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Патент USA US2410397

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Patented Oct. 29, 1946
2,410,397
UNITED STATES PATENT OFFICE
V PREPARATION OF ARYLIDES OF AROMATIC
ORTHO-HYDROXY CARBOXYLIC ACIDS
Robert H. Weiss, Plain?eld, and Andrews C.
Wintringham, Glen Ridge, N. J., assignors to
American Cyanamid Company, New York, N. Y.,
a corporation of Maine
7
'
No Drawing. Application May 2c, 1943,
Serial No. 488,591
20 Claims. (Cl. 260-559)
1
2
This invention relates to an improved process I ‘v diiferent method. ‘The reaction mixture con
for producing arylides of aromatic o-hydroxy
.carboxylic acids and more particularly to im
provements in the isolation of these products
from crude reaction mixtures.
Arylides of aromatic o-hydroxy carboxylic
acids are usually prepared by reacting the cor
responding arylamine with the acid in the pres
ence of a condensing agent such as phosphorus
trichloride or thionyl chloride, or reacting the
acid chloride of the carboxylic acid with the
amine in the presence of an acid binding agent
capable of reacting with the hydrochloric ‘acid
set free in the reaction.
.
In either case it is desirable and in fact custo
mary to use diluents such as toluene, monochloro
benzene and the like. An excess of the amine it
self may also be used as a diluent, but because of
its higher cost it is customary to use cheaper
liquids.
In every case a reaction mixture is ob- -
tained which contains the arylide, unreacted
materials, the diluent and other products, some
of which are tarry in nature.
’
Several methods have been used in the past
to isolate the arylide from the reaction mixture.
One of the methods treats the reaction mixture
with water and an alkaline agent to neutralize
any free acid, followed by stripping off the diluent
taining the arylide is neutralized with a dilute
aqueous solution of an alkali, such as sodium
carbonate or bicarbonate, as described in the last
mentioned method, and then ,a large part, but
not all, of the organic solvent is stripped off or,
if desired, all of the organic solvent may be
stripped oil and a measured quantity of organic
solvent added to the reaction mixture. The
charge, containing a small amountof organic
solvent, after cooling to room temperature, is ?le
tered ‘and the cake washed,- ?rst with asmall
amount of organic solvent, and then with dilute
aqueous solutions of mild alkali, and of ‘acid, and
?nally with water. The removal of the major
portion. of solvent avoids difficulties involved
where there is some solubility of the arylide'inv
the solvent, and at the same time'all of the ad-‘
vantages due to the presence of solvent are‘re
tained because it requires only a small amount of
solvent to maintain in solution or redissolve the
tarry alkali insoluble impurities,v At the‘ same
time the small amount of solvent present does
not introduce any particular di?iculties ‘dueto
emulsion formation.
I
'
-
1
_
The‘method of the present invention avoids all
of the di?iculties of the prior‘art, and at the same
time does not introduce either complicated ‘or
expensive additional steps. In fact, the procedure
and the unreacted amine by the use of steam.
This method‘has a serious disadvantage in that 30 is more simple, and no compromise between high
the tarry impurities produced remain behind with
the arylide and are ‘very di?icult to remove.
Another method involves the use of a diluent
in which the arylide has low solubility, and in
this case the reaction mixture is ?ltered without
steam stripping. This procedure is useful only
where an inert solvent is used in which the arylide
recovery, cheap process and high purity of the
product
is
necessary.
.
l
v
»
The present invention is applicable in general
to the arylides of aromatic o-hydroxy carboxylic
acids. Typical of such acids are those belonging
to the benzene series, such as salicylic acid and
various mono- and dimethyl substituted salicylic
is not , appreciably soluble. Otherwise large
acids, o-hydroxy acids of the naphthalene series,
losses occur. Even in the case of solvents which
such as the various o-hyclroxy naphthoic acids,
have little or no solvent action on the arylide 40 o-hydroxy acids of the anthracene series such as
the ?ltration is not readily effected because a
dense ?rmly packed ?lter cake frequently results,
and this cannot be readily washed with aqueous
solutions, which washing step is necessary, of
course, in order to remove impurities and excess
organic solvent.
