The reactions of nitrosyl chloride and dinitrogen tetroxide with acetylated glycals. Acetylated 2-deoxy-2-nitroso-c-D-hexopyranosyl chlorides and nitrates

and acetylated 2-nitroglycalsl

R. U. LEMIEUX, T. L. NAGABHUSHAN,~ AND I. K. O'NEILL Department of Cl~emistry, Utziversity of Alberta, Edt1zotiton, Alberta

Received August 9, 1967

Reaction of nitrosyl chloride with acetylated glycals affords, with a high degree of stereospecificity, dimeric acetylated 1,2-cis-2-deoxy-2-nitroso-~-~-aldopyranosyl chlorides. Reaction of acetylated glycals with dinitrogen tetroxide, depending on the reaction conditions, can give either acetylated 2-deoxy-2- nitroso-a-D-aldopyranosyl nitrates as dimers or acetylated 2-nitroglycals. The mechanisms of these reactions are discussed.

Canadian Journal of Chemistry, 46, 413 (1968)

Although nitrosyl chloride has been used extensively since its early introduction into organic chemistry (I), the mechanism and stereochemical route of the addition of nitrosyl chloride to olefinic double bonds has received attention only in recent years (2, 3). The kinetic studies by Beier and co-workers (2) led to the conclusion that the reaction proceeds by way of a moderately polar and highly ordered tran- sition state. Meinwald, Meinwald, and Baker (3) concluded that the cis-addition to strained olefins involves a four-centered addition mech- anism. Although no reference could be found to addition of nitrosyl chloride to vinyl ethers, it could be anticipated at the debut of this investigation that nitrosyl chloride would add readily to acetylated glycals in a cis-addition as previously noted for the chlorination of the triacetates of D-glucal and D-galactal (4). In the course of this research a publication by Ser- fontein, Jordaan, and White ( 5 ) appeared in which the nitrosyl chloride adducts of the acetates of D-glucal and D-arabinal were de- scribed as 3,4,6-tri-0-acetyl-2-nitroso-2-deoxy-cu- D-glucopyranosyl chloride and 3,4-di-0-acetyl- 2-nitroso-2-deoxy-/3-~-arabinopyranosyl chlor- ide, respectively. We accordingly con~municated (6) the results of our own investigation. The purpose of this comn~uilication is to report the

1This research was presented in theses by T. L. Naga- bhushan and I. K. O'Neill in partial fulfillment of the requirements for the Ph.D. degree, 1966, and also at the 150th Meeting of the American Chemical Society, Atlan- tic City, N.J., September 13-17, 1965. Abstract of Papers, p. 21D.

2Present address: R & L Molecular Research Ltd., 8045 Argyll Road, Edmonton, Alberta.

details of this research together with the addition of dinitrogen tetroxide to acetylated glycals.

The addition of dinitrogen tetroxide to alkenes has received much attention (7) and is known to provide a variety of products. The path of the reaction is strongly dependent on such factors as the solvent (7), the temperature (8), and the nature of the alkene (9). These characteristics are also exhibited in the reactions of dinitrogen tetroxide with alcohols and amines (10). Thus, although the reaction with alcohols and second- ary amines gave nitrites and nitrosoanlines at 0" with ether as solvent, nitrates, and nitramines were produced at -80" using inethylene chloride as solvent. These observations could be ration- alized on the basis that dinitrogeil tetroxide exhibits the properties of nitrosyl nitrate (2) and can undergo nucleophilic attack at either the nitro or the nitroso group depending on the nature of its activation by the environmental factors. However, physical measurements at very low temperatures indicate the dinitro structure (1) (11, 12). Thus, as suggested by Schaar- schmidt (13) in 1924, dinitrogen tetroxide is an equilibrium mixture of structural isomers. The isomerization may involve homolysis to the monomeric nitrogen dioxide. However, in view of the powerful electrophilic nature of the reagent, heterolysis to nitronium and nitrite ions by way of intimate ion pairs can be envisaged. In nitric acid the compound exists as ionic nitro- nium nitrite (14). Certainly, nucleophilic attack on the dinitro form (1) can be expected to yield nitration with nitrite ion as leaving group. On the other hand, nucleophilic attack on the nitro- syl nitrate form (2) should lead to nitrosylation

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414 CANADIAN JOURNAL OF CHEIMISTRY. VOL. 46, 1965

with nitrate ion as leaving group in the manner observed for nitrosyl chloride. Indeed, the results of this investigation are in agreement with these contentions.

