Self-Assembly of m-Xylylene Type Dithioureas
J . Org. Chem., Vol. 63, No. 21, 1998 7487
(15),10 and 1,1′-thiocarbonyldiimidazole21 were prepared ac-
cording to literature procedures. Other solvents and reagents
used were of reagent grade and were employed as purchased
without further purification.
C24H42N4S2: C, 63.95; H, 9.39; N, 12.43. Found: C, 63.98; H,
9.58; N, 12.64.
5-ter t-Bu t yl-1,3-b is[(N′-4-m et h oxyb en zylt h iou r eid o)-
m eth yl]ben zen e (1h ). Obtained as a white solid after
recrystallization from ethanol: yield 88%; mp 174-175 °C; IR
Typ ica l P r oced u r e for th e Syn th esis of Dith iou r ea s.
P r ep a r a tion of 5-ter t-Bu tyl-1,3-bis[(N′-eth ylth iou r eid o)-
m eth yl]ben zen e (1b). Into a nitrogen-purged flask a solution
of 962 mg (5.0 mmol) of diamine 13 in 20 mL of THF was added
followed by a solution of 0.88 mL (10 mmol) of ethyl isothio-
cyanate in 10 mL of THF. The mixture was refluxed for 1 h
and concentrated to remove the solvent. The product was
purified by column chromatography (silica gel, 49:1 CHCl3-
MeOH) to afford 1.42 g (77%) of 1b as a white solid, which
was recrystallized from ethanol to give colorless crystals: mp
157-159 °C; IR (KBr) 3239, 876, 795, 705 cm-1; 1H NMR (270
MHz, CDCl3, 50 °C, 0.02 M) δ 0.83 (t, J ) 7.0 Hz, 6H), 1.31 (s,
9H), 2.92 (br s, 4H), 4.92 (br s, 4H), 6.97 (s, 1H), 7.1-7.3 (br
s containing s at 7.14, 6H); MS (FAB) m/z 367 (M+ + 1). Anal.
Calcd for C18H30N4S2: C, 58.97; H, 8.25; N, 15.28. Found: C,
59.29; H, 8.51; N, 15.46. The following compounds were
similarly prepared.
1
(KBr) 3245, 1550, 821, 701 cm-1; H NMR (270 MHz, CDCl3,
0.05 M, 30 °C) δ 1.35 (s, 9H), 3.75 (s, 6H), 3.90 (br s, 4H), 4.83
(br s, 4H), 6.73 and 6.85 (AA′BB′, J ) 8.6 Hz, 8H), 7.00 (s,
1H), 7.19 (s, 2H), 7.60 (br s, 4H); MS (FAB) m/z 550 (M+). Anal.
Calcd for C30H38N4O2S2: C, 65.42; H, 6.95; N, 10.17. Found:
C, 65.04; H, 6.96; N, 9.94.
5-ter t -Bu t yl-1,3-b is[[N ′-(4-(t r iflu or om e t h yl)b e n zyl)-
th iou r eid o]m eth yl]ben zen e (1i). Obtained as colorless
crystals after column chromatography (silica gel, 1:1 hexanes-
EtOAc) followed by recrystallization from methanol: yield
84%; mp 178-179 °C; IR (KBr) 3224, 1552, 854, 824, 703 cm-1
;
1H NMR (270 MHz, CDCl3, 0.05 M, 50 °C) δ 1.35 (s, 9H), 4.02
(br s, 4H), 4.88 (br s, 4H), 7.02 (s, 1H), 7.08 and 7.47 (AA′BB′,
J ) 8.0 Hz, 8H), 7.26 (s, 2H), 7.68 (br s, 2H), 7.80 (br s, 2H);
MS (FAB) m/z 627 (M+ + 1). Anal. Calcd for C30H32F6N4S2:
C, 57.49; H, 5.15; N, 8.94. Found: C, 57.40; H, 5.31; N, 8.70.
5-ter t-Bu tyl-1,3-bis[(N′-(3,5-diflu or oben zyl)th iou r eido)-
m eth yl]ben zen e (1j). Obtained as colorless crystals after
column chromatography (silica gel, 1:1 hexanes-EtOAc) fol-
lowed by recrystallization from benzene: yield 84%; mp 156-
5-ter t-Bu t yl-1,3-b is[(N′-b u t ylt h iou r eid o)m et h yl]b en -
zen e (1a ). Obtained as colorless crystals after recrystalliza-
tion from ethanol: yield 77%; mp 162-164 °C; IR (KBr) 3246,
1
1569, 898, 852, 702 cm-1; H NMR (270 MHz, CDCl3, 50 °C,
158 °C; IR (KBr) 3249, 1549, 855, 702 cm-1 1H NMR (270
;
0.01 M) δ 0.77 (t, J ) 6.9 Hz, 6H), 1.17 (m, 8H), 1.31 (s, 9H),
2.86 (br s, 4H), 4.93 (br s, 4H), 6.96 (s, 1H), 7.1-7.3 (br s
containing s at 7.14, 6H); MS (FAB) m/z 845 (2M+, 3% relative
to M+ + 1), 423 (M+ + 1). Anal. Calcd for C22H38N4S2: C,
62.51; H, 9.06; N, 13.25. Found: C, 62.45; H, 9.06; N, 13.25.