,
A further method involves neutralization with
water ‘and. alkali, followed by ?ltration without
stripping oil’ the solvent. This is objectionable
in the case of solvents which dissolve appreciable
quantitiesof the arylide, as described above, and
has the further objection that emulsions are fre
quently encountered which greatly interfere
with the smooth progress of ?ltration.
. .The present invention depends on an entirely
Z-hydroxy-S-anthroic acid, o-hydroxy carbaz'ole
carboxylic acids or benzocarbazole carboxylic
acids, and also o-hydroxy acids of higher molecu
lar weight series, such as chrysene, pyrene, fluo
rene, diphenylene oxide and diphenylene sul?de.
Of major practical importance are the arylides
‘of 2-hydroxy-3-naphthoic acid which form a'very
importantgroup of azo dye coupling components.
vAlso 5,6,7,8 - tetrahydro - Z-hydroxy-B-naphthoic
acid is included as it has the hydroxy and car
'boxylic groups on the aromatic ring.
The aromatic amines from which the arylides
useful in the process are derived may belong to
‘the benzene series, such as aniline and its homo
logues, e. g. toluidines and xylidines, and substi
2,410,397
3
ii
The invention will be described in greater detail
in conjunction with the following speci?c exam
ples in which the parts are by weight.
Example 1
188 parts of beta-hydroxy naphthoic acid, 123
parts of ortho-anisidine and 1500 parts of mono
tuted products such as chloro, bromo, alkoxy,
aryloxy, nitro, cyano, and sulionamide deriva
tives. Amines of condensed nuclei, such as
naphthylamines and amines of the biphenyl se
ries are also included, as well as heterocyclic
amines such as 2-amino-diphenyleneoxide.
The present invention is generally applicable to
. chlorobenzene are heated to 70° C., and 55 parts
of phosphorus trichloride are added. The reac
reactions using almost any inert diluent or solv
ent, that is to say liquids which do not react with
tion mixture is then heated up to boiling and re
Thereupon it is cooled and
a dilute aqueous solution of sodium bicarbonate
the o-hydroxy carboxylic acid,.the amine or the . 10, ?uxed until complete.
arylide. About the only limitation on the solvent
or diluent is that it should have adequate solvent
action on tarry impurities. Aromatic hydro
carbons, such as those of the benzene series, are
excellent solvents and the halogenated hydrocar
bons, particularly the chlorinated hydrocarbons,
added with agitation until the charge is faintly
alkaline. The neutralized reaction mixture is
15 then heated to boiling and all but 113 parts of
monochlorobenzene stripped oil. This represents
approximately 40% of the calculated weight of
the arylide. The partially stripped charge is
are even better suited and many of them are Very
cheap.
Typical diluents are toluenes, xylenes,
monochlorobenzene or o-dichlorobenzene.
For
technical operation monochlorobenzene is par
then cooled to room temperature, ?ltered, and
20 the ?lter cake washed with dilute aqueous solu
tions of a mild alkali, then acid, and ?nally with
pure water. These washings remove iuireacted
Because the present invention effects ?ltration
beta-hydroxy naphthoic acid and amine. The
in the presence of a relatively small amount of a
remaining arylide is then dried and melts at
solvent, which does not necessarily have to be a
162-104=o C., and dissolves in aqueous caustic soda
25
portion of the original reaction mixture, a fur
to give a clear solution. A high yield is obtained.
ther degree of ?exibility is imparted to the proc
When the above procedure is followed but all
ess in that it is entirely feasible to carry out the
of the monochlorobenzene stripped off the arylide
main reaction in the presence of one diluent,
obtained melts at -158-16l° C., and dissolves in
steam strip it, and then add a small amount of
aqueous caustic soda to form a solution‘ having
30
another diluent to e?ect the ?ltration step of
very marked turbidity.‘ Loss of yield by leaving
the present invention, This permits the. use of
in the small amount of monochlorobenzene is less
ticularly good.
