Synthesis of some furoic and thenoic esters of the methyl d -Glucopyranosides, and their stability to high-energy radiation

Curboh) d-ore Reward:, 53 (I 977) 57-66 $1 Else\ler Sc~~ot~fis Publlshlng Company,

Amslcrdan

Sk-THESIS

AND

OF

hlETHI’L

SOhlE

FUROIC

o-GLIJCOPYRANOSIDES.

HIGH-ENERGY

- Printed

In Belgium

THENOIC

AND

ESTERS

THEIR

OF

STABILITI’

THE TO

RADIATION

ABSTRACT

esters obtained

The \rirh.

respectively,

:1-, 4).

2-furoyl

5bromo-2-furoyl

S-methyl-3-rhenoyl

11: /3-, 12).

by complete

chloride

and

e.s.r. spectra of irradiated were examined substituted

(/IL, 5; x-.

(;I-. 9: /3-, IO),

%thiopheoexry!oyl

(2.Y x IO”’ eV/gjh)

irradiation

of methyl

6),

Z-theno;I

(irr.)

5-bromothlophenencq

lx-,

chloride

methyl Q- and rhr

o-glucopyrnno~idcs

nature

contain

chloride

chloride

13:

/;-.

in the solid state to 3 doage

to determIne

u-glucopyraoosidcs

C/i-. 1: I-. 21, 1-furanscrylogl

chloride chlorlds

esterlficatlon

(I-,

subjected

oi 7. I x IO”’ sV/g.

to Thz

and irr. esters I-14

damage:

one very strong doublet

3:

/I-, 8).

loyl chloride

1-I) \\ere

ranosldc

b-D-~lucop)

of the rndlstion

(/I-.

7:

tx-.

thwe

of the un-

and one very strong

indicating that cleavage of the C-I-O bond (doublet) and dehjdrogznation of the C-I-H bond (singlet) had occurred. The e.s.r. spectra of irr. furoares 1 and 2 conrain w-on? doubizts, but thosrl of -3-6 have none, shov.lng that the gl>cosldlc bonds singlet,

in the latter

are Ilighiy

stable

IO radiation

esters indicated initiaied

that

and those in 13 and glucopyranoside(\zry i$ere decreased sinzlels).

and

pyranoslde.

lofluencc

and 12 (strong 11 (very

Intramolecular of the energy.

on the localization

The e.s.r. spectra of the irr. thcooic

In 11 and

12 ore

those in 7-10

11 are more stable srrong doublet)

13. and

by dwiparion

bonds

ofdoublets).

for 7 ond 8 (vrnf II

may arl$e (roni

elycosidic _ _

(absence

clsn~ngr

(strong

s~nple~s). compared The

of energy

The anomeric of the energy.

iorm

9 and with

stable

radiation-

doublets).

dehydroscnatlon 10 (very

radialion

rexlions

wesk.

those of methyl stability

to the ester groups. of nxthyl

to

srable (peak

than that in methyl Q-D-

doublets)

singlets).

Won, 0 sinelets). _

highly

are faIrI)

Rodi2rlon-initiated.

\\ak

transfer

but those in 1 and 2 are stable

damage.

compared fo that in methyl a-D-glucopyranoside.

and

weak

z-D-@uCO-

of these ewrs and be follo\red

D-glucopyranoside

hr\s no

58

J.

A.

HARRIS,

1. C. ARTHUR,

JR., 0. HlNOJOSA,

G. J. BOUDRE4US,

E. R. hlCCALL

IKl-RODUCTION

We have reported and

o-glucosides’-4 trometry These

on the synthesis

of cellulose5,

to study intramolecular investigations

stability

of,

techniques

were

cellulose

thenoylated

methyl

of

the

spin

during

to synthesize,

and

stability

used electron

energy-transfer

extended

furoates6

to clucldation

and radiation

and

nature

of

radiolysis

and

2-thenoatzs’.

of aromatic

resonance

radiation

have

darnage

spec-

of these esters’.‘.

IO determine

M’c

esters of

(e.s.r.) the

radiation

now

applied

these

of

furoylated

and

D-glucopyranosides.

