6440 J . Org. Chem., Vol. 61, No. 18, 1996
Notes
lation of 1,2,4,5-tetracyanobenzene with MeCN.7 How-
ever, these examples are “unexpected” side reactions
accompanied by relevant major photoreactions. The
present photoinduced alkylation reactions provide a new
synthetic route using a combination of Ar2CO and t-
BuNH2 for the effective generation of •C(X)R1R2 from the
corresponding solvents.
126.56, 126.90, 128.22, 128.80, 130.18, 130.68, 135.63, 137.92,
141.17; exact mass calcd for C18H17N 247.1362, found 247.1353.
2-(Cya n om et h yl)-6-m et h oxy-1-p h en yl-1,2,3,4-t et r a h y-
d r on a p h th a len e (2e). The ratio of the trans to cis isomer was
32:68. Trans isomer; mp 110.0-110.5 °C (from hexane/benzene);
IR (CHCl3) 2240 (CN) cm-1; 1H NMR δ 1.75-1.91 (m, 1H), 2.14-
2.26 (m, 3H), 2.37 (dd, 1H, J ) 19.0, 6.8 Hz), 2.87-3.11 (m, 2H),
3.74 (s, 3H), 3.79 (d, 1H, J ) 10.6 Hz), 6.60-6.66 (m, 3H), 7.10-
7.36 (m, 5H); 13C NMR δ 22.14, 27.19, 28.74, 39.56, 50.31, 55.06,
112.42, 112.87, 118.43, 126.84, 128.65, 128.98, 130.27, 131.19,
136.98, 144.17, 157.77; exact mass calcd for C19H19NO 277.1468,
found 277.1474. Anal. Calcd for C19H19NO: C, 82.28; H, 6.90;
N, 5.05. Found: C, 82,01; H, 7.12; N, 4.83. Cis isomer; IR
(CHCl3) 2240 (CN) cm-1; 1H NMR δ 1.73-1.86 (m, 2H), 1.95 (dd,
1H, J ) 16.7, 7.8 Hz), 2.10 (dd, 1H, J ) 16.8, 7.8 Hz), 2.39-2.50
(m, 1H), 2.84-3.09 (m, 2H), 3.76 (s, 3H), 4.23 (d, 1H, J ) 5.2
Hz), 6.61-6.85 (m, 3H), 7.00-7.31 (m, 5H); 13C NMR δ 21.84,
23.18, 28.68, 36.28, 47.03, 55.05, 112.81, 112.81, 119.04, 126.72,
128.07, 129.98, 130.11, 131.48, 136.70, 141.35, 157.99; exact
mass calcd for C19H19NO 277.1468, found 277.1477.
Exp er im en ta l Section
Gen er a l. Melting points were measured using open capillary
tubes and are uncorrected. Only noteworthy IR absorptions are
listed. 1H and 13C NMR spectra were recorded in CDCl3 at 250
MHz and 75 MHz, respectively. Chemical shifts are reported
in ppm relative to TMS (0 ppm, 1H) or CDCl3 (77.0 ppm, 13C) as
internal standards. Mass spectra were operated at an ionization
voltage of 70 eV. GLC analysis was performed using a 25 m
fused-silica capillary column.
MeCN, EtCN, CH2Cl2, and CHCl3 were distilled from CaH2.
The amines and ketones were used as received. Commercially
available 1a was distilled from sodium under reduced pressure
before use, and 1b was prepared according to literature method.8
The other diarylethenes (1c-f) were prepared by reactions of
the corresponding ketones with PhMgBr or MeMgBr followed
by the dehydration of the diarylcarbinols using Ac2O.9
P h otor ea ction s. A solution of 1a -f (2 mmol), a diaryl
ketone (0.5-1 mmol), and t-BuNH2 (30 mmol) in MeCN, EtCN,
CH2Cl2, CHCl3, or acetone (60 mL) was poured into a Pyrex glass
tube, purged with argon gas, sealed with a rubber septum, and
irradiated with a high-pressure mercury lamp at the ambient
temperature. After the irradiation, the products were isolated
by removal of the solvent from the photolysates followed by
chromatography on silica gel (BW-300, Wako Chemicals). The
structure determination of the products was performed on the
basis of their spectroscopic and physical properties and, in the
case of 2a , 2b, and 3a , by comparisons of the data with those
published in literature.10 It was confirmed that similar results
can be obtained by the irradiation at 366 nm using an aqueous
filter solution of BiCl3 (>350 nm), though a longer period of
irradiation time was required.
