboxylic acid. Yield 63%, jj +26.5 (C 0.5% toluene), 5 Example 28, (R, S) -cyano-2- -nitro-1- (2-propynyl) -1-H-pyrrole -4- -ylJ-methyl 1R ester, 1shc (E) -2,2-dimethyl-3- (3-ethoxy-3-oxo-2-fluoro-1-propyl.) Or cyclopropane carboxylic acid. Yield 73%. s (d +42 (With 0.2% toluene).
Example .29. G3-nitro-1- (2- -propynyl) -1H-pyrrol-A-yl-methyl 1R ester, cis-2,2-dimethyl-3- (2,2-dibromoethenyl) -cyclopropyl carboxylic acid. Yield 88%. -26 ° (With 0.5% toluene).
Example 30. (1-Propadiene) - -1H Pyrrol-3-yl-methyl 1S 1R ester, cis- (E) -2,2-dimethyl-3- (3-ethoxy-3-oxo-2-fluoro-1 -propenyl) -cyclopropane carboxylic acid. Exit 63%.
 D
+ 17 ° (With 0.8% toluene).
Example 31. C (1 propadiene) -1 -1H-pyrrol-3-yl 1R methyl ester, cis 2,2-dimethyl- (3,3-dibromoethenyl) -cyclopropane carboxylic acid. Yield 75%. "Er -13.5 (C 1% toluene).
Example 32 1- (2-propyl) -2-trifluoromethyl-1H-pyrrol-3-yl) methyl 1R ester, cis-2,2-dimethyl-3- (2,2-dibromoethenyl) -cyclopropane carboxylic acid. Yield 77%. j) -12 (With 0.5% toluene).
Example 33. C 1- (2-propynyl) -2-trifluoromethyl-1H-pyrrol-3-yl} methyl 1R ester, cis- (E) -2,2-d11 methyl- 3- (3 ethoxy-3-oxo-2-fluoro-1-propenyl) cyclopropane carboxylic acid. The yield is 85.4%. btjj + 1 ° (with 0.5% toluene).
Example 34. Cyano-1- (2- -propinyl) -1H-pyrrol-3-yl J-methyl ester 1R, cis-2,2-dimethyl-3- - (2,2-dibromoethenyl) -cyclopropane carbon acid.
Example 35. C2-trifluoromethyl-1 (2-propynyl) - (1H) pyrrol-3- -yl} -methyl 1R ester, cis (E) -2,2- -D11 methyl-3- (3) -tbutyloxy -3-ok-so-2-fluoropropenyl-cyclopropane carboxylic acid.
A solution containing 455 mg of dicyclohexylcarbodiimide, 3 mg of dimethylamino pyridine and 5 cm of anhydrous methylene chloride is added dropwise to the mixture, cooled on an ice bath and containing 450 mg of 1- (2-propynyl) 2-trifluoromethyl- W-pyrrole-methanol, 5.70 mg of 1R, cis (E) - -2,2-dimethyl-3- (3-tertbutoxy-3-oxo -2-ft6p-1-propenyl) -cyclopropane carboxylic acid and 4 cm anhydrous methylene chloride. Reaction mixture
allowed to reach the ambient temperature and stirred for 5 hours. The precipitate formed is removed by filtration. The filtrate is concentrated and taken up in isopropyl ether. The insoluble matter is filtered off. The filtrate is concentrated and the residue is chromatographed on silica;
eluted with hexane-ethyl acetate acetic acid 9-1. Thus, 518 mg of the expected product are obtained. 7) With 0.5% toluene).
Example 36. f2-trifluoromethyl-1- (2-propynyl) - (1I) -pyrrole-3- -yl-1X-1-methyl methyl ester, cis-2,2-dimethyl-3-etheyl-cyclopropane of carboxylic acid.
Acting as in Example 1 and starting from 610 mg of tPv., Cis-2,2-dimethyl-3-β-ethenyl-cyclopropane carboxylic acid and 800 mg of 1- (2-gropyl) -2 -2-trifluoromethyl-3-pyrrole of methanol,
1.28 g of the expected product are obtained. , + 9 ° (0.2% toluene).
Example 37, (2-trifluoromethyl-1- (2-propynyl) -1H-pyrrol-3-yl) -methylorpine ether 1R, cis- (7,) - 2,2-dimethyl-3- -3- methoxy- (3-oxo-1-propenyl) -1; iclopropane carboxylic acid.
Acting as in Example 1 and proceeding from 860 mg of 1R, cis- (g) -2,2-dimethyl-3- (3-methoxy-3-oxo) -1-propenyl-cyclopropane carboxylic acid and 800 mg of 1- ( 2-propynyl) -2-trifluoromethyl-3-pyrrole-methanol, 1.18 g of the expected product are obtained. in (.p +17,5
(0.7% toluene).
