Patent EP-2133341-A1 (EP)
IPC: C07D231/12
Filed: 2008-02-25
Abstract: Preparation of 1-alkyl-3-haloalkyl-pyrazol-4-carboxylic acid derivative (I), comprises (a) reacting a 2-acylated or 2-iminoalkylated acrylic acid derivative (II) with a N-alkyl hydrazone compound (III) to obtain an acrylic acid hydrazone compound (VI); (b) acylating (VI) with an acyl halide compound (X); (c) iminoalkylating (VI) with an alpha ,alpha -dihalo amine compound (XI); and (d) cyclizing the obtained intermediate products. Preparation of 1-alkyl-3-haloalkyl-pyrazol-4-carboxylic acid derivative of formula (I), comprises (a) reacting a 2-acylated or 2-iminoalkylated acrylic acid derivative of formula (II) with a N-alkyl hydrazone compound of formula ((R 8>)(R 9>)-C=N-N-R 1>) (III) to obtain an acrylic acid hydrazone compound of formula (VI); (b) acylating (VI) with an acyl halide compound of formula (R 2>-C(=O)-X) (X); (c) iminoalkylating (VI) with an alpha ,alpha -dihalo amine compound of formula ((R 2>)(X) 2-C-N(R 1> 0>)(R 1> 1>)) (XI); and (d) cyclizing the obtained intermediate products. R 1> : 1-12C-alkyl, 3-8C-cycloalkyl, 2-12C-alkenyl, 2-12C-alkynyl, 6-8c-aryl, 7-19C-arylalkyl or 7-19C-alkylaryl (all optionally substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CONR1a); R1a : H or 1-12C-alkyl; R 2> : 1-4C-alkyl (optionally substituted by 1-3 halo atoms of F, Cl or Br, or CF 3); Y 1> : (C=O)OR 3>, CN or (C=O)NR 4>R 5>; either R 3>-R 5> : 1-12C-alkyl, 3-8C-cycloalkyl, 2-12C-alkenyl, 2-12C-alkynyl, 6-8C-aryl, 7-19C-arylalkyl or 7-19C-alkylaryl (all optionally substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2); or R 4>R 5>N : a 5-6-membered ring optionally containing O, S or SO 2group and optionally substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2; Z : O, N +>R 1> 0>R 1> 1>(both preferred) or S; either R 1> 0>, R 1> 1> : 1-12C-alkyl, 3-8C-cycloalkyl, 2-12C-alkenyl, 2-12C-alkynyl, 6-8C-aryl, 7-19C-arylalkyl- or 7-19C-alkylaryl (all optionally substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2); or R 1> 0>R 1> 1>N : 5-6-membered ring optionally containing 1 or 2 further heteroatoms of O, S or SO 2and substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2; A : a leaving group, which is OR 1> 2>, SR 1> 2>or NR 1> 2>R 1> 3>; either R 1> 2>, R 1> 3> : 1-12C-alkyl, 3-8C-cycloalkyl, 2-12C-alkenyl, 2-12C-alkynyl, 6-8C-aryl, 7-19C-arylalkyl or 7-19C-alkylaryl (all optionally substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2); or R 1> 2>R 1> 3>N : 5-6-membered ring optionally containing 1 or 2 further heteroatoms of O, S or SO 2and substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2; either R 8>, R 9> : 1-12C-alkyl, 3-8C-cycloalkyl, 2-12C-alkenyl, 2-12C-alkynyl, 6-8C-aryl, 7-19C-arylalkyl or 7-19C-alkylaryl (all optionally substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2); or R 8>R 9>C : a 5-6-membered ring optionally containing O, S or SO 2and substituted by one or more R1a, X, OR1a, SR1a, N(R1a) 2, Si(R1a) 3, COOR1a, (C=O)R1a, CN or CON(R1a) 2; and X : F, Cl, Br or I. An independent claim is included for a 2-acylated or 2-iminoalkylated acrylic acid hydrazone compound of formula (VII). [Image] [Image].