ROGERlv.JEANLOZ
5692
AND
DOROTHY A.
VOl.
JEANLOZ
so
needles, m.p. 206-207". Admixture with material obtained 2-Deoxy-2-(2 '-hydroxynaphthylideneamino)-6-O-methylfrom V did not depress the melting point. 0-D-galactose (XI).-To a solution of 42 mg. of X in 1 ml. of Acetylation of 53 mg. of VI11 with 0.5 ml. of acetic anwater was added a solution of 90 mg. of 2-hydroxynaphthalhydride and 1.0 ml. of pyridine was carried out in the usual dehyde and 60 mg. of CH3COONa,3H20in 6 ml. of methway. The sirupy residue obtained after evaporation of the anol. The mixture was treated as previously described.8 solvents by codistillation in uacuo with toluene crystallized The residue was suspended in benzene and chromatographed in the presence of small amounts of ether and pentane on on silicic acid. Elution with mixtures of ethyl acetate and cooling with Dry Ice. Purification by chromatography acetone 1:1 and with pure acetone gave 59 mg. of crystalline on silicic acid gave 62 mg. (87%) of the 3,4-di-O-acetyl de- fractions. Recrystallization of the main fractions from a rivative. By recrystallization from a mixture of ether and mixture of methanol and acetone afforded 28 y g . (45%) of pentane, 49 mg. (69%) of long needles were obtained, m.p. small yellow clusters of needles, m.p. 189-191 , with slight 83.5-85". 1 0 1 1 ~ ' ~+lo1 f.2" (in chloroform. c 0.99). A n d . decomposition. The compound showed mutarotation from Calcd. for'&Hz&N: C, 50.44; H, 6.95. Found: C, [ C Y I ~ ~fU O I (after 20 minutes) to [aI2'6461 280" 258 =I= 3" 50.45; H, 7.01. after 17 and 45 hours (in methanol, c 0.98). Anal. Calcd. for C18H2106N: C, 62.24; H, 6.09. Found: C, 62.39; H, One hundred and thirteen mg. of crude VIII, obtained 6.15. from 130 mg. of VI1 by hydrolysis with 60% acetic acid, was 2-Acetamido- 1,3,4-tri-O-acety1-2-deoxy-6-O-methyl-arefluxed overnight with 4 ml. of acetone and 10 ml. of methyl D-galactopyranose (XII).-Crude X, obtained by hydrolysis iodide in the presence of 0.5 g. of silver oxide. After a new addition of 0.5 g. of silver oxide, reflux was continued for 10 of 150 mg. of VII, was acetylated with 2 ml. of acetic anhydride and 3 ml. of pyridine for 20 hours a t room temperahours. The suspension was filtered through a layer of Celite and the silver residue washed with acetone. After evapora- ture. The crystalline residue, obtained after removal of the solvents by codistillation with toluene and absolute ethanol, tion, the combined filtrates gave 114 mg. of a crystalline reswas chromatographed on silicic acid. Mixtures of ether and idue, further chromatographed on silicic acid. Mixtures of ethyl acetate, 2 : l and 1:1, eluted 171 mg. of crystalline ethyl acetate and acetone 1 : l eluted 60 mg. of crystalline fractions. Recrystallization from a mixture of ethanol, ether fractions. Recrystallization from a mixture of acetone, ether and pentane gave methyl 2-acetamido-2-deoxy-3,4,6-and pentane gave 103 mg. (%yo)of needles, m.p. 219-220", [ a I z 3 D +lo1 k 2" (in chloroform, c 1.03). Anal. Calcd. tri-0-methyl-a-D-galactopyranoside (IX), m.p. 190-191 .So, forC1hH~a09N:C,49.86; H,6.42. Found: C,49.94; H,6.44. showing no depression of melting point in admixture with 2-Acetamido-2-deoxy-6-O-methyl-~-galactose (XIII).authentic material6; [ a I z 3 D +143 & 2" (in chloroform, c To a solution of 75 mg. of XI1 in 1.5 ml. of methanol was 0.94). 6-0-Methyl-a-~-galactosamineHydrochloride (2-Amino- added 0.15 ml. of 1.6 N barium methoxide. After standing 15 hours a t 0" and 2 hours a t room temperature, the solution 2-deoxy-6-0-methyl-a-~-galactose Hydrochloride) (X) .--A solution of 163 mg. of VI11 in 5 ml. of 3 N hydrochloric acid was diluted with 2 volumes of water and neutralized by a was heated for three hours in a sealed tube a t 100". A4fter stream of carbon dioxide. After filtration, traces of barium cooling, the solution was evaporated in V Q C U O in the presence ion were removed by passing through a column of Dowex 50, of absolute ethanol and gave 156 mg. of a crystalline res- and the solution was evaporated to dryness in zlacuo. The residue crystallized from a mixture of methanol and acetone idue. It was dissolved in methanol, the solution was filtered through a double layer of Darco G-60 and Celite, and to give 15 mg. (307,) of fine needles, m.p. 165-168', [ a I z 4 D 92 + 5" (in water, c 1.12), n o mutarotation being obconcentrated under a stream of nitrogen to a volume of 2 ml. served. Anal. Calcd. for C ~ H ~ O O N . H C, ~ O42.68; : H, By addition of 4 ml. of acetone, 140 mg. (93y0) of clusters of small prisms were obtained. The compound decomposed a,t 7.56. Found: C, 42.68; H, 7.63. 190-195' and showed mutarotation from [ a I z 3 D +107.5 Acknowledgments.-The authors are indebted to -1-92 2' after 16 and 60 hours (after 5 minutes) to l a l Z 3 ~ Hoffmann-La Roche, Basel, for a generous gift of (in water, c 1.04). A d . Calcd. for C ~ H I G O ~ HC, C ~36.61; : D-galactosamine hydrochloride. H , 7.02; C1, 15.44; OCH3, 13.51. Found: C, 36.42; H, BOSTON, MASS. 6.89; C1, 15.47; OCH3, 13.69.