RISLILTS

The e 3.r. spectrum lery

strong doublet

singlet

(generated

irr. methyl

P-o-glucopyranoside (I)

spectrum

generated

and

by cleavage

is probnbly

(irr.)

by cleavage

bj dehydrogenntion

tetra-0-(I-furoyI)-Pdoublet

of Irradiated

(gwxrarsd

generated

ana

methyl fx-D-glucopyranosidc of the C-I-O

of the C-l-H

bond)

bond)‘.

contains one

and one wry

\vas the same as that of the Irr. ry anomcr. -x- (2)

a very

o-glucopyranoside

\+eak,

of the C-1-O by two

five-line

bond,

radxals:

rcjpccti\ely

spectrum.

whereas

The

triplet

of

Irr. methyl

gi\ e a strong,

doubler

the very weak,

a Lcry weak,

strong

The e.s.r. spectrum

spectrum

fi\e-lint:

spectrum

is

spectrum

(generated

hy

H dehydrogenatlon

of the

methyl

group

IO yield

-0-C)

and

a very

peak,

doublet

H

I

TABLE

RESONANCE SPECTRA OF IRRADIATED

CLECTRON-SPIN bfrTHbL

Merh,

FCIROIC ESTFRS

OF

D-GLUCOP~RAI*rO5lDE~

i D-ghoprranosrde

Conrpolrnd ItO.

No. of hes (tn vact10)~

l (vs)

a-

Lim ILldrh (/IIF)

p I’ulrr#

L.

2.0047

c

2.0040 20042

2 (Vj) +e:Iil-O-(l-TUiOyl)-B-

I

2 (5) 5 (\-=)

3nomer

2

2 (5) 5 (VW)

c

Tcln-U-(‘-~Jr~nacryloyl)-8-

3

I (3) 3 (5) I (5)

2.0 0.7

2.0030

I .9 c

2.0030

*

il anomr’r

-l

3 (9 Tclra-O-(S-hromo-_‘-illroyl)-G-

8x;Lnomer

I

I (Vi%)

14

_7.0045

6

I (VU)

I.4

1.OOJY

“Irrzhslea tn the sohd SKIW. h} 60Co ;-rxltuton to a dosage 01’7.1 * 10”’ eV!g. e~cpl ior compound a-, whtsh \~zY, tmdtaied IO a dosag oi 5.2 * IO’ 3 eV/g. biicy 5. arong; \. xer4. W. wcah =h!ain line. dCdsohlcd

for cectrr oispeclrum. ‘Lines oicrlappcd.

59

FUROIC AND THENOIC ESTERSOF D-GLUCOSIDES spectrum

(generated

furanac~loyl)-/3spectrum and

by

and a strong,

-I-

(6)

triplet

in Table

of the clearly

Irr. methyl

doublet

and a weak.

?-thiophcneacryloyl)-zspectra.

It-r.

pyranoside recorded

TABLE

methyl

(9)

in Table

weak,

spectra.

the center

or very weak,

(10) singlet

II. were almost

For

are also recorded

srnglet spectrum.

D-plucopyranoside

all

(-5)

of ihe

spectrum.

Irr.

doublet

methyl

spectrum

value.

mrrhyl

strong, (14)

tetra

doublet

-p-

singlet D-gluco-

and a very strong

in Table

I.

tetra-O-(5bromo-

and

the same as the free-electron

e.s.r.

respectively

gerxrate

for the center of the respecrwc

e.s.r. spectra are also recorded

Irr.

Irr.

in Table

give a weak

(12) D-glucopyranosidc tetra-O-(3-thiophcneacryloyl)-x(13)

resolved.

stnglet

of the respective

-/I-

a strong,

terra-O-(3-

a strong,

the same as the free-electron

e.s.r. spectra

and a very weak.

generate

methyl gve

(7) and +I?- (8) D-glucopyranoslde

and $5

(11) and

Irr.

tetra-0-(5bromo-7-furoyl)-/3-

singlet

for

I. iieere almost

The g values, calculated

of the clearly

bond).

respectively

Irr. methyl

resolved,

spectrum

respectively

spectrum.

C-5-O

calculated

tetra-0-(Z-thenoyl)-r-

0-(5methyl-2-thenoyI)-rspectrum

the

give very

the ,g values.

and recorded

The line width give a kieak,

of

spectrum.

D-&rlucopyranostde

D-glucopyranosides. spectrum

clcsvage

(3) and -II- (‘4) D-glucopyranoside

singlet

e.s.r. spectrum

and

value. The line \vidths II.

It

ELECTRON-SPIN

RESONANCE

SPE(TIR?\

OF IR%ADIAiiD

THEVOlC

ESTERS OF

I (vs) :! (\3)

c

2.QoJ7

I 0%)

d

1.0033

c

1.0033

I (\S) 1 (b$) 2 fw)

c

2.005?

I (VW)

c

3.0051

I.2 I.?. I.2 c

x047 3.0048

I.2 c

2.0030

METHkL D-GLUCOPYR\NGSIDEh=

Corr?polrrrd ml. I-

Te:Lr;L-O-(l-thenoyl:-1-

1. (w) I (VW) 7, (w)

@ anomer

/3 anomer

IO

I (4 2 (w) Tetn-O-(5bromo-2lhiopheneacDloyl)-z/3 anomer Tefr~-O-(2-thiophene~crylo}I)-x-

II I2

13 1-l

2 0030

lo a dosage of 7.1 x lO-‘O cV/g. exczpr for compound “IITXII~W~ io the solid 5131e by boCo y-radlallon a. uhlsh WE, lrradlated IO 3 dosage oi 5.2 x lOi cV/g. “Key: s. srroog: v. \cry; w, weah. ’ hlain Ilne. “Calculrlted for cenlcr oi speclrum. ‘Lmes o\srlapprd.

