JOURNALꢀOFꢀCHEMICALꢀRESEARCHꢀ2009ꢀ 375
I2
O
I2
O
O
S
OH
Ar
H
NH
I2
NH
N
H
S
S
S
S
S
O
O
H
NH
-
H O
2
NH
Ar
C
ArCH
S
S
S
S
HO
Scheme 2
1H,ꢀNH).ꢀ13CꢀNMRꢀ(DMSO-d6,ꢀ100ꢀMHz)ꢀd:ꢀ123.8,ꢀ128.6,ꢀ130.4,ꢀ
Experimental
MeltingꢀpointsꢀwereꢀdeterminedꢀonꢀanꢀXT4Aꢀelectrothermalꢀapparatusꢀ
1
33.8,ꢀ135.2,ꢀ137.5,ꢀ145.8,ꢀ147.5,ꢀ166.6,ꢀ199.8.ꢀIRꢀ(KBr)ꢀ n:ꢀ3433ꢀ
-
1
1
13
(N–H),ꢀ1701ꢀ(C=O),ꢀ1643ꢀ(C=C),ꢀ1189ꢀ(C=S)ꢀcm .ꢀAnal.ꢀCalcdꢀforꢀ
C H N O S :ꢀC,ꢀ45.11;ꢀH,ꢀ2.26;ꢀN,ꢀ10.53.ꢀFound:ꢀC,ꢀ45.23;ꢀH,ꢀ2.14;ꢀ
equippedꢀwithꢀaꢀmicroscopeꢀandꢀareꢀuncorrected.ꢀ HꢀNMRꢀandꢀ Cꢀ
NMRꢀspectraꢀwereꢀrecordedꢀonꢀaꢀBrukerꢀAvanceꢀ400ꢀspectrometerꢀ
10
6
2
3 2
1
13
N,ꢀ10.65%.
-(4-Nitrophenylmethylene)-2-thioxothiazolidin-4-one (3g):ꢀ M.p.ꢀ
(
H:ꢀ400ꢀMHz,ꢀ C:ꢀ100ꢀMHz)ꢀinꢀDMSO-d ꢀwithꢀTMS asꢀanꢀinternalꢀ
6
5
standard.ꢀ IRꢀ spectraꢀ wereꢀ determinedꢀ onꢀ a Nicoletꢀ FTIR-750ꢀ
spectrometer.ꢀ Benzaldehydeꢀ andꢀ 2-furaldehydeꢀ wereꢀ distilledꢀ priorꢀ
toꢀuse.ꢀAllꢀotherꢀreagentsꢀwereꢀcommerciallyꢀavailableꢀproductsꢀandꢀ
were used without further purification.
8
ꢀ
1
250–251ꢀ°Cꢀ (lit., 250–251ꢀ°C).ꢀ Hꢀ NMRꢀ (DMSO-d6,ꢀ 400ꢀ MHz)ꢀ
d:ꢀ 7.74ꢀ (s,ꢀ 1H,ꢀ CH=ꢀ ),ꢀ 7.86ꢀ (d,ꢀ Jꢀ =ꢀ 8.8ꢀ Hz,ꢀ 2H,ꢀ ArH),ꢀ 8.35ꢀ (d,ꢀ
1
3
Jꢀ =ꢀ 8.8ꢀHz,ꢀ 2H,ꢀArH),ꢀ 13.85ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ (DMSO-d6,ꢀ
1
00ꢀMHz)ꢀd:ꢀ122.7,ꢀ129.8,ꢀ132.9,ꢀ145.2,ꢀ147.9,ꢀ152.4,ꢀ167.5,ꢀ199.6.ꢀ
-1
General procedure for the synthesis of 5-(arylmethylidene)
rhodanines
IRꢀ(KBr)ꢀn:ꢀ3439ꢀ(N–H),ꢀ1723ꢀ(C=O),ꢀ1641ꢀ(C=C),ꢀ1192ꢀ(C=S)ꢀcm .ꢀ
Anal.ꢀCalcdꢀforꢀC H N O S :ꢀC,ꢀ45.11;ꢀH,ꢀ2.26;ꢀN,ꢀ10.53.ꢀFound:ꢀC,ꢀ
1
0
6
2
3 2
Aꢀ mixtureꢀ ofꢀ aromaticꢀ aldehydeꢀ (1ꢀ mmol),ꢀ rhodanineꢀ (1ꢀ mmol),ꢀ
andꢀiodineꢀ(0.1ꢀmmol)ꢀwasꢀgroundꢀinꢀaꢀmortarꢀwithꢀaꢀpestleꢀatꢀroomꢀ
temperatureꢀuntilꢀtheꢀreactionꢀwasꢀcompletedꢀ(monitoredꢀbyꢀTLC).ꢀ
Theꢀreactionꢀmixtureꢀwasꢀtreatedꢀwithꢀ5%ꢀaqueousꢀsodiumꢀthiosulfate.ꢀ
Theꢀprecipitatedꢀproductsꢀwereꢀthenꢀseparatedꢀandꢀrecrystallisedꢀfromꢀ
45.27;ꢀH,ꢀ2.16;ꢀN,ꢀ10.70%.
