Tertiary acetylenic alcohols and peroxides derived from 4,4′-bis(dimethylamino)benzophenone (michler's ketone)

Article abstract of DOI:10.1023/B:RUGC.0000015988.84852.9d

Tertiary acetylenic alcohols were obtained by treatment of 4,4′-bis(dimethylamino)benzophenone with 1-alkynyl- and 2-phenylehynyl, as well as lithium tert-alkylperoxyacetylides.

Full text of DOI:10.1023/B:RUGC.0000015988.84852.9d

Russian Journal of General Chemistry, Vol. 73, No. 9, 2003, pp. 1406 1409. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 9, 2003,
pp. 1488 1491.
Original Russian Text Copyright
2003 by Dikusar.
Tertiary Acetylenic Alcohols and Peroxides Derived
from 4,4 -Bis(dimethylamino)benzophenone (Michler’s Ketone)
E. A. Dikusar
Institute of Physical Organic Chemistry, National Academy of Sciences of Belarus, Minsk, Belarus
Received November 6, 2001
Abstract Tertiary acetylenic alcohols were obtained by treatment of 4,4 -bis(dimethylamino)benzophenone
with 1-alkynyl- and 2-phenylehynyl, as well as lithium tert-alkylperoxyacetylides.
Previously we reported on the synthesis of acetyle-
nic nitrogen-containing peroxy alcohols by the action
of lithium peroxyacetylides on aminobenzaldehydes,
IVa IVl from lithium acetylides IIa IIl obtained by
metalation of 1-alkynes Ia Il with butyllithium, and
4,4 -bis(dimethylamino)benzophenone
(Michler’s
2e-methyldecahydroquinolin-4-one, and
-amino-
ketone) (III). Alcohols IVa IVl were isolated with
ketones [1 3]. Acetylenic alcohols with various
preparative yields (69 86%). The O O bond in comp-
functional groups, including nitrogen-containing, have ounds IIf IIl does not prevent reaction and does not
been studied in terms of biological activity [4].
adversely affect the yields of the target products [1 3].
In the present work we describe the synthesis of
tertiary acetylenic nitrogen-containing alcohols
The reaction of Michler’s ketone (III) with butylli-
thium gave alcohol V in 84% yield.
BuLi
RC CH
Ia Il
RC CLi,
IIa IIl
1) IIa IIl;
2) H2O
(4-Me2NC6H4)2C(OH)C CR,
IVa IVl
(4-Me2NC6H4)2CO
1) BuLi;
2) H2O
(4-Me2NC6H4)2C(OH)CH2CH2CH2Me,
V
I, II, IV, R = H (a), (CH2)3Me (b), (SH2)14Me (c), (CH2)15Me (d), Ph (e), CMe2OOCMe3 (f), CMe2OOCMe2Et (g),
CMe2OOCMe2Pr (h), CMe2OOCMe2(CH2)4Me (i), CMe2OOCMe2C6H11-cyclo (j), CMe2OOCPh3 (k), CMe2OOCMe2C
CCMe2OOCMe3 (l).
Compound IVa IVl and V are colorless crystals.
They can be handled for a long time in sealed ampules
in the dark but darken quickly on contact with air and
light. The composition and structure of compounds
IVa IVl and V were proved by TLC, elemental
analysis (Table 1), and H NMR (Table 2), IR, and
UV spectroscopy (Table 3).
at 118 128 C, cycloalkylperoxy alcohol IVj, at
116 C, whereas bis(alkylperoxy) alcohols, at 130 C.
The weight losses in the first stage (up to 185 225 C)
are 17 30 (IVf IVj) and 40% (IVl). The weight loss
for arylalkylperoxy alcohol IVk up to 145 C is no
more than 4%, which is associated with the formation
of nonvolatile decomposition products.
1
It was found by thermal analysis [5] that peroxy
alcohols IVf IVl are rather fairly stable thermally.
Alkylperoxy alcohols IVf IVi begin to decompose at
appreciable rate and a well-defined exothermic effect
EXPERIMENTAL
The IR spectra were measured on a Specord IR-75
1
instrument in KBr pellets. The H NMR spectra were
1070-3632/03/7309-1406$25.00 2003 MAIK Nauka/Interperiodica