60

J. A. HAR.RI.5. J. C. ARTHUR,

Stable

free-radicals

pyrsnojides.

The

y-radiation

to

nonlocalized,

were formed

mechanism

the

The

2-Furovl

bonds,

spectrum, given

and

hq irr.

that

groups

D-glucopyranosik

iveal,. sinslet, compsrcd

irr.

methyl

The

presence

carbohvdrate

that indicated

localization

molecule.

2-Thcnoyl

and

spectrum,

singlet

e.5.r.

radiation-inltinted doublet,

and

clcs\age

singlet

groups or

totally

(generation

than

3 the

spectrum,

form groups

tn the carbohydrate

the

a very as

of the methyl on the locnlimolecules.

on the msrh) I D-,olucop> ranosides of

the

secondary 7 and

(compounds

than

protected of only

of dsh)drogenntion.

anomeric

of these furoyl

that

gilen

(compounds

pljcojldlc

e.3 r. spaztrum.

triplet

electrons 8)

bonds and dehydrogenation

respcctlvely.

5-hlethjl-3-theno>l

respectively.

v.enher

low extent

groups

groups

clra\ayc of plycosldic

of

groups (compounds

6) almost

The

the sncrky

radlatlon-initiated pyrsnoGde).

a \rry

Axirons

thrnoyl of

clen\sge

bonds. and decreased

and

degrndatlon

a-D-glucopyranoside).

of substituted

the

D-gluco-

(\\eakrsr-doublet

e.s r. spectrum.

spectrum

ronosides

and dehydro,ocnarion.

the radiation-initiated

5 and

radtanon

of the high-energy

respectively).

8X-D-glUCOpgranOSide).

did not change the intluence

of the ener,? intiucnced

e.s.r.

of

in the methyl

2-Furonnc~lo~l

(compounds

from

e s.r. spectrum

\sith

D-glucopyrsnoside zntion also

of doublet

of

In formation

clcs\age ofglgcosidic

bond

cleavage of ,ol}cosidic

and

localizarion

strong sinslet,

the deh>drogenation triplet

given by trr. methyl

5Bromo-2-furojl

methvl

plus

doublet

high-cner,oy,

merh! I D-glucop>

on

of the glqco$dlc

dwrcxed

D-gluco-

random

The

resulted

the electrons

82-D-glucopgrano5ids).

(absence

than

groups of

1 and 2) decreased

radiation-initiated

dchydrogenatlon respectively.

furoyl

significantly

mz’thql

and 1) eliminated

electron;3.

an e.s.r. spectrum indicating

In cleavage

and very ~enk

inirially

a-D-glucopyranoside

of the cnrrsy

and rcsulrcd

incident,

by the

sod \ery

E. R. hlcCALL

esters of methyl

probably,

of high-energy

substltured

groupb (compound5

glycosidic that

of

Ci. J. BOtiDREALis,

furoic

\vas.

(very suon, 0 doublet

the localization

pyranosldcs.

molecule

that generated

presence

rnfluenced

Hl?‘iOJOS\.

the 105s of energ

in merh>l

bonds and deh)drogenntioo

0.

in irradiated,

by generation

of these electrons

stable free-radicals

e.s.r

of

carbohydrate

follovcd

the energ

JR.,

bonds

respectively.

by irr.

on

the

decreased

the

(weaker doublet, methyl

4r-~-gluco-

101 also decreased

9 and aud

deh>drogeuation

than

that

giLen

by

the

(i\eaher irr.

mcth]I

I-D-giucopyranoside). 5Bromo-2-thiophcnexrylcyl radiation-initiated (absence that

oFdoublet

giLen

pounds

by irr.

13 and

(weaher-doublet The

intensities

bonds

and decreased

and a weaker

r-D-_elucopyranoslde).

11) decreased e.s.r. spectra differ

11 and

,nroups (compounds of slycojidic

e.s r. spectrum. methyl

L’.S r. spectra

D-glucopyranosldes relate

clesvqe

singlet spectrum, 2-Tluophrnescn

the radtatlon-initiated

cleavage

than that given by irr. methyl

recorded from

of the doublers

for

irr.

furoic

those

for

the

and singlets

12) ellminsted

irr.

and

respectively, loyl

groups

of glycosidic

than (cornbonds

8r-D-glucopyranoside).

thenoic

methyl

the

the deh}drogcnation

esters of the

D-glucopyranosides.

in the e.s.r. spectra

recorded

methyl The for the

FUROIC

irr.

