前苏联专利SU1422996A3 Method of producing derivatives of pyrazole

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专利摘要:
5-Cyano-1-substituted-1H-pyrazole-4-carboxamide derivatives useful as terrestrial and aquatic herbicides and aquatic algicides.
公开号:SU1422996A3
申请号:SU843812255
申请日:1984-11-06
公开日:1988-09-07
发明作者:Ричард Бек Джеймс
申请人:Эли Лилли Энд Компани (Фирма)；
IPC主号:

专利说明:

s
The invention relates to a process for the preparation of novel pyrazole derivatives of the general formula
3J -T-GN
H II-
iiJL- °
(Ij
where K is C, -Sb-alkyl or group
mule
Iro
m
m
FIR)
m
or
R and 1C - H, C, -C-apkyl, alkenyl, C-C-cycloalkyl or C | -C3-alkok-; SI 25
Or
Rj and RJ, taken together with the nitrogen atom to which they are attached, form a piperidino morpholine 30 or pyrrolidine ring; R is halogen, C -C4-alkyl,
C-C-alkoxy, C4-C4-ga-. loidalkyl, cyano; m 0..3.35
possessing herbicidal activity, which can be used in agriculture.
The aim of the invention is a process for the preparation of new pyrazole derivatives, 40 having a herbididal activity that exceeds the activity of the known herbicides of the pyrazole range.
Example 1. 5-Diano-1- (2-pyridinyl) -Y-methyl-1H-pyrazole-4-carboxamide45 A-5-amino1-ethyl ester - (2 pyridine-1) -1 H-pyrazole-4-carboxylic acid.
A solution of 21.83 g of 2-hydrazinpyridine and 38.2 g of ethyl (ztoxymethylene) cyano; Adipate cjj is dissolved in 150 ml of acetic acid and 50 ml of water, heated on a ball bath for 16 hours. The reaction mixture is cooled to room temperature and placed in a refrigerator to form crystals. The precipitated 1 substance is collected by filtration and washed with cold 50% aqueous ethanol to obtain 23.62 g of complex
five
0
five
0
five
0
five
jj
5-amino-1- (2-pyridinyl) -1H-pyrazole-4-carboxylic acid ethyl ester. Yield 50.9%. M.p. 89-9G.
B. 5-ChLOR-1- (2-pyridinyl) -1H-pyrazole-4-carboxylic acid ethyl ester.
Nitrazyl chloride is bubbled into a solution of 23.62 g of 5-amino-1- (2-pyridinyl) -1H-pyrazole-4-carboxylic acid ethyl ester in 100 ml of chloroform for 5 minutes. The reaction mixture is heated on a steam bath for 5 minutes. The volatiles are removed under reduced pressure to give an oil. The residue is cooled, to obtain a solid, which is crystallized from ethanol, 16,, 3 g of 5-chloro-1- (2-pyridinyl) -1H-pyrazole-4-carboxylic acid ethyl ester are obtained. The output of 64.8%. M.p. .
Found,%: C 52.22; H 3.75; N 16.59.
With „H.oClNjO.
Vyagisleno,%: C 52.50; H 4.01j N 16.70.
C. 5-Cyano1 - (, 2-pyridinyl) -1H-pyrazole-4-carboxylic acid ethyl ester.
7.36 g of 5-chloro-1- (2-pyridinyl) -1H-pyrazole-4-carboxylic acid ethyl ester was dissolved, 3.2 g of sodium cyanide in 25 ml of DMF, heated at 100 ° C in for 3 hours. The reaction mixture is cooled and diluted with 300 ml of ice-cold water. The precipitated solid is collected by filtration to obtain 5.79 g of a solid, which is recrystallized from ethanol, to obtain 4.72 g of ethyl ester of 5-diano-1- (2-pyridinyl) - li H-pyrazole-4-carboxylic acid. Mp about P2-114 ° C.
Found,%: C-59.43; H 4.11; N 23.06.
C4zH, o, N402,
Calculated,%: C 59.90; H 4.16; N 23.13.
D. To a solution of 2.5 g of ethyl 5-cyano-1- (2-pyridinyl) -1 H-pyrazole-4-carboxylic ester
20 ml of DMF is added in excess of 40% (tonomethylamine so that the initial pyrazole does not precipitate. After 24 hours, additional amounts of monomethylamine are added to the reaction mixture and to keep these reactants in solution. The reaction mixture is heated, added to her
t50 ml of ice water. The precipitated solid is collected by filtration and recrystallized from methanol to obtain 1.2 g of 5-cyano-1- (2-pyridine) 1-N-methyl-1H-pyrazole-4-carboxamide. M.p. 200-202 0.
Found,%: C 58.87; H 3.83; N 30,53.
With „HqN40i
Calculated,,: C 58.15; H 3.99; N 30.82.
Example 2. 5-Cyano-1- 2- (trifluoromethyl) -4-chlorophenyl | -M-methyl-1H-pyrazole-A-carboxamide.
A. 5-Amino-1 (trifluoromethyl) -4-chlorophenyl -1H-pyrazole-4-carboxylic acid ethyl ester.
A solution of 31.58 g of 2- (trifluoromethyl) -A-chlorophenylhydrazine and 27.92 g of ethyl (ethoxymethylene) cyanoacetate, dissolved in 225 g of acetic acid and 75 ml of water, is heated in a steam bath for approximately 16 hours. The reaction mixture is cooled to room temperature is 25 N 12.23.
C. 5-Cyano-1 - - (. Trifluoromethyl) -4-chlorophenyl -1N-pyrazole-carboxylic acid ethyl ester.
A solution of 3.15 g of 5-chloro-1- 2- (trifluoromethyl) -4-chlorophenyl -1H-pyrazole-4-carboxylic acid ethyl ester and 1.1 g of sodium cyanide in 25 m of dimethylformamide is heated at 100 ° C for 4 , 5 hours. To the reaction mixture are added 3 g of molecular solutes. The reaction mixture is cooled and 300 ml of ice water is added. The precipitated solid is collected by filtration and recrystallized from ethanol (charcoal) to give 1 g of 5-cyano-1-2- (trifluoromethyl) -4-chlorophenyl -1K-pyrazole-4-carboxylic acid ethyl ester. M.p. 70-72 ° C.
Found,%: C 49.16; H 2.39; N 11.93.
C, 4H, ClF.,. I.
Calculated,%: - C 48.93; H 2.64;
thirty
The baths are placed in a refrigerator. The precipitated solid is collected by filtration and combined with the solid separated from the filtrate to obtain 43 g of 5-amino-1-2- (graftormethyl) -4-chlorophenyl -1H-pyrazole-4-carbsnova ethyl acid ethyl ester. M.p. 114-11.
B. Ethyl ester of 5-chloro.p- (trifluoromethyl) -4-chlorophenyl -1H-pyrazole-4-carboxylic acid.
Gaseous hydrochloric acid is bubbled through a solution of 26 g of 5-amino-1- 2- (trifluoromethyl) -4-chlorofensh1 -1H-pyr-o-N 17 20 ethyl ester as sol-4-carboxylic acid dissolved in 250 ml chloroform for 1 min. The nitrosyl chloride is then bubbled through the solution for 10 minutes. The reaction mixture is heated in a steam bath and the volatiles removed under reduced pressure. The residue is dissolved in hot ethanol, purified with charcoal and the product is crystallized; 16.6 g of 5-chloro-1- 2- (tritoromethyl) -4-chlorophenyl -1H-pyrazole-carboxylic acid tyl ester is obtained. M.p. 67-69 pp .:
D. Pure new-4-x new ki mono-network is monitored by cm of water, 35 тал 355 mg 535 mg 5 4-chloro; fairy carbox
Find
N
C ,, Hg
Calculate 17.05.
P p and 45 chlorphene boxamid
A. Sl 1- (2,4-d Bon
A solution of ether of 5 pyrazolcyanide l DMF, under 55 for the duration of the addition heat the solid
50
Found,%: C 44.48; H 2.33; 75.80.
C ,, HqCVF, NiO.
Calculated,%: C, 44.22; H 2.57; 7.93.
N 17 20.
