Ir aq i J.Pharm.Sc i., Vol.15 (1 )  ,2006 58

Synthesis of 3 - 3 - gem – di – C –Nitromethyl Nucleoside Analogues 
of Possible Biological Activity 

Yousif A. Al-Ftahi *  , Fuad H.Al – Jawad* * , Nidhal F.Al – Mejwel** * 
Rece ived 31-8-2002         Ac cepted 20-2-2005  

ABSTRACT  
     Synthe sis of new nucleo side a nalogue s of the  type : 3 , 3 - gem – d i – C – nitro methly , exp ec te d to  
ha ve us eful app lica tion in the  c hemo therap eutic tre atment of AIDS  , c ancer and  mic ro bia l infec tions. 
The  synthes is  involve d the co nde ns atio n of the app ro pria te  s ugar d eriv ativ e ( i.e  . 3 , 3 –  ge m – di – C 
– nitromethly – 1–  ribo fura no se ) with nitro gen b as es  , suc h as  , urac il and theop hllin following a  multi 
step  s cheme s ta rting fro m diace to ne  goluco se  (1) (s che me 1) .The prep ared co mpo und  we re  id entified  
by s pec tros co pic metho ds ; ir , mas s , 1H and 13C nmr.  

  الخالصة 
ة         – C –التوائم ثناائي 3 , 3 ر مماثالت نيوكليوسيد جديدة من نوع  يتحض ي المعالجـة الكيمائـي ل محتمـل االسـتفادة منهـا ـف نيترومثـي

 )che mothe ra py  ( المراض نقص المناعة والسرطان ولالمراض الجرثومية .  
فيورانوز مع قواعد نتروجينية مثل  – D –نيترومثيل  – C –ئي التوءم ثنا - 3 , 3تضمن التحضير تكثيف مشتقات الجزء السكري 

  ) .1المخطط ) ( 1(اليوارسيل والثيوفلين باتباع مسار متعدد الخطوات يبدأ من ثنائي اسيتون كلوكوز 
وني ونظير تم تشخيص المركبات المحضرة بواسطة الطرق الطيفية االشعة تحت الحمراء والكتلة والرنين النووي المغناطيسى البروت

  . 13الكاربون 
  
  
    

INTRODUCTION  
   The  2 , 3 – d id exy  nuc le oside s ha ve  s ho wn 
importa nc e in s eve ra l es ta blis he d 
chemotherapies  (a nticance r , a ntiv iral and 
antiba cteria l ) and o ther a ttractive  fie ld  like 
immuno mod ulatio n  o r regulation o f gene 
express io n which ma y constitute  new 
therap eutic ap proac he s (1,3) . The bo ard 
ap plic atio n of modifie d nucleos id es  e sp ecially 
in the inhib ition o f the  huma n 
immuno de ficiency v irus  (HIV)(4,5) , hav e 
ta rgeted  the inves tigatio n for utilizing new 
nucleos id e analogues  .Effo rts ha ve prima rily 
fo cused  o n modific atio n o f the ca rb ohydrate 
portio n o f the natural nucleo side s b eca us e 
ce llular kinas es are mo re  tolerant o f thes e 
changes  than changes  within the  b as e 
moiety(6) . The se ob se rva tio ns , hav e le d us to 
co mmet the synthe sis of a va riety of 
nucleos id e analogues  c onta ning   3 , 3 - gem 
– di – C – nitro methyl substituent at the sugar 
portio n .  
 
