Nelson K. Richtmyer

D-glucose diphenyl dithioacetal, phenyl 1-thio-α-D-glucopyranoside, phenyl 1-thio-α-D-glucofuranoside, and some related compounds

Abstract D -Glucose diphenyl dithioacetal has been prepared for the first time, in a 71% yield, by the action of benzenethiol and concentrated hydrochloric acid on D -glucose. It has been converted by acid into phenyl 1-thio-α- D -glucopyranoside and by mercuric chloride—mercuric oxide into phenyl 1-thio-α- D -glucofuranoside; the ring structures of these thioglucosides were established by reductive desulfurization. The thioglucoside acetates, upon oxidation with hydrogen peroxide in glacial acetic acid, yielded the corresponding α- D -glucopyranosyl and α- D -glucofuranosyl phenyl sulfones. An α- D -glucofuranosyl phenyl sulfoxide could be obtained only in very small yield. Some infrared data on these compounds are included.

The formation of 1,6-anhydro-α-d-galactofuranose and 1,6-anhydro-β-d-galactopyranose by the action of acid on d-galactose

Abstract d -Galactose has been transformed by hot dilute acid to 1,6-anhydro-α - d - galactofuranose (0.95%) and 1,6-anhydro-β- d -galactopyranose (0.71%). The tri- O -methylsulfonyl and tri- O - p -tolylsulfonyl derivatives of 1,6-anhydro-α- d -galactofuranose have been described.

The isolation of d-manno-heptulose, perseitol, d-glycero-d-manno-octulose, and other compounds from pichi tops (Fabiana imbricata ruiz & pav.)

Abstract An aqueous extract of Phichi tops (the dried herbage of Fabiana imbricata ) has yielded d - manno -heptulose, the closely related perseitol ( d - glycero - d - galacto -heptitol), and d - glycero - d - manno -octulose; d -arabinitol, d -mannitol, galactitol, myo -inositol, d -xylose, d -galactose, and primeverose (6- O -β- d -xylopyranosyl- d -glucose) were also obtained. A search for d - erythro - d - galacto -octitol in the extract was unsuccessful, as also it had earlier been in Sedum spectabile extracts.

The isolation of D-erythro-L-galacto-nonulose from the avocado, together with its synthesis and proof of structure through reduction to D-arabino-D-manno-nonitol and D-arabino-D-gluco-nonitol☆

Abstract D -erythro- L -galacto-Nonulose was isolated as a sirup from the avocado fruit, in very low yield, by chromatography. The structure of the sugar was determined by degradation from the reducing end with lead tetraacetate, and from the non-reducing end with sodium metaperiodate. The two sets of reaction products thus obtained were identified with known compounds whose structures could be “overlapped” to conform with the D -erythro- L -galacto-nonulose configuration. This sugar was synthesized, and its identity with that of the avocado nonulose was established by reduction, followed by isolation of crystalline D -arabino- D -manno-nonitol and D -arabino- D -gluco-nonitol from each nonulose. Assigment of configurations to the two pairs of nonitols was determined by oxidation with Acetobacter suboxydans.

Primeverulose (6-O-β-D-xylopyranosyl-D-fructose) and some derivatives thereof

Abstract Primeverulose (6- O -β- D -xylopyranosyl- D -fructose) has been prepared by the partial rearrangement of primeverose (6- O -β- D -xylopyranosyl- D -glucose) with aqueous ammonia followed by separation of the two disaccharides on a cellulose column. The syrupy primeverulose had [α] d 20 −27.5° in methanol, and was characterized by its crystalline (2,5-dichlorophenyl)hydrazone. Some derivatives that are common to both primeverose and primeverulose, namely, the phenylosotriazole, phenylosotriazole hexaacetate, and (2,5-dichlorophenyl)osazone, are also described.

