LIBRARY
UNIVERSITY OF CALIFORNIA.
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WORKS TRANSLATED BY
J.

BISHOP TINGLE,

Ph.D.,

PUBLISHED BY

JOHN WILEY & SONS.
Determination of Radicles in Carbon Compounds.
By Dr. H. Meyer, Imperial and Royal University,
Prague. Authorized Translation by J. Bishop TinSecond American Edition,
Ph.D., F.C.S.
including matter specially prepared by Dr. Meyer
for this edition. i2mo, xii+ 162 pages, cloth, $1.00.

gle,

Spectrum Analysis.
By John Landauer, Member of the Imperial German Academy of Naturalists. Authorized English
Edition by J. Bishop Tingle.
44 figures, cloth, $3.00.


8vo, x

+ 239 pages,

Application of Some General Reactions to Investigations in Organic Chemistry.
By Dr. Lassar-Cohn, Professor of Organic Chemistry at the University of Konigsberg. Authorized
Translation by J. Bishop Tingle, Ph.D. izmo,
vii -f 101 pages, cloth, $1.00.

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APPLICATION
OF

SOME GENERAL REACTIONS
TO INVESTIGATIONS IN

ORGANIC CHEMISTRY.
BY

DK. LASSAR-COHJST,
Professor of Organic Chemistry at the University of Konigsberg.

AUTHORIZED TRANSLATION
BY
J.

BISHOP TINGLE,


Ph.D. (Munich), F.C.S.,

Johns Hopkins University,

FIRST EDITION.
[D.

OF THE

UNIVERSITY
or
\h-

JOHN WILEY &
LONDON:

SONS.

CHAPMAN & HALL,
1904.

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LIMITED.


Copyright, 1904,

BY
J.


BISHOP TINGLE.

ROBERT DRUMMOND, PRINTER, NEW YORK.

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.

(

TRANSLATOR'S PREFACE.

PROBABLY every student
some period

of his career,

it

only as he

is


chemistry,

becomes more or

immense mass

the

powered by
encounters, and

of organic

of

detail

at

less over-

which he

able to apprehend

is

and generalizations underthat he can emerge from the labyrinth.


the fundamental principles
lying these facts

The

considered

topics

in

this

latest

little

book of

Professor Lassar-Cohn are of considerable importance,

and have hitherto

ment

to

failed

receive


adequate treat-

hoped that the volume

may

who

are

with

the difficulty mentioned above,

and

in other works.

prove

appeal

useful

to

to

It is


students

threatened
also that

and others engaged

teachers

in

it

may

research

work, both on account of the broad, suggestive discussion of the subjects
it

which

includes mention of

it

embraces, and also because

numerous themes which demand


investigation.
J.

BISHOP TINGLE.

CHEMICAL LABORATORY,
JOHNS HOPKINS UNIVERSITY,
October 1904.
iii

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AUTHOE'S PEEFACE.

A

SURVEY

of the

enormous number

which are constantly appearing

in the


of investigations

domain

of organic

chemistry reveals the fact that, although their theoretical

portions are based, in the most severely logical

fashion,

on the tetravalency

technique

An

the

of

research

connection

intimate

extending over


many

of the
is

with

carbon atom, the

essentially

organic

empirical.

investigation,

years, has convinced

me

of the

availability of certain general principles in the practical

part of the work; they are
practical in their nature,

praxis of organic research


partly theoretical,

and
is

partly

their application

to

the

capable of affording general

help and improvement in an enormously large number
In this book I have presented all the material
of cases.

bearing on the subject which I have accumulated.

LASSAR-COHN.
KoNIGSBERG

I.

PH.,

July 1904.


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CONTENTS.

CHAPTER

I.

PAGE

INTRODUCTORY.

FIXATION OF LABILE HYDROGEN ATOMS..

CHAPTER

1

II.

MODIFICATION OF REACTIONS

CHAPTER
IMPROVEMENT


IN

23

III.

THE CONDITIONS OF REACTION.

OVERSTRAIN
48

OF REACTIONS

CHAPTER

IV.

INFLUENCE OF NEIGHBORING ATOMS AND ATOMIC COMPLEXES.
vii

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.

76


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APPLICATION OF SOME GENERAL
EEACTIONS TO INVESTIGATIONS
IN ORGANIC CHEMISTRY.

CHAPTER

I.

INTRODUCTORY. FIXATION OF LABILE HYDROGEN
ATOMS.

ALL

investigations in the

domain

of organic chemistry

and most complete manner,
general theory which apply to the

are based, in the firmest

on those parts of

carbon atom, but only a comparatively small number
of
of


them

retain these higher

and more exhaustive points

view in the experimental

portions

Should the desired result not be

tried,

or

less

by one
suitable,

the selection being usually haphazard.

time has arrived
for the

the work.

obtained


method, another, apparently more
is

of

when

it

is

possible

to

The

formulate,

conduct of some operations, a number of general
\

rules derived

from the enormous mass

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of experimental



2

APPLICATION OF SOME GENERAL REACTIONS.

material which has accumulated, and, as a corollary,

many methods which are
chemical investigations. It may

to develop considerably

in

use for organic

be

hoped

process
is

and

that, in course of time, the blind, trial

may

offered as


be increasingly restricted; this

book

an attempt to systematize methods

work, and treats of the following topics:
labile

failure

little

hydrogen atoms;

of

fixation o)

im^

modification of reactions;

provement in the conditions of reaction by due recognition
of the circumstances in

which the product

fluence of neighboring atoms


formed; in-

is

and atomic complexes;

some remarks on the "overstrain"

also

of reactions.