 
 

MATERIAL and METHOD   
  Melting points  we re  determined  using 
electrotherma l  melting point ap paratus  and  a re  
unc orre cted .IR sp ec tra were re corde d using 
either . Shimadzu (40 8) Ja sc o (J – 008 5 ) 
infrared  sp ec trop hotome ter .  H – NMR and 
13C – NMR s pe ctra  we re  de te rmine d o n a  
Varia n XR – 30 05 (pha rm 3 00) spe ctro meter at 
299 .9 08 a nd  75.41 18 MHz res pec tiv ely . 
CDC13 or DMS O wa s us ed as  the so lv ent and  
TMS a s interna l standard . Ge ne ra l mass  
spe ctro meter mode l 51 1 v alza r was  used  for 
re cording ma ss  s pec tra .TLC was  pe rformed  
on glas s plants  c oated  with 0.25mm laye r of 
silica  gel (Fluka ) and spo t were de te cted  by 
io dine vap our. Co lumn chro matograp hy was  
carrie d out with s ilica ge l 60  ( Fluka  ) . Urac il 
from Merk Compa ny . 1 ,2  : 5 ,6  – Di – O – 
Is oprop ylid ene   –  – D – gluc ofuranose  (1) 
was prepa re d from 1 ,2 : 5 ,6  – Di – O – 
Is oprop ylid ene  – –D – ribo  – hexofuranose  – 
3 – ulos e (2) wa s p re pa re d a s p re vious ly 
des crib ed (19,20) . 

  
 

 

 

 
 
* College  o f Ed uca tion , Ibn  – Al – Haitham , Ba ghd ad Univers ity . 
** Ba ghd ad  Colle ge  o f Pha rma cy , S ynd ic ate of Ira qi phar mac is ts  . 
*** College  o f ph arma cy ,  Univer sity of Ba ghd ad. 



Ir aq i J.Pharm.Sc i., Vol.15 (1 )  ,2006 59

1,2 : 5,6 – Di – O – Iso pro pylide ne – 3 – C – 
nitromethyl –  –    – D – a llofuranose  ( 3 ) 
and 3 – de oxy – 1,2 :5,6 – di – O – 
is op rop ylidene – 3 ,3 – ge m – d i – C 
nitromethyl – – D – ribo – he xofuranos e (5) 
were prep ared as  pre viously (7) .  
3 – Deo xy – 1 ,2  :5,6 – di – O – is op rop ylidone 
– 3 – C – nitrome thylene – – D – ribo – 
he xofuranos e (4) wa s prepa re d acc ording to 
the method de sc ribe d (21) .Bis (the ophylline – 7 
– yl )mercury (1 0) was  prep ared  as  in the 
metho d des crib ed  (12) .2,4 – Bis (trime thylis ly 
urac ia l (13 ) was synthes ized  as  de sc ribe d 
be fo re(15) .  
3 – Deoxy – 1,2 :5,6 – di – O – 
isopropylide ne – 3,3 – ge m – di – C – 
nitrome thyl –  – D – ribo – 
hexofur anose (6)  
 3  – Deoxy – 1,2 :5 ,6  – d i O – is oprop ylid ene 
– 3,3 – gem – di – C nitromethyl –  – D – 
ribo hexofuranose  (5) (8.3g, 22 .9  mmo l ) wa s 
diss olved  in methanol a nd IN H2S O4(30 ml) 
was  a dde d . The rea ction mixture was left to 
stand at room te mperature for 3hr .The 
re sulting mixture  was  then ne utra lize d b y 
ad ding so lid so dium hyd ro gen c arbonate and 
then extrac ted with chloroform .The 
chlo roform extrac t was  d ried  ov er a nhydrous 
so dium sulphate and gave  upon e vap oratio n 
the diol (6) as  a  syrup (6.0 g , 
80.4 %).IR(s mear)v(345 0)c m-1 (OH) . 
3 – De oxy – 1 , 2 – O – 
isopropylide ne – 3 ,3 – gem – di – C 
– nitr omethyl –  – D – r ibo –
furanose (7)  
The  d io l (6) (2g ,6.2mmo l ) was  d is so lv ed in 
etha nol (40ml) and we ll – s tirre d , the n 
sa tura te d so lution o f so dium hydro ge n 
ca rb ona te  (2ml) was  ad ded  follo wed by a 
so lution o f  sod ium metap eriod ate ( 1 .3 2g ,6.2 
mmol ) in 70  ml w ater the  res ulting rea ctio n 
mixture was  s tirre d 3hr a fte r which the  exc es s 
so dium metaa pe rida te  wa s de stroye d by a dding 
fe w d ro ps of ethylene  glycol .The res ulting 
alde hyd o sugar was  imme diately re duc ed  with 
so dium borohydride (0 12g).After the  rea ctio n 
mixture was  kept with s tirring for 4 hr ,ac etone 
(0 .5 ml) was  a dde d and the mixture was  further 
stirred for 3 0 minutes  . The  s olid  res id ue wa s 
re mov ed by filtratio n a nd the filtra te wa s 
extrac te d with me thylene chloride , d ried  o ver 
anhyd ro us  so dium sulphate the s olve nt wa s 
re mov ed to give (7) as  a s yrup  (1 .3 9g, 
76.8 %).IR (s mea r )v(345 0)cm-1 (OH).1H – 
NMR  5.82(d,1H,H – 1 )4.72 – 4.70  (q,1H, H 
– 4 ), 4 .6 6 – 4 .6 0 (d,1H,H – 2 ),4.10 (s ,4 H , 
2CH2NO2),3.5 3(d ,2 H,H – 5 ,H – 5 ,1.38 – 
1.23 (2s ,6H,2CH3).

