A R T I C L E S
Holzinger et al.
equiv) and 2.05 mL (21.7 mmol) of 1g. Formula: C
4
H
7
ClO
2
S. MW:
73.0, 70.7, 70.6, 70.5, 69.9, 69.7, 69.5, 67.3, 66.5, 15.0 ppm. IR
(film): ν ) 3080.6, 3040.9, 2972.1, 2930.3, 2870.9, 1776.7, 1596.5,
1449.6, 1348.7, 1322.5, 1297.2, 1246.1, 1136.8, 1106.5, 1068.1, 949.9,
1
1
3
6
1
1
9
55. Colorless oil. Yield: 2.5 g (16.2 mmol, 75%). H NMR (CDCl
3
,
3
3
00 MHz): δ ) 2.10 (s, 3H), 2.74 (t, J ) 6.95 Hz, 2H), 4.37 (t, J )
1
3
-1
+
.95 Hz, 2H) ppm. C NMR (CDCl
3
, 75 MHz): δ ) 14.5, 30.6, 68.9,
842.3, 685.6 cm . MS (FAB, NBA): m/z ) 1087 [M H].
49.4 ppm. IR (film): ν ) 2966, 2922, 2337, 1777, 1456, 1430, 1374,
2-Phenylethyl Chlorocarbonate (2m). Quantities used: 26.86 mL
of 20% phosgene solution in toluene (50.28 mmol of phosgene, 2 equiv)
and 3 mL (25.14 mmol) of 1m. Formula: C H ClO . MW: 185.
-1
+
295, 1145, 1058, 999, 927, 825, 665 cm . MS (EI): m/z ) 154 [M ],
1 [M - COCl], 75 [M - OCOCl], 61 [M+ - OCOCl - CH
+
+
3
].
9
9
2
1
2-[2-(2-Ethoxyethoxy)ethoxy]ethyl Chlorocarbonate, [G0]-OCOCl
Colorless oil. Yield: 4.65 g (25 mmol, 99%). H NMR (CDCl
3
, 300
MHz): δ ) 2.94 (t, J ) 7.1 Hz, 2H), 4.41 (t, J ) 7.1 Hz, 2H), 7.21
(m, 5H) ppm. 13C NMR (CDCl
, 75 MHz): δ ) 34.4, 71.9, 126.8,
3
3
(2h). Quantities used: 40 mL of 20% phosgene solution in toluene
(75.6 mmol of phosgene, 2 equiv) and 6.7 g (6.6 mL, 37 mmol) of 1h.
3
1
C
9
H
17ClO
5
. MW: 240. Colorless oil. Yield: not determined. H NMR
128.5, 128.6, 135.9, 150.3 ppm. IR (film): ν ) 3031, 2964, 2283, 1951,
3
3
(CDCl
3
, 400 MHz): δ ) 4.19 (t, J ) 4.9 Hz, 2 H), 3.57 (t, J ) 4.7
1776, 1605, 1498, 1456, 1375, 1146, 1086, 1031, 9734, 824, 749, 699,
3
3
-1
+
+
Hz, 2 H), 3.49 (s, 2 H), 3.48 (t, J ) 5.4 Hz, 2 H), 3.43 (t, J ) 5.2 Hz,
2
682, 571 cm . MS (EI): m/z ) 184 [M ], 122 [M - COCl], 104
3
3
+
2+
H), 3.41 (t, J ) 5.4 Hz, 2 H), 3.36 (q, J ) 6.9 Hz, 2 H), 1.04 (t,
[M - OCOCl], 91 [M ].
