Iraqi National Journal of Chemistry,2011,volume 44,602-614
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
A New Method for the Synthesis of Dinitrogen Tetroxide
Impregnated On Charcoal (N2O4/Charcoal) and It's Application as
Selective Oxidant of Thiols to Disulfides Organic Compounds
Hussein Ismael Khalaf
Polymer Research Unit, Science College, AL-Mustansiryia University
(NJC)
(Recevied on 7/3 /2011 )
(Accepted for publication 27/9 /2011)
Abstract
A new laboratory method was investigated to prepare a liquid dinitrogen tetroxide (purity,
99%) from nitric acid and Al-Zahdi date. N2O4 was easily impregnated on charcoal to give a
stable homogeneous reagent N2O4 / charcoal.
A fast and efficient method for the
chemoselective oxidative coupling of heterocyclic thiols to afford their corresponding
heterocyclic disulfides using liquid dinitrogen tetroxide (N2O4) as the reagent in CH2Cl2 at
room temperature is described. The stability, easy preparation, high selectivity of the reagent
and high percent of products make this method as a useful procedure. The purity of liquid N2O4
was determined by titration method. The chemical structure and purity of the disulfide products
were proved by using melting point measurement, elemental analysis, and FTIR spectroscopy.
‫ﺍﻟﺨﻼﺼﺔ‬
(99%) ‫( ﺍﻟﺴﺎﺌل ﻭﺒﻨﻘﺎﻭﻩ ﻋﺎﻟﻴﻪ‬N2O4 )‫ﺘﻡ ﺍﺴﺘﺤﺩﺍﺙ ﻁﺭﻴﻘﻪ ﻤﺨﺘﺒﺭﻴﻪ ﺠﺩﻴﺩﻩ ﻟﺘﺼﻨﻴﻊ ﺭﺒﺎﻋﻲ ﺍﻭﻜﺴﻴﺩ ﺍﻟﻨﺎﻴﺘﺭﻭﺠﻴﻥ‬
‫ ﻋﻠﻰ ﺍﻟﻔﺤﻡ ﺍﻟﺤﻴﻭﺍﻨﻲ ﻟﻠﺤﺼﻭل ﻋﻠﻰ ﻜﺎﺸﻑ‬N2O4 ‫ ﺘﻡ ﺘﺤﻤﻴل ﺴﺎﺌل‬. ‫ﻭﺫﻟﻙ ﻤﻥ ﺘﻔﺎﻋل ﺤﺎﻤﺽ ﺍﻟﻨﺘﺭﻴﻙ ﻭﺘﻤﺭ ﺍﻟﺯﻫﺩﻱ‬
‫ ﺘﻡ ﺍﺴﺘﺨﺩﺍﻡ ﻫﺫﺍ ﺍﻟﻜﺎﺸﻑ ﻓﻲ ﻤﺫﻴﺏ ﺜﻨﺎﺌﻲ‬.‫( ﺍﻟﺫﻱ ﺘﻤﻴﺯ ﺒﺎﺴﺘﻘﺭﺍﺭﻴﻪ ﺠﻴﺩﻩ ﻭﺴﻬﻭﻟﺔ ﺍﻟﺘﺤﻀﻴﺭ‬N2O4/Charcoal) ‫ﻤﺘﺠﺎﻨﺱ ﻤﻥ‬
‫ﻜﻠﻭﺭﻴﺩ ﺍﻟﻤﻴﺜﺎﻥ ﻋﻨﺩ ﺩﺭﺠﺔ ﺤﺭﺍﺭﺓ ﺍﻟﻐﺭﻓﻪ ﻓﻲ ﻁﺭﻴﻘﻪ ﻜﻔﻭﺀﻩ ﻭﺍﻨﺘﻘﺎﺌﻴﻪ ﻟﻼﻜﺴﺩﻩ ﺍﻟﺘﺯﺍﻭﺠﻴﻪ ﻟﻤﺭﻜﺒﺎﺕ ﺍﻟﺜﺎﻴﻭل ﺍﻟﺤﻠﻘﻴﻪ ﻏﻴﺭ‬
‫ ﺘﻤﻴﺯﺕ ﺍﻟﻁﺭﻴﻘﻪ ﺒﺎﻻﻨﺘﻘﺎﺌﻴﻪ ﺍﻟﻌﺎﻟﻴﻪ ﻭﺍﻟﻨﺎﺘﺞ‬. ‫ﺍﻟﻤﺘﺠﺎﻨﺴﻪ ﻟﺘﻌﻁﻲ ﺍﻟﻤﺭﻜﺒﺎﺕ ﺍﻟﺤﻠﻘﻴﻪ ﻏﻴﺭ ﺍﻟﻤﺘﺠﺎﻨﺴﻪ ﺜﻨﺎﺌﻴﺔ ﺍﻟﻜﺒﺭﻴﺕ ﺍﻟﻤﻨﺎﻅﺭﻩ‬
. ‫ﺍﻟﻌﺎﻟﻲ ﻤﻤﺎ ﺠﻌﻠﻪ ﻜﺎﺸﻑ ﻤﻨﺎﺴﺏ ﻭﻤﻔﻴﺩ‬
