R. Skupin, G. Haufe / Journal of Fluorine Chemistry 92 (1998) 157±165
163
2
3
(m) (2.8%), 233.60 (dt, CH2F, JH;F 47:7 Hz, JH;F
171 (2) [M ±CH2F], 160 (3) [M ±C2H4O], 141 (7) [M ±
19:1 Hz) (49.4% 4e). MS (GLC±MS, 70 eV) m/z (%) 4e:
198 (55) [M ], 178 (4) [M ±HF], 165 (6) [M ±CH2F], 154
C2H4FO], 130 (33), 128 (100) [C6H5ClO , chlorophenol],
113 (6), 111 (13) [M ±C3H6FO2], 99 (4), 93 (1), 86 (2), 84
(5) [M ±C2H4O], 135 (22) [M ±C2H4FO], 123 (40), 122
(2), 75 (8), 65 (7) C5H5 , 59 (2), 49 (5), 43 (6) [C2H3O ,
(100) [C8H10O , dimethylphenol], 107 (36) [178 ±
oxiranyl, C2H4FO ±HF], 39 (3) C3H3 . 5h: 207 (2), 206
C3H5O2], 105 (38), 94 (15) [C8H10O ±CO], 91 (13)
(13), 204 (40) [M ], 141 (4) [M ±C2H4FO], 130 (42), 128
(100) [C6H5ClO , chlorophenol], 113 (4), 111 (8) [M
C7H7 , 79 (14), 77 (20) C6H5 , 65 (6) C5H5 , 63 (5),
±
51 (5), 43 (7) [C2H3O , oxiranyl, C2H4FO ±HF]. 5e: 198
(70) [M ], 183 (4), 165 (2), 135 (12) [M ±C2H4FO], 123
C3H6FO2], 99 (6), 77 (4) C6H5 , 75 (8), 65 (7) C5H5 , 49
(6), 39 (6) C3H3 .
(20), 122 (100) [C8H10O , dimethylphenol], 121 (20), 107
(48) [178 ±C3H5O2], 105 (26), 94 (22) [C8H10O ±CO], 79
3.2.10. 2-(4-Bromo-phenoxymethyl)-oxirane (3i)
with PyÁ9HF
(20), 77 (30) C6H5 , 67 (2), 65 (8) C5H5 , 63 [C2H3O ,
oxiranyl, C2H4FO ±HF], 41 (8), 39 (16) C3H3 .
19F NMR ꢄ: 193.90 to 194.05 (several multiplets) (Æ
19.1%), 194.46 to 194.78 (several multiplets) (Æ 5.2%),
196.26 (m) (24.1% 5i), 230.94 to 231.10 (several
multiplets) (Æ 6.3%), 231.29 (m), 231.33 (m) (Æ
3.2.7. 2-(4-Fluoro-phenoxymethyl)-oxirane (3f)
with PyÁ9HF
2
3
19F NMR ꢄ: 122.9 (tt, not completely resolved, Ar±F),
193.94to 194.01(severalmultiplets)(Æ 19.9%), 194.03
to 194.80 (several multiplets) (Æ 4.6%), 196.50 (m)
(23.5% 5f), 230.94 to 231.37 (several multiplets) (Æ
8.2%),
19:1 Hz) (37.1% 4i). MS (GLC±MS, 70 eV) m/z (%) 4i:
232.70 (dt, CH2F, JH;F 47:7 Hz, JH;F
251 (5) [M 1], 250 (37) [M ], 249 (5) [M 1], 248 (40)
[M ], 230 (3) [M ±HF], 228 (3) [M ±HF], 217 (3) [M ±
CH2F], 215 (3) [M ±CH2F], 206 (4) [M ±C2H4O], 204 (4)
2
3
15.9%), 233.60 (dt, CH2F, JH;F 47:7 Hz, JH;F
19:1 Hz) (36.1% 4f). MS (GLC±MS, 70 eV) m/z (%) 4f:
189 (4) [M 1], 188 (34) [M ], 155 (2) [M ±CH2F], 144
[M ±C2H4O], 197 (2), 188 (2), 187 (8) [M ±C2H4FO],
185 (8) [M ±C2H4FO], 175 (9), 174 (100) [C6H5BrO ,
(6) [M ±C2H4O], 137 (4), 125 (10) [M ±C2H4FO], 113
bromophenol], 173 (12), 172 (100) [C6H5BrO , bromophe-
nol], 171 (3), 157 (12), 155 (12), 136 (6), 106 (2), 94 (4), 93
(10), 112 (100) [C6H5FO , ¯uorophenol], 111 (6), 97 (5),
95 (19) [M ±C3H6FO2], 83 (6), 75 (7), 63 (4), 57 (5)
(12) [C6H5BrO ±Br], 78 (4), 77 (10) C6H5 , 76 (11), 75
[C3H5O , methyloxiranyl], 49 (2), 43 (2) [C2H3O , oxira-
(10), 65 (16), 63 (8), 51 (4), 43 (8) [C2H3O , oxiranyl,
nyl, C2H4FO ±HF], 39 (1) C3H3 . 5f: 189 (4) [M 1], 188
C2H4FO ±HF], 39 (7) C3H3 . 5i: 251 (5) [M 1], 250 (44)
(31) [M ], 113 (8), 112 (100) [C6H5FO , ¯uorophenol],
111 (3), 95 (8) [M ±C3H6FO2], 83 (7), 75 (4), 57 (6)
[M ], 249 (6) [M 1], 248 (44) [M ], 230 (1) [M ±HF],
228 (1) [M ±HF], 187 (3) [M ±C2H4FO], 185 (3) [M ±
C2H4FO], 174 (96) [C6H5BrO , bromophenol], 172 (100)
[C3H5O , methyloxiranyl], 47 (2), 39 (2) C3H3 .
