(KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A A

)1 (2 2003

treatment of ethylchloroacetate (I) with The cyclo condensation of 3-(N-methyl

(o-phenylene diamine). acetamido) -2- chloro pyridine gives
The I.R. Spectrum [Tab. (1)] N- methyl-2-arylpyrido [2,3-b] [1,5]
showed bands at 3310 and 1580 cm-1 thiazepin-4[5H] ones[10]. Treatment of
corresponding to N-H stretching and 2-chloronicotinic acid with methyl amino
bending respectively, indicates that acetonitrile hydrochloride and carbon
primary amine was converted to disulphide gave pyrido [3,2-f- [1,4]
secondary amine. Whilst a second band thiazepine derivateves[11]. Cylic mono
at 1670 cm-1 could be attributed to the sulphidediamide N , N − - ethylen thio
carbonyl group of the secondary amide diacetamide prepared in good yields from
this low absorption frequency due to the
the reaction of N , N − -ethylene bis-
meseomeric effects in amide .
(chloro acetamide) with hydrous sodium
The 1H-N.M.R. spectrum [Tab.(2)]
sulphide[12]. Unsubstituted 10,11 and 13-
gave a singlet at (3.7) ppm for four
membered ring cyclic disulphide
protons of two methylene groups with
diamides result from reaction of ethylene
a broad single at (4.4) ppm
diamine and -3, 3- dithiodipropionic acid
corresponding to one proton of N-H
in the absence of solvent[13,14] .
group, while the ortho substituted protons
High yeild medium ring of
of two phenyl groups appeared as a
thiocycloalkanes were obtained from the
multiplet at (6.6)ppm. Therefore,
reaction of sodium sulphide with
according to spectral studies and
[15]
dibromo alkanes . Herein, we describe
elemental analysis the product could be
in detail the synthesis of a novel nine –
N , N − -(o-phenylene) bis (chloroacet
membered ring cyclic mono
amide)(II). sulphidediamide, and its sulphone. From
The reaction of compound (II) with
the reaction of N , N − (o-phenylene) bis
hydrous sodium sulphide (Na2S.9H2O)
(chloro acetamide) (II) and hydrous
leads to formation of a cyclic mono
sodium sulphide Na2S.9H2O
sulphidediamide N , N − -(o-phenylen)
Scheme (I).
thiodiacetamide (III) in good yield.
The I.R. spectrum for the product (III)
Results and Discussion
[Tab(1)] gave a strong absorption band
N , N − -(o-phenylene) bis (chloro
at 1670 cm-1 for C=O Stretching of
acetamide)(II) was synthesized from

24
(KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A A
)1 (2 2003

The 1H-N.M.R spectrum [Tab.(2)] secondary amide, another strong band

gave a singlet at (3.0) ppm for four was appeared at 3310 cm-1 for N-H
protons of two methylene groups with a stretching .In this spectrum, the
multiplet at (6.6) ppm for four protons absorption peaks for C-Cl was
of phenyl group, while a broad singlet at disappeared and a new weak band
(4.4) ppm due to N-H proton. appeared at (600,700) cm-1 for C-S
Stretching .

II

IV III

Scheme (1)

25
 (KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A A
)1 (2 2003

The sulphone was indicated by of the compound (III) with potassium

the I.R. and elemental analysis . The I.R.
spectrum showed two extra bands at 1320
cm-1 and 1035 cm-1 indicating the
formation of sulphone (SO2).
permanganate in %80 acetic acid , after it
was noted that other oxidizing agent,
sodium periodate and hydrogen peroxide
provided a mixture of sulphoxide and
sulphone.

Table (1) : The I.R. data of the prepared compounds in (cm-1 )

Compounds N-H C=O C-O C-Cl O=S=O

I ……….. 1760 1220 750 …………
II 3300,1580 1670 ……. 750 ………..
III 3300,1580 1970 ……. ……… ………….
IV 3300,1580 1670 …….. ………. 1320,1035

Table (2) : 1H.n.m.r data of the prepared Compounds

Solvent DMSO-d6

compounds δPPM Intensity Multiplicity Assignment

I 1.2 3 t -CH- of methyl groups
4.0 4 m -CH2- of two methylen groups
II 3.7 2 s -CH2- of two methylen groups
4.4 1 b -NH- proton
6.6 2 m 4-H aromatic protons
III 3 2 s -CH2- of two methylen groups.
4.4 1 b -NH- proton
6.6 2 m 4-H aromatic protons

was more sensitive than thio compound Hetrocyclic compound containing

(III) [Tab(3)].
This difference in biological
activity could be due to the attachment of
sulphur atom to two oxygen atoms with
high electronegativity, which make the
carbon–sulpher bond, in sulphon
derivative, weaker than corresponding
sulphur and amide group known to have
antibacterial activity [16].
The prepared compounds are
similar to these compounds and they were
showed antibiotic activity .It has been
noted that the sulphone compound (IV)