-(4-Dimethylaminophenylmethylene)-2-thioxothiazolidin-4-one
5
6
1
(
3h):ꢀ M.p.ꢀ 269–270ꢀ°Cꢀ (lit., ꢀ 270–271ꢀ°C).ꢀ Hꢀ NMRꢀ (DMSO-d ,ꢀ
6
4
00ꢀMHz)ꢀd:ꢀ3.03ꢀ(s,ꢀ6H,ꢀ2CH ),ꢀ6.90ꢀ(d,ꢀJꢀ=ꢀ8.9ꢀHz,ꢀ2H,ꢀArH),ꢀ7.47ꢀ
3
(
d,ꢀJꢀ=ꢀ8.8ꢀHz,ꢀ2H,ꢀArH),ꢀ7.55ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.66ꢀ(br,ꢀ1H,ꢀNH).ꢀ
DMF/H Oꢀ(Vꢀ:ꢀVꢀ=ꢀ2 ꢀ: ꢀ1)ꢀtoꢀaffordꢀtheꢀpureꢀproducts.
13
2
CꢀNMRꢀ(DMSO-d ,ꢀ100ꢀMHz)ꢀd:ꢀ94.9,ꢀ109.2,ꢀ111.4,ꢀ121.2,ꢀ140.8,ꢀ
6
5
-(Phenylmethylene)-2-thioxothiazolidin-4-one (3a):ꢀ M.p.ꢀ 205–
1
55.5,ꢀ156.2,ꢀ167.7,ꢀ198.8.ꢀIRꢀ(KBr)ꢀn:ꢀ3439ꢀ(N–H),ꢀ1687ꢀ(C=O),ꢀ1583ꢀ
8
1
2
7
07ꢀ°Cꢀ(lit., ꢀ204.5–206ꢀ°C).ꢀ HꢀNMRꢀ(DMSO-d ,ꢀ400ꢀMHz)ꢀd:ꢀ7.50–
6
13
-1
(C=C),ꢀ 1171ꢀ (C=S)ꢀ cm .ꢀAnal.ꢀ Calcdꢀ forꢀ C H N OS :ꢀ C,ꢀ 54.55;ꢀ
12 12 2 2
.80ꢀ(m,ꢀ5H,ꢀArH),ꢀ7.65ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.85ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ
H,ꢀ4.55;ꢀN,ꢀ10.61.ꢀFound:ꢀC,ꢀ54.50;ꢀH,ꢀ4.46;ꢀN,ꢀ10.68%.