13C – NMR  10 4.32 ( C – 

1 ),81 .9 5 (C – 2 ),5 8.74 , 5 8.40(C – 3 ), 81.7 4 
( C – 4 ), 84 .1 9 (C – 5 ), 8 0.31 , 78.42  
(CH2NO2),1 10.51 ( O – CMe2 – O ) , 26 .5 2 ,  
 
26.06  ,. – C (CH3)2 . 
                         
5 – O – Benzoyl – 3 – deoxy – 1,2 – O 
– isopropylidene  – 3,3 – gem – di – 
C – nitr otmethyl  –   – D –   ribo – 
fur anose (8) 
The  3  – d eoxy – 1 , 2 – O – is oprop ylid ene – 
3 ,3 – gem – d i – C nitrome thyl – – D  
ribofura nos e (7) (2.4g , 8 .2  mmol ) was  
disso lv ed  in a nhydrous p yrid ine (6.7ml ,83  
mmol ) afte r e xterna l c oo ling with ic e , 
benzo yl chlo ride (0 .9 6ml ; 8.3mmo l )was  
add ed dropw is e . The  reac tion mixture  was  
kep t at roo m te mperature for 24  hr then iced  
water was  a dde d .The res ulting s yrup  was  
extracte d with petroleum ether (b.p. 4 0 – 60  
C ) ,then drie d with anhyd ro us  sod ium 
sulphate , filtered  and c onc entrated  under 
re duc ed pres sure  . Trac es of p yrid rne we re  
re move  by co eva poration with dry 
to luene  .The  be nzo ate d eriv ativ e (8) was  
obtaine d as  s yrup (1 .6 g , 50 % ).IR (s mea r )v  
(3 100  – 30 00 ) c m-1(aromatic C – 
H ) ,(171 0)cm-1( C = O) , (1 590  )cm-1 , ( C – 
C ) . Ma ss  s pec trum , ga ve  M – 3 96 ( 5 – 
benzo ate d eriv ativ e 8  ) ,a nd m/e  261  (– 
[ phCO2CH2] ) .