AND

THENOIC

ESTERS OF D-GLUCOSIDES

D-glucopyranosidcs

decreases

clea\agr

the

Indlcrlrr

that

the

of the gl>cosldic

61

presence

bonds

and

of

furoyl

and

tkno>l

the deh>drogenatlon

groups

reaclions

of

the D-plucopyranoades. The locnlvatlon

of energy 15 probably

of energy.

partlcuiarly

or rhenoyl

goups,

or selsctlw

iurovl

or rhenoyl

accr~t

the energy.

dissiparsd

the locallzalion

groups,

of

of the group

Irracila[cd

and

rhenoic

e\ci~ed

causing

intramolecular

groupsj

gl>co>idic

hair

sbjtems bond

appcnr

tv

electrons

by the

should

he able

to

could

be

clcn~a~r:

sho\\n

etTccts an

trrlnsfx

to the furoyi

the energ)

Slmikr

bsn

Thcsc

corboh>draies

rlcctron~

>~atrls; ihen,

D-~iucop>ranoside.

by tluorescena’.3.

substlrutcd

rr-elecrron

Furoic

nlrrt?yl

aromatic

through

of energy of the secondary

detincd.

v,ithout

thr? sut?>tlIuIed

5Lructures (for eximpk. SINK

well

as heni or lighr,

genntlon

absorption

or borh.

to form

zifectcd

of energy of secondary

and

t)p?s

dehydro-

of n-electron

10 dc~~ct~~a~e Ihe. ckiilrd locallzallon

L~2 characLcri>tlc

uf energy

lor

groups

b>

ha> Ins

slructures’.‘-’

EYPERlhlTNT,\L

Gtw~v-~l. -

hlelrln~

were not corrected. 621

i r.

for

merh~lsilanc

solutions

v:crc detcrmlned

Nuclear standard.

probe.

pure, and In Ihe form of

conducted

In the SRRC

Pyre\

dostmetq”.

lubes

rmnjferred recorded

at

to

a lotal

solid

@“Co radiation

po\\ders

source”.

oi

A-60

-

3-furznacrbllc

acid

spectra \\lth

\pcc1romcter

were tetra-

cqu~pped

\icrc

Irrndlalwns

\\ere

M hich had a dose rate. determined sa~nples

The

NCIC

Irradiated

Irradiated

b!,

in air

samplcj

In

\\ere

e.5 r. speara

The

b>jrcni,

Liere in chc form of

lint.

2-Furnnacryloyl (m.p.

and

hlod?l

D-glucop~ranos~Je~

u hell Irradlnred.

7.1 x IO”’ evig.

of the absorpllon

fnrerllrcciiafL~s

(n m.r.)

trmpcrarurc,

The suhsriruled

of 1.S n 1O’0 e\‘ig, h. The dosage

room

in a dry bo\ from the Pyrea to quartz tubes. ~\ith a I’arlan -1502-15 EPR spcctromacr -25;

the first dcrl\arlvc of

re>onanc‘r: at

apparatus

wirh n Perbin-Elmer

by usms ;1 I’arlnn

variable-temperature

chcmlcslly ierrous-ferric

msgntxic

in deuleriochloroform

as the internal

a L’-60-H)

In n Fisher-Johns

(1.r.) spccrrcl \jc‘re rscordcd

spcctrophoromcrcr+.

determined wlih

points

Infrared

I-II’-:

chlorlJe 41 8,

t1.a~ prepared

0.30 rnok)

and

b\

boiling

Ihion)

a solution

I clllorlilc

I 53 g,

0.15 mole) In dry benzene (I 20 ml) ior 20 h under a reflu\ condenser tcalciunl chlorldr: tube). ihe solution ~a3 evaporawd to dryness at 35 torr. dnd Lhe rzjiduc \‘.a~ Jisrilkd at 7%SI”/O.45

torr. The Jibtlllate,

had m.p. S-31

5Bromo-?-furobl furolc

(90 ml)

xld

obtained

In 90 1,, y~&l.

sohdltied

on sranding.

and

‘. chloride

(33 g, 0.16 mole)

for 20 h under

rellu\.

\\a~

and anti

prepared

Ihionbl

by boiling

chloride

then elaporatlng

a soiurion

(26 g. 0.22 mole) to dryness

of

5-bromo-2-

In dry

benzene

at 60 IO.5 torr.

