International Journal of ChemTech Research

CODEN( USA): IJCRGG ISSN : 0974-4290

Vol.2, No.3, pp 1856-1859, July-Sept 2010
Applications of Green Chemistry in Organic
Synthesis
V. K. Redasani*, V. S. Kumawat, R. P. Kabra, P. Kansagara, S. J. Surana
R.C. Patel Institute of Pharmaceutical Education and Research, Shirpur,
Dist-Dhule: 425 405, India
*Corres Author: minvi224@rediffmail.com
Mobile no. +91-9822027806, Tel: +91-2563-255189; Fax: +91-2563-252808
A Ab bs st tr ra ac ct t: : G Gr re ee en n c ch he em mi is st tr ry y i is s t th he e n ne ew w a an nd d r ra ap pi id d e em me er rg gi in ng g f fi ie el ld d o of f c ch he em mi is st tr ry y. . I It ts s g gr ro ow wi in ng g i im mp po or rt ta an nc ce e i is s i in n u ut ti il li iz za at ti io on n
o of f m ma ax xi im mu um m p po os ss si ib bl le e r re es so ou ur rc ce es s i in n s su uc ch h a a w wa ay y t th ha at t, , t th he er re e i is s n ne eg gl li ig gi ib bl le e o or r m mi in ni im mu um m p pr ro od du uc ct ti io on n o of f c ch he em mi ic ca al l w wa as st te e. . I It t i is s
o on ne e o of f t th he e b be es st t a al lt te er rn na at ti iv ve es s f fo or r t tr ra ad di it ti io on na al l c ch he em mi ic ca al l s sy yn nt th he es si is s p pr ro oc ce es ss s. . F Fe ew w d de er ri iv va at ti iv ve es s o of f a ac ce et ta an ni il li id de e ( (c co om mp po ou un nd ds s I I- - I IV V) )
w we er re e s sy yn nt th he es si iz ze ed d b by y c co on nv ve en nt ti io on na al l m me et th ho od d a as s w we el ll l a as s b by y g gr re ee en n c ch he em mi is st tr ry y m me et th ho od d. . B By y a ap pp pl ly yi in ng g t th he e g gr re ee en n s sy yn nt th he es si is s
m me et th ho od d, , w we e h ha av ve e n no ot t o on nl ly y a av vo oi id de ed d t th he e u us se e o of f a ac ce et ti ic c a an nh hy yd dr ri id de e w wh hi ic ch h i is s h ha az za ar rd do ou us s o on ne e b bu ut t a al ls so o t th he e f fo or rm ma at ti io on ns s o of f b by y
p pr ro od du uc ct ts s a ar re e a av vo oi id de ed d. . T Th he e a at to om m e ec co on no om my y w wa as s c ca al lc cu ul la at te ed d o on n t th he e b ba as si is s o of f m mo ol le ec cu ul la ar r w we ei ig gh ht t o of f d de es si ir re ed d p pr ro od du uc ct t a an nd d i it t w wa as s
f fo ou un nd d t to o b be e i in n t th he e r ra an ng ge e o of f 7 72 2% % t to o 8 82 2% % w wh hi ic ch h s si ig gn ni if fi ie es s t th he e u ut ti il li it ty y o of f g gr re ee en n s sy yn nt th he es si is s m me et th ho od d. .
Key words: Green synthesis, green chemistry, acetanilide, atom economy.
Introduction :
(1,2)
Green Chemistry is the new branch of chemistry
which involves pulling together tools, techniques and
technologies. It is helpful to chemists and chemical
engineers in research, development and production for
development of more eco-friendly and efficient
products which may also have significant financial
benefits. It is now going to become an essential tool in
the field of synthetic chemistry. The development of
Green Chemistry redefines the role of a solvent: An
ideal solvent facilitates the mass transfer but does not
dissolve. In addition, a desirable green solvent should
be natural, nontoxic, cheap and readily available with
additional benefits of aiding the reaction, separation or
catalyst recycling. Of the various principles of green
chemistry, the important one is maximizing the Atom
Economy which evaluates the efficiency of chemical
transformation and is calculated as:
% atom utilization
(3)
= Molecular weight of desired product X 100
Molecular weight of
(desired product + waste product)
In the present study, few derivatives of acetanilide (I-
IV) are synthesized by conventional method as well as
green synthesis method. The synthesized compounds
are characterized by their physical constants and FTIR.
Both the method gives the desired products, but by
applying the green synthesis method, we can able to
avoid the use of acetic anhydride and formation of by
products. Moreover, the atom economy was obtained
in the range of 72% to 82% which indicates the
complete use of chemicals. Thus, concept of green
chemistry can be applied to various synthetic methods.
