Synthesis of D-glucose-1-C-14 and D-mannose-1-C-14

Isbell, Horace S.; Karabinos, J. V.; Frush, Harriet L.; Holt, N.B.; Schwebel, A.; Galkowski, T. T.

doi:10.6028/jres.048.023

Cited by 68 publications

(21 citation statements)

References 10 publications

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“…Application of the same sequence to glucose first gave the lactone of glucoheptonic acid and then n-heptanoic acid. Mo~vry (29) reviewed the general applications of the cyanohydrin synthesis, and its value for the preparation of higher sugars was discussed in detail by Iludson (12); others (3,13,32) studied the preparation and hydrolysis of the sugar cyanohydrins, and the synthesis has been recently used to estimate carbonyl groups in hydrocelluloses and reducing sugars (11,39), as well as to obtain sugars co11-taining radioactive carbon (14). The reduction of the sugar acids to hydrocarbon acids, on the other hand, has received little attention since the time of Kiliani. As early as 1860, Lautemann (24) employed concentrated hydriodic acid a t 140" C., or "phosphorus di-iodide" and a little water near 100" C., to reduce lactic t o propionic acid.…”

Section: Introductionmentioning

confidence: 99%

Kiliani's Reduction of Glucose and Fructose Cyanohydrins to the Corresponding Heptanoic Acids and Lactones

Perlin¹,

Purves²

1953

Can. J. Chem.

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Kiliani's classic reduction of cr-glucoheptonic (D-gluco-D-guloheptonic) lactone led to small, variable yields of n-heptanoic acid and varying amounts of the lactone of a hydroxy-11-heptar~oic acid. A repetition of this work showed that the combined yields of these two products reached a maximum near 70% of theory when the reduction with constant-boiling hydriodic acid (b.p. 127" C.) and phosphorus was limited to two hours. Under these conditions up to Y/lOths of the product consisted of the lactone. After purification through the hydrazide, m.p.8'3" C., the fragrant smelli~~g lactone boiled a t 61" to 62' C. a t 10 mm. pressure, had a density of 0.9948, and a refractive index of nD, 1.4405, both a t 20' C. The supposition that this lactone referred to 4-hydroxy-n-heptanoic acid was confirmed by preparing it from the known 4-keto-n-heptanoic acid, which in turn was synthesized by an improved method.The optimum time for reducing a n u~lcrystallized mixture of a-and 8-fructoheptonic acids under similar conditions was three to four hours, and the optimum yield of product was again near 70% of theory. This prodi~ct consisted almost exclusively of the lactone of 2-methyl-4-hydroxyhexanoic acid. After p~~rification through the crystalline hydrazide, 1n.p. 122' C., the lactone was recovered a s a fragrant oil boiling a t 48' to 4'3" C. a t 2 mnl. pressure, with density 0.0806 and refractive index n~ 1.4332 a t 25' C. The structure of this lactone was not in doubt.These lactones, prepared in good yield and with well defined hydrazides, were rnore readily characterized than the fully reduced heptanoic acids upon which ICiliani relied. INTRODUCTIONWhile considering possible ways of locating carbonyl groups in oxystarches and oxycelluloses, it appeared that the method Kiliani used in 1885 to 1888 to solve the same problem for reducing sugars might be capable of development. In the case of fructose (structure I), for example, the addition of the elements of hydrogen cyanide gave the cyanohydrin which was hydrolyzed to the a,Pmixture of the corresponding fructoheptonic acids (11). Reduction of these acids with red phosphorus and hot hydriodic acid then yielded methyl-n-butyl acetic acid (III), and the result clearly showed that the ketone group occupied the second position in the fructose. Application of the same sequence to glucose first gave the lactone of glucoheptonic acid and then n-heptanoic acid. Mo~vry (29) reviewed the general applications of the cyanohydrin synthesis, and its value

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Section: Introductionmentioning

confidence: 99%

Kiliani's Reduction of Glucose and Fructose Cyanohydrins to the Corresponding Heptanoic Acids and Lactones

Perlin¹,

Purves²

1953

Can. J. Chem.

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“…fl-'3C]glucose (92 at.%) was synthesised as described by Isbeh et al [6] except that the ghmonolactone was reduced to glucose using 3. RESULTS…”

Section: Chemicalsmentioning

confidence: 99%

Radiorespirometry evidence for the discrimination between ¹³C‐enriched glucose and unlabelled glucose molecules by Paracoccus denitrificans

et al. 1990

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Paracoccus aknitrifcans was grown on either unlabelled glucose, [lJ3c]glucose or [dl'C]glucose as the sole carbon source for growth. The cells were then incubated with a range of r4C-glucose substrates to compare the 14COz-evolution rates between cells grown on the glucose and the r3C-labelled glucose. Cells grown on %-glucose had significantly faster rates of '*CO,-evolution than those grown on unlabelled glucose. The % yields of %ZO,, per [l-Y]-, [6-r4c]-and [UJY&lucose supplied were also substantially greater than those measured for cells grown on unlabelled glucose. The data indicated that growth of Paracoccus on Y-enriched glucose substrates resulted in cells with notably different *4C-glucose oxidation metabolism compared to that observed in cells grown on unlabelled glucose.