Example 38.-cyano-1- (2- -prb-pinyl-1H-pyrrol-3-yl) methyl 1R ester, cis- (g) -2,2-dimetsh-3- (2- -chloro 3,3 , 3-trifluoro) -1-propenyl-cyclopropane carboxylic acid.
430 mg of 2-cyano-1- (2-propinyl-1H- -pyrrole) - 3-methanol, 600 mg of 1R, cis (Z) -2,2-dimethyl-3- (2-chloro-3, 3, 3-β-trifluor) -1-propenyl-cyclopropane
carboxylic acid is introduced into 12 cm of methylene chloride, a solution of 509 mg of dicyclohexylcarbodiimide and 3 mg of dimethylamino is added dropwise to the solution obtained drop by drop
pyridine in 2 cm of methylene chloride, stirred for 5 hours at, filtered, the filtrate is concentrated to dryness, isopropyl ether is added, the
residual, or unreactive, concentrate the filter until dry, add a mixture of i-exane and isopropyl etgra (1-), filter, concentrate the filtrate, dry the residue, chromatograph on silica, elute with hexane - isopropyl ether). 2 cm-isopropyl ether is added to the product containing a little more urea, the filter is removed, and the insoluble material formed is concentrated by distillation under reduced pressure to dryness to obtain 896 mg of the desired product. d (, p + 7 °. (С 0,% - 1п.1Й toluene).
Found,%: C 56.3; H A, 4; C1 9.0 F 14.9; N 7.2.
  (384, 789)
Calculated,%: C 56.19, -} 4.19, C1 9.21, F 14.8, N 7.28.
Example 39. 11. iano-1- (2-propinyl) -1H-pyrrh (w-3-yl-methyl ester 1R, sch1c- (E) -2,2 dimethyl-3- (3--ethoxy- 2-fluoro-3-oxo - 1 -propenyl) - -cyclopropane carboxylic acid.
In 30 cm of methylene chloride, 2 g of R-cyano-1 - (2-propynyl) -1 -1 I-pyrrol-3-i1t-4-mestanol, 2.48 g 1R, cis (E) -2,2- dimethyl-3- (3-ethoxy--2-fluoro-3-oxo-1-propenyl) -cyclopropane carboxylic acid at + 10 ° C and a solution of 2.22 g of dicyclohexgylcarbodiimide and 13 mg of 4-dimethyl-amio-pyridine. in 30 cm of methylene chloride, stirred for 18 hours at 20 ° C. filter was concentrated to dryness, added with ethyl ether, filtered, concentrated to dryness, and the residue was chromatographed on silica using an hexane-ethyl mixture ether vinegar nd acid (7-3) and poluchayut- 3.14 g of the expected acid. djj + 40 ° (With 1% toluene).
Found,%: C 63.4; H 5.1, F 4.8 - N 10.3.
C in or NsO (397, 409)
Calculated,%: C 63.47; H 5.07,
F 4.78; N 10.57.
Example 40. 1- (2-propynyl) -3-trifluoromethyl-1H-pyrrol-4-yl J-methyl 1R ester, cis- (E) -2,2-dimethyl-3- (2- fluoro-3-oxo-e-tertbutoxy-
propynyl) -cyclopropane carboxylic acid.
1 g of 1- (2-propynyl) 3-trifluoromethyl 11l-rinppti is dissolved in 25 cm of methylene chloride: i-i-M -T, -i i-b. ia, 1, t i - 1R, nnc-CE iZ, 2 - ;; them (- TI -; - - i: -ft (p-3-oxo-3-tr (tG; ut (: k (- i-pr1 Igkil - -cyclopropane carg-mkttno; kpglpty at 0 C, gradually vp (; 1 mixture of 1.3 g of dicyclohexylcarbo; 1and 1 - p1, -n, 150 mg of 4-dimethyl-pmino-pyr1; dine in chloride methylene, 15 in at 0 ° C, and then 2 hours at 20 ° C, is filtered, the filtrate is removed, the filtrate is added, the isopropyl alcohol is added, the mixture is taken to C ,, fi: Ip Iot, xy. and by distillation under reduced pressure, the Cromltog-RL 1 residue is carried out in two on silica with elution of SMPC) U grksmm-; iTii, acetic acid ester (85-15), and get 1.7 g of price. KTA. o (j, 40,5 ° (c 0,7% -Hbii i chloroform).
Found,%: C 59.2; H 5.7; F 17.1 N 3.2.
С ,, П 5Р4Ь 0, 443).
Calculated:: C 59.6; H 5.68, - F 17.14; N 3.16.
