Note on the Constitution of Diparabromben-Zylcyanamide Author(s): C. Loring Jackson and R. W.

Fuller Reviewed work(s): Source: Proceedings of the American Academy of Arts and Sciences, Vol. 35, No. 11 (Dec., 1899), pp. 231-236 Published by: American Academy of Arts & Sciences Stable URL: http://www.jstor.org/stable/25129921 . Accessed: 12/06/2012 04:37
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CONTRIBUTIONS FROM THE CHEMICAL LABORATORY OF HARVARD COLLEGE.

NOTE ON THE CONSTITUTION OF DIPARABROMBEN

ZYLCYANAMJDE.
By C. Lorlng Jackson and R. W. Fuller.

Received November 24,1899. The silver of the work salt described in into this this a

Presented December 13,1899. consists of the and conversion the of the

paper

of cyanamide of constitution a paper

finished) Gesellschaft," cyanamides amines. Wallach

appeared Wallach* in which by of the

dialkylcyanamide, summer Last body. " in the der Berichte described of bromide too further near study work a of

determination

was this work (after deutschen chemischen number cyanogen field of on substituted

obtained For we fear shall

action

approaching the abandon

the

secondary reserved by of dialkylcyanamides, but thus

the study of alkyl compounds of dicyandiamide

taken already up in this Laboratory; in fact on in progress.

and dicyanimide will be

this latter substance is

Theoretically
cyanamide R2=N-CN, formulas this sort

a dialkylcyanamide
have either of the

derived
following

from the
formulas which a single ago

silver
R-N=C=N-R of

salt of
or two of and

might to determine and it is easy far as we is correct. So has been tried; this was

by experiment can find, but some

these

published

years

experiment by Fileti

Robert
iodide extracted and gave

Schiff,f who prepared diethyl cyan amide by the action of ethyl

on at 100? for some hours. cyanamide argentic two portions into and divided with ether, a and of 186?, whereas Cloez point boiling of ethyl the decomposition cyanamide, by ; one was product was distilled, t who Cannizzaro, The found a boiling

prepared'it

point of 190?. Fileti and R. Schiff analyzed their distillate, and ob tained carbon 60.66 instead of 61.22 and hydrogen 10.11 instead of 10.30.
* Ber. d. chem. Ges., XXXII. t Id., X. 425 >(1877). X Ann. Chem., XC. 95. 1872.

232 The

PROCEEDINGS OF THE AMERICAN ACADEMY. other portion

by obtained into two

of their product (which had not been distilled) was

of hydrochloric the and acid on the water acid bath; solution the were they with by evaporating hydrochloric when fractionally, crystallized was the platinum in which determined

decomposed chlorides converted obtained the

means

following

chlorplatinates fractions end ? results:

I.

Platinum (C2H5NH3)2PtCl6
In that considering the

44.04 *

Found. II. (NH4)2PtCl6

((C2H5)2NH2)2PtCl6

42.51

36.3

35.30*

* per cent of platinum. requires 39.24

these results of Fileti and R. Schiff, it is to be observed

was not and that no very cri purified, sharp diethylcyanamide was states that are these substances terion of purity (Wallach given so that under the distillation pressure, ordinary by decomposed boiling in this respect), further that their analyses value of is not of much point near to those calculated. numbers did not salts the platinum very give to try similar wrorth while to us, therefore, It seemed with, experiments if possible, obtained yield We a crystalline in a state amines selected disubstituted of undoubted cyanamide, purity, and than which also could with therefore one and which diethyl

be

would amine. since and melting zylamine,

more for

separated easily the this purpose compounds if show

ammonia

the parabrombenzyl the

diparabrombenzylcyanamide, a to crystallize, great tendency its recognized by the parabromben a definite with without difficulty

diparabrombenzylamine, 50? point, (dibenzylamine if that and were both the these product, amines

could be formed, is a liquid), while a carbonate gives could be separated a well

point, melting from ammonia. The melting

diparabrombenzylcyanamide at 133?. On decomposition ammonia,

proved with and

to be dilute

diparabrombenzylamine, ? : reaction

carbonic

sulphuric dioxide by

crystallized acid the

solid, it gave

following

(C6H4BrCH2)2NCN
Our no doubt results, that and of the therefore,

+ 2H20 = (C6H4BrCH2)2NH + NH3 + C02.

confirm those of Fileti from they and leave Schiff, are cyanamide cyan argentic are formed by direct replace the same by the alkyl radicals, They would be some and R.

amides ment

the dialkyl derivatives not If carbodiimides. silver in argentic

cyanamide

* These what altered

are

the numbers modern

by using

and R. Schiff. given by Fileti atomic weights.