2-(2-Cya n oet h yl)d ib en zo[a ,d ]cycloh ep t a n e (2f): mp
1
107.5-108.0 °C (from hexane); IR (CHCl3) 2240 (CN) cm-1; H
NMR (at 40 °C) δ 2.10 (t, 2H, J ) 9.1 Hz), 2.37 (q, 2H, J ) 8.3
Hz), 2.89-3.02 (m, 2H), 3.20-3.33 (m, 2H), 4.06 (t, 1H, J ) 8.0
Hz), 6.99-7.32 (m, 10H); 13C NMR (at 40 °C) δ 16.04, 33.35,
33.35, 52.42, 119.25, 126.41, 127.18, 130.01, 130.67, 139.55,
139.55; exact mass calcd for C18H17N 247.1362, found 247.1378.
Anal. Calcd for C18H17N: C, 87.41; H, 6.93; N, 5.66. Found:
C, 87.28; H, 6.96; N, 5.49.
3-(Eth yla m in o)-1,1-d ip h en ylbu ta n e (3b). 3b was acety-
lated with Ac2O. The acetamide was obtained as a mixture of
two isomer. IR (CHCl3) 1610 (CdO) cm-1 1H NMR δ 1.04 (t,
;
3H, J ) 7.1 Hz), 1.15-1.22 (m, 9H), 1.52 (s, 3H), 1.94 (s, 3H),
2.09-2.34 (m, 3H), 2.45 (dt, 1H, J ) 14.2, 8.1 Hz), 2.85 (dq, 1H,
J ) 15.9, 7.4 Hz), 3.05 (dq, 1H, J ) 14.7, 7.3 Hz), 3.17 (dq, 1H,
J ) 13.7, 6.8 Hz), 3.42 (dq, 1H, J ) 13.8, 6.9 Hz), 3.57-3.71 (m,
1H), 3.85 (t, 1H, J ) 8.1 Hz), 3.88 (t, 1H, J ) 7.3 Hz), 4.26-4.41
(m, 1H), 7.11-7.35 (m, 20H); 13C NMR δ 14.81, 15.09, 19.09,
19.97, 21.53, 22.15, 35.53, 39.89, 40.33, 40.81, 48.03, 48.66, 49.64,
51.61, 126.14, 126.14, 126.47, 126.70, 127.37, 127.71, 127.77,
127.82, 128.41, 128.44, 128.67, 128.84, 143.18, 144.23, 144.43,
145.07, 170.34, 170.45; exact mass calcd for C20H25NO 295.1938,
found 295.1941.
2-(Cya n om eth yl)-1-p h en lyin d a n (2c). The ratio of the
trans to cis isomer was 34:66. IR (CHCl3) 2240 (CN) cm-1
.
3-(Dieth yla m in o)-1,1-d ip h en ylbu ta n e (3c): 1H NMR δ
1.04 (d, 3H, J ) 7.0 Hz), 1.05, (t, 6H, J ) 6.8 Hz), 2.09 (ddd, 1H,
J ) 14.4, 8.4, 6.0 Hz), 2.31 (ddd, 1H, J ) 14.1, 7.0, 7.0 Hz), 2.42
(dq, 2H, J ) 13.3, 6.9 Hz), 2.64 (dq, 2H, J ) 13.0, 7.3 Hz), 2.73-
2.81 (m, 1H), 4.35 (dd, 1H, J ) 8.7, 6.8 Hz), 7.16-7.64 (m, 10H);
13C NMR δ 13.68, 14.10, 14.10, 40.25, 43.05, 43.05, 47.72, 51.51,
125.80, 125.83, 127.73, 128.04, 128.17, 128.25, 144.97, 145.53;
exact mass calcd for C20H27N 281.2145, found 281.2116. Anal.
Calcd for C20H27N: C, 85.35; H, 9.67; N, 4.98. Found: C, 85.35;
H, 9.79; N, 4.80.
1
Trans isomer; H NMR δ 2.45 (d, 1H, J ) 7.3 Hz), 2.49 (d, 1H,
J ) 4.6 Hz), 2.55-2.67 (m, 1H), 2.88 (dd, 1H, J ) 15.1, 8.1 Hz),
3.24 (dd, 1H, J ) 15.5, 7.4 Hz), 4.03 (d, 1H, J ) 9.0 Hz), 6.84-
7.36 (m, 9H); 13C NMR δ 20.37, 37.06, 46.70, 56.59, 118.28,
124.34, 124.86, 126.89, 127.18, 128.39, 128.77, 128.89, 141.52,
141.94, 145.07; exact mass calcd for C17H15N 233.1206, found
233.1212. Cis isomer; 1H NMR δ 1.93 (d, 1H, J ) 6.7 Hz), 1.93
(d, 1H, J ) 8.3 Hz), 2.88 (dd, 1H, J ) 15.1, 8.1 Hz), 2.94-3.09
(m, 1H), 3.18 (dd, 1H, J ) 14.9, 7.2 Hz), 4.50 (d, 1H, J ) 7.6
Hz), 6.84-7.36 (m, 9H); 13C NMR δ 19.37, 37.06, 41.48, 53.68,
119.15, 124.70, 125.37, 127.18, 127.18, 127.36, 128.64, 128.89,
139.25, 141.79, 144.48.
