O~VATI~OIJsollgC~~~~~~~~~' B. Doblnmon, A.B. Forter8ndY.Sta0.

y
ChemletryDepartaent,TheUniveralty, Birml@mm, 15 (Reoelnd 16 January 1956)

TEE formation of the new aeymetrlo oarbon atom in the reaotlon of

tin-

saldeh@e (and other aldehydee exoept formaldehyde) ulth rtlgar derlvatlvee to yield 5- and 6- membered oyolle metals might be expeoted to yield dlaetereolromere. Apperently,and am predloted,lonly one dlaetereoleomer le formed ln moat bensylldenatlon reaotlone whloh afford a 6-membered oyollc aoetal (1:3-dloxanderivative).The expected * dlartereolsowr would have the phenyl group equatorial3 to the 1~3-dloxanring. However, ln oertaln oaeee two produot8 have been lrolated and there are frequently alted aa examplee of dlrtereoleomere. Thue jWoero-mlo-heptltol ("agluaoheptltol") yleldr 4 a mono+be~lldene derivative (m.p. 155456') (1.~.

whleh 10 converted to'3:5~~~lld~~~~~o~heptl~l~

218O) on reorystalllutlon from ethanol.4 Slmllarly~pereeltol (g-&oeroderlvatlvee mheptltol) ylelde 6 two 1:3-5:7-dl-Q-bensylldene -~-~-------_-__-_-~ ' A?&@ md =lti, w. Pure DDl. ChO8*2, 185 (1952);Yilla,

Adv. CerbohTdrateciw& g, : (1956).

3 Bartoa,Eueel,PltserandPrelog, 4 FImher, Ann. a, 6 Hem, Hum 64 (lS92);kr.

mmLona,u, 228 1524 (W4).

1096 (1953 1

5 Hum, lIe8e and wdron, J.

44, 1769 (1946).

emd lhxlum, J- IIYT. chew pko, 291 765 (1946). L

2 &

Some oarbohydrate benzyldene Derivatives m.p. 15F155O CQlD- 58.2' (midim);B, derivativez wera obtained on methylatlon
a~. 2W, fd,

-58.1'). Idenof 4 and 2

tioal

or benaoylation

and A was aonverted into 2 by repeated rearystalliaation pyridine. facile Parallel resultrr were obtained in

from ethanalseries.6 The

the g-perseltol

nrearrangement of the labile

forma and the \d R valuea suggests

polymorphism. Through the aourtemy of Dr. R.K. Riahtmyer samples 6 of the lr35r7-di-g-benzylidene able; the m.p.8. derivatives of g- and &- perseitol were made avallAll four compounds

of these compounds were ae reaorded.6 infra-red

gave indietinguishable Thle is compelling

speatra both in Rujol mulls and KRr diske.

evidence that the substances aomprlee two pairs of It is noteworthy that both ais7 were unaffeoted by treatment

polymorphio forma not diastereolaomers, and trans1:3-O_benzylldene glyaeritol

with hot ethanol-pyridine. From the reaotion a of magnesium dlphenyl with methyl
213~anhydro-

4:6-g-benzylldene-+allopranoeide -2-deoxy-2-G-phenyl-u-kgluoopyranoride

three forma of methyl 4;6-g-benzylidene were isolated (c, m,p. 163.5O, CC,.,+

143' (CHC13); 2, ma. 194.5',CalD

* MO;

2, m.p. 144.5',kr],+ 132O)

at the aaetal aarbon atom of C and eaponlflaatlon

and 2 were considered

to be diastereolsomerla

and 3

to be a mixture of 2 and 2. Renzoylation of

of the produat gave 2; rearyatallleation ethanol gave a product zith an

crude 3 (m.p. 139-l45O) from

even wider m.p. range.

Although the pattern of behaviour of thwe compounds resemble8 that of the di-O_benzylldene-perseitols the EJ, values suggests that
they

are not polymorphs. Specimens of 2, 2 and g were kindly provided for ______________I_-___ 7 Baggatt, 8 Richards, porter and Staoey, J. Chem. Soa, Chem. 6s Ind, 1229 (1958). 2013 (1955).

Someoarbohydrate benxyldene Derivatives

examination by Dr. G.R. Rlohards; storage spectra

the m.p.s.

of C and 2 had not changed on (150-1600). The lnfre-red

but that of g had become more diffuse

of s, 2 and E in KC1 disks suggested C and 2

to be different methyl

oompounds end E to be a mixture of Cand 2. If, 2t3-anhydro-4t6-~-benxylidene-a-~-ellopyrenoslde then any atereoohemloal reaction differenoe

as seems probable,

is a pure diastereoisomer in the

between C and 2 must arise

of the epoxide compound with magnesium diphenyl. The reaction of benzaldehyde ritb glvceritol products, cis-and w trans9represente a unique

case since glyceritol, aoetal

the relevant

lrj-g-bensylideneat either C2 or the w

may be considered

diastereoleomeric

carbon and further, influence

intra-molecular

hydrogen banding lo

significantly Similar

the amount of each Isomer formed in the reaction, apply to the reaction of R-nitrobensaldehyde and

considerations

glyoeritol.ll The reaotion diasterecisomerio of bensaldehyde with sugar derivatives acetala (lrJ-dioxolan to yield derivatives) yields l2 two

5-membered cyclio

is well substantiated; 3:4-Q-beneylidene [&)

thus methyl R+rabopyranoslde lsoleted as the bensoates + 2Y0).

derivatives

(m.p, 126-127O,

+ 1740 (CIiC13); m.p. 100-102, yield8

@R

Methyl a-@=nno(m.p. 181-182,

ppwoaide

l3 two d&Q-benmylidene m.~. 97-98, y

derivativea

[c]R + 0.9 -to1

(CRC4); (rtyzwitol)

caj R - 61.3) [&

as doer 1:5_enhydro-

(m.~. 1651

- 148 (C=13)r

gIrvine,Heodonelddsoutor , d.Cha.
lo m, Footer Bnd Staooy, l1 Rlbbert and Carter, ,I. Amer. Cha l2 ~Oldham and Emeymul n f. l3 Robertson, J. Chem. Soo, 330 (1934). 3, 1803 (1931). l4 4MMna arrd Takimoto, g&

191, 344 (1915).

Chem. & Ind, 1228 (1958). Soo, jQ, 3376 (1928). 986 (1946).

Some aarbohydrak

besyldene

Derivativo8

ID.& 19201950, [bJ,- W).

If aa wapl likelyrl theeeoompoundrr am 2:3-

4:6-di~benaylldeme dorlvative# then the differamermay well be due to rtereoohemhal varIatIona at the aaetalaarbona In the l:3-dloxolan rings.

The aad Dre.

author0thmk

Mr. A.S.

White

for meaawement of the epeotra

dlsauemlon.

K.J. Morgan and D.H. Whlffen for helphil