The

62

J. A. HARRIS, I. C. ARTHUR, JR., 0. FiINOJUSA, Q. J. BOUDRENJX, E. R. M&ALL

residue was distilled under vacuum; a fraction having b.p. 78-8 lo/Z5 torr was : : cjoller=teb~,gg~~~~l~;:~.~~~860ss; .. ‘. ” S;Mti~l-24moy1 chlotide was prepared by boiling a ~solutim of 5-methyl2=tl&$&n&&oxylic acid @Og; W4 mole) and thionyI chloride (25 g; 0.21 mole) in dry. bemene -(1’00rhl) for *V17 h under re&, and thenwapurating at W/O.5 torr to reinave the bbmme and the exms of thionyl chloride. The residue was distilled, and a fmction.having b.p, 160”/30torrwas Wetted (21 g, yield 93%); this solid&d at 25”. 2-Th13oylchloride was prepared by boiling a mixture of 2-thiopheaecarboxylic acid (Zs g, 0.20 mole) and thionyi chloride (35 g, 0.29 mole) in dry benzene (100 ml) for h 17 h under reflux, and then evapdratingat 60”/0,5 torr, to remove the benzene and the excess of thionyl chloride, The residue was distilled, and a fraction having b.p. 144-146”/30tom was collected; this solidified at 25” (24 g, yield 85%). 2-Thiopheneacryloyl chloride was prepared by boiling a mixture of 2-thiopheneacryIic acid (25 g, 0.16 mole) and thionyl chloride (30 g, 0.25 mole) in dry benzene (IOOmI) for H 17h under reflux, and then evaporating at 6WiO.5torr, to remove the &nzene and the excess of thionyl chloride. The residue was distilled, and a fraction having b.p. lnO_103”/0.2torr was collected that solidified at 25” (24 g, yield 85%), 5-Bromo-2=thiopheneacryloyl chloride was prepared by boiling a mixture of 5=bromo=2-thiopheneacrylic acid (28 g, 0.12 mole) and thionyl chloride (21 g, 0.18 male) in dry benzene 4100 ml) for -24 h under reflux, and then evaporating at W/O.5 torr, to remove the benzene and the excess of thionyl chloride. The residue was distilled, aud a fraction having b.p. ! 12-f I F/O. 1 torr was collected (26 g, yield 87%) that solidified; m.p. 73-74”. M&yJ 2,3,~,&tetru=~-(2~~~o~~)=~=~~Z~c~~~~~~~~~~e (1). - A solution of methyl b=u-glucopyranoside (3 g, 15 mmoles) in chloroform (100 ml) and anhydrous pyridine (15 g, 0.19 mole) was cooled in ice, and a precooled solution (0”) of 2=furoyl chlori& II2 g, 92 mmoles) in chloroform (20 ml) was added during 30 min, with stirriu&, at such a rate that the temperature did not rise above 0”. After about IS min of stir$g, the &u=glucoside had dissolved; the mixture was kept in the ice-bath and stirred for 2 h at 0”, and for 17 h at 25”. It was then cooled to O”, ice-cold water (lo0 ml) was added, and the chloroform layer was successively washed with ice=cold Mhydrochloric acid, aqueous sodium hydroxide (I .3~), and water, dried (anhydrous magnesium sulfate), and evaporated at 60*/0.5 torr to a thick syrup from which a solid separated on addition of ethanol’.The solid was dissolved in chloroform, ethanol was added and the solution was cooled, whereupon compound 1 crystallized (yield 92%). AfIer two recrystallizations from the same solvent-mixture, it had m.p. 166.5i6S”,id?jiz i- 34.Pic 6.i2, chloroform); v?: 1291(-CC&), ij?j(C<], and i724cm-' (CO); mn.t. data: T 2+44-3.72 (12 H, ring), 4.3C~5.50 (7 H, pyranoside), and 6.46 (3 II, Me). Anal. Calc for C2,H&34: C, 56.84; H, 3.89. Found: C, 56.65; H, 3.71. ~@~h~~2~,4,6=~etru=O=(roy~)~=~-gi~~o~~r~u~~d~(2). - The procedure was

the same as for 1, except that was dissolved in chloroform, cooling the solution, compound from the same solvent-mixture,

methyl z-u-glucopyranoside

was used. Compund

2

and on addition of ethanol, a solid separated. an 2 crystal] ized (yield SI o;b). After two recrystnflizations it had m.p. 167-168.5~. [XI;” +S7.4) (c 6.17. chloroform); vgi 1291 (-OCO-), 1575(C=C), and 1719 cm- r (CO); n.m.r. data. r 2.45-3.74 (12 H, ring), 4.30-5.50 (7 H, pyranoside), and 6.56 (3 I-T, Me). Anal. Calc. for C27HL20r4: C, 56.84; H, 3.59. Found: C’,57.08: H. 3.95. 2,3,4,Ci-r~rra-0-12~~~~~~uc~~~u~~)-B-~-~luca~~ranns~~~ (3). - A solution of methyl P-u-glucopyranoside (2 g, 10 mmole) in chloroform (IO0 ml) and anhydreus pyridine (8.4 g, 1 I mmoies) was cooled in ice, and a prccorkd solution (W) of 2-furanacryloyl chloride (9.6 g, 61 mmolcs) in chloroform (20 ml) was added dropping, Methvi

under anhydrous

conditions, with stirring. during 45 min so that the tempcraturc

not rise above 5”. It was and the chloroform

did

then stirred for I7 h at 5”. kc-cold water ( 150 ml) was added.

