3
12
C. Behloul et al.
PAPER
1
3
chloride (10.0 mmol) was added over ca. 5 min. After stirring for 1
h at the same temperature, the crude reaction mixture was adsorbed
onto basic alumina, transferred to a short column of basic alumina
and eluted with hexane. Evaporation of the solvent (15 Torr) afford-
ed the expected pure esters, thioesters and amides 1.
C NMR: d = 16.1 (2 C, CH Ph), 20.7 (CH Ph), 27.3 [3 C,
3
3
C(CH ) ], 39.2 [C(CH ) ], 129.1 (2 C, Ph), 129.6 (2 C, Ph), 134.9
3
(Ph), 145.9 (Ph), 176.1 (C=O).
3
3 3
+
MS: m/z (%) = 220 (M , 31), 137 (11), 136 (100), 135 (10), 121
(
25), 91 (15), 57 (38).
2
0
1-Decyl Pivalate (1a)
Colourless oil; yield: 66%; R 0.90 (hexane–EtOAc, 9:1).
9-(2,2-Dimethylpropanoyloxy)nonyl Pivalate (1f)
Colourless oil; yield: 30%; R 0.67 (hexane–EtOAc, 9:1).
f
f
–
IR (neat): 1732 (C=O), 1156 (CO) cm .
1
–1
IR (neat): 1730 (C=O), 1157 (CO) cm .
1
H NMR: d = 0.88 (t, 3 H, J = 6.6 Hz, CH CH ), 1.20 [s, 9 H,
2
1
3
H NMR: d = 1.20 (s, 18 H, CH ), 1.25–1.42 (m, 14 H, CH ), 4.05
3
2
C(CH ) ], 1.22–1.41 (m, 14 H, CH ), 1.55–1.68 (m, 2 H, CH CO),
3
3
2
2
(
t, 4 H, J = 6.7 Hz, CH O).
2
4
.04 (t, 2 H, J = 6.6 Hz, CH O).
2
1
3
C NMR: d = 23.8 (CH ), 25.9 (2 C, CH ), 27.2 (6 C, CH ), 28.6 (2
2
1
3
2
3
C NMR: d = 14.1 (CH ), 22.6 [3 C, C(CH ) ], 25.7 (CH ), 28.6
3
3 3
2
C, CH ), 29.1 (2 C, CH ), 38.7 [2 C, C(CH ) ], 64.4 (2 C, CO),
2
2
3 3
(
CH ), 29.25 (CH ), 29.3 (CH ), 29.4 (CH ), 29.6 (CH ), 31.9
2 2 2 2 2
1
78.6 (2 C, C=O).
(
CH ), 32.8 (CH ), 41.5 [C(CH ) ] 63.0 (CO), 171.3 (C=O).
3 3
2
2
+
MS: m/z (%) = 313 (M – 15, <1), 124 (46), 103 (76), 96 (16), 95
+
MS: m/z (%) = 185 (M – 57, 2), 140 (18), 111 (11), 103 (89), 97
15), 85 (27), 84 (10), 83 (13), 71 (11), 70 (15), 69 (12), 57 (100),
(12), 85 (27), 83 (16), 82 (29), 69 (24), 68 (12), 57 (100), 55 (15).
(
+
HRMS: m/z calcd for C H O [M – CH ] , 313.2379; found,
5
6 (19), 55 (15).
18 33
4
3
3
13.2372.
2
1
2-Octyl Pivalate (1b)
Colourless oil; yield: 88%; R 0.87 (hexane–EtOAc, 9:1).
2
4
1-Decyl Benzoate (1g)
Colourless oil; yield: 38%; R 0.38 (hexane–EtOAc, 9:1).
f
–
IR (neat): 1727 (C=O), 1166 (CO) cm .
1
f
IR (neat): 3093, 3063, 3022, 1602 (HC=C), 1721 (C=O), 1274 (CO)
–1
cm .
1
H NMR: d = 0.88 (t, 3 H, J = 6.8 Hz, CH CH ), 1.02–1.71 (m, 13
2
3
H, CH CH, 5 × CH ), 1.18 [s, 9 H, C(CH ) ], 4.78–4.94 (m, 1 H,
3
2
3 3
1
H NMR: d = 0.88 (t, 3 H, J = 5.8 Hz, CH ), 1.16–1.53 (m, 14 H,
3
CH).
CH ), 1.67–1.83 (m, 2 H, CH CO), 4.31 (t, 2 H, J = 6.7 Hz, CH O),
2
1
3
2
2
C NMR: d = 14.0 (CH CH ), 19.8 (CH CO), 22.5 (CH ), 25.3
2
3
2
3
7
2
.43 (t, 2 H, J = 7.3 Hz, Ph), 7.56 (t, 1 H, J = 7.3 Hz, Ph), 8.03 (d,
H, J = 7.3 Hz, Ph).
(
3
CH ), 27.1 [3 C, C(CH ) ], 29.1 (CH ), 31.7 (CH ), 35.9 (CH ),
2 3 3 2 2 2
8.7 [C(CH ) ], 70.5 (CO), 178.1 (C=O).
3 3
1
3
C NMR: d = 14.1 (CH ), 22.7 (CH ), 26.0 (CH ), 28.7 (2 C, CH ),
2
+
3
2
2
MS: m/z (%) = 157 (M – 57, <1), 129 (10), 112 (15), 103 (14), 85
35), 71 (33), 57 (100), 56 (11).
2
1
9.3 [CH (CH ) ], 29.5 (2 C, CH ), 31.9 (2 C, CH ), 65.1 (CO),
3 2 8 2 2
(
28.3 (Ph), 129.5 (2 C, Ph), 130.5 (Ph), 132.7 (2 C, Ph), 166.7
(
C=O).