This may leads to generation of eco friendly synthetic
chemistry.
Materials and Method:
Apparatus:
The melting points were determined by open capillary
method and are uncorrected.
Infrared spectra were recorded on FTIR 8400s
Shimadzu using KBr.
Chemicals and Reagents:
Aniline, p-chloroaniline, p-toluidine, p-nitroaniline,
acetic anhydride, conc. HCl, sodium acetate, glacial
acetic acid, zinc dust and methylated spirit are from
Loba Chem Pvt. Limited, Mumbai. All solvents were
distilled before use and dried whenever required.
V. K. Redasani et al /Int.J. ChemTech Res.2010,2(3) 1857
Synthesis of compounds (I-IV) by conventional
method:
(4, 5)
In a 250 ml beaker containing 125 ml of water, 4.6 ml
of conc. HCl and 5.1 g of aniline / substituted anilines
were introduced. Stirred until all the anilines passes
completely into solution. To the resulting solution, 6.9
g (6.4ml) of redistilled acetic anhydride was added and
stirred until it was dissolved. Poured immediately in a
solution of 3.8 g of crystalline sodium acetate in 25 ml
of water. Stirred vigorously and cooled in ice. Filtered
the acetanilide and substituted acetanilides with
suction, washed with 10 ml water, drained well and
dried upon filter paper. The crude products were
recrystallized from boiling water and methylated spirit.
Non green component: Acetic anhydride leaves one
molecule of acetic acid unused.
Synthesis of compounds (I-IV) by green chemistry
method:
(6)
A mixture of aniline / substituted anilines (3.3g) and
zinc dust (0.16g) in acetic acid (10ml) in 100 ml round
bottom flask was heated over a gentle flame using
water condenser. Heating was continued for about 45
min., the reaction mixture was then carefully poured in
cold water (33ml) in 250ml beaker with vigorous
stirring. The shining crystals of product were separated
slowly. After 15 min, crystals were collected by
filtration. The solid crystals were washed over the
Buchner funnel with water and product was dried and
crystallized in boiling water.
Green context: Minimize waste by-products, avoids
use of acetic anhydride.
Scheme of Synthesis
Scheme of Synthesis and Mechanism by conventional method :
( 4, 5)
NH
2
R
+
(CH
3
-
CO)
2
O
NHCOCH
3
R
+ CH
3
COOH
N H
O
CH
3
R
NH
+
CO
-
CH
3
R
CH
3
COHN+
R
Scheme of Synthesis and Mechanism by green chemistry method :
( 6)
N H
2
R
+
Glacial acetic acid
zn dust
R
CH
3
COHN
O
zn
C H
3 O
COCH
3
R
NH
2
-(ZNO
+
CH
3
COOH)
NH
H
R
COCH
3
R
CH
3
COHN
V. K. Redasani et al /Int.J. ChemTech Res.2010,2(3) 1858
Results and Discussion
The synthesis of acetanilide & its derivatives was
carried out successfully by using both conventional
method as well as green chemistry method. The
synthesized products were recrystallized and melting
point was taken which are compatible with the
reported melting points. The percent yield obtained by
green chemistry method was found to be more than
that of conventional method. All the compounds were
characterized by FTIR which shows the presence of
aromatic ring (3055-3122 cm
-1
), amine group (3275-
3481 cm
-1
), amide (1631-1676 cm
-1
) that characterized
the said compounds. The atom economy was
calculated on basis of the molecular weight of desired
product and the molecular weight of all the products.
From this calculation, it was seen that the atom
economy is more in case of green chemistry than by
the conventional method of synthesis. The found
values signify the utility of method in which atom
economy was obtained in the range of 70% to75%.
The detail results are tabulated.
Table
Green Synthesis Method Conventional Method
Comp. No. R
%Yield M. P. (
O
C) FTIR (cm
-1
)
(7)
%Yield M. P. (
O
C)
Atom
Economy
I -H 79.78% 112C
Aromatic- 3072
NH-3275
Amide-1676
Methyl-1448
55.66% 114C 69.92 %
II -CH
3
82.22% 146C
Aromatic- 3122
NH-3290
Amide-1662
Methyl-1454
Methyl-1402
76 .67% 148-149 C 71.29 %
III -NO
2
72.09% 210-212 C
Aromatic-3055
NH-3481
Amide-1631
Methyl-1444
Nitro-1402
64.78% 215-216C 75.00 %
IV -Cl 76.00% 182-183C
Aromatic-3066
NH-3304
Amide-1664
Methyl-1371
Chloro-707
59.67% 179C 73.34 %
V. K. Redasani et al /Int.J. ChemTech Res.2010,2(3) 1859
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