26
(KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A A
)1 (2 2003

Melting point were determined thio compound. Therefore, we were

with a Gallenkamp electrothermal proposed a simplified mechanism for
melting point apparatus .Infrared spectra inactivation of microbial organism by the
were recorded by using Unicam Model prepared thiol and sulphone compounds
Sp3-300S Spectrometer. The proton (scheme (2)).
nuclear magnetic resonance were obtained
using Varian A-60 instrument with
tetramethyl silane were performed by the
analyzer MOD 110 6 supplied by Carlo
Erba type.
1. N , N − -(o-phenylene)bis(chloro
acetamide) [12] II
A solution of (o-phenylendiamine
(4gm, 0.036 mole) in ethanol
(60 ml,99%)was added to a solution of
ethylchloro acetate (1) (8 ml. 9.06 gm. Scheme (2)
0.075 mole) heating the mixture under
reflex for 9 h . after cooling crush ice X = Ph
was added until the green precipitate was n= 0,2
formed. The precipitate was filtrated and
Table: (3) Antimicrobial activity of
washed with water and dried in a
prepared compounds
vacuum desicator over CaCl2, , yielding
the product as a green solid after Compounds E. coil Sta. Aur
Control - -
recrestalized in water. (1gm. 25%),
III + -
m.p= (160-161)Co ; I.R. (KBr), υmax . IV ++ -
3300, 1580, 1970, 760 cm-1; Elemental
analysis: Calculated for C10H10O2N2Cl2: Control =KBr
C,44;H,4.03;N,10.7Found:C,44.02;H,4.03 += inhibition (3.5)mm
;N,10.5%. ++ = inhibition(5.5)mm
­ = not inhibition
2. N, N − -(o-Phenylene)–
Experimental
[12]
thiodiacetamide (III)

27
(KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A
)1 (2 2003
3. N , N − -(o-phenylene)Sulphone
diacetamide [12]. (IV)
A solution of potassium permanganate
(0.18gm, 0.0012 mole) in water (5 ml)
was added to a stirred solution of N , N − -
(o-phenylene) thiodiacetamide (0. 11 gm )
0.0005 mole in acetic acid (5 ml , 80%)
during 30 minutes at room teperature .
The mixture was neutralized with 10%
Na2 CO3, A brown solid was provided
after recrestalized in water. (0.05 gm,
25%), m.p= 300C0 dec., I. R.(KBr) υmax
3300, 1580 , 1670 , 13 20 , 1035 cm- ;
Elemental analysis: Calculated for
C10H10O4N2S;C,47.24;H,3.93,N,11.02:
Found : C, 47.03; H, 3.35; N, 11.01 % .
References
1. Lawson J. K.; Easley W. K.and Wanger W. S., five-membered
28
A
To a stirred hot solution
(70–80 Co )of N , N − -(o-phenylene) bis
(chloro acetamide)(II), (0.65 gm., 0.0025
mole ) in ethanol (13.9 ml) , a solution of
Na2S.9H2O (0.6 gm ,0.0025 mole) in
distilled water (4ml) was added. The
mixture was stirred with heating till
yellow precipitate formed. The solid
product was filtered off, and dried in
vacuo over CaCl2 yielding the product as
yellow Solid after recrestalized in water.
(0.2 gm , 36% ) m. p. (280 Co dec.), I.R.
(KBr) υmax(3300), 1580,1970 cm-1,
Elemental analysis: Calculate for
C10H10O2N2S: C, 54.05; H, 4.5, N, 12.6:
Found: C, 53.09; H,4.20; N, 12.5%.
(KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A A
)1 (2 2003

heterocyclic compounds, Organic Synthesis, IV, 1963, 892.

2. Tarbell D. S and Weaven C., Chemistry of five-membered
Heterocyclic compounds, J. Am. Chem. Soc, 1941, 63, 2939.
3. Sumrell G. and Hornbaker E. D., chemistry of five-membered
Heterocyclic compounds, J. Org. chem. 1953, 23, 1219.
4. Crombie R. L. and Ridey D. D., Chemistry of seven-membered
Heterocyclic compounds, J. chem., 1976, 32, 2777.
5. Ando W. and Huang L. An Efficien, one-pot synthesis, J. Synth.
1986, 139.
6. Rauter S. and Clarke H. T. Thhe Action of formal dehyde upon Cystein,
J. Am. Chem. Soc. 1937, 59, 200.
7. Kyrides L. p., phthalyl chloride, J. org. chem. 1982, 47, 4005.
8. Hawaizy F. E. M. Sc. Thesis, University of Salahadin (1998).
9. Rahimzadeh M., Heravi M. M. and Abedince A. Synthesis of Novel
Heterocyclic system, J. Sci. I. R. Iran 1998, 9, 163.
10. Couture A. and Grand C. A New synthetic Route J. org. chem. 1990,
55, 4337.
11. Dolling W. and Hartung H. A facile Synthesis. Eur. J. org. chem.
1998, 1237.
12. Hussain F. H. and Hadi K. S. Chemistry of Nine-membered
Heterocyclics. Zanco, 1990, 3, 7.
13. Owen T. C and Fayad J. M. A ten-membered Ring J. org. chem, 1970,
35, 3198.
14. Owen T. C and Fayad J. M., Heterocyclic compounds. J. org. chem.
1973, 36, 937.
15. Singh A. and Regen S. L, Heterocyclic Compounds. Synthetic
Communication; II. 1981, 5, 409.
16. Al-Hamadi F. M., M. Sc. Thesis, University of Baghdad 1993.

