Org. Synth. 1946, 26, 40
DOI: 10.15227/orgsyn.026.0040
JULOLIDINE
[Benzo[ij]quinolizine, 1,2,3,5,6,7-hexahydro-]
Submitted by D. B. Glass and A. Weissberger.
Checked by Cliff S. Hamilton and Carol K. Ikeda.
1. Procedure
A mixture of 66.5 g (0.5 mole) of tetrahydroquinoline and 400 g. of trimethylene chlorobromide (Note 1) is placed in a 1-l. round-bottomed flask attached to a reflux condenser, and heated in an oil bath held at 150–160° for 20 hours (Note 2). The reaction mixture is cooled, a solution of 50 ml. of concentrated hydrochloric acid in 500 ml. of water is added, and the excess trimethylene chlorobromide is removed by distillation with steam (Note 3). The acid residue from the steam distillation is made alkaline with a 40% solution of sodium hydroxide (about 75 ml.), and the julolidine is extracted with two 150-ml. portions of ether. The ethereal solution is washed with 150 ml. of water and dried over sodium hydroxide pellets. The ether is evaporated and the residue distilled under reduced pressure. The portion that boils at 105–110°/1 mm. is collected (Note 4) and (Note 5). The yield is 67–70 g. (77–81%).
2. Notes
1.
The
tetrahydroquinoline and trimethylene chlorobromide were Eastman grade materials of the Eastman Kodak Company.
2.
The heating should be carried out in a
hood, or a
gas trap should be used to remove the hydrogen halides that are evolved.
3.
The
trimethylene chlorobromide recovered may be dried over
calcium chloride and used in a subsequent run.
4.
The
julolidine solidifies in the
receiver, m.p.
39–40°.
5.
After standing in contact with air for several weeks, the
julolidine may become colored by the formation of a red compound. This red compound may be removed by distillation or by dissolving the amine in
2 or 3 volumes of hexane, treating the
hexane solution with
Norit or Darco, and filtering. The
julolidine is crystallized from the
hexane solution by cooling in an
acetone-Dry Ice bath. The resulting product melts at
39–40° and amounts to
85–90% of the original.
3. Discussion
Julolidine has been prepared by the reaction of
trimethylene chlorobromide with
formanilide,
1 aniline,
1 methylaniline,
1 and
tetrahydroquinoline;
1,2 by the reduction of
8,10-diketojulolidine;
1 by the intra-molecular condensation of
N-(γ-bromopropyl) tetrahydroquinoline;
3 and by dehydration of
N-(γ-hydroxypropyl) tetrahydroquinoline or
di-(γ-hydroxypropyl) aniline with
phosphorus pentoxide.
4
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
Darco
calcium chloride (10043-52-4)
hydrochloric acid (7647-01-0)
ether (60-29-7)
aniline (62-53-3)
sodium hydroxide,
sodium hydroxide pellets (1310-73-2)
Norit (7782-42-5)
Trimethylene chlorobromide (109-70-6)
methylaniline (100-61-8)
Julolidine,
Benzo[ij]quinolizine, 1,2,3,5,6,7-hexahydro- (479-59-4)
tetrahydroquinoline (635-46-1)
hexane (110-54-3)
formanilide (103-70-8)
8,10-diketojulolidine
N-(γ-bromopropyl) tetrahydroquinoline
N-(γ-hydroxypropyl) tetrahydroquinoline
di-(γ-hydroxypropyl) aniline
phosphorus pentoxide (1314-56-3)
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