A new class of fused bis[1,2,3] selena and/or thiadiazoles

Article abstract of DOI:10.1081/SCC-100106035

A novel class of bis selena and/or thiadiazoles were prepared by the reaction of semicarbazones of 3,6-dithiaoctahydrophenanthrene-1,8-dione, 3,6-dithiaoctahydroanthracene-1,8-dione and 3,7-dithiaoctahydroanthracene-1,5-dione with SeO₂ and SOCl₂, respectively. The latter, in turn, were obtained from 1,2-, 1,3-and 1,4-xylylenedimercaptoacetic acids.

Full text of DOI:10.1081/SCC-100106035

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A NEW CLASS OF FUSED BIS [1,2,3] SELENA AND/OR
THIADIAZOLES
D. Bhaskar Reddy a , A. Balaiah a , V. Padmavathi a & A. Padmaja a
a Department of Chemistry , Sri Venkateswara University , Tirupati, 517 502, India
Published online: 20 Aug 2006.
To cite this article: D. Bhaskar Reddy , A. Balaiah , V. Padmavathi & A. Padmaja (2001) A NEW CLASS OF FUSED BIS
[1,2,3] SELENA AND/OR THIADIAZOLES, Synthetic Communications: An International Journal for Rapid Communication of
Synthetic Organic Chemistry, 31:21, 3265-3272, DOI: 10.1081/SCC-100106035
To link to this article: http://dx.doi.org/10.1081/SCC-100106035
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SYNTHETIC COMMUNICATIONS, 31(21), 3265–3272 (2001)
A NEW CLASS OF FUSED BIS [1,2,3]
SELENA AND/OR THIADIAZOLES
D. Bhaskar Reddy,* A. Balaiah,
V. Padmavathi, and A. Padmaja
Department of Chemistry, Sri Venkateswara University,
Tirupati 517 502, India
ABSTRACT
A novel class of bis selena and/or thiadiazoles were prepared
by the reaction of semicarbazones of 3,6-dithiaoctahydrophe-
nanthrene-1,8-dione, 3,6-dithiaoctahydroanthracene-1,8-dione
and 3,7-dithiaoctahydroanthracene-1,5-dione with SeO2 and
SOCl2, respectively. The latter, in turn, were obtainedfrom
1,2-, 1,3- and 1,4-xylylenedimercaptoacetic acids.
Over the years, a variety of mercaptoacetic acids have been used as
intermediates in the synthesis of a,b-unsaturatedcompounds, carbocyclic
1–13
andheterocyclic systems.
Recently, the preparation of selena andthia-
diazole fused heterocycles from arylmercaptoacetic acids have been
reported.14,15 The present communication describes the use of 1,2-, 1,3-
and1,4- xylylenedimercaptoacetic acids ( 4–6) for the preparation of a new
*Corresponding author.
3265
Copyright & 2001 by Marcel Dekker, Inc.
www.dekker.com

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BHASKAR REDDY ET AL.
class of bis selena and/or thiadiazole units or mixed systems of selena and
thiadiazole rings in one molecule, which hitherto not reported.
The synthetic scheme involves the cyclization of mercaptoacetic acids
4–6 with phosphorus pentoxide to obtain the respective diones 7–9.
Exposure of these diketones to two moles of semicarbazide hydrochloride
followed by oxidative cyclization with selenium dioxide in acetic acid gave
bis selenadiazoles, 12, 16 and 20. Similarly, the semicarbazone derivatives of
7–9 on Hurd–Mori reaction process16 with excess thionyl chloride afforded
bis thiadiazoles 13, 17 and 21. On the other hand, reaction with one mole of
semicarbazide hydrochloride only, followed by cyclization with selenium
dioxide in acetic acid led to the formation of selenadiazoles, 10, 14 and
18. Formation of their semicarbazones followedby treatment with excess
thionyl chloride furnished selena and thiadiazoles 11, 15 and 19. In sum-
mary, we here report a methodfor the preparation of bis selena/thiadiazoles
or selena and thiadiazole units fused to dithiaoctahydroanthracene and
phenanthrene diones (Scheme).
EXPERIMENTAL
Melting points were determined on a Mel–Temp apparatus and are
uncorrected. The IR spectra were recorded on a Perkin–Elmer grating infra-
redspectrophotometer in KBr pellets. The 1H NMR spectra were recorded
at 200 MHz on a Bruker spectrospin andVarian EM-360 spectrometer in
CDCl3 with TMS as an internal standard. The purity of the compounds was
checkedby TLC (silica gel H, BDH hexane : ethyl acetate, 3 : 2). The micro-
analyses were performedby the Regional SophisticatedInstrumentation
Centre, Punjab University, Chandigarh, India.
3,6-Dithiaoctahydrophenanthrene-1,8-dione(7)/
3,6-Dithiaoctahydroanthracene-1,8-dione (8)/and
3,7-Dithiaoctahydroanthracene-1,5-dione (9)
General procedure: To a solution of dimercaptoacetic acid 4/5/617–19
(1.6 g, 0.01 mol) in dry benzene (30 mL) an excess of phosphorus pentoxide
(5 g) was added and the mixture refluxed for 6–8 h. The reaction was mon-
itoredat frequent intervals by TLC. After completion of the reaction the
cooledcontent was extractedwith benzene. The combinedbenzene extracts
were washedwith water, saturatedsodium bicarbonate solution andagain
with water. The organic layer was dried over anhydrous sodium sulfate.

