Ping Zhong

Pd(II)-Catalyzed Dehydrogenative Olefination of Terminal Arylalkynes with Allylic Ethers: General and Selective Access to Linear (Z)-1,3-Enynes

This work demonstrates a green and efficient method to prepare 1,3-enynes via Pd(II)-catalyzed direct dehydrogenative olefination of terminal arylalkynes with unactived allylic ethers. Various terminal arylalkynes can participate in the reaction, stereoselectively affording the desired conjugated (Z)-1,3-enynes in moderate to good yields.

One-pot synthesis and crystal structure of N -acyl- N ′-[1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-1 H -pyrazol-5-yl]thioureas

Nine novel thiourea derivatives containing pyrazole rings have been prepared in good yields by the reaction of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole with acylisothiocyanates, which were generated in situ by potassium thiocyanate and different acyl chlorides in one pot. N-Benzoyl-N‘-[1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-1H-pyrazol-5-yl]thiourea was characterised by a single crystal X-ray diffraction study.

N-Acetyl-N′-{3-cyano-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]pyrazol-5-yl}thiourea

In the title molxadecule, C14H8Cl2F3N5OS, all bond lengths and angles are normal. Intraxadmolecular N—H⋯O hydrogen bonding influences the molxadecular conformation. The pyrazole and benzene rings make a dihedral angle of 72.5u2005(1)°. Weak interxadmolecular N—H⋯S hydrogen bonds link the molxadecules into centrosymmetric dimers.

1‐[2,6‐Dichloro‐4‐(trifluoro­meth­yl)phen­yl]‐5‐(4‐methyl­phenyl­sulfonamido)‐1H‐pyrazole‐3‐carbonitrile

The title compound, C18H11Cl2F3N4O2S, is a tricyclic amide with an overall `Y shape. The dihedral angle between the pyrazole and attached benzene rings is 97.6u2005(2)°. Interxadmolecular N—H⋯O hydrogen bonds, with an N(amide)⋯O(sulfonxadyl) separation of 2.929u2005(4)u2005A, link the molxadecules into centrosymmetric dimers.

1‐[2,6‐Dichloro‐4‐(trifluoro­meth­yl)phen­yl]‐5‐(phenyl­acetamido)‐1H‐pyrazole‐3‐carbonitrile

The molxadecule of the title compound, C19H11Cl2F3N4O, is a tricyclic amide with an overall U shape. The dihedral angles between the pyrazole and outermost benzene and phenyl rings are 89.4u2005(1) and 114.5u2005(1)°, respectively. In the crystal structure, interxadmolecular N—H⋯N hydrogen bonds, with an N(amide)⋯N(cyano) separation of 3.220u2005(7)u2005A, link the molxadecules into linear chains along the [110] direction.

5-Amino-1-[2,6-dichloro-4-(trifluoro­meth­yl)phen­yl]-4-(trifluoro­methyl­sulfan­yl)-1H-pyrazole-3-carbonitrile

The molxadecule of the title compound, C12H4Cl2F6N4S, exhibits disorder of both trifluoroxadmethyl groups. Crystal packing is realised by N—H⋯N hydrogen bonds.

Bis{5-amino-3-cyano-1-[2,6-di­chloro-4-(tri­fluoro­methyl)­phenyl]-1H-pyrazol-4-yl} di­sulfide aceto­nitrile disolvate

The dixadsulfide moiety in the title compound, C22H8Cl4F6N8S2·2C2H3N, has an overall Z shape. The molecule possesses a crystallographically imposed twofold rotation axis. The pyrazole and adjacent benzene ring make a dihedral angle of 88.16u2005(12)°. Intermolecular N—H⋯N hydrogen bonds link the amine groups with the acetoxadnitrile solvent molxadecules.

Synthesis and insecticidal activity of 5-substituted-sulfonylaminopyrazole derivatives

The reaction of 5-amino-3-cyano-1-(2, 6-dichloro-4-trifluoromethylphenyl) -1H-pyrazole and 5-amino-1-[2, 6-dichloro-4-(trifluoromethylphenyl]-4-trifluoromethylsulfinyl-1H-pyrazole-3-carbonitrile (Fipronil) with arylsulfonyl chlorides gave the 5-arylsulfonamides at room temperature in high yields. Some of these compounds had insecticidal activity against pests such as army worm and rice plant hopper.

5-Amino-1-(2-chlorophenyl)-1H-pyrazole-4-carbonitrile

In the title compound, C10H7ClN4, the dihedral angle between the pyrazole and benzene ring planes is 69.48u2005(7)°. The crystal structure is stabilized by two N—H⋯N hydrogen bonds.

4-Bromo-5-[(4-chlorobenzylidene)amino]-1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-1H-pyrazole-3-carbonitrile

The title compound, C18H7BrCl3F3N4, is an imine relevant to insecticides. The dihedral angles between the central pyrazole ring and the benzene ring planes are 84.3u2005(2) and 68.5u2005(2)°.