D. A solution of 1.23 g of 5-5-cyano-2- (trifluoromethyl) -4-chlorophenyl -1 -H-pyrazole-4-carboxylic acid ethyl ester and 8 ml of 40% aqueous monomethylamine in 20 ml of DMF stirred at 25 ° C for 16 hours. The reaction mixture was poured into 150 ml of ice-water, the precipitated solid was collected by filtration and purified by recrystallization from ethanol, yielding 535 mg of 5-cyano-1- 2- (trifluoromethyl) -4- chlo; phenyl) -N-methyl-1 H-pyrazole-4-- carboxamide. M.p. 162-164 C.
Found,%: C 47.74; H 2.67;
About N 17 20.
N
C ,, HgClFjN O.
Calculated,%: C 47.51; H 2.45; 17.05.
EXAMPLE 3: 5-Cyano-1- (2,4-di-45 chlorophenyl) -N-methyl-1H-pyrazole-4-carboxamide.
A. Ethyl ester of 5-cyano-1- (2,4-dichlorophene1) -1H-pyrazole-4-carboxylic acid.
A solution of 5.4 g of ethyl chloro 5-chloro-1- (2,4-dichlorophenyl) -1H-pyrazole4-carboxylic acid and 2 g of lithium cyanide dissolved in 30 ml of DMF is reacted at 55 for 23 hours. To the reaction mixture another 1 g of lithium cyanide is added and heated for another 7 hours. The mixture is poured into ice water, the precipitated solid is collected by filtration
50
It and perestallitel from alcohol (charcoal), get 3,75 g of ethyl ester of 5-cyano-1- (2,4-dichlorophenyl) -1H-pyrazole-4-caranoic acid. Yield 61%. M.p. 79-8G.
AND
Found,%: C 50.12; H 3.11; 13.29.
C, jH ,, Cl2N, 0. Calculated,%: C 50.35; H 2.93;
13.55.
B. To a solution of 2.5 g of ethio-jioBoro 5-cyano-1- (2,4-dichlorophenyl) -1H-pyrazole-4-carboxylic acid-jjioTH ester in 20 ml of DMF is added 20 ml of 40% aqueous monomethylamine. The reaction mixture is stirred at 1 atomic temperature for 2.5 hours, the solution is poured into ice water. The precipitate was collected by filtration and recrystallized from methanol and water, and 1.3 g of 5-cyano-1 - (2,4-diclorophenyl) Yetil-1 H-pyrazole-4-carboxamide was obtained. Mp: 82-183 ° C.
On ydeno,%; C 48.69; H 2.74; And 19.23.
.C, iHgCl N40.
C 48.84; H 2.73;
Calculated,% 18,98.
EXAMPLE 4 5-Cyano-1- (4-bromophenyl) -M-metsh1-1H-pyrazole-4-carbox 1F1L,
A, Ethyl ester 5-Cyano1- (4-bromophenyl) -1H-pyrazole-4-carbono ™
aoy acid
A solution of 6.6 ethyl ester of 5-chloro-1- (4-bromophenyl) -1H-pyr aeol-4-.1-: arbonic acid in-30 ml LH, with 2 g of sodium cyanide is heated at 3 hours The reaction mixture is poured into ice water and the precipitated solid is collected by filtration. The product is recrystallized from 3a-alcohol to give 5.3 g of ethyl ester of 5-cyano-1- (4-bromobutyra) -1H-pyrazole-4-carboxylic acid. M.p. 104-105 C.
Found,%: C 48.90; H 2.91; N 13.23.
, o BrN, 02.
Calculated,%: C 48.77; H 3, T5; N13.13 ,.
B. A solution of 3.2 g of 5-cyano-1- (4-bromophenyl) -1H-pyrazole-4-carboxylic acid ester complex in 40 ml of an THA-alcohol and 10 ml of 40% aqueous monomethylamine is heated in reverse. fridge for 2 hours
0
five
0
five
0
ti
An additional 10 ml of 40% aqueous monomethylamine is added to the reaction mixture, the reaction mixture is heated under reflux for 3 hours. The mixture is cooled and the precipitated solid is collected by filtration to give 1 g of 5-cyano-1- (4-bromophenyl) -K-methyl - 1H-pyrazole-4-carboxamide. M.p. 240-241 ° C ..
Found,%: C 47.39; H 3.07; N 18.49.
, BrN40.
Calculated,%: C 47,29; H 2.97; N 18.36.
The following compounds are prepared analogously to Examples 1-4.
Example 5: 5- Diano-1-phenyl-Y-cyclopropyl-1H-pyrazole-4-carboxamide, m.p. 220-222 C.
Found,%: C, 66.47; H 4.68; N 22.06.
C, 4H, iN40.
Calculated,%: C 66,, 66; H 4.79; N 22.21.
Example 6. 5-Cyano-1- (3-bromophenyl) -N-methyl-1H-pyrazole-1-carbox-MID, m.p. 178.5-180, 5 ° C.
Found,%: C 47.33; H 3.03; N 18.26.
.
Calculated,%: C 47.24; H 2.97; N 18.36.
Example 7. 5-Cyano-1- (3-bromo phenyl) -N-ethyl-1 H-pyrazole-4-carbox °. .MID, m.p. 154.5-156 C.
Found,%: C 48.74j H 3.4 6; N 17.34. . C, jH "BrN40,
Calculated,%: C 48.92; H 3.47; N 17.55.
Example 8. 5-1-1-f3- (trifluoromethyl) phenyl 3 -N-methyl-1H-pyrazole 4-carboxamide, mp. 151-153 ° C.
Found,%: C 53.29; H 3.28; N 18.88.
C, 5H, F, N4.0.
Calculated,%: C, 53.07; K 19.04.
3.08;
Example 9. 5-Cyano- - z- (trifluoromethyl) phenyl.-N-ethyl - 1 H-pyrazole-4-carboxamide, mp. 143-145 C.
Found,%: C 54.75; And 3.39; N 18.28.
N
0.4 And „F, N40.
Calculated,%: C 54.55; H 3.60; 18.17.
Example 10. 5-Cyano-1- (2,4-dibromophenyl) -N-methyl-1H-pyrazole-4-carboxamide, m.p. 198-200 S.
Found,%: C 37.50; H 2.15; N 14.47.
C, 2H8B4 N40.
Calculated,%: C 37.53; H 2.10; N 14.59.
Pr and Ie p 11. 5-Cyano-1- (3-methylphenyl) -M-methyl-1H-pyrazole-4-carboxamide, m.p. 159-161 ° C.
Found,%: C 64.70; H 5.09; N 23.18.
C, H, 4N40.
Example 17. 5-Cya 2-pyridine) -N-methyl-1H carboxam p, so pl. 218-2
Found,%: C 50.29; N 26.53.
C, 1 HgClNjO.
Calculated,%: C 50.49 N, 27.76.
10 Example 18. 5-cia di-yl) -Y-ethyl-1H-pyrazole mead, so pl. 210.5-212 ° C.
Found,%: C 59.72; H N 29.02.
Calculated,%: C 64.99; H 5.03; N 23.32.
Example 12. 5-Cyano-1- (3-fluorophenyl) -N-methyl-1H-pyrazole-4-carboxamide, m.p. 188-189.5 s.
Found,%: C 58.8T; H 3.62; N 22.70.
C,; (H, FN40.
Calculated,%: C 59.02; H 3.71; N 22.94.
Example 13. 5-Cyano-1- (3-fluorophenyl) -H-ethyl-1H-pyrazole-4-carboxamide, m.p. 163-164 C. Found,%: C 60.64; H 4.11; N 21.46.
With „H4, FN40.
Calculated,%: C 60.46; H 4c29; N 21.69;
PRI me R 14. 5-Cyano-1- (4-pyridinyl) -N-methyl-1H-pyrazole-4-carbox 15
С, гН „К50.
Calculated,%: C 59.74; N 29.03.
Example 19. 5-Zia 20 phenyl) -N-netil-1H-pyrazo amide, m.p. T81-183 ° C.
Found,%: C 55,56; N 21.36.
C, HqClN40.
25 Calculated,%: C 55.29; N 21.49. ..
Example 20. 5-Cya toxifenil) -N-Netil-1H-p carboxamide, so pl. 190.5 30 Found: C 60.66; H N 21.61.
C ,, H, N402.
Calculated,%: C 60.93; N 21.86.
PRI me R 21. 5-Cya dichlorophenyl) -N-methyl-1H-carboxamide, m.p. 196-1
Found,%: C 48.54; H N 18.89.
,
Calculated,%: C 48.44; N 18.98.
Example 22. 5-Zia chlorophenyl) -N-etshl-1H-pyr
35
40
MFA, m.p. 216-218 s.
. Found,%: C 57.93; H 3.86; N 30.66.
WITH, .
Calculated,%: C 58.14; H 3.99; N 30.82.
Example 15. 5-Cyano-1- (3-chloro.,
phenyl) -N-methyl-1H-pyrazole-4-carbox-xamide,. m.p. 151-153 p. MFA, m.p. 181-182 ° C.
Found,%: C 55.44; H 3.56; N 21.63.
ClNyO.
calculated,%: C 55.28; H 3.48; N 21.49.
Example 16. 5-Cyano-1- (3-chloro-phenyl) -N-ethyl-1H-pyrazole-4-carbox-135-136 ° C.
MFA, m.p.
Found,%: C 56.94; H 4.06; N 20; 38.
CoH, C1N40.
Calculated,%: C 56.84; H 4.04; N 20.39.
Found,% 1 C 50.72; H N 18.27.
C ,, H, Cl2N40.
Calculated,%: C 50.51 N 18,12.
Example 23. 5-Cya fluoromethyl) phenyl-N-methyl 4-carboxamide, m.p. 182 Found: C, 52.99; H
; N 18.84.
N40.
Calculated,%: C 53.07; N 19.04.