5-ter t-Bu tyl-1,3-bis[(N′-p h en ylth iou r eid o)m eth yl]ben -
zen e (1c). Obtained as a white solid after recrystallization
from methanol: yield 89%; mp 158-160 °C; IR (KBr) 3240,
MHz, CDCl3, 0.05 M, 30 °C) δ 1.36 (s, 9H), 3.96 (br s, 4H),
4.90 (d, J ) 4.5 Hz, 4H), 6.48-6.53 (m, 4H), 6.64 (tt, J ) 8.9,
2.3 Hz, 2H), 6.96 (s, 1H), 7.24 (s, 2H), 7.63 (br s, 2H), 7.72 (br
s, 2H); MS (FAB) m/z 1124 (2M+, 2% relative to M+ + 1), 563
(M+ + 1). Anal. Calcd for C28H30F4N4S2: C, 59.77; H, 5.37;
N, 9.96. Found: C, 59.39; H, 5.41; N, 9.81.
5-ter t-Bu t yl-1,3-b is[(N′-(2,3,4,5,6-p en t a flu or ob en zyl)-
th iou r eid o)m eth yl]ben zen e (1k ). Obtained as colorless
crystals after recrystallization from benzene: yield 90%; mp
1
3206, 1533, 748, 694 cm-1; H NMR (270 MHz, CDCl3, 0.05
M, 50 °C) δ 1.59 (s, 9H), 4.84 (d, J ) 5.4 Hz, 4H), 6.27 (br s,
2H), 7.00-7.60 (m, 13H), 7.87 (br s, 2H); MS (FAB) m/z 463
(M+ + 1). Anal. Calcd for C26H30N4S2: C, 67.49; H, 6.54; N,
12.11. Found: C, 67.29; H, 6.79; N, 12.27.
161-163 °C; IR (KBr) 3259, 1558, 703 cm-1 1H NMR (270
;
MHz, CDCl3, 0.05 M, 30 °C) δ 1.24 (s, 9H), 4.07 (br s, 4H),
4.86 (br s, 4H), 6.76 (s, 1H), 7.16 (s, 2H), 7.62 (br s, 2H), 7.93
(br s, 2H); MS (FAB) m/z 671 (M+ + 1). Anal. Calcd for
5-ter t-Bu tyl-1,3-bis[(N′-ben zylth iou r eid o)m eth yl]ben -
zen e (1d ). Obtained as a white solid after recrystallization
from ethanol: yield 68%; mp 177-179 °C; IR (KBr) 3242, 1554,
C
28H24F10N4S2: C, 50.15; H, 3.61; N, 8.35. Found: C, 50.38;
H, 3.41; N, 8.38.
5-Br om o-1,3-bis[(N′-bu tylth iou r eid o)m eth yl]ben zen e
(3). Obtained as colorless crystals after recrystallization from
methanol: yield 72%; mp 155-156 °C; IR (KBr) 3336, 857,
706 cm-1; 1H NMR (270 MHz, CDCl3, 50 °C, 0.03 M) δ 0.82 (t,
J ) 7.2 Hz, 6H), 1.20 (m, 8H), 2.90 (br s, 4H), 4.91 (d, J ) 4.7
Hz, 4H), 7.05 (s, 1H), 7.11 (br s, 2H), 7.30 (s, 2H), 7.54 (br s,
2H); MS (FAB) m/z 447 (M+ + 3), 445 (M+ + 1). Anal. Calcd
for C18H29Br N4S2: C, 48.53; H, 6.56; N, 12.58. Found: C,
48.43; H, 6.53; N, 12.57.
1
867, 766, 733, 697 cm-1; H NMR (270 MHz, CDCl3, 0.05 M,
50 °C) δ 1.35 (s, 9H), 4.00 (br s, 4H), 4.84 (br s, 4H), 6.95-
7.21 (m, 13H), 7.49 (br s, 4H); MS (FAB) m/z 491 (M+ + 1).
Anal. Calcd for C28H34N4S2: C, 68.53; H, 6.98; N, 11.42.
Found: C, 68.81; H, 7.18; N, 11.53.
