Dalton Transactions
Page 26 of 38
DOI: 10.1039/C7DT02008B
Synthesisꢀofꢀ28:ꢀIntermediateꢀKꢀ(0.277ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(3ꢀmL).ꢀ4-ethyl-3-
thiosemicarbazideꢀ(0.191ꢀg,ꢀ1.6ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(5ꢀmL)ꢀandꢀaddedꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀwasꢀ
added.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(14ꢀmL)ꢀwasꢀ
added,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL).ꢀTheꢀcrudeꢀproductꢀ
wasꢀdissolvedꢀinꢀDMSOꢀ(8ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-ionisedꢀwaterꢀ(16ꢀmL).ꢀTheꢀ
precipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL),ꢀethanolꢀ(5ꢀxꢀ10ꢀmL)ꢀ
andꢀdried.ꢀAꢀyellowish-whiteꢀsolidꢀ(0.168ꢀg)ꢀwasꢀrecoveredꢀ(38%ꢀyield).ꢀδHꢀ10.29ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.19ꢀ
(
1ꢀH,ꢀs,ꢀN-NH),ꢀ8.40ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ8.60ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH
2
C-NH),ꢀ7.74ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ3.54ꢀ(2ꢀH,ꢀdq,ꢀJꢀ=ꢀ
),ꢀ2.14ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.09ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀN-CH -CH ),ꢀ
3
).ꢀδCꢀ179.28ꢀ(C=S),ꢀ177.90ꢀ(C=S),ꢀ152.19ꢀ(C=N),ꢀ147.86ꢀ(C=N),ꢀ39.35ꢀ(HN-
7
0
.2,ꢀ6.0,ꢀHN-CH
.84ꢀ(3ꢀH,ꢀt,ꢀJꢀ=7.2,ꢀC-CH
2 3 3 2 3
),ꢀ17.04ꢀ(C-CH ),ꢀ14.89ꢀ(N-CH -CH ),ꢀ12.39ꢀ(N=C-CH ),ꢀ11.44ꢀ(C-CH -CH ).ꢀIR:ꢀνmax/cm ꢀꢀ3428ꢀ(w),ꢀ
2
),ꢀ2.80ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀC-CH
2
3
2
3
2
-CH
-
1
CH
2
2
3
210ꢀ(w),ꢀ2982ꢀ(w),ꢀ1601ꢀ(m),ꢀ1537ꢀ(m),ꢀ1493ꢀ(s),ꢀ1435ꢀ(m),ꢀ1290ꢀ(m),ꢀ1213ꢀ(m),ꢀ1146ꢀ(m),ꢀ1080ꢀ(s),ꢀ
-
1
059ꢀ(m),ꢀ926ꢀ(w),ꢀ837ꢀ(m),ꢀ777ꢀ(w),ꢀ716ꢀ(w),ꢀ652ꢀ(w),ꢀ565ꢀ(m),ꢀ517ꢀ(m).ꢀRamanꢀ(632.81ꢀnm):ꢀνmax/cm
1
ꢀ
