7012 J . Org. Chem., Vol. 66, No. 21, 2001
Tanaka et al.
added dropwise with refluxing, and the reaction mixture was
refluxed for 4 h under a nitrogen atmosphere. The residue
obtained by solvent evaporation was poured into water, and
the product was extracted with chloroform twice. The crude
brown liquid product (71%) obtained by solvent evaporation
was used for the subsequent preparation after removing low-
boiling material under vacuum conditions at 100 °C. 1H NMR
(CDCl3, 400 MHz): δ 1.27 (6H, t, J ) 7.6 Hz, CH3), 1.69 (1H,
s, NH), 2.58 (4H, q, J ) 7.3 Hz, SCH2CH3), 2.7-2.8 (12H, m,
SCH2), 2.84 (4H, t, J ) 6.2 Hz, NCH2).
N-Dod ecylm on oa za tr ith ia -12-cr ow n -4 (1). Under a ni-
trogen atmosphere, monoazatrithia-12-crown-4 (446 mg, 2
mmol), bromododecane (747 mg, 3 mmol), sodium carbonate
(530 mg, 5 mmol), and acetonitrile (50 mL) were put into a
three-necked flask, and the reaction mixture was refluxed for
48 h. The cooled reaction mixture was poured into 5 wt %
aqueous sodium hydroxide, and the product was extracted with
chloroform. The product was purified by gel permeation
chromatography to give a 15% yield of 1 as a colorless solid.
Mp: 54-56 °C. 1H NMR (CDCl3, 500 MHz): δ 0.88 (3H, t, J )
7.0 Hz, CH3), 1.2-1.4 (18H, m, (CH2)9), 1.48 (2H, m, NCH2CH2),
2.46 (2H, m, NCH2CH2), 2.6-2.9 (16H, m, SCH2, NCH2). Anal.
Calcd for C20H41NS3: C, 61.38; H, 10.49; N, 3.58; S, 24.55.
Found: C, 61.15; H, 10.47; N, 3.54; S, 24.05. m/z: 391 (M+).
IR (neat, cm-1): 2915, 2845 (-CH2-).
Dodecanoyl chloride (657 mg, 3 mmol) was added dropwise,
and the reaction mixture was stirred for 6 h at room temper-
ature under a nitrogen atmosphere. The reaction mixture was
poured into water, and the product was extracted with
chloroform. The product was purified by gel permeation
chromatography to give 90% of 6 as a colorless solid. Mp: 85-
1
86 °C. H NMR (CDCl3, 500 MHz): δ 0.88 (3H, t, J ) 7.0 Hz,
CH3), 1.2-1.4 (16H, m, (CH2)8), 1.63 (2H, m, COCH2CH2), 2.31
(2H, t, J ) 8.0 Hz, COCH2), 2.7-2.9 (12H, m, SCH2), 3.5-3.6
(4H, m, NCH2). Anal. Calcd for C20H39NOS3: C, 59.26; H, 9.63;
N, 3.46; S, 23.70. Found: C, 59.23; H, 9.96; N, 3.43; S, 23.60.
m/z: 405 (M+). IR (neat, cm-1): 2920, 2845 (-CH2-); 1645
(CdO).
N-Dod eca n oylm on oa za tetr a th ia -15-cr ow n -5 (7). The
preparation procedure was the same as that used for 6, except
monoazatetrathia-15-crown-5 (566 mg, 2 mmol) was used
instead of monoazatrithia-12-crown-4 to give 90% of 7 as a
1
colorless solid. Mp: 71-73 °C. H NMR (CDCl3, 500 MHz): δ
0.88 (3H, t, J ) 8.0 Hz, CH3), 1.2-1.4 (16H, m, (CH2)8), 1.63
(2H, m, COCH2CH2), 2.30 (2H, t, J ) 7.5 Hz, COCH2), 2.7-
2.9 (16H, m, SCH2), 3.4-3.6 (4H, m, NCH2). Anal. Calcd for
C
22H43NOS4: C, 56.77; H, 9.25; N, 3.01; S, 27.53. Found: C,
56.59; H, 9.16; N, 2.97; S, 27.40. m/z: 465 (M+). IR (neat, cm-1):
2920, 2845 (-CH2-); 1635 (CdO).
