摘要:

All the seven monomethylindoles and 18 of the 21 possible dimethylindoles have been synthesized by unambiguous methods. Eleven were prepared by the Fischer ring closure applied to the appropriate phenylhydrazone, five of which through the appropriate phenylhydrazone of ethyl pyruvate. The rest were prepared by the Tyson ring closure. The picrates of each indole and the styphnates of all but three were prepared and their properties recorded. The three unrecorded styphnates (those of 1,6-, 5,6-, and 5,7-dimethylindole) could not be isolated without decomposition although they seemed to exist in solution.

ISSN:1923-4287    

DOI:10.1139/cjr47b-001

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

The syntheses of 2-sulphanilamido-4-hydroxypyrimidine, 2-sulphanilamido-4,6-dihydroxypyrimidine, and several other sulphanilamidopyrimidines are described. An improved method for the preparation of sulphaguanidine is given.

ISSN:1923-4287    

DOI:10.1139/cjr47b-002

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

In the course of a study of antidotes to lewisite the following thiols have been prepared from the corresponding di- and trihalides by the action of sodium hydrosulphide or ammonium hydrosulphide in ethanol under pressure: 1,2-dimercaptoethane, 1,2-dimercaptopropane, 1,3-dimercaptopropane, 1,2,3-trimercaptopropane, 1,2-dimercapto-n-butane, 2,2′-dimercaptoethyl ether, 3,3′-dimercaptopropyl ether, 2,2′-dimercaptoisopropyl ether, and 1,3-dimercapto-2-propanol.1,2-Dimercaptopropane has been prepared by a new method, namely, by the interaction of ammonium hydrosulphide and allyl bromide. This method involves the addition of hydrogen sulphide to an unsaturated compound by the action of ammonium hydrosulphide in ethanol under pressure.The toxicity of the above thiols and their antidotal activity to lewisite have been compared with those of 2,3-dimercaptopropanol (BAL, British anti-lewisite) and the results of these studies will be published later.

ISSN:1923-4287    

DOI:10.1139/cjr47b-003

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

Four α-amino acids, namely, norleucine, isoleucine, methionine, and S-benzylhomocysteine, have been prepared from the corresponding alkylcyanoacetic esters. Methionine has been obtained in excellent yield.The intermediate alkylcyanoacethydrazides formed 4-alkyl-3-aminopyrazolones. Four members of this new series, 4-n-butyl-, 4-sec-butyl-, 4-(β-methylthiolethyl)-, and 4-(β-benzylthiolethyl)-3-aminopyrazolones are described and their ultraviolet absorption spectra given.The following compounds have also been isolated: ethyl α-cyano-γ-methylthiolbutyrate, ethyl α-cyano-γ-benzylthiolbutyrate, α-cyano-n-caprohydrazide, isopropylidene α-cyano-n-caprohydrazide, anisal α-cyano-β-methylvalerhydrazide, anisal α-cyano-γ-methylthiolbutyrhydrazide, and anisal α-cyano-γ-benzylthiolbutyrhydrazide.

ISSN:1923-4287    

DOI:10.1139/cjr47b-004

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

The reaction of β,β′-dichlorodiethyl sulphide with various proteins and their constituents has been tested under relatively mild conditions. Most reactions have been carried out in aqueous media at 25 °C., usually in the presence of sodium chloride. The rate of disappearance of mustard has been followed iodimetrically as an index of the reaction.No reaction could be demonstrated with the prolamins, zein and gliadin, in ethanol. There was a definite reaction with keratin of human skin in which a 24% increment in total sulphur occurred and a more doubtful one with keratein from human hair.The most notable reaction took place with yeast and thymus nucleoproteins in which increases of 250 and 156% in sulphur occurred, respectively. Combination of mustard with both the protein and nucleic acid portions was demonstrated. The extent of these reactions is indicated in terms of milligrams of mustard per gram of substrate as follows: yeast nucleoprotein, 216; thymus nucleoprotein, 47; salmine, 47; globin, 22; yeast nucleic acid, 126. The purines, adenine and guanine, were found to combine readily with mustard at 25 °C., forming thiazans. No reaction could be demonstrated with uracil or thiamine.These experiments have led us to the conclusion that one of the major effects of mustard in its physiological action is the combination and precipitation of the nucleoproteins of the cell, thus inhibiting natural processes of cellular regeneration.