Example 41. RS-cyano-H (1-benzoyl) -1 H-pyrrol-3-yl (1R methyl ester, cis-2,2-dimethyl-3- (2,2-dibromo-ethenyl) -cyclopropane carboxylic acid. Exit 457. aixi, 5 (C - 0.4% chloroform).
Example 42 I- (2-propynyl -2-methoxy-2-oxo-1H-pyrrol-3 yl) 3-methyl 1R ester, cis-2,2-dimethyl-3- (2, 2-d ibromztenyl) -; 1, iclopropane carboxylic acid. Yield 90%. -6 ° (C 0,5l-11g toluene).
Example 43. 1- (2-propynyl-2-cyano-1H-pyrrol-3-yl) -methyl ester 1R, trans-E 1 (3) and Z 2 (3) -2,2-dimethyl-3 - (2-chloro 2-trifluoromethyl-etenyl) -cyclopropane carbonic acid. Yield 84%. o / j, -5 ° (C 0.3% - Hbrfi toluene).
Example 44. 1- (2-propynyl) -2 -2 cyano-1H-pyrrol-3-yl D-methyl 11 ester 1R, cis-2,2-dimethyl-3- (3-methoxy-3-oxo -1-propenyl) -cyclopropane carboxylic acid. The yield is 78%. + 39 ° (With 0.6% toluene).
Example 45. 1- (2-propynyl) -2 -2 cyano-1H-pyrrol-3-yl methyl 1R ester, cis-2,2-dimethylp-3- (2-fluoro--2-ETOXI-2- OXO-1-propenyl) -cyclopropane carboxylic acid. Output 92% e (Gd +18 (With 0.4% toluene).
Example 46. t1- (2-pro-6pen) - -2-cyano-1H-pyr-4-yl-methyl
1R, uiicd-;) 2, 2-d {metiJl-3- (2-fluorop-2-sucroxy-2-oxy-1-propyl) -glc-propyl KapfioHOHort acid ester. Yield 83%. o (jj +25 (C P, 7% toluene).
An example. 1- (2-propeiyl) -2 -2 cyano-1H-pyrrol-4-yl 1-methyl ester 1R, cis-2,2-dimethyl-3- (2,2-dibromoethenyl) -cyclopropane carboxylic acid .. Yield 89.5%. t / jj + 11.5 ° (with 0.5% toluene).
Example D8. K, 5-cyano-1- (2-propyl yl) -2-cy-but-1H-pyrrol-4-yl-methyl 1R ether, cis-2, 2-dimethyl-3- (2 , 2-dibromoethenyl) -cyclopropane carboxylic acid. Yield 96%. s / d +7 ° (with 0.5% toluene).
Example 49. Cl- (2-propinyl) -2 -2-cyano-1H-pyrrol-4-ylJ-nponHH-2-yl 1R, cis (E) 2,2-dimethyl-3- (2- -fluoro- 3-ethoxy-3-oxo-1-propenyl) -cyclopropane carbopic acid. The yield is 78%. + 19 ° (With 0.5% toluene).
Example 50. l- (2-propynyl) -2 -2 cyan0-1H-pyrrol-4-yl J-1-ethyl ester 1R, cis 2,2-dimethyl-3- (2,2-dibromoethenyl) cyclopropane carboxylic acid. Yield 79%. -n 6.5 ° (with 0.6% toluene).
Example 51 (1- (2-propynyl) -2-cyano-1H-pyrrol-4-yl} ethyl 1R ester, cis (E) 2,2-dimethyl-3- - (2-fluoro-3- 3tokei-3-oxo-1-propenyl) -cyclopropane carboxylic acid. You. +21
(With 0,6% takhod 58%. Luol).
Example 52. 1R, Sf1- (2-propinyl) -2-cyano-1H-pyrrol-A-yl J-2-propynyl ether-IR, cis 2,2-dimethyl-3- (2, 2-dibromoethenyl) -cyclopropane carboxylic acid. 75% yield. o (. p -10 ° (C 0.5% toluene).
Example 53. C1- (2-propynyl) -4-cyano-1H-pyrrol-3-yl} methyl 1R ester, cis 2,2-dimethyl-3- (2,2-dibromoethenyl) -cyclopropane carboxylic acid. Yield 96%. -10.5 (with 0.5% toluene).
Example 54. C1- (2-propynyl) -4-cyano-1H-pyrrol-3-yl J-methyl ester 1R, (E) 2,2-dimethyl-3- (2- -fluoro-3-ethoxy) 3-oxo-1-propenyl) - cyclopropane carboxylic acid. Yield 83%. о.р +3,2 (С 0.5% toduol),
Example 55. R, 5-cyano-f1- (2-propynyl) -4-cyano-1H-pyrrol-3-yl J-methyl ester 1R, cis-2.20
five
0
five
 -dimethyl-3- (2,2-dibromoethenyl) -cyclopropane carboxylic acid. Yield 80%. 5.5 (With 0.5% toluene).
Example 56. (2-nnaHo-1-f3-chlorine 2- (Z) -propenyl -1H-pyrrole-4-yl-methyl tR ester, cis (E) -2,2-dimethyl-3- ( 2-fluoro-3-ethoxy-3-oxo--1-propenip) -cyclopropane carboxylic acid.
