TRANSFORMATIONS OF para-SUBSTITUTED BENZYLCYCLOPROPANES
415
(Irel, %): 205 (21.6) [M – 1]+, 204 (26.8), 188 (63.9),
172 (39.8), 162 (37.6), 146 (86.4), 134 (62.3), 128
(88.1), 115 (100), 103 (21.1), 91 (66.9), 77 (36.3), 65
(21.1), 63 (19.2), 55 (32.4), 51 (19.1).
tert-butyl-2-nitrobenzene (XLVIII) and 6.1 g (85%) of
1-tert-butyl-4-nitrobenzene (XVII); compound XVII
was identical to a sample obtained by nitration of XI
(see above).
Compound XLVIII. Viscous oily substance.
1H NMR spectrum, δ, ppm (J, Hz): 1.05 s [9H, C(CH3)3],
3.67 d (2H, CH2C6H3, J = 6.6), 5.14 m (2H, CH=CH2),
6.01 m (1H, CH=CH2), 7.21 d (1H, 6-H, Jo = 8.1),
7.33 d.d (1H, 5-H, Jo = 8.2, Jm = 2.0), 7.83 d (1H, 3-H,
Jm = 2.0). Mass spectrum, m/z (Irel, %): 219 (2.5) [M]+,
204 (11.2), 187 (2.0), 173 (6.1), 162 (78.7), 143 (67.2),
128 (77.1), 116 (96.7), 115 (100), 103 (3.4), 91 (25.4),
77 (8.2), 63 (6.6), 57 (80.6), 51 (3.3), 43 (43.4).
1
Compound XLVI. H NMR spectrum, δ, ppm
(J, Hz): 1.29 d (6H, CH3, J = 7.7), 3.38 sept [1H,
CH(CH3)2], 3.42 d (2H, CH2C6H3, J = 6.8), 5.14 m
(2H, CH=CH2), 5.91 m (1H, CH=CH2), 7.36 d.d (1H,
6-H, Jo = 8.2, Jm = 2.0), 7.38 d (1H, 5-H, Jo = 8.2),
7.52 d (1H, 2-H, Jm = 2.0). Mass spectrum, m/z
(Irel, %): 205 (7.9) [M]+, 188 (10.3), 170 (7.1), 160
(34.8), 147 (66.8), 129 (25.3), 128 (51.6), 115 (100),
93 (22.1), 91 (84.8), 77 (45.1), 65 (33.9), 63 (26.1), 55
(9.9), 51 (31.3).
Nitration of bis(4-fluorophenyl)methane (XL).
The nitration of 4.1 g (0.02 mol) of compound XL
according to the standard procedure gave 5.4 g of
a mixture of products; by column chromatography we
isolated 1.28 g (65%) of 1-fluoro-4-nitrobenzene (LII),
bp 80–81°C (10 mm), nD20 = 1.5310 [23]; 1.29 g (54%)
of 4-fluorobenzyl acetate (LIII); 0.27 g of (11%) of
4-fluorobenzyl nitrate (LIV); and 0.85 g (24%) of
4,4'-difluoro-2-nitrodiphenylmethane (L).
1
Compound XVI. H NMR spectrum, δ, ppm
(J, Hz): 1.30 d (6H, CH3, J = 7.0), 3.03 sept [1H,
CH(CH3)2], 7.37 d (2H, 2-H, 6-H, Jo = 8.8), 8.14 d
(2H, 3-H, 5-H, Jo = 8.8). Mass spectrum, m/z (Irel, %):
165 (47.5) [M]+, 150 (100), 120 (18.7), 104 (31.7), 91
(42.9), 77 (30.2), 65 (9.4), 63 (8.6), 51 (15.8).
1
Compound XLIII. H NMR spectrum, δ, ppm
(J, Hz): 1.25 d (6H, CH3, J = 6.9), 3.24 sept [1H,
CH(CH3)2], 3.51 d (2H, CH2C6H3, J = 6.4), 5.01 m and
5.19 m (2H, CH=CH2), 5.99 m (1H, CH=CH2), 7.42 d
(1H, 3-H, Jo = 8.6), 8.02 d (1H, 6-H, Jm = 2.3), 8.05 d.d
(1H, 4-H, Jo = 8.6, Jm = 2.3). Mass spectrum, m/z
(Irel, %): 205 (9.1) [M]+, 190 (100), 173 (11.2), 144
(46.3), 129 (53.7), 115 (36.4), 103 (6.3), 91 (17.5), 77
(12.5), 63 (8.1), 51 (8.6).
