GB1575860A - Process for the manufacture of m-aminophenols - Google Patents
Process for the manufacture of m-aminophenols Download PDFInfo
- Publication number
- GB1575860A GB1575860A GB1265778A GB1265778A GB1575860A GB 1575860 A GB1575860 A GB 1575860A GB 1265778 A GB1265778 A GB 1265778A GB 1265778 A GB1265778 A GB 1265778A GB 1575860 A GB1575860 A GB 1575860A
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- GB
- United Kingdom
- Prior art keywords
- phosphoric acid
- resorcinol
- amine
- salt
- temperature
- 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
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- 238000000034 method Methods 0.000 title claims description 34
- CWLKGDAVCFYWJK-UHFFFAOYSA-N 3-aminophenol Chemical class NC1=CC=CC(O)=C1 CWLKGDAVCFYWJK-UHFFFAOYSA-N 0.000 title claims description 19
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 59
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 58
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 claims description 42
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 150000001412 amines Chemical class 0.000 claims description 15
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- MESJRHHDBDCQTH-UHFFFAOYSA-N 3-(dimethylamino)phenol Chemical compound CN(C)C1=CC=CC(O)=C1 MESJRHHDBDCQTH-UHFFFAOYSA-N 0.000 claims description 8
- RZXMPPFPUUCRFN-UHFFFAOYSA-N p-toluidine Chemical compound CC1=CC=C(N)C=C1 RZXMPPFPUUCRFN-UHFFFAOYSA-N 0.000 claims description 8
- 150000003335 secondary amines Chemical class 0.000 claims description 8
- 229940018563 3-aminophenol Drugs 0.000 claims description 7
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 7
- 238000000746 purification Methods 0.000 claims description 7
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methyl-N-phenylamine Natural products CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005292 vacuum distillation Methods 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- -1 heterocyclic amine Chemical class 0.000 claims description 4
- 150000003016 phosphoric acids Chemical class 0.000 claims description 4
- 239000000047 product Substances 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- TZMSYXZUNZXBOL-UHFFFAOYSA-N 10H-phenoxazine Chemical compound C1=CC=C2NC3=CC=CC=C3OC2=C1 TZMSYXZUNZXBOL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000009935 nitrosation Effects 0.000 claims description 3
- 238000007034 nitrosation reaction Methods 0.000 claims description 3
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 claims description 2
- TWYLNUMRYUFZIN-UHFFFAOYSA-N 3-(4-methylanilino)phenol Chemical compound C1=CC(C)=CC=C1NC1=CC=CC(O)=C1 TWYLNUMRYUFZIN-UHFFFAOYSA-N 0.000 claims description 2
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 claims description 2
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical compound ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 229940111759 benzophenone-2 Drugs 0.000 claims description 2
- 238000009529 body temperature measurement Methods 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 230000003247 decreasing effect Effects 0.000 claims description 2
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 125000000018 nitroso group Chemical group N(=O)* 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 7
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 3
- NDACNGSDAFKTGE-UHFFFAOYSA-N 3-hydroxydiphenylamine Chemical compound OC1=CC=CC(NC=2C=CC=CC=2)=C1 NDACNGSDAFKTGE-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 150000001448 anilines Chemical class 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- QURGRYZJKCDXKY-UHFFFAOYSA-N 3-(4-methoxyanilino)phenol Chemical compound C1=CC(OC)=CC=C1NC1=CC=CC(O)=C1 QURGRYZJKCDXKY-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- KUDPGZONDFORKU-UHFFFAOYSA-N n-chloroaniline Chemical compound ClNC1=CC=CC=C1 KUDPGZONDFORKU-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003142 primary aromatic amines Chemical class 0.000 description 1
- 150000005619 secondary aliphatic amines Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000004992 toluidines Chemical class 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B19/00—Oxazine dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
(54) PROCESS FOR THE MANUFACTURE OF M-AMINOPHENOLS
(71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, 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:
The present invention relates to the manufacture of m-aminophenols.
m-Aminophenols are valuable starting compounds for the manufacture of dyestuffs, optical brighteners and antioxidants. They can be prepared by reacting resorcinol (1,3-dihydroxybenzene) with ammonia or a primary or secondary aliphatic or aromatic amine (cf. U.S. Patent Specifications Nos. 2,376,112, 3,102,913 and 3,450,764; German
Patent Specifications Nos. 121,683 and 49,060, and German Offenlegungsschrift No.
