Insecticidal aryl pyrrolidines
View Patent ↗The present invention provides novel aryl pyrrolidines having an excellent insecticidal action as insecticides. Aryl pyrrolidines represented by the formula (I) and use thereof as insecticide.
1. A method for the preparation of a compound of formula (I)
wherein
X which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylthio, C 1-12 alkylsulfinyl, C 1-12 alkylsulfonyl, C 1-12 haloalkylthio, C 1-12 haloalkylsulfinyl, C 1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C 1-12 alkylcarbonylamino, C 1-12 haloalkylcarbonylamino, benzoylamino, C 1-12 alkoxy-carbonylamino, C 1-12 haloalkoxy-carbonylamino, C 1-12 alkylsulfonylamino or C 1-12 haloalkylsulfonylamino;
Y which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylthio, C 1-12 alkylsulfinyl, C 1-12 alkylsulfonyl, C 1-12 haloalkylthio, C 1-12 haloalkylsulfinyl, C 1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C 1-12 alkylcarbonylamino, C 1-12 haloalkylcarbonylamino, benzoylamino, C 1-12 alkoxy-carbonylamino, C 1-12 haloalkoxy-carbonylamino, C 1-12 alkylsulfonyl amino or C 1-12 haloalkylsulfonylamino;
R represents C 1-12 alkyl or C 1-12 haloalkyl;
m represents 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2, or 3;
G is selected from the group consisting of
or a group selected from G1 to G9:
wherein
R 1 and R 2 each independently represent hydrogen; optionally substituted C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 3-7 cycloalkyl; C 1-12 alkylsulfonyl, C 1-12 haloalkylsulfonyl or CH 2 —R 7 ; or when taken together represent C 2-6 alkylene;
R 3 and R 4 each independently represent hydrogen, cyano; optionally substituted C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 3-7 cycloalkyl; or C 1-12 alkoxycarbonyl; or when taken together represent C 2-6 alkylene;
l represents 1 or 2 or 3;
R 5 represents hydrogen; C 1-12 alkyl; optionally substituted C 3-7 cycloalkyl; C 1 -6 haloalkyl; cyano; C 2-12 alkenyl; C 2-12 alkynyl; C 1-12 alkylcarbonyl; or CH 2 —R 7 ;
R 6 represents formyl, cyano, C 1-6 alkylcarbonyl, C 1-12 alkylthiocarbonyl, C 1-12 haloalkyl-carbonyl, C 1-12 haloalkylthiocarbonyl, C 1-12 alkylaminocarbonyl, C 1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C 1-12 alkoxyaminocarbonyl, C 1-12 alkoxyaminothiocarbonyl, C 1-12 alkoxycarbonyl, C 1-12 alkoxythiocarbonyl, C 1-12 thioalkoxycarbonyl, C 1-12 thioalkoxythiocarbonyl, CO—R 7 , CS—R 7 , C 1-12 alkylsulfonyl or C 1-12 haloalkylsulfonyl; or
R 5 and R 6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
Z which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylsulfonyl, C 1-12 haloalkylsulfonyl, hydroxyl or mercapto;
k 1 represents 0, 1, 2, 3 or 4;
k 2 represents 0, 1, 2 or 3;
k 3 represents 0 or 1;
k 4 represents 0 or 1;
R 7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C 1-12 alkyl; and
A represents C or N;
comprising reacting a compound of formula (II)
wherein
X, R and m are as defined above, with a compound of formula (III) or formula (III-a)
wherein
Y, A, G and n are as defined above, and
L 1 is halogen or a C 1 -C 4 haloalkylsulfonyloxy group.
2. The method according to claim 1 , wherein the compound of formula (II) and the compound of formula (III) or formula (III-a) are reacted in the presence of a base or in the presence of at least one metal catalyst.
3. The method according to claim 2 , wherein the metal catalyst is a transition metal catalyst selected from Pd 2 (dibenzylidene acetone) 3 , Pd 2 (dibenzylidene acetone) 3 CHCl 3 , Pd(OAc) 2 , CuI, and Cu 2 O.