Nitronitrite Nitrosonitrate

F Reaction of tri-0-acetyl-D-glucal (3) at -40' in ethyl acetate and a nitrogen atmosphere with nitrosyl chloride resulted in a product (5) readily isolated in near quantitative yield with the com- position expected for addition across the double bond. No evidence for the formation of more than one isomer was obtained and it is assumed that the compound has the trans configuration shown. The molecular weight was in agreement with the dimeric structure shown and this was confirmed by hydrogenation to a substance characterized as the corresponding azoxy com- pound. Thus, the intermediate adduct (4) did not tautomerize to the chlorooxime. Solutions of (5) were only a very light blue-green indicating a highly stable dimer. The monomeric form appeared to be a deep blue-green since this was the color of the first product of the reaction. The

spacing of the doublet for the anomeric protons of 3.5 c.p.s. together with the spacings, 9.0 and 3.5 c.p.s. of the quartet for the 2-protons require the configuration of the compound to be a a-D- gluco on both moieties. The nuclear magnetic resonance (n.m.r.) parameters for 5 and related compounds are given in Table I.

TABLE I Nuclear magnetic resonance parameters for dimeric

acetylated 2-deoxy-2-nitrosoaldopyranosyl chlorides and nitrates*

Chemical shifts (7) Spacings (c.p.s.) H-1 H-2 H-3 J1.2 J 2 . 3 J3.4

Chlorides or -~ -~Iuco (S ) 3.33 4.54 3.95 3.5 9.0 9.5

Nitrates o r - D - ~ ~ U C O (9) 3.23 4.49 4.06 4.2 11.1 9.4 or-D-gnlacto (11) 3.26 -? -i 3.7 - -

*In each case, the s i~nals for the other protons (acetyl, C-5, and C-6 positions) were in the normal posit~ons.

'(Part of a multiplet in the r 4-5 region.

The cis-addition of nitrosyl chloride to tri-0- acetyl-D-glucal (3) is in keeping with the facts that the initial electrophilic attack provides a relatively stable carbonium (oxocarbonium) ion and that the solvent is of relatively low polarity. Thus, both bridging of the double bond in the cation and separation of the ions are not to be expected and addition by way of an intermediate (probably with considerable intimate ion-pair character) as depicted in (6) is both sterically and electronically favorable. It is noteworthy in this

H20Ac

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LEMIEUX ET AL.: REACTIONS O F ACETYLATED GLYCALS 415

regard that Ohno, Okamoto, and Nukada (15) have found the addition of nitrosyl chloride to cyclohexene to give the trans dimeric adduct in liquid sulfur dioxide and the cis isomer in methylene chloride, chloroform, and trichloro- ethylene. The preference of the route to the a- gluco rather than the p-manno configuration in the addition to (3) is considered likely as a result of the stereoelectronic considerations advanced by Lemieux and Fraser-Reid (4) to explain the cis-addition of chlorine to (3) to yield the a-gltrco dichloride.

Dimeric tri-0-acetyl-2-deoxy-2-nitroso-a-D- galactopyranosyl chloride (7) was readily pre- pared in the manner described for the prepara- tion of 5. A lower temperature and the use of methylene chloride as solvent seemed desirable for the preparation of dimeric di-O-acetyl-2- deoxy-2-nitroso-a-D-xylopyranosyl chloride (8). Attempts to purify this substance led to its con- version to di-0-acetyl-2-nitro-D-xylal (15) in low yield. This latter compound, as will be seen below, is readily obtained by reaction of di-0-acetyl-D- xylal with dinitrogen tetroxide.

