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1. |
The reactions of the trifluoromethyl disulfide group, CF3SS—, with ammonia and amines. A new preparation of sulfenamides |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 429-432
M. E. Peach,
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摘要:
Bistrifluoromethyl disulfide reacts with ammonia and primary and secondary amines, forming the compounds CF3SNH2, RNHSCF3, and R2NSCF3, respectively; also produced are ammonium fluoride and thiocyanate, or a substituted thiourea and hydrogen fluoride, which forms a salt with the amine or thiourea.Simple sulfenamides, RSNH2, can be prepared from ammonia and a trifluoromethyl disulfide, RSSCF3; ammonium fluoride and thiocyanate are also produced. Since the trifluoromethyl disulfides are formed from thiols and trifluoromethanesulfenyl chloride, the reaction offers a simple method for the conversion of thiols into sulfenamides.The new compoundsN-propyltrifluoromethanesulfenamide,N,N-diethyltrifluoromethanesulfenamide, bispentafluorobenzenesulfenimide, pentafluorophenyltrifluoromethyl disulfide, andn-propyltrifluoromethyl disulfide have been prepared and characterized.
ISSN:0008-4042
DOI:10.1139/v67-076
出版商:NRC Research Press
年代:1967
数据来源: NRC
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2. |
The alkaloids ofLycopodium cernuumL. I. The structures of cernuine and lycocernuine |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 433-443
W. A. Ayer,
J. K. Jenkins,
S. Valverde-Lopez,
R. H. Burnell,
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摘要:
Structures IV and V are proposed for cernuine and lycocernuine, respectively, the major alkaloids present inLycopodium cernuumL. The chemical and physical properties on which these structures are based are described. A possible mode of biogenesis of these alkaloids is discussed.
ISSN:0008-4042
DOI:10.1139/v67-077
出版商:NRC Research Press
年代:1967
数据来源: NRC
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3. |
The alkaloids ofLycopodium cernuumL. II. The stereochemistry of cernuine and lycocernuine |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 445-450
W. A. Ayer,
J. K. Jenkins,
K. Piers,
S. Valverde-Lopez,
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摘要:
The relative stereochemistries of cernuine (I) and lycocernuine (II) have been derived by a combination of chemical and physical methods. Evidence is presented which indicates that I and II also represent the absolute stereochemistry of these alkaloids. The stereochemistry of allocernuine is discussed, and the isomerization of allocernuine into epiallocernuine is described.
ISSN:0008-4042
DOI:10.1139/v67-078
出版商:NRC Research Press
年代:1967
数据来源: NRC
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4. |
The alkaloids ofLycopodium cernuumL. III. The synthesis of dihydrodeoxyepiallocernuine |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 451-459
W. A. Ayer,
K. Piers,
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摘要:
The synthesis of dihydrodeoxyepiallocernuine (IV) is described, as is the synthesis of the tricyclic compound XVI, a degradation product of lycocernuine. These syntheses provide a rigorous proof of the constitution of cernuine and lycocernuine, and also provide strong support for the stereochemistry assigned to these alkaloids.
ISSN:0008-4042
DOI:10.1139/v67-079
出版商:NRC Research Press
年代:1967
数据来源: NRC
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5. |
Pyrazolines. VII. Concerning the formation of olefins from the pyrolysis of pyrazolines |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 461-468
Donald E. McGreer,
Weh-Sai Wu,
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摘要:
The geometrically isomericcis- andtrans-5-3-methyl-4-ethyl-3-carbomethoxy-Δ1-pyrazolines were prepared and their pyrolysis and photolysis studied. The isomeric pyrazolines gave cyclopropane products of mixed stereochemistry, but predominantly with retention of the stereochemistry present in the starting pyrazoline. Each pyrazoline gave stereospecifically a different α,β-unsaturated ester product. This stereospecificity can be related to the structure of the pyrazoline through the requirement that the loss of nitrogen must be from the side of the pyrazoline that istransto the hydrogen at C-4.
ISSN:0008-4042
DOI:10.1139/v67-080
出版商:NRC Research Press
年代:1967
数据来源: NRC
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6. |
The C=S stretching vibration in the infrared spectra of some thiosemicarbazones |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 469-473
D. M. Wiles,
B. A. Gingras,
T. Suprunchuk,
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摘要:
The infrared spectra of some aldehyde and ketone thiosemicarbazones have been compared over the region 1 200 to 700 cm−1with the spectra of the corresponding selenosemicarbazones. A band in the former at 830 to 805 cm−1is replaced by a band in the latter at 800 to 775 cm−1, attributed tov(C==Se). No other systematic differences are observed in this spectral region. The formation of 1:1 Cu(I) complexes of the thiosemicarbazones results in the removal of bands in two regions, 1 110 to 1 075 cm−1and 830 to 805 cm−1, from the spectra of the uncomplexed thiosemicarbazones. It is concluded that there is a contribution fromv(C==S) in both regions, but that absorption in the lower region represents the more nearly pure C==S stretching vibration. Examination of the spectra ofN–methyl substituted thiosemicarbazones indicates that, even in this 830 to 805 cm−1region, C==S stretching is coupled with other vibrations, perhaps N—C—N stretching.