4. The method according to claim 3 , wherein the reaction is performed in the presence of a phosphine ligand selected from 2,2′-bis(diphenylphosphino)-1,11′-binaphthaliene (BINAP), 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (Xantphos), and tributylphosphine, or in the presence of an amine ligand selected from 8-quinolinol, proline, and N,N-dimethylglycine.
5. The method according to claim 4 , wherein 1 mole of the compound of formula (II) is reacted with 1 to 3 moles of the compound of formula (III) or formula (III-a) in the presence of 1 to 3 moles of the base and a catalytic amount of Pd 2 (dibenzylidene acetone) 3 CHCl 3 and Xantphos in toluene.
6. The method according to claim 5 , wherein the compound of formula (II) is 3-(3,5-dichlorophenyl)-3-(trifluoromethyl)pyrrolidine and the compound of formula (IIIa) is N-(4-bromo-2-methylbenzyl)acetamide.
7. A method for the preparation of a compound of formula (I)
wherein
X which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylthio, C 1-12 alkylsulfinyl, C 1-12 alkylsulfonyl, C 1-12 haloalkylthio, C 1-12 haloalkylsulfinyl, C 1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C 1-12 alkylcarbonylamino, C 1-12 haloalkylcarbonylamino, benzoylamino, C 1-12 alkoxy-carbonylamino, C 1-12 haloalkoxy-carbonylamino, C 1-12 alkylsulfonylamino or C 1-12 haloalkylsulfonylamino;
Y which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylthio, C 1-12 alkylsulfinyl, C 1-12 alkylsulfonyl, C 1-12 haloalkylthio, C 1-12 haloalkylsulfinyl, C 1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C 1-12 alkylcarbonylamino, C 1-12 haloalkylcarbonylamino, benzoylamino, C 1-12 alkoxy-carbonylamino, C 1-12 haloalkoxy-carbonylamino, C 1-12 alkylsulfonylamino or C 1-12 haloalkylsulfonylamino;
A represents C or N;
R represents C 1-12 alkyl or C 1-12 haloalkyl;
m represents 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2, or 3;
G represents
wherein
R 3 and R 4 each independently represent hydrogen, cyano; optionally substituted C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 3-7 cycloalkyl; or C 1-12 alkoxycarbonyl; or when taken together represent C 2-6 alkylene;
l represents 1 or 2 or 3;
R 5 represents hydrogen; C 1-12 alkyl; optionally substituted C 3-7 cycloalkyl; C 1-6 haloalkyl; cyano; C 2-12 alkenyl; C 2-12 alkynyl; C 1-12 alkylcarbonyl; or CH 2 —R 7 ;
R 6 represents formyl, cyano, C 1-6 alkylcarbonyl, C 1-12 alkylthiocarbonyl, C 1-12 haloalkyl-carbonyl, C 1-12 haloalkylthiocarbonyl, C 1-12 alkylaminocarbonyl, C 1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C 1-12 alkoxyaminocarbonyl, C 1-12 alkoxyaminothiocarbonyl, C 1-12 alkoxycarbonyl, C 1-12 alkoxythiocarbonyl, C 1-12 thioalkoxycarbonyl, C 1-12 thioalkoxythiocarbonyl, CO—R 7 , CS—R 7 , C 1-12 alkylsulfonyl or C 1-12 haloalkylsulfonyl; or
R 5 and R 6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo;
R 7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C 1-12 alkyl;
comprising reacting a compound of formula (VIII) or formula (VIII-b):
wherein
X, Y, R, R 3 , R 4 , A, l, m, and n are as defined above, and
L 3 represents chlorine, bromine, iodine, C 1-4 alkylsulfonyloxy, C 1-4 haloalkylsulfonyloxy, arylsulfonyloxy or azolyl,
with a compound of formula (IX):
wherein
R 5 and R 6 are as defined above, optionally in the presence of a base.
