Novel alkylsulfanylisothiazoles and alkylsulfanylthiophenes using sodium α-cyanoketene dithiolates as starting materials

Article abstract of DOI:10.1080/00397910500449534

A novel and efficient method for the synthesis of alkylsulfanylisothiazoles and alkylsulfanylthiophenes using sodium α-cyanoketene dithiolates as starting components is described. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910500449534

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Novel Alkylsulfanylisothiazoles and
Alkylsulfanylthiophenes Using Sodium
α‐Cyanoketene Dithiolates as Starting
Materials
G. H. Elgemeie a , A. M. Elzanaty b , A. H. Elghandour b & S. A. Ahmed b
a Department of Chemistry, Faculty of Science, Helwan University, Helwan,
Cairo, Egypt
b Department of Chemistry, Faculty of Science, Cairo University (Bani Suef
Branch), Bani Suef, Egypt
Published online: 16 Aug 2006.
To cite this article: G. H. Elgemeie , A. M. Elzanaty , A. H. Elghandour & S. A. Ahmed (2006): Novel
Alkylsulfanylisothiazoles and Alkylsulfanylthiophenes Using Sodium α‐Cyanoketene Dithiolates as Starting
Materials, Synthetic Communications: An International Journal for Rapid Communication of Synthetic Organic
Chemistry, 36:6, 825-834
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Synthetic Communicationsw, 36: 825–834, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500449534
Novel Alkylsulfanylisothiazoles
and Alkylsulfanylthiophenes
Using Sodium a-Cyanoketene Dithiolates
as Starting Materials
G. H. Elgemeie
Department of Chemistry, Faculty of Science, Helwan University,
Helwan, Cairo, Egypt
A. M. Elzanaty, A. H. Elghandour, and S. A. Ahmed
Department of Chemistry, Faculty of Science, Cairo University
(Bani Suef Branch), Bani Suef, Egypt
Abstract: A novel and efficient method for the synthesis of alkylsulfanylisothiazoles
and alkylsulfanylthiophenes using sodium a-cyanoketene dithiolates as starting
components is described.
Keywords: Alkylsulfanylisothiazoles, alkylsulfanylthiophenes, cyanoketene dithio-
acetals, heterocycles, sodium a-cyanoketene dithiolates
During the course of our studies directed toward exploring the synthetic
potential of cyanoketene dithioacetals for synthesizing new classes of hetero-
cycles,[1–3] we have recently reported a successful approach for synthesis of
new sodium a-cyanoketene dithiolates 2, obtained through a reaction of sub-
stituted acetanilides with carbon disulfide in the presence of sodium ethoxide
at room temperature.[4] Thus, it has been found that sodium a-ketene dithio-
late derivatives 2a–d reacted with sulfur in the presence of piperidine acetate
to give the corresponding sodium isothiazole-3,5-dithiolates 4, which were
Received in the USA September 15, 2005
Address correspondence to G. H. Elgemeie, Department of Chemistry, Faculty of
Science, Helwan University, Helwan, Cairo, Egypt. E-mail: elgemeie@hotmail.com
825

826
G. H. Elgemeie et al.
acidified with acetic acid to give the novel dimercapto products 5. The struc-
tures of 5 were established on the basis of their elemental analysis and spectral
data (IR, MS, and 1H NMR). The formation of 4 from 2 and sulfur is assumed
to proceed via addition of anionic sulfur to the nitrile group to give the inter-
mediate 3, which cyclized via elimination of anionic sulfur to yield the final
novel sodium isothiazole-3,5-dithiolates 4. Salts 4 are readily alkylated to
give 3,5-bis(alkylthio)-isothiazole derivatives. Thus, reaction of 4 with two
equivalents of methyl iodide, benzoyl chloride, or benzyl chloride gave the
corresponding dialkylated products 6 and 7 in good yield (Table 1). The
structure of compounds 6 and 7 was established on the basis of their
1
elemental analysis and spectral data (IR, MS, and H NMR). Compounds 6
can also be prepared by alkylation of the dimercapto-isothiazoles 5 with
methyl iodide in refluxing sodium ethoxide. The sodium a-cyanoketene
dithiolates 2 reacted with two equivalents of substituted phenacyl bromides
as alkylating agents to give the intermediate S-alkylated derivatives 8,
which could not be isolated but cyclized to the thiophene derivatives 9. The
structures of 9 were established on the basis of their elemental analysis and
1
spectral data (MS, IR, and H NMR) (Table 2).
