foxy2 Ethylamine and Triethylamine Synthesis Bookmark

(Distinctive (Rated as: excellent)

Doe)
07-10-02 A MODIFIED METHOD FOR THE PREPARATION OF
18:46 TRIETHYLAMINE
No 330880 Jitendra Nath Rakshit
J Am Chem Soc, 1913 35(11): 1781-1783

Considerable difficulty has been experienced in the

investigation of triethylammonium nitrite,(l) in the preparation
of triethylamine. In order to obtain the base in a pure
condition, it was thought feasible to prepare
tetraethylammonium bromide by the method described by
Scott;(2) next, to convert it into the quaternary hydroxide by
the interaction with moist silver oxide, which on heating would
decompose into triethylamine and ethylene. But, as has been
already noticed,(3) the method was not found suitable for the
purpose; the lack of success has been, reasonably enough,
assigned to the higher atmospheric temperature of this tropical
country. Next Hofmann’s(4) method was tried; and in spite of
the want of the indespensable details of this classical memoir,
the base has been prepared by it. But the yield being
comparatively poor, it was thought worth while investigating
the exact condition under which the triethylamine can be
conveniently prepared.

Ethylamine Synthesis
Of the two alkyl halides, ethyl iodide and bromide, the latter
has been found easier to prepare, the former invariably
yielding a mixture of all four bases under different
circumstances. Seventy-five cc. of ethyl bromide and 50 cc. of
strong ammonia (sp. gr. 0.88) were taken in a 750 cc. thick
glass flask, sufficient absolute alcohol was then added to effect
solution, and the flask immediately closed with a rubber cork
and tied with wire. Next the flask was placed in a steam oven
for three hours. After cooling, it was opened and the alcohol
(which may be again used for the same purpose after
rectification) was distilled off. The residue was disolved in a
minimum quantity of water and distilled with an excess of
caustic soda solution. The alkaline distillate was collected
under dilute hydrochloric acid (1 in 3). This hydrochloric acid
solution was evaporated on the water bath till there was no
odor of the acid and the product, when removed from the water
bath, solidified to a crystalline mass after a few minutes. If this
solid mass be again placed on the water bath, it melts partially
and remains as a mixture of fine, white crystals of ammonium
chloride and a transparent liquid, which was expected to be a
mixture of hydrochlorides of ethylamines. The ammonium
chloride might have been quite efficiently eliminated by
extraction with a mixture of ether and alcohol;(5) but, in
dealing with larger quantities, the following method was found
more convenient and less expensive.

A hot water funnel was filled with brine and heated to boiling.
The funnel was fitted with a filtering flask, which was
connected with a filter pump, and the molten mixture was
rapidly filtered by suction. The residue was proved to be
ammonium chloride. The filtrate, on cooling, solidified to a
lustrous crystallin mass. A portion of it was converted into the
chloroplatinate.
0.4580 gram gave 0.1786 gram Pt.
Found Pt=38.99, theory for (C2H5NH3Cl)2PtCl4 : 38.93%.
It is thus seen that in this way practically pure primary
ethylamine was obtained.

Triethylamine Synthesis
About 60 grams of sticks of caustic soda were taken in a 500
cc. distilling flask, fitted with a tap funnel and a condenser
circulated by ice cold water. Sixty-two grams of ethylamine
hydrochloride were dissolved in minimum quantity of water
and put into the tap funnel for introducing into the flask drop
by drop. The alkaline distillate was collected in a stout 500 cc.
glass flask and cooled by freezing mixture. Finally it was
heated to boiling for about five minutes. To the collected free
base, 44 cc. of ethyl bromide were added and the flask closed
with a rubber cork and tied with wire. The mixture was then
kept in a steam oven for three hours, after which time the
contents of the flask formed two distinct layers. It was left in
the over over night, slowly cooling with it. The next day the
lower layer solidified to a crystallin mass, and the upper one
remained as a slightly brownish, transparent liquid. When the
flask was opened the odor of amine was noticeable and the
amine product had a strongly alkaline reaction. The liquid was
decanted off into a conical flask and cooled with ice and salt,
then neutralized with dilute hydrochloric acid and evaporated
on a water bath. The resulting product has been proved to be
pure triethylamine hydrochloride. The yields in the first,
second, and third experiments were 20, 18 and 18.6 grams,
respectively.
Substance I, 0.3534; II, 0.4628; III, 0.3842,
gave I, 0.1122; II, 0.1473; III, 0.1221 gram Pt.
Pt found=31.76, 31.84 and 31.80%; calculated for
2{(C2H5)3NHCl}PtCl4, 31.86%.

