GB1576608A - Catalytic reduction of nitronaphthalene sulphonic acids - Google Patents
Catalytic reduction of nitronaphthalene sulphonic acids Download PDFInfo
- Publication number
- GB1576608A GB1576608A GB50645/75A GB5064575A GB1576608A GB 1576608 A GB1576608 A GB 1576608A GB 50645/75 A GB50645/75 A GB 50645/75A GB 5064575 A GB5064575 A GB 5064575A GB 1576608 A GB1576608 A GB 1576608A
- Authority
- GB
- United Kingdom
- Prior art keywords
- nitronaphthalene
- autoclave
- reduction
- catalyst
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
- C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
- C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/08—Preparation of nitro compounds by substitution of hydrogen atoms by nitro groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) CATALYTIC REDUCTION OF NITRONAPHTHALENE
SULPHONIC ACIDS
(71) We, IMPERIAL CHEMICAL
INDUSTRIES LIMITED, Imperial
Chemical House, Millbank, London SWIP
3JF, a British Company, do hereby declare
the invention, for which we pray that a
patent may be granted to us, and the
method by which it is to be performed, to be
particularly described in and by the
following statement:- This invention relates to a chemical
reduction process and more particularly to a
catalytic reduction process for the
manufacture of aminonaphthalene
sulphonic acids.
It is well known to reduce nitronaphthalene
sulphonic acids to the corresponding
naphthylamine sulphonic acids by contacting
with iron and mineral acid. This process
sometimes produces difficulties in filtration
and disposal of the iron oxide formed, and it
is desirable to find an alternative method
which does not pose these problems.
Catalytic hydrogenation using small
amounts of such well-known catalysts as
Raney nickel or palladised carbon provides
one potential alternative. Unfortunately,
unpurified nitronaphthalene sulphonic acids
contain compounds which can poison the
catalyst and affect their activity. This is
particularly evident in systems where all the
nitro and catalyst are charged prior to
reduction. Rates of reduction can be much
slower than normal allowing build up of reduction intermediates such as azoxy
compounds, these being very difficult to
reduce further to amine. It has now been
found that these difficulties can be
overcome and the nitronaphthalene
sulphonic acids reduced by hydrogenation
catalysts by introducing the nitro compound
into a reduction chamber containing the
catalyst and hydrogen under pressure at a
rate substantially equal to that at which
hydrogenation takes place.
As examples of nitronaphthalene
sulphonic acids which can be reduced by
the new process there may be mentioned more especially those of the general formula:
where X represents H, halogen, NO2 or
SO3H, and Y represents H, halogen or
SOCH.
As specific examples of these, there may be mentioned:
8 - nitronaphthalene - 1,3,6 - trisulphonic acid
8 - nitronaphthalene - 1 - sulphonic acid
8 - nitronaphthalene - 1,6 - disulphonic acid.
The nitronaphthalene sulphonic acids may be in an unpurified form, in which case the process of the invention minimises the difficulties previously experienced.
Metals which may be used as hydrogenation catalysts are the metals of
Group VIII in Meldeleef's Period System of the Elements especially cobalt, nickel, platinum and palladium. Nickel and palladium are the preferred metals. The art of preparing such metals in a catalytically active form is well known. In the process of the invention the metal catalysts may be used in supported or unsupported form.
More particularly the following catalysts are usable:
Raney nickel, Raney cobalt,.pjatinum black, nickel-on-kieselguhr, cobalt-onkieselguhr, platinised charcoal, palladised charcoal. The preferred catalyst is Raney nickel.
The amount of catalyst used and the conditions used for reduction are factors defending mainly on the catalyst used. It is well known, for example, that Raney nickel is less effective as a hydrogenation catalyst than palladium or platinum and must be
present in a larger amount and/or the
hydrogenation must be carried out under
higher pressure and/or higher temperature
than if the latter two are used.
The process can conveniently be carried
out in hydrogenation autoclaves fitted for
pump feeding and preferably one fitted with
agitation and means for gas recirculation.
