10.1002/adsc.201900402
Advanced Synthesis & Catalysis
SMe), 2.10 (s, 3 H, SMe), 1.82 (m, 2 H, CH2CH2CN).
13C{1H} NMR (100 MHz, CDCl3) δ 195.3 (Cq, C=O),
163.9, 145.1, 135.4 and 129.1 (Cq), 131.4 and 114.1
(aromatic CH), 119.3 (CN), 55.6 (OMe), 32.8
((C=O)CCH2), 24.2 (CH2CH2CN), 17.2 and 16.3 (SMe),
16.7 (CH2CN). HRMS Calcd for C16H19NO2S2 [M+H]+:
322.0935; Found: 322.0936.
6,6-Bis(methylthio)-5-(4-(trifluoromethyl)benzoyl)-
hex-5-enenitrile (3f): 81 mg, 75% yield, yellow liquid. 1H
NMR (400 MHz, CDCl3) δ 7.93 (d, J = 8.1 Hz, 2 H,
aromatic CH), 7.73 (d, J = 8.2 Hz, 2 H, aromatic CH), 2.80
(m, 2 H, (C=O)CCH2), 2.40 (m, 5 H, CH2CN and SMe),
2.05 (s, 3 H, SMe), 1.85 (m, 2 H, CH2CH2CN). 13C{1H}
NMR (100 MHz, CDCl3) δ 195.4 (Cq, C=O), 143.5, 139.8
and 139.1 (Cq), 134.4 (q, J = 32.4 Hz, i-C of CF3C6H4),
129.1 (aromatic CH), 125.8 (q, J = 3.7 Hz, o-C of
CF3C6H4), 123.7 (q, J = 271.0 Hz, CF3), 119.2 (CN), 32.9
((C=O)CCH2), 24.3 (CH2CH2CN), 17.1 and 16.4 (SMe),
16.9 (CH2CN). HRMS Calcd for C16H16NOF3S2 [M+H]+:
360.0704; Found: 360.0701.
5-(4-Fluorobenzoyl)-6,6-bis(methylthio)hex-5-eneni-
trile (3g): 70.5 mg, 75% yield, yellow solid, m.p.: 74-75
oC. 1H NMR (400 MHz, CDCl3) δ 7.86 and 7,13 (m each,
2:2 H, aromatic CH), 2.77 (m, 2 H, (C=O)CCH2), 2.38 (m,
5 H, CH2CN and SMe), 2.08 (s, 3 H, SMe), 1.83 (m, 2 H,
CH2CH2CN). 13C{1H} NMR (100 MHz, CDCl3) δ 195.0
(Cq, C=O), 166.0 (d, J = 254 Hz, i-C of FC6H4), 144.2 and
137.1 (Cq), 132.8 (d, J = 2.9 Hz, p-C of FC6H4), 131.6 (d,
J = 9.4 Hz, m-C of FC6H4), 119.3 (CN), 116.0 (d, J = 21.9
16.7 (CH2CN). HRMS Calcd for C13H15NO2S2 [M+H]+:
282.0622; Found: 282.0619.
6,6-Bis(methylthio)-5-(thiophene-2-carbonyl)hex-5-
1
enenitrile (3k): 41.2 mg, 46% yield, yellow liquid. H
NMR (400 MHz, CDCl3) δ 7.68 (dd, J = 4.9 and 1.1 Hz, 1
H, aromatic CH), 7.56 (dd, J = 3.8 and 1.1 Hz, 1 H,
aromatic CH), 7.13 (dd, J = 4.9 and 3.8 Hz, 1 H, aromatic
CH), 2.80 (m, 2 H, (C=O)CCH2), 2.38 (m, 5 H, CH2CN
and SMe), 2.15 (s, 3 H, SMe), 1.85 (m, 2 H, CH2CH2CN).
13C{1H} NMR (100 MHz, CDCl3) δ 189.1 (Cq, C=O),
144.6, 143.9 and 137.3 (Cq), 134.6, 133.2 and 128.4
(aromatic CH), 32.8 ((C=O)CCH2), 24.3 (CH2CH2CN),
17.5 and 16.4 (SMe), 16.8 (CH2CN). HRMS Calcd for
C13H15NOS3 [M+H]+: 298.0394; Found: 298.0394.