The reaction of acetylated glycals with di- nitrogen tetroxide could be made to yield either dimeric acetylated 2-deoxy-2-nitrosoglycosyl ni- trates or acetylated 2-nitroglycals depending on the reaction conditions used. In all experiments, an approximately equimolar mixture of di- nitrogen tetroxide and oxygen was passed through the solution of the acetylated glycal in order to suppress the formation of dinitrogen trioxide (8). When the reactions were carried out at 0" using diethyl ether as solvent, the nitrosyl nitrate adducts were readily isolated in crystalline form. Thus, tri-0-acetyl-D-glucal was converted to dimeric tri-0-acetyl-2-deoxy- 2-nitroso-a-D-glucopyranosyl nitrate (9) in 91 % yield. The structure of this compound was evi- dent froin its composition, molecular weight, and n.m.r. spectrum (see Table I). Furthermore, treatment of (9) with acetic anhydride and sodium acetate was found to yield the same

penta-0-acetyl-2-oximino-D-arabino-hexose (10) as was formed on a similar treatment of the nitrosyl chloride adduct (5). The inorganic residue from this reaction was found to contain nitrate but not nitrite ion. The yield of nitrosyl nitrate adduct (11) from tri-0-acetyl-D-galactal was only 58%. These compounds, particularly the latter, were extremely prone to decomposi- tion. The product expected to be dimeric di-0- acetyl-2-deoxy-2-nitroso-a-D-xylopyranosyl ni- trate was too unstable to allow its isolation. In all these decompositions, as for that noted above for the decomposition of dimeric di-0-acetyl- 2-deoxy-2-nitroso-a-D-xylopyranosyl chloride, the main product was the acetylated 2-nitro- glycal.

When the acetylated glycal was reacted at -70" in methylene chloride, no evidence for the formation of the nitrosyl nitrate adduct was obtained. On work-up, gases were evolved and virtually pure acetylated 2-nitroglycal was ob- tained directly. In the case of the reaction with tri-0-acetyl-D-glucal, it was evident that the nitrosyl nitrate adduct (9) was not an inter- mediate since its treatment with dinitrogen tetroxide under the same conditions resulted in less than 10 % change to tri-0-acetyl-2-nitro-D- glucal (12). In view of this result and the fact that the reactions of dinitrogen tetroxide are known to be strongly solvent and temperature dependent, it seems likely that the initial attack by the dinitrogen tetroxide introduced a nitro group at the 2-position. Such an event could conceivably lead to dinitro or nitronitrite inter- mediates (7). However, it is also possible that the only intermediate was a dipolar ion which suffered loss of the 2-proton perhaps in a con- certed mechanism as depicted in (13.)

The acetylated 2-nitroglycals are highly prone to nucleophilic attack at the anomeric center and enter into a multistage reaction sequence with, for example, alcohols. The stereochemical routes of these reactions are primarily set by the conformation of the acetylated nitroglycal tl~rough operation of the effect (16, 17) involving strong interaction between the nitro group, in conjugation with the olefinic double bond, and the 3-acetoxy group. Thus, tri-0- acetyl-2-nitro-D-glucal has the conformation shown in (12). These matters will be considered in detail in separate communications (18, 19). The nitrosyl chloride adduct (5) provides a highly

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416 CANADIAN JOURNAL OF CHEMISTRY. VOL. 46, 1968

OAC P U C \ A -

stereospecific synthesis of 2-oximino-a-D-arabino- hexopyranosides which in turn can be converted in high yield to either 2-amino-2-deoxy-a-D- glucopyranosides (20) or to a-D-glucopyrano- sides (21). The nitrosyl chloride or nitrosyl nitrate adducts can be used to synthesize 2- amino-2-deoxysugars (22). Thus, it is considered that this research has opened a number of important synthetic approaches in carbohydrate chemistry.

Experimental The melting points were determined on a heating stage

and are uncorrected. Unless otherwise stated, the n.m.r. spectra were obtained with a Varian Associates A-60 spectrometer using deuteriochloroform as solvent and tetramethylsilane as internal standard.