N-Dod ecylm on oa za tetr a th ia -15-cr ow n -5 (2). The prepa-
ration procedure was the same as that used for 1, except
monoazatetrathia-15-crown-5 (566 mg, 2 mmol) was used
instead of monoazatrithia-12-crown-4 to give 74% of 2 as a
N-Dod eca n oylm on oa za p en ta th ia -18-cr ow n -6 (8). The
preparation procedure was the same as that used for 6, except
monoazapentathia-18-crown-6 (686 mg, 2 mmol) was used
instead of monoazatrithia-12-crown-4 to give 69% of 8 as a
1
colorless solid. Mp: 37-38 °C. H NMR (CDCl3, 500 MHz): δ
1
colorless solid. Mp: 49-50 °C. H NMR (CDCl3, 400 MHz): δ
0.88 (3H, t, J ) 7.0 Hz, CH3), 1.2-1.4 (18H, m, (CH2)9), 1.45
(2H, m, NCH2CH2), 2.50 (2H, t, J ) 7.5 Hz, NCH2CH2), 2.6-
2.9 (20H, m, SCH2, NCH2). Anal. Calcd for C22H45NS4: C,
58.54; H, 9.98; N, 3.10; S, 28.38. Found: C, 58.48; H, 9.98; N,
3.08; S, 28.22. m/z: 451 (M+). IR (neat, cm-1): 2920, 2845
(-CH2-).
0.85 (3H, t, J ) 7.2 Hz, CH3), 1.2-1.4 (16H, m, (CH2)8), 1.61
(2H, m, COCH2CH2), 2.34 (2H, t, J ) 7.6 Hz, COCH2), 2.6-
2.9 (20H, m, SCH2), 3.5-3.7 (4H, m, NCH2). Anal. Calcd for
C
24H47NOS5: C, 54.86; H, 8.95; N, 2.67; S, 30.48. Found: C,
55.00; H, 8.90; N, 2.62; S, 30.17. m/z: 525 (M+). IR (neat, cm-1):
2920, 2850 (-CH2-); 1640 (CdO).
N-Dodecylm on oazapen tath ia-18-cr own -6 (3). The prepa-
ration procedure was the same as that used for 1, except
monoazapentathia-18-crown-6 (686 mg, 2 mmol) and iodo-
dodecane (888 mg, 3 mmol) were used instead of monoaza-
trithia-12-crown-4 and bromododecane, respectively, to give
38% of 3 as a pale-yellow solid. Mp: 42-44 °C. 1H NMR (CDCl3,
400 MHz): δ 0.88 (3H, t, J ) 6.8 Hz, CH3), 1.2-1.4 (18H, m,
(CH2)9), 1.58 (2H, m, NCH2CH2), 2.6-2.9 (26H, m, NCH2CH2-
SCH2, NCH2). Anal. Calcd for C24H49NS5: C, 56.36; H, 9.59;
N, 2.74; S, 31.31. Found: C, 55.97; H, 9.42; N, 2.67; S, 31.33.
m/z: 511 (M+). IR (neat, cm-1): 2920, 2850 (-CH2-).
N-Dod eca n oyl-3,9-d ith ia -6-m on oa za u n d eca n e (9). The
preparation procedure was the same as that used for 6, except
3,9-dithia-6-monoazaundecane (386 mg, 2 mmol) was used
instead of monoazatrithia-12-crown-4 to give 93% of 9 as a
1
colorless liquid. H NMR (CDCl3, 500 MHz): δ 0.88 (3H, t, J
) 7.0 Hz, CH3), 1.2-1.4 (22H, m, SCH2CH3, (CH2)8), 1.6-1.7
(2H, m, COCH2CH2), 2.32 (2H, t, J ) 7.5 Hz, COCH2), 2.5-
2.6 (4H, m, SCH2CH3), 2.68 (4H, q, J ) 8.0 Hz, SCH2), 3.50
(4H, t, J ) 7.5 Hz, NCH2). Anal. Calcd for C20H41NOS2: C,
64.00; H, 10.93; N, 3.73; S, 17.07. Found: C, 63.81; H, 11.08;
N, 3.74; S, 17.04. m/z: 375 (M+). IR (neat, cm-1): 2940, 2845
(-CH2-); 1650 (CdO).