layer was successively washed with ice-cold dilute hydrochloric

acid (MM), aqueous potassium carbonate (C).4111), and water, dried (anhydrous potassium

carbonate), and evaporated at StYi0.5 tow to ;I thrck ~:+‘ruythat rv;rs dissolved in petroleum ether (b.p. 40-W). The compound was purified by chromatography on a column of neutral silica gel (actkted

for 2 h at I IO’), and the product was dissolved

in ethyl acetate (100 ml)-petroleum

ether (130 ml;

solution, compound (c 4.39, chloroform): Methyl

b.p. 40-60”:.

3 separated as a solid (yield 25X), YE!: I301 (-OCO-),

On cooling

m.p. KI X!‘,

IX];”

1553, 1632 (C -CL and 1732 cm”’

2,3,4,6- mra - 0-f .?-furanncryloyi)

- CI- r,-gl~~cnp?,rurrfl.~~~~ (4).

(CO). I-.

procedure was the same as for 3, c~ccpt (hat mcthyt r-I)-&rluc(rpyr;lnosiclc vx Compound

4 separated as a solid (~icld lY’%). m.p. SJ- S5 , [x]f,’

chloroform);

tf,f:

1300 (--oco-).

1553. lhrl

of methyl P-r,-gl’iPcopyranr,nidc ( I.9 g, 9.K mm(k)

The us&.

t K1.4’ (c 6.33, i fi'0)

~rrf,~l)-l~-I,-y~~r~np~.ro~ls~lirl~D (5,.

hfrlhyl 2,3,4,6-ferra-0-(.5-h,.rlinrl-3solution

(<‘ C’). nnd 1702cm

the

-t- 59.2”

IU ;~nhydrou\

“I 0 IL pyritlinc

(93 g, I .I8 moles) at 25’ ~ati added 5-hramti---? f’uroyf chltrr*dc ( 11 li p, rr5 iTlIwdC\), and the mixture was stirred

for 24 h. The swqension ~VV:S\ filtered, and 10 the trltratc

was added ice-cold water ( 100 ml); potassium

hydrogen

carbonate

rhc mi~turc

(0.5~).

\qas macic neutral with aqueau*

and then cxtrxted with dichloromethanc.

The extract was dried (anhydrous magncrium sulfate) and c~apornlcd al 60’!8.5 trrrr, to yield a solid which was dissolved

in ethyl acetate t 10 ml) hcranc (IO IT?!), end

purified by column

ah for 3. The product

chromatography

wilt etutcd from

the

column by ethyl acetate (100 ml)-hcxune f 120 sni). ami rhc eluilkz c’b.ir~orarcli rrt 6Q”/(i,5 torr.

Compound

S was obtained

as 3 tan sqlid t~icltl 85%1. mp.

81 Mz’,

[2]i3 -t-32.0” (U 7.59, chloroform); r:fi: 12’)O( -0ct”‘) ), 1575 (I’ I’), 2nd I710 cn\ ’ (CO); n.m.r. data: r 1.77-3.65 (H H, ring), 4.20 5.50 (7 14, ()~;rcrn~$ri*k), irnd 6 46 (3 l-L Me). Anal. Calc. for Cz ,H, ,3r,C3, 4 <‘. 36.00; t1, 1 41s; BF. Ih ta. FClU;ld~ f.“. !fi h”: H, 1.98; Br, 35.93. Mrr/r,vl

2,3,4,&fefTa-0-(

S-bramu-,l-firrrr,rrl )-J-l?-!llnnrp?,fff~~~.~~~~ (6).

I hc

FUROIC

\ND

1-HEXOIC

The solution product \\as column

ESTERS OF D-CLLICOSIDLS

was passed through a column of act~\a:ed aluminum oklde. and clutch! xlth cth>l acr’tate (ISO ml). the cluate ~3s passed through

of sillca gel. and rhe cflluent

solld : 2.9 p. birld (-OCO-).

42”.;).

I53 I (C=Ck

-INI/.

Cnlc.