602
Iraqi National Journal of Chemistry,2011,volume 44,602-614
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
‫ ﺍﺠﺭﻱ ﻓﺤﺹ ﻭﺍﺜﺒﺎﺕ ﺍﻟﺘﺭﻜﻴﺏ ﺍﻟﻜﻴﻤﻴﺎﺌﻲ ﻟﻠﻤﻭﺍﺩ ﺍﻟﻤﺤﻀﺭﻩ ﺒﻭﺍﺴﻁﺔ‬. ‫( ﺒﻁﺭﻴﻘﺔ ﺍﻟﺘﺴﺤﻴﺢ‬N2O4) ‫ﺘﻡ ﺘﻘﺩﻴﺭ ﻨﻘﺎﻭﺓ‬
. ‫ﺘﺤﻠﻴل ﺍﻟﻌﻨﺎﺼﺭ ﻭﻁﻴﻑ ﺍﻻﺸﻌﻪ ﺘﺤﺕ ﺍﻟﺤﻤﺭﺍﺀ‬،‫ﻗﻴﺎﺱ ﺩﺭﺠﺔ ﺍﻻﻨﺼﻬﺎﺭ‬
.N2O4 reacts also with some metals to
Introduction
form a good, stable ,and highly
Dinitrogen tetroxide (N2O4) is the
efficient reagents [Fe (NO3)3. 1.5
chemical compound that forms an
N2O4. and Cu (NO3)2.N2O4] which
equilibrium mixture with nitrogen
dioxide (N2O4
NO2
were used also to transformate the
) .It is a
sulfides to sulfoxides(17). Recently,
powerful oxidizer and hypergolic with
N2O4 was impregnated on silica gel or
various forms of hydrazine compounds
(1)
activated charcoal to give stable
. NO2 gas is made by the catalytic
heterogeneous reagents, which were
oxidation of ammonia as industrial
employed
Haber process (2).On laboratory scale, a
(3)
corresponding alcohols
, heating reaction of
of thiol
100% HNO3 and 98% H2SO4 in the
presence of Arsenic oxide
(4)
(5)
in
nature,
for the selective oxidative coupling of
thiols (23), but most of them suffer from
one or more disadvantages such as
commercial unavailability, toxicity or
and
high cost of the required reagent, long
handling problems, N2O4 was used as
reaction times. In this work we
complexes with organic polymeric
compounds(12,13)
,
important
Numerous methods have been reported
organic
agent(6-9),.oxidizing
corrosive
are
synthetic and biochemical area(22).
agent(10,11).In order to reduce of high
reactivity,
,
unique and diverse chemistry in the
transformation, they have been used as
nitrating
(20)
organosulfur compounds possessing
, provides
N2O4 and its complexes have found
application
, oxidation
sulfides and disulfides
urea’s(21).Disulfides
one of the source of N2O4 gas.
