1 -Methyl-5-nitro-4-piperidino

The ortho indirect deactivating effect of the two methyl groups in 2,6-dimethyl-4-nitropyridine 1-oxide (163) necessitates a much higher temperature (about 195°, 24 hr) for nucleophilic displacement of the nitro group by chloride (12iV HCl) or bromide ions N HBr) than is required for the same reaction with 4-nitropyridine 1-oxide (110°). With 5-, 6-, or 8-methyl-4-chloroquinolines, Badey observed 2-7-fold decreases in the rate of piperidino-dechlorination relative to that of the des-methyl parent (cf. Tables VII and XI, pp. 276 and 338, respectively). 

Chlor-2-nitro-l -piperidino- 692 4-Chlor-l-nitroso- 478 Chlorsulfonyl-methyl- 680 Deutero- 623... 

Nitromethyl-l-oxo-cycloalkane bzw. 1-Nitromethyl-cycloalkene lassen sich mit Pyrro-lidinen oder (S,)-2-Methoxymethyl-pyrrolidin bzw. -piperidin in Acetonitril bei 20° unter Austausch der Nitro-Gruppe in guten Ausbeuten in 2-(Pyrrolidino-methyl)-l-oxo-cycloalkane3 bzw. l-(Piperidino-methyl)-cycloalkene8 uberfuhren (s.a. S. 378) ... 

Some fragmentation pathways of 4(5)-piperidino-, 4(5)-pyrrolidino- and 4(5)-morpholinosubstituted 5(4)-nitro-2-methylimidazoles [1303], and l-organyl-2-methyl-4-nitroimidazoles and their 5-iodo derivatives have been studied [1304],... 

Azido-2,2-dimethyl-8-oxo-E16b, 723 (CH - C-N3) lH-Pyrazol 4-Nitro-3(5)-piperidino-E8b, 598 (N02 - NR2) Pyrimidin 5-Ethoxycarbonyl-2-hydrazino-4-methyl- El 6a, 771 (SR - NH-NH2) lH-Tetrazol l-(l-Carboxy-2-methyl-... 

Methylenamino- 1 32 (4-Methyl-phenyl)- 124 (4-Methyl-piperazino)- 122 [ l-Mcthyl-piperidyl-(3)]- 141 Morpholino- 132 (4-Nitro-benzoylamino)- 527 (2-Nitro- 4.5-dimethoxy-phenyl)- 465 [2-(bzw. 3, bzw. 4)-Nitro-phenyl]-527 Phenyl- 25. 113, 114, 115, 117, 119, 123, 683 Phenyl-(3-amino-phenyl)- 545 Piperidino- 122, 132 (2-Piperidino-athylamino)- 132 (3-Pipcridino-propylamino)- 132 Piperidyl-(3)- 268 Pyridyl-(2)- 119 (3,4,5-Trimethyl-phenyl)- 315 Triphenyl- 683... 

Nitro- o) -(4-methyl-piperidino)- 52 7 -oxim 157, 252. 669 -1-phenyl-athylimin 233 -phenylimin 695 -1-phenyl-propylimin 233... 

Nitro-l-(l-chlor-phenyl)- 495 2-(l-Nitro-cyclohexyl)-l-pyridyl-(4)- 494 2-Nitro-1-furyl-(2)- 496 2-Nitro-l-pyridyl-(4)- 494 2-(4-Octyl-piperidino)-1-phenyl- 268 2-Oxo- l,2-bis- 4-methoxy-phenyl]- 601 2-Oxo- l,2-bis-[4-methyl-phenyl]- 601 2-Oxo-l,2-difuryl-(2)- 25 2-Oxo-1,2-diphenyl- 601... 

Nucleophilic and Radicaloid Substitution Reactions of Monocyclic Thio-phens. - The rate constants for the reaction of 5-substituted 2-bromo-3-nitrothiophens, in methanol, with various substituted anilines to give 5-substituted iV-(3-nitro-2-thienyl)anilines have been measured at various temperatures, It was found that the sensitivity parameters that were obtained from Hammett and Bronsted correlations were practically independent of the starting system. The kinetics of piperidino-substitution of methyl 2-methoxy-3-nitrothiophen-5-carboxylate and 5-acetyl-2-methoxy-3-nitrothio-phen, in which the methoxy-group is the leaving group, have been investigated and the mechanism has been discussed. 

Spinelli and co-workers have shown that linear free-energy or/Ao-correlations can be successfully established for the nucleophilic displacement reactions on activated halogenothiophenes. This has been validated on the benzenethiolate debromination of 2-bromo-3-A -5-nitrothiophenes (557) <91JCR(S)270>, the chlorine-isotopic exchange between ClLi, and some 2-chloro-3-3T-5-nitro-thiophenes (558) <88JCR(S)198>, and the piperidino-debromination of some 2-bromo-3-A -4-methyl-5-nitrothiophenes (559) <85JCS(P2)519>. 

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