The Journal of Organic Chemistry
Article
Cyclohexyl acetate (3ah).56 colorless oil (193 mg, 85% yield); H
NMR (400 MHz, CDCl3) δ 4.66 (td, J = 8.5, 3.9 Hz, 1H), 1.95 (s, 3H),
1.78−1.76 (m, 2H), 1.69−1.61 (m, 2H), 1.53−1.43 (m, 1H), 1.39−1.15
(m, 5H) ppm; 13C NMR (101 MHz, CDCl3) δ 169.6, 71.7, 30.6, 24.4,
22.8, 20.4 ppm; GC-MS m/e 142.150.
(m, 1H), 0.79 (d, J = 7.0 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3) δ
155.5, 78.4, 54.5, 47.0, 40.7, 34.1, 31.4, 26.0, 23.3, 22.0, 20.7, 16.3 ppm;
GC-MS m/e 214.160; HRMS (EI) Found: 214.1571. Calcd for
C12H22O3: 214.1569.
1
Ethyl phenethyl carbonate (3gd).67 colorless oil (334 mg, 86%
yield); 1H NMR (400 MHz, CDCl3) δ 7.32−7.26 (m, 2H), 7.25−7.18
(m, 3H), 4.37−4.28 (t, J = 7.2 Hz, 2H), 4.21−4.12 (t, J = 7.0 Hz, 2H),
2.96 (q, J = 6.8 Hz, 2H), 1.29 (t, 7.1 Hz, 3H) ppm; 13C NMR (101 MHz,
CDCl3) δ 155.1, 137.3, 129.0, 128.6, 126.7, 68.2, 63.9, 35.2, 14.3 ppm;
GC-MS m/e 194.100.
Menthyl (1R,2S,5R)-(−)-acetate (3ai).55 colorless oil (263 mg, 83%
yield); 1H NMR (400 MHz, CDCl3) δ 4.60 (td, J = 10.9, 4.4 Hz, 1H),
1.96 (s, 3H), 1.92 (m, 1H), 1.85 (m, 1H), 1.65−1.56 (m, 2H), 1.48 (m,
1H), 1.34 (m, 1H), 1.05 (m, 1H), 0.96(m, 1H), 0.83 (d, J = 6.8, 3H),
0.82 (d, J = 6.2, 3H), 0.80−0.74 (m, 1H), 0.70 (d, J = 7.0 Hz, 3H) ppm;
13C NMR (101 MHz, CDCl3) δ 170.7, 74.1, 47.0, 40.9, 34.2, 31.4, 26.3,
23.5, 22.0, 21.3, 20.7, 16.4 ppm; GC-MS m/e 198.200.
Ethyl l-menthyl carbonate (3gi). colorless oil (383 mg, 84% yield);
1H NMR (400 MHz, CDCl3) δ 4.51 (td, J = 10.9, 4.2 Hz, 1H), 4.18 (q, J
= 7.1 Hz, 2H), 2.08 (m, 1H), 1.96 (m, 1H), 1.68 (m, 2H), 1.53−1.36 (m,
2H), 1.34−1.25 (m, 3H), 1.06 (m, 2H), 0.91 (d, J = 6.9 Hz, 6H), 0.84
(m, 1H), 0.79 (d, J = 7.0 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3) δ
153.9, 77.1, 62.6, 46.0, 39.8, 33.1, 30.4, 25.0, 22.2, 21.0, 19.7, 15.2, 13.3
ppm; GC-MS m/e 228.180; HRMS (EI) Found: 228.1727. Calcd for
C13H24O3: 228.1725.
Butane-1,4-diol diacetate (3ak).61 colorless oil (256 mg, 92%
yield); 1H NMR (400 MHz, CDCl3) δ 4.01 (t, J = 5.1 Hz, 4H), 2.00 (s,
6H), 1.64 (t, J = 12.6 Hz, 4H) ppm; 13C NMR (101 MHz, CDCl3) δ
170.9, 63.8, 25.2, 20.8 ppm; GC-MS m/e 174.100.
Diethylene glycol diacetate (3al).62 colorless oil (274 mg, 90%
yield); 1H NMR (400 MHz, CDCl3) δ 4.30−4.17 (m, 4H), 3.79−3.65
(m, 4H), 2.09 (s, 6H) ppm; 13C NMR (101 MHz, CDCl3) δ 170.0, 68.0,
62.4, 19.9 ppm; GC-MS m/e 190.100.
tert-Butyl phenethyl carbonate (3hd).63 colorless oil (351 mg, 79%
yield); 1H NMR (400 MHz, CDCl3) δ 7.32−7.29 (m, 2H), 7.24−7.22
(m, 3H), 4.27 (t, J = 7.3 Hz, 2H), 2.97 (t, J = 7.3 Hz, 2H), 1.47 (s, 9H)
ppm; 13C NMR (101 MHz, CDCl3) δ 153.5, 137.4, 128.9, 128.5, 126.6,
82.0, 67.4, 35.2, 27.8 ppm; GC-MS m/e 222.120.
