First synthesis of N-substituted amino and N-sulfonylaminated methylthiopyrimidines: Reaction of dimethyl N-cyanodithioiminocarbonate with substituted hydrazides

Article abstract of DOI:10.1080/00397910500449427

A novel and efficient method for the synthesis of a new variety of methylsulfanylpyrimidines by the reaction of dimethyl N- cyanodithioiminocarbonate with substituted hydrazides. The synthetic potential of the method is demonstrated. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/00397910500449427

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First Synthesis of N‐Substituted
Amino and N‐Sulfonylaminated
Methylthiopyrimidines: Reaction of
Dimethyl N‐Cyanodithioiminocarbonate With
Substituted Hydrazides
Galal H. Elgemeie a & Soha A. Sood a
a Chemistry Department, Faculty of Science, Helwan University, Ain‐Helwan,
Cairo, Egypt
Published online: 16 Aug 2006.
To cite this article: Galal H. Elgemeie & Soha A. Sood (2006): First Synthesis of N‐Substituted Amino
and N‐Sulfonylaminated Methylthiopyrimidines: Reaction of Dimethyl N‐Cyanodithioiminocarbonate With
Substituted Hydrazides, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 36:6, 743-753
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Synthetic Communicationsw, 36: 743–753, 2006
Copyright # Taylor & Francis Group, LLC
ISSN 0039-7911 print/1532-2432 online
DOI: 10.1080/00397910500449427
First Synthesis of N-Substituted Amino and
N-Sulfonylaminated
Methylthiopyrimidines: Reaction of
Dimethyl N-Cyanodithioiminocarbonate
With Substituted Hydrazides
Galal H. Elgemeie and Soha A. Sood
Chemistry Department, Faculty of Science, Helwan University,
Ain-Helwan, Cairo, Egypt
Abstract: A novel and efficient method for the synthesis of a new variety of methyl-
sulfanylpyrimidines by the reaction of dimethyl N-cyanodithioiminocarbonate with
substituted hydrazides. The synthetic potential of the method is demonstrated.
Keywords: Antimetabolites, cyanoacetohydrazide, dimethyl N-cyanodithioimino-
carbonate, heterocycles, methylsulfanylpyrimidines, substituted hydrazides
Pyrimidine derivatives, which are structurally related to purine bases and
many other biologically active compounds, have attracted much attention
from the viewpoint of medicinal chemistry. Because the direct introduction
of specific substituents into the pyrimidine nucleus is not easy, syntheses
directed to the construction of the ring bearing useful functional groups
have been developed.[1] As part of our program directed toward the prep-
aration of potential antimetabolites,[2,3] we have recently reported different
successful approaches for the syntheses of purine, folic acid, and pyrimidine
analogues.[4–6] Derivatives of these ring systems are interesting as
Received in the USA September 15, 2005
Address correspondence to Galal H. Elgemeie, Chemistry Department, Faculty of
Science, Helwan University, Ain-Helwan, Cairo, Egypt. E-mail: elgemeie@hotmail.
com
743

744
G. H. Elgemeie and S. A. Sood
antimetabolites in biochemical reactions.[7] The present research deals with
novel synthesis of (3)N-substituted amino-6-methylsulfanyl-4-oxo-
a
pyrimidine-5-carbonitriles 6, 7, 12, and 14 and deaza analogues of purine
10 by the reaction of dimethyl N-cyanodithioiminocarbonate with substi-
tuted hydrazides. As far as we know this is the first example of this
approach to be reported for pyrimidine derivatives. Thus, it has been
found that S,S-dimethyl N-cyanodithioimidocarbonate 2, prepared by the
reaction of cyanamide 1, carbon disulfide, and methyl iodide in the
presence of alkali, reacted with 1-cyanoacetyl-4-arylmethylidene-semicarba-
zide 3a–f at room temperature in the presence of pulverized potassium
hydroxide in 1,4-dioxane to give the corresponding 4-oxopyrimidine-(3)N-
Schiff bases 6. The structures of 6 were established on the basis of
1
elemental analysis and spectral data (IR, H NMR, 13C NMR, and MS).
