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Der Pharmacia Sinica, 2012, 3 (2):278-288

ISSN: 0976-8688
CODEN (USA): PSHIBD

Synthesis and investigation of mass spectra of some nitrogen

heterocycles and salycylaldazine derivatives
Haya A. Abubshait

Chemistry Department, Collage of Medicine, University of Dammam, Saudia Arabia

_____________________________________________________________________________________________

ABSTRACT

Reaction of cynoacetic acid hydrazide (1) with thiophene-2- carboxaldehyde, phthalic anhydride, 5-
bromosalicylaldehyde and 2-hydroxyacetophenone yielded the corresponding hydrazone derivative (2), phthalazin-
1,4-diones (5) and salicylaldazine derivatives (10a-b). Pyrazolo[5-,1-a] pyrimidinone (4) was prepared via the
reaction of hydrazone (2) with malononitrile in the presence of triethyl amine. Bromination and hydrazonylsis of
phthalazin-1,4-diones derivative (5) with bromine and hydrazine hydrate gave the corresponding 2-(bromo
cyanomethyl ) carbonyl phthalazin-1,4- dione (6) and phthalazin-1,4-dione (8). The electron impact mass spectra of
both of the above some series of compounds have also recorded and their fragmentation pattern are discussed.

Keywords: Synyhesis, Mass spectra, nitrogen heterocycles, salycylaldazine derivatives.

_____________________________________________________________________________________________

INTRODUCTION

Many publications1-7 report the synthesis of different heterocyclic compounds using cyanoacetic acid hydrazide as
key starting material. The biological properties of some heterocyclic compounds were prepared from cyanoacetic
acid hydrazide is reported8-15.

In this work, reported the preparation of some hetero-cyclic compounds containing nitrogen atoms and
salicylaldazine derivatives using cyanoacetic acid hydrazide (1) as a key starting material which was obtainable in
the reaction of ethyl cyanoacetate with hydrazine hydrate according to literature methods. The electron impact (EI)
mass spectral fragmentation patterns of some synthesized compounds are described.

MATERIALS AND METHODS

The melting points were determined in capillaries with MEL-TEMP II laboratory Devices, USA, and are
uncorrected. Infrared spectra were recorded on Perkin-Elmer 337 Spectrophotometer using KBr wafers. Proton
NMR spectra were obtained on a Varian EM 360 spectrometer using solution in hexadeuteriodimethyl sulphoxide
with tetramethyl silane as the internal standard. Mass spectra were recorded on a VG Autspec GEIFAB and a
Hewlett Packard MS-Engine thermospray and ionization by electron impact at 70 eV. The acceleration voltage was
6 kV, the emission current ≈ 100 MA. Microanalysis was conducted using a Perkin-Elmer 2408 CHN analyzer.

1-(Thiophen-2-carboaldehyde)-cyanoacetic acid hydrazone (2)

A mixture of cyanoacetic acid hydrazide (0.01 mole) and thiophene-2-caboxaldehyde (0.01 mole) in methanol (30
ml) was heated under reflux for 2 hrs. The solid formed after cooling was filtered off, dried and purified by
recrystallization with ethanol to give 2 as yellow crystals, yield 76% mp 165°C. IR (KBr): 3222(NH), 2254(CN),
1678(C=O), 1625 (C=N) cm-1. 1H-NMR (DMSO-d6): δ 3-25(s, 2H, COCH2CN), 7.35-7.86(s, 3H, thiophene-H),
8.62(s, 1H, CH= N), 10.83(s, 1H, NH). Anal. Calcd for C8H7N3OS: C, 49.74; H, 3.63; N, 21.76; S, 16.58. Found: C,
49.48; H, 3.36; N, 21.4; S, 16.29.

