Advances in Heterocyclic Chemistry, 82, 1-99 (2002)

Synthesis and Properties of Acetylenic Derivatives of Pyrazoles

Sergei F. Vasilevsky and Eugene V. Tretyakov

Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, 630090, Novosibirsk, Russian Federation.

José Elguero

Instituto de Quimica Medica, Centro de Quimica Organica "Manuel Lora Tamayo", C.S.I.C., Juan de la Cierva, 3, E-28006 Madrid, Spain.

Table I. Dependence of the Yield of Alkynylpyrazoles and their N-Methyl Derivatives on the Composition of Diyne/Diazomethane Mixture and Reaction Time [71CAS1731]. 

Table II. Alkynylpyrazoles Prepared by Cyclization of 1,3-Diynes with Diazomethane [41LA279, 57CB124, 57JCS2012, 58CB1841, 60CB1931, 65ZOR610, 68LA113, 68LA124, 69IZV2546, 71CAS1731, 71ZOB2230, 76MI1, 78MI3, 84MI1, 86MI2, 87MI1, 87MI2, 87TL3981, 93ZOB1107, 94BSJ1717, 95JMC5015]. 

Table III. Alkynylpyrazoles Prepared by Cyclization of Alkynes with Diazocompounds [68CB3700, 68LA113, 88JOM247, 91ZOB2286]. 

Table IV. 4-Alkynylpyrazoles Prepared from Enynes and Diazomethane [97JCS(P1)695]. 

Table V. Alkynylpyrazoles Prepared by Cyclization of Diynones with Hydrazine [68LA113, 68T4285, 73S47, 74JOC843, 74ZOR136, 74ZOR730, 74ZOR1510]. 

Table VI. Alkynylpyrazoles Prepared by Cyclization of Diynones with Substituted Hydrazines [68T4285, 74JOC843, 74ZOR136, 74ZOR730, 75ZOR47, 76T1293]. 

Table VII. Monosubstituted Acetylenylpyrazoles Prepared by Elimination [69IZV927, 69KGS1055, 76IZV2288, 87KGS915]. 

Table VIII. Halogenopyrazoles Prepared by Elimination [69IZV927, 76IZV2288, 99USP5925769]. 

Table IX. Disubstituted Acetylenylpyrazoles and Acetylenylindazoles Prepared by Elimination [73JCS(P1)2008, 75KGS1678, 87KGS787, 89EUP299209, 90EUP379979, 92USP510286993EUP571326]. 

Table X. 5-Alkynylpyrazoles Prepared by Pd/Cu or Cu-Catalyzed Couplings between Acetylenes and Pyrazolyliodides [71IZV1764, 83IZV688, 85MI1, 86TH1, 90IZV2089, 92IZV507, 99JCS(P1)3713, 2000TL4713]. 

Table XI. 3-Alkynylpyrazoles Prepared by Pd/Cu-Catalyzed Couplings between Acetylenes and Pyrazolylhalides [81IZV1342, 86TH1, 99JCS(P1)3713] 

Table XII. 4-Alkynylpyrazoles Prepared by Pd/Cu or Cu Catalyzed Couplings between Acetylenes and Pyrazolylhalides [71IZV1764, 72IZV2524, 81IZV1342, 85MI2, 86TH1, 87USP4663334, 88MOC253, 93EUP571326, 93JHC755, 95SL1115, 96ADD193, 96INP9640704, 96MCR293, 96BML1279, 97EUP770610, 98JOC1109, 98EUP846686, 98MO76, 99EUP933363, 99EUP967205, 99JCS(P1)3713, 2000JMC953]. 

Table XIII. Polyalkynylpyrazoles Pprepared by Cu or Pd/Cu-Catalyzed Couplings between Acetylenes and Pyrazolylhalides [71IZV1764, 72IZV2524, 86TH1, 92IZV507]. 

Table XIV. Alkynylpyrazoles Prepared by Condensation of Copper(I) Acetylides with Pyrazolyliodides [83IZV688, 86MI1, 90IZV2089, 99JCS(P1)3713, 2001UP5]. 

Table XV. Acetylenic Derivatives of Annelated Pyrazoles Prepared by Pd/Cu-Catalyzed Couplings between Acetylenes and Hetarylhalides [92T8089, 97NN821, 98JCS(P1)3233, 99H513, 99HCA1640, 99JCS(P1)479]. 

Table XVI. (Pyrazol-3-yl)-alk-3-yn-2-ols and the (Indazol-3-yl)-alk-3-yn-2-ol Prepared by Favorsky Reaction [68KGS695, 78KGS1535]. 

Table XVII. Examples of Alkynylpyrazoles Prepared from 1-Bromoalkynes (99USP5925769). 

Table XVIII. Di(pyrazolyl)butadiynes and Di(pyrazolyl)octatetraynes Prepared by Homo-coupling Reaction [69IZV2546, 69KGS1055, 86TH1] 

Table XIX. Alkynylpyrazoles Prepared by Cross-coupling Reactions of Ethynylpyrazoles with sp- and sp2-halides [69IZV2546, 69KGS1055, 86TH1, 96MC98, 2001IZV1210, 2001UP3]. 

Table XX. Aminomethylethynylpyrazoles Prepared by the Mannich Reaction [72IZV2524, 90MIP1]. 

Table XXI. Halogenoethynylpyrazoles Prepared by Reaction of Ethynylpyrazoles with KOX [76IZV2292, 77IZV2306, 86TH1]. 

Table XXII. Ethynyl- and Polyethynylpyrazoles Prepared by Retro-Favorsky Reaction [69IZV2546, 69KGS1055, 71IZV1764, 72IZV2524, 86TH1, 88MOC253]. 

Table XXIII. Ethynyl- and Polyethynylpyrazoles Prepared by Desilylation, Destannylation and Decarboxylation Reaction [71ZOB2230, 73S47, 75KGS1678, 88MOC253, 96BML1279, 96MCR293]. 

Table XXIV. Reactions of Halogenoethynyl-1-methyl-pyrazoles with NaNH2 [69IZV2546, 69KGS1055, 73IZV2166, 76IZV2148, 76IZV2292, 77IZV2306]. 

Table XXV. Pyranopyrazoles Prepared by Cyclocondensation of vic-Iodopyrazolecarboxylic Acid with Copper(I) Acetylides [86TH1, 78IZV1175, 81IZV902, 81IZV1342]. 

Table XXVI. Pyranopyrazoles Prepared by Cyclization of Vicinal (Alkyn-1-yl)pyrazolecarboxylic acid [81IZV1342]. 

Table XXVII. 1-Methyl-1,6-dihydro-pyrazolo[3,4-c]pyridin-7-ones Prepared by Cyclization of Vicinal 4-(Alkyn-1-yl)pyrazole-5-carboxylic acid Amides [90IZV2089]. 

Table XXVIII. 6-Amino-1-methyl-1,6-dihydro-pyrazolo[3,4-c]pyridin-7-ones Prepared by Cyclization of 4-(Alkyn-1-yl)pyrazole-5-carboxylic acid Hydrazides [85IZV1367, 85MI2]. 

Table XXIX. 1-Methyl-1,6-dihydro-pyrazolo[3,4-d]pyridazin-7-ones Prepared by Cyclization of 4-(Alkyn-1-yl)pyrazole-5-carboxylic acid Hydrazides [85IZV1367, 85MI2]. 

Table XXX. Pyrazolopyridazines Prepared by Cyclization Followed by Diazotization of Vicinal (Alkyn-1-yl)aminopyrazoles [95LA775, 98HC519, 99JCS(P1)3721].