In summary, we have achieved a regiospecific synthesis of interesting
novel alkylsulfanylisothiazoles and alkylsulfanylthiophenes utilizing the
reaction of sodium a-cyanoketene dithiolates with sulfur or phenacyl
bromide (Scheme 1). The compounds obtained seem promising for futher
chemical transformations and for biological evaluation studies (Scheme 2).
EXPERIMENTAL
All melting points were determined in open glass capillaries on a Gallenkamp
melting-point apparatus and are uncorrected. Their spectra were obtained
Table 1. Compounds 6 and 7
Compound
Ar
Ar1
7a
7b
7c
7d
7e
7f
Ph
COPh
COPh
COPh
COPh
CH2Ph
CH2Ph
CH2Ph
CH2Ph
4–CH3-C6H4
4–OCH3-C6H4
4–Cl-C6H4
Ph
4–CH3-C6H4
4–OCH3-C6H4
4–Cl-C6H4
Ph
4–CH3-C6H4
4–OCH3-C6H4
4–Cl-C6H4
7g
7h
6a
6b
6c
6d

Novel Alkylsulfanylisothiazoles and Alkylsulfanylthiophenes
827
Table 2. Compound 9
Compound
Ar
Ar1
C6H5
4-CH3-C6H4
4-OCH3-C6H4
4-Cl-C6H4
C6H5
4-CH3-C6H4
4-OCH3-C6H4
4-Cl-C6H4
C6H5
4-CH3-C6H4
4-OCH3-C6H4
4-Cl-C6H4
C6H5
9a
9b
9c
9d
9e
9f
C6H5
C6H5
C6H5
C6H5
4-CH3-C6H4
4-CH3-C6H4
4-CH3-C6H4
4-CH3-C6H4
4-OCH3-C6H4
4-OCH3-C6H4
4-OCH3-C6H4
4-OCH3-C6H4
4-Cl-C6H4
9g
9h
9i
9j
9k
9l
9m
9n
9o
9p
4-Cl-C6H4
4-CH3-C6H4
4-OCH3-C6H4
4-Cl-C6H4
4-Cl-C6H4
4-Cl-C6H4
(KBr disc) on a Perkin Elmer/1650 FT-IR instrument. The 1H NMR and 13
C
NMR. Spectra were measured in a Varian 400 or Wilmad 270-MHz spec-
trometer for (CD3)2SO solutions using SiMe4 as internal standard. Mass
spectra were recorded in a Varian MAT 112 spectrometer. Analytical data
were obtained from the Microanalytical Data Center at Cario University.
N-Aryl-2-cyano-acrylamide-3,3-dithiolates (2a–d), General
Procedure
A mixture of sodium ethoxide (1.36 g, 0.02 mol) and cyanoacetamide deriva-
tives 1a–e (0.01 mol) in ethanol (30 mL) was heated for 20 min and cooled,
and then carbon disulphide (0.76 g, 0.01 mol) was added. The reaction
mixture was stirred at room temperature for 30 min. The solution was evapor-
ated, and the formed solid product was collected by filtration and recrystal-
lized from ethanol.
2a: Yellow, mp . 3008C, yield 95%; nmax/cm21 (KBr) 3215 (NH), 2200
(CN), 1630 (CO). Found: C. 42.61; H, 2.33; N, 10.24; calcd. for
C10H6N2OS2Na2: C, 42.86; H, 2.14; N, 10.00%.