_'
a diluent in the main reaction which would not
be suitable for the puri?cation step because it
does not dissolve tarry impurities or because it
than 5%.
'
When the procedure of the above example'is
followed but none of the monochlorobenzene
has excessive solvent action on the arylide. A
stripped oil‘ only ‘75% as mucharylide is obtained.
very cheap diluent can, therefore, be used in the
Example 2
main reaction and, if necessary, a more expen
sive diluent or solvent in the ?ltration step be
The procedure of Example 1 is followed but
cause the amountv in the latter case is much
all of the monochlorobenzene is stripped off. Be
smaller. This greater ?exibility is an important 40 fore the charge is cooled to room temperature
advantage of the present invention and makes the
113 parts of monochlorobenzene are added with
choice of optimum conditions simpler for the
stirring. The results obtained are substantially
identical with those of Example 1, the product
plant chemist.
7
It is an advantage of the present invention that _ melting at 162-164" C., and the yield being prac
theamount of diluent which must remain in the
tically the same.
reaction mixture when partial stripping is used,
'
Example 3
or the amount of diluent which is added after
total stripping is effected, is not critical. In
generalpsmaller amounts than 25% of the weight
188 parts of beta-hydroxy naphthoic acid, 137
parts of ortho-phenetidine and 1500 parts of
in dissolving tarry impurities and permitting
parts of phosphorus trichloride added. The re
action mixture is then heated under re?ux until
reaction is complete, cooled and neutralized to
faint alkalinity with a dilute aqueous solution of
sodium bicarbonate. The neutralized mixture is
then heated to the boiling point of water and all
of the monochlorobenzene stripped oil by steam.
Thereupon 113 parts of monochlorobenzene are
returned to the kettle and the charge cooled to
60 room temperature, ?ltered, washed with dilute
of the arylide are not desirable as their effect 50 monochlorobenzene are heated to ‘70° C., and 55
ease of ?ltration is not suiiiceint. Amounts in
excess of 200% of the Weight of the arylide are
also in general undesirable, particularly where
there is some solvent action on the arylide, or
where the diluent is particularly easily emulsi?ed
with aqueous media. The preferred range of
quantities for best practical operation lies be
tween 40% and 200%, although in its broader
aspects the invention includes procedures in which
less diluent is used. In general it is desirable
aqueous solutions of mild alkali, and of acid, fol
to use as little diluent as possible consistent with
lowed by a pure water wash.
The dried ?lter
While it is an- advantage of the present inven
tion that in many cases, particularly when oper
ating under optimum conditions, a washed ?lter
cake is obtained of such high purity that it re 70
quires no further puri?cation, it should be un
derstood that the invention is not limited to the
tained melts at l55-157° C., and does not give a
clear solution in aqueous caustic soda. Loss of
yield by the presence of the 113 parts of mono
chlorobenzene amounts to only about 5%.
Example 4
cake consists of the phenetidide, which melts at
complete puri?cation, and the optimum amount
159-160° C.
_
will vary not only with the particular diluent
When the above procedure is followed but no
used, but also with the particular arylide pro 65
monochlorobenzene reintroduced the arylide ob
duced.
188 parts of beta-hydroxy naphthoic acid, 143
production of products of this extreme purity and
partsuof alpha-naphthylamine and 1800 parts of
in certain cases further puri?cation by conven
monochlorobenzene are heated to ‘70° C., and 55
75
tional means may be employed.