Prior to introducing the nitronaphthalene
sulphonic acid, the catalyst preferably in a
small amount of water, is charged to the
autoclave and the latter is closed, swept free
from oxygen, pressurised with hydrogen and
heated to the desired temperature.
Using Raney nickel as catalyst, e.g. a suitable amount is from 0.1-10%, preferably 0.53 /n by weight of the total amount of nitronaphthalene sulphonic acid to be reduced. Suitable reduction conditions are, e.g. from 70--1500C, preferably 95--1300C, and a pressure up to 600 p.s.i.g., preferably 150300 p.s.i.g.
The nitronaphthalene sulphonic acid is preferably reduced in the form of an alkali metal salt, preferably the sodium salt and can conveniently be introduced into the autoclave by pumping in an aqueous slurry of the salt, preferably a slurry containing from 20 to 33 /n by weight of the salt, circulation of hydrogen being continued at such a rate that the hydrogen pressure is maintained fairly constant. The reduction process is exothermic and this factor should
be taken into consideration as the reduction proceeds. Samples of the liquor may be taken from the autoclave at intervals to ensure that there is no build-up of nitro compound.
Provided that a proper balance of feed rate and reduction conditions is maintained, the process is completed shortly after that last of the nitronaphthalene sulphonic acid
has been fed to the autoclave and the latter
can be discharged and the contents be worked up by filtration of the catalyst and isolation of the amine sulphonic acid by
acidification of the filtrate.
The invention may be illustrated but is
not limited by the following Example in which parts and percentages are by weight.
Example
Into a hydrogenation autoclave fitted for
pump feeding and equipped with agitation
and gas circulation, there is charged 41 parts
of a Raney nickel catalyst in 2000 parts of
water. The autoclave is sealed, purged with
nitrogen then hydrogen and pressurised to
200 psig with hydrogen. Agitation and gas
circulation are commenced and the
autoclave contents are heated to 1300C.
11000 parts of a 25.0% aqueous slurry of 8 nitronaphthalene - 1,3,6 - trisulphonic acid trisodium salt, pH 7.5-9.5, are then pumped into the autoclave over 2 hours maintaining temperature at l30+50C and pressure 200+50 psig. Evolution of heat is observed to cease directly after termination of pumping and reduction is complete. The autoclave contents are discharged, filtered free of catalyst to yield 8 - aminonaphthalene - 1,3,6 - trisulphonic acid trisodium salt, (12900 parts at 19.5% w/w) equivalent to a yield of 99.0 /n. The product can be isolated in paste form by the addition of sulphuric acid (1420 parts) to yield Koch
Acid (7226 parts at 30.0% w/w) equivalent to an isolated yield of 85.0%.
WHAT WE CLAIM IS:
1. A process for reduction of nitronaphthalene sulphonic acids to the corresponding aminonaphthalene sulphonic acids by catalytic reduction, wherein the nitronaphthalene sulphonic acid is introduced into a reduction chamber containing the hydrogenation catalyst and hydrogen under pressure at a rate substantially equal to that at which hydrogenation takes place.
2. A process as claimed in claim 1 wherein there is used a nitronaphthalene sulphonic acid of the formula:
where X is H, halogen, NO2 or SO3H and Y is H, halogen or SO3H.
3. A process as claimed in claim 1 or claim 2 wherein there is used a platinum or nickel catalyst.
4. A process as claimed in claim 3 wherein there is used a Raney nickel catalyst.
5. A process as claimed in claim 4 wherein the amount of Raney nickel used is from 0.5-3% by weight of the total amount of nitronaphthalene sulphonic acid to be reduced.
6. A process as claimed in claim 4 or claim 5 wherein the reduction is carried out at a temperature of from 95 to 1300C and at a pressure of from 150 to 300 p.s.i.g.