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“…Pri o r publi cati ons fr o m thi s la bora tory have re ported me th ods for s ynth es izin g pe ntoses la be led with ca rbo n 14 at C-l and C-5 [I , 2,3 1,3 a nd hexoses la beled a t C-l , C-2, a nd C-6 [4,5,6, 7J, but , her etofo re , no me thod s ha ve bee n re ported for sy nth es izin g te trosesl_t 4C, pe ntoses-2-t 4C, and ·hexoses-3-t 4 C. In response to th e urge nt nee d fo r so me of th ese s ugars in biological rese arch , the preparation of o -glucose-3-1 4 C and ce rtain re lated co mpound s was und e rtak e n.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of D-glucose-3-14C and related compounds

Frush¹,

Sniegoski²,

Holt³

et al. 1965

J. RES. NATL. BUR. STAN. SECT. A.

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D·G lu cose·3~I4C has be e n pre pare d b y m ea ns of three, s uccess ive Kili a ni s ynth eses. Th e proc ess co ns ists of (a) the addition of I4C·l abelea. cyanid e to D·glycerald e h yde; (b) hydrolys is of t he c ya no hydr ins and co nve rsion of th e res ultin g e pim eric D·te troni c· i .14C ac id s into D·tetroses· i .14C by way of a n im · pro ve d Rose nmund re du cti on uf th e ace tyla te d te tro nyl c hl orid es : (c) additi on of nun la be led c ya nid e to th e mixture of th e aldehydo a ce ta te s of D·th reose· I · 1 4 C a nd D·erythrose·i ·1 4 C ; (d) hyd ro lys is of the cya noh ydrin s , and lac toni zation of th e res ultin g mixture of four D· pe nt oni c· , ·14C ac id s ; (e) c hrom a to· gra phi c se pa ra ti on of th ese int o three frac ti ons; (f) redu c ti o n of th e frac ti on c onta inin g D·a ra bin o no· 2· 14 C-a nd D· xy lono·2· 14 C· lac tone to th e co rres po nd in g suga rs, and c hroma togra phi c se pa rati on of th ese :and (g) co nve rsion of D·arabin ose-2·1 4 C into D·glu cose·3·1 4 C a nd D·ma nn os e·3·1 4 C b y a third Kili a ni s ynth es is. A pproxim a te ly 3 perce nt of the ra di oac t iv it y wa s o btai ne d in the form of D·glu cose·3·1 4 C, Th e process res ults in the p rod uc ti on of a la rge nu m be r of int e rmed ia te la be le d co m po und s.Ke y Words : Ald oni c a cid s; ea rbon·14·la be led c a rbo h yd rates ; c hroma togra ph y. pa pe r ; glu C'osc·3· ca rbo n· 14; hexoses·3·C' a rbon ·14; pe nt uses·2·ca rbo n·14; radi oac ti ve c a rbo ir yd ra tes ; Ruse nm u nd red uc ti on s; sy nth es is of radioac ti ve s uga rs; tetroses· l ·carbo n·14.

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Synthesis of D-glucose-1-C-14 and D-mannose-1-C-14

Cited by 68 publications

References 10 publications

Kiliani's Reduction of Glucose and Fructose Cyanohydrins to the Corresponding Heptanoic Acids and Lactones

Kiliani's Reduction of Glucose and Fructose Cyanohydrins to the Corresponding Heptanoic Acids and Lactones

Radiorespirometry evidence for the discrimination between ¹³C‐enriched glucose and unlabelled glucose molecules by Paracoccus denitrificans

Synthesis of D-glucose-3-14C and related compounds

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Synthesis of D-glucose-1-C-14 and D-mannose-1-C-14

Cited by 68 publications

References 10 publications

Kiliani's Reduction of Glucose and Fructose Cyanohydrins to the Corresponding Heptanoic Acids and Lactones

Kiliani's Reduction of Glucose and Fructose Cyanohydrins to the Corresponding Heptanoic Acids and Lactones

Radiorespirometry evidence for the discrimination between 13C‐enriched glucose and unlabelled glucose molecules by Paracoccus denitrificans

Synthesis of D-glucose-3-14C and related compounds

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Radiorespirometry evidence for the discrimination between ¹³C‐enriched glucose and unlabelled glucose molecules by Paracoccus denitrificans