1
Compound LIV. H NMR spectrum, δ, ppm:
5.41 m (2H, CH2C6H4), 7.09 m (2H, 3-H, 5-H), 7.39 m
(2H, 2-H, 6-H). Mass spectrum, m/z (Irel, %): 171 (9.7)
[M]+, 125 (35.5), 123 (34.2), 109 (50.1), 97 (27.6), 95
(100), 78 (20.2), 75 (27.1), 57 (3.7).
Compound LIII. 1H NMR spectrum, δ, ppm: 2.09 s
(3H, CH3), 5.03 m (2H, CH2C6H4), 7.01 m (2H, 3-H,
5-H), 7.33 m (2H, 2-H, 6-H). Mass spectrum, m/z
(Irel, %): 168 (37.1) [M]+, 126 (79.8), 109 (100), 108
(65.8), 97 (17.7), 83 (16.1), 75 (8.1), 57 (6.4), 43 (29.8).
1
Compound XLV. H NMR spectrum, δ, ppm
(J, Hz): 3.48 d (2H, CH2C6H4, J = 6.8), 5.16 m (2H,
CH=CH2), 5.93 m (1H, CH=CH2), 7.29 d (2H, 2-H,
6-H, Jo = 8.6), 8.15 d (2H, 3-H, 5-H, Jo = 8.6). Mass
spectrum, m/z (Irel, %): 163 (100) [M]+, 146 (10.8), 133
(12.9), 116 (29.1), 115 (61.9), 91 (15.8), 89 (6.5), 77
(3.3), 65 (2.7), 63 (2.6), 51 (1.9).
Compound L. Colorless crystalline substance,
1
mp 165–166°C. H NMR spectrum, δ, ppm: 4.09 m
(2H, CH2); 7.46 m (3H), 7.76 m (2H), and 8.18 m (2H)
(Harom). Mass spectrum, m/z (Irel, %): 249 (100) [M]+,
232 (9.2), 202 (53.2), 201 (75.8), 183 (41.9), 170 (6.4),
149 (9.7), 125 (35.5), 109 (48.4), 95 (8.4), 83 (16.5),
73 (6.4), 57 (14.2).
1
Compound XLVII. H NMR spectrum, δ, ppm
(J, Hz): 1.30 d (6H, CH3, J = 6.8), 3.23 sept [1H,
CH(CH3)2], 3.53 d (2H, CH2C6H3, J = 6.4), 5.07 m
(2H, CH=CH2), 5.91 m (1H, CH=CH2), 7.30 d (1H,
6-H, Jo = 8.6), 7.76 d (1H, 3-H, Jm = 2.3), 7.97 d.d
(1H, 5-H, Jo = 8.6, Jm = 2.3). Mass spectrum, m/z
(Irel, %): 205 (4.8) [M]+, 190 (100), 173 (10.2), 144
(56.9), 129 (70.1), 115 (49.6), 103 (6.1), 91 (28.3), 47
(22.5), 63 (16.2), 51 (20.1).
Nitration of 1-allyl-4-cyclopropylbenzene (LV).
The nitration of 3.16 g (0.02 mol) of compound LV
according to the standard procedure gave 3.43 g of
a mixture of products; by column chromatography on
aluminum oxide we isolated 1.13 g (35.7%) of initial
compound LV and 2.23 g (81%, calculated on the
reacted LV) of a mixture of 3- and 2-nitro-1-allyl-4-
cyclopropylbenzenes LVIII and LIX at a ratio of 1:6
(according to the GC–MS and 1H NMR data).
Nitration of 1-allyl-4-tert-butylbenzene
(XXXIX). The nitration of 6.96 g (0.04 mol) of com-
pound XXXIX according to the standard procedure
gave 8.3 g of a mixture of products; by column
chromatography we isolated 1.3 g (15%) of 1-allyl-4-
1
Compound LVIII. H NMR spectrum, δ, ppm
(J, Hz): 0.62 m (2H), 1.02 m (2H), and 2.39 m (1H)
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 41 No. 3 2005