摘要:

trans-3-Methoxycyclohexene oxide (II), when treated with ethereal hydrogen chloride, gives the chlorohydrindl-1α-chloro-2β-hydroxy-3α-methoxycyclohexane (IVa), and thecisoxide III givesdl-1β-chloro-2α-hydroxy-3α-methoxycyclohexane (Va). The point of scission of the oxide ring (remote from the methoxyl) is therefore the same as in other reactions observed by ourselves and others. The reaction of 3-methoxycyclohexene (I) withN-chlorosuccinimide and water at 100° gives three chlorohydrins:dl-1β-chloro-2α-hydroxy-3α-methoxycyclohexane (VI),dl-2β-chloro-1α-hydroxy-3α-methoxycyclohexane (VIa), anddl-2α-chloro-1β-hydroxy-3α-methoxycyclohexene (VIIa) (approximately in the ratio 10:38:50, respectively). Two of the chlorohydrins were solids, and the homogeneity of the liquid isomers was demonstrated in several ways. The structures were proven by the nuclear magnetic resonance spectra of thep-nitrobenzoates, and by chemical methods. The results are of considerable interest with regard to the theory of addition and substitution reactions. There is a close parallel with the results in the bromohydrin series.

ISSN:0008-4042    

DOI:10.1139/v67-306

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The behavior ofN-benzoylaspartic acid andN-benzoylglutamic acid has been investigated at 100° in dilute solution in water and aqueous hydrochloric acid within the pH range 3.1–0.5. Some data are presented concerning the hydrolysis of theN-benzoyl derivatives of alanine, β-alanine, leucine, glycine, serine, and β-ethanolamine in water, 0.1 Nhydrochloric acid, and 2 Nhydrochloric acid. Benzoylglutamic acid undergoes a pH-independent conversion into pyrrolid-2-one-5-carboxylic acid, which then hydrolyses in mineral acid to glutamic acid; however,N-benzoylaspartic acid, under similar conditions, hydrolyses much more rapidly by a route which does not involve the corresponding lactam as an intermediate. In anhydrous alcohols the solvolysis ofN-benzoylaspartic acid gives mixtures of aspartic acid and the β ester.First-order rate constants have been obtained for the acid-catalyzed hydrolysis of pyrrolid-2-one-5-carboxylic acid (I) and azetidin-2-one-4-carboxylic acid (II) in water over this pH range.

ISSN:0008-4042    

DOI:10.1139/v67-307

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Acylation of 5,5-diphenylimidazolid-4-one gives 1,3-diacyl-5,5-diphenylimidazolid-4-ones, and not 2-acyl-4,4-diphenyl-2,5-diaza-7-oxabicyclo[3.2.0]heptan-3-ones as claimed by Biltz and his co-workers. The reason for the unusual stability of theN1-acyl groups to acid and alkaline hydrolysis is discussed. The revised formulation allows the oxidation products of 1-acetyl-5,5-diphenylimidazolid-4-one to be rationalized in a simple fashion.

ISSN:0008-4042    

DOI:10.1139/v67-308

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The biosynthesis of dictamnine, a furoquinoline alkaloid, was studied in intactDictamnus albusplants. The quinoline ring system is derived from anthranilic acid and acetate. Tryptophan is not a precursor. Anthranilic acid concentration appears to control the rate of dictamnine biosynthesis in intactD. albus.

ISSN:0008-4042    

DOI:10.1139/v67-309

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Conclusive spectral evidence for the structure of categallin (V), pyrogallin (VI), and erycetin (VIII), three flavanotropolones related to theaflavin (I) and purpurogallin (IX), is presented. The synthetic, chromatographic, and spectroscopic data for four simpler hydroxybenzotropolones are also recorded and discussed.

ISSN:0008-4042    

DOI:10.1139/v67-310

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

Dimethylbis(p-tolyl)silane was converted into the mono- or di-benzyl bromides by reaction with appropriate equivalents ofN-bromosuccinimide; these were then converted into the nitriles, which were hydrolyzed to the corresponding phenylacetic acids or reduced to the phenethylamines. The mono- and di-phenethyl alcohols were prepared by reduction of the corresponding acids with lithium aluminium hydride. The dialdehyde, dimethylbis(p-formylphenyl)silane, was prepared by hydrolysis of dimethylbis(p-dibromomethylphenyl)silane.

ISSN:0008-4042    

DOI:10.1139/v67-311

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The use of long, silver nitrate – ethylene glycol gas chromatographic columns has permitted a near base line separation to be achieved for deuterated olefins differing by only one deuterium atom. All of the six deuterated ethylenes and two deuterated butenes have been studied, and good separations have been obtained between the different isotopic species. The isotope effects(KD/KH)on the retention times have been calculated. Evidence of a difference in the relative retention times of two of the ethylene-d2isomers is presented for the first time. It has been demonstrated that the isotopic content of deuterated olefins can be determined by quantitative analysis with the same accuracy as by mass spectral analysis. A careful study of ethylene-13C failed to reveal an observable isotope effect on its retention time relative to light ethylene.

ISSN:0008-4042    

DOI:10.1139/v67-312

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

When defatted seed fromBrassica napusL. var. Regina II (a rapeseed) was autolyzed, its major thioglucoside (progoitrin) underwent degradation analogous to that for epiprogoitrin inCrambe abyssinicaseed meal. Depending on the conditions, (R)-1-cyano-2-hydroxy-3-butene and the diastereomeric forms of (2R)-1-cyano-2-hydroxy-3,4-epithiobutane were formed in autolyzedB. napusmeal instead of (S)-goitrin. The configuration at the chiral center containing the hydroxyl is assigned on the basis of known data. The configuration at carbon 3 of the episulfides is predicted on the basis of the optical rotatory dispersion data.

ISSN:0008-4042    

DOI:10.1139/v67-313

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The treatment of substituted quinones with acetic anhydride under acid catalysis gives substituted triacetoxybenzenes. Previous work on this reaction is summarized, and the reaction has been extended to include quinones having electron-withdrawing groups, and two quinones which had previously been reported as inactive.

ISSN:0008-4042    

DOI:10.1139/v67-314

出版商:NRC Research Press    

年代:1967

数据来源: NRC

摘要:

The synthesis of a series of 2,2-disubstituted-6-cyanocyclohexanones by hydrolysis of the precursor 3,3-disubstituted-2-amino-1-cyanocyclohexenes (2,2-disubstituted-6-cyanocyclohexanoneimines) is described. The appropriate disubstituted acetonitriles reacted with 1-chloro-4-bromobutane to give the chloro nitriles, which were converted into the 2,2-disubstituted-heptanedinitriles for cyclization. The cyclic imino nitriles (enamines) hydrolyzed to keto nitriles, keto amides, or ketones depending on the reaction conditions. The new compounds possess the following substituents: dimethyl, diethyl, ethyl phenyl, and diphenyl. The enolization of the β-keto nitriles is discussed.

ISSN:0008-4042    

DOI:10.1139/v67-315

出版商:NRC Research Press    

年代:1967

数据来源: NRC