5-(Bis(methylthio)methylene)-6-oxoheptanenitrile
1
(3l): 51.8 mg, 75% yield, yellow liquid. H NMR (400
MHz, CDCl3) δ 2.67 (m, 2 H, (C=O)CCH2), 2.40 (s, 3 H,
Me), 2.35 (m, 5 H, CH2CN and SMe), 2.29 (s, 3 H, SMe),
1.78 (m, 2 H, CH2CH2CN). 13C{1H} NMR (100 MHz,
CDCl3) δ 203.7 (Cq, C=O), 146.9 and 137.9 (Cq), 119.4
(CN), 32.3 ((C=O)CCH2), 30.5 (Me), 24.4 (CH2CH2CN),
17.5 and 16.7 (SMe), 16.8 (CH2CN). HRMS Calcd for
C10H15NOS2 [M+H]+: 230.0673; Found: 230.0677.
5-(Bis(methylthio)methylene)-7,7-dimethyl-6-oxooc-
1
tanenitrile (3m): 57.5 mg, 70% yield, yellow liquid. H
NMR (400 MHz, CDCl3) δ 2.66 (t, J = 7.4 Hz, 2 H,
(C=O)CCH2), 2.38 (t, J = 7.1 Hz, 2 H, CH2CN), 2.28 and
2.22 (s each, 3:3 H, SMe), 1.76 (m, 2 H, CH2CH2CN), 1.21
(s, 9 H, tBu). 13C{1H} NMR (100 MHz, CDCl3) δ 213.9
Hz, o-C of FC6H4), 32.8 ((C=O)CCH2), 24.3 (CH2CH2CN), (Cq, C=O), 147.6, 131.9 and 119.4 (Cq), 43.8 (C(CH3)),
17.1 and 16.3 (SMe), 16.8 (CH2CN). HRMS Calcd for
C15H16NOFS2 [M+H]+: 310.0736; Found: 310.0737.
5-(4-Chlorobenzoyl)-6,6-bis(methylthio)hex-5-eneni-
trile (3h): 77.5 mg, 79% yield, yellow solid, m.p.: 54-55
oC. 1H NMR (400 MHz, CDCl3) δ 7.77 (d, J = 8.5 Hz, 2 H,
aromatic CH), 7.43 (d, J = 8.5 Hz, 2 H, aromatic CH), 2.76
(m, 2 H, (C=O)CCH2), 2.38 (m, 5 H, CH2CN and SMe),
2.07 (s, 3 H, SMe), 1.81 (m, 2 H, CH2CH2CN). 13C{1H}
NMR (100 MHz, CDCl3) δ 195.3 (Cq, C=O), 143.9, 139.8,
137.6 and 135.0 (Cq), 130.3 and 129.1 (aromatic CH), 32.8
((C=O)CCH2), 24.2 (CH2CH2CN), 17.1 and 16.4 (SMe),
16.8 (CH2CN). HRMS Calcd for C15H16NOS2Cl [M+H]+:
326.0440; Found: 326.0435.
31.9 ((C=O)CCH2), 27.9 (C(CH3)), 24.0 (CH2CH2CN),
17.1 and 16.3 (SMe), 16.4 (CH2CN). HRMS Calcd for
C13H21NOS2 [M+H]+: 272.1143; Found: 272.1145.
5-(Cyclopropanecarbonyl)-6,6-bis(methylthio)hex-5-
1
enenitrile (3n): 62.1 mg, 81% yield, yellow liquid. H
NMR (400 MHz, CDCl3) δ 2.71 (dd, J = 8.3 and 6.9 Hz, 2
H, (C=O)CCH2), 2.35 (m, 5 H, SMe and CH2CN), 2.29 (s,
3 H, SMe), 2.20 (m, 1 H, cyclopropyl CH), 1.79 (m, 2 H,
CH2CH2CN), 1.14 and 0.97 (m each, 2:2 H, cyclopropyl
CH). 13C{1H} NMR (100 MHz, CDCl3) δ 206.3 (Cq),
147.5 and 138.0 (Cq), 119.4 (CN), 32.7 ((C=O)CCH2),
24.5 (CH2CH2CN), 22.1, 17.5, 16.7 and 16.6 (cyclopropyl
CH and CH2CN), 12.8 (SMe). HRMS Calcd for
C12H17NOS2 [M+H]+: 256.0830; Found: 256.0830.