+
+
[CONTRIBUTION FROM
THE
DEPARTMEXT OF MEDICINE, HARVARD MEDICALSCHOOL, AND MASSACHUSETTS GENERAL HOSPITAL]
THE
MEDICAL SERVICES OF
THE
The Solvolysis of Sulfonyl Esters of Methyl a-D-Glucopyranoside and Methyl WDAltropyranoside' BY
ROGERlv. JEANLOZ
AND
DOROTHY A.
JEANLOZ
RECEIVED APRIL 5, 1958 The solvolysis in methyl Cellosolve solution in the presence of sodium acetate of sulfonyl (methylsulfonyl and p-tolylsulfonyl) esters in position 2 and 3 vicinal to a carboxyl (acetyl, benzoyl, a-ethyl-n-butyryl) ester of methyl a-D-glucopyranoside and methyl a-D-altropyranoside has been studied. Positions 4 and 6 were blocked by a benzylidene group or benzoyl groups. Walden inversion a t the carbon linked to the sulfonyl group with retention of configuration a t the carbon bearing the carboxyl ester was not observed. Hydrolysis of the carboxylic ester group took place, followed eventually by solvolysis of the sulfonyl group with epoxide formation and subsequent opening of the epoxide ring. The solvolysis in the presence of sodium methoxide of the methvlsulfonyl and benzovl esters a t positions 2 and 3 of the 4,6-0-benzylidene derivatives was investigated.
In a series of papers started in 1942, Winstein and associates2 have shown the influence of neigh( I ) This is publication h-0. 235 of the Robert W. Lovett Memorial Foundation for the Study of Crippling Disease, Department of Medicine, Harvard Medical School; address: Massachusetts General Hospital, Fruit St., Boston 14. This investigation has been supported by research grants from the National Institute of Arthritis and Metabolic Diseases, National lnstitutes of Health, Public Health Service (Grant A-148-CZ and C 3 ) . This work was presented in part before the Division of Carbohydrate Chemistry a t the 128th Meeting of the American Chemical Society, Minneapolis, X i n n . , September, 1955.
boring groups on the solvolysis of sulfonyl esters. By varying the solvolytic medium, they were able to effect solvolysis with or without retention of the configuration a t the carbon linked to the sulfonyl group. These results were applied to the carbohydrate field by Baker and associates3 and led to ( 2 ) See S. Winstein, e l al., THISJOURNAL, 64, 2796 (19421, t o 74, 6584 (1952). (3) B. I < . Baker and I< E. Schaub, i h i d . , 76, 3804 (liJ.53); U. I ) See W.G . Uauben and K. S . I'itrer in "Steric B f i t u t - i i i C)rwnic Chemistry," 11, A I . S. S e w m a n , John Wiley and Sons,Inc., Xc.w Y w k ,
S . Y., IO.%, g . 48. (16) J. Honeyman and J. 'A*, W. Morgan,
J . Chenz. SIJC.,R I d d
(1955). (17) R E . Reeves, A d o . Cnrbohydrair Chem., 6, 108 (1951).