JACKSON

AND

FULLER. ?

DIPARABROMBENZYLCYANAMIDE.

233

constitution amide. additions disubstituted carbodiimide

must (Ag2NCN) on the other hand, If, bromide of the alkyl cyanamides formula, as

be

ascribed

to

this are off of from

substance formed argentic a silver reactions:

and by

to cyan successive the a

these with be by R

compounds splitting formed the

bromide, salt ? with

could is shown

following

*
C

NAg +RBr=C

Br

\/ ^

NAg =AgBr+C

NR

// ^
NAg
NR2 = C

^
NAg
NR C

NAg R
Br NR

//

+ RBr = C NAg

\/
NAg

/
+ AgBr. N

Our

results,

therefore,

prove

nothing

in

regard

to

the

true

formula

of

cyanamide. Preparation of Diparabrombenzylcyanamide,

(C6H4BrCH2)2NCN.
The Walther,# in the which yellow was silver mixed of salt of with two cyanamide, a benzol molecules Ag2NCN, solution of of the prepared according to

salt, was The mixture heated in a flask powdered. on the with until after four or five hours steam-bath, full yellow of the argentic the color had been cyanamide completely white color of bromide. The replaced by the yellowish argentic precipi tate was out and washed then filtered with hot benzol, and thoroughly the filtrate and washings to a thick when reddish evaporated dryness, left. To this oil was it was dissolved in hot alcohol, and yellow purify finely a return-condenser the at solution strong first followed by the solution allowed a white off to cool slowly; as of where the deposited obtained by soon as the to crystals began this sort the of melting-point it remained constant. It was was results: ? a yellow which oil was

proportion be should

parabrombenzylbromide to one bromide of the

pouring appear. the dried

crystalline from the oil

substance,

By substance in vacuo

repeated recrystallizations was to 133?, raised and analyzed * Journ. with

following

prakt.

Chem.,

1896, 510.

234

PROCEEDINGS

OF

THE

AMERICAN

ACADEMY.

I.
II.

0.1508 gram of the substance gave by the method

of argentic bromide. gram 0.3041 of the substance gram perature of 18?.6 and

of Carius 0.1494
at a tem

of 20.2 cc. gave nitrogen a pressure mm. of 760.4 Found. II. I. 42.18

Bromine

Calculated for (C7H6Br)2NCN 42.11

Nitrogen
In view of safer of gram a the

7.64 7.37
to of polymerize, the body it was by the ? : results produced *

thought method 0.375

of great cyanamides tendency to determine the molecular weight a benzol substance of 0?.28 solution, dissolved in the which gave

freezing of the

the following grams of benzol

in 16.25 freezing

depression

point. Found.

Calculated for (C7H6Br)2NCN.

Molecular
There can be no

weight
doubt, therefore,

380 337
that the substance is really

(C6H4BrCH2)2NCN.
Properties The substance the of Diparabrombenzylcyanamide.

from in sheaves benzol of white crystallizes crystals blade of a lancet, sometimes united into groups shaped laterally at 133?. It melts with comb ends. It is freely soluble in benzol, chlo or acetic soluble in toluol; soluble in cold acetone, ester; roform, slightly or or alcohol acetic in these soluble acid, ethyl glacial methyl freely like solvents or in hot when or are hot; in ether, carbonic soluble they disulphide, slightly cold water; in insoluble It is slowly essentially ligroine. cold unaffected strong acid; by sulphuric by apparently or nitric acid acid in the cold. best for it is The solvent

decomposed hydrochloric alcohol. hot In order

to

see

if

it could was acid for was the

form

brombenzylcyanamide with dry hydrochloric the mixture the this original experiment acid. work was done had stood

dissolved No gas. two weeks, recovered

a chloride, in anhydrous

portion benzol

of and

the dipara saturated even the seem unite after benzol from with

was precipitate on and evaporating unaltered. It

formed off would cannot

substance that

diparabrombenzylcyanamide

hydrochloric * This substituted

cyanamides

the appearance before of Wallach's show no tendency to polymerize.

statement

that di

JACKSON

AND

FULLER.

