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verted by ammonia into benzylsulphonamide, C 6 H 5 .CH 2 .SO 2 .NH 2 ,
which crystallizes from water in prisms melting at 105 . 1

Nitrolenzylsulphonic acid, C 6 H4(NO 2 )CH 2 .S0 3 H, is formed
by the action of fuming nitric acid on barium benzyl sulphate.
A mixture is thus obtained which contains, together with the
para-compound, a little of the orthonitro-acid and the dinitro-
acid, which cannot be completely separated. On boiling with a
mixture of nitric and sulphuric acids, dinitrobenzylsulphonic
acid, C 6 H 3 (NO2) 2 CH 2 .SO 3 H, is obtained; it forms salts, which
crystallize well. On reduction it is converted into diamido-
Icnzylsulphonic acid, C 6 H 3 (NH 2 ) 2 CH 2 .SO 3 H, which crystallizes
from hot water in silky needles. 2



SELENIUM COMPOUNDS OF BENZYL.

2074 Benzyl sclenide, (C 6 H 5 .CH 2 ) 2 Se, is prepared by treating
phosphorus pentaselenide with alcoholic soda solution in absence
of air, and heating the sodium selenide thus formed with benzyl
chloride to the boiling point of the latter. When the solution
cools, benzyl selenide separates out first and then some benzyl
diselenide, which is separated by recrystallization from hot
alcohol. Benzyl selenide crystallizes in long, white needles
or transparent prisms, which have a faint aromatic odour
and melt at 45'5. Like methyl selenide, it combines with
acids forming unstable salts.

Benzyl diselenide, (C e H 5 .CH 2 ) 2 Se 2 , is obtained by boiling crude
sodium selenide, prepared by igniting sodium selenite with char-
coal, with alcohol and benzyl chloride. It crystallizes from hot
alcohol in straw-yellow scales, resembling fat, which melt at
90 and become coloured red in the sunlight. Nitric acid
oxidizes it to l/enzylselenic acid, C 6 H 5 .CH .SeO>H, crystallizing
from hot water in needles which when impure possess a
nauseous smell, that of the pure compound being much less
unpleasant. It is a strong acid.

1 v. Pechmann, Ber. Deutsch. Chcm. Gcs. vi. 534.

2 MoLr, Ann. (Jhcm. Fhaiin. ccxxi. 215.



110 AROMATIC COMPOUNDS.

When benzyldiselenide is digested for some days with methyl
iodide, a black mass is obtained which is a mixture of benzyl
iodide, trimethylselenine iodide and lenzyldimethylselenine tri-
iodide :



Se 2 +5CH 3 I =
C 6 H 5 .CH 2 I + (CH 3 ) 3 SeI + C 6 H 5 .CH 2 (CH 3 ) 2 SeI 3 .

The latter crystallizes from hot alcohol in black, heavy needles
which have a metallic lustre, melt at 65 and possess a repulsive
odour. They commence to sublime below 100, and their
vapour attacks the eyes violently. If the alcoholic solution be
treated with silver nitrate, the excess of silver removed by
hydrochloric acid and the nitrate then treated with platinum
chloride, a precipitate of (C 6 H 6 .CH 2 .(CH 3 ) 2 Se) 2 PtCl 6 is obtained
consisting of microscopic, yellow, quadratic plates. 1



NITROGEN BASES OF BENZYL.

THE BENZYLAMINES.