2b: Buff, mp . 3008C, yield 95%; nmax/cm21 (KBr) 3241 (NH), 2200 (CN),
1608 (CO). Found: C, 44.80; H, 2.53; N, 9.34; calcd. for C11H8N2OS2Na2: C,
44.90; H, 2.72; N, 9.52%.

828
G. H. Elgemeie et al.
Scheme 1.
2c: Buff, mp . 3008C, yield 95%; nmax/cm21 (KBr) 3210 (NH), 2205 (CN),
1610 (CO). Found: C, 42.62; H, 2.71; N, 9.35; calcd. for C11H8N2O2S2Na2: C,
42.58; H, 2.58; N, 9.03%.
2d: Yellow, mp . 3008C, yield 95%; nmax/cm21 (KBr) 3243 (NH), 2203
(CN), 1622 (CO). Found: C, 38.36; H, 1.83; N, 8.61; calcd. for
C10H5N2OS2Na2Cl: C, 38.15; H, 1.58; N, 8.90%.
Sodium N-Arylisothiazole-4-carboxamide-3,5-dithiolates (4a–d),
General Procedure
A mixture of compounds 2a–d (0.01 mol), sulfur powder (0.32 g, 0.01 mol),
and piperidine acetate solution (2.5 mL of H2O, 2.5 mL of piperidine, and
1 mL of acetic acid) was heated for 5 min. The solution was then evaporated,
and the resulting formed solid product was collected and recrystallized from
ethanol.

Novel Alkylsulfanylisothiazoles and Alkylsulfanylthiophenes
829
Scheme 2.
4a: Buff, mp . 3008C, yield 75%; nmax/cm21 (KBr) 3250 (NH), 1650 (CO).
Found: C, 38.11; H, 2.00; N, 8.65; calcd. for C10H6N2OS3Na2: C, 38.46; H,
1.92; N, 8.97%.
4b: Yellow, mp . 3008C, yield 75%; nmax/cm21 (KBr) 3210 (NH), 1665
(CO). Found: C, 40.66; H, 2.11; N, 8.35; calcd. for C11H8N2OS3Na2: C,
40.49; H, 2.45; N, 8.59%.
4c: Yellow, mp . 3008C, yield 75%; nmax/cm21 (KBr) 3195 (NH), 1635
(CO). Found: C, 38.22; H, 2.63; N, 8.33; calcd. for C11H8N2O2S3Na2: C,
38.60; H, 2.34; N, 8.19%.

830
G. H. Elgemeie et al.
4d: Yellow, mp . 3008C, yield 75%; nmax/cm21 (KBr) 3212 (NH), 1625
(CO). Found: C, 34.22; H, 1.66; N, 8.33; calcd. for C10H5N2OS3Na2Cl: C,
34.68; H, 1.54; N, 8.09%.
N-Aryl-3,5-dimercapto-isothiazole-4-carboxamides (5a–d),
General Procedure
Compounds 4a–d (0.01 mol) in absolute ethanol (30 mL) were acidified by
adding few drops of acetic acid and stirred at room temperature for 1 h. The
formed solid product was collected by filtration and recrystallized from
ethanol.
5a: Yellow, mp 1948C, yield 70%; nmax/cm21 (KBr) 3271 (NH), 1674 (CO);
m/z ¼ 268.6. Found: C, 44.42; H, 2.64; N, 10.18; calcd. for C10H8N2OS3: C,
44.78; H, 2.99; N, 10.45%.
5b: Yellow crystals, mp 1968C, yield 90%; nmax/cm21 (KBr) 3250 (NH),
1647 (CO); H NMR (DMSO) d 2.35 (s, 3H, CH3), 7.16–7.63 (dd, 4H,
1
C6H4), 10.32 (s, 2H, 2SH), 12.09 (s, H, NH); m/z ¼ 282. Found: C, 46.62;
H, 3.33; N, 9.75; calcd. for C11H10N2OS3: C, 46.81; H, 3.55; N, 9.93%.