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2-Amino-6-thinyl-7-cyano-4-oxo-3-hydropyrazolo[5,1-a]pyrimidine (4)
A mixture of 2 (0.01 mole), malonoitrile (0.01 mole) and triethyl amine (0.03mole) in ethanol (50 ml) was heated
under reflux for 3 hrs. The solid formed after hot was frittered off, dried and purified by recrystallization from acetic
acid to give 4 as yellow crystals, yield 56%, m.p.30°C, IR (KBr): 3396, 3249(NH2), 3303( NH ), 2208(CN),
1683(CO), 1631(C=N) cm-1 .1H-NMR (DMSO-d6): δ 5.71 (s, 2H, COCH2), 7.20-7.90(m, 3H, Thiophene-H), 8.41-
8.63(br.s, 2H, NH2) ppm. Anal. Calcd for C11H7N5OS : C, 51.36; H, 2.72; N, 27.24; S, 12.45. Found: C, 51.08; H,
2.47; N, 27.02; S, 12.22.

2-(Cyanomethyl)carbonyl-phthalazien-1,4-dione (5)
A mixture of 2 (0.01 mole) and phthalic anhyaride (0.01 mole) in methanol (30 ml) was heated under reflux for 3
hrs. The solid obtained after cooling was filtered off, dried and purified by recrystallization from ethanol to give 5 as
colourless crystals, yield 81%, m.p. 186 °C. IR (KBr): 3294(NH), 2257(CN), 1748, 1680 (CO), 1611, 1583 (C=C)
cm-1. 1H-NMR (DMSO-d6):δ 3.22 (s, 2H, COCH2CN), 7.21-7.83 (m, 4H, Ar-H), 10.63 (s, 1H, NH) ppm. Anal.
Calcd for C11H7N3O3: C, 57.64; H, 3.06; N, 18.34. Found: C, 57.41; H, 2.89; N, 18.17.

1-(Bromo cyano methyl)carbonyl-phthalazine-1,4-dione (6)

A solution of 5 (0.01 mole) in glacial acetic acid (30 ml) was added to a solution of bromine (0.01 mole) in glacial
acetic acid (10 ml) with stirring at room temperature for 2hrs. The solid formed was filtered off, washed with water,
dried and recrystallized from ethanol to give 6 as colorless crystals , yield 63%, m.p. 240 °C, IR (KBr): 3229 (NH) ,
2254 (CN), 1744, 1687 (CO) , 1605, 1588 (C = C) cm-1. 1H-NMR (DMSO-D6): δ 5-91 (s, 1H, CHBrCN), 7.62-8.01
(m, 4H, Ar-H), 11.68 (s, 1H, NH) ppm. Anal. Calcd For C11H6BrN3O3: C, 42.99; H, 1.95; N, 13.68. Found: C,
42.71; H, 1.69; N, 13.36.

Phthalazine-1,4-dione (8)
A mixture of 5 (0.01 mole) and hydrazine hydrate (0.03 mole) was fused on a hot plate for 10-15 min. The reaction
mixture was added to boiling methanol (50ml) and heated under reflux for 2hr, then cooled. The solid formed was
filtered off, washed with methanol, dried and purified by recrystallization with acetic acid to give 8 as colorless
crystals, yield 47%, m.p. 256 °C, IR (KBr): 3165 (NH), 3300-2582 (br , OH), 1662 (CO), 1601, 1556 (C=C), 1261,
1080 (C-O) cm-1. 1H-NMR ( DMSO-d6): δ 7.61-8.10 (m, 4H, Ar-H), 10.80-11.01 (br. s, 2H, NH) ppm. Anal. Calcd
For C8H6N2O2: C, 59.26; H, 3.70; N, 17.28. Found; C, 59.04; H, 3.58; N, 17.12.