Nov. 3, 1958
SOLVOLYSIS OF SULONYL ESTERSOF PYRANOSIDES
5695
with one mole of pyridine. Recrystallization from a mixture of acetone, ether, pentane and a trace of pyridine gave 413 mg. (85Ojo) of rectangular platelets, m.p. 100-130". Anal. Calcd. for ClsHz"O&SCbH&N:C, 52.74; H, 5.53; N, 3.08; S, 7.01. Found: C , 52.hO; I I , 5.62; N, 2.96; S, 6.92. Methyl 2,4,6-Tri-0-benzoyl-3-~-methy~sdfonyl-~-~-glucopyranoside.-A solution of 0.5 ml. of benzoyl chloride in 2 ml. of pyridine was added a t -20" t o a solution of 300 Experimental7-l8 mg. of the pyridine adduct of methyl 2-O-benzoyl3-0Methyl Z-O-Methylsulfonyl-a-D-glucopyranoside.-To a methylsulfonyl-a-D-glucopyranosidedissolved in 10 ml. of solution of 500 mg. of methyl 4,6-0-benzylidene-2-0-methylethylene dichloride. After standing a t 0" for 3 days, the sulfonyl-a-~-g~ucopyranoside~ in 6 ml. of glacial acetic acid solution was treated with ice and extracted as usual. The heated on the steam bath was added dropwise 4 ml. of water. residual sirup was purified by chromatography, the main After one hour of heating, 10 ml. of water was added and fractions being eluted with a mixture of benzene and ether the solution was evaporated in vacuo, the last traces of sol- 9: 1. Crystallization from a mixture of ether and pentane vent being removed by codistillation with dry toluene. gave 235 mg. (61%) of prismatic needles, m.p. 156-157', After drying in the desiccator, the sirup was crystallized [aIz4~ $124 f 2' (in chloroform, c 1.36). Anal. Calcd. hv addition of methanol. Recrvstallization from a mixture for CzrH280&: C, 59.58; H , 4.83. Found: C, 59.39; H, of.acetone and ether gave 326 mg. (87%) of elongated 4.92. prisms, m.p. 117-118', [ a I z 6+I20 ~ f1 ' (in chloroform, Methyl 4,6-0-Benzylidene-2-0- (a-ethyl-n-butyryl) -(Y-Dc 3.22). Anal. Calcd. for C8H1608S: C, 35.29; H, 5.92; g1ucopyranoside.-To a solution of 10.0 g. of methyl 4,6-0S. 11.78. Found: C, 35.36; H, 5.92; S, 11.63. benzylidene-a-D-glucopyranoside in 50 ml. of pyridine, Application of the same procedure to methyl 4,6-0- cooled a t -20", was added 6.0 ml. (1.3 moles) of a-ethyl-nbenzylidene-2-0-~-tolylsulfonyl-cr-~-glucopyranos~de~ gave butyryl chloride. After standing one hour a t 0" and 0.5 in a 94% hour a t room temperature, the mixture was treated with ice methyl 2-0-p-tolylsulfonyl-a-D-glucopyranoside yield after recrystallization from a mixture of acetone, ether and extracted as usual. Crystallization from a mixture and pentane; m.p. 139-140", [ a I z a$. ~ 97 f 2' (in chloroof ether and pentane gave 10.25 g. of prismatic crystals; form, c 0.94)." Anal. Calcd. for C ~ & ~ D O c~ ,S 48.26; : m.p. 110-111", [aIZ6D+92 & 2" (in chloroform, c 2.14). H, 5.79; S, 9.20. Found: C,48.45; H, 5.85; S, 9.09. Anal. Calcd. for CZDH&: C, 63.14; H , 7.42. Found: Methyl 6-O-Benzoyl-2-O-methylsulfonyl-a-~-glucopy~anoC, 63.11; H , 7.43. side.-T?o a solution of 68 mg. of methyl 2-0-methylsulChromatography of the mother liquors gave 1.3 g. (130/,) fonyl-a-D-glucopyranoside in 0.5 ml. of anhydrous pyridine, of a sirup, eluted by a mixture of benzene and ether 99: 1, cooled a t -20", was added a cooled solution of 0.031 ml. corresponding to methyl 4,6-0-benzylidene-2,3-di-O-(~~(1.1 moles) of benzoyl chloride in 0.5 ml. of anhydrous pyriethyl-n-butyryl)-a-D-glucopyranoside,[ a I z 4 +46 ~ f 1 dine. After standing one day a t -20°, the solution was (in chloroform, c 3.44). Anal. Calcd. for C2d3808: C, left a t room temperature for a few hours. Ice was added 65.25; H, 8.00. Found: C, 64.35; H, 8.30. Mixtures of and the mixture was extracted with chloroform, After benzene and ether 19: 1 and 9: 1 eluted an additional crop of washing with dilute sulfuric acid, saturated sodium bicar- the 2-monosubstituted ester which weighed 0.85 g. after bonate and water, the solution was dried over sodium sulfate crystallization (total yield, 11.10 g., 82%). and evaporated in vacuo. The residue was dissolved in Mixtures of benzene and ether 9: 1 and 4: 1 eluted crystalbenzene and chromatographed on silicic acid. Elution with line fractions. Recrystallization from a mixture of ether a mixture of ether and ethyl acetate 9: 1 eluted crystalline and pentane gave 165 mg. (17,) of fine needles, m.p. 145fractions. Recrystallization from a mixture of acetone, 146', [ ( Y ] ~ ~$83 D & 1' (in chloroform, c 1.55), to which the ether and pentane gave 61 mg. (65%) of prismatic needles, structure of methyl 4,6-0-benzylidene3-0-(a-ethyl-n-b~D f 2' (in chloroform, c 0.59). tyry1)-a-mglucopyranoside was attributed. Anal. Calcd. m.p. 124-125", [ L Y ] ~ ~+64 Anal. Calcd. for CibHzoOaS: C, 47.77; H , 5.34. Found: for Cz&&: C, 63.14; H , 7.42. Found: C, 63.12; H, _.. C, 47.79; H , 5.46. I .ai. Methyl 3,4,6-Tri-O-benzoyl-2-O-rnethylsulfonyl-a-~-gluco- Methyl 4,6-0-Benzylidene-2-0-(a-ethyl-n-butyryl)-3-0pyranoside.