-(2,4-Dichlorophenylmethylene)-2-thioxothiazolidin-4-one (3i):ꢀ
(
1
1
DMSO-d ,ꢀ100ꢀMHz)ꢀd:ꢀ118.3,ꢀ127.2,ꢀ128.3,ꢀ134.1,ꢀ136.6,ꢀ150.7,ꢀ
6
5
64.7,ꢀ199.2.ꢀIRꢀ(KBr)ꢀn:ꢀ3435ꢀ(N–H),ꢀ1700ꢀ(C=O),ꢀ1673ꢀ(C=C),ꢀ
-1
7
1
M.p.ꢀ235–236ꢀ°Cꢀ(lit., ꢀ234–235ꢀ°C).ꢀ HꢀNMRꢀ(DMSO-d6,ꢀ400ꢀMHz)ꢀ
d:ꢀ7.50–7.65ꢀ(m,ꢀ2H,ꢀArH),ꢀ7.77ꢀ(s,ꢀ1H,ꢀArH),ꢀ7.89ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ
3.95ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ(DMSO-d ,ꢀ100ꢀMHz)ꢀd:ꢀ122.4,ꢀ127.3,ꢀ
128.5,ꢀ 129.6,ꢀ 132.2,ꢀ 133.8,ꢀ 134.8,ꢀ 152.6,ꢀ 163.8,ꢀ 202.4.ꢀ IRꢀ (KBr)ꢀ
176ꢀ(C=S)ꢀcm .ꢀAnal.ꢀCalcdꢀforꢀC H NOS :ꢀC,ꢀ54.30;ꢀH,ꢀ3.17;ꢀN,ꢀ
10 7 2
6
.33.ꢀFound:ꢀC,ꢀ54.41;ꢀH,ꢀ3.26;ꢀN,ꢀ6.20%.
-(4-Chlorophenylmethylene)-2-thioxothiazolidin-4-one (3b):ꢀM.p.ꢀ
1
3
1
5
6
6
1
2
7
29–230ꢀ°Cꢀ(lit., ꢀ227–228ꢀ°C).ꢀ HꢀNMRꢀ(DMSO-d ,ꢀ400ꢀMHz)ꢀd:ꢀ
6
13
-1
.66ꢀ(s,ꢀ4H,ꢀArH),ꢀ7.71ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.88ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ
n:ꢀ3433ꢀ(N–H),ꢀ1702ꢀ(C=O),ꢀ1645ꢀ(C=C),ꢀ1192ꢀ(C=S)ꢀcm .ꢀAnal.ꢀ
(
1
1
DMSO-d ,ꢀ100ꢀMHz)ꢀd:ꢀ119.8,ꢀ128.3,ꢀ130.9,ꢀ134.1,ꢀ137.7,ꢀ158.9,ꢀ
Calcdꢀ forꢀ C10H5Cl2NOS2:ꢀ C,ꢀ 41.38;ꢀ H,ꢀ 1.72;ꢀ N,ꢀ 4.83.ꢀ Found:ꢀ
C,ꢀ41.30;ꢀH,ꢀ1.83;ꢀN,ꢀ4.92%.
6
66.5,ꢀ199.3.ꢀIRꢀ(KBr)ꢀn:ꢀ3439ꢀ(N–H),ꢀ1708ꢀ(C=O),ꢀ1601ꢀ(C=C),ꢀ
-1
180ꢀ(C=S)ꢀcm .ꢀAnal.ꢀCalcdꢀforꢀC H ClNOS :ꢀC,ꢀ46.97;ꢀH,ꢀ2.35;ꢀ
5-(2-Furylmethylene)-2-thioxothiazolidin-4-one (3j):ꢀ M.p.ꢀ 229–
1
0
6
2
7
1
N,ꢀ5.48.ꢀFound:ꢀC,ꢀ46.91;ꢀH,ꢀ2.43;ꢀN,ꢀ5.38%.