29968
Example 17. 5-Cyano-1- (5-chloro-2-pyridinyl) -N-methyl-1H-pyrezol-4- - carboxes p, m.p. 218-219 C.
Found,%: C 50.29; H 3.27; N 26.53.
C, 1 HgClNjO.
Calculated,%: C 50.49; H 3.08; N 27.76.
10 Example 18. 5-Cyano-1- (2-pyridiyl) -Y-ethyl-1H-pyrazole-4-carbox-, MFA, m.p. 210.5-212 ° C.
Found,%: C 59.72; H 4.54; N 29.02.
С, гН „К50.
Calculated,%: C 59.74; H 4.60; N 29.03.
Example 19. 5-Cyano-1- (2-chloro-phenyl) -N-netil-1H-pyrazole-4-carboxamide, m.p. T81-183 ° C.
Found,%: C 55,56; H 3.46; N 21.36.
C, HqClN40.
Calculated,%: C 55.29; H 3.48; N 21.49. ...
Example 20. 5-Cyano-1- (4-metoxyphenyl) -N-netil-1H-pyrazole-4-carboxamide, mp. 190.5-192 ° C. Found,%: C 60.66; H 4.61; N 21.61.
C ,, H, N402.
Calculated,%: C 60.93; H 4.72; N 21.86.
EXAMPLE 21 5-Cyano-1- (3,4-dichlorophenyl) -N-methyl-1Npyrazole-4-carboxamide, mp. 196-197 ° C.
Found,%: C 48.54; H 2.79; N 18.89.
,
Calculated,%: C, 48.44; H 2.73; N 18.98.
Example 22. 5-Cyano-1- (3,4-dichlorophenyl) -N-etl-1 H-pyrazole-4-carbobo g
. .
xamid m.p. 151-153 p.