UZIS cooled.

m p. 6-l-65.. and

[Y]:’

Compound

~-53.2’

1715 cm - ’ (CO):

7.62 ( I2 H. ring Ale). 4.70-5.ES

H.4

65

n.m.r

(7 H. p\ rawside).

for C,,Hj,,O,,S,:

C. S3.N:

9 separated

((3 6.36,

as a white

clllorol’orm):

dala’

the a

vL,p: 1249

r 3Ll-3.6c)

(S H,

ring),

and 6.60 (3 H, 31~). H. 4.3s:

S. lS.57.

Found.

C, 5-l.00:

26: s, IS 53 lf~rl/l~./

prowdurc Compound t61.3’

-7.3.l.4-,crra-O-(s-!r,,~rlr1

\‘.a~ [he wme 10 ~3s

rsolarcd

I ml, hDr 1319 _ (-OCO-).

data.

r 3.35-3.43

ca H, rln_rl, 7.55(1:!

(

l(i).

p-D-plucopyranosldt:

as :I ~:vh~rc w,J~d (2.7 p. y~c!d ?l”.,).

(c 6.16. chloroform):

n.m.r.

/)-/i-D-~~~ucc7/7l.,‘n,ro.~/c/~

l-.I’-~l/wror

as for 9. s~.cepr [hat merh>l I5N

(C=C!.

m.p

and

-

7-I-75’,

[Y]”

’ (CO);

I7 I5 cm-

H, ring hle).-I.-!j-5.70(7

The

~33 used.

H. pyranoside),

and 6.50 (3 H. hle). Jrral. H. 4.36:

CJIC.

for C,,H,,,O,.S,:

C. 33.N:

H. -I._jS: 5.

15.57.

Found:

C, 5_7.70:

S. 15.31.

.~ftdl~ I 2.3, :.4-r~~rlw-O-(s-b~~~~ll~~~-2-rlri~i~~lrL~lliuCt.IIu.I~ J-r-n-!7lrrcop_~'~~7t7~1~7~ie ( II). .A solurlon of merhl I Y-D-glucop) ranoslde ( I g. 5. I mmol?s) In chloroform (90 ml) and anhydrou> p>rldine (20 g. 0.25 molt) was cookd I0 25 . 3 5olurioll (15-I of j-hromo-~-tlllo~hcn~3cr~ loyl chloride IS g_ _ 1’_ mmoles) in ch!oroform 1$;1s added. \\ith stIrring, at _‘S , alid the mixture NBS srlrred okernlght at 75’. and then cooled -

rn

rce

0.

IO

successively

60 10 5 torr

161s

3 SO-l.20

and CC=C).

used.

m.p.

n m.r.

XC’KIK

through ethkl

N;IS

sodium

(IOGmlJ-

3 column

of

acc’[a~c (100 ml).

solid (2.S g. >rcId 5O”b).

bKJUnl5h

chloroform):

$y:

II-L5

~1313. T 2.X-3.15

(-OCO-).

(I’

H.

ring).

and 6.55 i3 I-1. hlc). 12.16. FounG:C,-10.15:

2-fl~/,I/'/r‘~rlr:7cr I IO.1l~-p-D-~7/l/copr

~3s the same as for 11. c\ccpt 12.

ijolsted

as Ibr

11,

nluminum rk

S5-W,

elua~:.

oil&.

compound

[:]A”

(C-C),

and

chain),

-l.50-5.65

[he product

1~3s disiolvcd

1719cm-’

+7I!.3(CO):

lxlnz

I2 srlparared (c 6 81. n.m.r.

(7 H. pgranoslde),

rluted

In erhll

rcpnscd \tith

T

Y:!:

1.X1-3.05

(12).

BCCKI~Z

(-OCO-),

t I7 H. ring).

~3s

180 ml)-

a column I IO0

OT

ml). On

solId (3 I g. ~icld

I l-l5

and L-+5 (5 I-I. hle).

acetale

through

c~hyl

~1s a brwrnish

chloroljrm): darx

raf7osill~

Ihat methyl P-D-~lucop~ranoside

ether ( Iti{) ml. b.p. -l~7-60-). and the solution

ps[roleunl coolrn,o

n

\\lth

C.?C)56:H.?.IS;S.

_‘._~,~.i-I~~rfr7-O-(~-l~l~~?ll:~7-

Compo?lrld

ac(ii:ited

crhjl

~\;ls pa>jcd

(7 H. pyr:lnojrde).

f,rlrC!,H2,,Br10,,,S~

procedure

The

(CO):

li35cm-’

J.-IO-5.%X

a>

(c 6.69.

lalsr

aqueous

sull~~~e)_ and r\aporated iI1

\\a~ elurcd

si-pn~ated

(\I).

S. I2 30.

I~l~lh_l~l -

11

dljjoI!L’d

1 Th e ,oIu[lon

+91.0-

[he chloroform ac~il

ln;lgncsIum

\!;Is

and rhc product [z]A3

nnd

(-I H. charn).