-To a solution of 245 mg. of methyl 2-0-methylmethylsulf onyl-a-D-g1ucopyranoside.-To a solution o ' f 5.0 sulfonyl-a-D-glucopyranoside in 25 ml. of anhydrous pyrig. of methyl 4,6-0-benzylidene-2-O-(a-ethpl-n-butyryl)-adine, cooled a t -20°, was added 0.5 ml. of benzoyl chloride. D-glucopyranoside in 20 ml. of pyridine, previously cooled a t After 3 days a t O", ice was added, and the solution was -20", was added 2 ml. of methanesulforiyl chloride. After extracted as usual. The residual sirup, partially crystal- standing overnight a t Oo, the solution was treated as usual. line, was dissolved in benzene and chromatographed on Crystallization from a mixture of ether and pentadne gave silicic acid. Elution with a mixture of benzene and ether 5.75 (96%) of prismatic needles, m.p. 110-111 , [ a I z a ~ 9: 1 gave crystalline fractions, which afforded, after re+68 i= 1" (in chloroform, c 4.09). Anal. Calcd. for crystallization from a mixture of methanol and pentane or CzrHSoOgS: C, 55.00; H , 6.59; S,6.99. Found: C, 54.24; from aqueous methanol, 350 mg. (65%) of prismatic needles, H , 6.19; S, 6.42. In admixture with the starting material, m.p. 116-119", [a]% +65 f 2" (in chloroform, c 1.74). the m.p. was depressed to 85-105'. Anal. Calcd. for C ~ ~ H B O UC, S : 59.58; H , 4.83. Found: To a solution of 50 mg. of methyl 4,6-0-benzylidene3-0C, 59.61; H , 4.96. methylsulfonyl-a-D-glucopyranoside (for preparation, see Methyl 2-0-Benzoyl-3-0-methylsulfonyl-~-~-g~ucopyranobelow) in 0.5 rnl. of pyridine, previously cooled a t -20°, side.-A solution of 500 mg. of methyl 2-0-benzoyl-4,6-0was added 0.1 ml. of a-ethyl-n-butyryl chloride. After benzylidene-3-0-methylsulfonyl-cu-~-glucopyranos~de~ was standing overnight a t O " , the solution was treated as usual. hydrolyzed as described above with 10 ml. of 607, acetic Crystallization from a mixture of ether and pentane gave acid by heating for 0.5 hour. The residual sirup was purified 56 mg. (887,) of prismatic needles, m.p. 109-lll", [ a I Z 5 ~ by chromatography. Elution with a mixture of benzene +68 z!= 1' (in chloroform, c 0.87). In admixture with the and ether 4: 1 gave crystalline fractions. After recrystalli- product described above, the m.p. was not depressed. zation from a mixture of acetone, ether and pentane 36 mg. Methyl 4,6-O-Benzylidene-3-O-(~-ethyl-n-butyryl)-2-0(7p/0) of starting material was obtained. Elution with a mixture of ether and ethyl acetate 9 : l gave 360 mg. of methylsulfonyl-a-D-glucopyranoside.-To a solution of 100 mg. of methyl 4,6-0-benzylidene-2-~-methylsulfonyl-a-~~ i: 2" (in chloroform, c 2.30). In the sirup, [ a l Z r 4-152 presence of pyridine, the product crystallized as an adduct glucopyranoside' in 0.5 ml. of pyridine, previously cooled a t O " , was added 0.1 ml. of a-ethyl-n-butyryl chloride. After standing overnight a t 0" the solution was treated as (18) R . W. Jeanloz, THIS JOURNAL, 76, 555 (1954). Microanalyses usual. Crystallization from a mixture of ether and pentane by Dr. K . Ritter, Basel, Switzerland. gave 117 mg. (92%) of prismatic needles, m.p. 130-131", (19) Brown, Fasman, McGrath and Toddm reported m.p. 138-139'; [,I*~D +43 & l o(in chloroform, c 1.26). Anal. Calcd. Wood, Allerton, Diehl and Fletcher** reported m.p. 139-140°, DI.[ for C2&00&: C, 55.00; H, 6.59. Found: C, 55.12; H , +87.Z0 in chloroform. 6.75. (20) D . M. Brown, G. D. Fasman, D. I. Mcgrath and A. R . Todd, Methyl 2,3-Anhydro-a-~-mannopyranoside.-The prepaJ . Chem. SOC.,1448 (1954). ration of thio compound was carried out on 1.0 g. of methyl (21) H.B. Wood, Jr., R . Allerton, H. W. Diehl and H. G . Fletcher, 2,3-anhydro-4,6-0 benzylidene - a D-mannoside, as preJr., J . Org. Chem., 20, 875 (1955).