Found,% 1 C 50.72; H 3.16; N 18.27.
C ,, H, Cl2N40.
Calculated,%: C 50.51; H 3.26: N 18.12.
Example 23. 5-Cyano-1- 2-1 three fluoromethyl) phenyl-N-methyl-1H-pyrazole-4-carboxamide, m.p. 182-184 ° C. Found,%: C 52.99; H 3.04;
; N 18.84.
N40.
Calculated,%: C 53.07; H 3.08; N 19.04.
9142299610
PRI mme R 24. 5-Cyano-1- (4-fluoro-P r-i me R 31. 5 - Cyano-1-phenyl-phenyl) -N-methyl-1 H-pyrazole- 4 -carbox-N-2-propenyl-1H-pyr: 1ol-4-carboxamide. amide, so pl. tpl 163-164 C.
Found,%: C 58.80; H 3.49} Found;%: C 66.39; H 4.57;
N 22.71. N 22.08.
R1h 40..
Calculated,%: C 59.02; H 3.71; Calculated.%: C 66.66; H 4.7;
N 22.94.N 22.21.
10 Example 32. 5-Cyano-1-phenyl Example 25. .5-Cyanr-1- (4-fluoro-ethyl-1H-pyrazole-4-carboxamide,
PHENYL) -N-ethyl-1H-pyrazole-4-carb-T. pl. 199-200 S. Kamid, m.p. 163-165 C. Found,%: C 65.18; H 4.82;
; Found,%: C 60.21; H 4.17; N 23.48. Ni21.44. .
C „H„ FN40. Calculated,%: C 64.99; H 5.03;
; Calculated,%: C 60.46; H 4.29; N 23.32.
NJ21, 6.9. For example, 33. 5H iano-1-C4-chloro: Example 26. 5-Cyano-1- (3-chloro, Phenyl) -N-methyl-1H-pyrazC) l-4-carbox :
44methylphenyl) -N-methyl-1H-pyrazole-4-20zmid, mp .. 211-212 C. Kerboxamide, mp. 186-190 s.
; Found; : C 57-, 09; H 3.90; Found.%: C 55.13; H 3.43;
30.N. 21.32. , I C (, H C1N40. Ct-iHqClN O.
I Calculated,%: C 56.84; H 4.04; 25 Calculated,%: C.55,29; H 3.48;
N.20,39., N 21,49.
{Example 27, 5-Cyano-1- (2,3-PRI meper 34. 5-Cyano-1- (2,5-diDichlorophenyl) -N-methyl-1H-pyrazole-4-chlorophenyl) - N-methyl-1H-pyrazole-4-cage rboxamide, mp. 212-214 ° S.boxamide, m.p. 186-187 C.
Found,%: C 48.58; H 2.61; 30 Found: C, 48.73; H 2.60;
N, 19.09. N 18.84.
C, iH8Cl, N40.C, 2.HeClzN40.
It is allocated,%: C 48,84; H, 2.73; Calculated,%: C, 48.84; H 2.73;
N 18.98. N 18.98.
Example 28. 5-Cyano-1- (3,4-di- "Example 35. 5-1 ano-1- (2,5-di
methylphenyl) -N-methyl-1H-pyrazole-4-car-chlorophenyl) -K-ethyl-1H-pyrazole-4-carboxoxamide, mp. 195-197 secamid, m.p. 170-172 Co
. Found,%: C 50.67 ;; H 3.27;
Jadeno.%: C 65.86; H 5.29; N 18.22. H 21.75. . 40CHH, oC4N40.
C, 4n, 4N40. . Calculated,%: C 50.51; H 3.26;
Calculated,%: C :. 66.13; H 5.55; N18.12. N 22.03. EXAMPLE 36. 5-Cyano-1- (4-me Example 29. 5-Cyano-1- (2-quinotylphenyl) -N-methyl-1H-pyrazole-4-carbolinyl) -N-mets -1H-pyrazol-4-carbox-x-xamide, t. Pl. 205-207 sec. ashad 22b-227 ° C. Found,%: C 65.19; H 4.97;
Found,%; C 65.12; H 3.80; H 23.04. N 25.43. .
C, 5H „N50.C ,,.
Calculated,% :. C, 64.97; H 4.00; . Calculated,%: C 64.99; H 5.03;
H 25.26. 23.32.
Example 30. 5-Cyano-1-phenyl- Example 37. 5-Cyano-1- (4-MeH Popsh1-1H-pyrazole-4-carboxamide, tylphenyl) -H-eth11-1H-pyrazole-4-karbot. . 168-169 With. Zhsamid, so pl. 209-Z10 ° C.
Found,%: C 65.88; H 5.33; Found,%: C, 66.36; H 5.39;
.Sh 21.85 .. N 22.16.
C, 4NHM40.C 4H44N40.
Calculated,%: C 66.13; H 5.55; Calculated,%: C, 66.17; H 5.55;
22.03. N 22.03.
11142299612
PRI me R 38. 5-Cyano-1- (2,4-di-imide, followed by recrystallization
chlorophenyl) -M-ethyl-1N-pyrazole-4-carboxyamide, m.p. 140-141.
Found,%: C 50.68; H 3.28; N 18.25.
Cj HioCl N O.
Calculated,%: C 50.51; H 3.26; N 18.12.
from ethanol. M.p. 185-187 C.
Found,%: C 64.42; II 4.47; 5 N 24.88.
Clause and j (
C, 5H, jN, 0.
Calculated,%: C 64,51; H 4.69; N 25.07.
Example. 42. 5-Cyano-1- (4-chloro. Example 39. 5-Cyano-1- (4-chloro-to phenyl) -K-cyclopropyl-1H-pyrazole-4fennl) -Y-ethyl-1H-pyrazole-4 -carbo-xamide, so pl. 166-168 C.
Found,%: C 56.92; H 4.00; N 20.23.
C, 3H ,, C1N40.
Calculated,%: C 56.84; H 4.04; N 20.39.
EXAMPLE 40. 4-Cyano-1- (3-cyanophenyl) -N-methyl-1H-pyrazole-4-carboxyamide, m.p. 206-208 0.
Found,%: C 62.10; H 3.85; N 27.60:
C HqNyO.
Calculated,%: C 62.15; H 3.61; N 27.87.
EXAMPLE 41 5-Cyano-1- (3-cyanophenyl) -K-methyl-E-ethyl-1H-pyrazole-4-carboxamide. .
A. 5-Cyano-1- (3-cyanophenyl) -1H-pyrazole-4-carboxylic acid.
7.7 g of 5-cyaio-1- (3-cyanophenyl) -1H-pitazol-4-carboxylic acid ethyl ester is dissolved in 75 ml of hot ethanol. To reactive caroxamide.
A. 5-Cyano-1- (4-chlorophenyl) -1H-lazole-4-carboxylic acid.
Hot solution 5.61 g hydroxide
15 potassium dissolved in 110 ml of 3A-ethanol 7 is added to a hot solution of 11.3 g of 5-cyano-1- (4-chlorophenyl) -1H-pyrazole-4-carboxylic acid ethyl ester, dissolved in 225 ml
20 FOR-ethanol. The resulting salt is dissolved in 1 liter of water and the solution is acidified with concentrated hydrochloric acid. The precipitated solid is collected by filtration and recrystallized.
25 from toluene, 8.47 g of 5-cyano-1- (4-chlorophenyl) -1H-pyrazole 7-4-carboxylic acid are obtained, m.p. 192-195 S.
at room temperature 15 min. 7 ml of cyclopropylamine is added to the reaction mixture and the mixture is stirred
Found,%: C 53.25; H 2.50;
N 16.73. 30 C HbClNjO.
Calculated,%: C 53.35; H 2.24;
N 16.97.
B. A solution of 2.47 g of a 5-iftiaHO-1- (4 chlorophenyl) -1H-pyrazole-4-carboxylic mixture was added 3.2 g of an acid hydroxide and 2.03 g of carbonyldiimidazole. potassium dissolved in ethanol. The solution is dissolved in 25 mp DMF, and a large amount of water is stirred in to the reaction mixture, which is immediately poured into water. The solution is acidified with concentrated hydrochloric acid Q for 16 hours. The mixture is poured into 150 ml and the precipitated solid is ice water and the precipitated solid is collected by filtration, dried, and the substance is collected by filtration. 4.3 g of 5-cyano-1- (3-cyano-substance is recrystallized from phenyl) -H-pyrazole-4-carboxylic acid-ethanol, solid, dried, 5-cyano-1-tons are obtained, m.p. 190-192 C.D2 (4-chlorophenyl) -Y-cyclopropyl-1H-pyrazole-4-carboxamide. M.p. 204-20b with.
B. 2 g of carbonyldiimidazole is added; Found,%: C 58.70; H 4.05; to a solution of 2.0 g of 5-cyano-1- (3-N, 19.31. cyanophenyl) -1 H-pyrazole-4-carboxylic C, 4H (, C 1 N 40.