2075 Cannizzaro states in his first paper on the alcohol of
benzoic acid, that when the ethereal chloride prepared from it by
the action of hydrochloric acid is treated with alcoholic ammonia,
a base which differs from toluidine is formed (p. 89). Three
years later he found that this is tribenzylamine, (C 7 H 7 ) 3 N. 2 In
the year 1862, Mendius made the important discovery that the
nitrils of the fatty acids combine with hydrogen to form amines,
and that those of the aromatic series behave in a similar manner,
inasmuch as benzonitril, C 7 H 5 N, yields a powerful base, C 7 H 9 N,
which, however, is not identical with toluidine, " as might have
been expected from the hitherto accepted views as to the re-
lations of the bases homologous with aniline to the corresponding
members of the benzoic acid series," but differs both from it and
the isomeric methylaniline in its properties. It also appeared
to him improbable that it was identical with the lutidine con-
tained in coal-tar oil ; he, therefore, decided, in the absence of a
careful comparison between the two substances, " to introduce



Loring Jackson, Ann. Chcm. Pharm. clxxix.
Jahresb. 1856, 582.






NITROGEN BASES OF BENZYL. Ill

the base prepared from benzonitril into scientific literature as a
new compound and to denote it by a new name." l Two years
later, Cannizzaro published a paper on " The Amines of Benzyl
Alcohol " in which he says " Toluidine, C 7 H 9 N, is generally looked
upon as the primary benzylamine. I have obtained results which
do not agree with this supposition." He found that the primary
benzylamine, which he had prepared from benzyl cyanate (benzyl
isocyanurate), is a strong base resembling ethylamine and amy la-
mine in its properties. He also obtained it, together with dibenzyl-
amine and tribenzylamine, by heating benzyl chloride with
alcoholic ammonia, 2 and described the separation of these bases
and the properties of benzylamine. 3 In order to prepare the
latter, a mixture of benzyl chloride and alcoholic ammonia is
allowed to stand for some days ; a portion of the tribenzylamine
separates out in crystals, and a further quantity is left behind
when the alcohol is removed from the filtrate by distillation
and the residue treated with hot water. The solution is
then evaporated to dryness, and the most soluble portion of
the residue, consisting chiefly of benzylamine hydrochloride is
separated by fractional crystallization. This is then decomposed
by caustic potash and the base allowed to remain in contact
with some solid potash in order to dry it, and at the same time
avoid exposure to carbon dioxide. It is then purified as much
as possible by fractional distillation and treated with dry carbon
dioxide ; a solid compound is formed which is washed with
anhydrous ether to remove the last adhering traces of
dibenzylamine. The residue is then converted into the crystal-
lized hydrochloride and the pure base finally liberated by caustic
potash.

According to Limpricht, the base is prepared by heating
benzyl chloride with a solution of ammonia in commercial
absolute alcohol for twenty-four hours in a steam bath and re-
moving free ammonia and the largest portion of the alcohol by
distillation. The residue is treated with water to precipitate
the mixed bases, which are then dissolved in alcohol and treated
with hydrochloric acid, the acid solution being allowed to cool
gradually. Tribenzylamine hydrochloride separates out in prisms
or needles, and a mixture of this salt with plates of dibenzyl-
amine hydrochloride is obtained by the concentration of the
mother-liquor; the residual liquid after repeated evaporation

1 Ann. Chcm. riutrm. cxxi. 144. " Ibid, cxxxiv. 128. 3 Ibid. Suppl. iv. 24.



112 AROMATIC COMPOUNDS.

to a syrup, solution in hot water and reconcentration, yields
benzylamine hydrochloride. The water employed for the
precipitation of the bases contains some benzylamine, which
may be extracted by saturating the liquid with hydrochloric
acid, evaporating to dryness and extracting with hot absolute
alcohol, which leaves ammonium chloride undissolved. The
hydrochlorides of di- and tri-benzylamine are purified by
re-crystallization from water or alcohol.

The primary base is always present in the smallest quantity,
while the relative amounts of the other two are very variable ;
sometimes a large quantity of tribenzylamine is formed with
only traces of dibenzylarniue, while in other eases the relation
is the inverse of this. 1

2076 Benzylamine, C 6 H 5 .CH 2 .NH 2 . Mendius obtained this
compound by treating benzonitril in alcoholic solution with zinc
and hydrochloric acid, freeing the solution from alcohol and
unattacked nitril by distillation, saturating the residue with
caustic potash and extracting the benzylamine with ether. The
ethereal solution is then treated with hydrochloric acid, the
benzylamine hydrochloride, which is obtained on evaporating
the solution, re-crystallized from absolute alcohol and the pure
base then set free by caustic potash.

