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M. Escriba et al. / Tetrahedron 65 (2009) 10370–10376
10375
RMN (CDCl3),
d
: 164.5 (C]O), 134.4 (Car–Cl), 133.4, 131.9, 131.5,
J¼8.4 Hz, 1H, CHar), 7.84 (d, J¼8.8 Hz, 1H, CHar), 7.83 (d, J¼8 Hz, 1H,
CHar), 7.53 (m, 2H, 2CHar), 5.44 (quin, J¼4.8 Hz, 1H, O–CH), 3.88 (d,
129.1, 126.9 (Car), 72.9 (O–CH), 42.5 (CH2–Cl). GC–MS, m/z: 266
[M]þ, 156 [M-C3H5Cl2]þ; 139 [M-OC3H5Cl2]þ; 111 [M-CO2C3H5Cl2]þ.
IR (KBr), nmax: 3072, 3030, 2968, 1736, 1591, 1436, 1287, 1246, 1115,
1051, 747, 689 cmꢁ1. Elem. Anal. calcd for C10H9Cl3O2: C, 44.89; H,
3.39; Cl, 39.75; O, 11.96. Found: C, 45.04; H 3.40; Cl, 40.86; O, 10.70.
J¼4.8 Hz, 4H, 2CH2–Cl). 13C RMN (CDCl3),
d: 165.8 (C]O), 136.0,
132.7, 131.9, 129.7, 128.9, 128.6, 128.0, 127.1, 126.6, 125.4 (CHar), 72.4
(O–CH), 42.7 (CH2–Cl). GC–MS, m/z: 282 [M]þ, 212 [M-Cl2]þ; 172
[M-C3H5Cl2]þ; 155 [M-OC3H5Cl2]þ; 127 [M-CO2C3H5Cl2]þ. IR (ATR),
nmax: 3061, 2968, 1717, 1630, 1276, 1192, 1088, 775, 760, 703 cmꢁ1
.
4.6.7. 1,3-Dichloro-2-propyl salicylate (3g). [CAS: 64496-72-6]: 1H
mp: 62.5–65.9 ꢀC. Elem. Anal. calcd for C14H12Cl2O2: C, 59.39; H,
4.27; Cl, 25.04; O, 11.30. Found: C, 59.38; H, 4.29; Cl, 24.83; O, 11.50.
NMR (CDCl3),
d
: 7.89 (dd, J1¼8.2 Hz, J2¼1.6 Hz,1H, CHar), 7.49 (m,1H,
CHar), 7.01 (dd, J1¼8.6 Hz, J2¼0.8 Hz, 1H, CHar), 6.92 (m, 1H, CHar),
4.6.13. 1,3-Dichloro-2-propyl 2-furoate (3m). 1H NMR (CDCl3),
d:
5.46 (quin, J¼5.1 Hz, 1H, O–CH), 3.89 (d, J¼5.1 Hz, 4H, 2CH2–Cl). 13
C
7.57 (m, CHar), 7.21 (dt, J1¼3.5 Hz, J2¼0.8 Hz, 1H, CHar), 6.48 (m, 1H,
RMN (CDCl3), d: 169.1 (C]O),162.1 (Car-OH),136.7,130.3,119.7,117.9,
111.8 (Car), 72.7 (O–CH), 42.5 (CH2–Cl). GC–MS, m/z: 248 [M]þ, 137
[M-C3H5Cl2]þ; 120 [M-HOC3H5Cl2]þ; 93 [M-HCO2C3H5Cl2]þ. IR
(ATR), nmax: 3248, 3079, 2962, 1677, 1613, 1677, 1613, 1484, 1289,
1156, 1085, 755, 698 cmꢁ1. mp: 44.3–44.7 ꢀC. (49–50 ꢀC).17
CHar), 5.33 (quin, J¼5.1 Hz, 1H, O–CH), 3.80 (d, J¼5.1 Hz, 4H, CH2–
Cl). 13C RMN (CDCl3),
d: 156.9 (C]O), 146.5 (CHar), 143.7 (Car–C]O),
119.8, 112.1 (CHar), 72.3 (O–CH), 43.1 (CH2–Cl). GC–MS, m/z: 222
[M]þ, 187 [M-Cl]þ; 112 [M-C3H5Cl2]þ; 95 [M-OC3H5Cl2]þ. IR (ATR),
nmax: 3180, 3175, 2960, 1705, 1410, 1261, 1122, 1045, 750, 660 cmꢁ1
.