5-ter t -Bu t yl-1,3-b is[(cycloh e xylt h iou r e id o)m e t h yl]-
ben zen e (1e). Obtained as a white solid after recrystalliza-
tion from methanol: yield 77%; mp 143-145 °C; IR (KBr)
1
3252, 1546, 892 cm-1; H NMR (270 MHz, CDCl3, 0.05 M, 50
1,3-Bis[(N′-bu tylth iou r eid o)m eth yl]-5-(tr iflu or om eth -
yl)ben zen e (4). Obtained as a white solid after column
chromatography (silica gel, 1:1 hexanes-EtOAc): yield 51%;
mp 154-156 °C; IR (KBr) 3254, 1567, 860, 701 cm-1; 1H NMR
(270 MHz, CDCl3, 50 °C, 0.025 M) δ 0.77 (t, J ) 7.0 Hz, 6H),
1.13 (m, 8H), 2.83 (br s, 4H), 5.03 (br s, 4H), 7.20 (br s, 2H),
7.34 (s, 1H), 7.41 (s, 2H), 7.54 (br s, 2H); MS (FAB) m/z 435
(M+ + 1). Anal. Calcd for C19H29F3N4S2: C, 52.51; H, 6.73;
N, 12.89. Found: C, 52.82; H, 6.88; N, 12.80.
°C) δ 0.80-1.80 (m, 20H), 1.29 (s, 9H), 3.80 (br s, 2H), 4.71
(br s, 2H), 6.48 (br s, 2H), 6.88 (br s, 2H), 7.03 (s, 1H), 7.18 (s,
2H); MS (FAB) m/z 949 (2M+, 2% relative to M+ + 1), 475 (M+
+ 1). Anal. Calcd for C26H42N4S2: C, 65.78; H, 8.92; N, 11.80.
Found: C, 65.78; H, 9.08; N, 12.12.
5-ter t-Bu t yl-1,3-b is[(N′-ter t-b u t ylt h iou r eid o)m et h yl]-
ben zen e (1f). Obtained as a white solid after column chro-
matography (silica gel, 7:3 hexanes-EtOAc): yield 94%; mp
157-159 °C; IR (KBr) 3287, 1542, 787, 700 cm-1; 1H NMR (270
MHz, CDCl3, 0.05 M, 50 °C) δ 1.30 (s, 9H), 1.36 (s, 18H), 4.77
(d, J ) 5.2 Hz, 4H), 6.21 (br s, 4H), 7.09 (s, 1H), 7.25 (s, 2H);
MS (FAB) m/z 844 (2M+ - 1, 2% relative to M+ + 1), 423 (M+
+ 1). Anal. Calcd for C22H38N4S2: C, 62.51; H, 9.06; N, 13.25.
Found: C, 62.49; H, 9.28; N, 13.06.
5-ter t-Bu tyl-1,3-bis[(N′-n eop en tylth iou r eid o)m eth yl]-
ben zen e (1g). Obtained as a white solid after column
chromatography (silica gel, 8:2 hexanes-EtOAc): yield 74%;
mp 170-173 °C; IR (KBr) 3267, 1559, 703 cm-1; 1H NMR (270
MHz, CDCl3, 0.05 M, 50 °C) δ 0.73 (s, 18H), 1.32 (s, 9H), 2.66
(br s, 4H), 4.98 (br s, 4H), 6.97 (s, 1H), 7.0-7.3 (br s containing
s at 7.14, 4H), 7.70 (br s, 2H); MS (FAB) m/z 900 (2M+ - 1,
2% relative to M+ + 1), 451 (M+ + 1). Anal. Calcd for
5-ter t-Bu tyl-1,3-bis[(N′-bu tylu r eido)m eth yl]ben zen e (5).
Obtained as a white solid after recrystallization from metha-
nol: yield 73%; mp 195-197 °C; IR (KBr) 3333, 1631 cm-1
;
1H NMR (270 MHz, DMSO-d6, 30 °C) δ 0.87 (t, J ) 7.2 Hz,
6H), 1.25 (s, 9H), 1.20-1.41 (m, 8H), 3.01 (m, 4H), 4.16 (d, J
) 5.9 Hz, 4H), 5.85 (t, J ) 5.6 Hz, 2H), 6.18 (t, J ) 5.9 Hz,
2H), 6.91 (s, 1H), 7.13 (s, 2H); MS (FAB) m/z 782 (2M+ + 1,
22% relative to M+), 391 (M+). Anal. Calcd for C22H38N4O2:
C, 67.66; H, 9.81; N, 14.34. Found: C, 67.60; H, 9.76; N, 14.43.
3,3′-Bis[(N′-bu tylth iou r eid o)m eth yl]bip h en yl (6). To a
stirred solution of diamine 22 (641 mg, 3.0 mmol) in 20 mL of
CHCl3 was added dropwise a solution of butyl isothiocyanate
(0.73 mL, 6.0 mmol) in 10 mL of CHCl3 under nitrogen. The
reaction mixture was refluxed for 6 h, and then the solvent
was removed to dryness. Recrystallization from ethanol gave
755 mg (57%) of analytically pure sample 6 as a white solid:
(21) Pullukat, T. J .; Urry, G. Tetrahedron Lett. 1967, 1953-1954.