Synthesis and Identification of (8-And 9) - Membered Rings Via Alkylation Reactions

J. Chem. & Cheml. Sci. Vol.
3 (1), 37-47 (2013)
Synthesis and Identification of (8-and 9)Membered Rings

Via Alkylation Reactions
NAGHAM MAHMOOD ALJAMALI
Assistant Professor,
Chemistry Department, College of Education.,
University, Kufa, IRAQ.
(Received on: December 30, 2012)
ABSTRACT
In this paper , synthesis of compounds [1-7] are 8 and 9
membered hetero cycles which have two heteroatoms in content
by using alkylation reactions.
All prepared compounds [1-7] have been characterized by using
several chemical techniques such as, (H .NMRspectra, (C.H.N)
analysis), FT.IRspectra and melting points.
Keywords: eight membered, nine membered, heterocyclic, hetero
atom.
INTRODUCTION
The chemistry of cyclic compounds
has generated intensive scientific studies
throughout the world, especially interest
has been focused on the synthesis of
macrobiomolecular, and variety of drugs
such as: methyl seleno cystien, seleno
cystien1,2, diazepam drugs3, valium drugs.
These compounds have displayed a broad
spectrum of pharmacological activities such
as anti protozoal4,5, anti fungal6,7.
In the present study, synthesis of
(diazonin, diazocane, selenthinin, selenthicine) cycles which are 8 and 9
membered rings with two heteroatoms (Se,
S, N) as part of the portion in compounds[17].
These compounds are interesting

structural motifs in medicinal chemistry, in
recent times, their structures have been
widely used, some of these hetero cycles
have been indentified as antitumour a
gents8,9, antibiotics, antiHIV a gents10,11, in
organic synthesis and other applications12-13.
Synthesis of these compounds via
alkylation reaction give good yield by this
methods in this paper.
EXPERIMENTAL
All chemical used were supplied from

fluka and BDH chemical company
All measurements were carried out by:
1. Melting points: electro thermal 9300,

melting point engineering LTD, U.K
Journal of Chemistry and Chemical Sciences, Vol.3, Issue 1, 1 January, 2013 (1-47)
38
Nagham. Mahmood Aljamali, J. Chem. & Cheml. Sci. Vol.3 (1), 37-47 (2013)
mixture was heated at 85C for two hours,

the precipitate was filtered off to give
compound [1], then (0.01 mole, 2.8 g) of
compound [1] was reacted with one of (0.01
mole, 0.9 g of 1,2 di chloro ethane, 0.01
mole, 0.85 g of dichloromethane)
respectively under heating for (8 hrs ), the
precipitate was filtered off and recrystallized
to give 85% of 9 membered cycles of
compound [2] and 82% 8 membered
cycles of compound [3] respectively .
2. FT.IR-spectra:
fourrier
transform
infrared shimadzu 8300 (FT . IR ),
KBr disc was performed by CO.S.Q.C.
Iraq
3. H. NMR-spectra and (C.H.N)
analysis: in center lab-Jordan.
Synthesis of compounds [1-3]
To mixture of formaldehyde (15 ml,
40%) and sulphuric acid was added solution
of 4- nitro aniline (0.2 mole, 27.6 g), the
Reaction scheme:
NH 2
CL
NH 2
NH 2
CH2O / H2 SO4
NH
NH
NO2
No2
CL
DMF
[2]
NO 2
No2
[1]
CH2CL2
NO2
NH
NH
NO2
No2
[3]
OH
OH
OH
NO2
No2
CH2O / H2 SO4
NaSe
CoCl
NaSe C
O
C SeNa
O
OO
[5]
EtOH
NO 2
No2
[4]
NO2
Hs CoCl
EtOH
[6]
Hs CoCl
EtOH
[7]
39
Table (1) : FT.IR data (cm-1) of compounds [1-7]