5- bromosaliayladazine (10a)
Bis-1-(o-hydroxyphenylethylidene)amine (10b)
A mixture of 2 (0.01 mole) and carbonyl compounds (such as 5- bromosalicylaldehyde and 2-
hydroxyacetophenone, 0.01 mole) in methanol (50 ml) in presence of acetic acid (1 ml) was heated under reflux for
4hr. The solid formed after cooling was filtered off, dried and purified by recrystallization with ethanol to give to 10.
Compound 10a as pale yellow crystals , yield 63%, m.p 288 °C, IR (KBr): 3430-2890(br. OH), 1632(C=N), 1605,
1583(C= C), 1225, 1085(C-O) cm-1. 1H.NMR (DMSO-d6): δ 7.12-7.81 (m, 6H , Ar-H), 8.73 (s, 2H, 2x CH =N),
11.35 ( br.s, 2H, 2xOH) ppm . Anal Calcd for C14H10Br2N2O2: C, 42.42; H, 2.53; N, 7.07. Found: C, 42.18 ; H, 2.38;
N, 6.98.
Compound 10b as yellow crystals , yield 61%, m.p. 212 °C, IR (KBr); 3380-2700 (br.OH), 1635(C=N), 1063, 1587
(C=C), 1246, 1115(C-O) cm-1. 1H-NMR (DMSO-d6); δ 2.53 (s, 6H, 2xCH3), 6.99-7.88 (m, 8H, Ar-H), 12.83 (s, 2H,
2xOH) ppm. Anal. Calcd for C16H16N2O2; C, 71.64; H, 5.97; N, 10.45. Found: C, 71.41; H, 5.68; N, 10.22.

RESULTS AND DISCUSSION

Chemistry
Condensation of cyanoacetic acid hydrazide (1) with thiophene-2-carboxaldehyde12 in ethanol under reflux led to the
formation of 1-(thiophene-2-carboxaldehyde)-cyanoacetic acid hydrazone (2). 2-Amino-6-(thinyl)-7-cyano-4-oxo-3-
hydropyrazolo[5,1-a] pyrimidine (4) was prepared via the reaction of 4-(thiophene-2-carboxaldehyde)-cyanoacetic
acid hydrazone (2) with malononitrile in methanol in presence of triethyl amine under reflux to give 1-
(cyanomethyl)carbonyl-3-thinyl-4-cyano-5- amino pyrazole (3) as intermediate , followed by cyclization .

Treatment of cyanoacetic acid hydrazide (1) with phthalic anhydride in ethanol under reflux afforded the
corresponding to 3-(cyanomethyl)carbonyl-phthantazin-1,4-dione (5) .

Bromination 16 of 2-(cyanomethyl)carbonyl-phthalazine-1,4-diane (5) with one mole from the bromine in glacial
acetic acid at room temperature gave the corresponding 2-(bromocyanomethyl)carbonyl-phthalazin-1,4-diane (6),
scheme (1).

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H2C CN
O
H2 H S CHO
C O
NC C C N NH2
C N NH
H
O 2
R' H
N N C CH2CN O
O CH2(CN)2
OH O O
9
R' Piperdine
R
R R
OH O
R' R'
N N O
NH
N
OH HO N S N CH2CN
CN
10
O O
a, R= H, R' = Br NC NH2

b, R= CH3, R'= H cOH

Br 2 / A 5 3
N2H4
O

NH Br
N
CN O
O N
O O O S N
NH2
NH NH
NC N
NH N
NH2 4
O N NH
O
8 7

Scheme 1

Hydrazanylsis of 5 with hydrazine hydrate by fusion at 120oC, gave the corresponding to phthalazin-1,4-diane (8,
known), which does not give the expected structure 7(scheme 1). The formation of compound 8 takes place via the
following mechanism as shown in scheme (2).

O
O
NH
NH2NH2 NH
N NH2NH2
CN N
CN
O O
O O

- H+ ,+ H+

O O

H2NHN CN NH NH
+ NHNH2
NH N
O CN

O O O
H
8
Scheme 2

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The reaction of cyanoacetic acid hydrazide (1) with 5- bromosalicyladehyde and 2-hydroxyacetophenone in
presence of acid catalyst in ethanol under reflux was expected to give structure 9, but only 5- bromosalicylaldazine
(10a) and 1-(o-hydroxy-phenyl) ethylidene amine (10b) were yielded.

