Some piperazino analogues of methadone and related ketones: a novel conversion of an N-carbethoxy to a triethylmethyl group

1969 ◽  
Vol 47 (13) ◽  
pp. 2413-2419
Author(s):  
J. R. Dimmock ◽  
N. J. Harper ◽  
R. Islam ◽  
A. F. Casy
Keyword(s):  
Cyano Group ◽  
Magnesium Bromide ◽  
Dimethylamino Group ◽  
Ethyl Magnesium Bromide ◽  
Derivatives Of ◽  
Related Compounds

A number of derivatives of methadone and related compounds have been prepared, where the dimethylamino group has been replaced by a 4-substituted piperazino function. The preparation of these compounds involved the reaction of N-ω-cyanoalkyl-N′-carbethoxy piperazines with ethyl magnesium bromide, and various products were obtained. These included replacement of the N′-carbethoxy group by a triethylmethyl function and cleavage of the carbethoxy group. In some cases the ω-cyano group reacted to give the corresponding ketone. Reactions of 1-benzyl-4-carbethoxy piperazine with ethyl magnesium bromide and phenyl magnesium bromide gave no evidence for the formation of the triethylmethyl group. However, cleavage of the carbethoxy group occurred and there was evidence for the formation of the corresponding amide.

scholarly journals Laser Induced Fluorescence of 4-N,N-Dimethylaminobenzonitrile (DMABN) and Related Compounds

1988 ◽  
Vol 9 (4-6) ◽  
pp. 317-337 ◽  
Author(s):  
Anita C. Jones ◽  
David Phillips
Keyword(s):  
Polar Solvent ◽  
Cyano Group ◽  
Solvent Molecule ◽  
Laser Induced Fluorescence ◽  
Solvent Mixtures ◽  
Decay Kinetics ◽  
Dimethylamino Group ◽  
Fluorescence Studies ◽  
Decay Times ◽  
Related Compounds

The role of polar solvent in determining the photophysics of normal (b*) and anomalous (a*) fluorescence from 4-N,N-dimethylaminobenzonitrile (DMABN) and related compounds has been investigated by means of picosecond time-resolved fluorescence studies in non-polar/polar solvent mixtures, and by electronic spectroscopic studies on complexes of 1:1 stoichiometry prepared by nozzle expansion. The solution phase results indicate clearly that a DMABN-polar solvent complex is formed initially in either ground or excited state, and that this rearranges to a geometry from which the b* to a* state transition can occur. Specific solvent-solute interactions are clearly indicated by this work, and these lead to the necessity of modelling b* state decay kinetics in solution by a distribution of decay times.Laser induced fluorescence studies of jet-cooled solvated complexes of DMABN and the related molecule 4-aminobenzonitrile (4-ABN) provide evidence for the existence of 1:1 complexes involving interaction of a protic solvent molecule with either the cyano group or the amino group. In the case of 4-ABN both types of complex are fluorescent whereas in the case of DMABN, those complexes involving interaction with the dimethylamino group appear to be non-emissive. This behaviour may be due to formation of DMABN-solvent exciplex which constitutes a dark state under jet-cooled conditions. Neither the DMABN bare molecule nor the observed 1:1 solvated complexes exhibit a* emission in the jet.

Synthesis of 5,7-dihydroxynaphthoquinone derivatives and their reactions with nucleophiles: Nitration of 2,3-dimethylnaphthalene and subsequent transformations

1976 ◽  
Vol 29 (10) ◽  
pp. 2247 ◽  
Author(s):  
HJ Banks ◽  
DW Cameron ◽  
MJ Crossley ◽  
EL Samuel
Keyword(s):  
Unusual Reaction ◽  
Nitro Derivatives ◽  
Reactions With Nucleophiles ◽  
Derivatives Of ◽  
Related Compounds ◽  
Benzenoid Ring

5,7-Dihydroxy-2,3-dimethyl-l,4-naphthoquinone (5) and related compounds have been synthesized. The quinone affords an accessible substrate for studying an unusual reaction with nucleophiles, which involves attack at the 8-position, i.e. at the benzenoid ring. An unsuccessful approach to (5) has led to tri- and tetra-nitro derivatives of 2,3-dimethylnaphthalene. Reduction of the former and subsequent conversions have given aminonaphthoquinone and perimidinone derivatives.

A synthesis of alkylated 3-aminoisoquinolines and related compounds

1982 ◽  
Vol 35 (7) ◽  
pp. 1391 ◽  
Author(s):  
AJ Liepa
Keyword(s):  
Phosphoryl Chloride ◽  
Tertiary Amides ◽  
Derivatives Of ◽  
Related Compounds ◽  
Selection Of

N,N-Dialkyl derivatives of 3-aminoisoquinoline have been prepared by reaction of nitriles with various arylacetic acid tertiary amides in the presence of phosphoryl chloride. The synthesis has been extended to include a benzoisoquinoline and annulated isoquinolines by the selection of appropriate amide and nitrile precursors.

Structural preferences for the double bond position in some unsaturated 3,3-diphenylpyrrolidines

1970 ◽  
Vol 48 (23) ◽  
pp. 3742-3745 ◽  
Author(s):  
M. M. A. Hassan ◽  
A. F. Casy
Keyword(s):  
Double Bond ◽  
Methyl Iodide ◽  
Quaternary Salt ◽  
Double Bond Position ◽  
Magnesium Bromide ◽  
Free Base ◽  
Spectroscopic Evidence ◽  
Structural Preferences ◽  
Ethyl Magnesium Bromide ◽  
Sole Product

The reaction between 3,3-diphenyl-3-cyano-1-methylpropyl isocyanate and ethyl magnesium bromide leads to 2-ethyl-5-methyl-3,3-diphenyl-1-pyrroline rather than the isomeric 2-ethylidenepyrrolidine. The protonated N-methyl analogue (identical with a major metabolite of methadone) retains the 1-pyrroline structure, but the free base is a cis-trans mixture of the corresponding 2-ethylidenepyrrolidines; the cis Me/Ph isomer preponderates and is the sole product (obtained as a quaternary salt) when the mixture is treated with methyl iodide. 5-Methyl-2-methylene-3,3-diphenylpyrrolidine, a lower homologue of the methadone metabolite, isomerizes to a 1-pyrroline derivative when protonated or methylated. All structural conclusions are based on i.r. and p.m.r. spectroscopic evidence.

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