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Russ.Chem.Bull., Int.Ed., Vol. 52, No. 10, October, 2003
Shtamburg et al.
CH2CH2Me, J = 7.5 Hz); 2.87 (d, 3 H, NMe, J = 4.8 Hz); 3.82
(s, 3 H, NOMe); 4.00 (t, 2 H, NOCH2, J = 7.5 Hz); 6.15 (br.s,
1 H, NH). Found (%): C, 44.59; H, 8.86; N, 17.11. C6H14N2O3.
Calculated (%): C, 44.43; H, 8.70; N, 17.27.
1.69 (sext, 2 H, OCH2CH2Me, J = 7.2 Hz); 2.86 (d, 3 H,
NHMe, J = 4 Hz); 3.97 (t, 2 H, OCH2CH2Me, J = 7.2 Hz);
4.30 (sept, 1 H, OCHMe2, J = 6.3 Hz); 6.13 (br.s, 1 H, NH).
MS (EI, 70 eV), m/z (Irel (%)): 190 M+ (6.2); 189 (1.8); 188
(2.0); 133 (14.1); 132 (29.2); 131 (21.4); 130 (68.2); 118 (10.5);
90 (25.4); 89 (35.8); 88 (34.0); 73 (19.3); 59 (21.4); 58 (70.7); 43
(100). Found (%): C, 50.35; H, 9.42; N, 14.81. C8H18N2O3.
Calculated (%): C, 50.51; H, 9.54; N, 14.72.
NꢀIsopropoxyꢀN´,N´ꢀdimethylꢀNꢀpropoxyurea (49), colorless
liquid, nD20 1.4460. 1H NMR (300 MHz, CDCl3): 0.95 (t, 3 H,
OCH2CH2Me, J = 7 Hz); 1.25 (d, 6 H, OCHMe2, J = 6.3 Hz);
1.63 (sext, 2 H, OCH2CH2Me, J = 7 Hz); 3.01 (s, 6 H, NMe2);
3.86 (t, 2 H, OCH2CH2Me, J = 7 Hz); 4.21 (sept, 1 H, OCHMe2,
J = 6.3 Hz). MS (EI, 70 eV), m/z (Irel (%)): 204 M+ (1.1); 146
(3.5); 144 (3.0); 104 (19.4); 101 (18.5); 73 (17.1); 72 (100); 59
(45.8); 57 (12.6); 45 (16.3); 44 (29.2); 43 (24.3). Found (%):
C, 53.03; H, 9.94; N, 13.65. C9H20N2O3. Calculated (%):
C, 52.92; H, 9.87; N, 13.71.
Methyl N,Nꢀdimethoxycarbamate (50). A. A solution of meꢀ
thyl NꢀacetoxyꢀNꢀmethoxycarbamate (31) (0.29 g, 1.8 mmol)
in MeOH (2 mL) was kept at 20 °C for 8 days. Then MeOH was
distilled off in vacuo, the residue was extracted with pentane, the
extract was concentrated, and the residue was distilled in vacuo.
Methyl N,Nꢀdimethoxycarbamate (50) was prepared in a yield
of 0.14 g (58.2%) as a colorless liquid, b.p. 52—55 °C (9 Torr).
1H NMR (300 MHz, CDCl3): 3.83 (s, 6 H, NOMe); 3.88 (s,
3 H, CO2Me). MS (CI), m/z (Irel (%)): 136 [M + H]+ (2.2); 134
[M – H]+ (5.6); 133 (5.8); 105 (43.8); 104 (32.0); 76 (96.4); 61
(56.0); 58 (47.2);46 (27.6); 45 (32.2); 44 (100). Found (%):
C, 35.43; H, 6.81; N, 10.60. C4H9NO4. Calculated (%): C, 35.56;
H, 6.71; N, 10.37.