Mix 1.55 g of 2-cyano-1- | 3- -hlor-2- (Z + E) -propenyl-1H-pyrrol-4-yl-methanol, 1.8 g of 1R, cis (E) -2.2-dimethyl-3- (2-fluorine -3-ethoxy- - -oxo-1-propylene) -cyclopropane carboxylic acid, 20 cm of dichloromethane, at + 5 ° C, a mixture of 1.625 g of di1C1-cyclohexylcarbodiimide, 10 cm of dichloromethane and 29 mg of 4-dimethyl-aminopyridine is gradually introduced The mixture is stirred for 20 hours at 20 ° C, filtered, the filtrate is concentrated to dryness by distillation under reduced pressure, chromatographed on silica, eluted with a mixture of hexane - ethyl acetate (7-3) and then with a mixture of hexane - ethyl acetate ( 9-1) and get 0.83 g of integer evoy product
L +32,5 (C
 0.8% toluene).
Example 57. 2-cyano-1- 3- -chloro-2 (e) -propenyl -1 H-pyrrol-4- -ylj-methyl ester 1R, cis (E) -2,2-dimethyl-3- ( 2-fluoro-3-ethoxy-3-oxo--1-propenylcyclopropane carboxylic acid.
Continuing the chromatography of Example 56, 0.32 g of the expected product is obtained. + 28 ° (With 0.5% toluene). PRI me R 58. (R, S) cyano-, 1- - (2-propyn-1) -2-11 diano-1H-pyrrol-3- -yl} -methyl 1R ester, cis (E) 2.2 - -dimethyl-3- (2-fluoro-3-ethoxy-3-oxo--1-propenyl) -cyclopropane carboxylic acid. Yield 24%. (With 0.5% toluene).
from + 21 °
Example 59. (.RS) iaHo-Cl- - (2-propinsh1) -3-cyano-1H-pyrrol-4-yl) methyl 1R ester, cis (E) -2,2-dimethyl-3- (2-fluoro-3-ethoxy-3-oxo--1-propenyl) -cyclopropane carboxylic acid. Exit 44%. -jj 12.5 (C 0.6% toluene).
Example 60. (RS) cyano - - (2-propynyl) -2,2,2-trifluoromethyl-1H- -pyrrol-4-yl} -R methyl ester,
cis (Z) -2,2-dimethyl-3- (3-methoxy-3-oxo-1-propennl) cyclopropane carboxylic acid. The yield is 84.6%. + 59 ° (With 0.4% toluene).
Example 61.1- (2-propynyl) -2,2,2-three-litermethyl-1H-pyrrol-4-yl)-methyl 1R ester, cis (E) 2,2-dimethyl-3- (2-fluoro) 3-ethoxy-3-oxo-1-propenyl) -cyclopropane carboxylic acid. Yield 70%. +40.5 (With 0.5% toluene).
Example 62. 1- (2-propynyl-3, 3, 3-trnfluoromethyl-1H-pyrrol-4-yl) -1R methyl ester, cis (g) -2,2-dimethyl-3- (3 -methoxy-3-oxo-1-propene) - cyclopropane carboxylic acid. The yield is 78%. . + 41.5 ° (C P, 5% toluene).
Example 63. 1- (2-propynyl) -3.3,3-trifluoromethyl-1H-pyrrol-4-yl-1R methyl ester, cis (E) -2,2-dimethyl-3- (2- fluoro-3-ethoxy-3-oxo-1-propyl) -cyclopropyl carboxylic acid. Yield 73%. t / j, +23.5 (C 0.2% chloroform).
Example 64. 2-cyano-1- 3- -chlorop-2- (Z) -propyl J-1H-pyrrol-4-yl-methyl 1R ester, cis-2,2-dimethyl-3- (2, 2-dibromoethenyl) -cyclopropane carboxylic acid. o (jj -6 (With 1% toluene).
Example 65. 2-cyano-1-C3-chloro-2- (E) -propenyl J-1H-cirr-4-yl methyl 1R ester, cis-2,2-dimethyl- -3- (2,2- dibromoethenyl) -cyclopropane carboxylic acid. 0.6% toluene).
 -4 ° (C
Biological research.
The study of the activity of the blow on the housefly. The insects studied are domestic flies: females at the age of 4 days. Operate by direct spraying in a Kern and Marsh chamber, using as a solvent a mixture of acetone (5%) and isopair L (petroleum solvent), the amount of solvent used is 2 ml per second. 50 insects per experiment. The control is performed every minute up to 10 minutes and then 15 minutes, and the CT 50 is determined by conventional methods. The KTHz time required to kill 50% of the insects.
Activity impact on domestic flies is given in table.1.
Table 1; 1 1
Table 2 presents data comparing the insecticoacaricidal activity of compounds 1 with bioallethrin (R, S-3-α-allyl-2-methyl-A-oxocyclopent-2-α-yl-1, K-trans-chrysanthematon), where relative capacity is the ratio of CT Ud biopletrin to CTD of compound 1.
table 2
Continuation of table 2