MS: m/z (%) = 262 (M , 1), 140 (11), 123 (100), 122 (11), 105 (70),
7 (29).
3,7-Dimethyl-3-octyl Pivalate (1c)
Colourless oil; yield: 75%; R 0.69 (hexane–EtOAc, 9:1).
+
f
7
–
IR (neat): 1725 (C=O), 1175 (CO) cm .
1
1
25
Cyclohexyl Benzoate (1h)
Colourless oil; yield: 78%; R 0.70 (hexane–EtOAc, 9:1).
H NMR: d = 0.80–0.94 (m, 9 H, 2 × CH CH, CH CH ), 1.09–1.34
2
3
3
(
m, 2 H, CH ), 1.17 [s, 9 H, C(CH ) ], 1.42 (s, 3 H, CH CO), 1.46–
2
3 3
3
f
1
.99 (m, 7 H, 3 × CH , CH).
2
IR (neat): 3082, 3062, 3032, 1602 (HC=C), 1716 (C=O), 1278 (CO)
–1
cm .
1
3
C NMR: d = 7.8 (CH ), 21.2 (CH ), 22.5 (CH ), 23.1 (CH ), 27.2
3
3
2
3
[
3
4 C, C(CH ), CH], 27.7 (CH ), 30.9 (CH ), 38.0 (CH ), 39.2 (CH ),
2
1
3
3
2
2
H NMR: d = 1.05–2.02 (m, 10 H, CH ), 4.41–4.91 (m, 1 H, CHO),
2
9.3 [C(CH ) ], 84.2 (CO), 177.5 (C=O).
3 3
7
.15–7.67 (m, 3 H, Ph), 7.90–8.19 (m, 2 H, Ph).
+
MS: m/z (%) = 185 (M – 57, <1), 157 (11), 141 (57), 99 (10), 85
13
C NMR: d = 22.8 (2 C, CH ), 25.5 (CH ), 31.6 (2 C, CH ), 73.0
2
2
2
(
87), 73 (11), 71 (37), 70 (20), 69 (18), 57 (100), 55 (24).
(CO), 128.1 (Ph), 128.2 (2 C, Ph), 129.5 (2 C, Ph), 132.6 (Ph), 166.0
(C=O).
+
HRMS: m/z calcd for C H O (M ), 242.2246; found, 242.2241.
1
5
30
2
+
MS: m/z (%) = 204 (M , <1), 123 (99), 105 (100), 82 (18), 77 (36),
7 (17).
2
2
Cyclohexyl Pivalate (1d)
Colourless oil; yield: 56%; R 0.43 (hexane–EtOAc, 9:1).
6
f
–
IR (neat): 1728 (C=O), 1167 (CO) cm .
1
26
1-Decyl 4-tert-Butylbenzoate (1i)
Colourless oil; yield: 39%; R 0.81 (hexane–EtOAc, 9:1).
1
f
H NMR: d = 1.08–1.87 (m, 10 H, CH ), 1.19 [s, 9 H, C(CH ) ],
2
3 3
–
IR (neat): 3097, 3060, 1610 (HC=C), 1721 (C=O), 1276 (CO) cm .
1
4
.68–4.80 (m, 1 H, CH).
1
3
1
C NMR: d = 23.4 (2 C, CH ), 25.4 (CH ), 27.1 [3 C, C(CH ) ],
2
H NMR: d = 1.31 (t, 3 H, J = 6.6 Hz, CH CH ), 1.59–1.94 (m, 14
3
2
3 3
2
3
1.3 (2 C, CH ), 38.7 [C(CH ) ], 71.7 (CO), 177.9 (C=O).
2 3 3
H, CH ), 1.76 [s, 9 H, (CH ) C], 2.11–2.56 (m, 2 H, CH CO), 4.73
3 3
2
2
+
MS: m/z (%) = 184 (M , 1), 143 (45), 125 (11), 99 (12), 85 (54), 83
(t, 2 H, J = 6.9 Hz, CH O), 7.89 (d, 2 H, J = 7.8 Hz, Ph), 8.39 (d, 2
2
H, J = 7.8 Hz, Ph).
(
26), 69 (27), 57 (100), 55 (16).
1
3
C NMR: d = 14.1 (CH CH ), 22.7 (CH ), 26.0 (CH ), 28.8 (CH ),
3
2
2
2
2
2
3
Mesityl Pivalate (1e)
Colourless oil; yield: 91%; R 0.84 (hexane–EtOAc, 9:1).
29.25 (CH ), 29.3 (CH ), 29.5 (2 C, CH ), 31.1 [3 C, (CH ) C], 31.9
2 2 2 3 3
(CH ), 35.0 [C(CH ) ], 64.9 (CO), 125.2 (2 C, Ph), 127.8 (Ph),
2 3 3
f
–
IR (neat): 1751 (C=O), 1602 (HC=C), 1139 (CO) cm .
1
129.4 (2 C, Ph), 156.4 (Ph), 166.7 (C=O).
+
MS: m/z (%) = 318 (M , 1), 304 (11), 303 (50), 180 (10), 179 (83),
1
H NMR: d = 1.39 [s, 9 H, C(CH ) ], 2.08 (s, 6 H, CH Ph), 2.25 (s,
3
3
3
1
78 (29), 164 (12), 163 (100), 161 (34), 118 (12).
3
H, CH Ph), 6.84 (s, 2 H, Ph).
3
Synthesis 2006, No. 2, 309–314 © Thieme Stuttgart · New York