The formation of 6 from the reaction of 2 and 3 is assumed to proceed
via Michael addition of the methylene function in 3 onto the double bond
in 2. The formed Michael adducts then cyclized smoothly via CH3SH elim-
ination and addition to the cyano group. Compounds 6 can also be prepared
by the reaction of the corresponding (3)N-amino-4-oxopyrimidine 9 with
substituted aldehydes in refluxing ethanol containing catalytic amounts of
piperidine. When dimethyl N-cyanodithioiminocarbonate 2 is treated with
cyanoacetohydrazide 8 at room temperature for 24 h in the presence of
KOH/dioxane, 9 was obtained in good yield. Compounds 6 reacted with
hydrazine in refluxing ethanol contaning catalytic amounts of piperidine to
give the corresponding pyrazolo[3,4-d]pyrimidin-4(3H)-ones 10. The
structure of compounds 10 was established on the basis of elemental
analysis and spectral data. To explore the possibility that this reaction
applied to other classes of substituted cyanoacetohydrazide, we investigated
the reaction of 2 with cyanoacetobenzoylhydrazide 11. The latter was
prepared from cyanoacetohydrazide 8 with benzoyl chloride.[8] Thus, we
treated 11 with one equivalent of compound 2 in dioxane containing a
catalytic amount of potassium hydroxide for 24 h at room temperature and
obtained the corresponding substituted 6-alkylthio-(3)N-benzoylamino-4-
oxopyrimidine derivative 12 in moderate yield. The structure of 12 was
1
established on the basis of its elemental analysis and IR, H NMR, and
MS spectroscopies. Reaction of dimethyl N-cyanodithioiminocarbonate
with 1-cyanoacetylthiosemicarbazide was also examined. Thus, when 2
was treated with 4-phenyl-1-cyanoacetylthiosemicarbazide 13 in the
presence of KOH/dioxane, the N-(2-amino-5-cyano-3,4-dihydro-6-methyl-
sulfanyl-4-oxo-3-pyrimidinyl)phenyl thiourea derivative 14 was obtained.
Structure 14 was established on the basis of elemental analysis and
1
spectral data (IR, H NMR, 13C NMR, and MS). Compounds 12 and 14
can also be prepared by the reaction of the corresponding (3)N-amino-4-oxo-
pyrimidine 9 with benzoyl chloride and phenylisothiocyanate, respectively.
To investigate the scope of this reaction further and to establish whether
the reaction of dimethyl N-cyanodithioiminocarbonate with substituted

Reaction of Dimethyl N-Cyanodithioiminocarbonate
745
cyanohydrazides could be extended to provide a general approach to
(3)N-substituted-6-methylthio-4-oxopyrimidine-5-carbonitriles, we studied
the reaction of cyanodithioiminocarbonate 2 with other functionalized
cyanohydrazides. Thus, it has been found that cyanoacetohydrazide 8 reacts
with arylsulfonyl chloride in ethanol containing catalytic amounts of piper-
idine to afford the corresponding N-cyanoacetoarylsulfonylhydrazides 15 in
good yield. Compounds 15 reacted with 2 in dioxane containing a catalytic
amount of potssium hydroxide to yield a product assigned as (3)N-arylsulpho-
nylamino-6-alkylthio-4-oxopyrimidine 18. The structures of 18 were estab-
1
lished on the basis of their elemental analysis and spectral data (IR, H
NMR, and MS). The formation of 18 from 2 and 15 is assumed to proceed
via addition of the active methylene group of 15 to the double bond of 2 to
give intermediate Michael adducts. The latter loses elements of CH3SH to
yield the intermediate 16, which cyclized to yield the novel (3)N-arylsulpho-
nylamino-6-alkylthio-4-oxopyrimidine derivatives 18. Compounds 18 reacted
with hydrazine in refluxing ethanol containing catalytic amounts of piperidine
to give the corresponding purine analogues 19. The structure of compounds 19
was established on the basis of elemental analysis and spectral data.