M- CHO O M - CO
N
A N B
S
NH2
NH2
NH2 NC N N N
N N N
N 4
S CN
S m/z 257 (100%)
CN m/z 229 (7.70%)
m/z 228 (42.30%)
- NH2
- NH
N N
N N N

S CN
N
S m/z 213 (44.20%)
CN

m/z 213 (44.20%) - CN

- CN N
N

N
N S
CN
m/z 187 (3.30%)
S
CN
- HCN

m/z186 (14.90%)
N
- HCN S

CN
N
m/z 160 (4.80%)
CN -N
S
CN
m/z 159 (12.50%)

- CN S
m/z 146 (3.20%)

N - C2

NC
S

m/z 133 (12.30%) S

m/z 121 (1.80%)

Scheme 3: Main fragmentation pathway of compound 4

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Mass spectrometry
The mass spectral decomposition17-22 modes of various organic compounds such as hydrazone derivative,
pyrazolopyrimidinone, 1,4-phthalazindione derivative and salicylaldazine derivatives have been suggested and
investigated . Table (1) lists the m/z (relative abundance, %) values of the principle fragment of the prepared
compounds.

The mass spectrum of compound 2 (Fig.1) shows a weak intense molecular ion peak at m/z 143, corresponding to
the molecular formula C8H7N3OS.

The molecular ion of compound 2 (m/z 193) underwent fragmentation via pathway A to produce a peak at m/z 125
by losing cyanoacetyl (CNCH2CO) group. The lose of amino group (NH2) from the ion with m/z 125 resulted in a
stable fragment at m/z 109. The stable ion at m/z 109 underwent loss of cyano group and sulphur atom to give peaks
at m/z 83 and m/z 51, respectively.

Also the ion at m/z 193 underwent loss of cyanoketene (CN-CH=C= O) via pathway B to give peak at m/z 126. The
ion at m/z 126 underwent fragmentation to produce a peak at m/z 110, 96, and m/z 70 by losing amino group (NH2),
nitrogen atom and ethylene molecule, respectively.

The mass spectrum of compound 4 (Fig. 2) shows strong and intense molecular ion peak at m/z 257, corresponding
to the molecular formula C11H7N5OS. The molecular ion peak was found to be the base peak.

The molecular ion of compound 4 underwent fragmentation via pathway A to produce the peak at m/z 228 by losing
formyl group (CHO), The ion of m/z 228 was broken to give ion of m/z 213 by losing imino group (NH). Ion of m/z
213 underwent loss of two molecules from the hydrogen cyanide to give peak at m/z 186 and m/z 159. This
fragmentation led to the ions at m/z 133, 101, 76 and m/z 50, respectively.

Accordingly, the same molecular ion, of compound 4 (Scheme3) was found to undergo fragmentation via path way
B to produce ion at m/z 229 by losing carbon monoxide (C=O). The ion of m/z 213 was obtained by loss of amino
group (NH2) from the ion of m/z 229. Ion of m/z 213 underwent loss of cyano group (CN), nitrogen atom and
hydrogen cyanide (HCN) to give peaks at m/z 187, 173 and m/z 146, respectively. The loss of cyano group from the
ion of m/z 146 gives peak at m/z 120. This fragmentation led to the ion of m/z 82 and m/z 58.

Table (1) EI Mass Spectra (70 eV) of Compounds 2, 4,5,6,8 and 10

Pathway A Pathway B
Compd M+ Other ions
-M m/z -M m/z
[C5H5N2S]+ [C5H6N2S] +
COCH2CN NC – CH= = O
125 (15.50 ) 126(4.00) 194 ( M + +l, 3.4), 142 (M+-1, 2.60), 153 (2. 60), 124
[C5H3NS]+ [C5H4NS]+ (2.70), 112 (5.10), 111 (10.30), 105 (1.40), 99
NH2 NH2
[C8H7N3OS]+ 109 (100) 110(64.30) (6.90), 98 (34.90), 97 (11.00), 95 (10.50), 94 (4.80),
2
193 (24.60) [C4H3S]+ [C5H4S]+ 84 (6.20), 82 (6.20), 81 (12.10), 71 (9.30), 69 (15.00),
CN N
83 (7.60) 96(16.90) 68 (14.60), 63 (9.60), 62 (4.00), 58 (10.40), 57 (6.50),
[C4H3]+ [C3H2S]+ 54 (12.01), 53 (10.20), 52 (12.00), 50 (7.90)
S C2H2
51 (11.50) 70 (22.40)
[C10H6N5S]+ [C10H7N5S]+
CHO
228 (42.20)
CO
229 (7.70) 258 (M++l, 20.30), 256 (M+-1, 8.00), 242 (3.30), 241
(1.40), 227 (7.50), 214 (4.20), 200 (4.10), 199 (3.30). 197
[C10H5N4S]+ [C10H5N4S]+
NH NH2 (4.50), 192 (2.70), 192 (13.30), 185(7.90), 174(3.40),
213 (44.20) 213 (44.20)
171 (6.20), 169 (4.00), 160 (4.80), 158 I (3.90),
[C11H7N5OS]+ [C9H4N3S]+ [C9H5N3S]+
4 HCN CN 145(3.20), 135(3.30), 134 (8.90), 132(1.00), 121 (1.80),
257 (100) 186 (14.90) 187 (3.30)
118 (2.70), 1 15 (2.50), 1 14 (3.10), 108 (1.80) 107(2.70),
[C8H3N2S]+ [C9H5N2S]+
HCN N 106(2.20), 100 (5.00), 99(3.60), 95(2.80). 94(6.60),
159 (12.50) 173 (4.20)
93(3.30), 90(5.00), 89(5.20), 88(7.30), 87(5.30),
[C7H3NS]+ [C8H4NS]+ 84(3.70)
CN HCN
133 (12.30) 146 (5.10)