wide
(19)
(18)
N-nitrosation of amines amides and
, and
reaction of NaNO2 with 98% H2SO4 in
the presence of oxygen
chemoselective
deprotection of trimethylsilyl ether to
pure and dried lead nitrate at 500°C in
steel vessel
in
presented a new laboratory method for
Dioxane-NO2
preparation of liquid N2O4 and N2O4
(prepared from N2O4 and dioxane)(14),
/charcoal system from nitric acid and
complexation of N2O4 with 18-crown-
AL-Zahdi date in simple and efficient
6(15) and N2O4 has been supported on
procedure. We were also employed the
polyvinyl pyrolidine (PVP-N2O4)(16)
603
Iraqi National Journal of Chemistry,2011,volume
prepared N2O4 /charcoal reagent for
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
Preparation of liquid N2O4:
oxidation of some heterocyclic thiols
A three-neck round-bottom flask (1
to new corresponding heterocyclic
L) was fitted with, condenser for
disulfides. High yield and rates have
cooling, oxygen inlet and the third for
been obtained.
date feeding. It was constructed with
drying tower, oxidizing tower and
Experimental
condenser (Figure 1). 0.5 L of nitric
Al-Zahdi date was obtained from
locally
market.
Thiols
and
acid (65-98%) was added in the
other
reaction flask, and then150 g of sliced
chemicals were purchased from Fluka
date (AL-Zahdi) was added gradually
and Aldrich. The reactions were
along the time of reaction. After 5
monitored by T.L.C (silica-gel 60 F254,
minutes a brown gases was evolved,
n-hexane, ethyl acetate).The products
and blown by a stream of oxygen
were purified by flash chromatography
through condenser into a drying tower
on SiO2 (Eluent:CH2Cl2) and identified
(packed with nearly 80 g of the
by infrared spectra (KBr) which were
mixture of phosphorus pentoxide and
recorded on a Shimadzu 8261 Pc
quartz sand, P2O5:SiO2, 1 : 1 in wt),
Spectrometer. Elemental analysis (C.
then
H. N) was performed on a Perkin 240C
agent). Dimerzation of NO2 to N2O4
were obtained on a Gallen Kamp point
and liquidified was completely in the
apparatus are uncorrected. Evaporation
(cooled,-15◦C)
was carried out with Bunchier RE 120
pressure.
evaporator
under
The
oxidizing
tower
(packed with Ca.100 g of oxidizing
Elemental Analyzer. Melting point
rotary
through an oxidizing
condenser,
then
dropped into the receiver as yellow to
reduced
brown liquid of N2O4 (yield was 70%
agent
wt/wt of HNO3).
employed in the oxidizing tower was
Preparation of Charcoal-Supported
N2O4:
In 250 ml round bottom flask, 20 g
of activated charcoal and 50 ml of dry
dichloromethane were mixed and
cooled to the temperature at - 10°C. A
20 ml of liquid N2O4 was added slowly
with continuous gently stirring. After
4h of standing in the refrigerator, the
mixture was flashed with N2 gas until
removed the excess of N2O4. The
solvent was evaporated under reduced
prepared by dissolved 5 g of CrO3 in
5ml water then 95 g of quartz sand (2030 mesh) was added. The mixture was
stirred thoroughly for 5 minutes and
then dried at 120°C to give the quartz
sand carrying chromium trioxide.
604
Iraqi National Journal of Chemistry,2011,volume
washed with cooled water. The organic
pressure with rotary evaporator to give
34 g of N2O4 / Charcoal reagent. Each
1g of N2O4/Charcoal contains 0.4117g
of N2O4.
General procedure for the preparation
layer was dried on Na2SO4 then Passed
through silica gel column using a
mixture of ethyl acetate and methylene
of disulfide:
chloride as eluent to afford the pure
To a solution of thiol compound (5
disulfide compound after evaporation
mmol) in CH2Cl2 (25 ml), a 0.575 g of
of the solvent on rotary evaporator
(N2O4 /Charcoal) reagent was added
gradually
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
with
continuous
under reduced pressure. The melting
gently
point, reaction time, yield percent and
agitation for appropriate time at room
temperature.
