Merkley and Warkentin
947
1
19%, H NMR (200 MHz, C6D6) δ: 4.66 (6H), 5.46 (s, 1H),
159 (5), 108 (21), 91 (100), 65 (10); MS (CI, NH3) m/z:
((M + NH4)+, 5), 159 (5), 108 (21), 91 (100); HRMS calcu-
lated for C16H13O2F3: 294.0867, found: 294.0872.
7.02–7.20 (overlap with other signals); GC/MS (EI), m/z:
197 (9), 181 (10), 107 (10), 91 (100). Benzyl formate, 22%,
1H NMR (200 MHz, C6D6) δ: 4.91 (2H), 7.02–7.20 (m,
overlap with other signals), 7.60 (1H).
8f: pale yellow solid, mp 80–84°C, lit. (25) mp 90–92°C; 1H
NMR (300 MHz, CDCl3) δ: 3.76 (s, 2H), 5.14 (s, 2H), 7.29–
7.35 (m, 5H), 7.43 (d, 3J = 8.7 Hz, 2H), 8.16 (d, 3J = 6.6 Hz,
Synthesis of benzyl arylacetate reference compounds
The required arylacetyl chloride 8a, b, d–f (0.061 g,
6.4 mmol) was dissolved in benzene (5 mL) and added
slowly to a solution of benzyl alcohol (0.16 g, 0.8 mmol) in
pyridine (0.2 mL, 2.3 mmol) which was cooled in an ice
bath. After addition the stirring was continued for one hour.
The benzene layer was washed twice with water (5 mL), and
dried with magnesium sulphate. After filtration and evapora-
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2H); H NMR (300 MHz, C6D6) δ: 3.03 (s, 2H), 4.27 (s,
3
2H), 4.86 (s, 2H), 6.66 (d, J = 8.7 Hz, 2H), 6.93–7.07 (m,
3
5H), 7.69 (d, J = 8.7 Hz, 2H); 13C NMR (75 MHz, CDCl3)
δ: 40.96, 67.14, 123.73, 126.97, 128.61, 130.29, 135.35,
141.12, 169.98; MS (EI) m/z: 271 (M+, 8), 136 (8), 91 (100),
65 (9); MS (CI, NH3) m/z: 289 ((M + NH4)+, 6), 271 (M+, 3),
135 (10), 108 (9), 91 (100); HRMS calculated for
C15H13NO4: 271.0845; found: 271.0827.
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tion of the benzene, the H NMR spectrum in C6D6, refer-
enced to p-xylene at 2.10 ppm, was recorded.
Synthesis of 4-substituted-benzyl phenylacetates (7a–f)
A solution of phenylacetyl chloride (0.51 g, 3.0 mmol) in
benzene (5 mL) was added slowly to a cooled solution of the
appropriate arylmethanol (0.4 g, 3.0 mmol) in pyridine
(0.5 mL, 9.0 mmol). After one hour the benzene solution
was washed twice with water and dried with magnesium sul-
phate. Benzene was removed with a rotary evaporator. Some
of the esters were purified by radial chromatography
(Chromatotron, 10% EtOAc in hexanes).
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8c: (20) pale yellow oil; H NMR (200 MHz, CDCl3) δ:
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3.60 (s, 2H), 5.03 (s, 2H), 7.08–7.29 (m, 10H); H NMR
(300 MHz, C6D6) δ: 3.40 (s, 2H), 4.97 (s, 2H), 7.09–7.22
(m, 10H); 13C NMR (50 MHz, CDCl3) δ: 41.33, 66.61,
128.18, 128.54, 129.27, 135.83, 171.39 (C=O); 13C NMR
(75 MHz, C6D6) δ: 41.35, 66.42, 128.2, 128.3, 128.7, 129.6,
134.5, 170.92 (C=O). GC/MS (EI) m/z: 226 (M+, 1), 91
(100), 65 (10).
1
7a: (21,22) Oil; H NMR (300 MHz, CDCl3) δ: 3.61 (s,
1
8a: (21–23) Oil; H NMR (200 MHz, CDCl3) δ: 3.59 (s,
2H), 3.77 (s, 2H), 5.04 (s, 2H), 6.83–6.87 (m, 2H), 7.20–
7.28 (m, 7H); H NMR (300 MHz, C6D6) δ: 3.20 (s, 3H),
3
2H), 3.78 (s, 3H), 5.10 (s, 2H), 6.84 (d, J = 8.6 Hz, 2H),
7.16–7.30 (m, 7H); H NMR (300 MHz, C6D6) δ: 3.23 (s,
1
1
3
3.32 (s, 2H), 4.89 (s, 2H), 6.65 (d, J = 8.7 Hz, 2H), 7.00–
3
3H), 3.32 (s, 2H), 4.92 (s, 2H), 6.68 (d, J = 8.7 Hz, 2H),
7.10 (m, 7H); 13C NMR (75 MHz, CDCl3) δ: 41.28, 55.17,
66.37, 113.56 (C2), 126.97, 127.93, 128.46, 129.19, 129.89,
133.90, 159.55, 171.39 (C=O); MS (EI) m/z: 256 (M+, 21),
121 (100), 91 (37); MS (CI, NH3) m/z: 256 (M+, 8), 138 (8),
121 (100).
7.00–7.08 (m, 7H); 13C NMR (50 MHz, CDCl3) δ: 40.43,
55.26, 66.55, 114.00, 128.10, 128.51, 130.30, 132.29,
172.93 (C=O).