5
2,410,397
parts ofphosphorus trichloride added. The re
action mixture is then heated up and re?uxed un-,
til reaction is complete. Thereupon the mixture
is slightly cooled and dilute aqueous sodium bi
carbonate added to slight alkalinity. rI‘he neu
tralized reaction mixture is then heated to the
boil and the major portion of the monochloro
benzene stripped off by steam, leaving about 400
parts in the reaction mixture, which is then
cooled, ?ltered, washed with a small amount of
fresh monochlorobenzene and then with aqueous
alkaline. Thereupon, the mixture is heated to
the boil and all but 113 parts of monochloro
benzene stripped 0d‘.
The reaction mixture is then cooled to room
temperature, ?ltered, and the ?lter cake washed
with dilute solutions of mild alkali, acid and
water. On drying an arylide is obtained which
dissolves in aqueous caustic soda to form a clear
solution.
-
We 'claim:
.
1. In a method of isolating an arylide of an
solutions of mild alkali, and of acid, followed by '
aromatic orthohydroxy carboxylic acid from a
water. The dried ?lter cake consists of arylide
reaction mixture resulting from the reaction
melting at 219_221° C‘., which dissolves in aqueous
of the hydroxy acid with an aromatic amine
caustic soda to a clear solution.
15 in the presence of a condensing agent, the im- l
' When the above procedure is followed but all
provement which comprises neutralizing any acid
of the monochlorobenzene is stripped off the re
present and e?ecting ?ltration in the presence
sulting arylide melts at 215-2l6° 0., and gives a
of an inert organic solvent for tarry impurities
very turbid solution in aqueous caustic soda.
selected from the group consisting of liquid hy
Erample 5
drocarbons of the benzeneseries and liquid chlo
rinated hydrocarbons, the amount of the solvent
To a solution of 188 parts of beta-hydroxy
being from 25 to 200% by Weight of the arylide. '
napthoic acid in 1600 parts of monochloroben
2. In a method of isolating an arylide of an
zene, there is slowly added 48 parts of phos
aromatic orthohydroxy carboxylic acid from a re
phorus trichloride at room temperature, and the 25
action mixture resulting from the reaction of
reaction mixture is stirred for a number of hours
the hydroxy acid with an aromatic amine in the
to complete the _formation of the 2,3-hydroxy
presence of a condensing agent, the improvement
naphthoyl chloride. Toward the end of the
which comprises neutralizing any acid present
stirring 110 parts of ortho-toluidine are added
eiTecting ?ltration in the presence of an inert
and the temperature slowly increased to the boil 30 and
organic solvent for tarry impurities selected from
ing point with re?uxing. until evolution of hy
drogen chloride practically ceases.
The reaction mixture is then cooled slightly
and an aqueous solution of sodium bicarbonate
run in until the charge is slightly alkaline. All
but 400 parts of the monochlorobenzene is then
steam stripped oiT, and the charge cooled to room
temperature, ?ltered, and washed in the usual
manner with dilutev solutions of mild alkali, and
of acid. The resulting arylide melts at 195-197°
C. and dissolves in aqueous caustic soda to form
a clear solution.
' When the above procedure is followed, but all
of the monochlorobenzene removed by steam
stripping, the arylide produced has a 2° C. lower
melting point and dissolves in caustic soda to
form a cloudy solution.
Example 6
188 parts of beta-hydroxy naphthoic acid, ‘123
the group consisting of_ liquid hydrocarbons of
the benzene series and liquid chlorinated hy
drocarbons, the amount of the solvent being from
40 to 200% by weight of the arylide.
3. A method of recovering an arylide of an
orthohydroxy carboxylic acid from its reaction
mixture resulting from the reaction of the hy—‘
droxy acid with an aromatic amine in the pres
ence of a condensing agent and an inert organic
diluent capable of dissolving tarry impurities se
lected from the group consisting of liquid hydro
carbons of the benzene series and liquid chlo
rinated hydrocarbons, which comprisesneutraliz
ing any acid present, removing the major portion
of the diluent by vaporization, leaving from 25 to
200% on the weight of the arylide and recover
ing the arylide from the resulting mixture by ?l
tration.
