Synthesis, reactions and spectral properties of 3-chloro-2,6-diaryl-4h- thiopyran-4-ones. Synthesis of some new 3-chloro-spirothiopyran derivatives

Article abstract of DOI:10.1080/10426500490459696

3-Chloro-2-phenyl-6-p-tolyl and 3-chloro-2,6-di-p-tolyl-4H-thiopyran-4-ones have been synthesized in moderate yieldes from the reaction of 3-chloro-tetrahydrothiopyran-4-ones with phosphorus pentachloride. Their thiones, oximes, and hydrazones have been a

Full text of DOI:10.1080/10426500490459696

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SYNTHESIS, REACTIONS AND SPECTRAL PROPERTIES
OF 3-CHLORO-2,6DIARYL-4H-THIOPYRAN-4-ONES.
SYNTHESIS OF SOME NEW 3-CHLORO-SPIROTHIOPYRAN
DERIVATIVES
Abdel Moneim El-Ghanam a
a Alexandria University, Alexandria, Egypt
Version of record first published: 16 Aug 2010.
To cite this article: Abdel Moneim El-Ghanam (2004): SYNTHESIS, REACTIONS AND SPECTRAL PROPERTIES OF 3-
CHLORO-2,6DIARYL-4H-THIOPYRAN-4-ONES. SYNTHESIS OF SOME NEW 3-CHLORO-SPIROTHIOPYRAN DERIVATIVES, Phosphorus,
Sulfur, and Silicon and the Related Elements, 179:6, 1075-1083
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Phosphorus, Sulfur, and Silicon, 179:1075–1083, 2004
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ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500490459696
SYNTHESIS, REACTIONS AND SPECTRAL
PROPERTIES OF 3-CHLORO-2,6-
DIARYL-4H-THIOPYRAN-4-ONES. SYNTHESIS
OF SOME NEW 3-CHLORO-SPIROTHIOPYRAN
DERIVATIVES
Abdel Moneim El-Ghanam
Alexandria University, Alexandria, Egypt
(Received August 16, 2003; accepted October 9, 2003)
3-Chloro-2-phenyl-6-p-tolyl and 3-chloro-2,6-di-p-tolyl-4H-thiopyran-
4-ones have been synthesized in moderate yieldes from the reaction
of 3-chloro-tetrahydrothiopyran-4-ones with phosphorus pentachloride.
Their thiones, oximes, and hydrazones have been also prepared. Treat-
ment of thiones with malononitrile gave the corresponding 3-chloro-
4-thiopyrylidenemalononitriles which gave 3-chloro-spirothiopyran
derivatives of pyrazole, isoxazole, 1,3-thiazines when treated with hy-
drazine hydrate, hydroxylamine hydrochloride, thiourea and thiosemi-
carbazide, respectively. While treatment of 3-chloro-thiopyrylidene-
malononitriles with acetylacetone gave the corresponding 3-chloro-
spirothiopyran derivatives of pyran.
Keywords: 3-Chlorothiopyrones; 3-chlorothiopyrylidenemalononitr-
iles; NMR spectra; mass spectra; 3-chlorospirothiopyranes
Thiopyranes and their derivatives have been subject of interest for
chemists due to their importance as intermediates in the synthesis of
pyrylium dyes1 as well as their biological activities. Thiopyran-4-ones
are reported to be fungicidal,2 while 3-carboxylic acid of thiopyran-
4-one itself has been used as precursor in the preparation of noval
penicillins or the equivalent cephalosporins.2 Moreover, the alkylamino
substitution of fused thiopyran-4-ones affords analogues of the acri-
dine antimalarials which have been shown to intercalate into DNA and
I would like to thank Dr. Bassam El Ali and King Fahd University of Petroleum
and Minerals, Saudi Arabia, Chemistry Department for helping with the spectra and
elemental analysis of this work.
Address correspondence to Abdel Moneim El-Ghanam, Chemistry Department, Fac-
ulty of Science, Alexandria University, Ibrahimia PO Box 426, Alexandria 21321, Egypt.
E-mail: delghanam@yahoo.com
1075