Hofmann obtained benzylamine by the action of zinc and
hydrochloric acid on thiobenzamide, C 6 H 5 .CS.NH 2 , 2 which is
formed by the direct combination of sulphuretted hydrogen with
benzonitril :

C H 5 .CS.NH 2 + 4H = C 6 H 5 .CH 2 .NH 2 + H 2 S.

Both these methods are tedious, and, like the preparation from
benzyl chloride and ammonia, only give a small yield. Benzyl-
amine can, however, be readily prepared ir> large quantities by
heating benzyl chloride with an equivalent amount of silver
cyanate, until the violent reaction has ceased ; a mixture of
benzyl isocyanate and benzyl isocyanurate- is formed and after
distillation is re-distilled over caustic potash. The product thus
obtained contains some di- and tri-benzylamine, since the mix-
ture of isocyanates always contains some benzyl chloride. These
can be removed by converting the whole into the hydrochlorides
or by extracting the benzylamine by shaking out with water..

1 Ann. Chcm.. Pharm. cxliv. 304.

2 Ber. Dcutsch. Chcm. Ges. i. 102.



BENZYLAMINE. 113



It is then converted into the hydrochloride which is decomposed
by caustic potash, and the base dried over solid potash and
redistilled. l

It can also be readily obtained by decomposing benzylacet-
amide, C C H 5 .CH 2 .NH.(C 2 H 3 O), which is prepared by the action
of benzyl chloride on acetamide, with alcoholic potash. 2

Another simple method of preparation has been found by
Hofmann. On heating benzyl chloride with potassium cyanide,
phenylacetonitril, C 6 H 5 .CH 2 .CN, is obtained ; when water is
added to a solution of this compound in concentrated sulphuric
acid, phenylacetamide, C 6 H 5 .CH 2 .CO.NH 2 is precipitated. This
is then treated with a molecule of bromine, a 5 per cent, solution
of four molecules of caustic potash added with continual agita-
tion and the liquid heated by a current of steam : a mixture of
benzylamine and brominated benzylamine distils over, which is
converted into pure benzylamine when allowed to stand for
some time over sodium amalgam, all the bromine being replaced
by hydrogen. 3

Hofmann has shown that the amides of other monobasic acids
can readily be converted by this reaction into amines containing
one atom of carbon less in the molecule. He has carefully
investigated the course of the reaction in the case of acetamide,
and finds that acetbromamide, CH 3 .CO.NHBr, is first formed,
and that this loses hydrobromic acid with formation of methyl
isocyanate, which assumes the elements of water and splits
up into carbon dioxide and methylamine.

Benzaldehyde, which is now a cheap commercial product, can
also be readily converted into benzylamine. It combines with
hydrocyanic acid to form phenylhydroxyacetonitril, C 6 H 5 .CH
(OH)CN, which is converted by treatment with alcoholic
ammonia into phenylamido-acetonitril, C 6 H 5 .CH(NH 2 )CN.
On boiling this with dilute sulphuric acid, phenylamido-
acetic acid is formed and decomposes into benzylamine and
carbon dioxide on distillation. These products of decom-
position recombine to some extent forming benzylammonium
benzylcarbamate (p. 114), which is, however, readily decomposed
by alkalis. Pure benzylamine hydrochloride may also be
obtained by treating the distillate with hydrochloric acid. 4

Properties. Benzylamine is a colourless liquid which has a

1 Strakosch, Ber. Dcutsch. Chem. Ges. v. 692.

2 Rudolph, ibid. xii. 1297. 3 Ibid, xviii. 2734.
4 Fricdlander and Ticmaiin, Hid. xiv. 1969.

VOL. III. PART IV. I



114 AROMATIC COMPOUNDS.

characteristic, faint, aromatic odour, does not become coloured
in the light, boils at 185 and has a sp. gr. of 0'990 at 14.
It is soluble in water in every proportion, but is insoluble
in strong alkalis, and is therefore precipitated by caustic
potash from its aqueous solution. It has a strong alkaline
reaction, fumes with hydrochloric acid and rapidly absorbs
carbon dioxide, so that a drop exposed to the air is soon
converted into small, silky needles of the carbonate. It
combines with benzyl chloride to form dibenzylamine hydro-
chloride.