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BIS SELENA/THIADIAZOLES
3267
(i) HSCH2CO2H/NaOH/MeOH; (ii)P2O5/benzene; (iii) 2NH2NHCONH2/NaOAc/
MeOH (iv) SeO2, AcOH, 60–70ꢀC; (v)SOCl2, CH2Cl2,À10ꢀC, (vi) NH2NHCONH2/
NaOAc/MeOH
Scheme.

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BHASKAR REDDY ET AL.
Evaporation of the solvent gave a crude product which was filtered
through a column of silica gel (60–120 mesh) using ethyl acetate : hexane
(2:3) eluents.
7: m.p: 152–153ꢀC, Yield, 85%; IR: 1630 (C¼O); 1H NMR: d, 3.78 (s,
4H, SCH2), 4.16 (s, 4H, SCH2CO), 7.14 (s, 2H, Ar-H), 8: m.p. 167–168ꢀC,
1
Yield82%, IR: 1640 (C ¼O); H NMR: d, 3.65 (s, 4H, SCH2), 4.14 (s, 4H,
SCH2CO), 7.08 (s, 1H, Ar-H), 7.82 (s, 1H, Ar-H). 9: m.p. 185–186ꢀC, Yield
88%, IR: 1660 (C¼O), 1H NMR: d, 3.68, (s, 4H, SCH2), 4.25 (s, 4H,
SCH2CO), 6.99 (s, 2H, Ar-H).
3,6-Dithia-3,4,5,6-tetrahydrophenanthrene
[1,2-d;7,8-d ]bis[1,2,3]selenadiazole (12),
3,6-Dithia-3,4,5,6-tetrahydroanthracene
[1,2-d;7,8-d ]bis[1,2,3]selenadiazole (16)
and3,7-Dithia-3,4,7,8-tetrahydroanthracene-
[1,2-d;5,6-d ]bis[1,2,3]selenadiazole (20)
General procedure: The bis semicarbazone of 7/8/9 was preparedby
refluxing 7/8/9 (1.25 g, 0.01 mol) with semicarbazide hydrochloride (2.22 g,
0.02 mol) andsodium acetate (2.72 g, 0.02 mol) in 20 ml of methanol. The
reaction mixture was concentrated, cooled and poured into ice-cold water.
The solid separated was filtered, washed with water, dried and recrystallized
from ethanol to get pure sample, bis semicarbazone of 7: m.p. 195–197ꢀC,
yield88%, bis semicarbazone of 8: m.p: 202–204ꢀC, yield80%; bis semi-
carbazone of 9: m.p. 207–209ꢀC; yield83%. To bis semicarbazones of 7/8/9
(1.3 g, 0.01 mol) in glacial acetic acid (10 mL), selenium dioxide (3.8 g,
0.02 mol) was added in portions and the mixture stirred until the evolution
of gas ceased. The progress of the reaction was checked by TLC. After
completion of the reaction, the mixture was allowedto attain room
temperature. The deposited selenium was removed by filtration. The filtrate
was poured onto crushed ice and the solid obtained was filtered, dried
andpurifiedthrough a column of silica gel (60–120 mesh) using ethyl
acetate : hexane (1 : 3) as eluents.
12: m.p. 117–119ꢀC, Yield, 62%; IR: 1440 (N¼N); H NMR: d, 3.74
1
(s, 4H, SCH2), 7.20 (s, 2H, Ar-H); Anal. Calcd. for C12H6N4Se2S2: C, 33.65;
H, 1.41; N, 13.20; Found: C, 33.84; H, 1.49; 13.20. 16: m.p. 139–141ꢀC,
1
Yield66%; IR 1460 (N ¼N); H NMR: d, 3.62 (s, 4H, SCH2), 7.10 (s, 1H,
Ar-H), 7.22 (s, 1H, Ar-H); Anal. Calcd. for C12H6N4Se2S2: C, 33.65; H,
1.41, N, 13.08; Found: C, 33.54; H, 1.30; N, 13.00. 20: m.p. 135–137ꢀC,
1
Yield65%; IR: 1458 (N ¼N); H NMR: d, 3.48 (s, 4H, SCH2), 7.15 (s, 2H,