1076
A. M. El-Ghanam
strongly mutagenic in test system.2 On the basis of the above facts,
the synthesis of new thiopyrones, 3-chloro-4H-thiopyran-4-ones and
their reactions with bidentate and active methylene reagents have
been studied. While both a mixture of 2,6-diphenyl (2a) and 3-
chloro-2,6-diphenyl (2b)-4H-thiopyran-4-ones and a mixture of 2,6-di-p-
anisyl-3,5-dichloro (2c) and 2,6-di-p-anisyl-3-chloro (2d)-4H-thiopyran-
4-ones have been prepared by the reaction of 2,6-diphenyl (1a) and
2,6-di-p-anisyl (1c) -tetrahydro-4H-thiopyran-4-ones with phosphorus
pentachloride3 respectively. Under the same conditions, 2-phenyl-6-p-
tolyl (2e) and 2,6-di-p-tolyl (2f)-thiopyran-4-ones were formed from
2-phenyl-6-p-tolyl (1e) and 2,6-di-p-tolyl (1f) -tetrahydrothipyran-4-
ones4 respectively (Scheme 1). In order to repair this gab, in the
SCHEME 1
present work, 3-chloro-2-phenyl-6-p-tolyl (4e) and 3-chloro-di-p-tolyl
(4f)-4H-thiopyran-4-ones have been prepared in moderate yields from
the dehydrogenation of 3-chloro-2-phenyl-6-p-tolyl (3e) and 3-chloro-
2,6-di-p-tolyl (3f) –tetrahydro-4H-thiopyran-4-ones, prepared in the
previous publication,5 using phosphorus pentachloride in dry benzene
(Scheme 2).
RESULTS AND DISCUSSION
The structure of the newly prepared 3-chloro-thiopyran-4-ones 4e,f
(Scheme 2), where established from their spectral and analytical data
(Tables I and II). The IR spectra showed a strong carbonyl absorption

Spirothiopyran Derivatives
1077
SCHEME 2
in the range 1645–1662 cm−1, while their 1H-NMR spectra showed be-
side other characteristics, a singlet for H-5 proton at 7.06–7.20 δ. Fur-
ther weight was added to the structure of 3-chloro-thiopyrones 4e,f by
study of their electron impact mass spectra. These compounds gave a