In both reactions the results obtained were similar t o the ones obtained in the glucose series, and no evidence of Walden inversion a t Cz with retention of configuration a t CB or Walden inversion a t CBwith retention of configuration a t Cz was encountered.
- 2
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-
-
5696
ROGERmr. JEANLOZ
AND
DOROTHY -4. JEA41\TLOZ
Vol. 80
viously described by Myers and Kobertso~i.~ .Sfter recry+ H, 5.67; S, 6.09. These results are consistetlt with the tallization from a mixture of acetone and ether, 405 mg. presence of 10% of methyl 2,3-anhydro-4,6-0-benzplidene(750j0)of stout prisms was obtained, with physical constants a-D-mannoppranoside. different from those previously reported; m.p. 82-83", A solution of 119 mg. in 3 ml. of 1.0 N sodium methoxide [ a ] " D +lo8 =I= 1' (in chloroform, c 1.18).22 Anal. Calcd. was refluxed for 2 hours. After cooling, the solution was for C7H1205: C, 47.72; H , 6.87. Found: C, 47.60; H, 6.81. diluted with water, and extracted with chloroform. After Methyl 2,3-Anhydro-4,6-di-O-benzoyl-or-~-allopyranoside. washing with water and drying over sodium sulfate, the -To a solution of 235 mg. of methyl 2,3-anhydro-a-~- chloroform was evaporated in oacuo. The crystalline resiallopyranoside10 in 1 ml. of pyridine, cooled a t -20°, was due was recrystallized from a mixture of ether and pentane added 1.5 ml. of benzoyl chloride. -4fter standing one to give 65 mg. (977,) of methyl 2,3-anhydro-4,6-0-benzylday a t 0" the solution was extracted as usual. The residual idene-a-D-mannopyranoside, m.p. 148", [ L Y ] ~ ( D$103 f 1" product was dissolved in benzene and chromatographed on (in chloroform, c 1.30), and showing no depression of the silicic acid, crystalline fractions being eluted with a mixture m.p. in admixture with authentic ~nateria1.I~ of benzene and ether 49:l. After recrystallization from a Methyl 3-0-Benzoyl-4,6-0-benzylidene-2-0-methylsulmixture of ether and pentane, 326 mg. (647,) of prismatic fonyl-a-D-altropyranoside.-Treatment of 1.14 g. of methyl ~D =k 1' (in needles was isolated, m.p. 125-126", [ C Y ] ~ +I99 3-0-benzoyl-4,6-0-benzylidene-a-n-altropyranoside with 0.7 chloroform, c 3.48). Anal. Calcd. for C21H2007: C, 65.61; ml. of methanesulfonyl chloride, as described above, gave H, 5.24. Found: C, 65.69; H, 5.23. after chromatography a colorless sirup in quantitative Benzoylation of Methyl 4,6-O-Benzylidene-or-~-altropy-yield; [CZ]~'D +75 3~ 1" (in chloroform, c 2.15). Anal. Calcd. for C~2H2~09S: C, 56.89; H , 5.21; S,6.90. Found: ranoside with Benzoyl Chloride.-To a solution of 5.0 g. of C, 57.56; H , 5.72; S, 5.97. These results are consistent methyl 4,6-0-benzylidene-o-~-altropyranoside~~ (m.p. 172174') in 35 ml. of anhydrous pyridine, cooled a t -20", was with the presence of 10% of methyl 2,3-anhydro-4,6-0benzylidene-or-D-allopyranoside. added a cooled solution of 2.1 ml. (1.0 mole) of benzoyl h solution of 121 mg. in 3 ml. of 0.22 N sodium methoxide chloride in 21 ml. of anhydrous pyridine. After standing a t 0" for 24 hours and a t room temperature for 2 hours, ice was refluxed for one hour and subsequently treated as dewas added and the solution was extracted as usual. The scribed above. Recrystallization from a mixture of acetone, residue, weighing 7.0 g., was dissolved in benzene and chro- ether and pentane gave 61 mg. (88%) of methyl 2,3-anhydro-4,6-0-benzylidene-a-~-allopyranoside, m.p. 203-204", matographed on silicic acid. Elution with a mixture of [ L U ] ~ ~+138 D + 1' (in chloroform, c 0.91), and showing no benzene and ether 49: 1 gave 2.85 g. (33%) of methyl 2,3-di0-benzoyl-4,6-0-benzylidene-~-~-altropyranoside, as a depression of the m.p. in admixture with authentic matecolorless sirup, [(Y]"D +9 Z!C 1' (in chloroform, c 1.52). rial.= Reaction of the 0-Benzoyl-0-methylsulfonyl Esters at Anal. Calcd. C2sHzsOs: C , 68.56; H, 5.34. Found: C, 68.38; H, 5.48. Catalytic debenzoylation of this material Positions 2 and 3 of Methyl 4,6-O-Benzylidene-~-n-glucogave the starting material in a yield over 85% after re- pyranoside and Methyl 4,6-O-Benzylidene-or-~-altropyranoside with Sodium Methoxide.