1558
BAYGUZINA et al.
1
under argon. The sealed ampoule was put in the auto-
2,4,6-Tri-tert-butylphenol (6). Yield 25%. Н NMR
clave which was closed and heated at 150–250°С during
spectrum, δ, ppm: 1.30 s [18H, ortho-С(СH ) ], 1.46 s
3
3
3,5
6
–8 h at stirring. After cooling the reactor to ~20°С, the
[9H, para-С(СH ) ], 5.02 s (1H, OH), 7.25 s (2Н, С H).
3 3
1
3
ampoule was opened, the reaction mass was neutralized
with 10% aqueous solution of Na CO , and the organic
С NMR spectrum, δ , ppm: 30.20 [ortho-C(СH ) ],
С 3 3
32.10 [para-С(СH3)3], 32.84 [para-С(СH3)3], 35.15
2
3
4
3,5
layer was extracted with methylene chloride and filtered.
After removal of the solvent, the residue was separated via
chromatography (eluting with a 3 : 1 n-hexane–benzene
mixture on a column with l = 21 cm, d = 1.2 cm).
[ortho-С(СH3)3], 142.10 (С ), 122.30 (С ), 138.97
2,6
1
(
С ), 152.56 (C ). Mass spectrum, m/z (I , %): 262 (20)
М] , 247 (100), 205 (5), 128 (5), 116 (5), 91 (5), 57 (30).
rel
+
[
1
4-tert-Butyl-o-cresol (11). Yield 68%. Н NMR spec-
trum, δ, ppm: 1.39 s [9H, С(СH ) ], 2.33 s (3H, CH ),
3
3
3
Structure of the obtained alkylphenols 2–6, 11–19
was confirmed by means of NMR spectroscopy, mass
spectrometry, and comparison with reference samples
and data. Compounds 2–6, 11–19 were identified using
combined samples obtained in 3–6 experiments.
3
5
4
8
.78 s (1H, OH), 7.23 s (1Н, С H), 7.18 d (1Н, С H, J =
.0 Hz), 6.79 d (1Н, С H, J = 8.0 Hz). С NMR spectrum,
6
13
δ , ppm: 16.17 (CH ), 31.66 [С(СH ) ], 34.04 [С(СH ) ],
С
3
3 3
5
3 3
6
2
3
114.57 (С ), 123.18 (С ), 123.82 (С ), 128.06 (С ), 142.32
4
1
(
С ), 150.39 (C ). Mass spectrum, m/z (I , %): 164 (47)
[М] , 149 (100), 121 (20), 109 (10), 91 (15), 77 (10).
rel
1
+
2
-tert-Butylphenol (2). Yield 23%. Н NMR spec-
trum, δ, ppm: 1.38 s [9H, С(СH ) ], 4.75 s (1H, OH),
1
3
3
6-tert-Butyl-o-cresol (12). Yield 8%. Н NMR spec-
.50–7.40 m (4Н, С3,4,5,6H). С NMR spectrum, δ , ppm:
13
6
2
С
trum, δ, ppm: 1.59 s [9H, С(СH ) ], 2.35 s (3H, CH ),
3
3
3
6
9.60 [С(СH ) ], 34.38 [С(СH ) ], 116.52 (С ), 120.45
3,4,5
13
3
3
5
3 3
4.95 s (1H, OH), 6.80–7.10 m (3Н, С H). С NMR
spectrum, δ , ppm: 15.98 (CH ), 29.78 [С(СH ) ], 32.30
4
3
1
(С ), 126.78 (С ), 126.80 (С ), 153.90 (С ). Mass spec-
С
3
3 3
5
+
trum, m/z (I , %): 150 (25) [М] , 135 (100), 115 (85),
4
2
rel
[С(СH ) ], 120.03 (С ), 122.45 (С ), 124.14 (С ), 128.43
3 3
С ), 135.46 (С ), 152.45 (C ). Mass spectrum, m/z (I ,
%): 164 (30) [М] , 149 (100), 121 (75), 91 (20), 77 (15).
1
07 (100), 91 (20), 77 (15), 65 (10).