1078
A. M. El-Ghanam
TABLE I Spectroscopic Data of Compounds 4–13
Comp.
no.
IR (KBr) ν cm−1 1H-NMR δ (ppm)
/
4e
IR: ν = 2932 (CH Aliphatic), 1662 (C O), 1595 (C C); 1HNMR: (CDCl3): δ = 7.58
(m, 9H, Aromatic) 7.06 (s, 1H, H-5), 2.36 (s, 3, CH3).
4f
5e
5f
6e
6f
7e
7f
8e
8f
9e
IR: ν = 2946 (CH Aliphatic), 1645 (C O), 1590 (C C); 1HNMR: (CDCl3): δ = 7.45
(m, 8H, Aromatic) 7.20 (s, 1H, H-5), 2.42 (s, 6H, 2CH3).
IR: ν = 2920 (CH Aliphatic), 1432 (C S), 1588 (C C); 1HNMR: (CDCl3): δ = 7.42
(m, 9H, Aromatic), 7.88 (s, 1H, H-5), 2.28 (s, 3H, CH3).
IR: ν = 2898 (CH Aliphatic), 1450 (C S), 1592 (C C); 1HNMR: (CDCl3): δ = 7.62
(m, 8H, Aromatic), 8.36 (s, 1H, H-5), 2.48 (s, 6H, 2CH3).
IR: ν = 3328 (OH), 2936 (CH Aliphatic), 1622 (C N), 1HNMR (CDCl3): δ = 9.24
(s, 1H, OH), 7.42 (m, 9H, Aromatic), 7.19 (s, 1H, H-5), 2.40 (s, 3H, CH3).
IR: ν = 3435 (OH), 2920 (CH Aliphatic), 1618 (C N), 1HNMR (CDCl3): δ = 8.88
(s, 1H, OH), 7.38 (m, 8H, Aromatic), 7.20 (s, 1H, H-5), 2.44 (s, 6H, 2CH3).
IR: ν = 2300, 3216 (NH2), 2886 (CH Aliphatic), 1620 (C N), 1HNMR (CDCl3): δ =
7.48 (m, 9H, Aromatic), 7.22 (s, 1H, H-5), 5.48 (s, 2H, NH2), 2.30 (s, 3H, CH3).
IR: ν = 3318, 3220 (NH2), 2922 (CH Aliphatic), 1625 (C N), 1HNMR (CDCl3): δ =
7.52 (m, 8H, Aromatic), 7.19 (s, 1H, H-5), 6.00 (s, 2H, NH2), 2.42 (s, 6H, 2CH3).
IR: ν = 2920 (CH Aliphatic), 2196 (C N), 1586 (C C); 1HNMR (CDCl3): δ = 7.56
(m, 9H, Aromatic), 6.92 (s, 1H, H-5), 2.38 (s, 3H, CH3).
IR: ν = 2892 (CH Aliphatic), 2188 (C N), 1596 (C C); 1HNMR (CDCl3): δ = 7.58
(m, 8H, Aromatic), 7.12 (s, 1H, H-5), 2.42 (s, 6H, 2CH3).
IR: ν = 3386, 3332, 3220 (NH2 + NH), 2920 (CH Aliphatic), 2192 (C N), 1608
(C C); 1HNMR(CDCl3): δ = 10.92 (br, 1H, NH), 7.52 (m, 9H, Aromatic), 7.12
(s, 1H, H-5), 5.60 (br, 2H, NH2), 2.38 (s, 3H, CH3).
9f
IR: ν = 3362, 3346, 3262 (NH2 + NH), 2868 (CH Aliphatic), 2194 (C N), 1612
(C C); 1HNMR (CDCl3): δ = 11.22 (br, 1H, NH), 7.58 (m, 8H, Aromatic), 7.16
(s, 1H, H-5), 5.82 (s, 2H, NH2), 2.42 (s, 6H, 2CH3).
10e
10f
11e
11f
12e
12f
13e
13f
IR: ν = 3386, 3350, 3262 (NH2 + NH), 2960 (CH Aliphatic), 2190 (C N), 1608
(C C); 1HNMR (DMSO-d6): δ = 11.22 (br, 1H, NH), 7.58 (m, 9H, Aromatic), 7.12
(s, 1H, H-5), 5.82 (br, 2H, NH2), 2.32 (s, 3H, CH3).
IR: ν = 3392, 3370, 3256 (NH2 + NH), 2896 (CH Aliphatic), 2202 (C N), 1612
(C C); 1HNMR (DMSO-d6): δ = 10.98 (br, 1H, NH), 7.48 (m, 8H, Aromatic), 7.08
(s, 1H, H-5), 6.00 (s, 2H, NH2), 2.42 (s, 6H, 2CH3)
IR: ν = 3392, 3342 (NH2), 2976 (CH Aliphatic), 2190 (C N), 1630 (C N); 1598
(C C); 1HNMR (DMSO-d6): δ = 7.54 (m, 9H, Aromatic), 7.16 (s, 1H, H-5), 5.46
(br, 4H, NH2), 2.36 (s, 3H, CH3).
IR: ν = 3378, 3336 (NH2), 2896 (CH Aliphatic), 2182 (C N), 1622 (C N); 1602
(C C); 1HNMR (DMSO-d6): δ = 7.56 (m, 8H, Aromatic), 7.08 (s, 1H, H-5), 2.82
(br, 4H, 2NH2), 2.40 (s, 6H, 2CH3).
IR: ν = 3388, 3336, 3246 (NH2 + NH), 2960 (CH Aliphatic), 2186 (C N), 1636
(C N); 1608 (C C); 1HNMR (CDCl3): δ = 11.12 (br, 1H, NH), 2.54 (m, 9H,
Aromatic), 6.98 (s, 1H, H-5), 5.46 (br, 4H, 2NH2), 2.38 (s, 3H, CH3).
IR: ν = 3378, 3342, 3258 (NH2 + NH), 2982 (CH Aliphatic), 2179 (C N), 1628
(C N); 1598 (C C); 1HNMR (CDCl3): δ = 10.98 (s, 1H, NH), 7.48 (m, 8H,
Aromatic), 7.12 (s, 1H, H-5), 5.68 (br, 4H, 2NH2), 2.42 (s, 6H, 2CH3).
IR: ν = 3396, 3332 (NH2), 2938 (CH Aliphatic), 2188 (C N), 1674 (C O); 1602
(C C); 1HNMR (DMSO-d6): δ = 7.52 (m, 9H, Aromatic), 6.98 (s, 1H, H-5), 5.62
(br, 2H, NH2), 2.32 (s, 3H, CH3), 2.22 (s, 3H, COCH3).
IR: ν = 3388, 3362 (NH2), 2962, 2932 (CH Aliphatic), 2164 (C N), 1670 (C O); 1612
(C C); 1HNMR (DMSO-d6): δ = 7.58 (m, 8H, Aromatic), 7.16 (s, 1H, H-5), 5.92
(br, 2H, NH2), 2.38 (s, 6H, 2CH3), 2.20 (s, 3H, COCH3).

