Page 23 of 63
The Journal of Organic Chemistry
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Dimethyl 2-[(2E)-3-(4-fluorophenyl)-2-methylprop-2-en-1-ylidene]malonate (4j). General
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Procedure A; yellow solid (1.09 g, 78% yield); R
f
= 0.46 (petroleum ether : diethyl ether; 2:1);
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mp 82–83 °C; H NMR (500 MHz, CDCl ): δ 1.99 (d, J = 0.8 Hz, 3H, CH ), 3.82 (s, 3H,
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3
3
CH
3
3
O), 3.86 (s, 3H, CH O), 6.92 (br.s, 1H, CH=), 7.07 (dd, JHF = 8.7 Hz, J = 8.5 Hz, 2H, CH,
0
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Ar), 7.32 (dd, J = 8.5 Hz, JHF = 5.4 Hz, 2H, CH, Ar), 7.45 (q, J = 0.8 Hz, 1H, CH=); C NMR
2
(126 MHz, CDCl
3
): δ 14.5 (CH
3
), 52.45 (CH
3
O), 52.52 (CH
3
O), 115.5 (d, JCF = 22 Hz, 2×CH,
3
4
Ar), 123.6 (C), 131.4 (d, J = 8 Hz, 2×CH, Ar), 132.2 ( J = 3 Hz, C, Ar), 132.6 (C), 140.9
CF
CF
1
(
CH=), 147.4 (CH=), 162.4 (d, JCF = 249 Hz, C, Ar), 165.0 (CO
2
Me), 167.4 (CO
2
Me); IR (KBr)
ꢀ1
+
1727, 1691, 1264 cm ; LCꢀMS m/z 279 [M+H] . Anal. Calcd for C15H15FO : C, 64.74; H, 5.43.
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Found: C, 64.63; H, 5.75.
Dimethyl
2-[2-benzyl-3-(thiophen-2-yl)prop-2-en-1-ylidene]malonate
(4k).
General
Procedure A; yellow solid (1.22 g, 71% yields), isolated as mixture of isomers, A:B = 59:41; R
f
1
= 0.60 (petroleum ether : ethyl acetate 4:1); mp 35–38 °C; H NMR (500 MHz, CDCl
3
): 3.43 (s,
3
H, CH O, A), 3.68 (s, 2H, CH Ph, B), 3.77 (s, 3H, CH O, B), 3.79 (s, 3H, CH O, A), 3.85 (s,
3
2
3
3
3
H, CH
3
O, B), 4.08 (s, 2H, CH
2
Ph, A), 6.65 (br.s, 1H, CH=, B), 7.02–7.41 (m, 9H+8H, CH, A,
4
13
B), 7.54 (d, J = 0.7 Hz, 1H, CH= A), 8.04 (br.s, 1H, CH=, B); C NMR (126 MHz, CDCl
3
): δ
O, A),
26.4 (CH, A), 126.6 (CH, B), 127.57 (CH, A), 126.62 (CH, B), 128.0 (2×CH, A), 128.4 (CH,
2 2 3 3 3 3
34.8 (CH Ph, A), 40.6 (CH Ph, B), 52.1 (CH O, A), 52.5 (CH O+CH O, A, B), 52.7 (CH
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B), 128.5 (2×CH, A), 128.6 (2×CH, B), 129.2 (CH+2×CH, A, B), 130.0 (CH, B), 130.6 (CH, B),
131.4 (CH, A), 131.6 (C, A), 131.9 (C, B), 132.8 (C, A), 134.7 (C, B), 135.3 (CH, A), 136.8 (C,
2
A), 138.3 (C, B), 138.6 (C, A), 139.2 (C, B), 142.3 (CH, B), 146.3 (CH, A), 164.9 (CO Me, B),
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65.0 (CO
2
Me, A), 166.6 (CO
2
Me, B), 167.0 (CO
2
Me, A); IR (film) 1732, 1601 cm ; HRMS
+
(
ESI/QꢀTOF) m/z: [M + H] Calcd for C H O S 343.0999; Found 343.1001. Anal. Calcd for
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18
4
C
19 18 4
H O S: C, 66.65; H, 5.30. Found: C, 66.47; H, 5.31.
Dimethyl 2-[(2E)-3-(2-nitrophenyl)prop-2-en-1-ylidene]malonate (4l). General Procedure A;
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redꢀorange solid (1.08 g, 74% yield); mp 114–115 °C (lit. 114 °C ); H NMR (500 MHz,
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