The
reaction
characteristic infrared spectrum bands
was
values are shown in Table1.
monitored by TLC, using n-hexane:
Exemplary FTIR spectrum of 2, 2'dithio bis- benzothiazole is shown in
figure 2.
ethyl acetate (40: 60) as eluent. After
completion of the reaction, the mixture
was filtered and the filtrate was
Figure 1. Apparatus sitting for preparation of liquid dinitrogen tetroxide: 1)
Condenser (10ºC), 2) Drying Tower (packed with nearly 80 g of the mixture of
phosphorus pentoxide and quartz sand, P2O5: SiO2, 1: 1 in wt), 3) Oxidizing
Tower (packed with Ca.100 g of oxidizing agent), 4&5) Condensers (-15ºC), 6&7)
Cooling Vessel (-5ºC &25ºC).
605
Iraqi National Journal of Chemistry,2011,volume
Entr
y
1
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
Table1. Oxidative Coupling of Heterocyclic Thiols to Disulfide Compounds by
N2O4/Charcoal in CH2Cl2 .
Thiol
Disulfide
Tim Yiel
Infrared vibrations(cm-1 )
m.pºC
e
(ref.)
d %
(min
.)
3059 (υ,C-H,aromatic), 1558
10
2 ,2'-Dithio91
178-180
(υ,C=N), 1465,1429 (υ,C=C,
2-Mercapto
bis(benzothiaz
(178-179) aromatic) ,1311 , 1238, 1006, and
25a
ole)
758 (υ,C-s-s-C), 725 (ortho
benzothiaz
disub.) , 669 (υ,C-s-C)
ole
2
4-Mercapto
- pyridine
4 ,4'-Dithiobis(pyridine)
5
90
76-79
(76-78)25a
3
2-Mercapto
- pyridine
2 ,2'-Dithiobis( pyridine)
5
90
57-59
(56-60)25a
4
2-Mercapto
- thiazole
2 ,2'- Dithiobis(thiazole)
5
95
106-109
new
5
2-Mercapto
-5 methoxybenzoimidazole
2 ,2'–Dithiobis( 5-methoxy
benzoimidazol
e)
8
90
165-168
new
6
2-Mercapto
benzoxazol
e
2 ,2'- Dithiobis(benzoxazol
e)
8
90
90-94
(92-94)25b
7
2-Mercapto 2 ,2'-Dithiobis(bnzoimidaz
-benzo ole
imidazole
8
89
606
200-203
(202204)25c
3081(υ,C-H ,aromatic), 1600,
1570,1547 ,1498,1485
(υ,C=N,C=C,aromatic ring)
,1183,1010, 740, and485 (υ,C-s-sC)
3076,3010 (υ,CH,aromatic),1603,1563
,1552,1501,1483 (υ,C=N, C=C,
aromatic ring),1195, 1015, 750,
710, and490 (υ,C-s-s-C)
3030 (υ,CH,aromatic),1607,1573,1498,
691(υ,C=N, C=C,and C-s-C,
thiazole ring), 1177,1011, and
482 (υ,C-s-s-C)
3205 (υ,N-H),3070 (υ,CH,aromatic), 2956 (υ,CH3),1610,
1580,1550, 1490 (υ,C=N, C=C,
aromatic benzoimidazol ring),
1260,1190, 487 (υ,C-s-s-C), 840,
770 (subs. ring)
3100 (υ, C-Haromatic), 1617,
1605, 1467 (υ, C=N, C=C
aromatic benzo -oxazol ring),
1260, 1160,486 (υ, C-s-s- C), 744
(ortho disub.)
3198 (υ,N-H), 3085 (υ,CHaromatic),
1618,1585,1560,1493
(υ,C=N,C=C aromatic benzo
imidazol ring), 1127 ,1173,
480(υ,C-s-s-C), 750 (orthodisub.)
Iraqi National Journal of Chemistry,2011,volume
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
8
2-Mercapto 2 ,2' - Dithio-4-hydroxy bis (4-hydroxy
-pyrmidine - pyrmidine)
5
95
>300
new
9
2-Mercapto 2 ,2' - Dithio-5-amino - bis(5-amino thiadiazole thiadiazole)
10
90
233-236
new
10
3Mercapto5-amino1,2,4 triazole
2 ,2' - Dithiobis( 5-amino1,3,4-triazole)
8
92
>300
new
11
2Mercapto4-amino
purine
2 ,2' – Dithio bis(5minopurine)
8
90
without
any
reaction so, cooling with water is
nitric acid and Al-Zahdi date. The
necessary to keep the temperature of
purity was determined by titration
reaction flask not elevated.