Spirothiopyran Derivatives
1079
Cl
TABLE II Physical and Analytical Data of Compounds 4–13
Calculated/Found %
Comp.
no.
m.p.◦C Yield%
Formula
C
H
N
S
4e
142
166
171
182
148
156
172
183
198
160
226
216
186
202
194
212
202
221
188
212
62
58
53
56
70
71
76
80
68
70
77
82
69
71
68
66
61
63
58
62
C18H13ClOS
69.12 4.16
69.23 4.30
69.98 4.59
69.68 4.38
65.75 3.92
65.52 3.92
66.57 4.38
66.38 4.52
65.95 4.27
65.73 4.29
66.76 4.69
66.80 4.86
66.16 4.59
65.98 4.64
66.96 4.99
66.70 5.02
69.90 3.61
69.78 3.42
70.49 4.01
70.50 4.22
64.20 4.33 14.27
64.38 4.16 14.22
64.94 4.67 13.78
64.72 4.51 13.62
64.04 4.07 10.67
63.96 4.12 10.56
63.23 4.31 10.06
63.46 4.30 10.21
60.48 3.89 12.83 14.66
60.36 3.91 12.68 14.62
61.26 4.22 12.43 14.21
61.32 4.10 12.41 14.21
58.47 3.99 15.50 14.17
58.28 3.71 15.76 14.32
59.29 4.30 15.04 13.75
59.40 4.32 15.16 13.80
—
—
—
—
—
—
—
—
4.27
4.28
4.10
4.32
8.57
8.52
8.22
8.16
7.77
7.61
7.48
7.28
10.24 11.3
10.16 11.18
9.80 10.87
9.72 10.70
19.48 10.81
19.32 10.86
18.69 10.36
18.86 10.32
9.77 10.84
9.70 10.94
9.37 10.39
9.40 10.18
9.80 10.87
9.64 10.92
9.40 10.43
9.38 10.46
4f
C19H15ClOS
5e
C18H13ClS2
C19H15ClS2
5f
6e
C
18H14ClNOS
6f
C19H16ClNOS
7e
C
18H15ClN2S
C19H17ClN2S
21H13ClN2S
7f
8e
C
8.88
8.92
8.54
8.50
8.15
8.30
7.87
7.85
8.13
8.06
7.66
7.52
9.85
9.68
9.48
9.62
9.04
9.12
8.73
8.88
9.02
9.12
8.50
8.70
8.13
8.16
7.88
7.90
7.86
7.68
7.63
7.15
7.68
7.72
7.48
7.61
8f
C22H15ClN2S
C21H17ClN4S
9e
9f
C
22H19ClN4S
21H16ClN3OS
C22H18ClN3OS
22H17ClN4S2
C23H19ClN4S2
10e
10f
11e
11f
12e
12f
13e
13f
C
C
C
C
22H18ClN5S2
23H20ClN5S2
C26H21ClN2O2S 67.46 4.54
66.96 4.11
27H23ClN2O2S 68.28 4.85
67.76 4.81
6.05
6.23
5.90
6.34
6.92
6.90
6.74
6.72
C
moderately intense molecular ion peaks followed by a carbonyl lost
to give the base peak fragment, which undergo a subsequent frag-
mentation characteristic to 2,5-diaryl thiophens6 (Experimental sec-
tion). Treatment of 4e,f with phosphorus pentasulfide in dry benzene

