1110 J . Org. Chem., Vol. 62, No. 4, 1997
Nishio
C22H19NS: C, 80.21; H, 5.81; N, 4.25. Found: C, 79.88; H,
6.07; N, 4.38.
127.2 (d), 127.5 (d), 128.1 (d), 128.4 (d), 128.7 (d), 129.1 (d),
135.3 (s), 141.3 (s), 141.9 (s), 144.2 (s), 159.1 (s). Anal. Calcd
for C21H17NS: C, 79.96; H, 5.43; N, 4.44. Found: C, 79.64; H,
5.43; N, 4.37.
N -(3,3-Dip h e n yl-3-m e r ca p t op r op yl)t h iob e n za m id e
(8): mp 140-141 °C; IR (KBr) 3270 (NH), 2550 (SH) cm-1; 1H
NMR δ 2.93 (1H, s), 2.89 (2H, t, J ) 6.8), 3.88 (2H, q, J ) 6.6),
7.16-7.56 (15H, m); 13C NMR δ 42.2 (t), 43.7 (t), 56.7 (s), 126.5
(d), 127.0 (d), 127.3 (d), 128.2 (d), 128.3 (d), 128.4 (d), 130.9
(d), 141.3 (s), 146.6 (s), 198.5 (s). Anal. Calcd for C22H21NS2:
C, 72.69; H, 5.82; N, 3.85. Found: C, 72.80; H, 5.82; N, 3.86.
A solution of 8 (1 mmol) and LR (0.5mmol) in toluene (15 mL)
was refluxed for 10 min. After purification by column chro-
matography, 7s was obtained in 58% yield.
[2-(N-p-Tolu oyla m in o)p h en yl]eth a n e-1-th iol (13d ): mp
146-147 °C; IR (KBr) 3240 (NH), 2560 (SH), 1640 (CO) cm-1
;
1H NMR δ 1.74 (3H, d, J ) 6.8), 2.13 (1H, d, J ) 5.4), 2.43
(3H, s), 4.19-4.47 (1H, m), 7.06-7.41 (5H, m), 7.80-7.99 (3H,
m), 8.97 (1H, br s); 13C NMR δ 21.4 (q), 23.9 (q), 35.2 (d), 125.0
(d), 125.3 (d), 126.0 (d), 127.2 (d), 128.1 (d), 129.4 (d), 131.6
(s), 135.3 (s), 135.4 (s), 142.3 (s), 165.3 (s). Anal. Calcd for
C16H17NOS: C, 70.82; H, 6.31; N, 5.16. Found: C, 71.09; H,
6.31; N, 5.15.
N-(3,3-Di-p-tolyla llyl)th ioben za m id e (7t): mp 111-112
°C; IR (KBr) 3395 (NH) cm-1
;
1H NMR δ 2.32 (3H, s), 2.37
4-Meth yl-2-p-tolyl-3,1-ben zoth ia zin e (14d ): bp 195 °C (3
mmHg); 1H NMR δ 1.44 (3H, d, J ) 6.8), 2.36 (3H, s), 4.12
(1H, q, J ) 6.8), 7.04-7.55 (6H, m), 8.05 (2H, d, J ) 8.3); 13C
NMR δ 21.4 (q), 23.2 (q), 37.2 (d), 125.4 (d), 125.6 (s), 127.4
(d), 127.5 (d), 128.7 (d), 129.1 (d), 135.7 (s), 141.7 (s), 143.2
(s), 159.0 (s). Anal. Calcd for C16H15NS: C, 75.85; H, 5.97;
N, 5.53. Found: C, 75.85; H, 5.92; N, 5.57.
(3H, s), 4.49 (2H, dd, J ) 5.3, 6.9), 6.17 (1H, t, J ) 6.9), 7.05-
7.66 (14H, m); 13C NMR δ 21.0 (q), 21.2 (q), 46.1 (t), 120.6 (d),
126.6 (d), 127.4 (d), 128.3 (d), 128.9 (d), 129.1 (d), 129.4 (d),
130.9 (d), 135.8 (s), 137.5 (s), 137.6 (s), 138.7 (s), 141.6 (s), 146.3
(s), 198.5 (s). Anal. Calcd for C24H23NS: C, 80.63; H, 6.48;
N, 3.92. Found: C, 80.29; H, 6.66; N, 4.01.
