摘要:

The preparation of several deuterated steroids is described, viz.,(i) the trideuteroacetates of the following alcohols: Δ5,7,9-estratrienol-17β;Δ1,5:10estrienol-3-one-17 (estrone); androstanol-3a; androstanol-3β; an-drostanol-17β; pregnanol-20a; Δ5-pregnenol-3β -one-20; Δ5-pregnenol-3β -one-20-d4-17,21; Δ5-cholestenol-3β; Δ-cholestadienol-3β; ergostanol-3 β; Δ14-ergostenol-3β; Δ22-5-isoergostenol-3a.(ii) Δ5-pregnenol-3 β -one-20-d3-21 acetate; Δ -pregnenol-3 β -one-20-d4-17,21.(iii) androstanone-3-d4,-2,4; cholestanone-3-d4-2,4; Δ8:14-ergostenone-3-d4-2,4; cholestanone- 7-d2-6; androstanone-17-d2-16.From difficulties encountered in the preparation of cholestanone-7-d2-6, it is inferred that 7-ketones enolize less readily than 3-, 17-, or 20-ketones.

ISSN:0008-4042    

DOI:10.1139/v52-087

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

The reactions to form RDX and HMX in Bachmann-type mixtures are comparable in respect of optimum nitric acid concentrations and in the fact that optimal amounts of acetic anhydride and ammonium nitrate are necessary for maximum yields of either explosive. The activation energies for formation of RDX and HMX were also found to be comparable, at 15 ± 1 kcal. per mole. However, withholding ammonium nitrate from the reaction mixture was found to have a more deleterious effect on RDX production than on HMX production. A mechanism is proposed which attempts in a general way to represent the relation between RDX and HMX production in the type of reaction mixtures used.

ISSN:0008-4042    

DOI:10.1139/v52-088

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

The following heats of reaction have been determined, where the subscripts "c" and "s" refer to solid and solution respectively:Hexamine(c) + HNO3 (97.5%) = RDX(s); ΔH = −88.0 kcal. per mole.Hexamine mononitrate(c) + HNO3 (97.5%) = RDX(s); ΔH = −69.2 kcal. per mole.Hexamine dinitrate(c) + HNO3 (97.5%) = RDX(s); ΔH = −41.7 kcal. permole.Hexamine(s) + Bachmann reagents = RDX(s); ΔH = −140 kcal. per mole.Hexamine mononitrate(s) + Bachmann reagents = RDX(s); ΔH = −126 kcal. per mole.Hexamine dinitrate(c) + Bachmann reagents = RDX(s); ΔH = −118 kcal. per mole.These measurements, together with some on heats of solution of the reagents, indicate that hexamine dinitrate is an intermediate in the direct nitrolysis of hexamine to RDX, but that hexamine mononitrate is a probable intermediate in the Bachmann conversion of hexamine to RDX.

ISSN:0008-4042    

DOI:10.1139/v52-089

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Tyramine-α-C14, synthesized from C14-barium carbonate, was administered to sprouting barley and radioactive hordenine and N-methyltyramine isolated from the roots. Separation of these alkaloids by chromatography followed by degradation showed that all the activity was located in the α -carbon atom. The specific activity of the N-methyltyramine was about 10 times that of hordenine. From the results it is concluded that tyramine undergoes methylation in the barley root to N-methyltyramine and thence to hordenine.

ISSN:0008-4042    

DOI:10.1139/v52-090

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Pithecolobine, C22H46N4O2, has a lactam group, one primary and two secondary amino groups, and a hydroxyl group. Lithium aluminum hydride converts it into a monocyclic saturated compound, desoxypithecolobine, C22H48N4. Hofmann degradation of this compound gives tetramethylputrescine, trimethyl amine, a doubly unsaturated base C16H31N with a terminal methylene group, and a base C16H34N2. Heating with selenium yields a hydrocarbon, C12;H24–26, with a sequence of six or more CH2groups. A crystalline oxygen-free compound with two nitrogens (m.p.94 °C.) is also obtained, the ultraviolet spectrum of which is almost identical with aminopyridine.

ISSN:0008-4042    

DOI:10.1139/v52-091

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Temperature independent factors for a series of hydrogen abstraction reactions in the gas phase have been calculated using the absolute reaction rate theory of Eyring and co-workers. The calculated values have been compared with experimental values wherever possible. Reasonable agreement is obtained. The factors producing variations have been examined and the sources of error in this type of calculation are discussed.

ISSN:0008-4042    

DOI:10.1139/v52-092

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Relative transport fractions have been measured in the molten system silver nitrate - sodium nitrate at 330° over the range 5 to 25 mole% silver nitrate. The individual fractions for silver, sodium, and nitrate ion have been assessed within limits. The results indicate that transport by silver ion is greater than that by sodium ion at the same concentration, although the latter has the smaller radius. The usual assumption that the largest ion (nitrate) does not transport charge is within the interpretation of the results.

ISSN:0008-4042    

DOI:10.1139/v52-093

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Ammonium reineckate was found to react with methorphinan hydrobromide, codeine phosphate, and the hydrochlorides of methadone, phenadoxone, pipidone, cocaine, pethidine, ketobemidone, alphaprodine, morphine, diamorphine, and metopon to yield characteristic crystals. The molecular composition, decomposition range, optical rotation, solubility in water and ethanol, and spectral transmittance of these crystalline compounds are reported with the pKBvalues of the narcotics in water and in 50% acetone.

ISSN:0008-4042    

DOI:10.1139/v52-094

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

Codeine phosphate, amorphine sulphate, methorphinan hydrobromide, and the hydrochlorides of methadone, phenadoxone, alphaprodine, cocaine, pethidine, diamorphine, dilaudid, morphine, and papaverine were quantitatively determined with a precision of ±1.6% by ion exchange chromatography. The method was found to be applicable to pharmaceutical preparations and narcotic seizures, provided these did not contain additional ionizing constituents. Use of a solvent system in which the free base remained dissolved throughout the entire process was an important factor in the analysis. The dissociation constants of the narcotics in the solvent systems used are also reported.

ISSN:0008-4042    

DOI:10.1139/v52-095

出版商:NRC Research Press    

年代:1952

数据来源: NRC

摘要:

The reaction of CH3and CD3radicals with hydrogen and deuterium have been investigated, acetone being used as a source of methyl radicals. The results indicate (1) that the substitution of D2for H2has a considerable effect, (2) the substitution of CD3for CH3has relatively little effect. (3) It is concluded that, contrary to the results of Burtonet al., the activation energy of the reactionis 9.7 ± 0.6 kcal.

ISSN:0008-4042    

DOI:10.1139/v52-096

出版商:NRC Research Press    

年代:1952

数据来源: NRC