_ 4. A method of recovering an arylide of an
parts of ortho-anisidine and 1500 parts of tolu 50 orthohydroxy carboxylic acid from its reaction
mixture resulting from the reaction of the hy
ene are heated to ‘70° C. and 55 parts of phos
droxy acid with anaromatic amine in the pres
phorus trichloride added. The reaction mixture
ence of a condensing agent and an inert organic
is then slowly heated to the boil and re?uxed
diluent capable of dissolving tarry impurities se
until reaction is complete.
I
lected from the group consisting of liquid hydro
The reaction mixture is cooled and a dilute
carbons of the benzene series and liquid chlorin
solution of sodium bicarbonate added until the
ated hydrocarbons, which comprises neutralizing
mixture is faintly alkaline. This is then heated
any acid present, removing the major portion of
to the boil and all but 115 parts of the toluene
the diluent by vaporization, leaving from 40 to
steam stripped olT. Thereupon, the charge is
200% on the weight of the arylide and recover
cooled to room temperature, ?ltered, and the lil
ing the arylide from the resulting mixture by ?l
ter cake washed with dilute solutions of mild
alkali, acid, and ?nally water. After drying an
arylide is obtained melting at 162-164" C., which
dissolves in aqueous caustic soda to give a clear
solution.
Eatample 7
138 parts of salicylic acid, 137 parts of ortho
phenetidine, and 1500 parts of monochloroben
zone are heated to ‘70° C. and 55 parts of phos- '
phorus trichloride gradually added.
The mix
ture is then heated to the boil and re?uxed un
til reaction is complete. On cooling all of the
product remains in solution, and dilute sodium
bicarbonate is added until the mixture is faintly
tration.
.
5. A method of recovering an arylide of an
orthohydroxy carboxylic acid from its reaction
mixture resulting from the reaction of the hy
droxy acid with an aromatic amine in the pres
_ ence of a condensing agent and an inert organic
diluent capable of dissolving tarry impurities se
lected from the group consisting of liquid hydro
carbons of the benzene series and liquid chlo
rinated hydrocarbons, which comprise removing
substantially all of the diluent by vaporization,
adding to the charge an amount of an inert or
ganic diluent capable of dissolving tarry impuri
ties selected from the group consisting of liquid
2,410,397"
7
hydrocarbons of the benzene, series and. liopuidv
chlorinatedlhydrocarbons, the.- amount added be-i
ing from 25 to 200% of the Weight of- the ary-lide
and'recovering the arylide from the mixture by
filtration.
6..A- method of recovering an arylide of. an
orthohydroxy carboxylic acid from its reaction
mixture resulting from the reaction of the hy
inertorgan-ic diluentcapable of dissolving. tarry.
impurities selected from the group consisting of
liquid'hydrocarbons. of‘ the benzene series and
liquid. chlorinated hydrocarbons, the amount
added being from 25 to 200% of the weight of, the
arylide and recovering the ar-ylide from the mix
ture by ?ltration.
10. A method of recovering an arylide of beta-v
hydroxy naphthoic acid from its reaction mix.
droxy amine with an aromatic amine in the pres
ence of a condensing agent and an inert organic 10 ture resulting, from the reaction of thebeta-hy
droxy naphthoic acid withv an. aromatic, amine in
diluentcapableof dissolving» tarry impurities se
lected'irom- the‘ group. consisting of liquid hydro
carbons-‘of the, benzene series and liquid chlo
rinated hydrocarbons, which comprises remov
ing-substantially all of- the diluent by vaporiza
tion, adding- to the chargev an amount of an inert
organic diluentlcapable of dissolving tarry im
purities-selectedfrom the group consisting of liq
- the presence of a condensing agent and an inert
organic diluent capable of dissolving tarry, im
purities selected from- the. group consisting, ofpliqg
uid hydrocarbons of they benzene series and liq,
uid chlorinated, hydrocarbons, which, comprises
removing substantially all, of the diluent by va
porization, adding. to. the charge an amount of
an inert, organic diluent capable of dissolving
uidrhy-drocarbons of the benzene series and liq
tarry
impurities selectedfrom the group consist
20
uid.chlorinated hydrocarbons, the amount added
ing of liquid hydrocarbons of the benzene series
being from 40 to 200% of the weight of. the ar
andrliquid chlorinated hydrocarbons, the amount
ylide and. recovering the arylide from the mixture
added being from Zi0 to 200% of theweightof the
by. ?ltration.