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Pathway A Pathway B
Compd M+ Other ions
-M m/z -M m/z
[C8H6N2O2]+ [C4H5N2O3] +
CNCH=C=O CH2
162 (73 .80) 184(6.40)
[C8H5NO2]+ [C8H4N2O2]+
NH CO 164(0.80), 163(7.30), 160(1.50), 134(1.00),
147 (1.20) 161(75.50)
131(13.60), 118(1.50), 117(1.70), 116(0.90),
[C8H4O2]+ [C8H5O2]+
NH N2 106(2.00), 105(21.50), 102(2.40), 101(1.30),
[C11H7N3O3]+ 123 (15.10) 133(6.90)
5 91(4.50), 102(2.40), 101(1.30), 91(4.50), 90(6.10),
229 (15.90) [C7H4O]+ [C7H3O]+
CO CH2O 89(5.40), 78(3.30), 77(26.90), 74(38.70), 73(30.30),
104(70.70) 103 (75.90)
72(6.40), 68(46.60), 67(46.30), 66(5.10), 65(2.80),
[C6H4]+ [C6H3]+ 64(6.20), 53(6.90), 52(10.40)
CO CO
76(38.70) 75(88.60)
[C4H3]+ [C4H2]+
CH=C CH≡C
51(35.30) 500(100)
[C4H6N3O3]+ [C9H5N2O2]+
Br BrCHCN
228 (2.60) 184(79.50)
[C8H6N2O2]+ [C8H5N2O2]+
C=C=O CO
162 (100) 16(18.50) 309 (M + +2, 2.60), 292(0.80), 29190.70), 200(2.50),
[C8H5NO2]+ [C8H5O2]+ 191(0.80), 190(1.00), 188(1.10), 173(3.30),
NH N2
147 (0.70) 133(20.00) 164(1.90), 163(8..60), 148(1.70), 146(1.20), 45(5.60),
+
[C11H6N3BrO3] NH [C8H4O2]+ [C7H5O]+ 134(2.70), 130(1.60), 121(1.80), 120(7.40),
6 CO
307(2.60) 132 (2.10) 105(25.00) 119(1.50), 118(8.40), 117(2.80), 103(2.70),
[C7H4O]+ [C6H5]+ 102(2.90), 94(1.90), 92(1.60), 88(1.30), 78(1.80),
CO CO
104(71.20) 77(15.10) 75(11.50), 74(7.90), 67(5.10), 66(2.00), 64(2.40),
[C6H4]+ [C4H3]+ 63(1.80), 52(3.70),
CO C2H2
76(76.50) 51(11.50)
[C4H2]+
C2H2
50 (56.10)