TERTIARY ACETYLENIC ALCOHOLS AND PEROXIDES DERIVED
Table 1. Properties of compounds IVa IVl and V
Found, %
1407
Calculated, %
H
M
Comp. Yield,
mp,
C
Formula
no.
%
C
H
N
C
N
found calculated
IVa
86
78
71
80
83
141 142 77.84
7.71
8.81
9.40
8.06
5.21
5.53
7.56
C19H22N2O
C23H30N2O
C34H52N2O
C35H54N2O
C25H26N2O
77.52
78.82
80.90
81.03
81.05
7.53
8.63
9.52
7.99
5.55
5.40
7.56
290.1
341.2
493.0
506.3
359.8
294.4
350.5
504.8
518.8
370.5
IVb
IVc
IVd
IVe
44 45
54 55
55 56
79.16
81.22 10.50
81.31 10.48
10.38
10.49
7.07
166 167 81.17
101 102 73.91
7.27
IVf
IVg
IVh
IVi
IVj
73
72
81
78
81
8.70
8.99
9.11
9.07
9.06
6.51
6.07
5.95
5.49
5.91
C26H36N2O3
C27H38N2O3
C28H40N2O3
C30H44N2O3
C31H44N2O3
73.55
73.94
74.30
74.96
75.57
8.55
8.73
8.91
9.23
9.00
6.60
6.39
6.19
5.83
5.69
416.3
425.1
440.7
468.4
479.5
424.6
438.6
452.6
480.7
492.7
76 77
63 64
71 72
87 88
74.15
74.73
75.21
75.53
IVk
IVl
V
74
69
84
158 159 81.02
76 77 72.72
111 112 77.16
7.12
8.45
9.27
4.11
5.41
8.74
C41H42N2O3
C34H48N2O5
C21H30N2O
80.62
72.31
77.26
6.93
8.57
9.26
4.59
4.96
8.58
583.6
543.8
320.7
610.8
564.8
326.5
Table 2. 1H NMR spectra of compounds III, IVa IVl, and V
Comp.
no.
1H NMR spectrum, , ppm
III 3.04 s (12H, Me2N), 6.56 7.88 m (8H, 2C6H4)
IVa 2.67 s (1H, OH), 2.78 s (1H, C CH), 2.91 s (12H, 2Me2N), 6.55 7.55 m (8H, 2C6H4)
IVb 0.95 t (3H, Me), 1.12 2.15 m [4H, (CH2)2], 2.22 t (2H, CH2C C), 2.50 s (1H, OH), 2.92 s (12H, Me2N),
6.53 7.53 m (8H, 2C6H4)
IVc 0.89 t (3H, Me), 1.10 1.70 m [26H, (CH2)13], 2.28 t (2H, CH2C C), 2.54 s (1H, OH), 2.90 s (12H, Me2N),
6.48 7.48 m (8H, 2C6H4)
IVd 0.88 t (3H, Me), 1.10 1.70 m [28H, (CH2)14], 2.32 t (2H, CH2C C), 2.58 s (1H, OH), 2.91 s (12H, Me2N),
6.55 7.50 m (8H, 2C6H4)
IVe 2.78 s (1H, OH), 2.92 s (12H, 2Me2N), 6.57 6.80 m, 7.17 7.65 m (13H, 2C6H4 i Ph)
IVf 1.23 s (9H, Me3COO), 1.50 s (6H, Me2C), 2.69 s (1H, OH), 2.90 s (12H, Me2N), 6.50 7.55 m (8H, 2C6H4)
IVg 0.87 t (3H, Me), 1.18 s (6H, Me2COO), 1.51 q (2H, CH2), 1.52 s (6H, Me2C), 2.61 s (1H, OH), 2.90 s (12H,
Me2N), 6.55 7.55 m (8H, 2C6H4)
IVh 0.88 t (3H, Me), 1.20 s (6H, Me2COO), 1.50 s (6H, Me2C), 1.40 1.55 m [4H, (CH2)2], 2.68 s (1H, OH),
2.89 s (12H, Me2N), 6.48 7.48 m (8H, 2C6H4)
IVi 0.87 t (3H, Me), 1.20 s (6H, Me2COO), 1.22 1.70 m [8H, (CH2)4], 1.52 s (6H, Me2C), 2.64 s (1H, OH), 2.90 s
(12H, Me2N), 6.50 7.50 m (8H, 2C6H4)
IVj 1.00 1.90 m [11H, C6H11], 1.15 s (6H, Me2COO), 1.51 s (6H, Me2C), 2.60 s (1H, OH), 2.90 s (12H, Me2N),
6.55 7.50 m (8H, 2C6H4)
IVk 1.32 s (6H, Me2C), 2.41 s (1H, OH), 2.89 s (12H, Me2N), 6.45 7.50 m (23H, 2C6H4 i CPh3)
IVl 1.24 s (9H, Me3COO), 1.42 s, 1.48 s, 1.56 s (18H, 3Me2C), 2.62 s (1H, OH), 2.91 s (12H, Me2N), 6.50 7.50 m
(8H, 2C6H4)
V
0.87 t (3H, Me), 1.18 1.45 m [4H, (CH2)2], 1.95 s (1H, OH), 2.18 t [2H, CH_2C(OH)], 2.90 s (12H, Me2N),
6.55 7.30 m (8H, 2C6H4)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 9 2003