3
13
J ) 6.8 Hz, 3 H) ppm. C NMR (CDCl
3
, 100.4 MHz): δ ) 157.0,
0.3, 70.2, 70.1, 69.4, 68.1, 67.0, 66.1, 14.7 ppm. IR (film): ν ) 2974.1,
930.5, 2870.9, 1779.7, 1449.6, 1375.3, 1351.7, 1293.2, 1169.7, 1110.3,
1-Pyrenylmethyl Chlorocarbonate (2n). Quantities used: 13.8 mL
of 20% phosgene solution in toluene (25.8 mmol of phosgene, 2 equiv)
7
2
1
and 3 g (12.9 mmol) of 1n. Formula: C18
solid. Yield: 3.16 g (10.7 mmol, 83%). H NMR (CDCl
δ ) 5.15 (s, 2H), 8.12 (m, 9H) ppm. 13C NMR (CDCl
H
11ClO
2
. MW: 295. Yellow
, 300 MHz):
, 75 MHz):
-1
+
1
047.1, 946.6, 842.4, 688.2 cm . MS (FAB, NBA): m/z ) 241 [M H].
Poly(ethylene glycol)butyl Ether-oxy Chlorocarbonate (2i). Quan-
3
3
tities used: 15.4 mL of 20% phosgene solution in toluene (28.8 mmol
of phosgene, 2 equiv) and 3 mL (14.4 mmol) of 1i. To complete the
conversion of the alcohol, the reaction mixture was stirred for another
δ ) 45.2, 123.2, 125.1, 126.1, 126.6, 127.7, 128.1, 128.4, 128.8, 129.6,
130.7, 131.1, 131.6, 132.4, 206.5 ppm. IR (KBr): ν ) 3041, 1916,
1792, 1588, 1478, 1435, 1417, 1312, 1257, 1239, 1185, 1136, 1092,
-
1
1
9
1
2 h at 50 °C. MW: ∼269. Colorless oil. Yield: 4.17 g (14.3 mmol,
9%). H NMR (CDCl , 300 MHz): δ ) 0.85 (t, J ) 7.3 Hz, 3H),
.30 (m, 2H), 1.50 (m, 2H), 3.39 (t, 2H), 3.56 (m), 3.71 (t, 2H), 4.39
1055, 962, 876, 844, 829, 756, 722, 702, 687, 668, 569 cm . MS
1
3
+
+
(FAB, NBA): m/z ) 231 [M - COCl], 215 [M - OCOCl].
1-Hexylheptyl Azidocarbonate (3c). Quantities used: 0.91 g (14.0
3
1
3
(
q, 2H) ppm. C NMR (CDCl
3
, 75 MHz): δ ) 14.3, 19.6, 32.1, 68.6,
0.4, 71.0, 71.1, 71.1, 71.2, 71.6, 71.7, 151.2 ppm. IR (film): ν ) 2999,
952, 2871, 2246, 1968, 1779, 1456, 1353, 1296, 1250, 1168, 914,
mmol) of NaN
MW: 269. Colorless oil. Yield: 2.24 g (8.3 mmol, 83%) H NMR
(CDCl , 300 MHz): δ ) 0.81 (t, 6H), 1.21 (s, 16H), 1.45 (m, 4H),
4.76 (septet, 1H) ppm. C NMR (CDCl
3 27 3 2
and 2.65 g (10 mmol) of 2c. Formula: C14H N O .
1
7
2
8
3
-
1
+
13
42, 734, 688, 666 cm . MS (FAB, NBA): m/z ) 401 [M (4 ×
3
, 75 MHz): δ ) 14.0, 22.5,
+
+
glycol)], 269 [M (3 × glycol)], 226 [M (2 × glycol)].
25.1, 29.1, 31.7, 33.9, 80.2, 157.4 ppm. IR (film): ν ) 2929, 2859,
2413, 2132, 2034, 1728, 1467, 1378, 1240, 1122, 933, 751, 725, 639,
18-Crown-[6]-methyl Chlorocarbonate (2j). Quantities used: 3.64
-
1
+
+
mL of 20% phosgene solution in toluene (6.8 mmol of phosgene, 2
equiv) and 1 g (3.4 mmol) of 1j. To complete the conversion of the
alcohol, the reaction mixture was stirred for another 12 h at 50 °C.