N-(3-Meth yl-2-bu ten yl)th ioben za m id e (7u ) a n d N-(3-
m eth yl-3-bu ten yl)th ioben za m id e (9) could not completely
separated: bp (a 5:7 mixture of 7u and 9) 260 °C (1 mmHg);
1-[2-(N-r-Naph th oylam in o)ph en yl]eth an e-1-th iol (13e):
mp 124-125 °C; IR (KBr) 3260 (NH), 1640 (CO) cm-1; 1H NMR
δ 1.73 (3H, d, J 6.8), 2.00 (1H, d, J ) 5.9), 4.18-4.46 (1H, m),
IR (film) (a mixture of 7u and 9) 3320 (NH), 1645 (CdC) cm-1
;
7.05-7.63 (6H, m), 7.72-8.05 (4H, m), 8.40-8.68 (2H, m); 13
C
1H NMR δ (for 7u ) 1.79 (3H, s), 1.80 (3H, s), 4.35 (2H, t, J )
5.9), 5.37-5.44 (1H, m), 7.33-7.75 (5H, m); δ (for 9) 1.80 (3H,
s), 2.47 (2H, t, J ) 6.6), 3.91 (2H, t, J ) 6.6), 4.89 (2H, d, J )
16.5), 7.35-7.75 (5H, m); 13C NMR δ (for 7u ) 18.2 (q), 25.7
(q), 45.2 (t), 117.9 (d), 141.8 (s), 198.5 (s) in addition to aromatic
carbon peaks; δ (for 9) 21.8 (q), 36.0 (t), 43.8 (t), 113.2 (t), 142.4
(s), 198.9 (s) in addition to aromatic carbon peaks. Anal. Calcd
for C12H15NS: C, 70.20; H, 7.36; N, 6.82. Found (a mixture of
7u and 9): C, 70.43; H, 7.40; N, 6.85.
NMR δ 24.3 (q), 34.6 (d), 124.8 (d), 125.1 (d), 125.4 (d), 126.0
(d), 126.5 (d), 127.4 (d), 128.1 (d), 128.4 (d), 130.3 (s), 131.2
(d), 133.9 (s), 134.1 (s), 135.0 (s), 136.0 (s), 167.7 (s). Anal.
Calcd for C19H17NOS: C, 74.23; H, 5.57; N, 4.56. Found: C,
74.23; H, 5.50; N, 4.58.
4-Meth yl-2-(r-n a p h th yl)-3,1-ben zoth ia zin e (14e): bp 230
1
°C (2 mmHg); H NMR δ 1.56 (3H, d, J ) 6.8), 4.19 (1H, q, J
) 6.8), 7.11-7.68 (6H, m), 7.73-7.98 (4H, m), 8.54-8.68 (1H,
m); 13C NMR δ 23.8 (q), 37.9 (d), 124.7 (d), 125.3 (d), 125.7 (d),
126.1 (d), 127.0 (d), 127.4 (d), 128.1 (d), 129.0 (d), 130.8 (d),
Reaction s of [2-(N-Acylam in o)ph en yl]alkan ols 12, [4-(N-
a cyla m in o)p h en yl]a lk a n ols 18, a n d [2-[N-(Eth oxyca r bo-
n yl)a m in o]p h en yl]a lk a n ols 21 w ith LR. A solution of 12
(or 18 or 21) (2 mmol) and LR (1-2 mmol) in toluene (70 mL)
was heated to reflux under argon for 15-30 min. After
removal of the solvent, the residue was chromatographed on
a silica gel column with benzene-ethyl acetate (50:1-9:1) to
yield the products 13-17, 19, 20, 22, and 23.
133.9 (s), 136.1 (s), 142.5 (s), 160.3 (s). Anal. Calcd for C19H15
-
NS: C, 78.87; H, 5.23; N, 4.84. Found: C, 78.61; H, 5.08; N,
4.78.