8. A method for the preparation of a compound of formula (I)
wherein
X which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylthio, C 1-12 alkylsulfinyl, C 1-12 alkylsulfonyl, C 1-12 haloalkylthio, C 1-12 haloalkylsulfinyl, C 1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C 1-12 alkylcarbonylamino, C 1-12 haloalkylcarbonylamino, benzoylamino, C 1-12 alkoxy-carbonylamino, C 1-12 haloalkoxy-carbonylamino, C 1-12 alkylsulfonylamino or C 1-12 haloalkylsulfonylamino;
Y which may be same or different, represents halogen, C 1-12 haloalkyl, nitro, C 1-12 alkyl, C 1-12 alkoxy, cyano, C 1-12 haloalkoxy, C 1-12 alkylthio, C 1-12 alkylsulfinyl, C 1-12 alkylsulfonyl, C 1-12 haloalkylthio, C 1-12 haloalkylsulfinyl, C 1-12 haloalkylsulfonyl, hydroxyl, mercapto, amino, C 1-12 alkylcarbonylamino, C 1-12 haloalkylcarbonylamino, benzoylamino, C 1-12 alkoxy-carbonyl amino, C 1-12 haloalkoxy-carbonylamino, C 1-12 alkylsulfonylamino or C 1-12 haloalkylsulfonylamino;
A represents C or N;
R represents C 1-12 alkyl or C 1-12 haloalkyl;
m represents 0, 1, 2, 3, 4 or 5;
n represents 0, 1, 2, or 3;
G is
wherein
R 3 and R 4 each independently represent hydrogen, cyano; optionally substituted C 1-12 alkyl, C 2-12 alkenyl, C 2-12 alkynyl, C 3-7 cycloalkyl; or C 1-12 alkoxycarbonyl; or when taken together represent C 2-6 alkylene;
l represents 1 or 2 or 3;
R 5 represents hydrogen; C 1-12 alkyl; optionally substituted C 3-7 cycloalkyl; C 1-6 haloalkyl; cyano; C 2-12 alkenyl; C 2-12 alkynyl; C 1-12 alkylcarbonyl; or CH 2 —R 7 ;
R 6 represents formyl, cyano, C 1-6 alkylcarbonyl, C 1-12 alkylthiocarbonyl, C 1-12 haloalkyl-carbonyl, C 1-12 haloalkylthiocarbonyl, C 1-12 alkylaminocarbonyl, C 1-12 alkylaminothio-carbonyl, dialkylamino-carbonyl having from 2 to 8 carbon atoms, dialkylaminothio-carbonyl having from 2 to 8 carbon atoms, C 1-12 alkoxyaminocarbonyl, C 1-12 alkoxyaminothiocarbonyl, C 1-12 alkoxycarbonyl, C 1-12 alkoxythiocarbonyl, C 1-12 thioalkoxycarbonyl, C 1-12 thioalkox hiocarbonyl, CO—R 7 , CS—R 7 , C 1-12 alkylsulfonyl or C 1-12 haloalkylsulfonyl; or
R 5 and R 6 when taken together with the nitrogen to which they are attached to form a 3-6 membered ring which contains at least one N atom and, optionally at least another heteroatom selected from S and O, wherein the ring is optionally substituted with keto or thioketo; and
R 7 represents phenyl or a heterocyclic ring, which are optionally substituted with at least one substituent selected from fluorine, chlorine, bromine, iodine and C 1-12 alkyl;
comprising reacting a compound of formula (X) or formula (X-a):
wherein
X, Y, R, R 3 , R 4 , R 5 , A, l, m and n are as defined above, with a compound of formula (XI):
R 6 -L 4 (XI)
wherein
R 6 is as defined above, and
L 4 represents fluorine, chlorine, bromine, C 1-4 alkyl-carbonyloxy, C 1-4 alkoxycarbonyloxy, azolyl, C 1-4 alkylsulfonyloxy, C 1-4 haloalkylsulfonyloxy, or arylsulfonyloxy, optionally in the presence of a base.