563 cm . MS (FAB, NBA): m/z ) 272 [M ], 256 [M - N], 242
+
+
[M - N
2-Hexyldecyl Azidocarbonate (3d). Quantities used: 1.6 g (23.94
mmol) of NaN and 5.2 g (17.1 mmol) 2d. Formula: C17
MW: 311. Colorless oil. Yield: 4.81 g (15.5 mmol, 91%). H NMR
(CDCl , 300 MHz): δ ) 0.81 (t, 6H), 1.06 (s, 24H), 1.61 (m, 1H),
2
], 194 [M - CON
3
].
Formula: C14
H
25ClO
8
. MW: 357. Colorless oil. Yield: not determined.
3
33 3 2
H N O .
1
1
H NMR (CDCl
t, 1H), 4.39 (q, 2H) ppm. 1 C NMR (CDCl
3
, 300 MHz): δ ) 3.59 (m, 20H), 3.65 (t, 2H), 3.72
3
(
3
, 75 MHz): δ ) 70.4,
1.0, 71.1, 71.3, 71.4, 71.6, 71.9, 76.7, 151.1 ppm. IR (film): ν ) 2869,
337, 1779, 1599, 1495, 1451, 1352, 1296, 1252, 1126, 994, 946, 839,
3
3
13
7
2
7
4.03 (d, J ) 19.4 Hz) ppm. C NMR (CDCl , 75 MHz): δ ) 14.4,
3
14.5, 23.0, 23.1, 27.0, 29.6, 29.9, 29.9, 30.3, 31.3, 31.3, 32.2, 32.3,
-
1
+
+
71, 689, 665 cm . MS (FAB, NBA): m/z ) 357 [M ], 327 [M
-
37.7, 71.8, 158.0 ppm. IR (film): ν ) 2927, 2857, 2412, 2137, 1759,
+
+
-
-1
Cl], 289 [M - COCl], 275 [M
OCOCl].
1733, 1466, 1379, 1235, 1171, 987, 753, 723 cm . MS (FAB, NBA):
+
+
+
3
,5-Bis{2-[2-(2-ethoxyethoxy)ethoxy]ethoxy}benzyl Chlorocar-
m/z ) 311 [M ], 284 [M - N
Cyclohexylmethyl Azidocarbonate (3e). Quantities used: 1.31 g
(20.16 mmol) of NaN and 2.5 g (14.4 mmol) of 2e. Formula:
. MW: 183. Colorless oil. Yield: 2.27 g (12.4 mmol, 86%).
H NMR (CDCl , 300 MHz): δ ) 0.93 (m, 2H), 1.17 (m, 4H), 1.65
2
], 240 [M - OCON
3
].
bonate, [G1]-OCOCl (2k). Quantities used: 25 mL of 20% phosgene
solution in toluene (47 mmol of phosgene, 2 equiv) and 12.0 g (23
3
mmol) of 1k, [G1]-OH. Formula: C24
yellow oil. Yield: not determined. H NMR (CDCl
H
39ClO10. MW: 522. Bright
8 13 3 2
C H N O
1
1
3
3
, 400 MHz): δ )
3
3
13
6
3
.47 (s, 2 H), 6.45 (s, 1 H), 5.14 (s, 2 H), 4.05 (t, J ) 4.7 Hz, 4 H),
3
(m, 5H), 3.95 (d, J ) 6.4 Hz, 2H) ppm. C NMR (CDCl , 75 MHz):
3
3
3
.79 (t, J ) 4.4 Hz, 4 H), 3.67 (t, J ) 4.4 Hz, 4 H), 3.64 (t, J ) 4.5
δ ) 24.4, 26.5, 28.2, 72.5, 156.5 ppm. IR (film): ν ) 2928, 2855,
3
3
Hz, 4 H), 3.60 (t, J ) 4.7 Hz, 4 H), 3.53 (t, J ) 3.9 Hz, 4 H), 3.47
2673, 2408, 2135, 1731, 1451, 1388, 1352, 1233, 1114, 1074, 987,
3
3
13
-1
+
(
(
7
2
1
q, J ) 7.1 Hz, 4 H, 7), 1.15 (t, J ) 7.1 Hz, 6 H) ppm. C NMR
CDCl , 100.4 MHz): δ ) 160.0, 150.4, 135.1, 107.2, 102.1, 73.0,
0.6, 70.5, 70.4, 69.6, 69.4, 67.4, 66.4, 14.9 ppm. IR (film): ν ) 3092.6,
973.6, 2930.6, 2871.9, 1776.4, 1598.5, 1450.6, 1349.0, 1323.5, 1298.2,
891, 843, 752, 619, 563 cm . MS (FAB, NBA): m/z ) 155 [M
-
+
], 96 [M+ - OCON
3
N
2
], 112 [M - CON
3
3
].