1H – NMR  7.47 (m , 5 H , 
aromatic ) , 5 .9 5 (d, 1H ,H – 1 ), 4.76  – 4,6 3 
(c m , H – 4  , H – 5  ,H – 5 ) ,4.5 8 (d,1H, H – 
2 ), 4 .2 (d, 2H, CH2NO2 ),3 .9 5(s,2H,CH2NO2), 
1.50 – 1.32  (2s , 6H, 2CH 3).13C – NMR 
13 3.31, 130 .0 5 , 129 .8 5  , 12 8.52, 1 28.3 8 
(a romatic  ring c arbons ) ,17 0.62(ph – 
CO ) ,105 .3 0 ( C – 1 ),8 0.02 ( C – 2 ),60.49  ( C 
– 3 ) ,79.34  ( C – 4  ) , 77 .8 3 ( C – 5 ), 7 4.88  , 
74.62  ( CH2NO3) . 
1,2 – Di – O – ac etyl – 5 – O – 
Benzoyl – 3 – deoxy – 3 ,3 – gem – di 
– C – nitromethyl – a – D – 
ribofuranosyl br omide  (11) 
  The ace tylated suga r (9 ) (1 g,2.2 mmol) was  
trea te d with 50 %(W/V) hydroge n bromide in 
ace tic  (3ml) the so lution wa s ke pt a t 0C for 
one  ho ur the n p oured  in to an ic e c oole d 
dichlorome thane (5 0ml ) , wa shed with iced  
water , and  then with sa tura te d aq ue ous  
solution of sod ium bic arbo nate to re move  the  
re maining ac id .Afte r a fina l was h with iced  
water , the  d ic hlorome thane  layer wa s dried  
ove r a nhydrous s odium s ulphate a nd the  
solve nt wa s re move d to  give  (11) a s syrup 
(0 .9 g , 95 %). The  iso la te d sugar bromide (11) 
was use d dire ctly fo r the nucleo side s ynthe sis . 



Ir aq i J.Pharm.Sc i., Vol.15 (1 )  ,2006 60

Synthesis of theophylime nuc leoside 
analogue  
7 – ( 2 – O – acetyl – 5 – O – benzoyl 
– 3 – deoxy – 3 ,3 – gem – di – C – 
nitrome thyl –  – D – ribofuranosyl ) 
the ophyline  
The  the ophylline mercury sa lt (10 ) (0 .5 5 g , 
0.98 mmol ) was finely pow dered  , s us pe nde d 
in (150 ml )s od ium – drie d xylene  and the 
so lv ent was  p artially distilled  to remo ve tra ce s 
of wa ter a zeo trop ic ally .Whe n the temp erature 
of mixture  wa s ra is ed  to 13 7 C , the  res id ual 
suspe ns io n was  a llowe d to  c ool (below 50 
C ) . The a ce tyla te d sugar bromide  (11) 
(0 .9 gm , 1 .9 6mmol )in xlye ne  wa s then a dde d 
and the reac tion mixture re fluxed  with 
vigo rous stirring fo r 15 minute . The xlyene 
la ye r was  was hed  with 20 % a que ous po tassium 
io dide to re move  the  rema ining trac es  of the 
mercuric sa lt , wa she d with wa te r , d ried  o ver 
anhyd ro us  so dium s ulphate a nd  the so lv ent 
was  remo ved  to give  after s ilica ge l column 
chro matograp hy with c hloroform a s an eluent 
the ac etylated  nucle oside  (12 ) (0 .5 7g,52 %Ja s 
syrup .IR (s mea r ) v (2 850  – 29 50 )c m-1(C – 
H ) .  
Synthesis of protected uracil 
nucleoside analogue   
1 –(2 – O – Ace tyl – 5 – O – Benzoyl 
– 3  – dideoxy – 3 , 3 –  gem – di – 
C – nitr omethyl –  – D – 
ribofuranosyl ) – 4 – ( trime thylsily ) 
urac il (14)  
 The a cetylate d sugar (9) (0.44 g, 1mmol ) and 
silylated urac il (13 ) (0 .29 g ,1 .1 mmol ) were 
diss olved  in anhyd ro us 1,2 – dichloroe thane 
(1 0ml ) . Anhyd ro us  s ta nnic  c hlorid e (0 .0 8ml , 
0.68 4 mmol ) w as then a dd ed in the prese nc e 
of few p elle ts o f molecula r siev e 4 A and 
re ac tion mixture was stirred at 2 3 C , tIc 
(c hloroform -  mcthano l )9:1) s how ed the 
re ac tion was  co mplete afte r 16 hrs  . The 
re ac tion wa s then p oured  o n an exes s so dium 
bica rbo na te  solution a nd e xtra cted  with 
methyle ne  c hlorid e .The combined  me thylene 
chlo ride  extrac ts wa s drie d o ver a nhydrous 
so dium sulp hate  , and  the so lv ent was  re move d 
to  give (14) (0.6 g , 40,3%),IR (sme ar )v(285 0 
– 295 0 )c m-1(C – H ),(3 350 )c m-1(N – H ).  
The  pro duct wa s purified  o n silic a gel column 
us ing c hloroform as  elue nt .Two d ifferent 
frac tions were iso la te d , the firs t one  (14) 
(0 .0 18g) a s white se mis olid  which repres ente d 
The  silya te d nucleo side  .1H NMR  7 .9 6 
(s ,5H,aromatic ),7 .6 6 – 7.64 (2s ,2 H,CH=CH of 
urac il ),4.6 – 4 .4  (cm,4H,H – 2 ,H – 4 , H – 
5 ,H – 5  ), 4.2(d,4H,2CH 2NO2),2 .0 2 