method, by using KMnO4 solution in
The principle idea for N2O4 formation
the presence of conc. H2SO4 and ferric
is built on oxidation reduction between
ammonium sulfate as titrant(24).The
the aldoses sugar in date as reducer and
percentage yield of liquid N2O4 was
nitric
and
catalyst, moreover it was exothermic
high purity (99%) was prepared from
the
3490 ,3385 (υ, NH2), 3180 (υ,NH),1620 , 1599,1530,1489 (
υ,C=N, C=C aroma- tic purine
ring), 1188 , 1012, 487 (υ,C-s-sC),770,654
spontaneously
A liquid dinitrogen tetroxide with
on
3430,3388
(υ,NH2)1637,1593,1488, 1340,
690 ((υ,C=N, C-s-C, thiadiazol
ring), 1190, 1007, 490 (υ,C-s-sC)
3440,3378 (υ, NH2), 3100 (υ,NH),1619 , 1590, 1512, 1480
(υ,C=N,C-N,triazol ring) , 1177,
1014, 488490 (υ,C-s-s- C)
nitric acid. The reaction was occurred
Results and Discussion
depended
>300
new
3440 (υ,O-H), 3050 (υ,C-H
aromatic), 1614,1566,1477,1340
(υ,C=N,C=C aromatic, 1180,
1020, 488 (υ,C-s-s-C) ,810, 750
(subs. ring)
nitric acid as oxidizer
acid
(25, 26)
. The
aldoses consist of a good moderate
concentration, but in generally, method
reducing agent, aldehyde and hydroxyl
can be employed on a range of 65-98%
groups (Scheme 1).
607
Iraqi National Journal of Chemistry,2011,volume
CHO
COOH
OH
HC
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
n
+
4 HNO
HC
3
CH 2 OH
OH
+
+
4 NO 2
( 1)
H 2O
COOH
Glycaric Acid
Aldose
COOH
HC
n
COOH
OH
n
+
4 HNO
3
COOH
COOH
+
C
O
+
4 NO 2
+
H 2O
COOH
COOH
Oxalic acid
Glycaric Acid
MesoOxalic acid
Scheme 1
The residual by product gave a
reaction to convert the other nitrogen
dicarboxylic acid (mainly oxalic acid)
oxides (NO and N2O3) to N2O4
when it was left in the refrigerator.
(Scheme2).
(27, 28)
Oxygen current was used during the
2N2O3
+
O
Cooling
2N2O4
Yellow
Blue
2NO
+
O
Cooling
Cooling
2NO2
N2O 4
Scheme 2
Oxidative coupling of heterocyclic
N2O4/Charcoal reagent was prepared
(20 )
according to the reported procedure
thiols by treatment of N2O4 supported
from liquid N2O4and activated
on charcoal proceeds readily in CH2Cl2
charcoal at -10˚C.Reagent is a stable
at room temperature (Scheme 3). The
up to 60˚C, and can be stored at room
reaction times are usually between 5-
temperature in a capped bottle for
10 minutes as shown in Table1.
months without any loss of activity.
608
( 2)
Iraqi National Journal of Chemistry,2011,volume
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
R = heterocyclic ring or substituted heterocyclic ring
Scheme 3
Several molar ratios of N2O4 to
increases with dielectric constant of the
heterocyclic thiol were tried (1:1, 1:2,
solvent
1:3 and 1:4) to optimize the oxidation
converted
process. We were found that 1:2 molar
thionitrites
ratio was established as other ratios. It
dichloromethane at room temperature.
is reasonable to assume that 1 mole Of
Disulfides result from the hemolytic
N2O4
reacts with 2 moles of
cleavage of the sulfur–nitrogen bond of
thiohetrocyclic compounds to produce
the unstable thionitrites and subsequent
1 mole of the corresponding disulfide
coupling
radicals
and 1 mole of HNO3(Scheme 4) .
(14)
Thiols can be readily
.
to
their
with
of
(23d)
the
corresponding
a
N2 O 4
resultant
in
thiyl
.
