Org. Synth. 1948, 28, 34
DOI: 10.15227/orgsyn.028.0034
9-CYANOPHENANTHRENE
[9-Phenanthrenecarbonitrile]
Submitted by Joseph E. Callen, Clinton A. Dornfeld, and George H. Coleman
1.
Checked by Robert E. Carnahan and Homer Adkins.
1. Procedure
In a
2-l. Claisen flask (Note 1) are mixed
1 kg. (3.90 moles) of 9-bromophenanthrene (p. 134) (Note 2) and
400 g. (4.46 moles) of cuprous cyanide. A small
motor-driven spiral stirrer is inserted, and the flask is heated
(Note 3) at 260° for 6 hours
(Note 4). The flask is then provided with a
fine capillary inlet tube, a
thermometer, and a
2-l. distilling flask attached to the side arm of the Claisen flask as receiver. The
9-cyanophenanthrene is distilled at
190–195°/2 mm. The yield of crude product is
740 g. (
93%), m.p.
94–98°. One recrystallization from about
2 l. of dry ethanol yields
690 g. (
87%) of material melting at
105–107° (Note 5),
(Note 6), and
(Note 7).
2. Notes
1.
It is necessary to sacrifice the flask after the distillation, since the inorganic residue cannot be removed easily.
2.
The
9-bromophenanthrene need not be recrystallized if it has been purified by distillation.
3.
The heating may be readily controlled by the use of an
electric heating mantle and variable transformer.
4.
Increasing the heating period beyond 6 hours has no effect on the yield.
5.
The melting point can be raised to 110° by further recrystallization from
ethanol. The unrecrystallized product is probably pure enough for most purposes.
6.
The checkers operated on one-tenth the scale and duplicated the percentage yields obtained on the larger scale. Material melting at
109–110° was obtained in a
75–77% yield.
7.
It has been reported (W. R. Vaughan, private communication) that this reaction is highly exothermic, and that the flask contents may erupt when the mixture is heated to the prescribed temperature. Better control of the reaction may result if the
cuprous cyanide is added in portions after the reaction has been initiated at 260–280° with about one-third or less of the total amount of
cuprous cyanide.
3. Discussion
The procedure described above is an adaptation of methods of Mosettig and van de Kamp
2 and of Bachmann and Boatner.
3 9-Cyanophenanthrene has also been prepared from
9-phenanthrenesulfonic acid4 and from
phenanthrene-9-aldoxime.
5This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
ethanol (64-17-5)
Cuprous Cyanide (544-92-3)
9-Cyanophenanthrene,
9-Phenanthrenecarbonitrile (2510-55-6)
9-Bromophenanthrene (573-17-1)
9-phenanthrenesulfonic acid
phenanthrene-9-aldoxime
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