摘要:

The synthesis of a versatile intermediate 4a-(2-aminoethyl)-l,2,3,4,4a,9-hexahydro-6-methoxyphenanthrene (3a) and its utilization in the synthesis of 9α-hydroxy-3-methoxy-17-methylhasubanan (10), 3,14-dimethoxy-17-methylisomorphinan (9l), various 14-hydroxyisomorphinans (9), and 3-methoxy-Δ8,14-morphinan (11b) is described. A number of 17-alkyl-3,14-dihydroxyisomorphinans were prepared and tested for narcotic antagonist and analgesic activities in laboratory animals. Some of these new compounds have exhibited significant activities.

ISSN:0008-4042    

DOI:10.1139/v75-358

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

Hydroxylation and epoxidation, followed by the oxirane ring opening, of methyl 2,3-dideoxy-α and β-DL-pent-2-enopyranosides, readily available by the transformation of furfuryl alcohol, afforded the title compounds. Steric course of hydroxylation and epoxidation reactions were examined. The p.m.r. data of methyl 4-O-acetyl-2,3-anhydro-DL-pentopyranosides are reported.

ISSN:0008-4042    

DOI:10.1139/v75-359

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

In the presence of an alcohol, oxalic acid esters undergo diazomethane-catalyzed transesterification. Under mild reaction conditions, esters of homologous dicarboxylic acids and other polycarboxylic acids are unaffected.

ISSN:0008-4042    

DOI:10.1139/v75-360

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

Treatment ofN-(2,3,5,6-tetrafluorophenyl)-N′-thiobenzoylhydrazine and ofN-benzoyl-N′-(2,3,5,6-tetrafluorophenyl)hydrazine with acetic anhydride and triethylamine proceed without rearrangement to give 4-acetyl-2-phenyl-5,6,8-trifluoro-4H-1,3,4-benzthiadiazine and -benzoxadiazine, respectively. Structures follow from19F n.m.r. and n.O.e. data.

ISSN:0008-4042    

DOI:10.1139/v75-361

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

Perfluoroallyl iodide reacts with Zn[Co(CO)4]2to give π-C3F5Co(CO)3and CF3CF=CFCo-(CO)4. The reaction of π -C3F5Co(CO)3with PPh3gives two products;trans-CF3CF=CFCo(CO)3PPh3and a compound tentatively identified ascis-CF2=CFCF2Co(CO)3PPh3; (cisandtransrefer to configuration about cobalt). Infrared and n.m.r. data for the compounds are reported.

ISSN:0008-4042    

DOI:10.1139/v75-362

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

Crystalline MoS2catalysts were impregnated with cobalt over the total composition range, and their catalytic activity in the hydrodesulfurization of thiophene tested in a microreactor at 400° and near atmospheric pressure. Three principal composition regions could be distinguished in the sulfided catalysts: (1) Co/(Co + Mo) compositions 0–0.4. In this region intercalated Co enhances the intrinsic activity which reaches a maximum near a Co content of 0.25. The region is sulfur "deficient" with respect to MoS2 + Co9S8and there is no evidence for the presence of Co9S8. (2) Compositions 0.4–0.65. This region is characterized by the exact stoichiometry MoS2 + Co9S8and by the appearance of a Co9S8phase. Surface area experiences a fivefold increase, as does percent conversion, but intrinsic activity changes very little. (3) Compositions > 0.65. A region of lesser interest, it is sulfur "deficient", possibly through the formation of Co4S3, and surface area decreases steeply with Co content.