Benzylamine hydrochloride, C 7 H 7 NH 3 C1, forms quadratic
tablets, very soluble in water and alcohol ; its platinichloride
is a granular, crystalline precipitate.

Benzylamine nitrite, C 7 H 7 NH 3 .NO 2 , is obtained by shaking
the hydrochloride with silver nitrite and ether. It is extracted
from the silver chloride, which is simultaneously formed, by
cold absolute alcohol, and is deposited on the evaporation of
this solution in well-formed crystals, which decompose with
evolution of nitrogen when gently warmed. 1

Benzylammonium benzylcarbamate is formed by the com-
bination of benzylamine with carbon dioxide :

C0 2 +2NH 2 .CH 2 .C 6 H 5 = CO<' 3 * ' *
\NH(CH 2 .C 6 H 6 ).

It is readily soluble in water, volatilizes when the solution is
boiled, and crystallizes from alcohol in small, lustrous plates
which melt at 99.

2077 Dibenzylamine, (CgHg.CH^NH, is a thick liquid,
which has a sp. gr. of T033 at 14 and is insoluble in water, but
readily soluble in alcohol. When a small quantity is rapidly
heated it distils unaltered at above 300, but on gradual distilla-
tion it is decomposed with formation of ammonia, toluene,
dibenzyl, C M H 14 , stilbene, C 14 H 12 , lophine, C 21 H 16 N 2 , and other
bodies. 2 When heated to 260 in a stream of hydrochloric acid,
it gradually and incompletely decomposes into benzyl chloride
and benzylamine hydrochloride, while at 100 it combines with
benzyl chloride forming tribenzylamine. On treatment with



1 Curtius, Her. Dcutsch. Chem. Gex. xvii. 958.

2 Brunuer, Ann. Chem. Pharm. cli. 131.



DIBENZYLAMINE. 115



bromine and a large quantity of water, it decomposes into
benzylamine and benzaldehyde :

(C 6 H 5 .CH 2 ) 2 NH + H 2 0+Br 2 =
C 6 H 5 .COH+C 6 H 5 .CH 2 .NH 2 +2HBr.

Iodine has a similar action but requires a temperature of
14-0 (Limpricht).

Dibenzylamine hydrochloride, (C 7 H 7 ) 2 NH 2 C1, is readily
soluble in hot water and alcohol, but much less freely in the
cold, and crystallizes in large, flat, prisms, or, when its alcoholic
solution is rapidly cooled, in thin plates. The hydrobromide
and hydriodide are very similar.

Dibenzylamine nitrate, (C 7 H 7 ) 2 NH 2 .N0 3 , is less soluble than
the other salts and crystallizes in flat needles or prisms.

Tribenzylamine, (C 6 H 5 .CH 2 ) 3 N, is also formed, together with
other bodies, when benzaldehyde is gradually heated to 180
with ammonium formate. Formamide is the first product and
decomposes into carbonic oxide and ammonia, which then act
upon the benzaldehyde :

SC 6 H 5 .COH + SCO + NH 3 = (C 6 H 5 .CH 2 ) 3 N + 3CO 2 .