权利要求:
Claims (1)
[1]
From Table 2 it can be seen that the content of 1 is superior to bioalletry in insect-acaricidal activity. Invention Formula
subject to interaction with acid 35 obpey formula
The method of obtaining pyrrole derivatives of the general formula
About "5
R,
Lm "g" 1,
where R is CHi-CgH, -CH-C “CHt,
—CH —CH — CHi, —CH —CH — CH — C1 or —CO — 4H5
Editor V.Danko
R J - COOH
where R has the indicated values, or its acid chloride in methylene chloride in the presence of digschlohexyl-carbodiimide and 4-dimethylaminopropy1, at.
Priority by signs 14.08.84: with R, -, 45 -CH-C CH, R-H, NOi; R, - H, N0 ,; R4 - H, CN, R5 - H, CN; R7 is C1, CHF7; Rg - H, Rg R, H, F, C1, Br; R, «- F, Br, CFj, COOAlk (). 04/23/85 for R, --H; R ,, - H.
Compiled by I. Bocharova
Tehred A. KravchukKorrektor O. Kravtsova
RI is H, NOj, CFj or CN; Rj - H, NOj, CFj, CN or
SOOCH;
R4 - H, CN or CFj; Rj - H, CN, CHs or.
R - either (2)
CH (CH), where Rj is Cl or OCHF,
SNZ / SNZ R (
Rg
or
where Rj is H or CH3,
Rj - CH,,
I1
where R, is H, F, Cl or Br; RI, - H, F, Br, CFj or
COOAlk (C, -C4),
characterized in that the alcohol of the general formula
}
BUT-SHR,
I
R
where R, Rj, Rj, P. j. have indicated
11
subject to interaction with acid 35 obpey formula

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MX177515B|1995-04-04|

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AU577884B2|1988-10-06|

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AT58525T|1990-12-15|

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JPH0649680B2|1994-06-29|

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ZA856077B|1986-10-29|

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YU45923B|1992-09-07|

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MA20505A1|1986-04-01|

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FR2569189B1|1986-12-19|

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US4798901A|1989-01-17|

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FR2580637B2|1987-06-26|

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GR851967B|1985-12-03|

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MX8274A|1994-01-31|

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法律状态:

优先权:

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申请号 | 申请日 | 专利标题

---

FR8412791A|FR2569189B1|1984-08-14|1984-08-14|NOVEL PYRROLE DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES|

---

FR8506134A|FR2580637B2|1984-08-14|1985-04-23|NOVEL PYRROLE DERIVATIVES, THEIR PREPARATION PROCESS AND THEIR APPLICATION AS PESTICIDES|

---