Sometimes the crude product obtained was brownish, but

analyses proved that in such samples the quantity of foreign
matter was not appreciable. The best way to purify this is by
redistillation.
The solid lower stratum of the flask was taken out and distilled
with caustic soda, and the alkaline liquid collected was
carefully dried over caustic soda, when it distilled at 44-47C.
But the boiling points of primary and secondary ethylamines
are 16C and 56C, respectively. This fact is in conformity with
the observations of Lea,(6) who found that these amines cannot
be separated by fractional distillation, although there is a
reasonable difference in boiling points for such possibility. The
chloroplatinate of the mixed bases gave 37.82% of Pt. The
primary and secondary bases contain 39.93% and 35.07%,
respectively.

Discussion
From the heats of neutralization of primary, secondary, and
tertiary amines it is expected that the secondary one is more
basic than the tertiary, and the primary more basic than either.
On this hypothesis the intermediate steps of the reaction can be
represented as:

EtNH2 + EtBr = Et2NH.HBr

Et2NH.HBr + EtNH2 = Et2NH + EtNH2.HBr
Et2NH + EtBr = Et3N.HBr
Et3N.HBr + EtNH2 = Et3N + EtNH2.HBr
Et3NHBr + Et2NH = Et3N + Et2NH.HBr

The final products are hydrobromides of primary and

secondary ethylamines, and free triethylamine. This is what
was practically obtained. Calculated quantities of ethylamine
and ethylbromide were taken so that the reaction may proceed
according to the above equations, which when summed up are
represented by:

7EtNH2 + 5EtBr = 2Et3N + 4EtNH2.HBr + Et2NH.HBr

Actually the reaction does not proceed directly according to

this reaction, otherwise the yield would have been 29.8 grams,
instead of 18-20. However, notwithstanding this shortcoming,
the process is extremely convenient for the preparation of
triethylamine.

1. Ray and Rakshit, J. Chem. Soc., 101, 216 (1912).

2. J. Chem. Soc., 95, 1200 (1909).
3. Loc. cit.
4. Phil. Trans., 1850, Pt. L, 121.
5. THIS JOURNAL, 35, 444.
6. Allen's Commercial Organic Analysis, I, 4th ed., 19 (1909).
 foxy2 tertiary amines Bookmark
(Distinctive
Doe) Here is a related synthesis of tertiary amines.
07-10-02 Post 222680 (foxy2: "Re: Synthesis of TBAB", Chemicals &
18:54 Equipment)
No 330885
Those who give up essential liberties for temporary safety
deserve neither liberty nor safety

Antoncho Foxy, thank you a lot! Bookmark

(Official
Hive SWIM once tried to get iPr-NH2 in such fashion but fucked it
Translator) all up at the purification stage - to say the truth, the work-up
07-10-02 strategy SWIM chose was inherently idiotic Anyway. This
19:43 proc has been most helpful as SWIM plans to do that once
No 330901 again someday.

Now, he only wants a small-scale experiment and is very

interested in hearing the details on extraction/separation from
NH4Cl with ether/alcohol. Can you, please, post them? This
ref is from the same very journal.

Thanx ahead,

Antoncho

foxy2 Alkylcyanide to Amine (Acetonitrile to Bookmark

(Distinctive ethylamine)
Doe) (Rated as: excellent)
07-10-02
20:44 Here you go Antoncho
No 330913 foxy

ON THE MAXIMUM YIELD OF AMINES BY THE

REDUCTION OF ALKYL CYANIDES.
Jitendra Nath Rakshit
J Am Chem Soc, 1913 35(4): 444-446
Mendjus(1) prepared alkylamines by the reduction of their
cyanides with zinc dust and dilute hydrochloric acid.
Siersch(2) modified the method by arranging a series of
vertical tubes filled with granulated zinc, through which a
mixture of nitrile, hydrochloric acid, and alcohol had to
circulate. The principles involved in the improvement are the
exposition of a larger surface in a shorter duration and
prevention of hydrolysis by using an alcoholic medium for the
reaction. It was further modified by Ladenburg,(3) who
introduced alcohol and sodium for the hydrogenation.