1080
A. M. El-Ghanam
afforded the corresponding 3-chloro-thiopyran-4-thiones 5e,f. On the
other hand, the reaction of 3-chloro-thiopyran-4-ones 4e,f as well as
the thiones 5e,f with hydroxylamine hydrochloride in ethanol led to
the formation of the respective oximes 6e,f (Scheme 2). The IR spec-
tra of the oximes 6e,f are characterized by a strong intensity C N
absorption at 1618–1622 cm−1 as well as a broad hydroxyl absorp-
1
tion at 3328–3435 cm−1. On the other hand the H-NMR spectra of
the thiones 5e,f showed an downfield shift in the resonance of H-5
protons (7.88–8.36 δ) comparing to the parent 3-chloro-thiopyran-4-
ones 4e,f. Similar deshielding on replacement of carbonyl with thio-
carbonyl were also observed for other 4H-pyran-4-thiones.7,8 Such sig-
nificant deshielding in the resonance of H-5 protons of 5e,f can be
attributed to the increased magnetic anisotropy of the thione over
carbonyl. On the other hand, the reaction of 3-chloro- thiopyran-4-
ones 4e,f with hydrazine hydrate gave the corresponding hydrazone
derivatives 7e,f. The structures of the above hydrazones were fully
characterized by their spectral (IR, 1H-NMR) and analytical data
(Tables I and II). Also, 3-chloro-2-phenyl-6-p-tolyl and 3-chloro-2,6-di-
p-tolyl-4-thiopyrylidenemalononitriles, 8e,f, were synthesized from the
reaction of 3-chloro-2-phenyl-6-p-tolyl and 3-chloro-2,6-di-p-tolyl-4H-
thiopyran-ones, 4e,f or their thiones 5e,f with malononitrile in reflux-
ing ethanol in the present of triethylamine, respectively (Scheme 2).
The structures of 3-chloro-thiopyrylidenemalononitriles, 8e,f are con-
firmed from their spectral and analytical data (Tables I and II).
The IR showed a moderately C N absorption in the range 2188–
2196 cm−1, while their 1HNMR spectra showed beside other char-
acteristics, a singlet at 6.92–7.12 δ for H-5 protons of thiopyran
ring. Treatment of 8e,f with hydrazine hydrate, hydroxylamine hy-
drochloride, thiourea, or thiosemicarbazide in refluxing ethanol in
the present of pipredine afforded the corresponding 3-chloro- spiroth-
iopyran derivatives of pyrazole, 9e,f, isoxazole, 10e,f, 1,3-thiazines,
11e,f and 12e,f respectively (Scheme 2). The reaction involve the
addition of the amino or marcapto groups at the ethylenic dou-
ble bond and then nucleophilic attack of the amino or imino group
to give the cyclized spiro compounds.9 Also, the reaction of 3-
chlorothiopyrylidenemalononitriles 8e,f with active methylene com-
pound, acetylacetone, in ethanol in the present of pipredine gave
the spirothiopyran derivatives 13e,f (Scheme 2). A carbanion for-
mation is assumed in these reactions followed by nucleophilic addi-
tion at the ethylenic double bond and cyclization to give the spiroth-
iopyran derivatives9 13e,f. All spirothiopyran derivatives, 9e, f–13e,
f were confirmed from their spectral and analytical data (Tables I
and II).

Spirothiopyran Derivatives
1081
EXPERIMENTAL
Elemental analysis were preformed on a Perkin-Elmer 240 microana-
lyzer. Melting points were recorded on a Kofler Block and are uncor-
rected. Infrared spectra were measured with a Unicam SP 1025 spec-
trophotometer for KBr pellets. Theb 1H-NMR spectra were recorded on
Jeol Lambada-500 MHz spectrometer using TMS as internal standard.
Mass spectra were recorded at 70 eV with an AEI MS-9 spectrome-
ter coupled to a DS-50 data System using a direct insertion probe for
introduction of samples.
Synthesis of 3-Chloro-2,6-diaryl-4H-Thiopyran-4-ones
4e,f (Tables I and II)
A solution of 3-chloro-2,6-diaryl-tetrahydrothiopyran-4-ones,5 3e,f
(55 mmol) in dry benzene (370 ml) was treated with phosphorus pen-
tachloride (40 gm; 190 mmol) in one portion, with shaking and cool-
ing under the tap, and the mixture was heated under reflux for one
hour. The reaction mixture was treated as described earlier3 to give
4e,f which crystallized from methanol as needles. MS: m/z (relative
abundance) 4e: M+ 314 (22), 312 (61), 284 (100), 248 (16), 148 (29), 135
(23), 91 (12), 77 (16).
Synthesis of 3-Chloro-2,6-diaryl-4H-Thiopyran-4-thiones
5e,f (Tables I and II)
A solution of 3-chloro-thiopyrones 4e,f (2 mmol) in dry benzene (30 ml)
was heated under reflux with phosphorus pentasulfide (14 mmol). The
reaction mixture was worked up as described earlier.3 The isolated
thiopyran-4-thiones 5e,f was crystallized from benzene-petroleum
ether (b.p 40–60◦C) as brown needles.
Synthesis of 3-Chloro-2,6-diaryl-4H-Thiopyran-4-one
Oximes 6e,f (Tables I and II)
A solution of 3-chloro-thopyrones 4e,f or their thiones 5e,f (2 mmol) in
ethanol (40 ml) was heated under reflux with hydroxylamine hydrochlo-
ride (8 mmol) and sodium acetate (8 mmol) in water (2 ml) for 3 h. The
reaction mixture was then poured into ice-cold water to give the corre-
sponding oximes 6e,f which crystallized from ethanol as needles. MS:
m/z (relative abundance) 6e: M+ 329 (36), 327 (100), 311 (14), 286 (26),
275 (35), 262 (11), 229 (43), 150 ( 23), 91 (32), 77 (18).