The nitrosyl chloride (93%) and dinitrogen tetroxide was supplied by the Matheson Co., Inc., East Rutherford, New Jersey.

The acetylated glycals were prepared following stan- dard procedures (23). It was necessary to distill thecrude products in the preparations of di-0-acetyl-D-xylal (24) (b.p. 95-105' at 0.3 mm) and tri-0-acetyl-D-galactal (b.p. 140-145" at 0.3 nim) in order to achieve crystalline materials. Highly pure preparations of the latter com- pound, n1.p. 30°, were not necessary to obtain excellent yields of the nitrosyl chloride adduct. Preparations which were syrups at room temperature but which appeared better than 95% pure by n.m.r. spectroscopy were used.

Dirneric Tri-O-ocety/-2-deosy-~-11itroso-a-~-g/~icop)~rntf- osyl Clzloride (5)

Dry tri-0-acetyl-D-glucal (12 g) was dissolved in re- agent grade ethyl acetate (100 ml) in a 250 nil 3-neck flask equipped with a low temperature therniometer, gas inlet, and outlet tubes. Nitrogen was passed through the niagnetically-stirred solution while it was cooled to -40" in a dry ice - acetone mixture. The gas was then changed from nitrogen to a slow streani of nitrosyl chloride (see below). After 10 niin, tlie gas streani was reverted to nitrogen and the stirring was continued for 15 min while the solution was allowed to warm to 0". The solution was then rapidly evaporated in vnc~ro at room temperature to a residue using a rotatory evaporator. The residue was nornially a near white crystalline prod- uct. However, on occasions a blue-green syrup was obtained which soon crystallized. Recrystallization from chloroform - 71-hexane gave colorless needles (1 1.9 g, 80% yield) m.p. 129-130°, [a]i3 +149' (c, 2.15 in

chloroform). The n.1ii.r. parameters are given in Table I. Thin-layer chromatography on silica gel using 10% methanol in benzene as the mobile phase showed a single spot of Rr 0.67 on spraying with 25 % sulfuric acid.

Anal. Calcd. for CZ4H32NZ016C12 (11101. wt., 675): C, 42.67; H, 4.74; N, 4.15; CI, 10.52. Found (niol. wt., 600, osmometric): C, 42.50; H, 4.71; N, 4.10; CI, 10.49.

On occasions, the product of the reaction was tri-0- acetyl-2-nitro-D-glucal (12). The formation of this com- pound appeared related to the rate of addition of the nitrosyl chloride.

Ditneric Tri-O-ncet.v/-2-deo?cy-2-1fitroso-a-~-gnIncto- p)~ranosyl Chloride (7)

The procedure described above for the preparation of the gluco isomer was applied to syrupy tri-0-acetyl-D- galactal (47.5 g) and gave 49.5 g (84%) of conipound, m.p. 128-13l0, [a]:: +128" (c, 2.2 in chloroforni). The n.m.r. parameters are given in Table I. Thin-layer chron~atograpliy as above detected only one coniponent.

Anal. Calcd. for C24H3zN20,6C12 (mol. wt., 675): C, 42.67; H, 4.74; N, 4.15%. Found (mol. wt., 674, os- monietric):C, 42.44; H, 4.78; N, 4.16.

Ditneric Di-O-ncety/-2-deoxy-~-r1it,.oso-a-~-x)~/o~~)~rnr~osy/ Cfzloride (8 )

Di-0-acetyl-D-xylal (4.9 g) was reacted with nitrosyl chloride under tlie conditions described above except that dry methylene chloride (15 ml) was used as solvent and the reaction was conducted initially at about -80". The blue syrup obtained on solvent removal ill vacuo below 30" crystallized from a metliylene chloride - hexane mixture. The yield was 5.85 g (90%). After one recrystal- lization, the very labile compound, +164' (c, 3 in chloroform), nielted in tlie range 102-106°. Although satisfactory elementary analyses could not be obtained, the n.m.r. parameters for the compound listed in Table I are taken as unequivocal evidence for its identity. Also, the n.m.r. spectrum required tlie conipound to be of high purity. Attempts to further purify the substance by recrystallization froni metliylene chloride - hexane gave a partially crystalline material froni which a 29% overall yield of solid di-0-acetyl-2-nitro-D-xylal (15) was iso- lated. Recrystallization of this product froni ethyl acetate gave a colorless conipound, n1.p. 128-129", [a]i3 -31 9' (5, 2.1 in chloroforni), identical to that prepared in high y~eld by reaction of di-0-acetyl-D-xylal with dinitrogen tetroxide.