..IIIU/. Calc.

\\hich

and

h>drochlorlc

drred csnh>drolJs syrup

compound

33-9-l’.

\I.35 added.

d~lure

b.p. -KMO

o\dc.

ihe clunir.

SS-S9-

H. 2.59:

(100 ml)

Ice-cold.

3 rhich

aluminum

On cooling 1511.

lo

erller I IO0 Ilil

petroleum actlkated m.p.

\\a[cr ~l[h

( I ?f!). and i\aler

h>dro\lde 3t

Ice-cold \\a;hcd

1511. 3.73~-1.20

Wbj, 1615 (1 H.

J. A. HARRlS, 3. C. ARIIIUR, JR., 0. HUUOJOSA,G. J. BOUDREAUX, E. R. MCCALL

66

AnuL Cktlc.for CJ5H26Br40, &: C, 39.86; H, 2.48; S, 12.16. Found: cl, 40.01;

ET;2ga;,s,m3@ .‘.P i%isryI‘2~;4,~t~~~~yr~~~ soh&m of qne&yl d-r@ucopyranoside

(13). -

TO a

(2 g, 10 tinroles) : in-. anhydrous pyridiae (IoOg, I-2$ moles) was added .&lid 2-&iopheneacry~o$ chtoride (11 g, 64 mmcles), and the .ntixture was stirred for WI&h at 2!Y, and cooled in ice to. 0”. Potassium cc&mate solution (I JM) was added to neutralize the acid, and the mixture was extrncbzd with chloroform. The extract was successively washed with hydrochloric acidfna) and water, dried (anhydrous sodium sulfa+), and evaporated at 60e/0.5 torr to a solibsidue (IO & which was ~~ssolvkdin ethyl ac,etate(100 ml)-petroleum ether (loOmI, .b.p; 4WiO”). The soImion. was p&&d througli a column of activated aluminum oxide, and the product was &ted with ethyl acetate (100 ml). On cuoling the duate, compound 13 separated as a solid (6&g, yield 78%), m.p. Ri-87”, [a]i3 c NW$” (c 7.17, chloroform); v_ KBt1141 (-OCO-), 1505,1616 (0, and 1711cm-’ (CO); n.m.r. da% ~2.10-3.20 (16 H, ring), 3.65-4.10 (4 H, chain), 4.15-5.75 (7 N, pyranoside), and 6.55 (3 H, Me). Ad. Calc.for C3&-Jb1 &: C, 56.89; H, 4.09; S, 17.36. Found: C, 56.84; H, 4.22; s, 17.55. Methyl Z~,d,d-t~tr~~2-ri~phe~eacryloyl)-8(14). - The procedure wm t&e same as for 13, except that methyl #I-u-glueopyranoside was used, Cumpcund 14was isolated as a solid (6.0 g, yield 78%), m-p. 82-83’, [a];” +74-l”

(c 6.64, chloroform); v,,,, RBr1143 (-OC0-), 1510, 1620 (C=C), and 1719 cm”. (CO): n.m.r. data: ~2.05-3.15 (I6 H, ring), 3.644.05 (4 H, chain), 4.45-5,65 (7 H, pyranoside), and 6.45 (3 H, Me). Armi. Calc, for CJsH~OO,oS~: C, 56.89; H, 4.09; S, 17.36. Found: C, 57.07; H, 4.18; S, 17.56.

1 2 3 4 5

0. II. I. J.

Q. u F. A. BLOUZN,AND J. C. ARTHUR, JR., Rudiut. Res., 23 (1964) 527-536. M. SARRARiwr~ J. C. AR~IJR, JR+,Chem. Id (London), (1967) 2085-2087. M. SARIWEANDJ. C. ARTHUR,JR, Carbuhrydr. Rex.. 6 (1968) 207-213. M. Smm&J, C. ARTEWR,JR., AND 0, Hnaom~, Cmbohydr. Res., 6 (1968) 333-340. C Amm, h., D. J. ~~I-‘ANONIS, T. Maa, AND 0. HINCWSA,J. Appi. P&m. Scf., 1I (1967)

6 S. SXNGFI mn 1. C. ARTHWR, JR., Carbohyck. Rs., 14 (1970) 73-82. 7 S SIGH ANDJ. C. ARTIIVR,JR, Ckboky&. Res., 17 (1971) 353-363. 8 J. C. ARTBIIR,JR., F. A. Boom, AND R. 3. DIEMINT, W. S. Dep. Agric., Agric. Res. Sew. Rep., 72-21, (1960) 7 pp. 9 It. El. Sazmm~ AND A. 0. Aum, .F. Chem P&s., 24 (1956) 56-59.