-To 25 ml. of a 0.22 N solucrystallization. Elution with a mixture of benzene and ether 9 : l gave 1.44 g. (219&) of crude crystalline fractions. tion of sodium methoxide (0.55 millimole) was added in each Recrystallization from a mixture of ether and pentane af- experiment 100 mg. (0.22 millimole) of the following forded 1.31 g. (19y0) of methyl 2-0-benzoyl-4,6-0-benzyl- derivatives: methyl 2-0-benzoyl-4,6-0-benzylidene-3-0methylsulfonyl-a-~-glucopyranoside,~ methyl 3-0-benzoylidene-a-D-altropyranoside, as long needles, m.p. 138-139", 4,6 -0-benzylidene -2-0-methylsulfonyl-oc-~-glucopyrano[ c Y ] ~ ~-5 D i 1' (in chloroform, c 1.25). Anal. Calcd. for C21H220i: C, 65.28; H , 5.74. Found: C, 65.12; H, 5.90. side7, methyl 2-0-benzoyl-4,6-0-benzylidene-3-0-methylFurther elution with a mixture of benzene and ether 9: 1 gave sulfonyl-or-D-altropyranoside and methyl 3-O-benzoyl-4,B1.38 g. (207,) of methyl 3-0-benzoyl-4,6-0-benzylidene-~-0 -benzylidene - 2 -0-methylsulfonyl-a-D-altropyranoside. After one hour a t room temperature (20-30') the solution D-altropyranoside, as a colorless sirup, [ C X ] ~ O D +131 f 2" (in chloroform, c 1.39). Anal. Calcd. for C~lH2!07: C, was concentrated a t room temperature under a stream of nitrogen and the residue was extracted with chloroform. 65.28; H, 5.74. Found: C, 65.32; H, 5.81. Elution with ether gave 0.96 g. of the crude starting mat:rial, or 0.93 g. After washing with water and drying over sodium sulfate, the chloroform solution was evaporated in z~ucuoand the (187,) after recrystallization, m.p. 171-172 . residue recrystallized or purified by chromatography on Benzoylation of Methyl 4,6-O-Benzylidene-a-~-altropyranosiae with Benzoic Anhydride.-.% solution of 500 mg. silicic acid. of methyl 4,6-0-benzylidene-or-~-altropyranosideand 450 From the reaction of the first compound, 69 mg. ( 9 0 7 ~ ) mg. (1.1 moles) of benzoic anhydride in 2 ml. of anhydrous of methyl 4,6-0-benzylidene-3-O-methylsulfonyl-or-~-glucopyridine was heated a t 70" for 40 hours. After addition of pyranoside was isolated after recrystallization from a mixice, the reaction product was treated and chromatographed ture of chloroform, ether and pentane; m.p. 145O, [ o r I z 5 ~ as described above. Elution with a mixture of benzene +92 1' (in chloroform, c 1.74) and showing no depression and ether 49:l gave 38 mg. (4YG)of 2,3-dibenzoate as a of the m.p. in admixture with authentic material.'6 colorless sirup, [CY]'~D +9 =k 1' (in chloroform, c 1.17). From the reaction of the second compound, 13 mg. (13%) Elution with a mixture of benzene and ether 19: 1 gave 270 of starting material was recovered, in addition to 45 mg. mg. of crystalline fractions. After recrystallization from a (55YG) of methyl 4,6-0-benzylid~ne-2-0-methylsulfon~l-o1mixture of ether and pentane, 240 mg. (3570) of methyl D-glucopyranoside m.p. 135-136 , [ a ] 2 6 ~+75 zt 1 (iii 2-0-benzoyl-4,6-~-benzylide1ie-or-~-altropyranoside was ob- chloroform, c 1.76) and showing no depression of the m.p. tained, m.p. 138-139". Elution with a mixture of benzene in admixture with authentic material.iJ6 and ether 4: 1 gave 13 mg. (270) of impure 3-0-benzoyl deFrom the reaction of the third compound 46 mg. (82%) ~ f 3" (in chloroform, c 0.46). Elution rivative, [ a I z 6+110 of methyl 2,3-anhydro-4,6-0-benzylidene-or-~-mannopywith a mixture of benzene and ether 2 : l gave 230 mg. of ranoside was isolated, m.p. 148", showing no depression of starting material which, after recrystallization, weighed 195 the m.p. in admixture with authentic material.I4 mg. (397,) and melted a t 170-172". From the reaction of the fourth compound (907,). of A similar experiment carried out a t room temperature for methyl 2,3-anhydro-4,6-0-benzylidene-a-~-allopyranos1de 5 days gave nearly similar results, no 3-0-benzoyl derivative LWS isolated, m.p. 203-204', showing no depression of the being isolated. m.p. in admixture with authentic material.