1408
DIKUSAR
Table 3. IR and UV spectra of compounds III, IVa IVl, and V
Comp.
no.
UV spectrum, max, nm
1
IR spectrum, , cm
3
(
10 )
III
3090, 3040 (CHAr); 2980, 2895, 2820 (CHAlk); 1595 (C=O); 1560, 1525 (Ar); 208 (19), 247 (11), 368 (25)
825, 815, 760, 745 (CHAr)
IVa 3270 ( C H); 3205 (OH); 3100, 3075, 3030 (CHAr); 2995, 2960, 2910, 211 (15), 263 (11), 309 (10), 396
2880, 2855, 2810, 2800 (CHAr); 2100 (C C); 1605, 1560, 1510 (Ar); 1055 (15), 620 (15), 690 (22)
(C OH); 825, 815 (CHAr)
IVb 3290 (OH); 3090, 3070, 3035 (CHAr); 2965, 2935, 2800 (CHAlk); 2225 (C C); 208 (19), 258 (12), 390 (9), 420
1610, 1510 (Ar); 1445 (CH2); 1025 (C OH); 830, 810 (CHAr)
(15), 620 (14), 680 (70)
IVc 3245 (OH); 3095, 3975, 3040 (CHAr); 2955, 2920, 2850, 2800 (CHAlk); 2225 210 (18), 258 (12), 315 (25), 420
(C C); 1615, 1560, 1525, 1515 (Ar); 1470 (CH2); 1025 (C OH); 840, 820, (16), 445 (27), 655 (92)
805 (CHAr)
IVd 3260 (OH); 3090, 3075, 3040, 3005 (CHAr); 2980, 2955, 2945, 2850, 2805 208 (22), 258 (12), 328 (30), 420
(CHAlk); 2225 (C C); 1610, 1570, 1525, 1505 (Ar); 1025 (C OH); 840, 820, (18), 440 (30), 650 (100)
805 (CHAr)
IVe 3100, 3080, 3030 (CHAr); 2980, 2960, 2880, 2840, 2790 (CHAlk); 1605, 208 (16), 250 (12), 312 (15), 485
1590, 1520, 1505 (Ar); 1050 (C OH); 840, 820, 805, 790, 755, 690 (CHAr) (38), 675 (100)
IVf
3240 (OH); 3090, 3070, 3035 (CHAr); 2975, 2925, 2875, 2850, 2795 (CHAlk); 209 (16), 258 (9), 367 (9), 418
1605, 1505 (Ar); 1020 (C OH); 870 (O O); 830, 810, 775, 745 (CHAr) (10), 444 (10), 670 (60)
IVg 3250 (OH); 3095, 3075, 3040 (CHAr); 2975, 2930, 2880, 2845, 2800 (CHAlk); 208 (15), 255 (10), 370 (9), 400
1605, 1520, 1505 (Ar); 1470 (CH2); 1020 (C OH); 860 (O O); 835, 805, (9), 442 (9), 620 (20), 670 (58)
780, 750 (CHAr)
IVh 3425 (OH); 3100, 3080, 3040 (CHAr); 2985, 2960, 2935, 2890, 2870, 2805 208 (15), 255 (9), 370 (9), 400 (8),
(CHAlk); 1605, 1505 (Ar); 1470 (CH2); 1020 (C OH); 870 (O O); 825, 820, 441 (8), 620 (18), 670 (61)
810, 745 (CHAr)
IVi
3400 (OH); 3095, 3075, 3040 (CHAr); 2980, 2955, 2940, 2890, 2855, 2805 211 (14), 258 (8), 310 (7), 400 (8),
(CHAlk); 2225 (C C); 1610, 1565, 1510 (Ar); 1470 (CH2); 1020 (C OH); 440 (8), 610 (15), 650 (58)
870 (O O); 825, 810 (CHAr)
IVj
3400 (OH); 3090, 3080, 3040 (CHAr); 2955, 2930, 2850, 2805 (CHAlk); 211 (15), 258 (7), 312 (16), 420
1610, 1565, 1515 (Ar); 1475 (CH2); 1020 (C OH); 870 (O O); 820 (CHAr) (9), 440 (15), 650 (90)
IVk 3400, 3120 (OH); 3090, 3055, 3040, 3025 (CHAr); 2980, 2905, 2875, 2845, 211 (35), 258 (8), 315 (12), 425
2805, 2795 (CHAlk); 2230 (C C); 1610, 1565, 1510, 1495 (Ar); 1025 (7), 440 (14), 670 (65)
(C OH); 880 (O O); 840, 820, 775, 770, 750, 700 (CHAr)
IVl
3420, 3220 (OH); 3100, 3075, 3030 (CHAr); 2985, 2940, 2885, 2845, 2800 211 (20), 258 (12), 315 (10), 420
(CHAlk); 2230 (C C); 1610, 1565, 1520, 1510 (Ar); 1025 (C OH); 880 (12), 444 (22), 680 (90)
(O O); 840, 825, 810 (CHAr)
V
3280 (OH); 3100, 3080, 3040, 3015 (CHAr); 2960, 2940, 2880, 2850, 2800 210 (16), 265 (11), 300 (8), 605
(CHAlk); 1620, 1520 (Ar); 1475 (CH2); 840, 820, 805, 775 (CHAr)
(16)
obtained on a Tesla BS-567A instrument in CDCl3,
internal reference TMS. The UV and visible specta
were taken on a Specord UV-Vis instrument in 1
10 M solutions in methanol. Freshly prepared solu-
tions were used. Thermal analysis was performed on
estimated results, apparently, because of the presence
of a C C bond. The molecular weights were deter-
mined by cryoscopy in benzene.
4
Peroxy alkynes If Il and bytillithium were syn-
thesized by the procedures in [7, 8].
a
Paulik Paulik Erdey derivatograph in argon,
heating rate 7 deg/min. Sample 100 mg, DTA 1/10,
DTG 1/10. Purity control was performed by TLC on
Silufol plates, eluent hexane diethyl ether (3:1),
developer N,N-dimethyl-p-phenylenediamine dihydro-
chloride. The analysis of peroxides IVf IVl for active
oxygen by iodometry with conc. HCl [6] gave over-
1,1-Di[4,4 -bis(dimethylamino)phenyl]-2-propyn-
1-ol (IVa). Michler’s ketone (III), 0.02 mol, was
added in one portion to a solution of 0.03 mol of
lithium acetylide HC CLi (IIa) [obtained by adding
dropwise over the course of 0.5 h at 70 C a hexane
solution of butyllithium (0.03 mol) to 100 ml of
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 9 2003

