SHAINYAN, DANILEVICH
218
95.56 m (F3), 93.97 m (F5). Mass spectrum, m/z (Irel,
%): 273 (46) [M], 257 (6) [M NH2], 253 (6) [M HF],
210 (26) [M F CONH2], 178 (48) [257 Br], 150
(32) [178 CO], 131 (22) [210 Br], 81 (30) [C5H2F],
44 (100) [CONH2].
Methyl fluorobenzoate FC6H4CO2Me (XXII).
Mass spectrum, m/z (Irel, %): 154 (30) [M], 123 (100)
[M OMe], 95 (60) [M COOMe], 75 (40) [95 HF].
Methyl bromofluorobenzoate BrFC6H3COOMe
(XXIII). Mass spectrum, m/z (Irel, %): 232 (35) [M], 201
(100) [M OMe], 173 (50) [M COOMe], 153 (15)
[M Br], 122 (15) [201 Br], 94 (90) [173 Br], 75
(40) [95 HF].
2,4-Dibromobenzamide (XII). Mass spectrum,
m/z (Irel, %): 279 (72) [M], 263 (100) [M NH2], 235
(30) [263 CO], 154 (10) [235 Br], 75 (38) [154 Br],
44 (34) [CONH2].
Methyl
dibromofluorobenzoate
3,3,6,6-Tetrafluoro-2,4-dibromo-1,4-cyclohexa-
diene-1-carboxamide (XIII). 19F NMR spectrum,
d,
Br2FC6H2COOMe (XXIV). Mass spectrum, m/z (Irel,
%): 310 (25) [M], 279 (50) [M OMe], 251 (20) [M
COOMe], 172 (35) [251 Br], 93 (100) [172 Br], 74
[50, 93 F].
ppm: 89.82 m (F3), 90.45 m (F5). Mass spectrum, m/z
(Irel, %): 353 (100) [M], 337 (5) [M NH2], 290 (28)
[M F CONH2], 258 (24) [337 Br], 230 (18)
[258 CO], 211 (10) [290 Br], 177 (9) [258 Br], 149
(12) [230 Br], 130 (14) [209 Br], 80 (10) [Br], 44 (90)
[CONH2].
4-Bromobenzoyl fluoride 4-BrC6H4C(O)F (XXV).
Mass spectrum, m/z (Irel, %): 202 (40) [M], 183 (13)
[M F], 174 (100) [M CO], 155 (22) [M COF], 123
(10) [M Br], 79 (50) [Br], 47 (30) [COF].
4-Bromo-3,6-difluoro-1,4-cyclohexadiene-1-
carboxamide (XIV). Mass spectrum, m/z (Irel, %): 237
(24) [M], 217 (12) [M HF], 182 (100) [M HF F
NH2], 103 (24) [182 Br], 75 (78) [C6H3].
Dibromobenzoyl fluoride Br2C6H3C(O)F (XXVI).
Mass spectrum, m/z (Irel, %): 280 (45) [M], 261 (15)
[M F], 252 (60) [M CO], 233 (15) [M COF], 201
(21) [M Br], 173 (40) [M CO Br], 94 (40) [M
CO 2Br], 79 (68) [ Br], 47 (58) [COF].
4,5-Dibromo-2,3,3,6,6-pentafluorocyclohexene-
1-carboxamide (XV). Mass spectrum, m/z (Irel, %): 295
(14) [M], 277 (5) [M NH2], 214 (14) [M Br], 194
(20) [214 HF], 170 (14) [214 CONH2], 151 (10)
[170 F], 119 (12) [151 CHF], 101 (18) [151 CF2],
44 (100) [CONH2].
Electrochemical fluorination of 4-bromonitro-
benzene took 15.4 h. After the above described workup
the reaction mixture was analyzed by GLC and GC-MS.
3,4-Dibromonitrobenzene Br2C6H3NO2 (XXIX).
Mass spectrum, m/z (Irel, %): 281 (75) [M], 251 (20)
[M NO], 235 (45) [M NO2], 223 (32) [M CNO2],
170 (5) [253 Br], 154 (25) [235 Br], 153 (20) [154
H], 128 (5) [154 C2H2], 75 (100) [156 Br], 74 (85)
[75 H].
4-Bromobenzoic acid (XVI). Mass spectrum, m/z
(Irel, %): 220 (46) [M], 202 (100) [M H2O], 185 (80)
[202 OH], 155 (40) [M CH2COOH], 75 (60) [155
HBr].
3,4-Dibromobenzoic acid (XVII). Mass spectrum,
m/z (Irel, %): 278 (50) [M], 261 (28) [M OH], 233 [14,
M COOH], 154 (12) [233 Br], 75 (33) [C6H3], 74
(35) [C6H2].
4-Bromofluoronitrobenzene BrFC6H3NO2
(XXX). Mass spectrum, m/z (Irel, %): 221 (45) [M], 205
(5) [M O], 191 (25) [M NO], 173 (40) [M NO2],
153 (5) [173HF], 161 (18) [173 C], 94 (100) [175
Br], 74 (26) [94 HF], 68 (24) [94 C2H2], 50 (32)
[C4H2].
Methyl dibromobenzoate Br2C6H3CO2Me
(XIX). Mass spectrum, m/z (Irel, %): 292 (15) [M], 261
(30) [M OMe], 233 (12) [M COOMe], 75 (95)
[C6H3], 74 (100) [C6H2].
3,4-Dibromofluoronitrobenzene Br2FC6H2NO2
(XXXI). Mass spectrum, m/z (Irel, %): 299 (74) [M], 269
(25) [M NO], 253 (43) [M NO2], 241 (35) [253 C],
172 (55) [253 Br], 93 (100) [174 Br], 74 (38) [93
F], 61 (28) [74 CH].
Methyl 4-methoxybenzoate 4-MeOC6H4CO2Me
(XX). Mass spectrum, m/z (Irel, %): 166 (35) [M], 135
(100) [M OMe], 107 (25) [M COOMe], 92 (30)
[107 Me], 77 (35) [Ph].
Methyl 4-bromobenzoate 4-BrC6H4CO2Me
(XXI). Mass spectrum, m/z (Irel, %): 214 (35) [M], 183
(25) [M OMe], 155 (45) [M COOMe], 213 (5) [M
Br], 135 (15) [M Br], 104 (20) [183 Br], 76 (70)
[C6H4], 75 (80) [C6H3], 50 (100) [C4H2].
REFERENCES
1. Grakauskas, V., J. Org. Chem., 1970, vol. 35, p. 723.
2. Feiring,A.E., J. Org. Chem., 1979, vol. 44, p. 1252.
3. Shainyan, B. A., Danilevich, Yu.S., Belskii, V.K., Stash,A.I.,
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 42 No. 2 2006