The Journal of Organic Chemistry
Article
o-(Trifluoromethyl)phenyl Propiolate (60). Compound 60 (202
mg, 70%) (Rf = 0.6 in 1:2:3 v/v/v ethyl acetate/dichloromethane/
hexane) was prepared using General Procedure B and isolated as clear,
colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 8.0 Hz, 1H),
7.60 (m, 1H), 7.42 (m, 1H), 7.27 (d, J = 8.0 Hz, 1H), 3.12 (s, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 150.4, 147.1, 133.4, 127.3, 127.0,
124.2, 123.1 (q, JC−F = 32 Hz), 122.9 (q, JC−F = 272 Hz), 77.9, 73.7; IR
νmax (KBr): 3297, 2934, 2856, 2130, 1741, 1613, 1494, 1456, 1321,
1275, 1206, 1168, 1135, 1113, 1056 cm−1; MS (ESI, +ve) m/z: 277
(100%), 214 (M+•, 18), 186 (22). HRMS data could not be acquired on
this compound.
o-Bromophenyl Propiolate (61). Compound 61 (253 mg, 97%) (Rf
= 0.7 in chloroform) was prepared using General Procedure B and
isolated as clear, colorless oil. 1H NMR (400 MHz, CDCl3): δ 7.64 (dd,
J = 8.2 and 1.5 Hz, 1H), 7.36 (m, 1H), 7.18 (m, 2H), 3.11 (s, 1H);
13C{1H} NMR (100 MHz, CDCl3): δ 150.0, 147.4, 133.8, 128.8, 128.2,
123.6, 116.0, 77.6, 74.0; IR νmax (KBr): 3284, 2973, 2866, 2127, 1734,
1470, 1445, 1179, 1046, 1033 cm−1; MS (EI, 70 eV) m/z: 226 and 224
(M+•, both 13%), 198 and 196 (both 5), 174 and 172 (both 17), 145
(100); HRMS (ESI) m/z: [M + H]+ calcd for C9H679BrO2, 224.9546;
found, 224.9553.
(100 MHz, CDCl3): δ 150.2, 150.0, 130.8, 130.4, 126.3, 125.2, 117.6,
114.0, 78.1, 73.8; IR νmax (KBr): 3269, 2990, 2901, 2236, 2122, 1735,
1584, 1481, 1433, 1394, 1234, 1186, 1066, 1058 cm−1; MS (CI) m/z:
170 [(M − H)−, 27%], 143 (24), 115 (24), 53 (100); HRMS (ESI) m/
z: [M + H]+ calcd for C10H6NO2, 172.0393; found, 172.0397. This
compound was subjected to single-crystal X-ray analysis. Details of this
are presented in the Experimental Section and the Supporting
m-(Propioloyloxy)phenyl Benzoate (67). Compound 67 (105 mg,
42%) (Rf = 0.4 in 1:4 v/v diethyl ether/hexane) was prepared using
General Procedure B and isolated as a colorless, crystalline solid, mp
64−65 °C. 1H NMR (400 MHz, CDCl3): δ 8.20 (dd, J = 8.2 and 1.0 Hz,
2H), 7.65 (m, 1H), 7.55−7.35 (complex m, 3H), 7.20−7.00 (complex
m, 3H), 3.11 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 164.7,
151.6, 150.6, 150.3, 133.9, 130.3, 130.1, 129.3, 128.7, 120.1, 118.8,
115.5, 77.3, 74.2; IR νmax (KBr): 3262, 2990, 2901, 2122, 1734, 1699,
1483, 1452, 1262, 1235, 1189, 1124, 1079, 1061, 1025 cm−1; MS (EI,
70 eV) m/z: 266 (M+•, 16%), 105 (100); HRMS (ESI) m/z: [M + Na]+
calcd for C16H10O4Na, 289.0471; found, 289.0460. [M + H]+ calcd for
C16H11O4, 267.0652; found, 267.0640.
m-(Pivaloyloxy)phenyl Propiolate (68). Compound 68 (102 mg,
40%) (Rf = 0.5 in 1:4 v/v ethyl acetate/hexane) was prepared using
General Procedure B and isolated as clear, colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.38 (t, J = 8.2 Hz, 1H), 7.08−6.85 (complex m, 3H),
3.10 (s, 1H), 1.35 (s, 9H); 13C{1H} NMR (100 MHz, CDCl3): δ 176.6,
151.8, 150.5, 150.3, 129.9, 119.8, 118.5, 115.2, 77.3, 74.1, 39.2, 27.1; IR
νmax (KBr): 3260, 2975, 2875, 2123, 1737, 1599, 1481, 1398, 1368,
1272, 1241, 1188, 1124, 1107, 1032, 1005 cm−1; MS (EI, 70 eV) m/z:
246 (M+•, 16%), 162 (33), 134 (67), 57 (100); HRMS (ESI) m/z: [M
+ Na]+ calcd for C14H14O4Na, 269.0784; found, 269.0789. [M + H]+
calcd for C14H15O4, 247.0965; found, 247.0969.