FIXATION OF LABILE HYDROGEN ATOMS.
Before the actual investigation can be
it

is

commenced

frequently of the greatest importance to

protect, highly reactive (labile)

fix,

or

hydrogen atoms which


are present in the material to be used or in the reagents.

Methods

suitable for this purpose are

employed,

but

they

obviously

where the investigation

is

not

are

now
only

frequently
applicable

concerned with the


behavior of the labile hydrogen atom in the mother-

The object of fixation is to prevent the
hydrogen atom participating in reactions, and so either
substance.

complicating

the

the change which

phenomena
it is

or

entirely

inhibiting

desired to investigate.

Fixation

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FIXATION OF LABILE HYDROGEN ATOMS.

is

3

by substituting for the hydrogen
atom or group which must be of such

accomplished

some

suitable

a nature that

atom

it

will easily take the place of the

and be

the mother-substance,

in

hydrogen

itself


readily

displaced from the product of the main reaction by
hydrogen, which must enter the molecule in its original

Although the term "fixation"

position.

to designate this procedure,

that

will

fixation

amines, but

it

is

employed

only universally employed for

is


amino hydrogen

is

be readily understood

and reverse substitution.

consists of substitution

it

At present
the

it

in

the

nitration

just as important

of

aromatic

and suitable


for

the protection of the hydrogen of hydroxyl and imino
if

groups

these are present in the

investigation.

Even

in the case of

tives nothing of general application

although,

as will be apparent

is

compounds under
the amino derivaat present

from what

known,


follows,

a

very large number of isolated facts have been recorded.

A

amount

considerable

of

work

in various directions

has been done on the preparation of mononitranilines,

and a

brief consideration of

present

state

of


it

will best illustrate the

knowledge of the subject of

this

chapter.

Failure must, of necessity, attend any attempt to

by means of nitric acid, compounds
containing the amino group, because the acid oxidizes
this group more rapidly than it attacks the nucleus.

nitrate directly,

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4

APPLICATION OF SOME GENERAL REACTIONS.

In these circumstances, at an early stage of the investigation of aniline, attention was directed to the pro-

methods


vision of

of protecting the

the nitration process, or of fixing

hydrogen atoms.

may

amino group during
one or both of the

In the case of aniline protection

be obtained by dissolving

it,

before nitration,

in a large proportion of concentrated sulphuric acid;

of acid restricts the action of the nitric

this excess

amino

acid to the nitration of the nucleus, and, as the


group

is

protected, the complete decomposition of the

molecule

is

reaction

is

chief

metanitraniline, but

and paranitraniline
aniline

The

prevented.

nitrate

product


a mixture of

obtained by the

is

of

the

ortho

addition

of

to concentrated sulphuric acid.

These two methods

of course, only applicable

are,

to such amines as are stable towards sulphuric acid;

those about to be described, although hitherto only

employed


in

the

case

tolerably general utility.
anilines

of

A

aniline,

appear to be of

consideration of acylated

shows that the nitration of acetanilide yields

a mixture of the three nitranilines, the para derivative
predominating.

Benzanilide

behaves

in


a

similar

manner, except that the proportion of meta compound
These acylanilides were the first to be
is
small.

employed on a large

scale for the preparation of pure

orthonitraniline, but their use proved to be so trouble-

some that

since 1885

it

has been superseded by the

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FIXATION OF LABILE HYDROGEN ATOMS.
indirect

following


method.

Acetanilide

is

5

converted

into paracetanilide sulphonic acid,

NH-C H
2

3

\

\/
S0

which

is

3

H


nitrated in sulphuric acid solution;

the nitro

group enters in the ortho position relative to the acet-

amino group because the para position is occupied.
The acid solution is diluted and boiled, the dilute sulphuric acid hydrolyzes the acetamino group, and the
resulting,

readily

by means

precipitated

conversion
nitranfline

soluble,

of
is

the

of

acid


nitrosulphanilic

hydrogen

The

chloride.

acid

nitrosulphanilic

into

is

ortho-

by heating the former with

effected

hydrochloric acid, under pressure,

at

170-180.

Apart from the indirectness of the method, it suffers

from the further disadvantages that chemically pure

must be employed, and that, during the
sulphonation, the temperature must not be allowed

acetanilide

to- rise
is

unduly; inconsequence of these drawbacks

unsuitable for general use

1889
large

orthonitraniline

by the

inexpert.

it

Since

has been easily obtainable, in

quantity, by means


of a

patented process which

requires no special precautions,

the use of sealed tubes.

and does not involve

Oxanilide, which

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is

the start-


APPLICATION OF SOME GENERAL REACTIONS.