2934ꢀ(w),ꢀ1599ꢀ(s),ꢀ1589ꢀ(m),ꢀ1532ꢀ(w),ꢀ1457ꢀ(w),ꢀ1395ꢀ(w),ꢀ1368ꢀ(w),ꢀ1345ꢀ(w),ꢀ1247ꢀ(w),ꢀ1215ꢀ(w),ꢀ
1
C
120ꢀ(m),ꢀ1049ꢀ(w),ꢀ991ꢀ(w),ꢀ741ꢀ(w),ꢀ463ꢀ(w),ꢀ318ꢀ(w).ꢀFound:ꢀC,ꢀ39.5;ꢀH,ꢀ6.5;ꢀN,ꢀ30.55.ꢀCalc.ꢀforꢀ
o
9 18 6 2
H N S :ꢀC,ꢀ39.4;ꢀH,ꢀ6.6;ꢀN,ꢀ30.6%ꢀꢀMp:ꢀ>218ꢀ Cꢀ(dec.).ꢀ
Synthesisꢀofꢀ29:ꢀIntermediateꢀLꢀ(0.599ꢀg,ꢀ3.2ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(2ꢀmL)ꢀandꢀfiltered.ꢀ
Thiosemicarbazideꢀ(0.292ꢀg,ꢀ3.2ꢀmmol)ꢀwasꢀdissolvedꢀinꢀDMFꢀ(10ꢀmL),ꢀHClꢀ(10%,ꢀ2ꢀdrops)ꢀwasꢀaddedꢀ
andꢀfiltered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(24ꢀmL)ꢀwasꢀ
added,ꢀtheꢀprecipitateꢀwasꢀfilteredꢀoffꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀ
o
andꢀ50ꢀmL,ꢀ80ꢀ C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(31ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀ
de-ionisedꢀwaterꢀ(62ꢀmL).ꢀTheꢀprecipitateꢀwasꢀrecoveredꢀbyꢀfiltration,ꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ
o
(
(
50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀmL,ꢀ80ꢀ C)ꢀandꢀdried.ꢀAnꢀoffꢀwhiteꢀsolidꢀ(0.597ꢀg)ꢀwasꢀrecoveredꢀ
72%ꢀyield).ꢀδHꢀ10.29ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.21ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.39ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ8.27ꢀ(1ꢀH,ꢀq,ꢀJꢀ=ꢀ4.8,ꢀH
),ꢀ2.87ꢀ(2H,ꢀq,ꢀJꢀ=ꢀ7.2,ꢀCH ),ꢀ2.10ꢀ(3ꢀH,ꢀs,ꢀN=C-
).ꢀδCꢀ179.35ꢀ(C=S),ꢀ178.96ꢀ(C=S),ꢀ152.89ꢀ(C=N),ꢀ147.48ꢀ(C=N),ꢀ31.80ꢀ
3
C-
NH),ꢀ7.80ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ2.98ꢀ(3ꢀH,ꢀd,ꢀJꢀ=ꢀ4.8,ꢀHN-CH
CH ),ꢀ0.85ꢀ(3ꢀH,ꢀt,ꢀJꢀ=7.2,ꢀCH -CH
HN-CH ),ꢀ17.36ꢀ(CH ),ꢀ12.21ꢀ(N=C-CH
150ꢀ(m),ꢀ2978ꢀ(w),ꢀ2938ꢀ(w),ꢀ1603ꢀ(m),ꢀ1541ꢀ(m),ꢀ1491ꢀ(s),ꢀ1464ꢀ(s),ꢀ1439ꢀ(s),ꢀ1364ꢀ(m),ꢀ1227ꢀ(m),ꢀ
144ꢀ(m),ꢀ1082ꢀ(s),ꢀ1059ꢀ(s),ꢀ860ꢀ(m),ꢀ826ꢀ(m),ꢀ797ꢀ(m),ꢀ640ꢀ(m),ꢀ509ꢀ(s).ꢀRamanꢀ(632.81ꢀnm):ꢀ