3-Cya n o-1,1-d ip h en ylbu ta n e (4a ): mp 73.0-73.5 °C (from
hexane/benzene); IR (CHCl3) 2240 (CN) cm-1 1H NMR δ 1.27
;
(d, 3H, J ) 6.6 Hz), 2.15-2.42 (m, 3H), 4.15-4.21 (m, 1H), 7.13-
7.33 (m, 10H); 13C NMR δ 18.10, 23.93, 39.89, 48.77, 122.58,
126.62, 126.87, 127.46, 127.82, 128.64, 128.85, 142.55, 143.40;
exact mass calcd for C17H17N 235.1362, found 235.1359. Anal.
Calcd for C17H17N: C, 86.77; H, 7.28; N, 5.95. Found: C, 86.91;
H, 7.33; N, 5.90.
2-(Cya n om et h yl)-1-p h en yl-1,2,3,4-t et r a h yd r on a p h t h a -
len e (2d ). The ratio of the trans to cis isomer was 33:67. IR
(CHCl3) 2190 (CN) cm-1. Trans isomer; 1H NMR δ 1.76-1.85
(m, 1H), 2.18-2.26 (m, 2H), 2.21 (dd, 1H, J ) 19.4, 7.2 Hz), 2.37
(dd, 1H, J ) 19.4, 7.5 Hz), 2.90-3.10 (m, 2H), 3.85 (d, 1H, J )
8.7 Hz), 6.70 (d, 1H, J ) 7.7 Hz), 6.93 (d, 1H, J ) 7.5 Hz), 7.01-
7.34 (m, 7H); 13C NMR δ 22.37, 27.36, 28.61, 39.54, 51.02, 118.49,
126.09, 126.26, 127.01, 128.67, 128.87, 129.19, 130.27, 135.86,
138.15, 144.02; exact mass calcd for C18H17N 247.1362, found
1,1-Dich lor o-3,3-d ip h en ylp r op a n e (4b): mp 61.5-62.5 °C
1
(from hexane); H NMR δ 2.88 (t, 2H, J ) 7.3 Hz), 4.25 (t, 1H,
J ) 7.8 Hz), 5.35 (t, 1H, J ) 6.7 Hz), 7.12-7.34 (m, 10H); 13C
NMR δ 48.05, 49.05, 71.99, 126.80, 127.64, 128.74, 142.14; exact
mass calcd for C15H14Cl2 264.0474, found 264.0422. Anal. Calcd
for C15H14Cl2: C, 67.94; H, 5.32; Cl, 26.74. Found: C, 67.72; H,
5.17; Cl, 27.11.
1
247.1338. Cis isomer; H NMR δ 1.76-1.85 (m, 2H), 1.98 (dd,
1H, J ) 16.7, 7.8 Hz), 2.12 (dd, 1H, J ) 16.7, 7.8 Hz), 2.39-2.54
(m, 1H), 2.90-3.10 (m, 2H), 4.30 (d, 1H, J ) 5.2 Hz), 6.70 (d,
1H, J ) 7.7 Hz), 6.93 (d, 1H, J ) 7.5 Hz), 7.01-7.34 (m, 7H);
13C NMR δ 21.98, 23.35, 28.48, 36.19, 47.81, 119.15, 126.18,
1,1,1-Tr ich lor o-3,3-d ip h en ylp r op a n e (4c). The photore-
action of 1a with CHCl3 gave 4c in 53% yield, accompanying
the formation of 1,1-dichloro-2,2-diphenylcycropropane (9%, mp
111.5-112.0 °C, lit.11 mp 113-114 °C). Mp 33.5-34.0 °C (from
hexane); 1H NMR δ 3.55 (d, 2H, J ) 5.9 Hz), 4.51 (t, 1H, J ) 5.9
Hz), 7.10-7.29 (m, 10H); 13C NMR δ 49.45, 59.95, 99.04, 126.62,
127.85, 128.68, 143.41; exact mass calcd for C15H13Cl3 298.0085,
(7) Tsujimoto, K.; Abe, K.; Ohashi, M. J . Chem. Soc., Chem.
Commun. 1983, 984.
(8) Nakabayashi, K.; Kojima, J .; Tanabe, K.; Yasuda, M.; Shima,
K. Bull. Chem. Soc. J pn. 1989, 62, 96.
(9) Weiss, R. Organic Syntheses; Wiley: New York, 1959; Coll. Vol.
III, p 729.
(10) Yamashita, T.; Shiomori, K.; Yasuda, M.; Shima, K. Bull. Chem.
Soc. J pn. 1991, 64, 366.
(11) Hoeg, D. F.; Lusk, D. I.; Crumbliss, A. L. J . Am. Chem. Soc.
1965, 87, 4147.