In summary, we have achieved a regiospecific synthesis of interesting
N-substituted amino, N-sulfonylaminated-6-alkythio-4-oxopyrimidines, and
their corresponding purine analogues by the reaction of dimethyl N-cyano-
dithioiminocarbonate 2 with cyanohydrazides 8, 11, 13, and 15.
EXPERIMENTAL
All melting points were determined in open glass capillaries on a Gallenkamp
melting-point apparatus and are uncorrected. Their spectra were obtained
1
(KBr disc) on a Perkin Elmer/1650 FT-IR instrument. The H NMR and
13C 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 Cairo University.
2-Amino-4-(methylthio)-6-oxo-1-f[(1Z)-arylmethylene]aminog-1,6-
dihydropyrimidine-5-carbonitrile (6a–f) and 2-Amino-(3)N-
arylmethylideneamino-3,4-dihydro-6-methylthio-4-oxopyrimidine-
5-carbonitriles (6a-f), General Procedure
Dimethyl N-cyanodithioiminocarbonate 2 (1.46 gm, 0.01 mol) was added to a
stirred solution of the 1-cyanoacetyl-4-arylmethylidenesemicarbazid 3
(0.01 mol) in dry dioxane (50 mL) containing potassium hydroxide (0.56 g,
0.01 mol) at room temperature (258C). The solution was left stirring

746
G. H. Elgemeie and S. A. Sood
overnight at room temperature; the precipitate solid was collected by filtration
and crystallized from the appropriate solvent.
6a: Buff, mp 2288C (from EtOH), yield (84%). IR (KBr) nmax/cm21 3436,
3331(NH2), 2207 (CN), and 1629 (C55O). H NMR (DMSO) d 2.55 (s, 3H,
1
SCH3), 7.44–8.12 (m, 5H, C6H5), 8.97 (s, br, 2H, NH2), 9.00 (s, 1H,
55CH). 13C NMR (DMSO) d 12.50 (SCH3), 117.00 (CN), 126.35–132.80
(phenyl carbons), 152.87 (55CH), 155.87 (C-5), 161.01 (C-6), 167.15 (C-2),
169.86 (C-4). C13H11N5OS, calcd. C, 54.73; H, 3.85; N, 24.56; S, 11.22.
Found: C, 54.9; H, 4.0; N, 24.7; S, 11.3%.
6b: Buff, mp 3008C (from EtOH), yield (87%). IR(KBr) nmax/cm21 3427
(NH2) and 2210 (CN). H NMR (DMSO) d 2.05 (s, 3H, CH3), 2.55 (s, 3H,
1
SCH3), 7.39–7.96 (m, 4H, C6H5), 8.13 (s, br, 2H, NH2), 8.86 (s, 1H,
55CH). 13C NMR (DMSO) d 12.41 (CH3), 20.53 (SCH3), 117.4 (CN)
128.09–134.22 (phenyl carbons), 152.61 (55CH), 157.7 (C-5), 160.31 (C-
6), 167.38 (C-2), 172.68 (C-4). C14H13N5OS, calcd.: C, 56.19; H, 4.35; N,
23.41; S, 10.70. Found: C, 56.1; H, 4.3; N, 23.5; S, 10.7%.
6c: Brown, mp 3008C (from EtOH), yield (88%). IR (KBr) nmax/cm21 3316
(NH2), 2927 (55CH), and 2210 (CN). C13H11N5O2S, calcd.: C, 51.82; H, 3.65;
N, 23.25; S, 10.63. Found: C, 52.0; H, 3.9; N, 23.4; S, 10.7%.