-(2-Chlorophenylmethylene)-2-thioxothiazolidin-4-one (3c):ꢀM.p.ꢀ
230ꢀ°Cꢀ(lit., ꢀ228–229ꢀ°C).ꢀ HꢀNMRꢀ(DMSO-d ,ꢀ400ꢀMHz)ꢀd:ꢀ6.73ꢀ
6
5
(s,ꢀ1H,ꢀArH),ꢀ7.26ꢀ(d,ꢀJꢀ=ꢀ3.2ꢀHz,ꢀ1H,ꢀArH),ꢀ7.49ꢀ(s,ꢀ1H,ꢀArH),ꢀ8.12ꢀ
(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.75ꢀ(br,ꢀ1H,ꢀNH). CꢀNMRꢀ(DMSO-d ,ꢀ100ꢀMHz)ꢀ
8
1
1
7
1
1
81–182 ꢀ° Cꢀ (lit., ꢀ 181–182 ꢀ° C).ꢀ Hꢀ NMRꢀ (DMSO-d ,ꢀ 400ꢀ MHz)ꢀ d:ꢀ
.45ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ7.50–7.59ꢀ(m,ꢀ3H,ꢀArH),ꢀ7.62–7.70ꢀ(m,ꢀ1H,ꢀArH),ꢀ
3.95ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ(DMSO-d ,ꢀ100ꢀMHz)ꢀd:ꢀ121.8,ꢀ125.8,ꢀ
27.2,ꢀ128.1,ꢀ132.2,ꢀ133,ꢀ133.8,ꢀ150.3,ꢀ164.4,ꢀ199.7.ꢀIRꢀ(KBr)ꢀn:ꢀ3436ꢀ
ꢀ13
6
6
d:ꢀ111.4,ꢀ119.9,ꢀ120.2,ꢀ133.3,ꢀ142.2,ꢀ156.3,ꢀ164.6,ꢀ198.7.ꢀIRꢀ(KBr)ꢀ
13
6
-1
8
5
2 2
-1
(N–H),ꢀ1703ꢀ(C=O),ꢀ1597ꢀ(C=C),ꢀ1193ꢀ(C=S)ꢀcm .ꢀAnal.ꢀCalcdꢀforꢀ
H,ꢀ2.43;ꢀN,ꢀ6.56%.
C H ClNOS :ꢀC,ꢀ46.97;ꢀH,ꢀ2.35;ꢀN,ꢀ5.48.ꢀFound:ꢀC,ꢀ46.80;ꢀH,ꢀ2.46;ꢀ
10
6
2
N,ꢀ5.61%.
-(4-Methoxyphenylmethylene)-2-thioxothiazolidin-4-one
This work was financially supported by the Educational
5
(3d):ꢀ
7
1
M.p.ꢀ248–250ꢀ°Cꢀ(lit., ꢀ249–250ꢀ°C).ꢀ HꢀNMRꢀ(DMSO-d ,ꢀ400ꢀMHz)ꢀ
6
d:ꢀ3.06ꢀ(s,ꢀ3H,ꢀCH ),ꢀ7.10ꢀ(d,ꢀJꢀ=ꢀ8.7ꢀHz,ꢀ2H,ꢀArH),ꢀ7.53ꢀ(d,ꢀJꢀ=ꢀ8.7ꢀ
3
1
3
Hz,ꢀ2H,ꢀArH),ꢀ7.63ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.75ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ
(
DMSO-d ,ꢀ 100ꢀ MHz)ꢀ d:ꢀ 56.4,ꢀ 114.8,ꢀ 116.0,ꢀ 126.0,ꢀ 129.0,ꢀ 131.6,ꢀ
6
Published online: 3 July 2009
1
34.3,ꢀ 167.8,ꢀ 199.1.ꢀ IRꢀ (KBr)ꢀ n:ꢀ 3438ꢀ (N–H),ꢀ 1689ꢀ (C=O),ꢀ 1631ꢀ
-1
(C=C),ꢀ1170ꢀ(C=S)ꢀcm .ꢀAnal.ꢀCalcdꢀforꢀC H NO S :ꢀC,ꢀ52.59;ꢀH,ꢀ
11 9 2 2
3
.59;ꢀN,ꢀ5.58.ꢀFound:ꢀC,ꢀ52.73;ꢀH,ꢀ3.64;ꢀN,ꢀ5.47%.