NꢀEthoxyꢀNꢀmethoxyꢀN´ꢀ(1ꢀnaphthyl)methylurea (43), visꢀ
cous yellowish liquid. 1H NMR (300 MHz, CDCl3): 1.19 (t,
3 H, OCH2Me, J = 6.9 Hz); 3.73 (s, 3 H, NOMe); 4.02 (q, 2 H,
OCH2Me, J = 6.9 Hz); 4.83 (d, 2 H, CH2N H, J = 5.1 Hz); 6.31
(br.s, 1 H, NH); 7.26—7.63 (m, 4 H, C(3)H, C(5)H, C(6)H,
C(7)H); 7.71—7.86 (m, 2 H, C(2)H, C(4)H); 7.95 (d, 1 H,
C(8)H, J = 8 Hz). MS (EI, 70 eV), m/z (Irel (%)): 274 [M]+
(3.5), 243 [M – MeO]+ (19.3), 229 [M – EtO]+ (3.5), 201
(23.7), 200 (63.5), 182 (15.3), 156 (38.0), 155 (11.8), 154 (23.7),
142 (11.5), 141 (56.0), 129 (100), 128 (46.8), 127 (42.7).
Found (%): N, 10.03. C15H18N2O3. Calculated (%): N, 10.21.
NꢀEthoxyꢀNꢀmethoxyurea (44), colorless liquid, nD20 1.4493.
1H NMR (300 MHz, CDCl3): 1.32 (t, 3 H, OCH2Me, J =
7 Hz); 3.83 (s, 3 H, NOMe); 4.12 (q, 2 H, OCH2Me, J = 7 Hz);
5.50 and 5.93 (both s, 1 H each, NH). Found (%): C, 35.93;
H, 7.80; N, 20.69. C4H10N2O3. Calculated (%): C. 35.82;
H, 7.51; N, 20.88.
NꢀnꢀButoxyꢀNꢀmethoxyurea (45), yellowish liquid,
nD25 1.4495. 1H NMR (300 MHz, CDCl3): 0.95 (t, 3H, CH2Me,
J = 7.5 Hz); 1.42 (sext, 2 H, CH2CH2Me, J = 7.5 Hz); 1.67
(quint, 2 H, OCH2CH2CH2, J = 7.5 Hz); 3.81 (s, 3 H, NOMe);
4.04 (t, 2 H, OCH2CH2, J = 7.5 Hz); 6.05 and 6.38 (both s,
1 H each, NH). MS (CI), m/z (Irel (%)): 163 [M + H]+ (5.9),
161 (3.0), 160 (3.0), 146 (3.2), 133 (12.7), 131 (15.4), 119 (6.0),
116 (9.4), 105 (4.6), 104 (21.5), 89 (56.4), 88 (91.1), 77 (42.7),
76.6 (11.1), 75 (48.1), 73 (10.0), 70 (46.4), 61 (56.5), 60 (48.6),
59 (100), 58 (36.6), 56 (70.1), 54 (15.1), 46 (16.0), 45 (57.2), 44
(54.4). Found (%): C, 44.21; H, 8.51; N, 17.38. C6H14N2O3.
Calculated (%): C, 44.43; H, 8.70; N, 17.27.
B. Methanolysis of methyl NꢀmethoxyꢀNꢀpropionyloxyꢀ
carbamate (32) performed under analogous conditions afforded
methyl N,Nꢀdimethoxycarbamate (50) in 61.4% yield.
NꢀnꢀButoxyꢀNꢀethoxyurea (46), yellowish liquid, b.p.
56—58 °C (1 Torr) (with decomp.), nD 1.4465. 1H NMR
Methyl NꢀmethoxyꢀNꢀnꢀoctyloxycarbamate (51). A solution
of methyl NꢀacetoxyꢀNꢀnꢀoctyloxycarbamate (33) (0.28 g,
1.1 mmol) in MeOH (3 mL) was kept at 20 °C for 3 days. Then
MeOH was evaporated in vacuo, the residue was treated with a
mixture of hexane and aqueous NaHCO3. The hexane extract
was separated and concentrated in vacuo. The residue was kept
at 20 °C and 2 Torr for 0.5 h. NꢀMethoxyꢀNꢀnꢀoctyloxyꢀ
carbamate 51 was prepared in a yield of 0.245 g (98%) as a
25
(300 MHz, CDCl3): 0.91 (t, 3 H, O(CH2)3Me, J = 7.5 Hz);
1.27 (t, 3 H, OCH2Me, J = 6.9 Hz); 1.38 (sext, 2 H,
OCH2CH2CH2Me,
J = 7.5 Hz); 1.63 (quint, 2 H,
OCH2CH2CH2, J = 7.5 Hz); 3.99 (t, 2 H, OCH2CH2, J =
7.5 Hz); 4.06 (q, 2 H, OCH2Me, J = 6.9 Hz); 6.01 (br.s, 2 H,
NH2). MS (CI), m/z (Irel (%)): 178 [M + 2 H]+ (10.5), 177
[M + H]+ (100), 163 (12.4), 134 (10.1), 133 (37.0), 131 (25.9),
105 (27.9), 103 (43.7). Found (%): C, 47.54; H, 9.22; N, 15.50.