The isolation of perseitol and volemitol from Sedum. and some other observations on Sedum constituents

Because D-e~~t~l~O-D-g~~~C~O-OCtitOl is closely related to D-gijxero-D-mzmooctulose and both have been found in the avocado3, and because that octulose has been found also in Sedum3, a special search was made for the octitol in Sedum. To this end, 37.5 kg of S. speciabile Bor. was processed as described in the Experimental section, and &rally fractionated on a column of Dowex 5OW-X8 (Bat+) ion-exchange

Applications in the Carbohydrate Field of Reductive Desulfurization by Raney Nickel

Publisher Summary This chapter discusses various applications in the carbohydrate field of reductive desulfurization by Raney nickel. Reductive desulfurization with Raney nickel is a reaction that requires but the simplest of techniques, is carried out under rather mild conditions, and affords relatively good yields; it is a standard and well-recognized reaction, having found use in practically all the various fields of organic chemistry. The chapter discusses Raney nickels applications in sugar fields. Desulfurization carried out in aqueous alcohol has been observed to give rise to acetaldehyde; in view of the well-known dehydrogenating action of Raney nickel it seems likely that the solvent may play a part as a hydrogen donor in the reaction. In practice the sulfur-containing derivative is dissolved or suspended in a suitable solvent, treated with a sufficient quantity of Raney nickel, and either left at room temperature or heated under reflux, recovery of the product being effected by concentration of the liquid phase. The utility of Raney nickel desulfurization in solving problems of configuration in the sugar series is demonstrated in the ω-desoxyglycitol series. Reductive desulfurization with Raney nickel of the mercaptolysis products of streptomycin has supplied one of the keys to the elucidation of the structure and configuration of that antibiotic.

The 2-(aldo-polyhydroxyalkyl) benzimidazoles.

Publisher Summary This chapter discusses 2-( aldo -polyhydroxyalkyl)benzimidazoles and substances of this type containing hydroxylated side chains of one to seven carbon atoms in length. Typical is the benzimidazole from D -glucose through D -gluconic acid. The side chain is attached at position 2 of the benzimidazole nucleus while the numbering of substituents in the side chain proceeds in the customary manner for sugars and their derivatives—that is, from top to bottom in the accompanying example. The configuration of the side chain is designated by a prefix referring to the sugar from which it was derived—for example, D -gluco-benzimidazole. However, the more systematic name would be 2-( D -gluco-pentahydroxypentyl)-benzimidazole, the italicized portion indicating that the configurations of the asymmetric carbon atoms are the same as in D -glucose. The benzimidazole from the corresponding 6-desoxy sugar would be named 6-desoxy- D -gluco-benzimidazoloe,r 2-( D -gluco-1,2,3,4-tetrahydroxypentyl)-benzimidazole.

Crystalline d-glycero-L-gluco-octulose, crystalline methyl d-glycero-α-L-gluco-octulopyranoside, and some related compounds

Abstract Several compounds in the D - threo - L - ido -octose series are described. Syrupy D - threo - L - ido -octose was found to be converted, by long standing, into D - glycero - L - gluco -octulose ( 3 ). The same octulose has also been obtained by oxidation of D - threo - L - gulo -octitol with Acetobacter suboxydans . Treatment of D - glycero - L - gluco -octulose with methanol and an acid catalyst produced methyl D - glycero -α- L - gluco -octulo-pyranoside, whose structure was proved by degradation to methyl α- L - gluco -heptulo-pyranoside, the enantiomorph of methyl α- D - gluco -heptulopyranoside, whose pyranoside structure was proved in 1942. Some other compounds derived from octulose 3 are also described.

Preparation and reactions of some 1-amino-1-deoxyheptitols

Abstract The hydrochlorides of 1-amino-1-deoxy- D - glycero - D - gulo -heptitol ( 1 ), 1-amino-1-deoxy- D - glycero - D - galacto -heptitol ( 2 ), and 1-amino-1-deoxy- D - glycero - L - manno -heptitol ( 3 ), as well as the free aminoheptitol 2 , have been obtained in crystalline form. Deamination of 2 with nitrous acid yielded three products: perseitol ( 4 ) and two compounds that appear to be anhydroheptitols. Deamination of 3 gave similar results. In agreement with the accepted rule, compounds 1 and 2 were oxidized by Acetobacter suboxydans , whereas compound 3 was not. The oxidation product from 2 , presumably 7-amino-7-deoxy- L - galacto -heptulose ( 5 ), has been obtained crystalline.