3
2
3
2
3
-
1
(
3
2
3 2 3
),ꢀ11.53ꢀ(CH -CH ).ꢀIR:ꢀνmax/cm ꢀ3408ꢀ(m),ꢀ3337ꢀ(w),ꢀ3229ꢀ(m),ꢀ
3
1
-
1
ν
max/cm ꢀ2937ꢀ(w),ꢀ1604ꢀ(s),ꢀ1591ꢀ(m),ꢀ1591ꢀ(w),ꢀ1380ꢀ(w),ꢀ1341ꢀ(w),ꢀ1232ꢀ(w),ꢀ1144ꢀ(w),ꢀ1123ꢀ(m),ꢀ
1
024ꢀ(w),ꢀ985ꢀ(w),ꢀ737ꢀ(w),ꢀ675ꢀ(w),ꢀ481ꢀ(w),ꢀ460ꢀ(w).ꢀFound:ꢀC,ꢀ36.8;ꢀH,ꢀ6.2;ꢀN,ꢀ32.2.ꢀCalc.ꢀforꢀ
o
C
8 16 6 2
H N S :ꢀC,ꢀ36.9;ꢀH,ꢀ6.2;ꢀN,ꢀ32.3%.ꢀMp:ꢀ>202ꢀ Cꢀ(dec.).ꢀ
Synthesisꢀofꢀ30:ꢀIntermediateꢀMꢀ(0.322ꢀg,ꢀ1.6ꢀmmol)ꢀdissolvedꢀinꢀDMFꢀ(2.5ꢀmL)ꢀandꢀfiltered.ꢀ
Thiosemicarbazideꢀ(0.146ꢀg,ꢀ1.6ꢀmmol)ꢀdissolvedꢀinꢀDMFꢀ(5.5ꢀmL),ꢀaddedꢀHClꢀ(10%,ꢀ1ꢀdrop)ꢀandꢀ
filtered.ꢀTheꢀtwoꢀsolutionsꢀwereꢀcombinedꢀandꢀleftꢀtoꢀstirꢀforꢀ5ꢀh.ꢀDe-ionisedꢀwaterꢀ(16ꢀmL)ꢀwasꢀ
added,ꢀfilteredꢀoffꢀprecipitateꢀandꢀwashedꢀwithꢀde-ionisedꢀwaterꢀ(50ꢀmL,ꢀroomꢀtemperatureꢀandꢀ50ꢀ
o
mL,ꢀ70 C).ꢀTheꢀcrudeꢀproductꢀwasꢀdissolvedꢀinꢀDMSOꢀ(14ꢀmL),ꢀfilteredꢀandꢀrecrystallisedꢀwithꢀde-
ionisedꢀwaterꢀ(28ꢀmL).ꢀFilteredꢀoffꢀprecipitate,ꢀwashedꢀde-ionisedꢀwaterꢀ(50ꢀmL)ꢀandꢀdried.ꢀAꢀwhiteꢀ
solidꢀ(0.237ꢀg)ꢀwasꢀrecoveredꢀ(54%ꢀyield).ꢀδ
C-NH),ꢀ8.28ꢀ(1ꢀH,ꢀt,ꢀJꢀ=ꢀ6.0,ꢀH C-NH),ꢀ7.80ꢀ(1ꢀH,ꢀs,ꢀC-NH),ꢀ3.55ꢀ(2ꢀH,ꢀdq,ꢀJꢀ=ꢀ7.2,ꢀ6.0,HN-CH
q,ꢀJꢀ=ꢀ7.2,ꢀC-CH ),ꢀ2.10ꢀ(3ꢀH,ꢀs,ꢀN=C-CH ),ꢀ1.09ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀN-CH -CH ),ꢀ0.86ꢀ(3ꢀH,ꢀt,ꢀJꢀ=ꢀ7.2,ꢀC-CH
CH ).ꢀδCꢀ179.37ꢀ(C=S),ꢀ177.94ꢀ(C=S),ꢀ152.77ꢀ(C=N),ꢀ147.47ꢀ(C=N),ꢀ39.07ꢀ(HN-CH ),ꢀ17.48ꢀ(C-CH ),ꢀ14.89ꢀ
).ꢀIR:ꢀνmax/cm ꢀ3410ꢀ(w),ꢀ3333ꢀ(w),ꢀ3219ꢀ(m),ꢀ3152ꢀ
m),ꢀ2978ꢀ(w),ꢀ1601ꢀ(m),ꢀ1531ꢀ(m),ꢀ1493ꢀ(s),ꢀ1466ꢀ(s),ꢀ1439ꢀ(s),ꢀ1385ꢀ(m),ꢀ1292ꢀ(m),ꢀ1250ꢀ(m),ꢀ1207ꢀ
H
ꢀ10.30ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ10.15ꢀ(1ꢀH,ꢀs,ꢀN-NH),ꢀ8.38ꢀ(1ꢀH,ꢀs,ꢀ
2
2
),ꢀ2.86ꢀ(2H,ꢀ
2
3
2
3
2
-
3
2
2
-
1
(
(
2 3 3 2 3
N-CH -CH ),ꢀ12.20ꢀ(N=C-CH ),ꢀ11.50ꢀ(C-CH -CH
ꢀ
26