Pathway A Pathway B
Compd M+ Other ions
-M m/z -M m/z
[C8H4O2]+ [C8H5O2]+
N2H2 N2H2
132(18.00) 133(4.60)
163(M++1,5.50), 161(M+-1,3.40), 131(2.10),
[C7H4O]+ [C7H5O]+
+ CO CO 128(4.40),128(4.40), 118(2.90), 106(2.50), 103(6.30),
[C8H6N2O2] 104(100) 105(22.80)
8 101(2.30), 91(5.30), 90(1.60), 81(2.50), 79(1.70), 78(4.10),
162(80.10) [C6H4]+ [C6H5]+
CO CO 75(12.20), 74(11.20), 73(5.70), 66(3.30), 65(1.30), 64(3.80),
76(29.50) 77(29.50)
63(4.70), 62(4.60), 61(3.80), 58(12.50), 5315.20), 52(8.60).
[C4H2]+ [C4H3]+
C2H2 C2H2
50 (32.90) 51(28.10)
[C7H5NBrO]+ [C7H6NBrO]+
C7H5NBrO C7H4NBrO
198(37.70) 119(62.30)
[C6H4BrO]+ [C7H5NO]+ 400(M++4, 4.40), 398(M++3, 72.90), 396(M+, 37.30),
HCN HBr 383(16.30), 38(3.70), 379(15.00), 320(20.30), 318(20.10),
171(37.90) 199(25.50)
303(11 .7O), 301(12.00), 300(11.50), 227(16.20), 226(5.20),
[C5H4Br]+ [C7H5O]+
CO N 225(16.00), 201(58.30), 200(30.30), 197(13.80), 173(27.60),
[C14H10N2Br2O2]+ 143(28.90) 105(13.80)
10a 172(10.20), 169(13,10), 146(13,50), 145(26.90), 144(13.60),
396(37.50) [C5H3]+ [C6H3O]+
HBr CH2 121(16.10), 120(13.10), 118(8,30), 106(4.30), 93(19.00),
63(100) 91(24.20)
92(24.80), 90(18.50), 77(29.30), 76(18.40), 74(13.10),
[C6H3]+ 66(17.20), 65(47.90), 64(42.20), 62(28.90), 61(13.30),
O
75(12.20) 53(37.50)
[C4H3]+
C2
51(49.90)
[C15H13N2O2]+ [C16H15N2O]+
CH3 OH
253.(91.70) 251(93.60)
[C8H8N2O]+ [C13H12N2O]+
C7H5O C3H3
148(24.80) 212(26.60) 269(M+ +1, 21 .0), 254(34.90), 252(33,90)., 227(11.00),
[C16H16N2O2]+ [C4H4N2O]+ [C13H11N2]+ 211(9.20), 210(19.30), 180(7.30), 179(15.60), 175(7.30),
10b C4H4 OH
268(100) 96(7.10) 195(11.90) 173(3.70), 159(12.80), 127(8.30), 125(11.00), 124(11.00),
[C2H3N2O]+ [C10H10N2]+ 123(6.40), 97(7.30), 72(4.60).
C2H C3H
71(21.10) 158(11.90)
[CHN2O]+ [C5H8N2]+
CH2 C5H2
57(13.80) 96(7.30)

The mass spectra of compound 5 (Fig.3) showed intense molecular ion peak at m/z 229, corresponding to the
molecular formula C11H7N3O3. The molecular ion of m/z 229 fragmented via pathway A to give peak at m/z 162 by
losing cyanoketene (CNCHCO) molecule. The peak at m/z 162 underwent fragmentation to produce a peak at m/z
147, corresponding to the molecular ion of phthalaimide by losing group (NH). It further under went loss of imino

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group (NH), two carbon monoxide molecules and acetylene molecule to give peaks at m/z 132, 104, 76 and m/z 50,
respectively.

M- CNCR=C=O NH R M- CNCHRCO
A B
N
CN
O O O O
NH 5, R= H; m/z 229 (15.90%) NH
NH N
O O
m/z 162 (100%) m/z 161 (18.50%)

- N2H2
- N2

O
CHO

O C O
m/z132 (8.00%)

- CO m/z 133 (20.00%)

- CO

O
C
O

m/z104 (18.70%)

- CO m/z105 (25.00%)
- CO

m/z 76 (80.40%)

- C2H2 m/z 77 (15.10%)

- C2H2

m/z 50 (44.80%)

m/z 51 (11.50%)

Scheme 4: Main fragmentation pathway of compounds 5, 6 and 8

Also, the same molecular ion m/z 229 fragmented via the pathway B by cleavage of cyanomethyl (CNCH2) to give a
peak at m/z 189, which lost carbon monoxide to give a peak at m/z 161. Then it lost nitrogen molecule to give a peak
at m/z 133. It further underwent loss of formaldehyde, carbon monoxide molecules and acetylene cation (C2H) to
give peaks at m/z 103, m/z 75 and a base peak at m/z 50, respectively.