Having had to prepare amines in quantities from the nitriles(4)

Mendius', Siersch's and Ladenburg's methods have been
successively tried but the bases produced have been always
found to be considerably contaminated with ammonia. By the
former two only nominal quantities of amines were obtained
and by the latter some amines were produced. The yield was
much below the theoretical. It had been observed that on
increasing the dilution of the nitriles in alcohol the yield of the
amine improved. And it had been calculated that the quantity
of the nitrogen of ammonia
and amine together does not account for the total nitrogen of
the cyanide used. This is evidently due to the partial direct
action of the nitriles with sodium.(5) E.V. Mayef(6) has
shown that sodium acts on ethyl cyanide according to the
following equations :

2Na + 2EtCN = NaCN + C2H4 + C2H4NaCN;

C2H4NaCN + C2H4CN = C6H9NaN2.

The greater the concentration of the cyanide the more of it is

acted on by the sodium. On increasing the dilution the
formation of sodium cyanide becomes less and less, as is
observed by the decreasing amount of Prussian blue obtainable
from the resulting sodium ethoxide of the reduction. After a
certain dilution its formation and that of ammonia becomes
practically nil. The generation of ammonia in this case cannot
be ascribed to the hydrolysis of the nitrile because there is no
water present and if the ethyl hydroxide be taken for the water
and the hydrolysis be assumed, still ammonia cannot result, but
either a primary or a secondary base will be formed. It can,
however, be explained by assuming the excessive
hydrogenation of the nitrile:

RCN + 6H = RCH3 + NH3.

After several experiments it has been found that the following

method is most suitable for the maximum yield: Five cc. of the
nitrile are diluted with 75 cc. of absolute alcohol. Five grams
of freshly cut sodium are introduced into a 500 cc. flask fitted
with an inclined reflux condenser and a tap funnel. The
mixture is added in portions of 5 cc. at a time and the flask is
heated by means of a liquid paraffin bath at temperatures
between 50C and 60C. After four such additions 5 cc. of
absolute alcohol are to be added and the amine evolved by
distillation is absorbed in hydrochloric acid diluted with an
equal bulk of water. When all of the mixture has been added,
sufficient alcohol is next poured in so that a layer remains
above the surface of the solid sodium ethoxide in the flask.
When the evolution of hydrogen practically ceases some more
alcohol is added and the flask is heated up to the neck on a
water bath, taking off the condenser and directly connecting
the flask with the absorbing bottles containing acid. Heating is
continued as long as any alkaline vapor comes off. If all the
alcohol is distilled and yet some amine remains in the flask,
more alcohol is to be added and distilled. By evaporating the
acid solution on a water bath the crude amine hydrochloride is
obtained, which is then extracted with a mixture of 15 cc. of
absolute alcohol and 10 cc. water free ether. Thus pure amine
hydrochloride is obtained, free from any ammonium chloride,
as salammoniac is insoluble in the above menstruum,
especially when the amine hydrochloride is present in
excess.(7) Some typical results are given below:

Alkyl Cyanide : Nitrile cc. : Alcohol cc. : Amine HCl g. :

NH3Cl g. : Theory Amine g.
-------------------------------------------------------------
Methyl cyanide : 5 : 50 : 3.8 : 0.63 : 7.9
Methyl cyanide : 5 : 75 : 7.6 : 0.0 : 7.9
Methyl cyanide : 5 : 100 : 7.58 : 0.0 : 7.9
Ethyl cyanide : 5 : 50 : 4.36 : 0.5 : 7.0
Ethyl cyanide : 5 : 75 : 6.4 : 0.07 : 7.0
Propyl cyanide : 5 : 75 : 6.1 : 0.03 : 6.3
Propyl cyanide : 5 : 100 : 6.0 : 0.06 : 6.3
-------------------------------------------------------------

1. Ann., 121, 229.

2. Ibd., 144, 139.
3. Ber., 19, 1783.
4. Ray and Rakshit, Trans. Chem. Soc., 99, 1471, 101, 141.
5. Frankland and Kolbe, Ann., 65, 281.
6. Chem. Soc. Abs., 1889, 114.
7. Winkler, Ann., 93, 324; Ray and Rakshit, J. Chem. Soc., 99,
1471.