1082
A. M. El-Ghanam
Synthesis of 3-Chloro-2,6-diaryl-4H-Thiopyran-4-one
Hydrazones 7e,f (Tables I and II)
A solution of the 3-chloro-thiopyran-4-ones 4e,f (2 mmol) in ethanol
(20 ml) was heated under reflux with hydrazine hydrate ( 2 ml) for 2 h.
The reaction mixture was worked up as described earlier and crystal-
lized from methanol as needles. MS: M/z (relative abundance) 7e: 328
(34), 326 (100), 311 (16), 297 (22), 284 (20), 262 (25), 229 (17), 216 (22),
189 (13), 149 (24), 91 (11), 77 (8).
Synthesis of 3-Chloro-4-Thiopyrylidenemalononitriles
8e,f (Tables I and II)
3-Chloro-thiopyran-4-ones 4e,f was added to an equimolar amount of
malononitrile in ethanol (40 ml) and few drops of triethylamine. The
reaction mixture was refluxed for 5 h, concentrated and cold to give 8e,f
which crystallized from ethanol . MS: m/z (relative abundance) 8b: M+
377 (14), 375 ( 51), 359 (22), 323 (12), 299 (100), 263 (32), 172 (25), 96
(27), 91 (42).
Synthesis of 3-Chloro-Spirothiopyran Derivatives
9e,f---12e,f (Tables I and II). General Procedure
A solution of 3-chloro-4-thiopyrylidenemalononitriles 8e,f (2 mmol) in
ethanol (40 ml) was treated with equimolar amount of hydrazine hy-
drate or hydroxylamine hydrochloride or thiourea or thiosemicarbazide
and few drops of pipredene.
The reaction mixture was refluxed for 4 h, concentrated, cooled, and
filtered off and recrystallized from ethanol. MS: m/z (relative abun-
dance) 9e: M+ 394 (12), 392 (38), 376 (22), 350 (13), 326 (25), 295 (28),
283 (100), 218 (27), 206 (31), 174 (37), 91 (11), 77 (8); 10e: 395 (13), 393
(38), 377 (25), 351 (21), 327 (11), 311 (15), 296 (7), 284 (100), 252 (23),
207 (11),175 (21), 91 (14), 77 (19); 11e: 437 (15), 435 (44), 419 (21), 393
(23), 377 (27), 253 (11), 339 (17), 307 (32), 295 (100), 218 (21), 186 (23),
95 (7), 91 (20), 77 (8).
Synthesis of 3-Chloro-Spirothiopyran Derivative 13e,f
(Tables I and II)
3-Chloro-thiopyrylidenemalononitriles 8e,f (2 mmol) was added to a
stirred mixture of equimolar amount of acetylacetone in ethanol (40 ml)
and a few drops of pipredine. The reaction mixture was refluxed for
4 h, concentrated, cooled, and the separated solid was filtered off and

Spirothiopyran Derivatives
1083
crystallized from ethanol. MS: m/z (relative abundance) 13e: M+ 462
(11), 460 (32), 444 (23), 428 (11), 402 (23), 359 (27), 333 (15), 309 (18),
285 (25), 273 (100), 241 (31), 196 (23), 150 (34), 91 (26), 77 (12).
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(1977).
[9] A. M. El-Ghanam, Phosphorus, Sulfur, and Silicon, 178, 863 (2003).