DIPARABROMBENZYLCYANAMIDE.

235

A of sic

number the

of experiments

were

tried A the

hydrate in the cold with

diparabrombenzylcyanamide. on no effect produced or the mixture. by boiling a solution which from of ammonic

in the hope of polymeres obtaining dilute solution of sodic or potas either substance, by long standing The substance care being observed was taken boiled for two to replace the that the color

weeks ammonia turned since tered.

hydrate,

white

the melting Water

was but the only change escaped, to a to due slight evidently decomposition, pale brown, was of the substituted unal point cyanamide essentially no was tried at the boiling also but produced alone point,

its above the substance it remained point Upon melting heating first yellow, it turned to 160? this point and at higher ; above an we could which red, and on cooling gave temperatures oily product, was ob A similar not viscous for analysis. into a fit state product bring acetate. was sodic with In both heated tained the substauce these when change. unaltered cases a it seemed evident and these that our a decomposition had therefore, no taken confirm tendency place the to rather statement than of

polymerization, that Wallach

experiments,

dialkylcyanamides of

show

polymerize.

Decomposition As amide some was preliminary

Diparabrombenzylcyanamide. showed by that the substituted cyan

decomposed a dilute we adopted which has frequently grams of this of

experiments with difficulty acid sulphuric

given good were the diparabrombenzylcyanamide a return-condenser. in a flask with acid in the hot acid with an

acid in open vessels, hydrochloric a of 1.44, specific having gravity results in this Laboratory. Several boiled Soon with after a excess large the substance

melted the As gas

given

off

hours, On

did the oily drops reduced which

the whole cooling, we talline to stop the process at this determined, therefore, precipitate; and isolate this crystalline which could be easily substance, point separated the portion from in the hot undissolved acid. latter This sub sulphuric

was effervescence and upon observed, testing it proved to be carbonic dioxide. water, baryta not was the ten continued for disappear, heating the amount of oil, but did not remove it. entirely a voluminous filled with white liquid became crys

on stance to consist which solidified seemed of undecomposed cooling, as it gave a fresh of the crystalline diparabrombenzylcyanamide, quantity on with acid ; its amount was product sulphuric again boiling insignifi cant. To the crystalline it was the acid obtain filtered from product liquid, washed then dissolved undecomposed with in a hot little water, cold water left solution to free behind was it from the then which The adhering few black filtered, and acid, and

cyanamide.

lumps of the sul

236

PROCEEDINGS

OF

THE

AMERICAN

ACADEMY.

phate which base, stant

decomposed set free after melting

of a strong solution by the addition as a mass the base pasty solidifying from alcohol, purification by crystallization point 50?, For which is that of the the

of on

sodic

cooling. showed

hydrate, This the con *

greater (C6H4BrCH2)2NH. and analyzed. Chlorplatinic pared a the base gave precipitate, yellow in vacuo. and dried alcohol, 0.1783 gram of the salt gave on

security acid added which

diparabrombenzylamine was chlorplatinate to an purified alcoholic solution

pre of with

was

by washing

ignition

0.0309

gram

of platinum. Found.

Calculated for [(C7H(.Br)2NH2]2PtCl6,

Platinum
The amine a large sulphuric sulphate excess collected was of acid filtrate from at first

17.58
the with

17.34
diparabrombenzyl and finally with the acid. distillate After to

treated sodic

of the crystals sodic carbonate,

being the distillation

in a series was steam into

and distilled with steam, hydrate, of flasks hydrochloric containing of the flasks were the contents finished, bath, the and the white residue this washed following on dissolved was with a

on the dryness and converted crystallizing in vacuo, dried 0.2061 gram platinum. in

evaporated in a little water precipitate and alcohol,

octahedra, and of the

chlorplatinate; was which with the

analyzed

yellow water results: ?

chlorplatinate

gave

ignition

0.0903

gram

of

Calculated for (NH4)2PtCl6.

Found.

Platinum
It the lute is evident decomposition from of the experiment

43.91
described above

43.81
that when the products with of di and

are acid, sulphuric The ammonia. reaction,

diparabrombenzylcyanamide, carbonic dioxide, therefore, runs as

boiled

diparabrombenzylamine, ?: follows

(C6H4BrCH2)2NCN
*

+ 2H20 = (C6H4BrCH2)2NH
These Proceedings, XVI. 254.

+ NHS + C02.

Jackson,