acid dissolved in 50 ml of dIa). . Calculated.%: C 58.65; H 3.87; The reaction mixture was stirred at room temperature for 25 minutes. 740 mg of N-ethyl-N-methyl-amine was added. The reaction mixture was stirred for 24 hours, after which the solution was poured into ice-water.
water Precipitated solid with 55 amine. taken by filtration and dried, as described in Example 43. 5-Cyano-1- (4-chloro-ray is 1.2 g of 5-cyano-IT- (3-cyanophenyl) -phenyl) -M8K-dimesh1-1 H-pyrazole- 4-carbs) -N-mitshI-N-ethyl-1H-pyrazole-4-carbox-xamide, m.p. 123-125 C.
N 19,
The proposed compound in the wake; w; their examples are obtained by the reaction of pirz.-zolcarboxylic acid with the corresponding ethanol. M.p. 185-187 C.
Found,%: C 64.42; II 4.47; N 24.88.
Clause and j (
C, 5H, jN, 0.
Calculated,%: C 64,51; H 4.69 N 25.07.
caroxamide.
A. 5-Cyano-1- (4-chlorophenyl) -1H-lazole-4-carboxylic acid.
Hot solution 5.61 g hydroxide
potassium dissolved in 110 ml of 3A-ethanol 7 is added to a hot solution of 11.3 g of 5-cyano-1- (4-chlorophenyl) -1H-pyrazole-4-carboxylic acid ethyl ester, dissolved in 225 ml
FOR-ethanol. The resulting salt is dissolved in 1 liter of water and the solution is acidified with concentrated hydrochloric acid. The precipitated solid is collected by filtration and recrystallized.
from toluene, 8.47 g of 5-cyano-1- (4-chlorophenyl) -1H-pyrazole 7-4-carboxylic acid are obtained, m.p. 192-195 S.
at room temperature 15 min. 7 ml of cyclopropylamine is added to the reaction mixture and the mixture is stirred
chlorophenyl) -1H-pyrazole-4-carboxylic acid and 2.03 g of carbonyldiimidazole. dissolved in 25 mp DMF, stirred for 16 h. The mixture is poured into 150 ml of ice water and the precipitated solid is collected by filtration. The solid is recrystallized from ethanol, dried, get 5-cyano-1- (4-chlorophenyl) -A-cyclopropyl-1H-pyr Calculated.%: C 58.65; H 3.87;
N 19,
The proposed compound in the wake; w; their examples are obtained by the reaction of pirz.- zolcarboxylic acid with the corresponding Found.%: C 56.78; H 4.08; N 20.32.
C „H„ C1N40.
Vyagisleno,%: C 56.84; H 4.04;
N 20.39. .
EXAMPLE 44. 5-Cyano-1- (4-chloro-phenyl) -H-methyl-H-ethyl-1H-pyrazole-4-carboxamide, mp, 87-89 C.
Found 7.: C 57.98; H 4.49;
N: 19.34. ; C, 4H, C1N40.
Calculated,%: C 58.24; H 4.54; : N 19.40.
Example 45. 5-Cyano-1- (4-chloro (phenyl) -M, N-diethyl-1 H-pyrazole-4-carbo xamide, mp 109-1. Found: C 59.32 ; H 4.79; iN 18.33.
CijH ..
Calculated,%: C 59.51; H 4.99; 1N 18.50. .
; PRI me R 46. 5-Cyano-1- (4-chloro | phenyl) -N-ethyl-N-propyl-1 H-pyrazole-4, firebox amide, mp. 51-52 ° C.
Found,%: C 60.65; H 5.50; J7; 82 ....
: C, C1N40.
Calculated,%: C 60.66; H 5.41; N 17.69
Example 47. 5-Cyano-1- (4-chloro-phenyl) N, N-dipropyl-1H-pyrazole-4-car brxamide, m.p. 83-84 ° C.
Found,%: C 61.61; H 5.58; N 16.88.
WITH, .
Calculated,%: C, 61.72; H 5.79; N 1 6, 4.
.. P m p 48. (4-chlorophenyl) 4-cyano-1H-pyrazol-4-yl jcap-bonyl-piperidine, m.p. 124-125 ° C.
Found,%: C 60.74; H 4.74; N 17.60.
C.eH ..
Calculated,%: C 61.05; H 4.80; N 17.80.
Example 49. 5-Cyano-1- (3-wspor 4-methylphenyl) -N, K-dimethyl-1H-pyrazole 4-carboxamide, mp. 109-111 ° C.
Found,%; C, 57.96; H 4.34; N 19.39.
C, 4H, C1N40.
Calculated: C 58,24; H 4.54; N 19.40.
PRI me R 50. 5-Cyano-1- (2,4-dichlorophenyl) -N, N-dimethyl-1H-pyrazole 4 carboxamide, m.p. 117-119 C.
Found,%: C 50.25; H 3.26; N 17.80.
.C, .jHioCl N40.
Calculated,%: C 50.51; H 3.26; N 18.12.
PRI me R 51. 5-Cyano-1- (2,4-di-chlorophenyl) -N-cyclopropyl-1H-pyrazole-4-carboxamide, t, pl. 173-174 C.
Found,%: C 52.38; H 3.26; N 17.41.
.
Calculated%: C 52.36; H 3.14; N 17.44.
Example 52. 5-Cyano-1- (2,4-dichlorophenyl) -Y-methyl-H-ethyl-1H-pyrazole-4-carboxamide, mp. 75-77 C.
Found,%: C 51.76; H 3.74; N 17.28.
.
Calculated,%: C 52.03; H 3.74; N 17.34.
Example 53. 5-Cyano-1- (2,4-di chlorfetsst) -H, H-diethp-1H-pyrazole-4-carboxamide, so pl. 111-112,5 ° C.
Found,%: C 53.23; H 3.94; N 16.56.
С „Н, оС1, Н40 ..
Calculated,%: C 53.43; H 4.18; N 16.61.
Example 54.) -Ciano-1- (2,4-di chlorophenyl) -Y-methyl-H-methoxy-1H-pyra-zol-4-carboxamide, p. 143-145 s.
Found,%: C 47.88; H 3.09; N 17.16.
C, H, oCl, N402.
Calculated.%: C 48.02; H 3.10 N 17.32.
Example 55. 5-Cyano-1- (3-bromo phenyl) -N, N-dimethyl-1H-pyrazole-4-carboxamide, mp. 125 s
Found,%: C 49.17; H 3.30; N 17.29.
C, 5H ,, BrN40.
Calculated,%: C 48.92; H 3.47; N 17.55. . ,
Example 56. 5 Cyano-1 -: (, 3-bromo phenyl) -N-methyl-N-methoxy-tH-pyrazole-4-carboxamide, mp. 154-155 s.
Found,%: C 46.83; H 3.45; N 16.49.
C4, Ne BrN402.
Calculated,%: C 46.59; H 3.31; N 16.72.
EXAMPLE 57. 5-Cyano-1-GZ- (three fluoromethyl) phenyl-N, N-dimethyl-1I-pyr sol-4-carboxamide, m.p. 97-99 ° C.
Found,%: C 54.46; H 3.88; N 18.01.
C ,, H “F, N40.
Calculated: C 54} 55; H 3.60; N 18.17.
P p and m e p 58,5-Cyano-1- 3- (tri- 5 fluoromethyl) phenyl-H-cyclopropyl-1H-pyrazole-4-carboxamide, m.p. 180-182 s.
Found,%: C 56.28; H 3.50 | N17.40.10
C, UN "
Calculated,%: C 56.25; H 3.46; N17.49.
5-Cyano-1- 3- (triC, 5H, 5BrN40.
Calculated,%: C, 51.89; H N 16.41.
PRI me R 65. 5-Cyano phenyl) -N-cyclopropyl-1H-mon carboxamide, m.p. 217-218
Found,%: C 50.61; H 3 N, 16.80.
C, 4H ,, BrN40.
Calculated,%: C 50.78; N16.92.
PRI me R 66. 5-Cyano methyl) -N, N-dimethyl-1H-pyr
ll RI M with rw) .7 "l Aj" "gf t 1. ...--. -. y R,. ,- .. .P ....-
fluoromethyl) phenyl-N-methyl-N-ethyl-1H-jsboxamide, m.p. 132-133 C.
Pyrazole-4-carboxamvd, so pl. 67-68 ° C.
“Found X: C 55.61; H 4.03; N 17.64.
Found%: C 60.71; H 4 N 21.70.
Ci} H ,, FN40.
C, 5H ,, F, N40.
C. Calculated.%: C 55.90; H 4.07; N 17.38.
Example 60. 5-Cyano-1-Gfftormethyl) phenyl3-N-methyl-N-meth 1H-pyrazole-4-carboxamide, mp. 23 ° C
Found.%: C 52.11; H 3.51; N 17.35.