Phenethyl 2-chloroacetate (3bd).63 colorless oil (337 mg, 85%
yield); 1H NMR (400 MHz, CDCl3) δ 7.31 (t, J = 7.4 Hz, 2H), 7.27−
7.19 (m, 3H), 4.40 (t, J = 7.0 Hz, 2H), 4.04 (s, 2H), 2.98 (t, J = 7.0 Hz,
2H) ppm; 13C NMR (101 MHz, CDCl3) δ 167.3, 137.2, 129.0, 128.62,
126.8, 66.6, 40.9, 34.9 ppm; GC-MS m/e 198.050.
tert-Butyl l-menthyl carbonate (3hi). colorless oil (369 mg, 72%
yield); 1H NMR (400 MHz, CDCl3) δ 4.47 (td, J = 10.7, 4.0 Hz, 1H),
2.04 (m, 1H), 2.00−1.89 (m, 1H), 1.67 (m, 2H), 1.48−1.46 (m, 11H),
1.04 (m, 2H), 0.90−0.88 (m, 7H), 0.79 (d, J = 6.9 Hz, 3H) ppm; 13C
NMR (101 MHz, CDCl3) δ 154.7, 81.5, 77.8, 47.0, 40.8, 34.1, 31.4, 27.8,
26.1, 23.3, 22.0, 20.7, 16.2 ppm; GC-MS m/e 256.210; HRMS (EI)
Found: 256.2039. Calcd for C15H28O3: 256.2038.
Triethyl phenethyl orthosilicate (3id). colorless oil (477 mg, 84%
yield); 1H NMR (400 MHz, CDCl3) δ 7.24−7.17 (m, 2H), 7.17−7.08
(m, 3H), 3.94−3.65 (m, 8H), 2.81 (t, J = 7.2 Hz, 2H), 1.22−1.07 (m,
9H) ppm; 13C NMR (101 MHz, CDCl3) δ 138.7, 129.1, 128.3, 126.2,
64.5, 59.2, 39.0, 18.1 ppm; GC-MS m/e 284.150; HRMS (EI) Found:
284.1446. Calcd for C14H24O4Si: 284.1444.
Triethyl l-menthyl orthosilicate (3ii). colorless oil (483 mg, 76%
yield); 1H NMR (400 MHz, CDCl3) δ 3.88−3.81 (m, 6H), 3.67 (td, J =
10.6, 4.2 Hz, 1H), 2.35−2.17 (m, 1H), 2.15−1.98 (m, 1H), 1.67−1.56
(m, 2H), 1.50−1.32 (m, 1H), 1.28−1.20 (m, 10H), 1.10−0.92 (m, 2H),
0.89 (d, J = 7.0 Hz, 6H), 0.86−0.80 (m, 1H), 0.77 (d, J = 6.9 Hz, 3H)
ppm; 13C NMR (101 MHz, CDCl3) δ 73.2, 59.1, 49.7, 44.6, 34.5, 31.7,
25.3, 25.3, 22.8, 22.3, 21.2, 18.1, 15.7 ppm; GC-MS m/e 318.230; HRMS
(EI) Found: 318.2229. Calcd for C16H34O4Si: 318.2226.
2-Phenylethyl acrylate (3cd).64 colorless oil (306 mg, 87% yield); 1H
NMR (400 MHz, CDCl3) δ 7.34−7.27 (m, 2H), 7.26−7.18 (m, 3H),
6.38 (d, J = 17.3 Hz, 1H), 6.10 (dd, J = 17.3, 10.4 Hz, 1H), 5.80 (d, J =
10.4 Hz, 1H), 4.37 (t, J = 7.1 Hz, 2H), 2.98 (t, J = 7.1 Hz, 2H) ppm; 13C
NMR (101 MHz, CDCl3) δ 166.1, 137.8, 130.8, 129.0, 128.6, 128.5,
126.6, 65.0, 35.1 ppm; GC-MS m/e 176.120.
Phenethyl dodecanoate (3dd). colorless oil (541 mg, 89% yield); 1H
NMR (400 MHz, CDCl3) δ 7.33−7.26 (m, 2H), 7.25 (d, J = 6.6 Hz,
1H), 7.21 (d, J = 7.3 Hz, 2H), 4.29 (t, J = 7.0 Hz, 2H), 2.93 (t, J = 7.0 Hz,
2H), 2.27 (t, J = 7.5 Hz, 2H), 1.58−1.57 (m, 2H), 1.28−1.25 (m, 16H),
0.88 (t, J = 6.0 Hz, 3H) ppm; 13C NMR (101 MHz, CDCl3) δ 173.8,
137.9, 128.9, 128.5, 126.5, 64.7, 35.2, 34.4, 31.9, 29.6, 29.5, 29.4, 29.3,
29.1, 25.0, 22.7, 14.1 ppm; GC-MS m/e 304.250; HRMS (EI) Found:
304.2403. Calcd for C20H32O2: 304.2402.
Lauric acid (1R,2S,5R)-menthyl ester (3di). colorless oil (568 mg,
84% yield); 1H NMR (400 MHz, CDCl3) δ 4.75−4.60 (m, 1H), 2.27 (t,
J = 7.4 Hz, 2H), 1.98 (m, 1H), 1.91 (m, 1H), 1.76−1.55 (m, 4H), 1.39−
1.22 (m, 18H), 1.14−0.93 (m, 2H), 0.88 (m, 10H), 0.75 (d, J = 6.9 Hz,
3H) ppm; 13C NMR (101 MHz, CDCl3) δ 173.5, 73.8, 47.0, 41.0, 34.8,
34.3, 31.9, 31.4, 29.6, 29.5, 29.3, 29.2, 29.1, 26.2, 25.2, 23.4, 22.7, 22.0,
20.8, 16.3, 14.1 ppm; GC-MS m/e 338.320; HRMS (EI) Found:
338.3187. Calcd for C22H42O2: 338.3185
ASSOCIATED CONTENT
■
Phenethyl benzoate (3ed).65 colorless oil (407 mg, 82% yield); 1H
NMR (400 MHz, CDCl3) δ 8.01 (d, J = 8.0 Hz, 2H), 7.51 (t, J = 7.3 Hz,
1H), 7.39 (t, J = 7.5 Hz, 2H), 7.35−7.26 (m, 3H), 7.25−7.15 (m, 2H),
4.51 (t, J = 7.0 Hz, 2H), 3.05 (t, J = 7.0 Hz, 2H) ppm; 13C NMR (101
MHz, CDCl3) δ 166.6, 138.0, 133.0, 130.4, 129.6, 129.1, 128.6, 128.4,
126.7, 65.6, 35.3 ppm; GC-MS m/e 226.100.
S
* Supporting Information
1
Copies of H and 13C NMR spectra for the products. This
material is available free of charge via the Internet at http://pubs.
Benzoic acid (1R,2S,5R)-menthyl ester (3ei).38 colorless oil (426 mg,
82% yield); 1H NMR (400 MHz, CDCl3) δ 8.05 (d, J = 7.6 Hz, 2H), 7.55
(t, J = 7.3 Hz, 1H), 7.44 (t, J = 7.4 Hz, 2H), 4.94 (td, J = 10.7, 3.6 Hz,
1H), 2.13 (m, 1H), 1.97 (m, 1H), 1.73−1.71 (m, 2H), 1.57−1.53 (m,
2H), 1.21−1.03 (m, 2H), 0.97−0.87 (m, 7H), 0.79 (d, J = 6.8 Hz, 3H)
ppm; 13C NMR (101 MHz, CDCl3) δ 165.1, 131.7, 129.8, 128.5, 127.3,
73.8, 46.2, 39.9, 33.3, 30.4, 25.5, 22.6, 21.0, 19.8, 15.5 ppm; GC-MS m/e
260.200.
AUTHOR INFORMATION
■
Corresponding Authors
Notes
The authors declare no competing financial interest.
Methyl phenethyl carbonate (3fd).66 colorless oil (331 mg, 92%
yield); 1H NMR (400 MHz, CDCl3) δ 7.30 (t, J = 7.2 Hz, 2H), 7.22 (d, J
= 6.7 Hz, 3H), 4.33 (q, J = 7.4 Hz, 2H), 3.75 (s, 3H), 2.97 (t, J = 6.8 Hz,
2H) ppm; 13C NMR (101 MHz, CDCl3) δ 155.7, 137.3, 129.0, 128.6,
126.7, 68.4, 54.7, 35.2 ppm; GC-MS m/e 180.130.
ACKNOWLEDGMENTS
■
We acknowledge financial support by NSFC (20902001,
21102001), Natural Science Foundation of Education Depart-
ment of Anhui Province (KJ2014A013), 211 Project of Anhui
University, and Doctor Research Start-up Fund of Anhui
University.
Methyl l-menthyl carbonate (3fi). colorless oil (385 mg, 90% yield);
1H NMR (400 MHz, CDCl3) δ 4.51 (td, J = 10.9, 4.4 Hz, 1H), 3.77 (s,
3H), 2.13−2.04 (m, 1H), 2.02−1.91 (m, 1H), 1.74−1.63 (m, 2H),
1.56−1.35 (m, 2H), 1.14−0.99 (m, 2H), 0.91 (d, J = 6.9 Hz, 6H), 0.85
9251
dx.doi.org/10.1021/jo5016536 | J. Org. Chem. 2014, 79, 9246−9252