(s  ,3H ,CH 3), 0.90 (s ,9 H,SiMe 3 ).The s ec ond  
frac tion (1 4a ) (0.02 mg) ob ta ined  as  syrup 
id entified  a s the d es ilylated  fre e nuc le os ide  
ana lo gue .1H NMR  8 .0 5 (m,5H , 
aromatic ),7.48 – 7.43  (2 s,2H,CH=CH of 
uracil ),5.98(d,1H,H – 1 ),5 .2  – 4 .8 (c m,4H,H – 
2 ,H – 4  , H – 5 , H - 5) , 4.45 (d  , 2 H , 
CH2NO2) , 3.(d,2H ,CH2NO 2),2 .07(s,3H,CH3).  
RESULTand DISCUSSION  
1.Sythe sis of the  car bohydrate 
moie ty of the nucleoside  
3 – Deo xy – 1,2 :5,6 – di – O – is oprop ylid ene  
– 3 ,3  – d i – ge m – C – dinitro methyl –  – D 
– ribofuranose  (5) was  o btained  fro m D – 
gluco se  ac cording to the  metho d repo rted  
earlie r by o ne  o f us  (7) . Selec tive  hyd ro lysis of 
the 5,6 – isop io pylidene group of the 3,3 – ge m 
–di–C– nitrome thyl –– D – ribo hexofuranose  
(5 ) with in sulp huric acid in metha nol (8) gave  
the mo nois oropylide ne derivative (6 ) a s a  
syrup  in 80 .4% yield .Oxid atio n of the diol (6) 
with s odium pe riod ate effected  the clea vage of 
C5 – C6 Bond a nd res ulting intermed ia te  
aldehyd e derivative was  re duc ed immed ia te ly 
with s odium bo ro hyd ride  to  giv e the 3 – de oxy 
– 1,2 – O – is oprop ylid ene  – 3 , 3 ge m – di – C 
– nitrome thyl  –   – D – rib ofuranose  (8). The  
prima ry 5 – OH group in (7) was  then 
protected  b y convcrsion to the 5 – b enzoa te  
este r (8) . Trea tme nt of (7) with be nzo yl 
chloride in pyrid ine (9).ove rnight gav e the 5 – 
O–be nzoyl–3– de oxy–1,2 – O – iso propylidene 
– 3 ,3  – gem – di – C – nitro methyl – – D – 
ribofura nos e (8 ) as  s yrup in 5 0% yield . The  
fina l step  in the  synthe sis of the protected  
sugar moie ty before ca rrying o ut the  c oup ling 
re action with nuc le o – ba se s , wa s the remov al 
of 5 – O – 1 ,2  – ac etal o f 5 – O – be nzo yl 
derivative (8 ) with 99 % trifluo ro ac etic  ac id  
fo llowe d by a cetylation .Ace tylatio n of the  1 – 
and  2  – hydroxyl gro ups  wa s pe rformed  with 
ace tic  a nhydrid e in p yrid ine (9) which a fforde d 
1,2 – di – O – ac etyl – 5  – O – be nzoly – 3 – 
deo xy – 3 ,3 – ge m – d i – C – nitro methyl –  
– D – ribotura nos e (9) a s a s yrup in 90% yield .  
2- Synthesis of nucleoside analogue s   
    F or the  synthes is  of 7  – ( 2 – O – a cetyl – 5 
– O – b enzoyl – 3,3 – d i – C – nitrome thyl – 
– D – ribo – fura no syl ) theo phylline  (12 ) , 
the Koe nigs  – Knorr co nde ns atio n method was  
fo llowe d (10). Thus trea tment of 1,2  –d i – O – 
ace tylrlbofuranos e d eriv ativ e (9) with 
anhyd rous hyd ro gen bromide  in 
dichlorome thane re adily affo rd ed 1,2  – di – O 
bromide(11 ) whic h wa s use d immed ia te ly 
bec ause of its  ins tability . 
 