Comp.
No.
[1]
Structural formula
[2]
NH2
NH 2
NO2
No 2
NH
NH
NO2
No 2
NH
NH
NO2
No2
Name of compound
2.2`-methylene bis(4-nitro
aniline )
[3]
[4]
OH
NO2
No 2
[5]
NaSeC
[6]
Co
OO
SeNa
NO2
No 2
Se
O
NO2
[7]
Co
NO2
S=strong, M=medium,
(-NH2)endo cyclic :
3240 M
(C-N)endo cyclic : 1540 S
2.2`-methylene- bis(4-nitro
phenol sodium seleno
propanoate ).
(-OH): 3510 S
( C ) of ester : 1710
(CH2-Se) : 1520
(C-O-C) of ether : 1235
2.2`-methylene- bis{2-(4nitro phenoxy)-1,5-selen

Co thicine -6-one}.
(C-O-C) of ether : 1240
Co
( Se C ) carbonyl of
selenide : 1682
(C-S)endo cyclic :670
No2
Se
O
2,11-dinitro-6,7-dihydro 12H-dibenzo
diazonin
Se
S
(-NH2) endo cyclic:

3290 M
(C-N)endo cyclic: 1537S
2.2`-methylene- bis{2-(4nitro phenoxy)-1,5-selen

thinin -6-one}.
Se
S
2,11-dinitro-6,7-dihydro 13H-dibenzo diazonin
2.2`-methylene bis(4-nitro
phenol )
OH
Functional group in every

compound
(-NH2) :3480 S
S
O
( Se C ) carbonyl of
selenide : 1680
(C-S)endo cyclic :640
No2
VS = very strong
40
Synthesis of compounds [4-7]

The compound [4] was synthesized
by reaction between (0.2 mole, 27.8 g) of 4
nitro phenol with (15 ml of formaldehyde
40% and 25 ml sulphuric acid 98%) under
heating for four hours, the precipitate was
formed and filtered off to give compound
[4], which (0.01 mole, 2.9 g) of it was
reacted with (0.02 mole, 3.8 g) of sodium
seleno propoyl chloride under heating, the
precipitate was formed and filtered off to

give compound [5], (0.01 mole, 6.03 g) of
compound [5] was reacted with one of (0.02
mole, 2.7 g of mercapto butoyl chloride,
0.02 mole, 2.4 g of mercapto propoyl
chloride ) respectively under heating for (8
hrs)8,9, in alkali medium, the precipitate was
formed and filtered off and recrystallized to
yield 83% 9- membered cycle of compound
[6] and 86% 8 membered cycle of
compound [7] respectively.
Table (2) :Melting points, M.F , & (C.H.N)- analysis of compounds [1-7]
Comp. No.
M.F
M.P C (+2)
Calc./ Found C%
H%
N%
[1]
C13H12N4O4
131
54.166
4.166
19.444
54.064
4.076
19.328
57.324
4.458
17.834
57.207
4.319
17.681
56.000
4.00
18.666
55.891
3.864
18.417
53.793
3.448
9.655
53.581
3.237
9.518
37.755
2.649
4.636
37.678
2.574
4.484
44.510
3.571
3.846
44.387
3.409
3.702
42.862
3.143
4.000
42.729
3.038
3.967
[2]
[3]
[4]
[5]
[6]
[7]
C15H14N4O4
C14H12N4O4
C13H10N2O6
C19H16N2O8Se2Na2
C27H26N2O8S2Se2
C25H22N2O8S2Se2
162
169
139
167
192
205
Fig. 1 FT.IR Spectrum of compound [1]

41
42

Fig. 5 HNMR - Spectrum of compound [2]