ISSN:0008-4042
DOI:10.1139/v67-081
出版商:NRC Research Press
年代:1967
数据来源: NRC
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7. |
The synthesis of lα-methylcortisone and lα-methylhydrocortisone |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 475-479
Masato Tanabe,
David F. Crowe,
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摘要:
The addition of methylmagnesium iodide to 17α,20;20,21-bismethylenedioxy-1,5-pregnadiene-3,11-dione and 17α,20;20,21-bismethylenedioxy-1,4-pregnadiene-3,11-dione yields 1α-methyl derivatives. These derivatives can be converted further into 1α-methylcortisone and 1α-methylhydrocortisone. The isolation of a 3-methylene-Δ1,4derivate is also described.
ISSN:0008-4042
DOI:10.1139/v67-082
出版商:NRC Research Press
年代:1967
数据来源: NRC
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8. |
Reductive cleavage with metal in liquid ammonia. II. Olefin formation in attempts at selective cleavage of methylS-benzyl-4,6-O-benzylidene-3-O-methyl-2-thio-α-d-altropyranoside and itsS-methyl analogue by sodium metal in liquid ammonia diluted with 1,2-dimethoxyethane |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 481-494
U. G. Nayak,
M. Sharma,
R. K. Brown,
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摘要:
When methyl S-benzyl-4,6-O-benzylidene-3-O-methyl-2-thio-α-d-altropyranoside (VI) in liquid ammonia was treated with metallic sodium, a reductive cleavage occurred to give methyl 3-O-methyl-2-thio-α-d-altropyranoside in an 85% yield. In the solvent 1,2-dimethoxy-ethane, the reaction of sodium with VI gave little, if any, reductive cleavage. Instead, a base-catalyzed elimination of methanol took place togivethe two olefins methyl,S-benzyl-4,6-O-benzylidene-2,3-didehydro-3-deoxy-2-thio-α-d-erythro-hexopyranoside (IX) andS-benzyl-4,6-O-benzylidene-l,2-didehydro-1-deoxy-3-O-methyl-2-thio-d-ribo-hexopyranose (X). Under the alkaline reaction conditions, IX isomerized partly to a third olefin, methyl.S-benzyl-4,6-O-benzylidene-3,4-didehydro-3-deoxy-2-thio-α-d-erythro(threo)-hexopyranoside (XI).In the mixed solvent liquid ammonia and 1,2-dimethoxyethane, sodium reacted with VI to give a 33% yield of the 2,3-olefin IX. Other products, no doubt present, were not isolated in this experiment.Three analogous olefins were obtained from the reaction of sodium or basic reagents with methyl 4,6-O-benzylidene-3-O,S-dimethyl-2-thio-α-d-altropyranoside (VIa) in 1,2-dimethoxyethane.
ISSN:0008-4042
DOI:10.1139/v67-083
出版商:NRC Research Press
年代:1967
数据来源: NRC
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9. |
The selective phosphylation of ethanolamine |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 495-500
R. Greenhalgh,
M. A. Weinberger,
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摘要:
In nonaqueous solvents under conditions where phosphylation of either of the functional groups of ethanolamine can occur, it is found that phosphofluoridates react exclusively with the hydroxyl group. ThisO-phosphylation appears to be specific for phosphofluoridates, since phosphochloridates, tetraethyl pyrophosphate, and ethylN,N-dimethylphosphoramidocyanidate react predominantly with the amino moiety. However, with these compounds the reaction is not as specific, someO-phosphylation being observed, especially with the last compound. Possible reasons for this difference in behavior are discussed.
ISSN:0008-4042
DOI:10.1139/v67-084
出版商:NRC Research Press
年代:1967
数据来源: NRC
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10. |
Structural biochemistry. IV. 3β-Hydroxy-17β-(l-prolyl)amino-androst-5-ene |
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Canadian Journal of Chemistry,
Volume 45,
Issue 5,
1967,
Page 501-507
G. R. Pettit,
R. L. Smith,
A. K. Das Gupta,
J. L. Occolowitz,
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摘要:
The synthesis of the title compound III was studied in detail and the following combination of methods was found reliable and convenient. The oxime derivative Ibof ketone lawas reduced with sodium–ethanol to 3β-hydroxy-17β-amino-androst-5-ene. The configurational assignment for amine IIawas supported by the results of a comparison with the 17α-epimer and by a proton magnetic resonance study of both isomers. Selective reaction between amine IIaand carbobenzoxy-l-proline was achieved with Woodward's reagent K. Of several procedures explored for removing the carbobenzoxy protecting group from amide IIc, palladium-catalyzed hydrogenolysis proved quite satisfactory. Hydrogenolysis of carbamate IIbto yield prolyl amide III was realized without affecting the Δ5olefin system. A mass spectral study of amine III and the corresponding 5α-derivative IV confirmed the latter observation. A brief review of procedures for the synthesis of steroidal amines was also presented.
ISSN:0008-4042
DOI:10.1139/v67-085
出版商:NRC Research Press
年代:1967
数据来源: NRC
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