1,543,368 The present invention provides a process for the manufacture of m-aminophenols, which comprises reacting resorcinol with ammonia or a primary or secondary amine in the presence of a catalytic amount of at most 0.05 mol of phosphoric acid or a salt thereof per mol of resorcinol.
The phosphoric acid or salt thereof is preferably used in an amount of from 0.001 to 0.02 mol for each mol of resorcinol; within the indicated limits the amount of catalyst to be used in each case is not critical. For practical reasons it is generally preferred to use as low as possible an amount of catalyst. Phosphoric acid is the preferred catalyst. Preferred salts of phosphoric acid are those with weak bases, especially a salt with ammonia or a primary or secondary amine used as a starting component.
Phosphoric acid is generally used in a concentrated, water-containing form. Instead of phosphoric acid itself there may also be used oligomers thereof, polyphosphoric acids, or salts thereof, preferably the amine or ammonium salts. Mixtures of two or more of the catalysts may be used.
To carry out the process of the invention generally 1 mol of resorcinol is reacted with at least one mol of a primary or secondary amine or ammonia in the presence of, for example, from 0.001 to 0.02 mol of phorphoric acid or an amine or ammonium salt thereof, at an elevated temperature, preferably in the range of from 1500 to 250"C.
Depending on the type of the amine component and its volatility, optimum reaction conditions can be chosen for each individual case. When using a relatively involatile amine, for example a primary aromatic amine such as aniline or a substituted aniline, it is advantageous, for example, to carry out the reaction by mixing 1 mol of resorcinol with approximately 1.2 mol of aniline or aniline derivative and 0.007 mol of phosphoric acid or the aniline salt thereof, and slowly heating the mixture to a temperature in the range of from 1800 to 200"C while stirring. In general, the reaction starts at that temperature and the respective 3-hydroxydiphenyl amine is formed with separation of water. The process of the reaction can be readily determined from the amount of water distilled off. When the reaction is complete, the 3-hydroxydiphenyl amine can be obtained in the pure state and in a good yield by vacuum distillation.
More readily volatile amines, for example dimethyl amine, can be reacted with resorcinol and the catalytic amount of phosphoric acid or salt thereof in an autoclave at approximately 200"C to give 3-dimethylaminophenol. For this reaction either a commercial aqueous dimethyl amine solution (for example of 40 or 60% strength) or anhydrous dimethyl amine can be used. When using an aqueous solution the reactants can be mixed with one another and then heated to reaction temperature over a period of approximately 1 hour. The reaction takes place without a significant temperature increase. When using anhydrous dimethyl amine, it is advantageous to add the amine in small quantities to a mixture of resorcinol and the phosphoric acid catalyst at a temperature in the range of from 1500 to 1600C, and to control in this manner the exothermal course of the reaction. When the reaction is complete excess dimethyl amine, if any, and the reaction water can be distilled off. Depending on the intended use, the 3-dimethylaminophenol can be purified by vacuum distillation or in some cases the crude product may be used directly for further reactions.
This is especially advantageous for the synthesis of some phenoxazin dyes (cf., for example,
German Auslegeschrift No. 2,458,347) wherein the nitrosation of the crude product which may be obtained according to the present invention is possible without previous purification.
In the process of the invention there can be used, besides ammonia, all primary or secondary amines, for example aliphatic, aromatic, araliphatic, or heterocyclic amines, that are stable under the reaction conditions, as well as corresponding substituted amines.
Preferred amine components are, for example, ammonia, methylamine, dimethyl amine, ethyl amine, aminoethanol, butyl amine, dibutyl amine, aniline, chloroaniline, toluidine, anisidine. N-methylaniline, xylidene, cyclohexyl amine and aminophenol, dimethyl amine being especially preferred.
The amines are generally used in stoichiometric amounts, calculated on the resorcinol. In some cases a small excess, sometimes even a large excess, of the amine may be advantageous, the excess possibly being in the range of from a fraction of to one or more times the molar amount of the stoichiometrically required amount.