5c: Yellow crystal, mp 1708C, yield 90%; nmax/cm21 (KBr) 3272 (NH), 1663
(CO); H NMR (DMSO) d 3.73 (s, 3H, OCH3), 6.93–7.54 (dd, 4H, C6H4),
1
10.29 (s, 2H, 2SH), 11.97 (s, 1H, NH), dC 55.17 (OCH3), 113.21–121.69
(Phenyl-C), 130.48 (C-3), 155.86 (C-5), 161.62 (C-4), 183.91 (C55O); m/
z ¼ 298.8. Found: C, 44.50; H, 3.53; N, 9.21; calcd. for C11H10N2O2S3: C,
44.30; H, 3.36; N, 9.40%.
5d: Buff, mp 2258C, yield 90%; nmax/cm21 (KBr) 3300 (NH), 1660 (CO).
Found: C, 39.41; H, 2.11; N, 9.53; calcd. for C10H7N2OS3Cl: C, 39.60; H,
2.31; N, 9.24%
N-Aryl-3,5-bis(methylthio)-isothiazole-4-carboxamides (6a–d),
General Procedure
Method A
Methyl iodide (2.8 g, 0.02 mol) was added to a solution of compounds 4a–d
(0.01 mol) in ethanol (30 mL), and the solution was stirred at room tempera-
ture for 2 h. The reaction mixture was acidified by few drops of hydrochloric
acid, and the resulting solid product was collected by filtration and recrystal-
lized from ethanol.

Novel Alkylsulfanylisothiazoles and Alkylsulfanylthiophenes
831
Method B
A mixture of compounds 5a–d (0.01 mol), sodium ethoxide (1.36 g,
0.02 mol), and methyl iodide (2.8 g, 0.02 mol) in ethanol (30 mL) was
stirred at room temperature for 3 h. The reaction mixture was poured over
iced water (50 mL) and then neutralized with hydrochloric acid. The formed
solid product was collected by filtration and recrystallized from ethanol.
6a: Buff, mp 1468C, yield 70%; nmax/cm21 (KBr) 3275 (NH), 1639 (CO); 1H
NMR (DMSO) d 2.69 (s, 3H, SCH3), 2.77 (s, 3H, SCH3), 7.31–7.67 (m, 5H,
C6H5), 10.23 (s, 1H, NH), dC13.52 (SCH3), 17.31 (SCH3), 119.58–128.69
(Phenyl-C), 138.42 (C-3), 159.93 (C-5), 162.61 (C-4), 166.23 (C55O); m/
z ¼ 296.8. Found: C, 48.73; H, 4.31; N, 9.32; calcd. for C12H12N2OS3: C,
48.65; H, 4.05; N, 9.46%.
6b: Buff, mp 1608C, yield 76%; nmax/cm21 (KBr) 3330 (NH), 1655 (CO).
Found: C, 50.40; H, 4.32; N, 9.21; calcd. for C13H14N2OS3: C, 50.32; H,
4.52; N, 9.03%.
6c: Buff, mp 1568C, yield 65%; nmax/cm21 (KBr) 3270 (NH), 1661 (CO).
Found: C, 47.61; H, 4.41; N, 8.25; calcd. for C13H14N2O2S3: C, 47.85; H,
4.29; N, 8.59%.
6d: Yellow, mp 2158C, yield 75%; nmax/cm21 (KBr) 3433 (NH), 1650 (CO);
1H NMR (DMSO) d 2.61 (s, 3H, SCH3), 2.68 (s, 3H, SCH3), 7.11–7.66
(m, 5H, C6H5), 8.56 (s, 1H, NH); m/z ¼ 331. Found: C, 43.40; H, 3.51; N,
8.23; calcd. for C12H11N2OS3Cl: C, 43.57; H, 3.30; N, 8.74%.