5-Benzoyl-6,6-bis(ethylthio)hex-5-enenitrile (3o): 73.5
mg, 76% yield, yellow liquid. 1H NMR (400 MHz, CDCl3)
δ 7.84, 7.57 and 7.45 (m each, 2:1:2 H, aromatic CH), 2.82
(m, 4 H, SCH2 and (C=O)CCH2), 2.62 (q, J = 7.4 Hz, 2 H,
SCH2), 2.38 (t, J = 7.2 Hz, 2 H, CH2CN), 1.84 (m, 2 H,
CH2CH2CN), 1.30 (t, J = 7.3 Hz, 3 H, CH2CH3), 1.02 (t, J
= 7.4 Hz, 3 H, CH2CH3). 13C{1H} NMR (100 MHz, CDCl3)
δ 196.8 (Cq, C=O), 147.2, 136.2 and 133.6 (Cq), 133.5,
129.1 and 128.8 (aromatic CH), 119.4 (CN), 32.7
((C=O)CCH2), 28.1, 27.3, 24.4, 16.7, 15.4 and 14.3 (CH2
and CH3). HRMS Calcd for C17H21NOS2 [M+H]+:
320.1143; Found: 320.1141.
5-(4-Bromobenzoyl)-6,6-bis(methylthio)hex-5-eneni-
trile (3i): 93.2 mg, 83% yield, yellow solid, m.p.: 64-65 oC.
1H NMR (400 MHz, CDCl3) δ 7.70 (d, J = 8.4 Hz, 2 H,
aromatic CH), 7.60 (d, J = 8.4 Hz, 2 H, aromatic CH),2.77
(m, 2 H, (C=O)CCH2), 2.39 (m, 5 H, CH2CN and SMe),
2.07 (s, 3 H, SMe), 1.82 (m, 2 H, CH2CH2CN). 13C{1H}
NMR (100 MHz, CDCl3) δ 195.5 (Cq, C=O), 143.9, 137.7,
135.4 and 128.5 (Cq), 132.1 and 130.4 (aromatic CH),
119.3 (CN), 32.8 ((C=O)CCH2), 24.3 (CH2CH2CN), 17.2
and 16.4 (SMe), 16.8 (CH2CN). HRMS Calcd for
C15H16NOS2Br [M+H]+: 369.9935; Found: 369.9939.
5-(Furan-2-carbonyl)-6,6-bis(methylthio)hex-5-eneni-
o
trile (3j): 36 mg, 42% yield, yellow solid, m.p.: 55-56 C.
1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 0.9 Hz, 1 H,
aromatic CH), 7.09 (d, J = 3.4 Hz, 1 H, aromatic CH), 6.55
(dd, J = 3.5 and 1.7 Hz, 1 H, aromatic CH), 2.78 (m, 2 H,
(C=O)CCH2), 2.40 (m, 5 H, CH2CN and SMe), 2.16 (s, 3
H, SMe), 1.83 (m, 2 H, CH2CH2CN). 13C{1H} NMR (100
MHz, CDCl3) δ 184.5 (Cq), 152.6, 143.6 and 138.8 (Cq),
119.4 (CN), 147.2, 118.5 and 112.7 (aromatic CH), 32.7
((C=O)CCH2), 24.3 (CH2CH2CN), 17.5 and 16.4 (SMe),
5-(1,3-Dithiolan-2-ylidene)-6-oxo-6-phenylhexaneni-
trile (3p): 66.2 mg, 76% yield, yellow liquid. H NMR
1
(400 MHz, CDCl3) δ 7.44 (m, 5 H, aromatic CH), 3.38 (m,
4 H, SCH2CH2S), 2.73 (dd, J = 8.6 and 6.9 Hz, 2 H,
(C=O)CCH2), 2.21 (t, J = 7.2 Hz, 2 H, CH2CN), 1.75 (m, 2
H, CH2CH2CN). 13C{1H} NMR (100 MHz, CDCl3) δ
193.6 (Cq, C=O), 162.3, 139.4 and 122.9 (Cq), 130.9,
128.4 and 127.5 (aromatic CH), 119.2 (CN), 39.1, 36.5,
7
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