4.6.8. 1,3-Dichloro-2-propyl m-nitrobenzoate (3h). 1H NMR (CDCl3),
HRMS (EIþ) calcd for C8H8Cl2O3: 221.9850, found: 221.9840.
d
: 8.81 (t, J¼2.0 Hz, 1H, CHar), 8.37 (m, 2H, CHar), 7.64 (t, J¼8.2 Hz,
1H, CHar), 5.43 (quin, J¼5.1 Hz, 1H, O–CH), 3.85 (d, J¼5.1 Hz, 4H,
2CH2–Cl). 13C RMN (CDCl3),
: 163.8 (C]O), 151.1 (Car-NO2), 134.7
4.6.14. 1,3-Dichloro-2-propyl 2-thiophencarboxylate (3n). 1H NMR
(CDCl3),
d
: 7.79 (dd, J1¼3.9 Hz, J2¼1.2 Hz, 1H, CHar), 7.61 (dd,
d
J1¼5.1 Hz, J2¼1.2 Hz, 1H, CHar), 7.05 (dd, J1¼5.1 Hz, J2¼3.9 Hz, 1H,
(Car–C]O), 130, 129.8, 122.7 (CHar), 73.3 (O–CH), 42.5 (CH2–Cl). GC–
MS, m/z: 278 [M]þ, 231 [M-NO2]þ; 150 [M-OC3H5Cl2]þ; 122 [M-
CO2C3H5Cl2]þ; 104 [M-NO2OC3H5Cl2]þ; 76 [M-NO2CO2C3H5Cl2]þ. IR
(ATR), nmax: 3111, 2966, 1726, 1525, 1343, 1262, 1100, 1014, 872, 716,
670 cmꢁ1. Elem. Anal. calcd for C10H9Cl2NO4: C, 43.19; H, 3.26; Cl,
25.50; N, 5.04; O, 23.01. Found: C, 43.48; H, 3.28; Cl, 24.50; N, 5.08;
O, 23.66. mp: 56.5–56.7 ꢀC.
CHar), 5.31 (quin, J¼5.1 Hz, 1H, O–CH), 3.79 (d, J¼5.1 Hz, 4H, CH2–
Cl). 13C RMN (CDCl3),
d: 161.1 (C]O), 144.8 (CHar), 143.8 (Car–C]O),
122.5, 118.1 (CHar), 72.2 (O–CH), 42.8 (CH2–Cl). GC–MS, m/z: 238
[M]þ, 202 [M-Cl]þ; 128 [M-C3H5Cl2]þ; 111 [M-OC3H5Cl2]þ. IR (ATR),
nmax: 3170, 2988, 1710, 1430, 1251, 1152, 1145, 760, 640 cmꢁ1. HRMS
(EIþ) calcd for C8H8Cl2O2S: 237.9622, found: 237.9611.