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8b: (24) Oil; H NMR (200 MHz, CDCl3) δ: 2.33 (s, 3H),
3.63 (s, 2H), 5.13 (s, 2H), 7.10–1.33 (m, 9H); H NMR
1
1
7b: (24) Oil; H NMR (300 MHz, CDCl3) δ: 2.34 (s, 3H),
6.65 (s, 2H), 5.08 (s, 2H), 7.13–7.31 (m, 9H); H NMR
(300 MHz, C6D6) δ: 2.02 (s, 3H), 3.34 (s, 2H), 4.90 (s, 2H),
6.87–7.12 (m, 9H); 13C NMR (50 MHz, CDCl3) δ: 21.03,
40.91, 66.53, 128.09, 128.49, 129.24, 130.83, 135.92,
136.70, 171.57 (C=O); MS (EI) m/z: 240 (M+, 25), 193 (13),
181 (16), 105 (100), 91 (76); MS (CI, NH3) m/z: 258 ((M +
NH4)+, 13), 241 ((M + H)+, 5), 216 (79), 108 (51), 91 (100).
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(300 MHz, C6D6) δ: 2.00 (s, 3H), 3.32 (s, 2H), 4.91 (s, 2H)
6.85–7.12 (m, 9H); 13C NMR (75 MHz, CDCl3) δ: 21.16,
41.36, 66.57, 127.06, 128.27, 128.55, 129.21, 129.27,
132.89, 133.95, 138.03, 171.41(C=O); MS (EI) m/z: 240
(M+, 16), 209 (5), 105 (100), 91 (46), 65 (12); MS (CI,
NH3) m/z: ((M + NH4)+, 26), 154 (16), 105 (100), 91 (34),
65 (5).
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8d: (23) oil; H NMR (300 MHz, CDCl3) δ: 3.60 (s, 2H),
5.10 (s, 2H), 7.16–7.32 (m, 9H); H NMR (300 MHz, C6D6)
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δ: 3.13 (s, 2H), 4.88 (s, 2H), 6.76 (d, 3J = 8.4 Hz, 2H), 6.79–
7.15 (m, 7H); 13C NMR (75 MHz, CDCl3) δ: 40.52, 66.69,
128.09, 128.24, 128.49, 130.60, 132.25, 133.04, 170.91
(C=O); MS (EI) m/z: 260 (M+, 10), 181 (10), 127 (24), 125
(60), 91 (100), 65 (16), 63 (10); MS (CI, NH3) m/z: 278
((M + NH4)+, 55), 125 (44), 108 (49), 91 (100), 80 (42);
HRMS calculated for C15H13O2Cl: 260.0604, found:
260.0603.
7d: Oil; 1H NMR (300 MHz, CDCl3) δ: 3.63(s, 2H), 5.05 (s,
2H), 7.17–7.29 (m, 9H); H NMR (300 MHz, C6D6) δ: 3.29
1
3
(s, 2H), 4.69 (s, 2H), 6.73 (d, J = 8.4 Hz, 2H), 6.93–7.12
(m, 7H); 13C NMR (75 MHz, CDCl3) δ: 41.23, 65.64,
127.10, 128.52, 128.62, 129.17, 133.67, 134.29 (C2), 171.19
(C=O); MS (EI) m/z: 260 (M+, 8), 125 (87), 91 (100), 65
(18), 51 (5); MS (CI, NH3) m/z: 278 ((M + NH4)+, 55), 260
(M+, 5), 184 (42), 125 (100), 108 (19), 91 (39); HRMS cal-
culated for C15H13O2Cl: 260.0604 found: 260.0603.
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8e: Oil; H NMR (300 MHz, CDCl3) δ: 3.71 (s, 2H), 5.13
(s, 2H), 7.28–7.35 (m, 5H) 7.38 (d, J = 8.1 Hz, 2H), 7.56
(d, J = 8.1 Hz, 2H); H NMR (300 MHz, C6D6) δ: 3.13 (s,
3
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7e: Yellow solid, H NMR (300 MHz, CDCl3) δ: 3.66 (s,
2H), 5.14 (s, 2H), 7.22–7.29 (m, 5H), 7.35 (d, J = 8.0 Hz,
2H), 7.55 (d, J = 8.1 Hz, 2H); H NMR (300 MHz, C6D6)
δ: 3.31 (s, 2H), 4.69 (s, 2H), 6.80 (d, 3J = 8.0 Hz, 2H), 7.00–
7.12 (m, 5H), 7.20 (d, 3J = 8.1 Hz, 2H); 13C NMR (75 MHz,
CDCl3) δ: 4.21, 65.45, 125.40, 127.17, 127.87, 128.53,
129.17, 133.53 (C2), 139.76, 171.06 (C=O); 19F NMR
3
1
3
3
3
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2H), 4.88 (s, 2H), 6.76 (d, J = 8.0 Hz, 2H), 6.79–7.15 (m,
7H); 13C NMR (75 MHz, CDCl3) δ: 29.69, 66.95, 125.48,
125.55, 128.24, 128.38, 128.54, 128.61, 129.37, 129.71,
135.61, 137.84, 170.55 (C=O); 19F NMR (282 MHz, CDCl3,
ref. CCl3F) δ: –62.82 (s); MS (EI) m/z: 294 (M+, 3), 181 (8),
© 2000 NRC Canada