[C6H5BrO , bromophenol], 157 (6), 155 (6), 145 (5), 143
3.2.8. 2-(2-Chloro-phenoxymethyl)-oxirane (3g)
with PyÁ9HF
(5), 94 (3), 93 (12) [C6H5BrO ±Br], 92 (2), 76 (7), 75 (7),
74 (3), 65 (15), 63 (9), 62 (3), 50 (6), 39 (6) C3H3 .
19F NMR ꢄ: 194.19 to 194.33 (several multiplets) (Æ
21.5%), 194.66 (m), 195.07 (m) (Æ 8.0%), 196.83 (m)
(20.0% 5g), 231.70 to 231.89 (several multiplets) (Æ
3.2.11. 2-(2-Nitro-phenoxymethyl)-oxirane (3j)
with PyÁ9HF
2
3
18.5%), 233.09 (dt, CH2F, JH;F 47:7 Hz, JH;F
19F NMR ꢄ: 194.46 (m), 194.48 (m) (Æ 18.3%),
196.69 (m) (15.9% 5j), 232.37 (m), 232.43 (m) (Æ
19:1 Hz) (32.0% 4g). MS (GLC±MS, 70 eV) m/z (%) 4g:
207 (2), 206 (8), 204 (24) [M ], 171 (3) [M ±CH2F], 160
2
3
20.1%), 233.13 (dt, CH2F, JH;F 47:7 Hz, JH;F
(4) [M ±C2H4O], 141 (6) [M ±C2H4FO], 130 (33), 128
19:1 Hz) (45.7% 4j). MS (GLC±MS, 70 eV) m/z (%) 4j:
216 (4) [M 1], 215 (26) [M ], 182 (6) [M ±CH2F], 140
(100) [C6H5ClO , chlorophenol], 127 (4), 111 (10) [M
±
C3H6FO2], 99 (4), 92 (4), 84 (2), 77 (6) C6H5 , 75 (7), 65
(8), 139 (100) [C6H5NO3 , nitrophenol], 124 (16), 123 (62)
(3) C5H5 , 64 (8), 63 (7), 49 (4), 43 (5) [C2H3O , oxiranyl,
C6H5NO2 , 122 (24) C6H4NO2 , 109 (16), 106 (34) [123 ±
C2H4FO ±HF], 39 (3) C3H3 . 5g: 206 (8), 204 (26) [M ],
OH], 94 (8), 93 (12), 92 (9), 81 (12), 78 (17), 77 (9) C6H5 ,
131 (3), 130, (33), 128 (100) [C6H5ClO , chlorphenol], 99
65 (21), 63 (14), 53 (6), 51 (12), 43 (9) [C2H3O , oxiranyl,
(4), 92 (4), 75 (5), 64 (8), 62 (2), 47 (2), 39 (3) C3H3 .
C2H4FO ±HF], 39 (11) C3H3 . 5j: 215 (22) [M ], 140 (12),
139 (100) [C6H5NO3 , nitrophenol], 124 (4), 123 (13)
3.2.9. 2-(4-Chloro-phenoxymethyl)-oxirane (3h)
with PyÁ9HF
C6H5NO2 , 122 (7) C6H4NO2 , 109 (17), 106 (8) [123
±OH], 92 (8), 84 (5), 81 (14), 76 (7), 65 (15), 64 (14), 59 (4),
19F NMR ꢄ: 193.99 (m), 194.05 (m) (Æ 19.2%),
51 (10), 50 (6), 39 (10) C3H3 .
194.43 to
194.78 (several multiplets) (Æ 6.1%),
196.42 (m) (23.0% 5h), 231.04 to 231.32 (several
multiplets) (Æ 15.1%), 232.82 (dt, CH2F, 2JH;F 47:7 Hz,
3JH;F 19:1 Hz) (36.6% 4h). MS (GLC±MS, 70 eV) m/z
3.2.12. 2-(4-Nitro-phenoxymethyl)-oxirane (3k) with
PyÁ9HF
19F NMR ꢄ: 193.90 (m), 193.92 (m) (Æ 15.8%),
195.69 (m) (14.3% 5k), 230.52 to 231.06 (several
(%) 4h: 207 (1), 206 (10), 204 (30) [M ], 184 (2) [M ±HF],