‫ فينيلين) ثايو دوو‬- ‫ئامادةكردن و ئؤكساندنى ئاويَتةى (ئورثو‬

‫ئةمايدى سركةيي‬
‫و داليا عارف عبدول‬ ‫فائق حمة سعيد‬
‫ هةريَمى كوردستانى عيَراق‬/‫ زانكؤى سةلح ةدي ن‬/ ‫ كؤليذى زانست‬/‫بةشى كيميا‬
‫ هةريَمى كوردستانى عيَراق‬/‫ زانكؤى سليَمانى‬/ ‫ كؤليذى زانست‬/‫بةشى كيميا‬

29
‫‪(KAJ)Kurdistan Academation JournalSept 2003, 2(1) Part ,A‬‬ ‫‪A‬‬
‫‪)1 (2‬‬ ‫‪2003‬‬

‫ثايؤ دوو ئةمايد‬ ‫‪( - N , N −‬ئؤرثو‪ -‬فينيلين )‬ ‫نويَ‬ ‫ئةلقةيي‬ ‫لةم ليَكؤليَنةوةيةدا ئاويَتةيةكى‬
‫‪( -‬ئؤرثو‪ -‬فينيلين) دووانة (كلؤريدي ئةمايدي سركةيي) لةطة َ‬
‫ل‬ ‫ئامادةكراوة لة كارليَكردني ‪N , N −‬‬
‫‪−‬‬
‫) وةهةروةها ئاويَتةي ‪( - N , N‬ئؤرثو‪ -‬فينيلين) سةلفؤن‬ ‫‪2‬‬ ‫‪Na S.9H O‬‬
‫طؤطردي سؤديؤمي ئاوي ( ‪2‬‬
‫َ‬
‫دوو ئةمايدي سركةيي بةرهةم هات لةئةنجامي ئؤكساندني ثايؤلةكة‪ .‬ثيَكهاتةي ئةو ئاويَتة نويَ يانة‬
‫ضةسثيَنراوة بة هؤي شةبةنطي ذي َر سوور و لةرينةوةي ناوكي موطناتيسي و شيكردنةوةي‬
‫توخمةكان‪.‬‬

‫تخليق و اكسدة مركب ‪( - N , N −‬اورثو ‪ -‬فينيلين) ثايو ثنائي خلت المايد‬

‫و داليا عارف عبدول‬ ‫فائق حمة سعيد‬

‫قسم الكيمياء ‪ /‬كاية العلوم ‪ /‬جامعة صلح الدين‪ /‬اقليم كردستان العراق‬
‫قسم الكيمياء ‪ /‬كاية العلوم ‪ /‬جامعة السليمانية‪ /‬اقليم كردستان العراق‬

‫الخلصة‬
‫‪−‬‬
‫‪( -‬اورثو – فينيلين)‬ ‫عية جديدة وهو ‪N , N‬‬ ‫في هذا البحث تم تحضير مركب ذات حلقة تاس‬
‫لت الميد) مع كبريتيد‬ ‫(اورثو – فينيلين ) ثنائي (كلوريد خ‬ ‫ثايو ثنائي خلت الميد من تفاعل ‪N , N −‬‬
‫(اورثو– فينيلين )‬ ‫‪-‬‬ ‫وديوم المائي ‪ ) )Na2S.9H2O‬و اكسدة الثايول أدت الى تكوين ‪N , N −‬‬
‫الص‬
‫سلفون ثنائي خلت الميد ‪.‬‬
‫وقد تم تشخيص المركبات الجديدة باستخدام طيف الشعة تحت الحمراء والرنين النووي‬
‫المغناطيسي و تقنية تحليل العناصر ‪.‬‬

‫‪.Received 20/8/2002 Accepted 11/6/2003 .‬‬ ‫‪1/6/2003‬‬ ‫‪2002 /20/8‬‬

‫‪30‬‬