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3269
Ar-H); Anal. Calcd. for C12H6N4Se2S2: C; 33.65, H, 1.41; N, 13.08; Found:
C, 33.79; H, 1.48; N, 13.00.
3,6-Dithia-3,4,5,6,7,8-hexahydrophenanthrene [1,2-d ]
[1,2,3]selenadiazole-8-one (10), 3,6-Dithia-3,4,5,6,7,8-
hexahydroanthracene[1,2-d ][1,2,3]selenadiazole-8-one
(14) and3,7-Dithia-3,4,5,6,7,8-hexahydroanthracene-
[1,2-d ][1,2,3]selenadiazole-5-one (18)
General procedure: The mono semicarbazone of 7/8/9 was preparedby
refluxing 7/8/9 (1.25 g, 0.01 mol), semicarbazide hydrochloride (1.11 g,
0.01 mol) andsodium acetate (1.36 g, 0.01 mol) in methanol (20 mL). The
work-up procedure was similar to bis semicarbazone of 7/8/9. Mono semi-
carbazone of 7: m.p. 175–177ꢀC; yield68%; mono semicarbazone of 8: m.p.
178–180ꢀC, yield74%; mono semicarbazone of 9: m.p. 194–196ꢀC, yield
88%. The cyclization was carriedout with mono semicarbazone of 7/8/9
(1.3 g, 0.01 mol) and selenium dioxide (1.9 g, 0.01 mol) in glacial acetic acid
as mentionedabove. The solidobtainedwas purifiedover a column of silica
gel (60–120 mesh) using ethyl acetate : hexane (1 : 3) as eluents.
10: m.p. 129–131ꢀC, Yield72%; IR: 1645 (C ¼O), 1452 (N¼N);
1H NMR: d, 3.68 (s, 4H, SCH2), 4.24 (s, 2H, SCH2CO), 7.11 (d, 1H, Ar-
H, J ¼ 8.2 Hz), 7.18 (d, 1H, Ar-H, J ¼ 8.2 Hz); Anal. Calcd. for
C12H8N2OSeS2: C, 42.47; H, 2.30; N, 8.25; Found: C, 42.26; 2.30; N, 8.12.
14: m.p. 146–148ꢀC, Yield75%; IR: 1640 (C ¼O), 1460 (N¼N); H NMR:
1
d, 3.42 (s, 4H, SCH2), 4.32 (s, 2H, SCH2CO), 7.14 (s, 1H, Ar-H), 7.34 (s, 1H,
Ar-H); Anal. Calcd. for C12H8N2OSeS2: C, 42.47, H, 2.37; N, 8.25; Found:
C, 42.40; H, 2.42; N, 8.10. 18: m.p. 137–139ꢀC, Yield62%; IR: 1620 (C ¼O),
1
1440 (N¼N); H NMR: d, 3.42 (s, 4H, SCH2), 4.18 (s, 2H, SCH2CO), 6.99
(s, 1H, Ar-H) 7.16 (s, 1H, Ar-H); Anal. Calcd. for C12H8N2OSeS2: C, 42.47;
H, 2.37; N, 8.25; Found: C, 42.27; H, 2.47; N, 8.39.
3,6-Dithia-3,4,5,6-tetrahydrophenanthrene[1,2-d;
7,8-d ]bis[1,2,3]thiadiazole (13), 3,6-Dithia-3,4,5,6-
tetrahydroanthracene[1,2-d;7,8-d ]bis[1,2,3]
thiadiazole (17) and 3,7-Dithia-3,4,7,8-
tetrahydroanthracene[1,2-d;5,6-d ]bis
[1,2,3]thiadiazole (21)
General procedure: Bis semicarbazones of 7/8/9 (1.3 g, 0.01 mol) was
added portion wise to well cooled excess thionyl chloride (10 mL) at ꢁ10ꢀC.