= I n the two Methyl 2-0-Benzoyl-4,6-0-benzylidene -3 O-methylsullast experiments, most of the material separated in less than fonyl-a-D-a1tropyraoside.-To a solution of 1.O g. of the five minutes, was filtered off, and the mother liquors were 2-0-benzoyl ester in 6 ml. of anhydrous pyridine, cooled a t left to react for one hour and treated as described. -25', was added 0.6 ml. of methanesulfonyl chloride. Reaction with Sodium Acetate in Methyl Cellosolve After standing a t 0' for 2 days, the red colored solution was Solution.-Unless stated, 1 part of sugar was distreated with ice and extracted as usual. The residue was solved in 19 parts otherwise of methyl Cellosolve. One part of water dissolved in benzene and chromatographed on silicic acid. and 1 part of CH3COOSa.3H20 was added and the solution Elution with a mixture of benzene and ether 19: 1 gave one refluxed for 40 hours. After cooling, the solution wzs peak of a colorless sirup, weighing 1.20 g. r l O O q , , [ o 1 I z 6 ~ was with a large amount of chloroform, washed twice with -12 =t 1' (in chloroform, c 1.72). Anal. Calcd. for diluted and dried over sodium sulfate. After evaporation C22H2409S: C, 56.89; H , 5.21; S, 6.90. Foutld: C, 57.41; mater, of the chloroform and most of the methy1,Cellosolve i n (22) Myers and Robertson9 reported m.p. 07O, [ a ]1~4 4 . 8 ' in vacuo, a t a temperature not exceeding 50°, the residue was chloroform, dissolved in 100 parts of benzene and the solution was
+
-
Nov. 5, 1958
MANNAN PORTION FROM SITKA SPRUCEHEMICELLULOSE
5697
chromatographed on silicic acid. The traces of methyl for C14HlaO~: C, 59.57; H, 6.43. Found: C, 59.46; H, Cellosolve left in the residual material were eluted in the 6.54. In admixture with authentic material the m.p. was first benzene fraction. The results are reported in Table I. not depressed. In a general way, the starting materials were eluted by Methyl 6-0-benzoyl-2-0-methylsulfonyl-or-~-glucopyranomixtures of benzene and ether 49: 1, 19: 1 or 9: 1. Methyl side was eluted with a mixture of ether and ethyl acetate 4:1, 2,3-anhydro-4,6-O-benzylidene-or-~-allopyranoside and whereas methyl 4,6-~-benzylidene-or-~-glucopyranoside was eluted with a mixture of ether and methanol 9:l. methyl 2,3-anhydro-4,6-O-benzylidene-a-~-mannopyranoside were eluted immediately afterward with the same mixI n view of the low yields in crystalline material resulting tures of solvents. Methyl 4,6-0-benzylidene-2-O-p-tolyl- from the reaction of methyl 3,4,6-tri-O-benzoyl-3-O-methylsulfonyl-or-D-glucopyranoside was eluted by mixtures of ben- sulfonyl-a-D-glucopyranoside and methyl 2,4,6-tri-O-benzene and ether 19:l and 9:1, whereas the 2-0-methylsul- zoyl-2-0-methylsulfonyl-a-~-glucopyranos~de due to probfonyl derivative required the same solvents in proportions able loss of debenzoylated product during the extraction procedure, the mixture resulting from the reaction was evapo4 : l and 2 : l . rated to dryness. The residue was refluxed with an excess Methyl 4,6-0-benzylidene-3-0-1nethylsulfonvl-a-~-glucopyranoside was eluted with the same mixture of solvents in of 2 N HC1 for two hours. The solution then was passed 1: 1 proportion and was recrystallized from a mixture of through a column of Dowex 50 in acid form and a column acetone, ether and pentane as prismatic needles, m.p. 145of Amberlite IRA 400 in carbonate form and evaporated 146', [ Q ] ~ ~ +90 D f 1' (in chloroform, c 2.73).23 Anal. zn uacuo. The residue was chromatographed on Whatman Calcd. for ClaHsoO&3: C, 49.89; H, 5.59; S , 8.90. Found: No. 54 and No. 1 papers and developed with a mixture of C, 49.91; H, 5.67; S,8.87. In admixture with authentic butan-2-one, mater and concentrated ammonia in propormaterial, the m.p. was not depressed. The compound was tions 55: 4: 1.5. The standards used were glucose, mannose, characterized by acetylating 50 mg. with acetic anhydride a mixture of altrose and altrosan, and allose. Identification in pyridine solution in the usual manner. After crystalliza- of the spots was made with alkaline silver nitrate. Yo spot corresponding to mannose could be observed with the first tion from a