I
S. Chong et al.
Paper
Synthesis
HRMS (ESI): m/z calcd for C8H6Cl2O4Na [M + Na]+: 258.9535; found:
2-Benzoyl-2-chlorocycloheptanone (4cd)
258.9537.
Yield: 61 mg (94%); yellow oil.
IR (neat): 3381, 2931, 1732, 1693, 1596, 1448, 1236, 1126, 941, 865,
759, 698 cm–1
1H NMR (600 MHz, CDCl3): δ = 7.93 (d, J = 7.8 Hz, 2 H), 7.54 (t, J = 7.8
Hz, 1 H), 7.42 (t, J = 7.8 Hz, 2 H), 3.02–3.00 (m, 1 H), 2.62–2.57 (m, 1
H), 2.49–2.44 (m, 1 H), 2.42–2.38 (m, 1 H) 1.96–1.82 (m, 4 H), 1.78–
1.71 (m, 1 H), 1.44–1.40 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 205.3, 191.7, 133.6, 133.2, 130.1,
128.3, 79.3, 40.2, 37.3, 27.7, 24.2, 23.8.
HRMS (ESI): m/z calcd for C14H16ClO2 [M + H]+: 251.0833; found:
251.0836.
Methyl 2-Chloro-3-cyclohexyl-3-oxopropanoate (4bl)
Yield: 41 mg (72%); yellow oil.
.
IR (neat): 3463, 2945, 2866, 1775, 1734, 1445, 1246, 1005, 858, 843
cm–1
.
1H NMR (400 MHz, CDCl3): δ (3:1 tautomer ratio) = 12.46* (d, J = 1.2
Hz, 1 H), 4.93 (s, 1 H), 3.83 (s, 3 H), 2.86–2.79 (m, 1 H), 1.91–1.79 (m, 4
H), 1.75–1.68* (m, 4 H), 1.54–1.17 (m, 6 H); asterisk denotes minor
tautomer peaks.
13C NMR (100 MHz, CDCl3): δ (3:1 tautomer ratio) = 201.5, 165.6,
59.4, 53.6, 52.7*, 47.6, 41.0*, 28.8, 28.6, 28.4*, 25.8*, 25.7*, 25.5, 25.4,
25.3; asterisk denotes minor tautomer peaks.
2,2-Dichloro-1,3-diphenylpropane-1,3-dione (4ce′)
Yield: 68 mg (90%); yellow oil.
HRMS (ESI): m/z calcd for C10H15ClNaO3 [M + Na]+: 241.0602; found:
241.0598.
IR (neat): 3396, 3071, 1699, 1595, 1442, 1238, 1207, 1180, 1000, 821,
685, 636 cm–1
.
2-Chloro-2-(4-methoxybenzoyl)-2,3-dihydro-1H-inden-1-one
(4ca)
1H NMR (600 MHz, CDCl3): δ = 7.97 (d, J = 7.8 Hz, 4 H), 7.54 (t, J = 7.8
Hz, 2 H), 7.40 (t, J = 7.8 Hz, 4 H).
13C NMR (150 MHz, CDCl3): δ = 185.3, 134.2, 131.5, 130.4, 128.7, 87.5.
HRMS (ESI): m/z calcd for C15H10Cl2O2Na [M + Na]+: 314.9950; found:
314.9954.
Yield: 74 mg (95%); white solid; mp 98–99 °C.
IR (neat): 3064, 2930, 1744, 1600, 1473, 1265, 1177, 1022, 858, 757,
594 cm–1
.
1H NMR (600 MHz, CDCl3): δ = 8.16 (d, J = 9.0 Hz, 2 H), 7.83 (d, J = 7.8
Hz, 1 H), 7.68 (t, J = 7.8 Hz, 1 H), 7.49 (d, J = 7.8 Hz, 1 H), 7.45 (t, J = 7.8
Hz, 1 H), 6.92 (d, J = 9.0 Hz, 2 H), 4.37 (d, J = 16.8 Hz, 1 H), 3.86 (s, 3 H),
3.58 (d, J = 17.4 Hz, 1 H).
2,2-Dichloro-1-phenyl-3-(p-tolyl)propane-1,3-dione (4cf′)
Yield: 73 mg (92%); yellow oil.
13C NMR (150 MHz, CDCl3): δ = 196.3, 189.7, 163.8, 150.3, 136.3,
133.1, 133.0, 128.5, 126.1, 125.9, 125.7, 113.5, 73.6, 55.5, 43.3.
IR (neat): 3727, 2918, 1695, 1604, 1442, 1244, 1192, 1000, 838, 698
cm–1
.
