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Culture Documents
Iat 514
'Markham,
iThe
1
J.
H.
CARLI: Consortium
of
Libraries
in Illinois
http://www.archive.org/details/preparationofsalOOmark
thesis
PRESENTED BY
J.
H.
MARKHAM AND
TO THE
B.
W. LEWIS
BACHELOR OF SCIENCE
IN
CHEMICAL ENGINEERING
MAY
29, 1919
APPROVED
I'lnA-^scr ^(.r of i.f CtKiiiicnl C
KiiK'iitrcrinsr
^H\C^GO. ^^
"
Dran
of Cultunil Sl.iilies
H D S X
PAGE
PROBLEM
OCGUEHENCE
MD
LETHODS OF PREPAHATIOil
3
7
KOLBE'S PROCESS
PHYSICAL PROPERTIES
10
14
20
25
OP PREPARATIOII
EXPSRIMEITTAL RUIIS
30
3^
PURIEICATIOE
THE CHEMISTRY OE TEE SCHMIDT METHOD
36
COECLUSIOH
^
^^
REEEREKCES
2S1S5
1.
This work
v;as
and supervision of
for which
made.
PROBIEI.I.
to
It was
originally
in-
lov;
price,
Ortho-hyuroxy-carboxylic acid, or
ortho-hydroxy-'bensoic acid or ortho-hydroxyc
H
6
C
6
H
4
OH.COOH
(1-2)
COOH
H
H
OE
Calhours
In 1653 A. Ho f nan
Finally Ilolbe
following plants:
Gaulterla fragrantissima,
ortho-cresol-sulphonic
amldobenzoic acid.
4.
6 5
OH+CCl
KOE
-*
H .OZ.GOOX
6 4
ZOL
SHgO
By oxidation of toluene ortho-phos-
7.
acid.
10.
zoic acid
11.
to
acetic acid.
KOIBE'S PROCESS.
This method has teen used for the manu-
When the
The mass
ly raised to 180G.
hours.
When
the resinous substances precipitated with a mineral acid, a further addition of acid precipitates
sodium phenate:-
C-HpOH ^ ITaOH
6 5
C-H^ONa
6 5
H^O
E
E.
C^H^OHa
6
CO^
E
C^H^.OCO^.lTa
6
This stage is completed v.hen the mass is heated to about 110G for one hour.
3.
C^H,.0H.C001Ia
6
caroxyl group.
4.
H .OH.COOIIa-C 64 65
H^.OlIa
H .Ol^Ta.COOlIa 64
* G
H^OH 65
heating.
10,
physicjVI properties
irotn ^vater
gent taste.
1.48
1593.
Small
slov/ly
needles; when rapidly heated to 200C it valatilizes and the vapors undergo a partial dis-
254.9
l-a2
7/here P^pressure in cm.
of mercury,
a=rdegree of dissociation.
This is an irreversible
reaction.
11.
cule.
v.-ith
12.
50.47 of acid
42.09
100
15.
solutions.
"be
distilled in
The para-acid and traces of the metaacid usually accompany the ortno-acid if extreme
14.
CHEMICAL PROPiiRTIES.
Salicylic acid is both an acid and a
phenol.
It forms three sets of
salts; acid,
well as ethers.
to
heated
200
it
decomposes
CgK^.OH.COOH
GgHg.OH
CO^
or with
Phosphorous
15,
Phosphorous oxychloride
gives on heating salicylic anhydride. Salicylic acid or its salts give a deep
violet coloration in a neutral solution v/ith ferric salts.
cylic acid.
1:550,000.
give
hy acetic acid.
of salicylic acid
sodium nitrate or 36 parts of sodium chloride. Dry hot ammonia breaks up salicylic
acid into phenol and carbon dioxide.
On oxidation with potassium bichromate
in sulphuric acid carbon dioxide and v.ater are
produced.
16,
oxybenzophenone.
chiefly
to
pimelic acid.
obtained.
17,
Y/hen
homologue
01
azo-compounds.
diaao-oxyhenzoic acids.
At 210 aiiiline gives phenol and
C.H^(OH).GOIIPhH. o 4
C
7
10^5
Geo
C,H_OH
o
GaCO_
o
16.
to a
H (CO K)OSO K
140^^
^ 4
cue
C;.Hr;Br.O,
Oct
GgH^KODCOgZ.
of
*^7E^11 ^^'18^^82
2C H
7
and is soluble in
6 S
19.