7. A process as claimed in any preceding claim substantially as herein described with reference to and as illustrated by the
Example.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (8)
- **WARNING** start of CLMS field may overlap end of DESC **.present in a larger amount and/or the hydrogenation must be carried out under higher pressure and/or higher temperature than if the latter two are used.The process can conveniently be carried out in hydrogenation autoclaves fitted for pump feeding and preferably one fitted with agitation and means for gas recirculation.Prior to introducing the nitronaphthalene sulphonic acid, the catalyst preferably in a small amount of water, is charged to the autoclave and the latter is closed, swept free from oxygen, pressurised with hydrogen and heated to the desired temperature.Using Raney nickel as catalyst, e.g. a suitable amount is from 0.1-10%, preferably 0.53 /n by weight of the total amount of nitronaphthalene sulphonic acid to be reduced. Suitable reduction conditions are, e.g. from 70--1500C, preferably 95--1300C, and a pressure up to 600 p.s.i.g., preferably 150300 p.s.i.g.The nitronaphthalene sulphonic acid is preferably reduced in the form of an alkali metal salt, preferably the sodium salt and can conveniently be introduced into the autoclave by pumping in an aqueous slurry of the salt, preferably a slurry containing from 20 to 33 /n by weight of the salt, circulation of hydrogen being continued at such a rate that the hydrogen pressure is maintained fairly constant. The reduction process is exothermic and this factor should be taken into consideration as the reduction proceeds. Samples of the liquor may be taken from the autoclave at intervals to ensure that there is no build-up of nitro compound.Provided that a proper balance of feed rate and reduction conditions is maintained, the process is completed shortly after that last of the nitronaphthalene sulphonic acid has been fed to the autoclave and the latter can be discharged and the contents be worked up by filtration of the catalyst and isolation of the amine sulphonic acid by acidification of the filtrate.The invention may be illustrated but is not limited by the following Example in which parts and percentages are by weight.Example Into a hydrogenation autoclave fitted for pump feeding and equipped with agitation and gas circulation, there is charged 41 parts of a Raney nickel catalyst in 2000 parts of water. The autoclave is sealed, purged with nitrogen then hydrogen and pressurised to200 psig with hydrogen. Agitation and gas circulation are commenced and the autoclave contents are heated to 1300C.11000 parts of a 25.0% aqueous slurry of 8 nitronaphthalene - 1,3,6 - trisulphonic acid trisodium salt, pH 7.5-9.5, are then pumped into the autoclave over 2 hours maintaining temperature at l30+50C and pressure 200+50 psig. Evolution of heat is observed to cease directly after termination of pumping and reduction is complete. The autoclave contents are discharged, filtered free of catalyst to yield 8 - aminonaphthalene - 1,3,6 - trisulphonic acid trisodium salt, (12900 parts at 19.5% w/w) equivalent to a yield of 99.0 /n. The product can be isolated in paste form by the addition of sulphuric acid (1420 parts) to yield Koch Acid (7226 parts at 30.0% w/w) equivalent to an isolated yield of 85.0%.WHAT WE CLAIM IS: 1. A process for reduction of nitronaphthalene sulphonic acids to the corresponding aminonaphthalene sulphonic acids by catalytic reduction, wherein the nitronaphthalene sulphonic acid is introduced into a reduction chamber containing the hydrogenation catalyst and hydrogen under pressure at a rate substantially equal to that at which hydrogenation takes place.
- 2. A process as claimed in claim 1 wherein there is used a nitronaphthalene sulphonic acid of the formula:where X is H, halogen, NO2 or SO3H and Y is H, halogen or SO3H.
- 3. A process as claimed in claim 1 or claim 2 wherein there is used a platinum or nickel catalyst.
- 4. A process as claimed in claim 3 wherein there is used a Raney nickel catalyst.
- 5. A process as claimed in claim 4 wherein the amount of Raney nickel used is from 0.5-3% by weight of the total amount of nitronaphthalene sulphonic acid to be reduced.
- 6. A process as claimed in claim 4 or claim 5 wherein the reduction is carried out at a temperature of from 95 to 1300C and at a pressure of from 150 to 300 p.s.i.g.