TERTIARY ACETYLENIC ALCOHOLS AND PEROXIDES DERIVED
1409
absolute THF through which we barboted acetylene
Ia. The reaction mixture was stirred for 4 h at 20
23 C and left to stand for 18 h. The lithium alcoholate
that formed was treated with 300 ml of water, alcohol
VIa was extracted with ether, and the extract was
dried with CaCl2. The solvent was removed, and the
reaction product was recrystallized from hexane.
and treated with 300 ml of water. Alcohol V was ex-
tracted with ether, the extract was dried with CaCl2,
the solvent was removed, and the reaction product
was recrystallized from hexane.
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kynyl)methanols IVb IVl. A hexane solution of
0.011 mol of butyllithium was added under argon
over the course of 0.5 h to a cooled ( 40 to 20 C)
and vigorously stirred solution of 0.013 mol of
1-alkyne Ib Il in 20 ml of absolute THF. The mixture
was stirred for 1 h, and, after addition of 0.01 mol of
Michler’s ketone (III), heated to 0 5 C 0.02 over the
course of 1 2 h, stirred for an additional 3 4 h,
left to stand for 18 h at 20 23 C, and treated with
300 ml of water. Alcohols VIb VIl were extracted
with ether, the extracts were dried with CaCl2, the
solvent was removed, and the reaction products were
recrystallized from hexane.
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of absolute THF. The mixture was stirred of 1 h, heated
to 20 23 C over the course of 1 2 h, stirred for an
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 9 2003