-tert-Butylphenol (3). Yield 65%. Н NMR spec-
trum, δ, ppm: 1.37 s [9H, С(СH ) ], 5.32 s (1H, OH),
3
6
1
(
rel
+
1
4
1
4,6-Di-tert-butyl-o-cresol (13). Yield 51%. Н NMR
spectrum, δ, ppm: 1.40 s [9H, para-С(СH ) ], 1.53 s
[(9H, ortho-С(СH ) ], 2.34 s (3H, CH ), 4.90 s (1H, OH),
3 3 3
7.11 s (1Н, С H), 7.40 s (1Н, С H). С NMR spectrum,
δ , ppm: 16.36 (CH ), 29.95 [ortho-С(СH ) ], 31.73
[para-С(СH ) ], 34.27 [para-С(СH ) ], 34.82 [ortho-
3 3 3 3
С(СH ) ], 122.08 (С ), 122.38 (С ), 125.43 (С ), 134.86
С ), 143.42 (С ), 150.39 (C ). Mass spectrum, m/z (I ,
): 220 (20) [М] , 205 (100), 189 (5), 161 (3), 149 (3),
3
3
2,6
3,5
6
8
3
.88 d (2Н, С H, J = 8.0 Hz), 7.32 d (2Н, С H, J =
3 3
1
3
.0 Hz). С NMR spectrum, δ , ppm: 31.62 [С(СH ) ],
С
,6
3 3
3
5
13
2
3,5
4.11 [С(СH ) ], 115.01 (С ), 126.48 (С ), 143.41
3
3
1
4
(
[
(
С ), 153.23 (С ). Mass spectrum, m/z (I , %): 150 (25)
М] , 135 (100), 119 (4), 107 (49), 95 (18), 77 (10), 65
7), 51 (4), 41 (14).
С
3
3 3
rel
+
5
2
3
3 3
6
4
1
(
%
1
rel
1
2
,4-Di-tert-butylphenol (4). Yield 52%. Н NMR
+
spectrum, δ, ppm: 1.61 s [9H, ortho-С(СH ) ], 1.49 s [9H,
3
3
21 (3), 115 (3).
-tert-Butyl-m-cresol (14). Yield 74%. Н NMR
spectrum, δ, ppm: 1.50 s [9H, С(СH ) ], 2.35 s (3H,
6
para-С(СH ) ], 5.35 s (1H, OH), 6.75 d (1Н, С H, J =
.0 Hz), 7.25 d (1Н, С H, J = 8.0 Hz), 7.51 s (1Н, С H).
С NMR spectrum, δ , ppm: 29.91 [ortho-С(СH ) ],
3
3
1
6
5
3
8
3
3
1
3
С
3 3
2
CH ), 5.07 s (1H, OH), 6.56 s (1Н, С H), 6.70–6.88 m
1Н, С H), 7.18–7.30 s (1Н, С H). С NMR spectrum,
δ , ppm: 20.63 (CH ), 29.77 [С(СH ) ], 34.27 [С(СH ) ],
17.46 (С ), 121.23 (С ), 126.98 (С ), 133.27 (С ), 136.96
3
3
1.72 [para-С(СH ) ], 34.44 [ortho-С(СH ) ], 34.93
3 3 3 3
4
5
13
(
6
5
3
[para-С(СH ) ], 116.26 (С ), 123.71 (С ), 124.20 (С ),
3 3
С
3
3 3
5
3 3
2
4
1
1
35.51 (С ), 143.05 (С ), 152.05 (C ). Mass spectrum,
2
4
6
1
(
[
+
m/z (I , %): 206 (33) [М] , 191 (100), 175 (4), 161 (3),
rel
3
1
С ), 154.15 (C ). Mass spectrum, m/z (I , %): 164 (35)
rel
1
47 (2), 115 (3), 91 (4), 74 (3), 57 (25), 41(10).
+
М] , 149 (100), 133 (2), 121 (63), 115 (9), 91 (19), 77
1
(10), 65 (3), 51 (4), 41(7).
2
,6-Di-tert-butylphenol (5). Yield 13%. Н NMR
spectrum, δ, ppm: 1.54 s [18H, С(СH ) ], 4.85 br. s (1H,
OH), 6.75 t (1Н, С H, J = 8.0 Hz), 7.20 d (2Н, С H, J =
4,6-Di-tert-butyl-m-cresol (15). Yield 36%. 1Н NMR
3
3
4
3,5
spectrum, δ, ppm: 1.44 s [9H, para-С(СH ) ], 1.45 s [9H,
3
3
1
3
8
3
(
.0 Hz). С NMR spectrum, δ , ppm: 30.20 [С(СH ) ],
ortho-С(СH ) ], 2.58 s (3H, CH ), 4.97 s (1H, OH), 6.56
С
4
3 3
3 3
3
13
3,5
2
5
4.85 [С(СH ) ], 120.10 (С ), 124.30 (С ), 137.17
С ), 153.95 (C ). Mass spectrum, m/z (I , %): 206 (25)
М] , 191 (100), 175 (5), 163 (15), 131 (10), 115 (10).
s (1Н, С H), 7.45 s (1Н, С H). С NMR spectrum, δ ,
3
3
1
С
2,6
ppm: 20.63 (CH ), 31.12 [ortho-С(СH ) ], 31.30 [para-
rel
3
3 3
+
[
С(СH ) ], 34.67 [ortho-С(СH ) ], 35.66 [para-С(СH ) ],
3 3 3 3 3 3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 89 No. 8 2019