摘要:

Attempts to preparedl-erythro-N,N-dimethyl-2,3-dihydroxy-3-phenylpropionamide by the usual organic peracid hydroxylation ofdl-trans-N,N-dimethylcinnamamide gave unexpectedly a 40:60 mixture of both diastereomers, thethreoform being predominant. The anomaly prompted a closer investigation of each of the intermediate stages in the overall hydroxylation process. Epoxidation ofdl-trans-N,N-dimethylcinnamamide by monoperphthalic acid gave onlydl-trans-N,N-dimethyl-3-phenylglycidamide. Opening of the epoxide ring by acids gave a mixture ofdl-erythroanddl-threodiols in a ratio of 40:60.cis-N,N- Dimethyl-3-phenylglycidamide, when subjected to the same ring-opening processes, also gave a mixture, but in a ratio of 75:25.

ISSN:0008-4042    

DOI:10.1139/v67-345

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The product (styrene) derived from the deoxidation of 2-phenyl-1-14C-ethanol showed 22–26% rearrangement of the14C label from C-1 to C-2. The extent of this rearrangement is quite close to the values reported for the analogous rearrangement in the deamination of 2-phenyl-l-14C-ethylamine, thus giving further support to the suggested similarity between deoxidation and deamination reactions. The 2-phenylethanol recovered from the deoxidation reaction mixture also showed 3–5% rearrangement of the14C label from C-l to C-2. This constitutes the first observation of the formation of a rearranged alcohol in a deoxidation reaction. Other mechanistic implications of the results are discussed.

ISSN:0008-4042    

DOI:10.1139/v67-346

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The infrared absorption spectra of partially deuteratedo-phenylenediamine and 4,5-di-methyl-, 4-methyl-, and 4-chloro-o-phenylenediamine in dilute CCl4solution show double intramolecularhydrogen bonds in which the two NHD groups are equivalent and each group acts as both a proton donor and a proton acceptor. The ring substituent effect on this interaction in these compounds is small. In 4-methoxy-o-phenylenediamine, the amino groups are not equivalent, but double intramolecular hydrogen bonds are still present. In 4-nitro-o-phenylenediamine, only one intramolecularhydrogen bond appears to exist. The effect ofN-substitution on some of these observations is discussed.

ISSN:0008-4042    

DOI:10.1139/v67-347

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The fundamental NH stretching bands of 22 aliphatic diamines have been investigated in dilute C2Cl4solution.N,N′-Dimethyl-1,3-propanediamine andN,N′-dimethyl- andN,N,N′-trimethyl-ethylenediamine exist predominantly in an intramolecularly hydrogen bonded conformation. Such bonding also exists inN-methyl- andN,N-dimethyl-ethylenediamine, inN-methyl- andN,N-dimethyl-1,3-propanediamine, and in amines of the type H2N(CH2-CH2NH)xCH2CH2NH2. For all of the diamines investigated, intramolecular NH···N bonding disappears sharply when the intervening methylene chain length exceeds three units. Integrated band intensity measurements for primary aliphatic diamines H2N(CH2)nNH2over the rangen = 2–12 suggest that intramolecular hydrogen bonds may also play an important role in the conformation of ethylenediamine and 1,3-diaminopropane.

ISSN:0008-4042    

DOI:10.1139/v67-348

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

A series of β-hydroxyketones, CH3CR(OH)CH2COCH3, has been converted into substituted aromatic hydrocarbons in 80–90% yields by a double dehydration with cyclization in the presence of acids. The nuclear magnetic resonance spectra of the compounds, several of which are new, have been measured.

ISSN:0008-4042    

DOI:10.1139/v67-349

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The ring proton spectrum of triptycene (2.2 mole % in CS2) was analyzed after the methine proton was decoupled. The modified ring current model accounts for most of the internal shift. Bond anisotropies and electron density contributions are also present. The latter account for the mean proton shift. The agreement between the predicted and calculated shifts is excellent for the proton meta to the methine substituent, but a discrepancy of 0.1 p.p.m. is found for the ortho proton. Correction for the ring anisotropy effects produces excellent agreement of the methine proton shift with the empirical correlation between the C—H proton shifts and the13C–H coupling constants. The ring proton–proton coupling constants are little different from those in benzene, but a small strain in the bonds near the methine carbons is implied.

ISSN:0008-4042    

DOI:10.1139/v67-350

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

By using α-cyanostilbenes as Lewis acids, Lewis acidity scales have been established in ethanolic and methanolic dimethyl sulfoxide containing the appropriate 0.01 Msodium alkoxide and in the system sodium methoxide – methanol. This scale, designated, describes the ability of the solvent to add an alkoxide ion to an alkene. Thevalues range from 11.73 in methanol to 21.74 in 93.27 mole % dimethyl sulfoxide in ethanol.The most acidic indicator used to establish the scale was α-cyano-2,4-dinitrostilbene, with a pKAof 12.73 in dimethyl sulfoxide – methanol. The least acidic was α-cyano-3-trifluoro-methylstilbene, with a pKAof 21.98 in dimethyl sulfoxide – ethanol.The increase in the system's ability to add alkoxide ion to the cyanostilbenes as the dimethyl sulfoxide concentration rises is ascribed chiefly to its effect on the activity of the alkoxide ion. The functionsH−and, unlike their analogues in acid systems (H0andHr), do not diverge greatly as the concentration of the hydroxylic solvent component is decreased.

ISSN:0008-4042    

DOI:10.1139/v67-351

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The effect of substituents in the two aromatic rings of α-cyanostilbene on the Lewis acidities of these compounds towards alkoxide ions has been examined. Substituents in the β ring produce effects on the acidity which correlate with the σ values of the substituents and yield an average ρ value of + 2.22. Substituents in the α ring, however, are correlated by the σ−values and yield an average ρ value of + 4.62. Ap-nitro group in the α ring exhibits a greatly enhanced σ−value (+ 1.73).

ISSN:0008-4042    

DOI:10.1139/v67-352

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The structure of isamic acid, prepared by the reaction of isatin with ammonia, has been established. It is that of the ylid XIIaor XIIc, different from the ylid XIIbfirst suggested by the present authors in an earlier communication. The difference lies in an unsuspected exchange of nitrogen functions.The nature of the oxidation products with hydrogen peroxide (VII), with nitric acid, and with potassium permanganate (XXVII) has been elucidated; these do not differ from those suggested earlier.In the Appendix the action of diazomethane onN-acetyl isatoic acid is described. Three molecules of reagent are consumed in esterification, homologation, and epoxide formation.

ISSN:0008-4042    

DOI:10.1139/v67-353

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

In the infrared spectra of mono- and di-nitrate esters of the l,4;3,6-dianhydrides ofd-mannitol,d-glucitol, andl-iditol in benzene solution (0.04 Min nitrato groups), the frequencies of theva(NO2) andv(ON) bands (singlets) were 1 645 ± 3 and 843 ± 3 cm−1, respectively, whereas thevs(NO2) band occurred at frequencies characteristic of either anendo(1 282 ± 1 cm−1) or anexo(1 274 ± 1 cm−1) configuration of the nitrato group; the ratios of the band areas were 1.5:1.0:1.0, respectively.The stereospecific frequency of thevs(NO2) band was attributed to non-bonded intramolecular interaction between the nitrato group and vicinal oxy groups on the basis of the spectra run in a series of solvents and the molecular conformations determined by X-ray crystallography. This new stereochemical probe permitted the assignment of the structure, configuration, and conformation in a series of nitrate esters.

ISSN:0008-4042    

DOI:10.1139/v67-354

出版商:NRC Research Press    

年代:1967

数据来源: NRC