mixture of ether and pentane, 55 mg. (98y0) of methyl 2-0-acetyl-4,6-0-benzylidene-3-0-methylsulfonyl-or- compound. For the second compound no very satisfactory solvent D-ghcopyranoside, m.p. 153-154", was obtained, [ a I z 6 D +72 f 2" (in chloroform, c 1.08), showing no depression was found for the separation of D-allose from D-altrose. However, it was possible to ascertain that no significant of the m.p. in admixture with authentic material.' Methyl 4,6-0-benzylidene-a-~-altropyranoside was eluted amount of D-allose had been formed from D-glucose during with pure ether. Recrystallization from a mixture of ace- the course of the reaction. tone, ether and pentane gave shinv platelets, m.p. 173-174", Acknowledgments.-The authors wish to thank [ o r I z 4 ~+114 f 2' (in chloroform, c l.02).24 Anal. Calcd. (23) Honeyman and Morgan's reported m.p. 14?-143', [a]17~ +SOa (in chloroform, c 1.0). (24) Robertson and Griffith'z reported m.p. 169-170° and DI.[ +1!266.80 (in chloroform, c 0.567); Richtmyer and Hudson13 reported m.p. 109-170°, [ a ]f 1~1 5 0' (in chloroform, c 2.0).
Dr. J. Honeyman for a sample of methyl 4,6-0benzylidene - 3-O-methylsulfonyl - a-D-glUCOpyranOside and Dr. N. K. Richtmyer for a sample of crystalline D-allOSe. BOSTON, MASS.
[CONTRIBUTION FROM THE DEPARTMEXT O F CHEMISTRY, UNIVERSITY
OF
BRITISHCOLUMBIA]
The Constitution of the Hemicellulose of Sitka Spruce (Picea sifchensis). 11. Structure of the Mannan Portion1 BY G. G. S. DUTTONAND K. HUNT^ RECEIVED APRIL15, 1958 Extraction of Sitka spruce chlorite holocellulose with aqueous sodium hydroxide yielded a hemicellulose fraction rich in D mannose and D-glucose. Methylation studies show that the sugar units are joined by ,5-1,4-links and that the chains, which are apparently unbranched, contain 40-60 sugar residues. One sample contained D-galactose in a terminal position. The structural features of these glucomannans are discussed.
It is commonly stated that one of the main chemical differences between the hemicelluloses of soft and hard woods is that the latter are predominantly xylans while the former are mixtures of xylans and appreciable amounts of mannan^.^ It is apparent that these two terms are oversimplifications in that there has been no evidence for the existence of a pure mannan in a wood hemicellulose and in the case of western hemlock hemicellulose the xylan fraction has been shown to be an arabomethoxyglucuronoxylan.4 The observation5 that the mannan-rich fraction of hemicelluloses is more soluble in sodium hydroxide than in (1) Presented in part a t the 40th Annual C.I.C. Conference, Vancouver, June, 1957, and a t the 133rd A C.S. Meeting, San Fxancisco, Calif., April, 1958. ( 2 ) We acknowledge with thanks a grant from the National Research Council of Canada and the award of a summer research associateship. (3) W. J. Polglase, Adv. Cnvbohydrale Chem., 10, 283 (1955). (4) G. G. S. Dutton and F. Smith, THIS JOURNAL, 78, 2505 (1956). ( 5 ) J. K. Hamilton, H. W. Kircher and N. S. Thompson, ibid., 78, 2608 (1956).
potassium hydroxide has enabled a good separation of these components to be made. I n the present work, Sitka spruce chlorite holocellulose was extracted with 10% potassium hydroxide and the washed and air-dry residue re-extracted with 18yo sodium hydroxide. The composition of the potassium hydroxide extract has been discussed and the structure of the aldobiouronic acid provede6 This paper is concerned with the nature of the sodium hydroxide extract and the approach to the problem has been in two ways. I n one instance the crude extract was methylated with dimethyl sulfate and sodium hydroxide7 and since the partially methylated material did not readily separate, the solution was dialyzed and evaporated between each of six successive treatments. Three further treatments with Purdie reagents8 yielded the fully methylated polysaccharide which was fractionated from chloro( 6 ) G. G. S. Dutton and K. Hunt, ibid., 80, 4420 (1958). (7) W. N. Haworth, J . Chem. Soc., 107, 8 (1915). (8) T. Purdie and J. C . Irvine, ibid., 83, 1021 (1903).