m-(Benzyloxy)phenyl Propiolate (69). Compound 69 (196 mg,
78%) (Rf = 0.6 in 1:4 v/v diethyl ether/hexane) was prepared using
General Procedure B and isolated as clear, colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.45−7.30 (complex m, 6H), 6.90 (m, 1H), 6.80 (m,
2H), 5.06 (s, 2H), 3.06 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ
159.9, 150.8, 136.6, 130.2, 128.8, 128.3, 127.6, 113.8, 113.4, 108.4, 76.9,
74.4, 70.5 (one signal obscured or overlapping); IR νmax (KBr): 3271,
2990, 2901, 2123, 1732, 1607, 1588, 1486, 1454, 1394, 1383, 1287,
1257, 1192, 1129, 1077, 1066, 1044, 1027 cm−1; MS (EI, 70 eV) m/z:
252 (M+•, 10%), 91 (100); HRMS (ESI) m/z: [M + H]+ calcd for
C16H13O3, 253.0859; found, 253.0854.
o-Chlorophenyl Propiolate (62). Compound 62 (530 mg, 87%) (Rf
= 0.3 in 1:9 v/v diethyl ether/hexane) was prepared using General
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Procedure B and isolated as clear, colorless oil. H NMR (400 MHz,
CDCl3): δ 7.59 (d, J = 7.6 Hz, 1H), 7.43 (m, 1H), 7.36 (m, 1H), 7.32
(d, J = 7.6 Hz, 1H), 3.24 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ
150.0, 146.0, 130.7, 128.1, 128.0, 126.8, 123.5, 77.6, 73.8; IR νmax
(KBr): 3286, 2128, 1738, 1583, 1474, 1448, 1262, 1181, 1062 cm−1;
MS (EI, 70 eV) m/z: 182 and 180 (M+•, 8 and 25%), 145 (100); HRMS
(EI) m/z: M+• calcd for C9H537ClO2, 181.9949; found, 181.9942. M+•
calcd for C9H535ClO2, 179.9978; found, 179.9972.
m-Methoxyphenyl Propiolate (63). Compound 6344 (280 mg,
99%) (Rf = 0.6 in 1:4 v/v diethyl ether/hexane) was prepared using
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General Procedure B and isolated as clear, yellow oil. H NMR (400
MHz, CDCl3): δ 7.30 (t, J = 8.2 Hz, 1H), 6.83 (dd, J = 8.2 and 2.4 Hz,
1H), 6.76 (dd, J = 8.2 and 2.4 Hz, 1H), 6.71 (broad s, 1H), 3.79 (s, 3H),
3.11 (s, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 160.6, 150.9, 150.7,
130.1, 113.4, 112.5, 107.3, 77.1, 74.2, 55.5; IR νmax (KBr): 3267, 2120,
1727, 1609, 1588, 1488, 1468, 1453, 1439, 1315, 1286, 1263, 1183,
1128, 1077, 1037, 997, 945, 906 cm−1; MS (EI, 70 eV) m/z: 176 (M+•,
80%), 124 (100), 123 (58); HRMS (EI) m/z: M+• calcd for C10H8O3,
176.0473; found, 176.0475.
m-Acetylphenyl Propiolate (70). Compound 70 (219 mg, 79%) (Rf
= 0.2 in 1:4 v/v ethyl acetate/hexane) was prepared using General
Procedure B and isolated as a colorless, crystalline solid, mp 61−62 °C.
1H NMR (400 MHz, CDCl3): δ 7.86 (d, J = 7.9 Hz, 1H), 7.73 (m, 1H),
7.51 (t, J = 7.9 Hz, 1H), 7.36 (dm, J = 7.9 Hz, 1H), 3.11 (s, 1H), 2.60 (s,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 196.7, 150.8, 150.2, 138.9,
130.0, 126.6, 126.1, 121.3, 77.4, 74.1, 26.8; IR νmax (KBr): 3258, 2924,
2123, 1733, 1686, 1586, 1483, 1360, 1263, 1190 cm−1; MS (EI, 70 eV)
m/z: 188 (M+•, 25%), 187 (73), 173 (49), 160 (38), 145 (66), 121
(56), 53 (100); HRMS (ESI) m/z: [M + Na]+ calcd for C11H8O3Na,
211.0366; found, 211.0369. [M + H]+ calcd for C11H9O3, 189.0546;
found, 189.0551.
