Electronic Supplementary Information
One-pot Synthesis of 3,5-Disubstituted 1,2,4-Thiadiazoles from
Nitriles and Thioamides via I2-Mediated Oxidative Formation of N-S
Bond
Ling Chai,a,‡ Yuanqing Xu,a,‡ Tao Ding,a,‡ Xiaomin Fang,a Yanpeng Wang,a Wenkai Zhang,a Minghua Lu,a Hao Xu,*,a Xiaobo Yang*,b
a College of Chemistry and Chemical Engineering, Henan University, Kaifeng 475004, P. R.
China.
b College of Chemistry & Chemical Engineering, Shenyang Normal University, Shenyang,
Liaoning, 110034, P. R. China.
E-mail : [email protected]; [email protected]
Table of contents
General experimental procedures P2
Scheme S1 P3
Figure S1 P4
Figure S2 P6
Reference P7
The 1H and 13C NMR spectra of compounds 3a-3b’, III-1, 4a P8
S1
Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017
General experimental procedures
All reactions were carried out under air. Proton and carbon magnetic resonance
spectra (1H NMR and 13C NMR) were recorded using tetramethylsilane (TMS) in the
solvent of CDCl3 as the internal standard (1H NMR: TMS at 0.00 ppm,CHCl3 at 7.26
ppm; 13C NMR: CDCl3 at 77.16 ppm) or were recorded using tetramethylsilane (TMS)
in the solvent of d6-DMSO as the internal standard (1H NMR: TMS at 0.00 ppm,
DMSO at 2.50 ppm; 13C NMR: DMSO at 39.51 ppm).
Compounds 2b-j was synthesized by previous method.[1]
S2
Alk2
SN
NAlk1S
Alk2H2NAlk1 CN +
1
standard conditons
Alk1 = methyl, ethyl, benzyl; Alk2 = methyl, ethyl
(D)
Ph
SN
NPhS
PhH2N+
2a 4a
standard conditons(E)
Ar = 4-CH3Ph, 4-ClPh
+ Ar
SN
NAr Ph
SN
NArAr CN +
Ph
SN
NRS
PhH2NR CN +
standard conditons(B)
R=4-NH2Ph, 4-N(CH3)2Ph, N
SN
NBn
S
H2N+
standard conditonsCN(A)O
CH3CH3
O
1g
2a
(C) t-BuCNS
PhH2N2a
+Ph
SN
Nt-Bustandard conditons
Scheme S1. (A) Employing 4-acetylbenzothioamide as the substrate to react with 1g; (B) Employing amino-substituted nitriles as the substrates to react with 2a; (C) Employing pivalonitrile as the substrate to react with 2a; (D) Employing aliphatic thioamides as the substrates to react with aliphatic nitriles 1 under standard conditions; (E) Employing aromatic nitriles as substrates to react with 2a.
S3
Figure S1. ESI-MS [M+H]+ spectrum of reaction solution of p-methylbenzonitrile with
thiobenzamide 2a.a [aReaction condition: (1) 1 (0.8 mmol), 2 [0.4 mmol, added (4×0.1 mmol per 5
min)], AlCl3 (0.8 mmol), n-BuAc (1 mL), reaction time (5 h) at 70 oC in air; (2) then H2O (0.3
mL), I2 (0.8 mmol), reaction time (24 h) at room temperature. The resulting solution was
S4
Ph
SN
NPh
4a
Ph
SN
NH3C
SN
NH3C CH3
quenched with saturated aqueous solution of Na2S2O3. The organic and aqueous layers were
separated, and the aqueous layer was extracted with EtOAc (3×10 mL). The combined organic
layers were dried over anhydrous Na2SO4, concentrated and purified by column chromatography
on silica gel, and the crude product is used to do the ESI-MS test. ]
S5
Figure S2. ESI-MS [M+H]+ spectrum of reaction solution of p-chlorobenzonitrile with
thiobenzamide 2a.a [aReaction condition: (1) 1 (0.8 mmol), 2 [0.4 mmol, added (4×0.1 mmol per 5
min)], AlCl3 (0.8 mmol), n-BuAc (1 mL), reaction time (5 h) at 70 oC in air; (2) then H2O (0.3
mL), I2 (0.8 mmol), reaction time (24 h) at room temperature. The resulting solution was
S6
Ph
SN
NPh
4aPh
SN
NCl
SN
NCl Cl
quenched with saturated aqueous solution of Na2S2O3. The organic and aqueous layers were
separated, and the aqueous layer was extracted with EtOAc (3×10 mL). The combined organic
layers were dried over anhydrous Na2SO4, concentrated and purified by column chromatography
on silica gel, and the crude product is used to do the ESI-MS test.]
References
(1) Goswami, S.; Maity, A. C.; Das, N. K. J. Sulfur Chem. 2007, 28, 233.
S7