2-Methoxyethyl Azidocarbonate (3f). Quantities used: 0.77 g (11.8
mmol) of NaN
3
and 1.17 g (8.4 mmol) of 2f. Formula: C
4
1
H
7
N
3
O
2
.
-
1
245.1, 1134.5, 1112.0, 1071.1, 1011.5, 949.2, 843.3, 686.6 cm . MS
MW: 145. Colorless oil. Yield: 1.06 g (7.3 mmol, 87%). H NMR
+
(FAB, NBA): m/z ) 523 [M H].
(CDCl
3
, 300 MHz): δ ) 3.32 (s, 3H), 3.55 (q, 2H), 4.28 (q, 2H) ppm.
C NMR (CDCl , 75 MHz): δ ) 57.3, 65.7, 68.2, 155.9 ppm. IR
(film): ν ) 2963, 2411, 2184, 2138, 1734, 1454, 1407, 1370, 1359,
13
3
,5-Bis(3,5-bis{2-[2-(2-ethoxyethoxy)ethoxy]ethoxy}benzyloxy)-
3
benzyl Chlorocarbonate, [G2]-OCOCl (2l). Quantities used: 8 mL
of 20% phosgene solution in toluene (15.6 mmol of phosgene, 2 equiv)
-
1
1701, 1301, 1033, 954, 870, 844, 800, 751 cm . MS (FAB, NBA):
+
and 8.2 g (7.8 mmol) of 1l, [G2]-OH. Formula: C54
H
83ClO20. MW:
m/z ) 145 [M ].
1
1
086. Yellow oil. Yield: not determined. H NMR (CDCl
3
, 400
2-Methylthioethyl Azidocarbonate (3g). Quantities used: 1.47 g
MHz): δ ) 6.54 (s, 4 H), 6.54 (s, 2 H), 6.41 (s, 2 H), 6.41 (s, 1 H),
(22.68 mmol) of NaN
3
and 2.5 g (16.2 mmol) of 2g. Formula:
3
3
5
.17 (s, 2 H), 4.91 (s, 4 H), 4.07 (t, J ) 4.9 Hz, 8 H), 3.80 (t, J ) 4.8
4 7 3 2
C H N O
. MW: 161. Colorless oil. Yield: 1.15 g (7.1 mmol, 44%).
3
3
1
3
Hz, 8 H), 3.67 (t, J ) 4.5 Hz, 8 H), 3.65 (t, J ) 4.8 Hz, 8 H), 3.60
3
H NMR (CDCl , 300 MHz): δ ) 2.09 (s, 3H), 2.70 (t, J ) 6.9 Hz,
3
3
3
3
13
(t, J ) 4.9 Hz, 8 H), 3.54 (t, J ) 4.9 Hz, 8 H), 3.48 (q, J ) 7.1 Hz,
2H), 4.30 (t, J ) 6.9 Hz, 2H) ppm. C NMR (CDCl
3
, 75 MHz): δ )
3
13
8
3
H), 1.16 (t, J ) 7.1 Hz, 12 H) ppm. C NMR (CDCl , 100.4 MHz):
16.2, 32.5, 67.2, 157.8 ppm. IR (film): ν ) 2922, 2362, 2341, 2137,
1731, 1478, 1380, 1233, 1116, 1013, 919, 862, 750, 687, 657 cm .
-
1
δ ) 160.3, 160.01, 150.5, 138.6, 135.3, 107.5, 105.9, 102.6, 101.0,
8
578 J. AM. CHEM. SOC. VOL. 125, NO. 28, 2003
9