6d: Buff, mp 2448C (from EtOH), yield (85%). IR (KBr) nmax/cm21 3427 and
3276 (NH2), 3049 (55CH), 2206 (CN), and 1658 (C55O). 1H NMR (DMSO) d
2.53 (s, 3H, SCH3), 3.82 (s, 3H, OCH3), 7.00–7.95 (m, 4H, C6H4), 8.04 (s, br,
2H, NH2), 8.82 (s,1H, 55CH). 13C NMR (DMSO) d 12.44 (SCH3), 55.42
(OCH3), 114.18(CN), 127.81 (phenyl carbons), 152.88 (55CH), 160.31(C-
5), 162.91 (C-6), 169.03 (C-2), 172.31 (C-4). C14H13N5O2S, (Mþ ¼315),
calcd.: C, 53.33; H, 4.12; N, 22.22; S, 10.15. Found: C, 53.6; H, 4.0; N,
22.3; S, 10.2%.
6e: Brown, mp 2608C (from EtOH), yield (87%). IR (KBr) nmax/cm21 3651
and 3434 (NH2), 2927 (55CH), 2212 (CN), and 1671 (C55O). C13H10ClN5OS,
calcd.: C, 48.92; H, 3.13; N, 21.90; S, 10.01. Found: C, 49.0; H, 3.3; N, 21.7;
S, 10.0%.
6f: Buff, mp 3008C (from EtOH), yield (80%). IR (KBr) nmax/cm21 3316
1
(NH2), 2209 (CN), and 1650 (C ¼ O). H NMR (DMSO) d 2.50 (s, 3H,
SCH3), 7.39–7.96 (m, 4H, C6H4), 8.13 (s, br, 2H, NH2), 8.16 (s, 1H,
55CH). 13C NMR (DMSO) d 12.53 (SCH3), 117.41 (CN), 128.09–134.20
(phenyl carbons), 152.41 (55CH), 156.10 (C-5), 157.12 (C-6), 160.10 (C-2),
167.38 (C-4). C13H10ClN5OS, calcd.: C, 48.82; H, 3.12; N, 21.90; S, 10.01.
Found: C, 49.0; H, 3.4; N, 22.0; S, 10.1%.

Reaction of Dimethyl N-Cyanodithioiminocarbonate
747
2-Amino-(3) N-arylmethylideneamino-3,4-dihydro-6-anilino-4-
oxopyrimidine-5-carbonitriles (7a-f), General Procedure
A mixture of 6a–f (0.01 mol) and aniline (0.093 g, 0.01 mol) was heated at
1508C (bath temperature) for 30 min; after cooling, the resulting solid
product was triturated with water, filtered off, and crystallized from the
appropriate solvent.
7a: Yellow, mp . 3008C (from EtOH), yield (80%). IR (KBr) nmax/cm21
3506, 3428 (NH2), 2928 (55CH), and 2209 (CN). C18H14N6O, calcd.: C,
65.45; H, 4.24; N, 25.45. Found: C, 65.7; H, 4.3; N, 25.7%.
7b: yellow, mp 2008C (from EtOH), yield (87%). IR (KBr) nmax/cm21 3418
(NH2), 2926 (55CH), 2208 (CN), and 1645 (C55O). 1H NMR (DMSO) d 2.05
(s, 3H, CH3), 6.63 (s, br, 2H, NH2), 7.29–7.39 (m, 9H, C6H5 and C6H4), 8.04
(s, br, 1H, NH), 9.00 (s, 1H, 55CH). C19H16N6O, calcd.: C, 66.28; H, 4.65; N,
24.42. Found: C, 66.3; H, 4.7; N, 24.6%.
7c: Colorless, mp 1408C (from EtOH), yield (82%). IR (KBr) nmax/cm21
3528 and 3417 (NH2), 2212 (CN), and 1620 (C55O). C18H14N6O2, calcd.:
C, 62.42; H, 4.04; N, 24.27. Found: C, 62.7; H, 4.0; N, 24.5%.