N-Dodecyl-3,9-dith ia-6-m on oazau n decan e (4). The prepa-
ration procedure was the same as that used for 1, except 3,9-
dithia-6-monoazaundecane (386 mg, 2 mmol) was used instead
of monoazatrithia-12-crown-4 to give 56% of 4 as a colorless
N-Dod eca n oyl-3,6,12,15-tetr a th ia -9-m on oa za h ep ta d e-
ca n e (10). The preparation procedure was the same as that
used for 6, except 3,6,12,15-tetrathia-9-monoazaheptadecane
(626 mg, 2 mmol) was used instead of monoazatrithia-12-
crown-4 to give 37% of 10 as a colorless liquid. 1H NMR (CDCl3,
500 MHz): δ 0.88 (3H, t, J ) 8.0 Hz, CH3), 1.2-1.4 (22H, m,
SCH2CH3, (CH2)8), 1.6-1.7 (2H, m, COCH2CH2), 2.32 (2H, t,
J ) 8.0 Hz, COCH2), 2.5-2.6 (4H, m, SCH2CH3), 2.7-2.8 (12H,
1
liquid. H NMR (CDCl3, 500 MHz): δ 0.88 (3H, t, J ) 7.0 Hz,
CH3), 1.2-1.4 (24H, m, SCH2CH3, (CH2)9), 1.54 (2H, m,
NCH2CH2), 2.58 (4H, q, J ) 7.3 Hz, SCH2CH3), 2.6-2.9 (10H,
m, SCH2, NCH2). Anal. Calcd for C20H43NS2: C, 66.48; H,
11.91; N, 3.88; S, 17.73. Found: C, 65.83; H, 11.85; N, 3.83; S,
17.43. m/z: 361 (M+). IR (neat, cm-1): 2920, 2850
(-CH2-).
N -Dod e cyl-3,6,12,15-t e t r a t h ia -9-m on oa za h e p t a d e -
ca n e (5). The preparation procedure was the same as that
used for 1, except 3,6,12,15-tetrathia-9-monoazaheptadecane
(626 mg, 2 mmol) and iodododecane (888 mg, 3 mmol) were
used instead of monoazatrithia-12-crown-4 and bromodode-
cane, respectively, to give 12% of 5 as a colorless liquid. 1H
NMR (CDCl3, 500 MHz): δ 0.88 (3H, t, J ) 7.5 Hz, CH3), 1.2-
1.4 (24H, m, SCH2CH3, (CH2)9), 1.43 (2H, m, NCH2CH2), 2.57
(4H, q, J ) 7.3 Hz, SCH2CH3), 2.6-2.8 (18H, m, SCH2, NCH2).
Anal. Calcd for C24H51NS4: C, 59.88; H, 10.60; N, 2.91; S,
26.61. Found: C, 60.14; H, 10.46; N, 2.81; S, 26.33. m/z: 481
(M+). IR (neat, cm-1): 2920, 2845 (-CH2-).
m, SCH2), 3.5-3.6 (4H, m, NCH2). Anal. Calcd for C24H49
-
NOS4: C, 58.18; H, 9.90; N, 2.83; S, 25.86. Found: C, 57.92;
H, 9.95; N, 2.86; S, 25.86. m/z: 495 (M+). IR (neat, cm-1): 2920,
2845 (-CH2-); 1650 (CdO).
Solven t Extr a ction . Equal volumes (10 mL) of a chloro-
form solution containing a thiacrown ether (1 × 10-4 mol dm-3
for dodecyl- and 1 × 10-3 mol dm-3 for dodecanoylthiacrown
ethers) and an aqueous solution of metal picrates (5 × 10-5
mol dm-3) were thoroughly shaken in a 50 mL flask at 30 °C.
The picrate concentration in the organic phase was determined
by following its absorbance decrease in the aqueous phase. In
control experiments, no distribution of thiacrown ether to the
aqueous phase was observed under these conditions.
N-Dod eca n oylm on oa za tr ith ia -12-cr ow n -4 (6). Under a
nitrogen atmosphere, monoazatrithia-12-crown-4 (446 mg, 2
mmol), triethylamine (303 mg, 3 mmol), and chloroform (50
mL) were put into a three-necked flask at room temperature.
J O015709I