N-Aryl-3,5-bis(substitutedthio)-isothiazole-4-carboxamides (7a–h),
General Procedure
Benzoyl chloride or benzyl chloride (0.02 mol) was added to a stirred suspen-
sion of 4a–d (0.01 mol) in ethanol (50 mL). The mixture was stirred for 2 h
and then neutralized with few drops of hydrochloric acid. The solid precipitate
formed was isolated by suction and crystallized from the appropriate solvent.
7a: Yellow, from ethanol, mp 1408C, yield 85%; nmax/cm21 (KBr) 3340
(NH), 1715, 1660 (3CO). Found: C, 60.31; H, 3.53; N, 5.64; calcd. for
C24H16N2O3S3: C, 60.50; H, 3.36; N, 5.88%.
7b: Buff, from ethanol, mp 1898C, yield 85%; nmax/cm21 (KBr) 3395 (NH),
1726, 1666 (3CO), [dH (CD3)2SO] 2.49 (s, 3H, CH3), 7.10–7.54 (m, 14H,
C6H4 and 2C6H5), 10.21 (s, 1H, NH); m/z ¼ 487. Found: C, 61.34; H,
3.73; N, 5.52; calcd. for C25H18N2O3S3: C, 61.22; H, 3.67; N, 5.71%.

832
G. H. Elgemeie et al.
7c: Yellow, from ethanol, mp 1608C, yield 85%; nmax/cm21 (KBr) 3385
(NH), 1713, 1662 (3CO). Found: C, 59.44; H, 3.32; N, 5.41; calcd. for
C25H18N2O4S3: C, 59.29; H, 3.56; N, 5.53%.
7d: Yellow, from ethanol, mp 1858C, yield 80%; nmax/cm21 (KBr) 3305
(NH), 1700, 1656 (3CO). Found: C, 56.53; H, 3.02; N, 5.61; calcd. for
C24H15N2O3S3Cl: C, 56.47; H, 2.94; N, 5.49%.
7e: Buff, from ethanol, mp 1608C, yield 75%; nmax/cm21 (KBr) 3350 (NH),
1666 (CO). Found: C, 64.51; H, 4.53; N, 6.41; calcd. for C24H20N2OS3: C,
64.29; H, 4.46; N, 6.25%.
7f: Yellow, from ethanol-DMF, mp 1508C, yield 80%; nmax/cm21 (KBr) 3379
(NH), 1658 (CO); 1H NMR (DMSO) d 2.59 (s, 3H, CH3), 4.16 (s, 2H, CH2),
4.54 (s, 2H, CH2), 7.08–7.49 (m, 14H, C6H4 and 2C6H5), 9.17 (s, 1H, NH);
m/z ¼ 464. Found: C, 64.70; H, 4.58; N, 6.29; calcd. for C25H22N2OS3: C,
64.94; H, 4.76; N, 6.06%.
7g: Yellow, from ethanol, mp 1558C, yield 75%; nmax/cm21 (KBr) 3340
(NH), 1670 (CO). Found: C, 62.52; H, 4.43; N, 5.59; calcd. for
C25H22N2O2S3: C, 62.76; H, 4.60; N, 5.86%.
7h: Buff, from ethanol-DMF, mp 1798C, yield 70%; nmax/cm21 (KBr) 3544
(NH), 1639 (CO); 1H NMR (DMSO) d 4.19 (s, 2H, CH2), 4.31 (s, 2H, CH2),
7.22–7.47 (m, 14H, C6H4 and 2C6H5), 7.78 (s, 1H, NH). Found: C, 59.44; H,
3.73; N, 5.64; calcd. for C24H19N2OS3Cl: C, 59.63; H, 3.93; N, 5.80%.