This is the most convenient method for the preparation of
tribenzylamine, 100 grms. of benzaldehyde yielding 40 grms.
of the pure product. 1 It is slightly soluble in cold alcohol
and crystallizes from a hot solution in needles, plates, or
monoclinic tablets (Panebianco) melting at 91. Small
quantities can be distilled without decomposition, but larger
quantities split up, yielding the same products as the secondary
base. It also resembles the latter in its behaviour towards
bromine and iodine, benzaldehyde and dibenzylamine being
formed. When its hydrochloride is heated to 250 in a stream
of hydrochloric acid, it decomposes into benzyl chloride and
dibenzylamine hydrochloride, while Lauth -obtained benzyl
chloride and ammonium chloride by treating the free base in a
similar manner at 180 2 . It does not combine with benzyl
chloride, and hence no tetrabenzylammonium chloride is formed
in its preparation from benzyl chloride and ammonia ; it com-
bines with ethyl iodide, however, on heating to form a crystal-
lized compound, which does not yield a hydroxide on treatment
with silver oxide, but decomposes into its constituents. 3 It

1 Leuckart, Her. Deutsch. Chcm. Ge.s. xviii. 2341.

- Ibid. vi. 678. 3 Vasca-Lanza, ibid. vii. 82.

I 2



116 AROMATIC COMPOUNDS.

also forms a crystallized compound when heated with methyl
sulphate to 100 . 1

The salts of tribenzylamine have been crystallographically
investigated by Panebianco. 2

Tribenzylamine hydrochloride, (C 7 H 7 ) 3 NHC1, is slightly soluble
in cold alcohol and water, and crystallizes from its hot solution
in quadratic prisms. It decomposes above 270, a large quantity
of toluene being formed (Rohde). The platinichloride crystal-
lizes in orange-coloured, monoclinic needles.

Tribenzylamine nitrate, (C 7 H 7 ) 3 NHNO 3 , forms rhombic
crystals which are insoluble in water and slightly soluble in
alcohol.

Tribenzylamine sulphate, (C 7 H 7 ) 3 NH) 2 SO 4 , forms monoclinic
crystals, is insoluble in water, slightly soluble in alcohol, and
combines with aluminium sulphate forming tribenzylammonium
alum, (C 21 H22N) 2 A1 2 (SO 4 ) 4 + 24H 2 O, which is deposited in regular
crystals and is soluble in water but not in alcohol.

Nitrosodibenzylamine, (C 7 H 7 ) 2 N(NO). Rohde obtained this
compound, together with benzaldehyde, by distilling a con-
centrated alcoholic solution of tribenzylamine with nitric
acid:

/CH 2 .C 6 H 5 /CH 9 .C 6 H 5

N^^EcSj + N0 2 .OH = N^-NO + COH.C 6 H 6 +H 2 0.

\CH 2 .C 6 H 5 \CH 2 .C 6 H 5

It is readily soluble in alcohol and ether, and crystallizes in
quadratic tablets, melting at 52; it does not combine with
acids, and is converted into dibenzylamine by the action of
nascent hydrogen or hydrochloric acid.



AMIDO-SUBBTITUTED BENZYLAMINES.

2078 Diethylbenzylamine, C 6 H 5 .CH 2 .N(C 2 H 5 ) 2 , is obtained by
heating benzylamine with ethyl iodide, or benzyl chloride with
diethylamine. It is a transparent, oily liquid, which boils at
211 212, and combines with ethyl iodide on heating with
formation of triethylbenzylammonium iodide, N(C 6 H 5 .CH.,)
which can also be prepared from benzyl iodide and

1 Claesson and Lundvall, Bcr. Dcutsch. Chem. Ges. xiii. 1703.

2 Jahrcsb. 1878, 476.



ETHYLBENZYLAMINE. 117

triethylamine, and forms large colourless crystals, which are
readily soluble in water ; on dry distillation it is decomposed
into triethylamine and benzyl iodide, while it is not attacked
when heated with concentrated hydriodic acid. 1 When iodine
is added to it in alcoholic solution, the periodide, N(C 6 H 5 .CH 2 )
(C H 5 ) 3 I 3 , separates out in blue-black monoclinic prisms, which
have a metallic lustre.