Calculated,%: C, 51.86; H 3, -42; N 17.28.
Example 61 5-Cyano-1- (4phenyl) -N, N-dimethyl-1H-pyrazole-4 boxamide, m.p. 131-133 ° C.
C, 48.79; H
Found,%: N 17.51.
C, 5H ,, BrN40.
Calculated,%: C 48.92; H 3.47; N 17.55.
PRI me R 62. 5-Cyano-1- (4-phenyl) -N-methyl-N-methoxy-1H-pypa 4-carboxamide, so pl. 147 C.
Found,%: C 46.42; H 3.24; N 16.52.
. C. „H BrN4 iCalculated,%: C 46.59; H 3.31 N 16.72.
EXAMPLE 63. 5-Cyano-1- (4phenyl) -N-methyl-M-ethyl-1H-pyrazole carboxamide, m.p. 91-93 0.
Found,%: C 50.41; H 3.76; N16.63.

S, dN, VGY40.
B; Calculated,%: C 50.47; H 3.93; N 16.82.
For example 64. 5-Cyano-1- (4-bromo phenyl) -N-diethyl-1H-pyrazol-4-carbox-x-1 MCM, mp. 108-110 C.
Found,%; C, 51.83; “4.32; S 16.12.
C, 5H, 5BrN40.
Calculated,%: C, 51.89; H 4.35; N 16.41.
EXAMPLE 65 5-Cyano-1- (4-bromo phenyl) -N-cyclopropyl-1H-pyrazole-4-carboxamide, m.p. 217-218 C.
Found,%: C 50.61; H 3.35; N16.80.
C, 4H ,, BrN40.
Calculated,%: C 50.78; H 3.35; N16.92.
PRI me R 66. 5-Cyano-1- (3-fluoro methyl) -N, N-dimethyl-1H-pyrazole-4-car ...--. -. y R,. ,- .. .P ....-
boxamide, m.p. 132-133 C.
oxamide, m.p. 132-133 C.

five
Q N 19.40.
Found%: C 60.71; H 4.07; N 21.70.
Ci} H ,, FN40.
Calculated,%: C 60.46; H 4.29; 20 N 21.69.
Example 67. 5-Cyano-1-C3-chlorophenyl) -N, N-dimethyl-1H-pyrazole-4-carboxamide, m.p. 110-113 ° C.
Found,%: C 56.66; H 3.72; 5 N 20.21.
C ,, H, C1N40.
Calculated,%: C 56.84; H 4.04; N 20.39.
EXAMPLE 68 5-Cyano.-1- (3-chloro-3Q phenyl) -N-cyclopropyl-1H-pyrazole-4-carboxamide, m.p. 178-179 p.
Found,%: C 58.88; H 3.84; N 19.68.
,, C1N40.
Calculated,%: C 58.65; H 3.87; N 19.54.
Example 69. 5-Cyano-1- (3-chlorophenyl) -N-methyl-N-methoxy-1H-pyrazole-4-carboxamide, m.p. 164-166 C.
Found,%: C 53.79; H 3.81;
N 19.40.
C, jH ,, ClN40.
Included in%: C 53.71; H 3.81; N 19.27.
EXAMPLE 70 5-Cyano-1- (3-pyridinyl) -N, N-diethyl-1H-pyrazole-4-carboxyamide, m.p. .
Found,%: C 62.37; H 5.38; N, 26.21.
, sNs-0.
Calculated,%: C, 62.44; H 5.61; N 26.00.
Example 71. 5-Cyano-1- (2-pyridinyl) -N-methyl-N-ethyl-1H-pyrazap-4-carboxamide, m.p. 106-108 S.