".'.Tien
EO,
USES 0? SAIICYLIC
ACID.
preparation of pharmaceuticals.
The acid is
production of salicylates.
V/hen
ethyl alcohol
Allyl salicylate
another derivative of
but the acid is a very important pharmaceutical; are subbecause of its cost, other salicylates
21.
stituted.
V/hen
phosphorous oxychloride is
acetyl chloride.
decomposition of the
compound.
salts
vi'hich
tolypyrinesalicylate
B2.
bodies.
The first of these "bodies to receive
consideration is Saligenin.
CH OH
(y-3)
OH This "body is prepared from salicylic acid, thru the amide, and the reduction of the
V/hen
salicylic acid.
25.
to
form
iodo- or
crom-
"ceni'-oic
acid.
This "body on
This same tody
gives p- nitrophenol,
can be reduced to p-
amidophenol
alkaline solution.
OCH
E4.
benzoylacetic ester.
Euxanthone
Indian
Yellov.-.
method.
There are numerous other bodies that are prepared synthetically by means of the sali-
25,
OUR
Iffi'xHOD
OP PREPAHATIOH.
(4th Ruii)
120 grans
This
ce evaporated
dryness.
process.
The mass will gradually begin to
completely solid.
It
is now
26,
half an hour.
The pov/der thus obtained is sodium
phenate.
in
the
thick.
autoclave.
27.
diameter; it is filled v;ith granular calcium c'nloride protected at both ends with glass v.ool and
wire gauze.
The carbon
dioxide gas is turned on, the pressure in the autoclave is not allowed to exceed 10 lbs.
This is
hour.
8.
The cooling during the first stages of the carhon dioxide ahsorhtion is quite a
A paraffin bath
is nov;
brought under
The temper-
kept at 120-140C.
The latter
V.'hen
29.
acid added.
cylic acid.
The impure acid is collected by fil-
Yield 44 gr. or
16;^
of
30.
EZPERILffiKTAI RUKS.
(1st Run)
lEO gr. of sodium hydroxide were aissolved in an equal amount of water and mixed into
260 gm. of phenol.
and 14" vacuum.
tained.
hygroscopic.
The
The cover
".vat
re-
130-145C.
31,
were examined.
The mass
v.as
of a dark brov.n
stals of phenol.
dov.Ti
the tarry
The remaining
calcium cartonate.
presence of salicylate.
32.
EZPERIIJIEKTAI RUNS.
(End Run)
Evapor-
It was poudered
The press-
The pressure
However, there
v.as
34.
ESPSRIMEIITAL RUUS.
(Srd Run)
hydroxide used.
groscopic.
It v.as
clave.
pressure of
Run 4.
odor of phenol.
four hours.
35.
to
an evaporating dish. It
was collected
36,
PURIi'ICATIOlI
Oi'
The impure acid is dissolved in "boiling v.-ater and then neutralii:ed v/ith calcium
Calcium sali-
A fairly pure acid yields almost pure white crystals, hut an impure acid gives brov.nish crystals.
little cold v.ater and finally crystallized out from dilute aloohol.
This gives a very pure
retical yield.
The chief impurities found in impure
37.
acid are:
to
crystallize from
dilute alcohol in the form of a mass of interlaced crystals instead of well defined large
prisms.
It
75 lbs.
38.
TEE
CH3LII'i?Ry
OF THE
SCffi.IITT
LETHOD.
(Ber.1905,
H OH
6 5
* llaOH
C
6
H OKa
5
H
2
OUa.CgH^.COgH
--
It
cylate.
slov?ly absorbs
It
is not
S9.
2-12 hours
at 248'^,
it
changes
40.
CQKGIUSIOU.
The proper v^orking co adit ions for
the process are outlined under "Our Method
of Preparation."
should ce used.
To use an enameled autoclave with
must be dry and well powdered; the carbon dioxide must bo dry;
the temperature must be
closely controlled.
41.
RE?ESE^TCES
1890.
Dictionnaire de Ghiinie
1906.
1913.
1689.
1692.
J. Chern Soc.