REARRANGEMENT CLEAVAGE OF AMMONIUM SALTS
955
Thin-layer chromatography was performed on
Silufol UV-254 plates in n-butanol ethanol water
acetic acid (10:7:1:4), development in iodine vapor.
extracts were combined and dried with magnesium
sulfate. The ether was distilled off and the residue was
heated in a vacuum (2 mm) for 30 min at 50 C.
After GLC analysis, the residue was distilled in a
vacuum. Because of the vigorous decomposition and
tarring, the rearrangement product V was identified
without distillation. Compound V, viscous substance.
Rf 0.43 [eluent ether hexane (1:3)]. Its physicoche-
mical characteristics coincide with those of the sample
of amine V, obtained by the above procedure. Found,
%: C 87.47; N 7.78; N 4.23. M 315 (by mass spec-
trometry). C23H25N. Calculated, %: C 87.02; H 7.94;
N 4.44. M 315.
The mass spectra were obtained on an MKh-1320
instrument with direct inlet, ionizing voltage 70 eV.
Gas chromatography was performed on an LKhM-
80 instrument with a thermal conductivity detector,
column 2000 3 mm, 10% E-301 on Chromaton N-
AW-HMDS, carrier gas helium, rate 60 80 ml/min.
The starting ammonium salts were prepared by the
reactions of 1,2-dibromomethane and 2-alkenyl and
2-alkynyl bromides with dimethyl(3-methyl-2-naph-
thylmethyl)amine by the procedures in [10, 11]
(Table 1).
In a similar way, from compound Ig we obtained
product VI, bp 161 162 C (1 mm), n2D0 1.6105. Found,
%: C 87.98; H 7.41; N 4.60. C23H23N. Calculated, %:
Dimethyl(3-methyl-2-naphthylmethyl)amine was
synthesized as described in [12].
1
C 88.18; H 7.35; N 4.47. By H NMR and IR spectral
Rearrangement cleavage of ammonium salts
Ia Ig. A mixture of 0.015 0.02 mol of salt and
0.045 0.06 mol of 25% aqueous potassium hydroxide
was heated for 5 6 h at 90 92 C in a flask equipped
with a reflux condenser connected to a trap with a
titrated solution of hydrochloric acid, and then treated
with ether. The ether layer was separated, and the
aqueous layer was treated with two portions of ether.
The combined ether extracts were treated with con-
centrated hydrochloric acid. The ether layer was dried
over magnesium sulfate and subjected to GLC ana-
lysis to determine the ratio of non-nitrogenous reac-
tion products. Low-boiling non-nitrogenous reaction
products were removed with ether and identified as
2,4-dinitrophenylhydrazones whose molecular weights
were determined by mass spectrometry. The colorless
semisolid material remaining after removal of ether
was subjected to column chromatography on alumina
(30 80 mm) in hexane ether (8:1) to obtain alcohol
and aldehyde. The aqueous layer was made alkaline
and treated with ether to extract amine reaction pro-
ducts. Their ratio was determined by GLC using as
references dimethyl(3-methyl-2-naphthylmethyl)- [12]
and dimethyl(3- phenyl-2-propynyl)amines [13]. The
amount of dimethylamine formed was determined by
back titration of trap contents. The melting point of
the picrate was 151 C. Mixed sample with an
authentic sample showed no melting point depression.
data, the product is identical to the sample of com-
pound VI, obtained by the above procedure.
REFERENCES
1. Indzhikyan, M.G., Minasyan, R.B., and Babayan, A.T.,
Arm. Khim. Zh., 1970, vol. 23, no. 4, p. 344.
2. Babayan, A.T., Indzhikyan, M.G., Minasyan, R.B.,
and Grigoryan, A.A., Arm. Khim. Zh., 1970, vol. 23,
no. 6, p. 516.
3. Oganesyan, N.R., Grigoryan, Dzh.V., and Ba-
bayan, A.T., Arm. Khim. Zh., 1989, vol. 42, no. 11,
p. 700.
4. Grigoryan, Dzh.V., Oganesyan, N.R., and Ba-
bayan, A.T., Arm. Khim. Zh., 1991, vol. 44, no. 4,
p. 245.
5. Heilbron, I. and Burnbury, H.M., Dictionary of Or-
ganic Compounds, London: Eyre and Spottiswood,
1946, vol. 1. Translated under the title Slovar’ orga-
nicheskikh soedinenii, Moscow: Inostrannaya Litera-
tura, 1949, vol. 1, p. 578.
6. Heilbron, I. and Burnbury, H.M., Dictionary of Or-
ganic Compounds, London: Eyre and Spottiswood,
1946, vol. 3. Translated under the title Slovar’ orga-
nicheskikh soedinenii, Moscow: Inostrannaya Litera-
tura, 1949, vol. 3, p. 516.
7. Heilbron, I. and Burnbury, H.M., Dictionary of Or-
ganic Compounds, London: Eyre and Spottiswood,
1946, vol. 2. Translated under the title Slovar’ orga-
nicheskikh soedinenii, Moscow: Inostrannaya Litera-
tura, 1949, vol. 2, p. 418.
Stevens rearrangement of ammonium salts Ie
and Ig. Salt, 0.01 0.015 mol, and 0.02 0.03 mol of
freshly powdered potassium hydroxide were thorough-
ly mixed. A weakly exothermic reaction developed.
After it had been complete, 5 ml of benzene was
added. The mixture was heated for 1 h on a boiling
water bath with intermittent shaking, and then ether
and water were added to it. The aqueous layer was
treated with two portions of ether, and the ether
8. Gordon, A.J. and Ford, R.A., The Chemist’s Compa-
nion, New York: Wiley, 1972. Translated under the
title Sputnik khimika, Moscow: Mir, 1976, p. 210.
9. Heilbron, I. and Burnbury, H.M., Dictionary of Or-
ganic Compounds, London: Eyre and Spottiswood,
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