c 60.91; H 4.98;
Calculated,%: C, 61.70; H 5.13; N 27, A3 ..
Example 72 5-Cyano-1- (2-pyridinyl) -N-cyclopropyl-1 1-pyrazole-4-carboxamide, m.p. 22t-222 ° C.
Found,%: C 61.59; H 4.48; fi 27.55. ; .
.) Calculated,%: C 61.65; H 4.38; C 27.65.
PRI me R 73. 5-Cyano-1- (2-piP and PM 79. 5-Cyano-1- (3,4-dichlorophenyl) -N, N-dimethyl-1H-pyrazole-4 -carboxamide, mp: 122-124 ° C. 5 Found: C 50.43; H 3.06; N 18.08.
C ,,, HioCl N40.
Calculated,%: C 50 „51; H 3.26; N 18.12. 10 PRI me R 80. 5 - Cyano-1- (3.4 dichlorophene) -N-cyclopropyl-1H-pyr, p,. -. H, ... .ow, part 11 ash-4-carboxamide, so pl. 194-19b with.
p; idinyl) -N-methyl-N-methoxy-1H-pyra-Found,%: S. 52,57; H 3.13;
S1ol-4-carboxamide, so pl. 113-116 C.N. 17 50.
5С, 4Н „С1гК40.
27.03. Calculated,%: C 52.36; H 3.14;
N 17.44.
EXAMPLE 81. 5-Cyano-1- (4-fluorophenyl; -N, N-dimethyl-1H-pyrazole-4-car .-. L
Found,%: C 55.81; H 4.01; 27.03.
С, Н „NyO-j ..
Calculated,% C 56.03; H 4.31; NJ 27.22.
I, -phenyl-IN, and-dimethyl-1 n-pyrazole Example 74. 5- Cyano-1- (2-pi-20 boxamide, mp 118-120 s.
Rdinil) -N.N-dimethyl-1H-pyrazol-4-Found ,, C 60.24; K 4.06,
ckdbdcamp m.p. 136-138 ° C. m oi lskrboxamide, m.p. 136-138 ° C.
1 Found: C, 59.55; H 4.87; N128.77.
i С ,, Н ,. .
(2 "
Calculated,%: C 59.75; H 4.56; Nl29.05.
N 21.66;
CijHuFN O.
5 Calculated,%: C 60.46; H 4.29; N 21.69.
PRI me R 82. 5- Cyano-1- (2-hino.: J, uj.
: Example II 75. 1- {5-Cyano-1- (2-linyl) -N, N-dimethyl-1H-pyrazole-4-carp idinyl) -1H-pyrazol-4-yl carbonyl boxamide m.p. 167-168 ° H.
i.1 IA 4 С Jt 4 П /. . -. ™. ,,, i
thirty
morpholine, T. mp, 115-118 C.
Found,%: C 59.24; H 4.79; N24.97.
C, 4H, Y40g.
Calculated,%: C H 4.63; N 24.72.
Example 76. 5-Cyano-1-phenyl-H-methyl-N-ethyl-1H-pyrazole-4-carbox-x;. Amide m.p. 79 ° C.
Found,%: C 65.85; H 5.31; yy22,80
Ci4H ,, N40, Calculated,%: C 66.13; H 5.55; N 22.03,
35
40
Found,%: C, 66.30; H 4.58; N 24.03.
C ..
Vmsleno,%: C 65.97; H 4.50; N 24.04.
PRI me R 83. 5- Diano-1-phenyl-N, N-dimethyl-1H-pyrazole-4-carbox-1-h, m.p. 109-1.
Found,%: C 64.87; H 5.03; N 23.41.
C ,, H, 2N40.
Calculated,%: C 64.99; H 5.03; 32
PRI me R 84. 5- iano-1-phenyl-N- (1-methylethyl i) -1 H-pyrazole-4-carbophenol and 77. 5-cyano-1- (4-methoxyphenyl ) -N5N-dimethyl-1H-pyrazole-xamide, so pl. 208-209 with „4-carb6xamide, so pl. 113-114 ° C.
Found,%: C 62.46; H-5.27; N 20.92. .
CuH, 4N40, t.
Calculated,% s C 62,21; H 5.22; K 20.73.
EXAMPLE 78. 5-Cyano-1- (4-methoxyphenyl) -N-ethyl-1H-pyrazole-4-car
. ft
boxamide, m.p. 121-123 p.
Found,%; C 63.32; H 5.77; M 19.65,
C, 5H, 6N404.
Calculated,% s C 63,37; H 5.67; N 19.71.
Found,%: C 65.88; H 5.39; N 21.90.
C ,.
..Calculated,%; C 65/13} H 5.55;
N 22.03.
P. and Mer 85. 5-Cyano-1-phenyl-1H-pyrazole-4-carboxamide, m.p. 178-179.
Found,%: C 62.13; H 3.76 | N 26.36.
.
N1,%: C 62.26; H 3.80; N 26J40.
Found ,,: C, 60.24; K 4.06,
m oi LSN 21.66;
CijHuFN O.
Calculated,%: C 60.46; H 4.29; N 21.69.
PRI me R 82. 5- Cyano-1- (2-quinolinyl) -N, N-dimethyl-1H-pyrazole-4-carboxamide, mp. 167-168 ° H.
. . -. ™. ,,, i
Found,%: C, 66.30; H 4.58; N 24.03.
C ..
Vmsleno,%: C 65.97; H 4.50; N 24.04.
PRI me R 83. 5- Diano-1-phenyl-N, N-dimethyl-1H-pyrazole-4-carbox-1-h, m.p. 109-1.
Found,%: C 64.87; H 5.03; N 23.41.
C ,, H, 2N40.
Calculated,%: C 64.99; H 5.03; 32
PRI me R 84. 5- iano-1-phenyl-N- (1-methylethyl i) -1 H-pyrazole-4-carboxamide, m.p. 208-209 with „
Found,%: C 65.88; H 5.39; N 21.90.
C ,.
Calculated,%; C 65/13} H 5.55;
N 22.03.
P. and Mer 85. 5-Cyano-1-phenyl-1H-pyrazole-4-carboxamide, m.p. 178-179.
Found,%: C 62.13; H 3.76 | N 26.36.
.
N1,%: C 62.26; H 3.80; N 26J40.
EXAMPLE 86 5-Cyano-1-phenyl-K-methoxy-1H-pyrazole-A-carboxamide m.p. 163-16 ° C.
Found,%: C 59.63; H 3.92; N 22.93.
CnHioN O.
Calculated,%: C 59.50; H 4.16; N 23.13.
Example 87. 5-Cyano-1-phenyl-N-methyl-N-methoxy-1K-pyrazole-4-carboxamide, mp. 129 ° C.
Found,%: C 61.06; And 4.57; N 21.68.
C ,, H, 2N40.
Calculated,%: C 60.93; H 4.72; N 21.86.
Example 88, 5-Cyano-1-Fensch-1-N, N-diethyl-1H-pyrazole-4-carboxamide oil.
Found,%: C 66.88; H 5.96; N 20.63.
C ,, H, 6N40.
Calculated,%: C 67.15; H 6.01;
N 20.88.
I
PRI me R 89. 1-G (5-Cyano-1-phenyl-1H-pyrazol-4-yl) carbonyl-pyrrolidine, mp. 139-140 C.
Found,%: C 67.87; H 5.52; N 21.07.
C, 5 H, 4 N40.
Calculated,%: C 67.65; H 5.30; N 21.04;
EXAMPLE 90. 5-Cyano-1-phenyl-N, N-dipropyl-1H-pyrazole-4-carboxamide, oil.
Found,%: C 68.70; H 6.57; N 18.89.
.
Calculated,%: C 68.90; H 6.80; N 18.90.
EXAMPLE 91 5-Cyano-1- (4-methylphenyl) -N, N-dimethyl-1H-pyrazole-4-carboxamide, m.p. 149-150 C.
Found,%: C 65.88; H 5.28; N 21.82.
С44Н „40Calculated,%: С 66.13; H 5.55. N 22.03.
Example 92 5-Cyano-1- (4-fluorophenyl) -H-cycloprop-11-1 H-pyrazole-4-carboxamide, m.p. 185-187 C.
Found,%: C 61.95; H 3.83; N 20.54,
C, 4H „FN40.
Calculated,%: C, 62.22; H 4.10; M 20.73.
PRI me R 93. H-Cyano-1-phenyl-N-methyl-N-2-propyl-1H-pyrazole-4-carboxamide, mp. 47-50 ° C. Found,%: C 67.83; H 5.09;
N 20.76.
C ,, H, 4N40.
Calculated,%: C 67.65; H 5.30; N 21.04.
Example 94. 5-Cyano-1-phenyl-N-methyl-M-cyclopropyl-1 H-pyrazole - carboxamide, m.p. 79-81 S.
Found,%: C 67.44; H 5.13; N 21, 0 (G., 4N40.
Calculated,%: C 67.65; H 5.30; N 21.04.
Herbicidal effect of compounds. Test solutions are prepared for use by dissolving the corresponding compound in a solvent containing Toximul R and Toximul S (mixtures of anionic and non-ionic surface active agents from Stepan Company, Northfield, Illinois) and a mixture of acetone and ethanol 1: 1 (1 v / v) The solution is diluted with deionized water and applied prior to emergence. The degree of herbicidal activity is determined by the distribution of the treated plants in categories 1 to 5 (1 - no damage, 2 - light damage, 3 - moderate damage, 4 - serious damage, 5 - plants did not yield any growth).
Lower concentrations of test compounds are obtained by serially dissolving the described formulation in a mixture of a surfactant containing solvent and deionized water.
The table shows the herbicidal activity of the compounds of formula (I) in comparison with the known compound.
As can be seen from the table, compounds (l) are superior to the lime herbicide against any of the weeds. In this way, the compounds (I) have a high herbicidal activity and can be used in agriculture.