 
 



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Ir aq i J.Pharm.Sc i., Vol.15 (1 )  ,2006 62

The  s ugar bromide  (11 ) was  c ond ens ed  with 
bis (theop hylline – 7 – yl )me rc ury (10 ) as  the 
ac tiva te d b ase  in a nhydrous  xylene  under 
re flex which afforded  the  des ired  the op hylline  
nucleos id e analogue (1 2) , afte r silic a column 
chro matograp hy , as  a  s yrup  in 52 % yie ld  .The 
theo phylline (1,3 – dimethylxanthine )b as e ha s 
be en us ed  b ec aus e of its a vailability a nd due to 
the fact that only one of its nitrogen a to m (N – 
7 ) is  rea ctive , the re fo re  mixture of d ifferent 
nucleos id e analogues  ma y b e avo id ed . The 
re ac tion o f the ophylline  w ith me rc uric  c hlorid e 
in aqueo us a lkali a fforde d the me rc ury 
de rivative  rathe r than the chlorome rc ury  one  , 
and it was  as signed that N – 7 wa s the 
predo minate po sitio n of a tta chme nt of me rc ury 
group in the theop hylline . It has  a ls o b ee n 
de mons tra te d tha t the mercury de riva tive  of 
theo phylline c oup le  with acylglyco syl ha lide s 
at N – 7 (12 – 14) and involve s dire ct disp la ceme nt 
of the  mercury group from nitroge n by the 
inco ming ac ylgyc os yl halid e (11) . 
 F or the  synthes is  o f 1 –  ( 2 – O – a ce tyl – 5 
– O – benzoyl – 3 – de oxy – 3 ,3 – gem – di 
– C – mitromethy –  – D – ribofuranose  ) – 4 
– (trimethylsilyl ) uracil (1 4), the modifie d 
Hilb ert – Jo hnson proc edure  us ing s imply 
Frie del – Crafts  ca ta lysts like  SnCl4 wa s 
fo llowe d (15) . The 1,2  – di – O – 
ac eylrib ofurano se  d eriva tiv e (9) was  c oup le d 
with the silylated  uracil (1 3) in 1 ,2  – 
dichoro etha ne  in the  p re sence  of a nhydrous 
stannic chloride as  Lewis acid .The  rea ctio n 
invo lve d the c onv ersion of the protec te d sugar 
(9 ) in to  the rea ctive e lectrophilic 1 ,2  – 
ac etyloxo nium io n fo llowe d b y the s ilyla te d 
urac il (13 ) attak to affo rd  the  p rote cted urac il 
nucleos id e analogue (14) with the  regenera tio n 
of the catalyst . The  fo rma tio n of 1 ,2  – 
ac etyloxo nium io n d etermined  the  exclus iv e 
fo rma tio n o f the –  – ano mer (14)(15 – 16) , 
which wa s se parated  a s white  s emiso lid and 
characterize d by its  1H NMR sp ectrum . 
Ano ther fra ction (1 4a) w as se parate d o n the 
silic a gel c olumn and ide ntified  fro m its  1H 
NMR sp ec trum a s be ing the  des ilyla te d 
nucleos id e (1 4a ) .  
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