ISSN:1923-4287    

DOI:10.1139/cjr47b-005

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

5-Aminoquinoline-8-carboxylic acid was prepared from 8-methylquinoline by nitration in the 5-position, oxidation of the methyl group to carboxyl, and reduction of the nitro group to amino. The 5-aminoquinoline-8-carboxylic acid was converted to 5-hydroxyquinoline-8-carboxylic acid through the diazonium salt. Some of the properties of the two new compounds were determined.A transmission curve was established for solutions showing the colour developed by the reagent and ruthenium. The standard ruthenium solution used for this purpose contained the metal as it is obtained when distilled as the tetroxide and collected in hydrogen peroxide. Ruthenium in a solution as ammonium chlororuthenate could be determined from the same curve. One γ (1 × 10−6 gm.) of ruthenium in 50 ml. of solution may be quantitatively determined.

ISSN:1923-4287    

DOI:10.1139/cjr47b-006

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

Under aerobic conditions both the Marburg and Ford types ofBacillus subtilisdissimilate glucose, giving carbon dioxide, acetoin, and 2,3-butanediol as the main products, and small amounts of glycerol and acetic, formic, lactic, andn-butyric acids. The Ford type cultures dissimilate the sugar more rapidly and also give a small amount of ethanol.Under anaerobic conditions Marburg type cultures will not ferment glucose while the Ford type cultures dissimilate it as rapidly as they do under aerobic conditions. Some strains give 2,3-butanediol, glycerol, and carbon dioxide as the major products while others give chiefly lactic acid. As much as 86% and as little as 8% of the glucose was converted to 2,3-butanediol plus glycerol. The 2,3-butanediol was a mixture of 65%meso- and 35%levo-isomers, while the lactic acid was approximately 90%dextro-isomer in most cases.It is suggested that the Ford type deserves separate species rank.

ISSN:1923-4287    

DOI:10.1139/cjr47b-007

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

Four strains ofSerratia marcescenswere found to dissimilate glucose under anaerobic conditions, producing 2,3-butanediol according to the equation: C6H12O6 → CH3∙CHOH∙CHOH∙CH3 + HCOOH + CO2. Under aerobic conditions little formic acid was produced and the reaction became. These reactions accounted for 40 to 60% of the glucose. The remainder was fermented to lactic acid (5 to 25%), ethanol (10 to 20%) and glycerol (1 to 4%). The lactic acid produced was 95 to 97% of thelevo-isomer; the 2,3-butanediol was ameso-dextromixture containing about 2% of thedextro-i

ISSN:1923-4287    

DOI:10.1139/cjr47b-008

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

Optically active 4,5-dimethyl-1,3-dioxacyclopentane derivatives can be easily obtained by condensinglevo-2,3-butanediol with aldehydes or ketones in the presence of small amounts of strong acids at ordinary temperatures. Condensations were effected with formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, 2-ethylbutyraldehyde, 2-ethylhexaldehyde, benzaldehyde, furfural, acrolein, acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl amyl ketone, diethyl ketone, acetophenone, cyclohexanone, acetoin, and diacetyl. The expected products were obtained, two compounds being formed from diacetyl since one or both carbonyl groups may react. Two compounds were obtained from formaldehyde also; in addition to the expected product (levo-4,5-dimethyl-1,3-dioxacyclopentane), 15 to 20% oflevo-6,7-dimethyl-1,3,5-trioxacycloheptane was obtained.

ISSN:1923-4287    

DOI:10.1139/cjr47b-009

出版商:NRC Research Press    

年代:1947

数据来源: NRC

摘要:

The dehydration of butanediol-2,3 over activated Morden bentonite has been investigated. Below 350 °C., liquid products butanone-2, isobutyraldehyde, and the isobutyral of butanediol-2,3 were produced. Butanone-2 was obtained in 86% yield. At higher temperatures, 450° to 700 °C., gaseous decomposition occurred. Only small amounts of butadiene were formed from the dry glycol while a 25% diolefin yield resulted using water vapour as diluent. The decomposition of dry butanone-2 over bentonite gave only traces of butadiene. Yields of diolefin increased using water as diluent, 44.8% being obtained at 700 °C. with a ketone–water molar ratio of 1 to 40. Butanone-2 was considered intermediate in the formation of butadiene from butanediol-2,3.

ISSN:1923-4287    

DOI:10.1139/cjr47b-010

出版商:NRC Research Press    

年代:1947

数据来源: NRC