权利要求:
Claims (1)
[1]
Invention Formula
The method of obtaining pyrazole derivatives of the general formula
H, l) J-Tr-N
Chg
N
R) - C-C-alkyl or a group of formulas
4 (R.)
m
m or
Rj and Rj are each independently hydrogen, C, -C-alkyl,, -alkenyl,
Sz C -cycloalkyl or
alkoxy.
RJ and RJ taken together with the nitrogen atom, the KJ to which they are attached, form a piperidine, morpholine or Nirrolidine ring;
0
R is each independently halogen, C-C4 alkyl, C (-C4 alkoxy, C4-C4-haloalkyl, cyano; m O.iJ, provided that when R is C-C4-alkyl, this substituent exists for something other than 2 or 6, the position of the phenyl ring, and when R is Ci-Cj-alkoxy, R3 is different from C, -C, -alkoxy,
characterized in that
pyrazole of general formula
Rn jng
OB 5
where R4 has the indicated meanings;
RJ is hydrogen or lower alkyl, 0 is reacted with an amine of the general formula
HNRgR where R,, 2. and R j have the indicated values ™
neither
5 with the selection of the target product in free form.
five
Table continuation
25
1A22996
26
Pr CL r-f;.: NEETA BLU XIL
27
0.5 (0.56) 4, -O- (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
4.0 (4.48)
2.0 (2.24)
1.0 (t, 12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24
4 4 5 4 2 3 3 2 2 5 3 3 4 4 3 1 3 3 3 4 4 4 2 5 4
1422996
28 Continuation of the table
4 4 4 4 3 4 4 3 1 5 4 4 4 4 4 3 3 3 2 4 3 3 2 4 3
4 4 5 5 4 3 4 5 1 4 4 2 4 A 3 3 4 4 3 4 4 3 3 5 4
5 4 4 3 3 4 2 1 1 4 4 4 1 4 2 2 3 3 2 3 3 3 3 3 4
5 5 5 4 3 4 5 5 1 3 2 2 2 2 4 1 3 3 3 3 3 3 3 2 5 5
29
1422996
3
four
6
7
9
2
1.0 (1.12)
0.5 (0.56) 4.0 (4.48) -2.0 (2.24) 1.0 (1.12) 0.5 (0.56) 4.0 (4.48) 2 , 0 (2.24) 1.0 (1.12), 6.5 (0.56) 4.0 (4.48; 2.0 (2.24) 1.0 (1.12 j 0.5 (0.56) 4.0 (4.48) 2.0 (2.24) 1.0 (1.12) 0.5 (0.56) 4.0 (4.48) 2.0 (2 , 24) 1.0 (1.12) 0.5 (0.56) 4.0 (4.48) 2.0 (2.24) 1.0 (1.12)
3 3 5 5 4 4 4 4 4 2 4 4 4 3 .2 2 2 2 4 4 3 3 4 4 4
four
3
five
five
five
five
five
five
five
four
five
five
four
four
five
five
four
four
five
five
five
four
five
five
five
30 Continuation of the table
3
2 5 5 5 4 4 5- 4 4 5
-i 5 4 4 4 2 2 5 5 4 1 5
H 5
3
one
four
3
2
3
five
five
four
one
3
2
3
one
2
2
2
. 1 5 5 2 2 4 2
. 2
3 2
5 5
. 5 3 5 4 4 4 5 5 4 5 k 2 2 2
. 5 5 3 2 2 5
31
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4, 48)
2.0 (2.24)
1.0 (1.12)
0.5 (0.56)
4.0 (4.48)
2.0 (2.24)
1.0 (1.12)
4 ,,, 48)
3 4 4 4 3 4 4 3 3 4 4 3
; 2
5 4 4
with
2 4 4 3 4
3 3 1 4
1A22996
32 Continuation of the table
4 5 4 5 4 5 5 4 4 4 5 4 2 5 5 3 3 4 2 2 1
1 1 1 5
3
five
five
four
four
four
four
four .
four
four
four
3
2
S
four
four ,
3
four
3
2
one
2 2 1 4
2 4 3 4 4 5 5 3 3 3 3 2 1 5 5 3 3 3 3 3 1
1 1 1 4
2
four
3
five
3
five
five
four
3
five
five
five
one
five
five
four
2
3
one
3
one
2 2 1
four
33
1422996
FOR Continuation of the table
Extended; Kenne Table
39
83
87
eight
one
2
four
0.5 (0.56) A, O (4, A8) 2.0 (2.24) 1.0. (1.12) 0.5 (0.56) 4.0 (4.48) 2 , 0 (2.24) 1.0 (1.12) 0.5 (0.56) 4.0 (4.48) 2.0 (2.24) 1.0 (1.12) 0.5 (0.56) 4.0 (4.48) 2.0 (2.24) 1.0 (1.12) 0.5 (0.56) 4.0 (4.48) 2.0 (2 , 24) 1.0 (1.12) 4.0 (4.48) 2.0 (2.24) 1.0 (1.12)
3
5 5 4 4 4 4 4 3 4 4
four
2:
four
3
2
2
five
5 5 5 5 4
1- (2-Occipro ps1) -3- nitro1422996
iO Continuation of the table
3 5 4 3 3 4 4 3 3 4 5 4 1
four
four
3
3
3
five
2
five
five
five
2 5 5 5 3 3 5 3 3 5 3 2 1
four
five
3
2
3
five
five
five
five
3
2 5 4 3 1
5 5 4 2 5 5 4 2 3 3
2 1 3
3 3 3 4 3
3 5 5 5 3 5 5 5 5 5 5
3 1
5 5
4 4 3 4 5 5 5 5
41
1422996
4.0 (4.48) 2.0 (2.24) (1.12)
2 2 2
.42 Continuation of the table
2 2 2
2 2 2
1 2 2
2 2 2

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同族专利:

公开号 | 公开日

AR240808A1|1991-02-28|

CY1517A|1990-11-16|

GB2149403A|1985-06-12|

HU196112B|1988-10-28|

GB8427972D0|1984-12-12|

DK527784A|1985-05-08|

EG17046A|1991-03-30|

GR80848B|1985-03-05|

IL73418A|1988-02-29|

SG75889G|1990-04-20|

BR8405645A|1985-09-10|

ES546905A0|1986-03-01|

FI844348L|1985-05-08|

ES8604886A1|1986-03-01|

EP0151867B1|1990-01-10|

AT49404T|1990-01-15|

IL73418D0|1985-02-28|

PH22069A|1988-05-20|

GB2149403B|1987-10-28|

ZA848666B|1986-01-29|

DK527784D0|1984-11-06|

CA1227483A|1987-09-29|

FI844348A0|1984-11-06|

AR240808A2|1991-02-28|

NZ210124A|1987-06-30|

ES8603837A1|1986-01-01|

KR850003719A|1985-06-26|

ES537400A0|1986-01-01|

SU1447281A3|1988-12-23|

PT79463B|1986-12-11|

AU572913B2|1988-05-19|

DE3480999D1|1990-02-15|

EP0151867A2|1985-08-21|

GT198400140A|1986-04-29|

HK2090A|1990-01-19|

HUT36345A|1985-09-30|

JPS60172968A|1985-09-06|

PT79463A|1984-12-01|

AU3514884A|1985-05-16|

EP0151867A3|1987-04-01|

引用文献:

公开号 | 申请日 | 公开日 | 申请人 | 专利标题

US4134987A|1976-01-14|1979-01-16|Huppatz John L|Compounds and compositions|

CA1156661A|1980-02-25|1983-11-08|Hoffmann-La Roche Limited|Phenoxy-aminopropanol derivatives|

EP0178035B1|1984-05-12|1990-01-03|FISONS plc|Anti-inflammatory 1,n-diarylpyrazol-3-amines, compositions containing them and processes for their preparation|DE3520330A1|1985-06-07|1986-12-11|Bayer Ag, 5090 Leverkusen|5-AMINO-1-PYRIDYL-PYRAZOLE|

EP0206523B1|1985-06-18|1991-12-04|Imperial Chemical Industries Plc|Heterocyclic compounds as fungicides|

DE3540839A1|1985-11-18|1987-05-27|Bayer Ag|1-ARYL-PYRAZOLE|

KR870008849A|1986-03-19|1987-10-21|메어리 앤 턱커|Pyrazoles having germ killing effect|

US4801326A|1986-03-19|1989-01-31|Eli Lilly And Company|1-phenylpyrazole-4,5-dicarboxylic acid derivatives, composition containing them, and pollen formation inhibiting method of using them|

EP0273572B1|1986-12-16|1996-01-24|Zeneca Limited|Pyrrole derivatives and their use in agriculture|

DE3934924C2|1989-10-20|1994-01-27|Huels Chemische Werke Ag|Process for the preparation of 4-alkoxycarbonyl-3-chloromethyl-2H-pyrazoles|

DE4007566C2|1990-03-09|1998-07-16|Siemens Ag|Power amplifier for feeding an inductance with switched transistors|

WO1992019615A2|1991-04-24|1992-11-12|E.I. Du Pont De Nemours And Company|Fungicidal pyrazoles, pyrazolines and tetrahydropyridazines|

ID21775A|1996-10-25|1999-07-22|Yoshitomi Pharmaceutical|COMPOUND 1-PHENILPIRAZOL COMPOUNDS AND THE USE OF PHARMACIES|

EP1275301A1|2001-07-10|2003-01-15|Bayer CropScience S.A.|Trisubstituted heterocyclic compounds and their use as fungicides|

AU2003292820A1|2002-12-27|2004-07-29|Sankyo Agro Company, Limited|4-amino-5-methylpyrazole derivatives and process for production thereof|

WO2009116151A1|2008-03-19|2009-09-24|アグロカネショウ株式会社|1-phenyl-5-difluoromethylpyrazole-4-carboxamide derivatives and herbicides containing the derivatives as the active ingredient|

CN104628645B|2014-12-23|2017-01-25|浙江工业大学|Pyrazole-containing bishydrazide compound and preparation method and application thereof|

法律状态:

优先权:

申请号 | 申请日 | 专利标题

US54913383A| true| 1983-11-07|1983-11-07|

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