S. Braverman et al. / Tetrahedron 56 (2000) 4521±4529
4527
282 (MH1, 30), 226(15), 211(25), 202(100), 181(10),
160(15); HRMS: calcd for C13H17NOBr 282.049350;
found 282.048452; IR (neat): 3020, 2410, 1611, 1680,
39.48 (CH2), 121.48 (C-2), 127.00 (C-o), 128.62 (C-m),
130.17 (C-p), 137.06 (C-i), 138.30 (C-3), 164.17 (CvO);
MS-CI (i-Bu) m/z 238 (MH1, 100), 195(10), 165(15);
HRMS: calcd for C13H17NOCl 238.099867; found
238.099241; IR (neat): 3037, 2410, 1680, 1516, 1431,
1525, 1431, 1224, 752, 683 cm21
.
2-Chloro-3,3-diphenyl-1-pyrrolidin-1-yl-propenone (6ex).
Yellow crystalline, mp 1418C, yield 52%. 1H NMR
(300 MHz, CDCl3) d 1.67 (m, 4H, CH2, pyr), 3.23 (t, 2H,
J6.4 Hz, CH2, pyr), 3.33 (t, 2H, J6.4 Hz, CH2, pyr), 7.34
(m, 10H, Ar); 13C NMR (75 MHz, CDCl3) d 24.18 (CH2),
25.54 (CH2), 45.49 (CH2), 46.99 (CH2), 109.16 (C-2),
122.61 (C-3), 138.65, 140.76, 164.34 (CvO); MS-EI m/z
311 (M1, 100); HRMS: calcd for C19H19NOCl 312.115517;
found 312.115080; IR (neat): 3029, 2419, 1645, 1448, 1224,
1233, 932,778, 683 cm21
.
Z-3-Bromo-N-t-butyl-3-phenyl acrylamide (7by). Pale
yellow crystalline, mp 1228C, yield 62%. 1H NMR
(300 MHz, CDCl3) d 1.49 (s, 9H, CH3), 5.96 (br, 1H,
NH), 6.61 (s, 1H, vCH), 7.38 (m, 3H, Ar), 7.56 (m, 2H,
Ar); 13C NMR d 28.81 (CH3), 52.01 (Cq), 126.07 (C-2),
127.84 (C-o), 128.50 (C-m), 129.18 (C-3), 129.81 (C-p),
139.05 (C-i), 164.07 (CvO); MS-CI (NH3) m/z 282
(MH1, 100), 226(5), 202(10); HRMS: calcd for
C13H17NOBr 282.049350; found 282.048546; IR (neat):
778, 674 cm21
.
2-Bromo-3-methyl-but-2-enoic acid-t-butylamide (6gy).
Oil, yield 20%. H NMR d 1.39 (s, 9H, CH3), 1.94 (s, 3H,
3038, 2412, 1682, 1234, 686 cm21
.
1
CH3), 2.05 (s, 3H, CH3), 5.83 (br, 1H, NH); MI-CI (NH3)
m/z 234 (MH1, 100), 220(40), 173(20), 156(15); HRMS:
calcd for C9H17NOBr 234.049350; found 234.049548; IR
Z-3-Bromo-N-n-butyl-3-phenyl acrylamide (7bz). Oil,
1
yield 45%. H NMR d 0.96 (t, 3H, J7.3 Hz, CH3), 1.43
(m, 2H, CH2), 1.59 (m, 2H, CH2), 3.40 (m, 2H, CH2), 6.29
(br, 1H, NH), 6.79 (s, 1H, vCH), 7.39 (m, 3H, Ar), 7.57 (m,
2H, Ar); 13C NMR d 13.71 (CH3), 20.15 (CH2), 31.42
(CH2), 39.44 (CH2), 125.07 (C-2), 127.82 (C-o), 128.48
(C-m), 129.93 (C-p), 129.99 (C-3), 138.91 (C-i), 164.68
(CvO); MS-EI m/z 282 (MH1, 60), 241(50), 226(25),
211(100), 202(30), 160(45), 143(45); HRMS: calcd for
C13H17NOBr 282.049350; found 282.049005; IR (neat):
(neat): 3063, 3003, 2324, 1671, 1448, 1267, 906, 752 cm21
.
Z-3-Chloro-3-phenyl-1-pyrrolidin-1-yl-propenone (7ax).
Oil, yield 50%. 1H NMR (300 MHz, CDCl3) d 1.95 (m, 4H,
CH2, pyr), 3.56 (m, 4H, CH2, pyr), 6.62 (s, 1H, vCH), 7.41
(m, 3H, Ar), 7.65 (m, 2H, Ar); 13C NMR (75 MHz, CDCl3)
d 24.42 (CH2), 25.86 (CH2), 45.54 (CH2), 46.88 (CH2),
120.68 (C-2), 126.77 (C-o), 128.53 (C-m), 129.80 (C-p),
138.12 (C-3), 136.91 (C-i), 164.00 (CvO); MS-CI (i-Bu)
m/z 236 (MH1, 100); HRMS: calcd for C13H15NOCl
236.084217; found 236.084083; IR (neat): 3020, 2419,
3029, 2419, 1671, 1542, 1431, 1233, 949, 752, 692 cm21
.
Z-3-Bromo-1-pyrrolidin-1-yl-but-2-en-1-one (7dx). Oil,
yield 20%. H NMR (300 MHz, CDCl3) d 1.93 (m, 4H,
1
1645, 1456, 1233, 786, 657 cm21
.