4,4-Dip h en yl-2-p-tolyl-3,1-ben zoth ia zin e (14f): mp 199-
200 °C; 1H NMR δ 2.35 (3H, s), 6.72 (1H, dd, J ) 1.0, 7.3),
7.11-7.65 (15H, m), 7.92 (2H, br d, J ) 7.8); 13C NMR δ 21.5
(q), 60.2 (s), 127.0 (d), 127.4 (d), 127.5 (d), 127.9 (d), 128.3 (d),
129.2 (d), 129.5 (d), 129.7 (s), 135.1 (s), 141.9 (s), 142.9 (s),
145.2 (s), 160.5 (s). Anal. Calcd for C27H21NS: C, 82.84; H,
5.41; N, 3.58. Found: C, 82.63; H, 5.36; N, 3.53.
4,4-Dip h en yl-2-p-tolyl-3,1-ben zoxa zin e (15f): mp 180-
181 °C; 1H NMR δ 2.37 (3H, s), 6.70 (1H, br d, J ) 7.3), 7.03-
7.42 (15H, m), 8.10 (2H, br d, J ) 7.8); 13C NMR δ 21.5 (q),
86.0 (s), 124.8 (d), 125.8 (d), 126.7 (d), 127.9 (d), 128.1 (d), 128.2
(d), 128.9 (d), 129.1 (d), 129.9 (d), 129.9 (s), 140.0 (s), 141.8
(s), 142.9 (s), 156.9 (s). Anal. Calcd for C27H21NO: C, 86.37;
H, 5.64; N, 3.73. Found: C, 86.09; H, 5.88; N, 3.65.
1-P h e n yl-1-[2-(N -p -t h iot olu oyla m in o)p h e n yl]e t h yl-
en e (16g): mp 127-128 °C; IR (KBr) 3350 (NH) cm-1; 1H NMR
δ 2.30 (3H, s), 5.41 (1H, d, J ) 1.0), 5.83 (1H, d, J ) 1.0), 6.91-
7.61 (13H, m), 8.70 (1H, br s); 13C NMR δ 21.2 (q), 117.6 (t),
125.1 (d), 126.5 (d), 127.0 (d), 128.2 (d), 128.8 (d), 128.9 (d),
130.9 (d), 135.8 (s), 136.5 (s), 139.1 (s), 139.8 (s), 141.4 (s), 146.0
(s), 197.2 (s). Anal. Calcd for C22H19NS: C, 80.20; H, 5.81;
N, 4.22. Found: C, 80.36; H, 5.74; N, 4.22.
2-Meth yl-4-p h en yl-3,1-ben zoth ia zin e (14a ): mp 64-65
1
°C; H NMR δ 2.33 (3H, s), 5.23 (1H, s), 6.91-7.49 (9H, m);
13C NMR δ 28.4 (q), 45.5 (d), 121.3 (s), 127.2 (d), 127.4 (d),
127.6 (d), 128.5 (d), 128.7 (d), 141.9 (s), 143.2 (s), 159.5 (s):
Anal. Calcd for C15H13NS: C, 75.28; H, 5.47; N, 5.85. Found:
C, 75.30; H, 5.48; N, 5.85.
r-[2-(N-P iva loyla m in o)p h en yl]-r-p h en ylm et h a n et h i-
ol (13b): mp 106-107 °C; IR (KBr) 3270 (NH), 1645 (CO) cm-1
;
1H NMR δ 1.14 (9H, s), 2.32 (1H, d, J ) 4.9), 5.51 (1H, d, J )
4.9), 6.99-7.40 (8H, m), 7.90-7.99 (2H, m); 13C NMR δ 27.4
(q), 39.5 (s), 44.8 (d), 124.8 (d), 127.7 (d), 127.8 (d), 128.4 (d),
128.7 (d), 129.0 (d), 133.3 (s), 135.6 (s), 140.2 (s), 176.6 (s).
Anal. Calcd for C18H21NOS: C, 72.20; H, 7.07; N, 4.67.
Found: C, 72.34; H, 7.09; N, 4.68.