Hydrogetration of (5) to arz Azoxy Colnpour~d Dimeric tri-O-acetyl-2-deoxy-2-nitroso-cc-~-~co~1yran-

osyl chloride (5) (2 g) in 20 nil of dioxane containing

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LEMlEUX ET AL.: REACTIONS OF ACETYLATED GLYCALS 417

five drops of acetic acid was hydrogenated over 0.5 g of 5 % palladium on carbon at atmospheric pressure and room temperature. Within 1 h, one mole-equivalent of hydrogen was consumed. The catalyst was removed by filtration through Celite and the filtrate was evaporated to about 10ml. Addition of water caused precipitation and the precipitate was collected, dried, and recrystal- lized from ether. The yield was 1.17 g (60%) of a com- pound, m.p. 201-202", [a]i3 +204" (c, 1.8 in chloroform). The infrared spectrum exhibited characteristic ester car- bony1 absorptions at 1725 cm-', 1740 cm-', and 1750 cni-I. In addition, bands at 1635 cm-' and 1295 cm-I attributable to N = N andN+O absorptions, respectively, were present. The n.m.r. spectrum showed the presence of six acetyl groups and two doublets at r 3.43 and 3.47 each with a spacing of 3.5 c.p.s. attributable to two nonequivalent anomeric protons.

Anal. Calcd. for C,4H32N2015C12 (mol. wt., 658.8): C, 43.71 ; H, 4.85; N, 4.25. Found (mol. wt., 654, osrno- metric): C, 43.85; H, 4.95; N, 4.24.

Pe t1 ta -O-ace ty l -2 -ox i , n i t1o -~ -arab ino -~1ose (10) Anhydrous sodium acetate (2.44 g) was added to a

solution of dimeric tri-0-acetyl-2-deoxy-2-nitroso-a-D- glucopyranosyl chloride (5) (5 g) in acetic anhydride (50 ml). The mixture was stirred vigorously for 30 min at 60". The product, 5.80 g (near quantitative yield), isolated in the usual manner, was a colorless syrup, [a]b3 +31.7" (c, 3.15 in chloroform).

The infrared and n.rn.r. spectra were identical to those of the product from the same reaction starting from dimeric tri-0-acetyl-2-deoxy-2-nitroso-a-D-glucopyrano- syl nitrate (9) (see below).

The same product was obtained when triethylamine was used as base and the reaction conducted at 0" during the addition of the base and then at room temperature for 30 rnin.

Pet1ta-O-acer~~l-2-oxitt1it1o-~-ly~o-I1exopyrai1ose Treatment of tri-0-acetyl-2-deoxy-2-nitroso-a-D-galac-

topyranosyl chloride (7) with acetic anhydride containing either sodium acetate or triethylamine as indicated above for the glrrco isomer gave a colorless syrup, [a]i3 +lSO (c, 2.76 in chloroform), with the same characteristic infrared absorption bands as reported below for coni- pound (10). In this case, however, the n.m.1. spectrum of the syrup showed it to be an about 1 :2 mixture of two isomeric compounds. The minor component produced a singlet at r 2.91 (anomeric proton) and a doublet with spacing of 3.5 c.p.s. at r 3.99 (3-proton). The major component had these signals at r 3.33 and 3.87, respec- tively.