Ethyldibcnzylamine, (C 6 H 5 .CH 2 ) 2 NC 2 H 5 , was obtained by
Limpricht from ethyl iodide and dibenzylamine ; it is an oily
liquid.

Dietliyldibenzylammonium iodide, (C 6 H r) .CH 2 ) 2 (C 2 H 5 ) 2 NI, is
formed by the combination of diethylbenzylamine with benzyl
iodide. It crystallizes from hot water in needles possessing a
diamond lustre ; when it is distilled with hydriodic acid, benzyl
iodide is liberated (V. Meyer).

Benzylplicnylamine, or Benzylaniline, C 6 H 5 .CH 2 .N(C 6 H 5 )H, is
formed when benzyl chloride is heated with aniline to 160.
The free base crystallizes from hot alcohol in four-sided prisms,
melting at 32. 2 It may also be obtained by the action of
hydrochloric acid and zinc-dust on thiobenzanilide, 3 C 6 H 5 .CS.N
(C 6 H 5 )H.

Benzylplicnyldimethyldmmonium chloride, (C 6 H 6 .CH 2 )C 6 H 5
(CH 3 ) 2 ~NC1, is readily formed by the direct combination of
benzyl chloride with dimethylaniline. It crystallizes from water
or alcohol in tablets, which melt at 110, and is split up into its
constituents by distillation. It is not decomposed by boiling
with water and silver oxide, but its decomposition may be
effected by employing silver sulphate. If the sulphuric acid be
removed by baryta water from the solution thus formed, and the
nitrate concentrated, the hydroxide is obtained as a strongly
alkaline, syrupy mass, which is converted into the carbonate in
the air. On distillation it decomposes smoothly into dimethyl-
aniline and benzyl alcohol, 4 while tetra-ethylammonium hydroxide
under similar conditions yields triethylamine, ethylene and
water.

Benzyldiplicnylaminc, C 6 H 5 .CH 2 .N(C 6 H 5 ) 2 , is formed when
diphenylbenzothiamide, C 6 H 5 .CS.N(C 6 H 5 ) 2 , is treated with
hydrochloric acid and zinc-dust. It crystallizes from hot alcohol

1 Ladenbur^ and Struve, Her. Dcutsch. Chcm. Ges. x. 43 ; Ladenburg, ibid. x.
561, 1153, 1634 ; Y. Meyer, ibid. x. 309, 964, 1291.

2 Fleischer, Ann. Chcm. Pfiarm. cxxxviii. 22.

3 Bernthsen and Trompetter, Bcr. Dcutsch. Chcm. Gcs. xi. 1760.

4 Miohler and Gradmann, ibid. x. 2079.



118 AROMATIC COMPOUNDS.

in long white needles which melt at 87, and does not combine
with acids (Bernthsen and Trompetter).

Dibenzyltolylamine, (C 6 H 5 .CH 2 ) 2 NC 6 H 4 .CH 3 . This base, which
is also known as dibenzyltoluidine, was prepared by Cannizzaro
by heating paratoluidine with alcohol and benzyl chloride. It
crystallizes from hot alcohol in very fine needles, melting at
54'5 55, and is a weak base ; it differs from the isomeric
tribenzylamine in forming salts which are decomposed by water. 1



SUBSTITUTION PRODUCTS OF THE
BENZYLAMINES.

2079 These are formed by the action of ammonia on the
corresponding haloid ethers.

Halogen substitution products. These compounds are strong
bases and form crystalline salts ; the primary compounds absorb
carbon dioxide from the air.

Melting-point.

Farachloro- ) n TT T TVTTT i-
benzylamine,* } C 6H 4 C1.CH 2 .NH 2 , liquid . .

Paradichloro- ) ( ~ w ni .
benzylamine, 3 } (WCLCH^NH, crystals . .