43
44


45
46
RESULTS AND DISCUSSION

Mechanisim of this reaction
involved polemerization of two mole from
p-nitro aniline via alkylation of orthoposition then cyclization reaction of
compounds to produce high yield from
compounds[1-7] due to reaction of dimer,
most of polymerization reaction give high
products.
All formated compounds [1-7] have
been characterized by their melting points &
spectroscopic methods (FT.IR-spectra ,
(C.H.N)-analysis , & H-NMR-spectra) :
FT.IR Spectra
In FT.IR spectra ,the reaction is
followed
by appearance amino group
(-NH2) absorption band at (3480)cm-1 in
compound [1] , which disappear and other
bands are appear at (3290, 1537) cm-1 due to
(-NH endo cyclic, C-N endo cyclic)
respectively in compound [2] and at (3240 ,
1540) cm-1 due to (- NH endo cyclic , C N
endo cyclic)14-16, respectively in compound
[3].
While FT. IR spectra of compound
[4] is appear absorption band at (3510) cm-1
due to hydroxyl17 group (- OH) of phenol in
compound [4], which also disappear and
other bands are appear at (1710, 1520) cm-1
due to (O-C=O )3, carbonyl of ester, CH2 Se) respectively in compound [5], at (1235,
1682 , 670) cm-1 due to (COC) of ether,
(SeC=O) carbonyl of selenide, (CS)18,19
endo cyclic ) respectively in compound [6] ,
and at (1240, 1680, 640) cm-1 due to (C-O
C) of ether, (Se C=O)1,2 carbonyl of
selenide, (C S)19 endo cyclic) respectively
in compound [7].
And other data of functional

groups19-21, shown in the following, table (1)
and some figures (1-4).
H.NMR Spectra
H.NMR spectrum of compounds
[1-7] showed :Singlet signal at 8.62 for
protons of amine group (-NH2) in compound
[1], which disappear and other signals are
appear : signals at (3.8, 4.28) for protons
NH
of
NH
)(3), endo cycle is compound [2]

NH
& at (3.9 ,4.4 ) for protons of ( NH )

endo cycle in compounds [3].
While the spectrum of compound
[4] showed: Singlet signal at 10.43 for
protons of hydroxyl group (-OH) in
compound [4], which also disappear & other
signals are appear: signals at (3.6, 3.9 ) for
protons of (-CH2CH2-Se) in compound [5],
signals at (3.83, 4.38 , 4.62) for protons of
S)
Se ) endo cycle , (
{ (
endo
cycle(19) } respectively in compound[6], and
signals at (4.10 , 4.40 , 4.70 ) for protons
of{( Se ) endo cyclic, ( S ) endo

cyclic19 } respectively in compound[7] .
Other peaks1-3, shown in the following,
some figure (5-8) .
(C.H.N) Analysis
It was found from compared the
calculated data with experimentally data of
these compounds, the results were
compactable, the data of analysis, M.F, and
melting points are listed in table (2).
ACKNOWLEDGEMENT
I would like to express my thanks to
((United Arabic Company)) & ((Zaidan
Company of Chemical)) in Jordan for
supplied some materials .And express thanks
to Mr. Audai. A, in Jordan for providing
(C.H.N) element analytical, H.NMRspectrum & melting points.
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J. Chem. & Cheml. Sci. Vol.

3 (1), 37-47 (2013)

Synthesis and Identification of (8-and 9)Membered Rings

These compounds are interesting

All chemical used were supplied from

1. Melting points: electro thermal 9300,

mixture was heated at 85C for two hours,

Table (1) : FT.IR data (cm-1) of compounds [1-7]

(C-O-C) of ether : 1235

2.2`-methylene- bis{2-(4nitro phenoxy)-1,5-selen

(C-O-C) of ether : 1240

(-NH2) endo cyclic:

2.2`-methylene- bis{2-(4nitro phenoxy)-1,5-selen

2,11-dinitro-6,7-dihydro 13H-dibenzo diazonin

Functional group in every

Synthesis of compounds [4-7]

precipitate was formed and filtered off to

Fig. 1 FT.IR Spectrum of compound [1]

Fig. 2 FT.IR Spectrum of compound [2]

Fig. 3 FT.IR Spectrum of compound [4]

Fig. 4 FT.IR Spectrum of compound [6]

Fig. 5 HNMR - Spectrum of compound [2]

Fig. 7 HNMR - Spectrum of compound [4]

Fig. 8 HNMR - Spectrum of compound [6]

RESULTS AND DISCUSSION

And other data of functional

)(3), endo cycle is compound [2]

& at (3.9 ,4.4 ) for protons of ( NH )

of{( Se ) endo cyclic, ( S ) endo

10. Zhong X, Fang J, Gang S. & Lin. L.,

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