Dirneric Tri-O-acety/-2-deoxy-2-i1i~roso-a-~-glifcopyra11- osyl Nitrate (9)

The cylinder of dinitrogen tetroxide was kept in a water bath to ensure a constant stream of the gas. The gas was blended with a stream of dry oxygen to provide an about equin~olar mixture. Tri-0-acetyl-D-glucal (4.00 g) was dissolved in ether (50 ml) in an apparatus similar to that described for its reaction with nitrosyl chloride. The flask was cooled to 0" in an ice-water bath and oxygen was briefly passed through the solution. The mix- ture of dinitrogen tetroxide and oxygen was then intro-

duced to the stirred solution until a slight excess of the dinitrogen tetroxide had been added (about 4 h). This amount was estimated by prior calibration of the flow rate. At this point, the gas stream was changed to a rapid stream of oxygen until most of the ether had evaporated. The semisolid residue was dissolved in the minimum amount of rnethylene chloride and this solution was added to n-hexane kept at 0". The crystalline preci- pitate was collected, washed with iz-hexane, and dried. The yield was 4.91 g (91 %), m.p. 120-12l0, [@]A7 + 165" (c, 1.7 in chloroform). The infrared spectrum contained a broad nitrate absorption band centered at 1680 cm-I. The n.m.r. parameters are given in Table I.

Anal. Calcd. for CZ4H32N4012 (mol. wt., 728.6): C, 39.56; H, 4.43; N, 7.69. Found (mol. wt., 701, osmo- metric in chloroform): C, 39.63; H, 4.53; N, 7.33.

Attempts to concentrate the ethereal solution to a solvent-free syrup led to extensive decomposition with the formation of tri-0-acetyl-2-nitro-D-glucal (12).

Reaction of (9) with sodium acetate in acetic anhydride as described above for the preparation of penta-o-acetyl- 2-oximino-~-arabir~0-hexopyranose (10) gave an identical product. The configuration of the anomeric center is not known but is most likely a-D in view of the high degree of stereospecificity in the reactions of the corresponding nitrosyl chloride adduct (5) with alcohols and phenols (25). The n.m.r. spectrum of compound (10) showed signals for H-l (singlet), H-3 (doublet), and H-4 (quar- tet) at r 3.35, 3.84, and 4.46, respectively. The spacings indicated approximate coupling constants of J3,, = 7.5 and J4,5 = 8 C.P.S. H-5 and the two H-6's gave their signals in the region r 5.5-6.1. Acetyl group signals were at r 7.84 (two), 7.87 (one), and 7.93 (two). The infrared spectrum contained a broad, weak C=N stretching at 1645 cm-I, and C=N-OAc at 1780cm-' (26) but no absorptions characteristic of the nitro group.

Anal. Calcd. for C16H21NOll (mol. wt., 403.3): C, 47.64; H, 5.25; N, 3.47. Found (rnol. wt., 385, osmo- metric): C, 47.94; H, 5.29; N, 3.55.

Dilution of the reaction mixture in the above prepara- tion with ether caused the precipitation of salts. The solid gave no liberation of iodine on adding to acidified aqueous sodium iodide solution but a dark blue colora- tion was produced on adding the liiaterial to diphenyl- amine in concentrated sulfuric acid (27). Therefore, nitrate but not nitrite was a product of the reaction.

Ditt~eric Tri-0-acetyl-2-deoxy-2-nitroso-a-D-galacto- pyrai~osyl Nitrote (11)

Tri-0-acetyl-D-galactal (1.72 g) in anhydrous ether (30 ml) was allowed to react with dinitrogen tetroxide as described above for 1.5 h. The yield of crystalline product was 1.18 g, m.p. 123-124" (decomp.), [a]A7 +187" (c, 2.6 in chloroform). The infrared spectrum contained a broad band centered at 1680 cm-I assigned to the nitrate group. The n.m.r. parameters are given in Table I.

Anal. Calcd. for Cz4H,zN40zz (mol. wt., 728.6): C, 39.56; H, 4.43; N, 7.69. Found (rnol. wt., 725, osmo- metric): C, 39.55; H, 4.56; N, 7.83.