ISSN:0008-4042    

DOI:10.1139/v75-363

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

The chemically induced dynamic nuclear polarization arising from irradiation of aliphatic aldehydes in D2O and various other solvents is reported. The aldehydes included acetaldehyde, propionaldehyde, isobutyraldehyde, and pivalaldehyde, and the solvents were benzene, acetonitrile, cyclohexane, methylcyclohexane, perfluoromethylcyclohexane, D2O, and D2O/acetonitrile. For propionaldehyde, the variation of c.i.d.n.p. with solvent can be explained by a variation of the relative importance of α-cleavagevs. hydrogen abstraction which occur via an excited triplet state. In addition, when D2O is the solvent, the c.i.d.n.p. provides information about secondary radical reactions not observed in the other solvents. For the other aldehydes, the nature of the solvent does not seem to affect the relative importance of α-cleavagevs. hydrogen abstraction. Acetaldehyde undergoes hydrogen abstraction whereas isobutyraldehyde and pivalaldehyde undgero α-cleavage via an excited triplet state.

ISSN:0008-4042    

DOI:10.1139/v75-364

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

A series of dimeric tertiary phosphine carboxylate complexes of palladium(II) of the general types [(PR3)Pd(O2CR)2]2and [(PR3)Pd(O2CR)(O2CR)]2have been synthesized and struc-turally characterized. The dynamic stereochemistry of the complexes where PR3 = Me2PhP has been investigated using variable temperature n.m.r. techniques. Exchange of the stereochemically nonequivalent methyl groups of the coordinated Me2PhP ligand occurs via a solvent assisted process involving ring opening of the "Pd2(OCO)2" bridged structure. For the trifluoroacetate complexes solution equilibria between monomer and dimer are readily apparent at low temperatures in the19F n.m.r. The observed equilibrium constants are a function of the solvent and the size of the PR3ligand. The reaction of [(PMe2Ph)Pd(O2CCF3)2]2with excess AgO2CCF3gives an unusual crystalline complex of stoichiometry Ag[(PMe2Ph)Pd(O2CCF3)3]. A quantitative measure of the ability of a coordinated carboxylate to stabilize intermediate species via chelation has been obtained from a variable temperature n.m.r. study of [(Π-2-methylallyl)Pd(O2CR)(Me2PhP)] (R=CH3, CH2Cl, CHCl2, CCl3, CF3, CMe3, CPh3, CH2Ph).

ISSN:0008-4042    

DOI:10.1139/v75-365

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

Under petroleum hydrotreating conditions and in the presence of a Co–M–alumina catalyst, quinoline is hydrodenitrogenated through a consecutive first order reaction involving a hydrogénation step followed by two hydrocracking steps. The first step is too fast to measure whereas the second step is the slowest. The ratio of the rate constants of the second to the third step ranges between 0.33 and 0.62 at reaction temperatures between 350 and 400 °C. The second step can be considered responsible for the relatively high activation energy and enthalpy values obtained for the overall reaction. The activation entropy obtained for the overall reaction is −38.2 e.u. mol−1, while the second and the third steps have values of −43.9 and −58.0 e.u. mol−1, respectively. These values indicate the progressive complexity of the steps involved in the reaction sequence as it proceeds towards ammonia production.

ISSN:0008-4042    

DOI:10.1139/v75-366

出版商:NRC Research Press    

年代:1975

数据来源: NRC

摘要:

An examination of spectroscopic data for 43 alkenes reveals the influence of increasing substitution at the carbon atoms α or β to the ethylenic bond. The presence of a particularly large steric constraint requires that there be a single preferred molecular conformation: in such a case the frequency of the νC = Cvibrator is strongly decreased (10 cm−1).A quantitative analysis of the phenomenon can be achieved using the "topological-chemical method D.A.R.C.". Topologic-information relationships could be developed for the two series 2-alkylethylenes and 2,2-dialkylethylenes. These permit the calculation of the contribution of each topological site to the frequency νC = C. For the first series, the relationship, based on 9 compounds, permits predictions about 30 others. For the second series, deductions are made concerning 159 compounds from a relationship established on a base of 13 compounds. [Journal translation]

ISSN:0008-4042    

DOI:10.1139/v75-367

出版商:NRC Research Press    

年代:1975

数据来源: NRC