6

ing-point in the process,

concentrated

group


sulphonic

product

with

sulphuric

acid;

is

by means

sulphonated

occupies

of the reaction

nitric acid,

is

in

the

case


this

para

cooled to

also

position.

of

the

The

40-50, and treated

which yields dimtroxanilidodisulphonic

acid,

NH-CO-CO.NH

\/

\/

S0 3H


S0

3

H

The

elimination of the oxalyl and sulphonic radicles

from

this

compound

is

readily accomplished

water and boiling at 120-150

At

first

there

is


by adding

in a reflux apparatus.

a considerable gas evolution, due to

the decomposition of the oxalyl group ; later the boiling

proceeds quietly, and after several hours the sulphonic
radicle
is

is

The

eliminated.

of

yield

orthonitraniline

75 per cent, of the crude oxanilide employed.

readiness with which the oxalic acid radicle

is


The

eliminated

and decomposed by means of dilute sulphuric acid
would indicate for it a more extended use than it has
hitherto
in

the

received.

In

preparation of

successfully

adapted

to

addition

to

its

orthonitraniline


the

employment
it

preparation

has been
of

dinitro-

diaminoanthraquinone from diaminoanthraquinone ;
is

this

converted into the oxalyl derivative, and the latter

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FIXATION OF LABILE HYDROGEN ATOMS.
nitrated in concentrated sulphuric acid solution.

most

reactions take place


was granted

7

The

In 1903 a patent

readily.

a process which not only allows of

for

the convenient preparation of paranitraniline, but also

permits of the regeneration of original acylated sub-

The

stance.

reactions

m

CJS/
XX
is-


nitrated

and

follows:

>N-C 6H 5

,

aniline

under pressure,

thus
acid

the

liberates

and regenerates phthalanil.

Derivatives of aniline and nitro acids
for

phthalanil,

yields chiefly paranitrophthanil, which,


when heated with
paranitraniline

as

are

production

of

higher

paranitrobenzanilide,

in

may

nitrated

derivatives;

concentrated sulphuric

on treatment with

solution, yields,

be used


nitric acid,

paratrinitrobenzanilide,

NH-CO-C

N0
N0
and,

by

hydrolysis,

preparing dinitraniline
erto

it

6

H N0
4

2

2

2


dinitr aniline.
is

This

method

of

mentioned here, because hith-

has not been adapted for the preparation of

a mononitraniline.

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8

APPLICATION OF SOME GENERAL REACTIONS.

Acyl derivatives of aniline are by no means the only
ones which have been employed for the production
of nitro derivatives; the readiness with which the

amino group combines with aldehydes has

led to the


use of these compounds also for nitration purposes.

A

typical derivative of this class

is

C 6H5 .CH:N-C 6H5
from benzaldehyde and
unstable substance, and
constituents

by the

temperature.

On

and therefore

of

aniline;
is

benzylidenaniline,

,


it

is

a somewhat

readily resolved into

its

action of dilute acids at the ordinary
account of the absence of water,

hydrogen and other

ions,

hydrolysis

of the benzylidene derivative does not occur in con-

centrated sulphuric acid solution, and

experiment that such a solution

it

is


found by

readily nitrated

is

without the production of resinous bodies; subsequent
dilution of the

acid liquid causes separation of the

By means

free nitro product.

yields

90

of this

acetic

benzylidenaniline

in

acetic anhydride,

and subsequent


glacial

method

aniline

Solution of the

per cent, of paranitraniline..

acid,

addition

of

nitration yields, in

addition to paranitraniline, 15 per cent, of the ortho
derivative

together

experimental

with

conditions


products.

The

obviously

more

resinous

here

are

complicated than in the previous case.

Purpurin (trihydroxyanthraquinone) has also been

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FIXATION OF LABILE HYDROGEN ATOMS.
employed for the purpose of combining with
which is subsequently nitrated; the purpurin

NH.C H
14

concentrated


in

with

by

aniline,
anilide,

4

7

sulphuric acid

nitric acid, and,

9

solution,

is

treated

boiling the resulting product

with sulphuric acid (70 per cent.), purpurin and orthonitraniline are obtained.

This appears to exhaust the


list

of readily

decom-

posable aniline derivatives which have been employed
the production of mononitranilines;

for

reference will be

made

to

subsequent

the production of ortho,

meta, and paranitranilines by the partial reduction of
a mixture of ortho and metadinitrobenzene, or by

its

treatment with ammonia, and also by the action of
alcoholic


ammonia on ortho and parachloronitrobenzene

(vide p. 84).

These methods have

all

been tested in

the laboratory, but, strictly speaking, they have nothing
to do with the nitration of aniline.

The same

is

true

more recently described process for the production
ortho and paranitraniline, from the corresponding

of a
of

chloronitrobenzenes,

monia

A


at

170.

The

by

interaction with aqueous

yield

is

am-

practically quantitative.

consideration of the previous pages demonstrates

that even in the case of aniline, which has been the

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