4.6.9. 1,3-Dichloro-2-propyl 3,5-dinitrobenzoate (3i). 1H NMR
4.6.15. 1,3-Dichloro-2-propyl palmitate (3a) and 2,3-dichloro-1-
propyl palmitate (4a). 3a Regioisomer: GC tr: 32,5 min. 1H NMR
(COCD6),
d
: 9.21 (t, J¼2.3 Hz 1H, CHar), 9.13 (d, J¼2.4 Hz, 2H, CHar),
5.67 (quin, J¼5.1 Hz, 1H, O–CH), 4.12 (d, J¼4.9 Hz, 4H, CH2–Cl). 13
C
(CDCl3),
hidden by the signals of the 4 regioisomer. 4a Regioisomer: GC tr:
32,8 min. 1H NMR (CDCl3),
: 4.45 (m, 2H, O–CH2), 4.18(m. 1H, CH–
d
: 5.18 (quin, J¼5.2 Hz,1H, O–CH). All other NMR signals are
RMN (COCD6), d: 164.4 (C]O), 149.1 (Car-NO2), 134.3 (Car–C]O),
d
128, 122.8 (CHar), 76.3 (O–CH), 43.5 (CH2–Cl). GC–MS, m/z: 323
[M]þ, 275 [M-NO2]þ; 229 [M-2NO2]þ; 252 [M-2Cl]þ; 195 [M-
OC3H5Cl2]þ. IR (KBr), nmax: 3099, 2963, 2884,1735,1544, 1346, 1275,
1165, 720 cmꢁ1. Elem. Anal. calcd for C10H8Cl2N2O6: C, 37.17; H,
2.50; Cl, 21.95; N, 8.67; O, 29.71. Found: C, 37.23; H, 2.51; Cl, 21.82;
N, 8.61; O, 29.83. mp: 131.6–131.8 ꢀC.
Cl), 3.75 (m, 2H, CH2–Cl), 2.37 (t, J¼7 Hz, 2H, CH2 ( ) (C]O)),1.65 (m,
a
2H, CH2 ( (C]O)), 1.26 (m, 24H, CH2), 0.88 (t, J¼7 Hz, 3H, CH3).
b
)
4.6.16. 1,3-Dichloro-2-propyl caprylate (3b) and 2,3-dichloro-1-pro-
pyl caprylate (4b). 3b Regioisomer: GC tr: 24,0 min. 1H NMR (CDCl3),
d
: 5.12 (quin, J¼5.2 Hz, 1H, O–CH), 3.80 (dd, J1¼5.7 Hz, J2¼2.2 Hz,
4H, 2CH2–Cl). All other NMR signals are hidden by the signals of the
4 regioisomer. 4a Regioisomer: GC tr: 24,5 min. 1H NMR (CDCl3),
4.6.10. 1,3-Dichloro-2-propyl 2,4-dinitrobenzoate (3j). 1H NMR
d
:
(CDCl3),
d
: 8.87 (d, J¼2.0 Hz, 1H, CHar), 8.58 (dd, J¼8.2, J¼2.0 Hz, 1H,
4.40 (m, 2H, O–CH2), 4,25 (m, 1H, CH–Cl), 3.75 (m, 2H, CH2–Cl), 2.37
(t, J¼7 Hz, 2H, CH2 ( ) (C]O)), 1.65 (m, 2H, CH2 ( ) (C]O)), 1.26 (m,
CHar), 7.96 (d, J¼8.2 Hz, 1H, CHar), 5.50 (quin, J¼5.1 Hz, 1H, O–CH),
a
b
3.88 (d, J¼4.7 Hz, 4H, CH2–Cl). 13C RMN (CDCl3),
d: 163.2 (C]O),
24H, CH2), 0.88 (t, J¼7 Hz, 3H, CH3).
149.8, 147.9 (Car-NO2), 132.7 (Car–C]O), 131.6, 129.1, 120.2 (CHar),
74.3 (O–CH), 42.1 (CH2–Cl). GC–MS, m/z: 323 [M]þ, 275 [M-NO2]þ;
4.6.17. 1,3-Dichloro-2-propyl pivaloate (3c) and 2,3-dichloro-1-pro-
pyl pivaloate (3c). 3c Regioisomer: GC tr: 17,0 min. 1H NMR (CDCl3),
230 [M-2NO2]þ; 252 [M-2Cl]þ; 195 [M-OC3H5Cl2]þ. IR (KBr), nmax
:
.