1H NMR (600 MHz, CDCl3): δ = 7.96 (d, J = 7.2 Hz, 2 H), 7.87 (d, J = 8.4
Hz, 2 H), 7.53 (t, J = 7.2 Hz, 1 H), 7.39 (t, J = 8.4 Hz, 2 H), 7.19 (d, J = 8.4
Hz, 2 H), 2.36 (s, 3 H).
HRMS (ESI): m/z calcd for C17H14ClO3 [M + H]+: 301.0626; found:
301.0623.
13C NMR (150 MHz, CDCl3): δ = 185.3, 184.9, 145.5, 134.1, 131.5,
130.6, 130.4, 129.4, 128.8, 128.6, 87.9, 21.7.
HRMS (ESI): m/z calcd for C16H12Cl2O2Na [M + Na]+: 329.0107; found:
329.0109.
2-Benzoyl-2-chloro-3,4-dihydronaphthalen-1(2H)-one (4cb)
Yield: 70 mg (94%); white solid; mp 93–95 °C.
IR (neat): 3410, 2935, 1681, 1656, 1595, 1447, 1296, 1221, 1170,
1044, 809, 698 cm–1
.
1H NMR (600 MHz, CDCl3): δ = 8.05 (d, J = 7.8 Hz, 1 H), 7.96 (d, J = 7.8
Hz, 2 H), 7.53 (q, J = 7.8 Hz, 2 H), 7.41 (t, J = 7.8 Hz, 2 H), 7.35 (t, J = 7.8
Hz, 1 H), 7.27 (d, J = 8.4 Hz, 1 H), 3.32–3.27 (m, 1 H), 3.21–3.10 (m, 2
H), 2.60–2.56 (m, 1 H).
2,2-Dichloro-4,4-dimethyl-1-phenylpentane-1,3-dione (4cg′)
Yield: 63 mg (89%); yellow oil.
IR (neat): 3429, 2974, 2913, 1718, 1706, 1597, 1457, 1226, 1064, 835,
681 cm–1
.
13C NMR (150 MHz, CDCl3): δ = 192.8, 190.2, 142.5, 134.4, 134.3,
1H NMR (600 MHz, CDCl3): δ = 8.01 (d, J = 7.8 Hz, 2 H), 7.62 (t, J = 7.2
Hz, 1 H), 7.49 (t, J = 7.8 Hz, 2 H), 1.26 (s, 9 H).
13C NMR (150 MHz, CDCl3): δ = 199.4, 185.0, 134.3, 131.8, 130.5,
133.1, 130.7, 130.1, 128.8, 128.7, 128.2, 127.3, 75.0, 35.7, 26.1.
HRMS (ESI): m/z calcd for C17H14ClO2 [M + H]+: 285.0677; found:
285.0676.
128.8, 88.5, 45.4, 29.1.
HRMS (ESI): m/z calcd for C13H18Cl2NO2 [M + NH4]+: 290.0709; found:
2-Benzoyl-2-chlorocyclohexanone (4cc)
Yield: 58 mg (95%); yellow oil.
290.0710.
IR (neat): 3462, 2949, 1732, 1685, 1584, 1448, 1244, 1122, 883, 683
cm–1
.
Modified Chlorination of 1,3-Dicarbonyl Compounds 1bc, 1be, 1bi,
1bj and 1ce–1ci; General Procedure
1H NMR (600 MHz, CDCl3): δ = 7.97 (d, J = 7.2 Hz, 2 H), 7.54 (t, J = 7.2
Hz, 1 H), 7.42 (t, J = 7.8 Hz, 2 H), 3.07–3.04 (m, 1 H), 2.81–2.78 (m, 1
H), 2.24–2.19 (m, 1 H), 2.14–2.09 (m, 1 H), 2.01–1.98 (m, 1 H), 1.96–
1.83 (m, 3 H).
13C NMR (100 MHz, CDCl3): δ = 203.4, 190.7, 134.2, 133.6, 130.0,
128.5, 77.1, 41.3, 41.1, 28.3, 22.9.
To a solution of a 1,3-dicarbonyl compound (0.26 mmol, 1 equiv) in
MeCN (3 mL) was added TMSCl (0.26 mmol, 1 equiv). After the reac-
tion mixture was stirred at r.t. for 10 min, PhI(OAc)2 (0.26 mmol, 1
equiv) was added. The mixture was stirred at r.t. and monitored by
TLC. After the starting material was no longer detected (TLC, 5–60
min), the reaction mixture was poured into ice–water (10 mL). The
mixture was extracted with CH2Cl2 and the combined organic phases
HRMS (ESI): m/z calcd for C13H14ClO2 [M + H]+: 237.0677; found:
237.0674.
© Georg Thieme Verlag Stuttgart · New York — Synthesis 2016, 48, A–L