7d: Buff, mp 2158C (from EtOH), yield (87%). IR (KBr) nmax/cm21 3629 and
3569 (NH2), 3000 (55CH), 2205 (CN), and 1630 (C55O). 1H NMR (DMSO) d
3.81 (s, 3H, OCH3), 6.53 (s, br, 2H, NH2), 6.91–7.07 (m, 9H, C6H5 and C6H4),
8.04 (s, br, 1H, NH), 8.36 (s, 1H, 55CH). 13C NMR (DMSO) d 51.16 (OCH3),
115.61 (CN), 123.83–131.71 (2 phenyl carbons), 152.27 (55CH), 155.17 (C-
5), 155.77 (C-6), 158.91 (C-2), 172.00 (C-4). C19H16N6O2, calcd.: C, 63.33;
H, 4.44; N, 23.33. Found: C, 63.7; H, 4.5; N, 23.8 %.
7e: Colorless, mp . 3008C (from EtOH), yield (71%). IR (KBr) nmax/cm21
3418 and 3317 (NH2), 2933 (55CH), 2201 (CN), and 1633 (C55O).
C18H13ClN6O, calcd.: C, 59.34; H, 3.57; N, 23.04. Found: C, 59.4; H, 3.3;
N, 23.1%.
7f: Buff, mp .3008C (from EtOH), yield (75%). IR (KBr) nmax/cm21 3838,
3752 and 3440 (NH2, NH), 2207 (CN), and 1647 (C55O). C18H13ClN6O,
calcd.: C, 59.27; H, 3.59; N, 23.04. Found: C, 59.6; H, 3.7; N, 23.3%.
2,(3) N-Diamino-3,4-dihydro-6-methylsulfanyl-4-oxopyrimidine-5-
carbonitrile (9), General Procedure
Dimethyl N-cyanodithioiminocarbonate 2 (1.46 g, 0.01 mol) was added to a
stirred solution of the cyanoacetohydrazide 8 (0.99 g, 0.01 mol) in dry

748
G. H. Elgemeie and S. A. Sood
dioxane (50 mL) containing potassium hydroxide (0.56 g, 0.01 mol) at room
temperature (258C). The solution was left stirring overnight at room tempera-
ture; the precipitate solid was collected by filtration and crystallized from the
appropriate solvent.
9: Brown, mp 2808C (from EtOH), yield (87%). IR (KBr) nmax/cm21 3493,
3317 (NH2), 2210 (CN). H NMR (DMSO) d 2.68 (s, 3H, SCH3), 5.52
1
(s, br, 2H, NH2), 8.42 (s, br, 2H, NH2). C6H7N5OS (Mþ¼ 197) calcd.: C,
36.55; H, 3.55; N, 35.53; S, 16.24. Found: C, 36.5; H, 3.7; N, 35.8; S, 16.6%.
2,5-Diamino-(3) N-arylmethylideneamino-7H-pyrazolo[3,4-
d]pyrimidine–4(3H)-ones (10a–f), General Procedure
A mixture of equivalent amounts of 6a–f (0.01 mol) and hydrazine hydrate
(0.05 g, 0.01 mol) was heated in ethanol (30 mL) containing a catalytic
amount of piperidine for 3 h. After cooling of the reaction mixture, the final
product was filtered off and recrystallized from the appropriate solvent
(Scheme 1).
10a: Buff, mp 2408C (from EtOH), yield (82%). IR (KBr) nmax/cm21 3450
(NH2). C12H11N7O, calcd.: C, 53.53; H, 4.089; N, 36.43. Found: C, 53.8; H,
4.0; N, 36.6%.
10b: Buff, mp 1408C (from EtOH), yield (79%). IR (KBr) nmax/cm21 3202
(NH2), and 1659 (C55O). C13H13N7O, calcd.: C, 55.12; H, 4.59; N, 34.62.
Found: C, 55.0; H, 4.4; N, 34.3%.
10c: Yellow, mp 2008C (from EtOH), yield (76%). IR (KBr) nmax/cm21 3454
and 3326 (NH2, NH), 1610 (C55O). C12H11N7O2, calcd.: C, 50.53; H, 3.87; N,
34.39. Found: C, 50.7; H, 3.8; N, 34.9%.
10d: Buff, mp 3008C (from EtOH), yield (80%). IR (KBr) nmax/cm21 3650,
3639, and 3447 (NH2, NH), 2933 (55CH), and 1668 (C55O). 1H NMR
(DMSO) d 3.36 (s, 3H, OCH3), 4.43 (s, br, 1H, NH2), 5.19 (s, br, 2H, NH2),
7.03–7.95 (m, 4H, C6H4), 8.05 (s, br, 1H, NH), 8.78 (s, 1H, 55CH).