4-Amino-5-aroyl-N-methyl-2-[(2-oxo-2-arylethyl)thio]thiophene-3-
carboxamides (9a–p), General Procedure
Phenacyl bromide (3.98 g, 0.02 mol) was added to a stirred suspension of
compounds 2a–d (0.01 mol) in ethanol (100 mL). The mixture was stirred
for 2 h. The solid precipitate formed was collected by filtration and crystal-
lized from ethanol.
9a: Buff, from ethanol, mp 1908C, yield 70% nmax/cm21 (KBr) 3444, 3055
(NH, NH2), 1686, 1643 (3CO); H NMR (DMSO) d 4.92 (s, 2H, CH2), 7.48
1
(s, 2H, NH2), 7.55–8.27 (m, 15H, 3C6H5), 10.79 (s, 1H, NH); m/z ¼ 473.
Found: C, 66.43; H, 4.01; N, 6.02; calcd. for C26H20N2O3S2: C, 6.10; H,
4.24; N, 5.93%.
9b: Yellow, from ethanol, mp 1808C, yield 80%; nmax/cm21 (KBr) 3446,
3270 (NH, NH2), 1686, 1645 (3CO). Found: C, 67.55; H, 4.60; N, 5.44;
calcd. for C28H24N2O3S2: C, 67.20; H, 4.80; N, 5.60%.

Novel Alkylsulfanylisothiazoles and Alkylsulfanylthiophenes
833
9c: Buff, from ethanol, mp 1928C, yield 85%; nmax/cm21 (KBr) 3450, 3230
(NH, NH2), 1680, 1655 (3CO). Found: C, 63.34; H, 4.46; N, 5.11; calcd. for
C28H24N2O5S2: C, 63.18; H, 4.51; N, 5.26%.
9d: Yellow, from ethanol, mp 2038C, yield 82%; nmax/cm21 (KBr) 3432,
3260 (NH, NH2), 1686, 1642 (3CO); 1H NMR (DMSO) d 4.85 (s, 2H,
CH2), 7.13 (s, 2H, NH2), 7.33–7.99 (m, 13H, C6H5, and 2C6H4), 8.04
(s, 2H, NH2), and 10.40 (s, 1H, NH); m/z ¼ 541. Found: C, 57.54; H, 3.22;
N, 5.13; calcd. for C26H18N2O3S2Cl2: C, 57.67; H, 3.33; N, 5.18%.
9e: Yellow, from ethanol, mp 1558C, yield 90%; nmax/cm21 (KBr) 3441,
3267 (NH, NH2), 1689, 1639 (3CO); 1H NMR (DMSO) d 2.39 (s, 3H,
CH3), 4.63 (s, 2H, CH2), 7.00 (s, 2H, NH2), 7.26–7.97 (m, 14H, 2C6H5,
and C6H4), and 10.38 (s, 1H, NH); m/z ¼ 487. Found: C, 66.37; H, 4.11;
N, 5.56; calcd. for C27H22N2O3S2: C, 66.66; H, 4.53; N, 5.76%.
9f: Yellow, from ethanol, mp 1808C, yield 77%; nmax/cm21 (KBr) 3455, 3252
(NH, NH2), 1680, 1648 (3CO). Found: C, 67.44; H, 5.22; N, 5.34; calcd. for
C29H26N2O3S2: C, 67.70; H, 5.06; N, 5.45%.
9g: Yellow, from ethanol, mp 1768C, yield 65%; nmax/cm21 (KBr) 3445,
3272 (NH, NH2), 1684, 1644 (3CO). Found: C, 63.66; H, 4.66; N, 5.32;
calcd. for C29H26N2O5S2: C, 63.74; H, 4.76; N, 5.13%.
