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9236 J . Org. Chem., Vol. 65, No. 26, 2000
Notes
Ta ble 1. Gen er a l Con d ition s for Ter tia r y Am in e Syn th esis fr om Ur ea
R3N no.
halide used
°Ca
product bp or mp
% yield
2
3
4
5
6
7
allyl chloride, 244.9 g
crotyl chloride, 290 g
methallyl chloride, 290 g
butyl bromide, 438.5 g
octyl bromide, 681 g
benzyl chloride, 783 g
80
80
80
120
200
120
148-150 °C, atm (lit.24 150-151)
106-107 °C, ∼70 mmHg
101-103 °C, ∼70 mmHg
56-58 °C, ∼4.0 mmHg
200-202 °C, ∼4.0 mmHg
93.4 (DSC)
55.8
50.0
72.0
76.5
75.0
81.8
a
Reaction temperature.
required 200 °C to proceed in less than 50% yields. Use
of butyl and octyl bromides generated the desired tertiary
amines in ∼80 and ∼75% yields at 120 and 200 °C,
respectively. Tribenzylamine (7) was produced by the
reaction of urea with benzyl chloride in aqueous base at
120 °C. Triallyl, trimethallyl, and tricrotylamines were
found in water even after the aqueous layers were
extracted three times with ether (observed by GC-MS).
It appeared that the water-soluble byproducts of these
amines might be increasing their solubility in water.
Byproducts (isolated by fractional distillation) of all
trisubstituted amine syntheses were alcohols and ethers
as determined by 13C NMR and GC-MS. When reactions
were conducted at ambient pressures, mixtures of mono-,
di-, and trisubstituted amines were obtained. When times
were less than about 30 h for reactions conducted in the
pressure vessel, yields of the trisubstituted amines were
lower. Thereafter, the reaction time of 40 h was set for
convenience. Quaternary ammonium salts were detected
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