C13H13N7O2, calcd.: C, 52.17; H, 4.35; N, 32.78. Found: C, 52.3; H, 4.3; N,
32.9%.
10e: Colorless, mp 3008C (from EtOH), yield (77%). IR (KBr) nmax/cm21
3434 and 3360 (NH2 and NH). C12H10ClN7O, calcd.: C, 47.46; H, 3.32; N,
32.28. Found: C, 47.7; H, 3.67; N, 32.7%.
10f: Colorless, mp 3008C (from EtOH), yield (75%). IR (KBr) nmax/cm21
3391 (NH2) and 1646 (C55O). C12H10ClN7O, calcd.: C, 47.46; H, 3.32; N,
32.28. Found: C, 47.5; H, 3.5; N, 32.1%.

Reaction of Dimethyl N-Cyanodithioiminocarbonate
749
Scheme 1.
2-Amino-(3) N-benzoylamino-3,4-dihydro-6-methylthio-4-oxo-
pyrimidine-5-carbonitriles (12), General Procedure
Dimethyl N-cyanodithioimino-carbonate 2 (1.46 g, 0.01 mol) was added to a
stirred solution of cyanoacetobenzoylhydrazide 11 (2.03 g, 0.01 mol) in dry
dioxane (50 mL) containing potassium hydroxide (0.056 g, 0.01 mol) at
(258C). The reaction mixture was stirred for 30 min at room temperature;
the precipitate solid was collected by filtration and crystallized from the
appropriate solvent.

750
G. H. Elgemeie and S. A. Sood
12: Buff, mp . 3008C (from EtOH), yield (70%). IR (KBr) nmax/cm21 3208
(NH2), 2222 (CN), and 1628 (C55O). 1H NMR (DMSO) d 2.52 (s, 3H, SCH3),
7.53–8.02 (m, 5H, C6H4), 7.98 (s, br, 2H, NH2), 8.58 (s, br, 1H, NH).
C13H11N5O2S, calcd.: C, 51.82; H, 3.63; N, 23.25; S, 10.63. Found: C,
52.1; H, 3. 6; N, 23.2; S, 10.6%.
N-(2-Amino-5-cyano-3,4-dihydro-6-methylsulfanyl-4-oxo-3-
pyrimidinyl)phenyl Thiourea (14), General Procedure
Dimethyl N-cyanodithioiminocarbonate (1.46 gm, 0.01 mol) was added to a
stirred solution of 4-phenyl-1-cyanoacetylthiosemicarbazide 13 (2.34 g,
0.01 mol) in dry dioxane (50 mL) containing potassium hydroxide (0.56 g,
0.01 mol) at room temperature (ꢀ25). The solution was left stirring
overnight at room temperature; the precipitate solid was collected by filtration
and crystallized from the appropriate solvent (Scheme 2.)
14: Buff, mp 3008C (from EtOH), yield (77%). IR (KBr) gmax/cm21 3433
(NH2), 2250 (CN). H NMR (DMSO) d 2.51 (s, 3H, SCH3), 6.53 (s, br, 2H,
1
NH2), 6.98–7.07 (m, C6H5, 5H), 8.04 (s, br, 1H, NH), 8.08 (s, br, 1H, NH).