-(4-Methylphenylmethylene)-2-thioxothiazolidin-4-one (3e):ꢀM.p.ꢀ
5
6
ꢀ
1
2
2
22–223ꢀ°Cꢀ (lit., 221–223ꢀ°C).ꢀ Hꢀ NMRꢀ (DMSO-d ,ꢀ 400ꢀ MHz)ꢀ d:ꢀ
.37ꢀ(s,ꢀ3H,ꢀCH ),ꢀ7.41ꢀ(d,ꢀJꢀ=ꢀ8.1ꢀHz,ꢀ2H,ꢀArH),ꢀ7.48ꢀ(d,ꢀJꢀ=ꢀ8.2ꢀ
6
References
3
ꢀ
ꢀ
1ꢀ F.C.ꢀBrown, Chem. Rev., 1961,ꢀ61,ꢀ463.
2ꢀ F.C.ꢀBrown,ꢀC.K.ꢀBradsher,ꢀS.M.ꢀBondꢀandꢀM.ꢀPotter, J. Am. Chem. Soc.,ꢀ
1
3
Hz,ꢀ2H,ꢀArH),ꢀ7.61ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.70ꢀ(br,ꢀ1H,ꢀNH).ꢀ CꢀNMRꢀ
DMSO-d ,ꢀ 100ꢀ MHz)ꢀ d:ꢀ 22.9,ꢀ 117.7,ꢀ 128.6,ꢀ 129.2,ꢀ 134.1,ꢀ 139.9,ꢀ
(
1
6
1
951,ꢀ73, 2357.
44.2,ꢀ 165.6,ꢀ 199.1.ꢀ IRꢀ (KBr)ꢀ n:ꢀ 3435ꢀ (N–H),ꢀ 1704ꢀ (C=O),ꢀ 1593ꢀ
ꢀ
ꢀ
3ꢀ R.G.ꢀ Giles,ꢀ N.J.ꢀ Lewis,ꢀ J.K.ꢀ Quick,ꢀ M.J.ꢀ Sasse,ꢀ M.W.J.ꢀ Urquhartꢀ andꢀ
L.ꢀYoussef,ꢀTetrahedron,ꢀ2000,ꢀ56,ꢀ4531.
4ꢀ M.M.ꢀ Chowdhry,ꢀ D.M.P.ꢀ Mingos,ꢀ A.J.P.ꢀ Whiteꢀ andꢀ D.J.ꢀ Williams,ꢀ
J. Chem. Soc., Perkin Trans. 1,ꢀ2000,ꢀ3495.
-1
(C=C),ꢀ1181ꢀ(C=S)ꢀcm .ꢀAnal.ꢀCalcdꢀforꢀC H NOS :ꢀC,ꢀ56.17;ꢀH,ꢀ
11 9 2
3
.83;ꢀN,ꢀ5.96.ꢀFound:ꢀC,ꢀ56.24;ꢀH,ꢀ3.96;ꢀN,ꢀ5.80%.
-(3-Nitrophenylmethylene)-2-thioxothiazolidin-4-one (3f): M.p.ꢀ
5
8
1
2
63–264ꢀ°Cꢀ (lit., ꢀ 263–265ꢀ°C).ꢀ Hꢀ NMRꢀ (DMSO-d ,ꢀ 400ꢀ MHz)ꢀ
ꢀ 5ꢀ Y.Q.ꢀZhang,ꢀC.ꢀWang,ꢀJ.J.ꢀMa,ꢀJ.C.ꢀLi,ꢀR.X.ꢀTangꢀandꢀY.P.ꢀWang,ꢀChin.
J. Appl. Chem.,ꢀ2008,ꢀ25, 122.
ꢀ 6ꢀ X.Z.ꢀLian,ꢀY.Q.ꢀLiꢀandꢀM.Y.ꢀZhou, Chin. J. Org. Chem., 2006, 26, 1272.
6
d:ꢀ7.80ꢀ(s,ꢀ1H,ꢀArH),ꢀ7.83–7.90ꢀ(m,ꢀ1H,ꢀArH),ꢀ7.95ꢀ(d,ꢀJꢀ=ꢀ7.6ꢀHz,ꢀ1H,ꢀ
ArH),ꢀ8.30ꢀ(d,ꢀJꢀ=ꢀ8.1ꢀHz,ꢀ1H,ꢀArH),ꢀ8.45ꢀ(s,ꢀ1H,ꢀCH=ꢀ),ꢀ13.91ꢀ(br,ꢀ