- 7. A process as claimed in any preceding claim substantially as herein described with reference to and as illustrated by the Example.
- 8. Aminonaphthalene sulphonic acidswhenever obtained by a process claimed in any of claims 1 to 7.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB50645/75A GB1576608A (en) | 1975-12-10 | 1975-12-10 | Catalytic reduction of nitronaphthalene sulphonic acids |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB50645/75A GB1576608A (en) | 1975-12-10 | 1975-12-10 | Catalytic reduction of nitronaphthalene sulphonic acids |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1576608A true GB1576608A (en) | 1980-10-08 |
Family
ID=10456762
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB50645/75A Expired GB1576608A (en) | 1975-12-10 | 1975-12-10 | Catalytic reduction of nitronaphthalene sulphonic acids |
Country Status (1)
Country | Link |
---|---|
GB (1) | GB1576608A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0475044A1 (en) * | 1990-08-08 | 1992-03-18 | Bayer Ag | Process for the production of aminoarylsulphonic acids |
CN100574877C (en) * | 2007-06-18 | 2009-12-30 | 大连理工大学 | A kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid |
-
1975
- 1975-12-10 GB GB50645/75A patent/GB1576608A/en not_active Expired
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0475044A1 (en) * | 1990-08-08 | 1992-03-18 | Bayer Ag | Process for the production of aminoarylsulphonic acids |
CN100574877C (en) * | 2007-06-18 | 2009-12-30 | 大连理工大学 | A kind of T-acid by hydrogenation of non-crystal-state nickel-aluminium alloy catalytic nitryl prepares the method for amino T acid |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4792626A (en) | Production of aromatic diamino compounds using a modified Raney catalyst | |
US4375003A (en) | Method for the hydrogenation of nitriles to primary amines | |
DE3017518C2 (en) | Process for the production of N-phosphonomethyl-glycine | |
US4020107A (en) | Catalytic reduction of halonitroaromatic compounds | |
IL38722A (en) | Process for preparing sulfited platinum on carbon catalysts | |
EP0253788B1 (en) | A method of preparing 5-amino salicyclic acid | |
DE3928329A1 (en) | METHOD FOR PRODUCING CHLORINE-SUBSTITUTED AROMATIC AMINES | |
GB1576608A (en) | Catalytic reduction of nitronaphthalene sulphonic acids | |
US2016963A (en) | Product comprising glucamines and related substances | |
US4948890A (en) | Process for the preparation of DAFNP | |
US4550207A (en) | Process for the preparation of benzene compounds | |
US4226809A (en) | Hydrogenation of unsaturated dinitriles using catalyst comprising reaction products of nickel compound and of a palladium compound each with an alkali metal borohydride | |
JPH0629267B2 (en) | Method for selective reduction of 2-quinoxalinol-4-oxide compound | |
EP1067114B1 (en) | Method of preparing amino-, imino- and nitrilocarbonxylic acids and silver-promoted copper catalyst for use in said method | |
EP0173202B1 (en) | Process for the preparation of chloro-o-nitroanilines | |
AU601851B2 (en) | Process for the production of 2-quinoxalines | |
EP0000805A1 (en) | Catalytic hydrogenation process for the manufacture of chlorinated aromatic amines | |
EP0034398B1 (en) | Production of 2-naphthylamine-4,8-disulphonic acid | |
EP0174563B1 (en) | Process for preparing 1-naphthyl amine | |
DE2331900C2 (en) | Process for the production of aromatic diamines | |
DE2646379A1 (en) | PROCESS FOR THE PREPARATION OF N-ALKYLANILINES | |
DE3303789C2 (en) | ||
DE3347452A1 (en) | METHOD FOR PRODUCING AROMATIC AMINOSULPHONIC ACIDS | |
EP0000634A1 (en) | Process for the manufacture of naphthylamine sulphonic acids | |
DE69730111T2 (en) | Process for the preparation of 3- (N, N-dimethylamino) benzoic acid |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
CSNS | Application of which complete specification have been accepted and published, but patent is not sealed |