13C NMR (DMSO) d 12.42 (SCH3), 115.73 (CN), 128.04–133.46 (phenyl
carbons), 148.76 (C-5), 152.70 (C-6), 168.30 (C-2), 169.65 (C-4), 184.00
(C55S). C13H12N6OS2 (Mþ ¼ 332), calcd.: C, 46.98; H, 3.61; N, 25.30; S,
19.27. Found: C, 47.1; H, 3.9; N, 25.6; S, 19.3%.
2-Amino-(3) N-arylsulphonylamino-3,4-dihydro-6-methylthio-4-
oxopyrimidine-5-carbonitriles (18), General Procedure
Dimethyl N-cyanodithioimino carbonate 2 (1.46 g, 0.01 mol) was added to a
stirred solution of N-cyanoacetoarylsulfonylhydrazides 15 (0.01 mol) in dry
dioxane (50 mL) containing potassium hydroxide (0.56 g, 0.01 mol) at
(ꢀ258C). The reaction mixture was stirred for 30 min at room temperature;
the precipitate solid was collected by filtration and crystallized from the
appropriate solvent (Scheme 3).
18a: Brown, mp .3008C (from EtOH), yield (82%). IR (KBr) nmax/cm21
3460 and 3425 (NH2), 2905 (CH), 2210 (CN), and 1660 (C55O). H NMR
1
(DMSO) d 2.41 (s, 3H, SCH3), 7.36–7.78 (m, 5H, C6H5), 8.93 (s, br, 2H,
NH2), 11.60 (s, br, 1H, NH). C12H11N5O3S2, (Mþ55337) calcd.: C, 42.72;
H, 3.26; N, 20.77; S, 18.99. Found: C, 42.9; H, 3.9; N, 20.3; S, 18.7%.
18b: Buff, mp 3008C (from EtOH), yield (89%). IR (KBr) nmax/cm21 3480
and 3439 (NH2), 2860 (CH), 2209 (CN), and 1656 (C55O). 1H NMR
(DMSO) d 2.30 (s, 3H, CH3), 2.49 (s, 3H, SCH3), 6.89 (s, br, 2H, NH2),
7.11–7.62 (m, 4H, C6H4), 8.21 (s, br, 1H, NH). 13C NMR (DMSO) d 12.09

Reaction of Dimethyl N-Cyanodithioiminocarbonate
751
Scheme 2.
(CH3), 20.78 (SCH3), (C-5), 116.54 (CN), 125.99–129.61 (phenyl carbons),
138.40 (C-5), 138.73 (C-6), 144.82 (C-2), 157.99 (C-4). C13H13N5O3S2,
calcd.: C, 44.44; H, 3.70; N, 19.94; S,18.23. Found: C,44.6; H, 3.9; N, 20.0;
S, 18.5%.
2,5-Diamino–(3) N-4-(methylbenzenesulfonamido)-7H-
pyrazolo[3,4-d] pyrimidine-4(3H)-one (19a, b), General Procedure
A mixture of equivalent amounts of 18 (0.01 mol) and hydrazine hydrate
(0.5 g, 0.01 mol) was heated in ethanol (30 mL) containing a catalytic
amount of piperidine for 3 h. After cooling of the reaction mixture, the final
product was filtered off and recrystallized from the appropriate solvent.
19a: Colorless, mp .3008C (from EtOH), yield (78%). IR (KBr) nmax/cm21
3482 and 3311 (NH2, NH). C11H11N7O3S, calcd.: C, 41.12; H, 3.42; N, 30.52;
S, 9.96. Found: C, 41.0; H, 3.5; N, 30.5; S, 10.0%.

752
G. H. Elgemeie and S. A. Sood
Scheme 3.
19b: Buff, mp 1858C (from EtOH), yield (82%). IR (KBr) nmax/cm21 3543,
3474, and 3328 (NH2, NH). H NMR (DMSO) d 2.20 (s, 3H, CH3), 5.82
1
(s, br, 2H, NH2), 7.42–7.65 (m, 4H, C6H4), 8.23 (s, br, 2H, NH2), 11.89
(s, br, 1H, NH). C12H13N7O3S, calcd.: C, 42.98; H, 3.88; N, 29.25; S, 9.55.
Found: C, 42.6; H, 3.5; N, 29.3; S, 9.6%.
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Reaction of Dimethyl N-Cyanodithioiminocarbonate
753
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