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BHASKAR REDDY ET AL.
The mixture was then allowedto attain room temperature. Then, it was
extractedwith idchloromethane (10 mL) andtreatedwith saturated
sodium carbonate solution. The organic layer was separated and washed
thoroughly with water and dried. The solvent was evaporated off and the
gummy product formed was solidified on treatment with pet.ether
(40–60ꢀC). However, a pure sample was obtainedon filtration through a
column of silica gel (60–120 mesh) using ethyl acetate : hexane (1 : 3) as
eluents.
13: m.p. 136–137ꢀC; Yield64%; IR: 1450 (N ¼N); H NMR: d, 3.76
1
(s, 4H, SCH2), 7.38 (s, 2H, Ar-H); Anal. Calcd. for C12H6N4S4: C, 43.09; H,
1.80; N, 16.75; Found: C, 43.00; H, 1.86; N, 16.62. 17: m.p. 154–155ꢀC,
1
Yield70%; IR: 1445 (N ¼N); H NMR: d, 3.56 (s, 4H, SCH2), 7.17 (s, 1H,
Ar-H), 7.30 (s, 1H, Ar-H); Anal. Calcd. for C12H6N4S4: C, 43.09; H, 1.80;
N, 16.75; Found: C, 43.29; H, 1.89; N, 16.64. 21: m.p. 142–144ꢀC, Yield
70%; IR: 1452 (N¼N), 1H NMR: d, 3.45 (s, 4H, SCH2), 7.12 (s, 2H, Ar-H);
Anal. Calcd. for C12H6N4S4: C, 43.09; H, 1.80; N, 16.75; Found: C, 43.18;
H, 1.75; N, 16.89.
3,6-Dithia-3,4,5,6-tetrahydrophenanthrene
[1,2-d ][1,2,3]selenadiazole[7,8-d ][1,2,3]thiadiazole (11),
3,6-Dithia-3,4,5,6-tetrahydroanthracene[1,2-d ][1,2,3]
selenadiazole[7,8-d ][1,2,3]thiadiazole (15) and 3,7-
Dithia-3,4,7,8-tetrahydroanthracene[1,2-d ][1,2,3]
selenadiazole[5,6-d ]thiadiazole (19)
General procedure: To a well cooledsolution of thionyl chloried
(5 mL), semicarbazone of 10/14/18 (1.1 g, 0.005 mol) was added in portions
andstirredat
ꢁ10ꢀC andthe process followedwas same as above.
The gummy substance obtainedwas soliidfiedon treatment with pet.
ether (40–60ꢀC) which was purifiedthrough a column of silica gel
(60–120 mesh) using ethyl acetate : hexane (1 : 3), as eluents.
11: m.p. 145–147ꢀC, Yield68%; IR: 1465 (N ¼N); H NMR: d, 3.74
1
(s, 2H, SCH2), 7.22 (s, 2H, Ar-H); Anal. Calcd. for C12H6N4SeS3: C, 37.79;
H, 1.58; N, 14.69; Found: C, 37.92; H, 1.66; N, 14.59. 15: m.p. 153–155ꢀC,
1
Yield72%; IR: 1458 (N ¼N); H NMR: d, 3.52 (s, 4H, SCH2), 7.12 (s, 1H,
Ar-H), 7.28 (s, 1H, Ar-H); Anal. Calcd. for C12H6N4SeS3: C, 37.79; H, 1.58;
N, 14.69; Found: C, 37.59; H, 1.74; N, 14.80. 19: m.p. 147–149ꢀC, Yield
74%; IR: 1460 (N¼N); 1H NMR: d, 3.45 (s, 4H, SCH2); 7.12 (s, 2H, Ar-H);
Anal. Calcd. for C12H6N4SeS3: C, 37.79; H, 1.58; N, 14.69; Found: C, 37.64;
H, 1.70; N, 14.74.

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ACKNOWLEDGMENT
The authors (DBR, AB & VP) greatly acknowledge the University
Grants Commission, New Delhi for financial assistance under major
research project.
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Receivedin the USA January 14, 2001

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