CH2, pyr), 2.40 (s, 3H, CH3), 3.49 (m, 4H, CH2, pyr), 6.37
(s, 1H, vCH); 13C NMR (75 MHz, CDCl3) d 24.42 (CH2),
25.93 (CH2), 29.62 (CH3), 45.62 (CH2), 47.19 (CH2), 124.43
(C-2), 128.07 (C-3), 164.63 (CvO); MS-EI (NH3) m/z 220
(MH1, 100), 218(98), 174(15), 138(20); HRMS: calcd for
C8H13NOBr 218.018050; found 218.017064; IR (neat):
E-3-Chloro-3-phenyl-1-pyrrolidin-1-yl-propenone (7ax).
Oil, yield 10%. 1H NMR (300 MHz, CDCl3) d 1.72 (m, 4H,
CH2, pyr), 3.15 (t, 2H, J3.0 Hz, CH2, pyr), 3.38 (t, 2H,
J3.0 Hz, CH2, pyr), 6.44 (s, 1H, vCH), 7.38 (m, 3H, Ar),
7.54 (m, 2H, Ar); 13C NMR (75 MHz, CDCl3) d 24.13
(CH2), 25.67 (CH2), 45.49 (CH2), 46.94 (CH2), 122.97
(C-2), 128.10 and 128.19 (C-o and m), 129.82 (C-p),
136.41 (C-i), 139.90 (C-3), 163.89 (CvO); MS-CI (i-Bu)
m/z 236 (MH1, 100); HRMS: calcd for C13H15NOCl
236.084217; found 236.084235. IR (neat): 3020, 2420,
3037, 2419, 1628, 1542, 1439, 1233, 795, 674 cm21
.
Z-3-Chloro-but-2-enoic acid-N-t-butylamide (7dy). White
crystalline, 2408C (d), yield 66%. 1H NMR (300 MHz,
CDCl3) d 1.33 (s, 9H, CH3), 2.31 (d, J1.3 Hz), 5.80 (br,
1H, NH), 6.10 (1H, q, J1.3 Hz); 13C NMR d 28.78 (CH3),
51.75 (Cq), 125.64(C-3), 127.32 (C-2), 163.81 (CvO);
MS-CI (NH3), m/z 220 (MH1, 100); HRMS: calcd for
C8H15NOBr 220.033700; found 220.032540; IR (neat):
1668, 1460, 1233, 769, 648 cm21
.
Z-3-Chloro-N-t-butyl-3-phenyl-acrylamide (7ay). Pale
yellow crystals, mp 1268C, yield 28%. H NMR d 1.48 (s,
1
3025, 2422, 1640, 1438, 1234, 798, 684 cm21
.
9H, CH3), 6.15 (br, 1H, NH), 6.46 (s, 1H, vCH), 7.40 (m,
3H, Ar), 7.61 (m, 2H, Ar); 13C NMR d 28.82 (CH3), 51.91
(Cq), 122.41 (C-2), 126.96 (C-o), 128.57 (C-m), 130.03
(C-p), 137.17 (C-i), 137.71 (C-3), 163.53 (CvO); MS-CI
(NH3) m/z 238 (MH1,100), 204(58), 182(36), 148(9);
HRMS: calcd for C13H17NOCl 238.099867; found
238.099735; IR (neat): 3020, 2419, 1671, 1542, 1233,
3-Phenyl-1-pyrrolidin-1-yl-propynone (8bx). Oil, yield
25%. H NMR (300 MHz, CDCl3) d 1.98 (m, 4H, CH2,
1
pyr), 3.55 (t, 2H, J6.6 Hz, CH2, pyr) 3.73 (t, 2H,
J6.6 Hz, CH2, pyr), 7.40 (m, 3H, Ar), 7.56 (m, 2H, Ar);
13C NMR (75 MHz, CDCl3) d 24.72 (CH2), 25.38 (CH2),
45.38 (CH2), 48.16 (CH2), 82.60 (C-2), 88.77 (C-3), 120.61
(C-i), 128.48 (C-m), 129.94 (C-p), 132.40 (C-o), 152.75
(CvO); MS-CI (NH3) m/z 200 (MH1, 100), 170(10),
129(15); HRMS: calcd for C13H14NO 200.107539; found
200.106691.
769, 695 cm21
.
Z-3-Chloro-N-n-butyl-3-phenyl acrylamide (7az). Oil,
yield 25%. H NMR (600 MHz, CDCl3) d 0.97 (t, 3H,
1
J7.2 Hz, CH3), 1.43 (m, 2H, CH2), 1.59 (m, 2H, CH2),
3.42 (q, 2H, J7.2 Hz, CH2), 6.37 (br, 1H, NH), 6.53 (s,
1H, vCH), 7.41 (m, 3H, Ar), 7.63 (m, 2H, Ar); 13C NMR
(75 MHz, CDCl3) d 13.77 (CH3), 20.18 (CH2), 31.52 (CH2),
3-Methyl-pyrrolidin-1-yl-propynone (8dx). Oil, yield
22%. H NMR (300 MHz, CDCl3) d 1.92 (m, 4H, CH2,
pyr), 1.99 (s, 3H, CH3), 3.46 (t, 2H, J7.0 Hz, CH2, pyr),
1