arylide and recovering the arylide from the mix
7.. A method of; recovering an arylide oi beta~
by ?ltration.
hydroxy naphthoic acid from its reaction mix 25 ture
11. A method of preparing an arylide of, beta
ture resulting from the reaction of the beta-hy
hydroxy- naphthoic acid which comprises. react
droxy- naphthoic acid. with an aromatic amine
ingv the beta-hydroxy. naphthoic acid in an inert
in. the presence of a condensing agent and an
organic diluent‘ capable of dissolving tarry- im
inert organic diluent capable of, dissolving tarry
impuritiesselected from the group consisting, of 30 purities and selected from the group. consisting
of, liquid hydrocarbons of the benzene. series, and
liquid-hydrocarbons of the benzene series and liq
liquid chlorinated hydrocarbons, with the, desired
uid: chlorinated. hydrocarbons, which comprises
aromatic amine in the presence of su?icient
neutralizing any acid, present, removing the
phosphorus, trichloride to, act as a, condensing
major portion: of, the diluent. by vaporization,
leaving from 25‘to 200% on the weight of the ar 35 agent, neutralizing any. acid present in, the re
action mixture and; effecting. ?ltration in the
ylide. and recovering the arylide from the result
presence of. an amount of the organic diluent
.ing- mixture, by filtration,
from25 to 200% of, the weight of the. ai‘ylide.
8. A method of recovering an arylide of beta
12. A. method according to. claim, 1 in which
hydroxy naphthoic acid from its reaction mix
the
solvent. is. monoch-lorobenzene.
ture resulting from the reaction of the beta-hy
which
13-. A. method, accordingto claim
droxy napthoic acid with an aromatic amine in
' the presence of a condensing agent and an inert
the diluent is monochlorobenzene
14. A method according to claim
which
organic diluent capable of dissolving tarry im
the, diluent is,.monochlorobenzene..
purities selected from the group consisting of, liq
. which
15. A method according to- claim
uid' hydrocarbons of the. benzene series and liq 45
the diluent is monochlorobenzene,
uid, chlorinated hydrocarbons, which comprises
16. A method according to. claim 10in which
neutralizing any acid present, removing the
the
diluent is monochlorobenzene.
major portion of the diluent by vaporization,
17. A method according to claim 8 in which
leaving. from 40, to 200% on the weight of the
arylide and recovering the arylide from the re 50 the arylideiis the orthoeanisidide and the diluent
sulting ' mixture by ?ltration.
is monochlorobenzene.
1.8. A method; according to claim 10 in which
the arylide is the ortho-anisidide; and the diluent
is monochlorobenzene.
19. A method according to claim 8 in which the
droxy naphthoic acid with an aromatic amine in 55
arylide is the ortho-phenetidide and the. diluent
the presence of a condensing agent and an inert
is monochlorobenzene.
organic< diluent capable of dissolving tarry im
20. A method according to. claim 10 in which
purities selected from the group consisting of liq
the arylide is the ortho-phenetidide and the dil
uid hydrocarbons of the benzene series and liquid
chlorinated hydrocarbons, which comprises re 60 uent is monochlorobenzene.
ROBERT H. WEISS.
moving substantially all of the diluent by vapor
ANDREWS C. WINTRINGHAM.
ization, adding to the charge an amount of an
9. A. method of recovering an arylide of beta
hydroxy naphthoic acid from its. reaction mix
ture resulting from the reaction of the beta-hy
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