9h: Yellow, from ethanol, mp 1958C, yield 84%; nmax/cm21 (KBr) 3433,
3256 (NH, NH2), 1686, 1641 (3CO); H NMR (DMSO) d 2.52 (S, 3H,
1
CH3), 4.84 (s, 2H, CH2), 7.15 (s, 2H, NH2), 7.56–7.98 (m, 12H, 3C6H4),
and 10.30 (s, 1H, NH); m/z ¼ 555. Found: C, 58.12; H, 3.45; N, 5.33;
calcd. for C27H20N2O3S2Cl2: C, 58.38; H, 3.60; N, 5.05%.
9i: Buff, from ethanol, mp 2068C, yield 75%; nmax/cm21 (KBr) 3430, 3266
(NH, NH2), 1684, 1649 (3CO). Found: C, 64.33; H, 4.46; N, 5.44; calcd.
for C27H22N2O4S2: C, 64.54; H, 4.38; N, 5.58%.
9j: Yellow, from ethanol, mp 1938C, yield 90%; nmax/cm21 (KBr) 3446, 3264
(NH, NH2), 1681, 1651 (3CO). Found: C, 65.44; H, 4.83; N, 5.31; calcd. for
C29H26N2O4S2: C, 65.66; H, 4.91; N, 5.28%.
9k: Buff, from ethanol, mp 1708C, yield 80%; nmax/cm21 (KBr) 3435, 3244
(NH, NH2), 1685, 1636 (3CO). Found: C, 61.75; H, 4.60; N, 5.01; calcd. for
C29H26N2O6S2: C, 61.92; H, 4.63; N, 4.98%.
9l: Buff, from ethanol, mp 1828C, yield 67%; nmax/cm21 (KBr) 3433, 3256
(NH, NH2), 1686, 1641 (3CO). Found: C, 56.68; H, 4.71; N, 4.79; calcd.
for C27H20N2O4S2Cl2: C, 56.74; H, 3.50; N, 4.90%.

834
G. H. Elgemeie et al.
9m: Yellow, from ethanol, mp 1988C, yield 90%; nmax/cm21 (KBr) 3400,
3102 (NH2, NH), 1690, 1655 (CO); H NMR (DMSO) d 4.65 (s, 2H, CH2),
1
7.27 (s, 2H, NH2), 7.33–7.99 (m, 14H, 2C6H5, and C6H4), 10.38 (s, 1H,
NH); m/z ¼ 506. Found: C, 61.46; H, 3.87; N, 5.37; calcd. for
C26H19N2O3S2Cl: C, 61.66; H, 3.75; N, 5.53%.
9n: Yellow, from ethanol, mp 2038C, yield 90%; nmax/cm21 (KBr) 3441,
3255 (NH, NH2), 1685, 1643 (3CO); 1H NMR (DMSO) d 2.38 (s, 3H,
CH3), 2.50 (s, 3H, CH3), 4.82 (s, 2H, CH2), 7.28 (s, 2H, NH2), 7.32–7.93
(m, 12H, 3C6H4), and 10.53 (s, 1H, NH); m/z ¼ 535. Found: C, 62.77; H,
4.46; N, 5.44; calcd. for C28H23N2O3S2Cl: C, 62.80; H, 4.30; N, 5.23%.
9o: Yellow, from ethanol, mp 1948C, yield 85%; nmax/cm21 (KBr) 3444,
3265 (NH, NH2), 1686, 1640 (3CO). Found: C, 59.43; H, 4.13; N, 4.99;
calcd. for C28H23N2O5S2Cl: C, 59.26; H, 4.06; N, 4.94%.
9p: Buff, from ethanol, mp 2158C, yield 90%; nmax/cm21 (KBr) 3436, 3257
(NH, NH2), 1685, 1641 (3CO); 1H NMR (DMSO) d 3.36 (s, 2H, CH2), 7.32–
7.72 (m, 12H, 3C6H4), 8.41 (s, 2H, NH2), 11.41 (s, 1H, NH); m/z ¼ 577.
Found: C, 54.22; H, 2.91; N, 4.77; calcd. for C26H17N2O3S2Cl3: C, 54.17;
H, 2.95; N, 4.86%.
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