ALCOHOLYSIS OF 2,2-DICHLOROPROPYL DERIVATIVES
115
dropwise over a period of 2 h to a mixture of 3.3 g
10.7 mol) of compound II, 35 ml of DMSO, and
ml (100 mmol) of methanol, continuously stirred
REFERENCES
(
4
1
2
.
.
Anfinogenov, V.A., Okhtemenko, I.N., and Ogorod-
nikov, V.D., Russ. J. Org. Chem., 1997, vol. 33,
no. 7, pp. 1024 1026.
Ivshin, V.P., Kamelin, M.S., and Belik, A.P.,
Zh. Org. Khim., 1980, vol. 16, no. 5, pp. 980 981.
at room temperature. The mixture was stirred for
an additional 1.5 h, and the product was isolated as
described above for compound IV. Yield 2.57 g
1
3
(
90%), mp 73 74 C (from methanol). C NMR spec-
1
2
3
3. Ivshin, V.P. and Kamelin, M.S., Zh. Org. Khim.,
983, vol. 19, no. 8, pp. 1652 1654.
trum, , ppm: 116.83 (C ), 125.32 (C ), 126.04 (C ),
C
1
4
10a
1
25.10 (C ), 141.52 (C ), 80.29 (HtCH), 76.50
4
.
Kostikov, R.R. and Khlebnikov, A.F., Sovremennye
problemy organicheskoi khimii (Current Problems
of Organic Chemistry), Leningrad: Leningr. Gos.
Univ., 1981, no. 7, pp. 36 66.
(
C ), 73.86 (HC ), 51.95 (CH O). Found, %:
3
C 71.79; H 4.32; N 5.23. C H NOS. Calculated, %:
1
6
13
C 71.87; H 4.91; N 5.24.
9
-(1-Methoxy-2-propynyl)phenoxazine (VII).
5. Krivdin, L.B., Trofimov, B.A., Zinchenko, S.V.,
Glukhikh, N.G., Pestunovich, S.V., Domnin, I.N.,
Akhachinskaya, T.V., and Donskaya, N.A., Zh. Org.
Khim., 1991, vol. 27, no. 7, pp. 1369 1382.
A 1.12 N solution of potassium tert-butoxide in
tert-butyl alcohol, 32 ml (35.8 mmol), was added
dropwise over a period of 2.5 h to a mixture of 3.3 g
11.3 mol) of compound III, 30 ml of DMSO, and
ml (100 mmol) of methanol, continuously stirred
at room temperature. The mixture was stirred for
an additional 4.5 h, and the product was isolated as
described above for compound V. Yield 2.38 g.
Analysis of the product by TLC showed the presence
of phenoxazine (30 mol %, according to the H
NMR data).
Hydrolysis of 9-(1-methoxy-2-propynyl)carba-
zole (IV) and 10-(1-methoxy-2-propynyl)phenothia-
zine (VI). A 0.249-g (1.06-mmol) portion of com-
pound IV was dissolved in 10 ml of dioxane, and
ml of 0.05 M H SO and 1.7 ml of water were
added. In a similar way, a solution of 0.267 g
1 mmol) of compound VI was prepared. The reaction
was carried out in dioxane water (3:2, by volume),
the initial concentration of compounds IV and VI was
6
7
8
.
.
.
Barlet, R. and Vo-Quang, Bull. Soc. Chim. Fr., 1969,
no. 10, pp. 3729 3760.
Shields, T.C. and Gardner, P.D., J. Am. Chem. Soc.,
(
4
1
967, vol. 89, no. 21, pp. 5425 5428.
Khlebnikov, A.I., Anfinogenov, V.A., Filimo-
nov, V.D., and Sokolova, I.V., Zh. Org. Khim., 1989,
vol. 25, no. 7, pp. 1547 1553.
1
9
.
Filimonov, V.D. and Sirotkina, E.E., Khimiya mono-
merov na osnove karbazola (Chemistry of Carbazole-
Based Monomers), Novosibirsk: Nauka, 1995,
pp. 37 55.
1
1
0. Anfinogenov, V.A., Filimonov, V.D., Zamyati-
na, Z.N., and Kroneval’d, G.V., Zh. Org. Khim.,
1983, vol. 19, no. 7, pp. 1505 1511.
1. Methoden der organischen Chemie (Houben Weyl),
Muller, E., Bayer, O., Meerwein, H., and Ziegler, K.,
Eds., Stuttgart: Georg Thieme, 1953, 4th ed., vol. 2.
Translated under the title Metody organicheskoi
khimii, Moscow: Gos. Nauch.-Tekh. Izd. Khim. Lit.,
1963, vol. 2, pp. 442 443.
2. Anfinogenov, V.A., Filimonov, V.D., and Sirotki-
na, E.E., Zh. Org. Khim., 1978, vol. 14, no. 8,
pp. 1723 1729.
3. Anfinogenov, V.A., Filimonov, V.D., Sirotkina, E.E.,
Tavobilov, M.F., and Svetlov, A.K., Ionnyi obmen
i khromatografiya (Ion Exchange and Chromatog-
raphy), Samsonov, G.V., Ed., Leningrad: Nauka,
5
2 4
(
2
6
1
10 M, and the sulfuric acid concentration was
.5 10 2 M. The mixture was stirred at 18 C, and
1
1
the progress of the reaction was monitored by TLC
until the initial compound disappeared completely.
The mixture was then diluted with 150 ml of water,
and the precipitate of carbazole, 0.148 g (84%), or
phenothiazine, 0.189 g (95%), was filtered off.
-Propynal was determined by the procedure reported
in [11]. In the hydrolysis of IV and VI we isolated,
respectively, 0.208 g (84%) and 0.215 g (92%) of
-propynal 2,4-dinitrophenylhydrazone whose struc-
2
1
984, pp. 175 178.
1
4. Filimonov, V.D., Anfinogenov, V.A., Sirotkina, E.E.,
and Rodionov, V.A., Zh. Org. Khim., 1980, vol. 16,
no. 11, pp. 2395 2399.
2
1
ture was confirmed by the H NMR spectrum (C D ),
6
6
,
ppm: 4.07 s (1H, CH), 7.00 s (1H, CH), 7.30 s
15. US Patent 2415252, 1947; Chem. Abstr., 1947,
(
1H, NH), 7.9 9.0 (3H, Harom).
vol. 41, p. 2756d.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 1 2001