Paratrichloro- 1 /p TT P1 ptr x ^r f rhombic > _

benzylamine, 4 | (C 6 H 4 C1.CH 2 ) 3 N, j '



prisms . . 7S-79



l^nzylamine, 6 f-Cftl-CH^NH,, liquid



needles . . 76



., needles . . 114-5'



C 6 H 4 B,CH,NH 2 , liquid



Ann. Chem. Phn.rm. Suppl. iv. 80.

Berlin, Ann. Chem. Pharm. cli. 137 ; Jackson and Field, Amcr. Che
Jotrn. ii. 95.



> .

Jackson ami Lowry, Bcr. Dmtsch. Chem. Ges. x. 1211

Jackson and Mabery, Amer. Chem. Journ. ii. 257.

Her. Deutsch. Chem. Ges. xi 58. * Hid

Jackson and White, Amer. Chem. Journ. ii. 317.



NITROBENZYLAMINES. 119



Melting-point.

(CABr.CHO.NH { 36"



Paranitrolenzylamines have been prepared by Strakosch by
heating paranitrobenzyl chloride with aqueous ammonia to
100. The primary base could not be isolated ; the secondary
base combines with acids, while the tertiary does not, thus
rendering the separation of these two a matter of no difficulty. 3

Paradinitrolenzylamine, (C 6 H 4 (NO 2 )CH 2 ) 2 NH, crystallizes
from hot alcohol in large, yellowish, lustrous plates, melting
at 93; its hydrochloride forms lustrous, yellow prisms, which
are only slightly soluble in water and alcohol, while its platini-
chloride, which crystallizes in yellow needles, is almost insoluble.

Paratrinitrobenzylamine, (C 6 H 4 (N0 2 )CH 2 ) 3 N, is slightly
soluble in hot alcohol, readily in glacial acetic acid and nitro-
benzene, and crystallizes in lustrous, white needles, which melt
at 163, and possess a pleasant odour.

Paranitrobcnzylphenylamine, C C H 4 (NO 2 )CH 2 .N(C 6 H 5 )H, is
formed by heating paranitrobenzyl chloride with aniline ; it
crystallizes from hot alcohol in pointed, lustrous, yellow needles.
Its hydrochloride crystallizes from hot hydrochloric acid in small
lustrous plates which are decomposed by water with separation
of the base (Strakosch).

Metanitrobenzylamines. Aqueous ammonia converts meta-
nitrobenzyl chloride into the secondary and tertiary amines,
while in the presence of alcohol only the former, together with
a small quantity of the primary base, is formed. 4

Metdnitrobenzylamine, C 6 H 4 (NO 2 )CH 2 .NH 2 , is a yellow, oily
liquid, which becomes solid in the air from absorption of carbon
dioxide. Its oxalate crystallizes in needles, which are only
slightly soluble in water.

Metadinitrobenzylamine crystallizes from alcohol in small
yellow, rhombic plates, melting at 87. Its hydrochloride and
platinichloride are only slightly soluble in water.

Metatrinilrobenzylamine is slightly soluble in alcohol, more
readily in benzene, and forms monoclinic prisms, melting at
162. It does not combine with hydrochloric acid.

Metanitrobcnzijlphenylamine is formed by the action of aniline

] Jackson and White, Amcr. Chem. Journ. ii. 317. 2 Jf'd.

3 L'er. Dcutttch. Ctwm. Gets. vi. 1056. 4 Boriuann, Chcm. Central b. 1885, 456.



120 AROMATIC COMPOUNDS.

on metanitrobenzyl chloride. The hydrochloride, which is thus
obtained, forms small white, lustrous plates. It is decomposed
by water with formation of the base, which crystallizes in long,
orange-red needles, melting at 86.

Amidobenzylamincs are obtained by the reduction of the
mtro-compounds with tin and hydrochloric acid.

Paradiamidobenzylamine, (C 6 H 4 (NH 2 )CH 2 ) 2 NH, is readily
soluble in hot water and alcohol ; it crystallizes in needles with a
satin lustre, or in plates which melt at 106, and volatilize without



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