N2O4 is known to be in equilibrium
with NO+ and NO3- in solution by its
self ionization and degree of ionization
+
NO NO3
+
2RSH
2[RSN=O]
.+
2[RSN=O]
.
2RS
+
HNO3
2NO
R-S-S-R
2RS
Scheme 4
Since charcoal is insoluble in the
pure disulfide heterocyclic compounds
organic solvent, the products were
in high yield.
easily isolated by washing the reaction
As may be seen, the method offers a
mixture
as
simple, mild and efficient reagent for
dichloromethane evaporation of the
the oxidation of variety of heterocyclic
filtrate under vacuum, followed by
thiols to corresponding disulfides. The
flash chromatography. Often produced
chemical structure and purity of the
with
suitable
solvent
disulfide products were proved by
609
Iraqi National Journal of Chemistry,2011,volume
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
using melting point measurement,
cm–1,in addition to a sharp peak at 758
elemental
cm–1 which assigned to characteristic
analysis,
and
FTIR
spectroscopy. The measured results in
vibration of
elemental
infrared
analyses
closely
C-S-S-C
spectra
of
bonds. The
the
disulfide
corresponded to the calculated ones
products as shown in the table 1,
(see table 2), demonstrating that the
confirmed the presence of C-S-S-C
expected compound was obtained.
bonds. The spectra also approved that,
Figure 2 displays FTIR spectrum of 2,
there was no weak band at (2500-
2'-Dithiobis
2600) cm-1 region related to S-H
(benzothiazole
)
as
group.
exemplary FTIR spectrum .It showed a
sharp peaks between 1311,and
1006
Figure 2. FTIR spectrum of 2, 2'-dithio bis(benzothiazole).
610
Iraqi National Journal of Chemistry,2011,volume
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
Table 2. Elemental Analysis of Disulfide Compounds
Disulfide
Formula
Found
(required)
(%)
Mol.wt
C
2 ,2‘– Dithio –
C14H8N2S4
332
bis(benzothiazole)
4 ,4 ‘ – Dithio – bis(pyridine)
2 ,2‘ – Dithio – bis(pyridine)
2 ,2‘ – Dithio – bis(thiazole)
C10H8N2S2
C10H8N2S2
C6H4N2S4
2 ,2‘ – Dithio – bis(5-methoxy -
C16H14N4O2
benzoimidazole)
S2
2 ,2‘– Dithio –
C14H10N2O2
bis(benzoxazole)
S2
2,2' – Dithio –
C14H4N4S2
220
220
232
358
300
298
bis(benzoimidazole)
2 ,2‘ – Dithio – bis(4 –hydroxy
C8H6N4S2
222
– pyrmidine )
2 ,2' – Dithio – bis(5 – amino–
C4H4N6S4
264
thiadiazole)
2,2 – Dithio – bis(5 – amino –
C4H6N8S2
230
1,3,4 – triazole)
2,2' – Dthio – bis(5 – amino –
C10H8N10S2
purine)
611
332
H
N
50.95
2.50
8.22
(50.60)
(2.40)
(8.43)
54.60
3.44
13.00
(54.54)
(3.63)
(12.72)
55.00
3.42
12.55
(54.54)
(3.63)
(12.72)
30.94
1.80
12.11
(31.03)
(1.72)
(12.06
52.99
3.66
15.22
(53.63)
(3.91)
(15.64)
55.87
2.45
9.50
(56.00)
(2.66)
(9.33)
57.00
3.70
18.82
(56.37)
(3.35)
(18.79)
43.11
2.66
25.43
(43.24)
(2.70)
(25.22)
18.50
1.48
31.22
(18.18)
(1.51)
(31.81)
21.00
2.51
49.00
(20.86)
(2.60)
(48.69)
35.95
2.44
41.89
(36.14)
(2.41)
(42.16)
Iraqi National Journal of Chemistry,2011,volume
‫ اﻟﻤﺠﻠﺪ اﻟﺮاﺑﻊ واﻻرﺑﻌﻮن‬2011-‫اﻟﻤﺠﻠﺔ اﻟﻌﺮاﻗﻴﺔ اﻟﻮﻃﻨﻴﺔ ﻟﻌﻠﻮم اﻟﻜﻴﻤﻴﺎء‬
44,602-614
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