Tri-O-acerj~l-2-11itr.o-~-gl~fcfl/ (12) Tri-0-acetyl-D-glucal (3.00 g) was dissolved in dry

methylene chloride (50 ml) in the apparatus described

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418 CANADIAN JOURNAL OF ( ZHEMISTRY. VOL. 46, 1968

above. With the oxygcn stream on, the solution was cooled to approximately -80" in a dry ice - acetone bath. The dinitrogen tetroxide stream was then admixed with the oxygen stream. At this point, the temperature of the solution rose by about 10" and there developed a very pale-blue coloration. After 10 min, the stream of dinitro- gen tetroxide was turned off and the stream of oxygen continued for a further 10 min. The resulting solution was then evaporated below 25" to a green syrup which evolved gases. Carbon tetrachloride was repeatedly evaporated in vacuo from this syrup until gases were no longer evolved. After thorough drying in a high vacuum, the hard colorless glassy material weighed 3.46 g (99% yield). The n.m.r. spectrum allowed the presence of only one compound, [ 1 ~ ] ~ ~ 2 0 " (c, 3 in chloroform) which resisted crystallization. The infrared spectrum contained strong absorptions for olefinic bond and nitro group asymmetric stretching at 1645 and 1510cm-', re- spectively. The n.m.r. spectrum at 100 Mc.p.s. showed signals at r 1.67, 4.01, 4.73, 5.26, 5.52, and 5.80 assigned to H-1, H-3, H-4, H-5, H-6, and H-6', respectively. The following coupling constants were estimated, J3,4 = 2.9, J4.5 =Z.O, J6 .6 , = 12.0, J1.3 = 0.3, J3.5 = 1.8 C.P.S. An interpretation of these data is reserved for a forthcoming publication (18). The acetyl-group signals were at r 7.89 (two) and 7.90 (one).

Anal. Calcd. for ClZHl5NO9 (mol. wt., 317.3): C, 45.43; H, 4.77; N, 4.42. Found (mol. wt., 337, osmo- metric in benzene): C, 45.37; H, 4.85; N, 4.12.

Tri-0-acetyl-2-nitro-D-galactal (14) Tri-0-acetyl-D-galactal (6.41 g) was treated with dini-

trogen tetroxide and oxygen as described above. The yield was 7.07 g (94%) of a hard glass, [ol]d3 +6S0 (c, 3 in chloroform), which could not be crystallized. The n.m.r. spectrum at 100 Mc.p.s. required a high degree of purity. The signals at r 1.77, 3.68, 4.52, 5.35, 5.46, and 5.63 were assigned to H-1, H-3, H-4, H-5, H-6, and H-6', respect- ively. The following coupling constants were estimated, J3.4 = 5.1, J4.5 = 4 .1 , J s .~ = 3.5,J5,6, = 4.1,J6.6.=1?.1, J1.3 1. 0.3, J S f 5 = 0.4 C.P.S. The acetyl-group signals were at r 7.89 (two) and 7.92 (one).

Di-0-acetyl-2-nitro-D-xylfll (15) Di-0-acetyl-D-xylal (4.13 g) was treated with dinitro-

gen tetroxide and oxygen as described above. The yield was 5.0 g of a crude crystalline product which was puri- fied by sublimation at 100' and 0.3 mm. The yield was 3.91 g (77%) of material, m.p. 128-129', [ol]g3 -319" (c, 2.1 in chloroform). The n.m.r. spectrum at 100 Mc.p.s. had signals at r 1.61, 4.02, 4.90, 5.46, and 5.92 which were assigned to the H-1, H-3, H-4, H-5, and H-5' protons, respectively. The following coupling constants were estimated, J3,4 = 3.0, JJV5 = 2.1, J4,50 = 1.5, J5,5. = 12.8, J1.3 5 0.3, J3,5 = 1.8, J3,5, = 0.6, and J 1 , 5 , = 0.9.

Anal. Calcd. for C9Hl1NO7 (mol. wt., 245.2): C, 44.08; H, 4.52; N, 5.71. Found (mol. wt., 237, osmo- metric): C, 44.19; H, 4.54; N, 5.69.

Acknowledgments

The authors are indebted to the National Research Council of Canada for grants (T-172) in aid of this research. The spectra and micro- analyses were provided by the service labora- tories of this department.

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