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NOTES
THE SYNTHESIS OF ETHANOLAMINE-1-C"
BY D. E. DOUGLAS AND ANNA ~ ~ I A R Y BURDITT
Pilgeram et al. (4) have reported a synthesis of uniformly labelled ethanol-
amine-C14 from barium carbonate-C14 via acetylene and ethylene oxide,
yielding di- and tri-ethanolamine as by-products.
We have synthesized ethanolamine-1-C1"rom radiocyanide through t he
formation of (C1"-cyano)methyl benzoate (1, 3) and its subsequent reduction
with lithium aluminum hydride t o ethanolamine in 30y0 over-all yield. Thi s
method involves only two stages and yields solely primary anline. The re-
actions are as follows:
H?O+HCHO+NaC14N $ HOCH?C14S+NaOH
I EXPERIMENTAL
I
(CIA-Cyano)methyl benzoate was prepared by the method of Aloy and
I
Rabaut (I) on a semimicro scale as follows: T o 0.154 gm. (2.9 mM.) of sodium
I
cyanide-C14 (3.28 X lo7 counts/min. total activity) in 0.5 ml. of water cooled
I in an ice-bath and stirred with a magnetic stirrer was added 0.24 ml. of 37%
I
forinalin (2.7 mlM. of formaldehyde). After one hour, 0.30 ml. (2.6 mM. ) of
benzoyl chloride was added, and stirring a t OC. continued three hours
longer. After t he addition of 3 ml. of 5% sodium bicarbonate, t he reaction
misture was extracted continuously with ether for two t o three hours. The
ether extract was dried thoroughly, first over calcium chloride, then over
Drierite.
The cyanomethyl benzoate was reduced without isolation by t he gradual
addition of t he dried ether solution t o 3.5 ml. of an ethereal solution of lithium
aluminum hydride (approximately 2.6 mM. per ml.). The complex was decom-
posed by stirring with 30 ml. of water, added slowly, the ether was removed
by evaporation, and t he aqueous phase was saturated with carbon dioxide.
The aluminum hydroxide was centrifuged off and washed thoroughly with
several portions of hot water. The supernatant and washings were combined,
1 ml. of ethylene glycol monobutyl ether (2) and 5 ml. of 0.5 N sodium hy-
droxide added, and t he ethanolamine and water removed by lyophilization
and condensed into a t rap cooled with dr y ice - isopropyl alcohol. The residue
remaining was talten up in water, 1 ml. of ethylene glycol monobutyl ether
added, and lyophilization repeated. Thi s process was carried out four times
altogether. The ethanolamine was recovered as hydrochloride by evaporation
1183
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1184 CAS ADI AS JOURNAL OF CHEMISTRY. VOL. 33
of the combined condensates from the cold trap with excess hydrochloric acid,
and the salt recrystallizecl from isopropyl alcohol - ether. Yield: 0.0946 gm.
(30.9y0, based on sodiuin cyanide). The material was recrystallized for activity
and melting point determinations. Specific activity: 132,000 counts per min.
per mgin. Melting point: 79.8-82' C. Mixed melting point with authentic
ethanolamine hydrochloride : 79.8-83' C.
Thirty-seven per cent of the initially added racliocyanide activity was found
in the aqueous phase after ether extraction of the cyanomethyl benzoate.
To check the radiopurity, ethanolamine hydrochloride prepared by the
above procedure was chromatographed on paper, with water-saturated phenol
as the developing solvent. Radioautography indicated that the material was
essentially free from radioactive contaminants. The Rf was 0.76.
1. .%LOT, J. and RABAUT, C. Bull. soc. chin]. France, (4) 13: 457. 1913.
2 HORSLEY, L. H. Bnnl . Chcm. 21: 838. 194'3.
3. MOWRY, D. T. J. Am. Chem. Soc. 66: 371. 1944.
4. PILGERAM, L. O., GAL, E. &I., SASSENRATH, E. N., and GREBSBERG, D. hI. J. Biol. Chem.
204: 367. 1953.
RECEIVED DECE~~BER 15, 195.1.
DIVISION or; ATOMIC CHEBIISTRY,
THE MOSTREAL GENERAL HOSI'ITAL, RESEARCH INSTITUTE,
MONTREIL, P.Q.
A SELF PUMPING DROPPING MERCURY ELECTRODE FOR USE
WITH STIRRED SOLUTIONS1
The theory of polarography assuines the formation of a polarized layer around
one electrode in an electrolysis cell. If through agitation of the solution this
layer is dist~irbed the current passing through the cell is no loilger diffusion
dependent and the Illcovic equation does not apply. Uiilson and Smith (12)
studied the effect of increasing flow rate of solution on the dropping mercury
electrode (DME) and found first of all a deviation from diffusion coiltrolled
current and finally a complete disruption of the regular drop formation.
By employing a slolv rate of flo~l7 in a horizontal direction they mere able t o
monitor continuousI~7 sulphur dioxide in industrial solutions by a polarographic
method (13). This principle has been used by a number of worliers (1, 11)
while others have employed baffles (4, 5, 6, 7, 14) and some have even aban-
doned the ordinary DAME in favor of the vibrating DME (2), or solid electrodes
(3, 9, 10).
This paper describes a cell in which the DllIE is situated in a side arin
and the solution is circulated past the electrode by the pumping action
of the detached drops descending through a capillary. Basically the cell
consists of a Lingane-Laitinen H cell (8) t o xx~hicl~ a side arm has been attached
IContribzition No. 45, Sciefzce Service Laboratory, Lo ~t d o n , Ontario.
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