摘要:

The gas-phase reaction of atomic hydrogen with ketene has been investigated over a temperature range of −130° to 232 °C using a low-pressure, fast-flow system. In most cases methane, carbon monoxide, and ethane were the major products, but trace amounts of glyoxal were also detected. Above −96 °C. considerable evidence exists for the occurrence of a chain reaction carried by HCO radicals. The surface reaction at −196 °C produced methane and glyoxal predominantly with only a minor amount of carbon monoxide.

ISSN:0008-4042    

DOI:10.1139/v64-001

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

The previous assignment of a cis conformation to cyclohexyl 2-carbamylcyclohexylamine, which was prepared by the condensation of urea with cyclohexanone, has been confirmed by equilibration in the presence of potassiumt-butoxide. The failure of 4-t-butylcyclohexyl 2-carbamyl-4-t-butylcyclohexylamine to equilibrate under the same conditions is discussed in relation to its structure. 1,2,3,4,5,6,7,8-Octahydroacridine was prepared by the condensation of 2,2′-methylene-bis-cyclohexanone with urea.

ISSN:0008-4042    

DOI:10.1139/v64-002

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

The structure of thiosemicarbazone–copper (I) complexes has been studied further and new data have been obtained. The most probable structure has the metal linearly coordinated to a sulphur atom of a thiosemicarbazone molecule and a nitrogen atom of a second molecule. The diamagnetism of the complexes can be accounted for by a copper–copper interaction. Molecular weights of two typical complexes have been measured by a vapor pressure lowering method in benzene. The complexes were found to associate in this solvent but appeared as dimers at infinite dilution.

ISSN:0008-4042    

DOI:10.1139/v64-003

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

The synthesis of methyl 4-acetamido-4-deoxy-L-erythrofuranoside fromD-ribose is described. The structural features that are believed to be necessary for the replacement of the ring oxygen of sugars by nitrogen are discussed.

ISSN:0008-4042    

DOI:10.1139/v64-004

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

The product from both the acid-catalyzed cyclodehydration of 4-methyl-4-phenyl-2-pentanone (1a) described by Hoffman (1) and by Barnes and co-worker (2) and the reaction of the saturated cyclic dimer of α-methylstyrene with aluminum chloride reported by Adams and co-workers (3) was shown to be 3,3,3′,3′-tetramethyl-1,1′-spirobiindane (IXa) by Curtis (4). A mechanism is postulated to explain the formation of the 1,1′-spirobiindane system. The reactions of several polyalkylindenes with α-methylstyrene and triphenylcarbinol were investigated. Several new polyalkyl-1,1′-spirobiindanes and a new polyalkylindene[1,2-a]indene were produced. Two of the 1,1′-spirobiindanes investigated were synthesized by unequivocal methods.

ISSN:0008-4042    

DOI:10.1139/v64-005

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

Infrared spectra of various types of organosulphur compounds have been examined and group frequencies arising from G—S, S—S, N—S, O—S, and C=S stretching vibrations have been assigned and discussed. The C—S bands of thioketals and S—S bands of tri- and tetra-sulphides show splittings due to vibrational coupling. The O—S and N—S stretching frequencies are found around 890 and 820 cm−1respectively, values which are much higher than the C—S stretching frequencies. Potassium alkyl xanthates exhibit the asymmetric and symmetric stretching frequencies of the CS2−ion. The splitting of C—O and C=S stretching bands in dialkyl dixanthogens have been interpreted in terms of the Fermi interaction with the combination tone of C—S and S—S stretching vibrations and with the overtone of S—S stretching vibrations respectively. The relative intensity of the C=S stretching bands in a few derivatives show marked dependence on the electronegativities of the elements directly linked to the thiocarbonyl group. It is found that the earlier assignments of the "bands" due to mixed vibrations in thioamide type derivatives have been found to be well justified on the basis of the recent normal coordinate treatment. Another band tentatively designated as the "IV band" has been assigned for these derivatives in the region 850–680 cm−1. Examination of the spectra of a number of thioamide type derivatives has shown no evidence for the presence of thiol tautomers. All of them exist as thiones exhibiting characteristic N—H absorption and "bands".

ISSN:0008-4042    

DOI:10.1139/v64-006

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

Infrared spectra of 5-membered N- and N,S-heterocyclic derivatives such as triazoles, tetrazoles, thiazoles, thiadiazoles, thiatriazoles, and dithiazoles have been examined and empirical assignments have been made. The spectra of the two dithiazolidine derivatives, isoperthiocyanic acid and oxidation product of dithiobiuret, have been studied in detail. Assignments for benzthiazole derivatives are reported. The CH out-of-plane deformation bands of benzene rings fused to five-membered heterocyclic rings have been found to be in the region 760–740 cm−1, characteristic of four adjacent benzenoid hydrogen atoms.

ISSN:0008-4042    

DOI:10.1139/v64-007

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

The preparation of chromium tetrafluoride reported by von Wartenberg has been repeated, and some physical and chemical properties have been studied. Chromium tetrafluoride is surprisingly inert and does not react with ammonia, sulphur di- or trioxide, pyridine, halogen fluorides, or selenium tetrafluoride at ordinary temperatures. In boiling bromine trifluoride or selenium tetrafluoride, chromium tetrafluoride is reduced to lower fluorides, while a refluxing mixture of bromine tri- and pentafluorides converts CrF4to CrOF3•0.25BrF3. Chromium (IV) fluoride complexes of the types ACrF5(A = K, Rb, or Cs) and A2CrF6(A = K or Cs) have been prepared and their magnetic moments and lattice constants have been determined.

ISSN:0008-4042    

DOI:10.1139/v64-008

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

The infrared spectra of solid crystalline films of ammonium nitrate were measured at temperatures ranging between the melting point (169 °C) and liquid air temperature (−190 °C). Four different spectra were obtained which are shown to belong to phase I, II, IV, and (very probably) VII. Phases III and V were not encountered; only transitions,, andwere observed. A spectrum measured at −190 °C after rapid cooling is shown to correspond to a mixture of phases IV and VII. The symmetry properties of the different phases are discussed in relation with their infrared spectra.

ISSN:0008-4042    

DOI:10.1139/v64-009

出版商:NRC Research Press    

年代:1964

数据来源: NRC

摘要:

Two products have been isolated from the reaction of anhydrosepedonin with alkali and identified as 3-hydroxy-5-methyl benzoic acid and 3,4-dimethyl-5-hydroxybenzoic acid. The structure of the latter compound was established by unambiguous synthesis. In the course of this work the remainingo- andm-hydroxybenzoic acids derived fromo-xylene were also prepared.

ISSN:0008-4042    

DOI:10.1139/v64-010

出版商:NRC Research Press    

年代:1964

数据来源: NRC