3107, 3058, 2960, 2885, 1743, 1541, 1349, 1283, 1110, 834 cmꢁ1
d
: 5.14 (quin, J¼5.2 Hz, 1H, O–CH), 3.76 (m, 4H, 2CH2–Cl). All other
NMR signals are hidden by the signals of the 4 regioisomer. 4a
Regioisomer: GC tr: 17,9 min. 1H NMR (CDCl3),
: 4.38 (m, 2H, O–
Elem. Anal. calcd for C10H8Cl2N2O6: C, 37.17; H, 2.50; Cl, 21.95; N,
8.67; O, 29.71. Found: C, 37.67; H, 2.50; Cl, 21.90; N, 8.57; O, 29.36.
d
CH2), 4.230 (m, 1H, CH–Cl), 3.66 (m, 2H, CH2–Cl), 2.37 (t, J¼7 Hz, 2H,
4.6.11. 1,3-Dichloro-2-propyl 1-naphthoate (3k). 1H NMR (CDCl3),
d:
CH2 ( ) (C]O)), 1.65 (m, 2H, CH2 ( ) (C]O)), 1.26 (m, 24H, CH2), 0.88
a
b
8.93 (dd, J1¼8.8 Hz, J2¼0.8 Hz, 1H, CHar), 8.28 (dd, J1¼7.6 Hz,
J2¼1.6 Hz, 1H, CHar), 8.07 (d, J¼8.4 Hz, 1H, CHar), 7.91 (d, J¼7.6 Hz,
1H, CHar), 7.65 (m, 1H, CHar), 7.54 (m, 2H, 2CHar), 5.54 (quin,
J¼4.8 Hz, 1H, O–CH), 3.96 (d, J¼4.8 Hz, 4H, 2CH2–Cl). 13C RMN
(t, J¼7 Hz, 3H, CH3).
4.6.18. 1,3-Dichloro-2-propyl benzoate (3d) and 2,3-dichloro-1-pro-
pyl benzoate (4d). 3d Regioisomer: GC tr: 24,3 min. 1H NMR (CDCl3),
(CDCl3),
d
: 166.3 (C]O), 134.4, 134.1, 131.6, 131.2, 128.9, 128.4, 126.6,
d
: 5.36 (quin, J¼5.3 Hz, 1H, O–CH). All other NMR signals are hidden
by the signals of the 4 regioisomer. 4d Regioisomer: GC tr: 24,8 min.
1H NMR (CDCl3),
: 8.00 (m, 1H, CHar ( ) (C]O)), 7.53 (m, 1H, CHar),
125.9, 125.8, 124.8 (CHar), 72.4 (O–CH), 42.8 (CH2–Cl). GC–MS, m/z:
282 [M]þ, 212 [M-Cl2]þ; 172 [M-C3H5Cl2]þ; 155 [M-OC3H5Cl2]þ; 127
[M-CO2C3H5Cl2]þ. IR (ATR), nmax: 3051, 2964, 1716, 1509, 1236, 1191,
1126, 1036, 776, 752, 655 cmꢁ1. mp: 65.4–65.8 ꢀC. Elem. Anal. calcd
for C14H12Cl2O2: C, 59.39; H, 4.27; Cl, 25.04; O, 11.30. Found: C,
59.41; H, 4.28; Cl, 24.93; O, 11.38.
d
a
7.39 (m, 2H, CHar), 4.58 (m, 2H, O–CH2), 4.35 (m, 1H, CH–Cl), 3.82
(m, 2H, CH2–Cl).
4.6.19. 1,3-Dichloro-2-propyl cinnamate (3e) and 2,3-dichloro-1-
propyl cinnamate (4e). 3e Regioisomer: GC tr: 27,9 min. 1H NMR
4.6.12. 1,3-Dichloro-2-propyl 2-naphthoate (3l). 1H NMR (CDCl3),
8.58 (s, 1H, CHar), 8.01 (dd, J1¼8.8 Hz, J2¼1.6 Hz, 1H, CHar), 7.92 (d,
d:
(CDCl3),
d
: 5.26 (quin, J¼5.2 Hz, 1H, O–CH), 3.81 (dd, J1¼5.2 Hz,
J2¼0.8 Hz, 4H, 2CH2–Cl). All other NMR signals are hidden by the