C7H16N2O3. Calculated (%): C, 47.71; H, 9.15; N, 15.90.
NꢀnꢀDodecyloxyꢀNꢀmethoxyurea (47), colorless crystals,
m.p. 46—49 °C. 1H NMR (300 MHz, CDCl3): 0.88 (t,
20
colorless liquid, nD 1.4345. 1H NMR (300 MHz, CDCl3):
0.88 (t, 3 H, (CH2)7Me, J = 6.9 Hz); 1.24—1.43 (m, 10 H,
OCH2CH2(CH2)5Me); 1.67 (quint, 2 H, OCH2CH2, J =
6.9 Hz); 3.80 (s, 3 H, NOMe); 3.87 (s, 3 H, CO2Me); 4.00 (t,
2 H, NOCH2, J = 6.9 Hz). MS (CI), m/z (Irel (%)): 234 [M + H]+
(3.8); 233 [M]+ (0.6); 232 (0.6); 203 (13.3); 202 (100); 121
(10.9); 111 (37.5); 106 (19.7); 104 (16.2). Found (%): C, 56.51;
H, 10.05; N, 5.82. C11H23NO4. Calculated (%): C, 56.63;
H, 9.94; N, 6.00.
3
H, O(CH2)11Me, J = 7 Hz); 1.20—1.40 (m, 18 H,
OCH2CH2(CH2)9Me); 1.66 (quint, 2 H, NOCH2CH2, J =
7 Hz); 3.83 (s, 3 H, NOMe); 4.04 (t, 2 H, NOCH2, J = 7 Hz);
5.32 (br.s, 1 H, NH); 5.9 (br.s, 1 H, NH). IR, ν/cm–1: 1708
(C=O). MS (EI, 70 eV), m/z (Irel (%)): 274 [M]+ (0.1), 259
[M – Me]+ (0.1), 245 [M – Et]+ (0.1), 113 (8.0), 111 (10.1), 99
(15.5); 86. (11.1), 85 (67.7), 84 (20.0), 71 (83.9), 70 (41.9), 69
(66.0), 68 (24.2), 67 (27.0), 63 (28.2), 58 (31.8), 57 (100), 56
(66.9), 55 (83.0), 54 (24.1). Found (%): C, 61.54; H, 10.95;
N, 10.14. C14H30N2O3. Calculated (%): C, 61.28; H, 11.02;
N, 10.21.
Methyl NꢀethoxyꢀNꢀnꢀoctyloxycarbamate (52) was syntheꢀ
sized as described above by ethanolysis of methyl NꢀacetoxyꢀNꢀ
nꢀoctyloxycarbamate (33) at 20 °C for 120 days. The yield was
20
78.5%, yellowish liquid, nD 1.4348. 1H NMR (300 MHz,
CDCl3): 0.88 (t, 3 H, (CH2)7Me, J = 6.7 Hz); 1.24—1.36 (m,
10 H, OCH2CH2(CH2)5Me); 1.29 (t, 3 H, NOCH2Me, J =
6.9 Hz); 1.66 (quint, 2 H, OCH2CH2, J = 6.7 Hz); 3.85 (s, 3 H,
CO2Me); 3.99 (t, 2 H, NOCH2, J = 6.7 Hz); 4.06 (q, 2 H,
NOCH2Me, J = 6.9 Hz). MS (CI), m/z (Irel (%)): 248 [M + H]+
NꢀIsopropoxyꢀN´ꢀmethylꢀNꢀpropoxyurea (48), colorless liqꢀ
20
uid, nD 1.4472. 1H NMR (300 MHz, CDCl3): 0.97 (t, 3 H,
OCH2CH2Me, J = 7.2 Hz); 1.28 (d, 6 H, OCHMe2, J = 6.3 Hz);