2-ter t-Bu tyl-4-p h en yl-3,1-ben zoth ia zin e (14b): mp 105-
1
107 °C; H NMR δ 1.18 (9H, s), 5.17 (1H, s), 6.94-7.51 (9H,
m); 13C NMR δ 27.7 (q), 41.9 (s), 44.8 (d), 122.5 (s), 127.1 (d),
127.2 (d), 127.5 (d), 128.3 (d), 128.4 (d), 141.4 (s), 143.6 (s),
170.9 (s). Anal Calcd for C18H19NS: C, 76.83; H, 6.80; N, 4.98.
Found: C, 76.62; H, 7.07; N, 4.70.
1-P h en yl-1-[2-(N-p-tolu oylam in o)ph en yl]eth ylen e (17g):
mp 81-82 °C; IR (KBr) 3430 (NH), 1670 (CO), 1615 (CdC)
1
r-P h en yl-r-[2-(N-p -t olu oyla m in o)p h en yl]m et h a n et h -
iol (13c): mp 123-124 °C; IR (KBr) 3290 (NH), 2540 (SH),
1635 (CO) cm-1; 1H NMR δ 2.34 (1H, d, J ) 5.4), 2.39 (3H, s),
5.56 (1H, d, J ) 5.4), 7.03-7.46 (10H, m), 7.61 (2H, d, J )
8.3), 8.02 (1H, d, J ) 7.8), 8.45 (1H, br s); 13C NMR δ 21.4 (q),
44.6 (d), 124.7 (d), 125.1 (d), 127.0 (d), 127.7 (d), 128.0 (d), 128.4
(d), 128.8 (d), 129.3 (d), 131.6 (s), 133.8 (s), 135.4 (s), 140.5 (s),
142.3 (s), 165.2 (s). Anal. Calcd for C21H19NOS: C, 75.64; H,
5.74; N, 4.20. Found: C, 75.75; H, 5.74; N, 4.20. A solution
of 13c (0.5 mmol) and LR (0.25 mmol) in toluene (50 mL) was
refluxed under argon for 15 min. After purification by flash
chromatography, 14c was obtained in 56% yield.
cm-1; H NMR δ 2.26 (s), 5.35 (1H, d, J ) 1.0), 5.83 (1H, d, J
) 1.0), 6.97-7.62 (12H, m), 7.79 (1H, br s), 8.49 (1H, dd, J )
1.0, 8.3); 13C NMR δ 21.1 (q), 117.4 (t), 120.8 (d), 123.4 (d),
126.4 (d), 128.5 (d), 128.7 (d), 128.8 (d), 130.3 (d), 131.4 (s),
131.7 (s), 135.3 (s), 138.7 (s), 141.7 (s), 146.2 (s), 164.6 (s). Anal.
Calcd for C22H19NO: C, 84.31; H, 6.11; N, 4.47. Found: C,
84.46; H, 6.16; N, 4.49.
r-P h e n y l -r-[4 -(N -p -t h i o t o l u o y l a m i n o )p h e n y l ]-
m eth a n eth iol (19): mp 77-78 °C; IR (KBr) 3400 (NH), 2540
1
(SH) cm-1; H NMR δ 2.28 (1H, d, J ) 4.9), 2.36 (3H, s), 5.42
(1H, d, J ) 4.9), 7.12-7.45 (10H, m), 7.52-7.78 (3H, m), 9.00
(1H, br s); 13C NMR δ 21.4 (q), 47.3 (d), 123.5 (d), 126.8 (d),
127.3 (d), 127.7 (d), 128.3 (d), 128.6 (d), 129.1 (d), 137.9 (s),
140.1 (s), 142.9 (s), 198.0 (s). Anal. Calcd for C21H19NS2: C,
72.16; H, 5.48; N, 4.01. Found: C, 71.97; H, 5.45; N, 4.05.
4-P h en yl-2-p-tolyl-3,1-ben zoth ia zin e (14c): mp 125-126
1
°C; H NMR δ 2.36 (3H, s), 5.33 (1H, s), 6.98-7.64 (11H, m),
7.98 (2H, d, J ) 8.3); 13C NMR δ 21.4 (q), 45.6 (d), 122.7 (s),