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R R
M- C7H5BrNO OH M - C7H4BrNO
N N
A
OH HO B

Br m/z 396 (50.00%)

N Br
NH
OH
OH
m/z 198 (37.70%)
m/z 199 (62.30%)
- HCN
- HBr

Br
NH

OH OH

m/z 171 (37.40%) m/z 119 (25.50%)

- CO
-N

Br

OH
m/z 143 (29.90%)
m/z 105 (13.80%)

- CH2O
- HBr

m/z 63 (100 %)
m/z 75 (18.90%)

Scheme 5: Main fragmentation pathway of compound 10a

The molecular ion peak of compound 6 (Fig4) was observed at m/z 307/309, corresponding to the molecular formula
C11H6N3BrO3. The M+2 was observed along with the molecular ion peak due to the presence of isotopes of bromine
atom in the compound.

The molecular ion of m/z 307 fragmented via the pathway A to give peak at m/z 228 by losing bromine atom, which
lost (CNC=C=O) to give peak at m/z 162. The ion of m/z 162 underwent fragmentation via pathway A in the same
fragmentation processes which was observed for compound 5.

Also, the same ion of m/z 307 fragmented via pathway B by a cleavage of bromocyanomethyl (CNCHBr) to give a
peak at m/z 189, which lost carbon monoxide to give a peak at m/z 161. The ion of m/z 161 underwent broken via
pathway B in the same fragmentation processes which was observed for compound 5.

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The molecular ion of compound 8 (Fig. 5) at m/z 162 fragments via pathway A to give peak at m/z 132 by losing
N2H2 molecule. The loss of carbon monoxide from the ion of m/z 132 gave the stable ion of m/z 104. This
fragmentation led to ions of m/z 76 and m/z 50. The same ion of m/z 162 fragmented to ion m/z 133 via pathway B.
Ion of m/z 133 underwent fragmentation to produce a peak at m/z 105 and m/z 77 by losing two carbon monoxide
molecules. The ion of m/z 77 was broken to give an ion of m/z 51.

The mass fragmentation pattern of compounds 5, 6 and 8 are summarized in scheme (4).

The mass spectrum of compounds 10a and 10b (Fig. 6 and 7) are fully consistent with the assigned structures. In
most cases, intense molecular ion peaks were observed. Thus, compound 10a and 10b showed strong intense
molecular ion peaks at m/z 396 and m/z 268, consistent with the molecular formula C14H10N2Br2O2 and C16H16N2O2,
respectively.

The molecular ion of compound 10a (Scheme 5) underwent fragmentation via pathway A to produce peak at m/z
198, corresponding to 5-bromo-2-hydroxy phenylmethylamion radical cation. It further underwent loss of hydrogen
cyanide (HCN), carbon monoxide and hydrogen bromide to give peaks at m/z 171, 143 and stable fragmentation at
m/z 63, respectively .

The molecular ion of compound 10a was also found to undergo fragmentation via pathway B to produce the ion of
m/z 199, which further broke to give an ion at m/z 119.

The ion of m/z 119 broke to give an ion at m/z 105 which lost nitrogen atom. It further underwent loss of methylene
group, oxygen atom and two carbon atoms to give peaks at m/z 91, 75 and m/z 51, respectively. The mass
fragmentation pattern of compound 10b was summarized in Table 1.

Fig. 1: mass spectra of compound 2

Fig. 2: mass spectra of compound 4

Fig. 3: mass spectra of compound 5

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Fig. 4: mass spectra of compound 6

Fig. 5: mass spectra of compound 8

Fig. 6: mass spectra of compound 10a

Fig. 6: mass spectra of compound 10b

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