m-[(tert-Butyldimethylsilyl)oxy]phenyl Propiolate (64). Com-
pound 64 (196 mg, 80%) (Rf = 0.3 in 1:2 v/v chloroform/hexane)
was prepared using General Procedure B and isolated as clear, yellow
oil. 1H NMR (400 MHz, CDCl3): δ 7.23 (t, J = 8.2 Hz, 1H), 6.76 (m,
2H), 6.65 (t, J = 2.3 Hz, 1H), 3.05 (s, 1H), 0.99 (s, 9H), 0.21 (s, 6H);
13C{1H} NMR (100 MHz, CDCl3): δ 156.8, 150.9, 150.7, 130.0, 118.5,
114.2, 113.6, 76.8, 74.5, 25.8, 18.3, −4.3; IR νmax (KBr): 3272, 2957,
2931, 2860, 2126, 1767, 1735, 1604, 1587, 1485, 1282, 1258, 1182,
1130 cm−1; MS (EI, 70 eV) m/z: 276 (M+•, 39%), 219 (54), 163 (100);
HRMS (ESI) m/z: [M + Na]+ calcd for C15H20O3SiNa, 299.1074;
found, 299.1063. [M + H]+ calcd for C15H21O3Si, 277.1254; found,
277.1250.
m-Fluorophenyl Propiolate (71). Compound 71 (575 mg, 79%) (Rf
= 0.8 in chloroform) was prepared using General Procedure B and
isolated as clear, yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.37 (m,
1H), 7.05−6.85 (complex m, 3H), 3.09 (s, 1H); 13C{1H} NMR (100
MHz, CDCl3): δ 163.0 (d, JC−F = 248 Hz), 150.7 (d, JC−F = 11 Hz),
150.5, 130.6 (d, JC−F = 9 Hz), 117.2 (d, JC−F = 4 Hz), 113.8 (d, JC−F = 21
Hz), 109.6 (d, JC−F = 25 Hz), 77.3, 74.1; IR νmax (KBr): 3291, 2981,
2126, 1735, 1603, 1486, 1450, 1254, 1187, 1117, 1073 cm−1; MS (EI,
70 eV) m/z: 164 (M+•, 28%), 136 (52). HRMS data could not be
acquired on this compound.
m-Chlorophenyl Propiolate (72). Compound 72 (670 mg, 95%) (Rf
= 0.7 in chloroform) was prepared using General Procedure B and
isolated as clear, yellow oil. 1H NMR (400 MHz, CDCl3): δ 7.36 (t, J =
8.1 Hz, 1H), 7.30 (m, 1H), 7.22 (broad s, 1H), 7.09 (m, 1H), 3.12 (s,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 150.5, 150.3, 135.1, 130.5,
127.1, 122.1, 119.8, 77.4, 74.1; IR νmax (KBr): 3288, 2128, 1734, 1590,
m-Acetoxyphenyl Propiolate (65). Compound 65 (120 mg, 45%)
(Rf = 0.6 in 1:2:3 v/v/v ethyl acetate/dichloromethane/hexane) was
prepared using General Procedure B and isolated as clear, yellow oil. 1H
NMR (400 MHz, CDCl3): δ 7.38 (t, J = 8.2 Hz, 1H), 7.05−6.95
(complex m, 3H), 3.11 (s, 1H), 2.26 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 168.9, 151.3, 150.5, 150.2, 129.9, 119.9, 118.7, 115.2,
77.4, 74.0, 21.0; IR νmax (KBr): 3262, 2990, 2901, 2123, 1767, 1734,
1601, 1485, 1371, 1182, 1121 cm−1; MS (EI, 70 eV) m/z: 204 (M+•,
25%), 162 (89), 134 (100); HRMS (ESI) m/z: [M + Na]+ calcd for
C11H8O4Na, 227.0315; found, 227.0305. [M + H]+ calcd for C11H9O4,
205.0495; found, 205.0488.
m-Cyanophenyl Propiolate (66). Compound 66 (202 mg, 70%) (Rf
= 0.6 in 1:2:3 v/v/v ethyl acetate/dichloromethane/hexane) was
prepared using General Procedure B and isolated as a colorless,
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crystalline solid, mp 112−113 °C. H NMR (400 MHz, CDCl3): δ
7.65−48 (complex m, 3H), 7.42 (m, 1H), 3.15 (s, 1H); 13C{1H} NMR
J
J. Org. Chem. XXXX, XXX, XXX−XXX