The process of the invention may be carried out in the presence of an inert organic solvent, which may be used in a usual amount, for example from 0.5 to five times the amount of resorcinol. Suitable solvents are, for example, aromatic, araliphatic or aliphatic hydrocarbons, higher alcohols or ethers. The process of the invention is, however, preferably carried out in the absence of inert organic solvents, which in part are readily combustible, so that it has a much smaller polluting effect on the environment and, because of the saving of volume, the spaced-time-yield of the apparatus used is considerably increased.
Compared with known processes for the manufacture of 3-aminophenols from resorcinol and amines in the presence of various condensing agents, the process of the invention is characterised by the use of very small, catalytic amounts, of preferably aqueous phosphoric acid, by an especially simple mode of operation and its non-polluting and anticorrosive effect, and a high conversion rate of the reactants to substantially uniform reaction products. Because the process is preferably carried out in the absence of combustible solvents and toxic substances the space-time-yield of the apparatus used is considerably increased.
The present invention also provides a process for preparing an oxazine dyestuff, wherein a m-aminophenol prepared acording to the invention is treated, without intermediate purification, with nitrous acid to introduce a nitroso group and the product is condensed with a m-phenylenediamine, and a process for preparing a xanthene dyestuff, wherein a m-aminophenol as above is condensed, without intermediate purification, with a 2-hydroxy-4-dialkylamino-benzophenone-2'-carboxylic acid.
The following Examples illustrate the invention.
Example 1
In a three-necked flask fitted with a stirrer, thermometer and water separator, 560 g of resorcinol (98.9% strength), 738 g of p-anisidine and 4 g of phosphoric acid (85% strength) were heated. The reaction started at 194"C with the separation of water. During the course of about 3 hours the temperature was raised to 220"C, whilst 90 ml of water were collected in the water separator. The p-anisidine in excess and a little resorcinol were then distilled off under reduced pressure (0.3 torr) at the sump temperature of up to 220"C. At a sump temperature in the range of from 220 to 230"C and a head temperature of 210 to 218"C 3-hydroxy-4'-methoxydiphenylamine of the formula
distilled over into a receiver in an amount of 915 g, corresponding to a yield of about 85% of the theory, calculated on the resorcinol used.
Example 2
560 g of resorcinol (98.9% strength), 642 g of p-toluidine and 4 g of phosphoric acid (85% strength) were heated as described in Example 1. After the separation of 90 ml of water, the product was distilled under reduced pressure. At 0.5 torr first unreacted p-toluidine distilled over. 880 g of 3-hydroxy-4'-methyldiphenylamine of the formula
were then obtained at a sump temperature of 192" to 230"C and a head temperature of 185 to 1950C. Yield: 88.4% of the theory.
Example 3
In a 2 litre steel autoclave with. electrical heating 667 9 of resorcinol (98.9% strength), 462 g of aqueous dimethyl amine solution (60% strength and 5 g of phosphoric acid (85% strength) were heated to 2000C during the course of 1 hour and maintained at that room temperature for about 12 hours. The pressure decreased from initially about 20 kg/cm2 to 14 kg/cm2. After completion of the reaction, the unreacted dimethyl amine and the water were distilled off and the oily/waxy reaction product was subjected to a vacuum distillation. At a sump temperature of 135 to 140"C and a head temperature of 132" to 1340C there were obtained at about 3 torr 687 g of 3-dimethylaminophenol of the formula
solidifying in the form of light crystals and having a content of pure substance of 83%, corresponding to a yield of about 69% of the theory, calculated on the resorcinol.
If the 3-dimethylaminophenol prepared as described above is used for the manufacture of phenoxazin dyes according to' German Offenlegungsschrift No. 2,458,347, its purification by vacuum distillation can be dispensed with and the crude product, freed from dimethyl amine and water, can be directly subjected to the nitrosation.
Example 4
In an autoclave fitted with a stirrer, temperature measurement and gas inlet, 1,320 g of resorcinol (98.9% strength) 10 g of phosphoric acid (85% strength) and 300 g of gaseous dimethyl amine were heated to 140"C while stirring. Heating was then discontinued.
Thereafter the temperature rose automatically to 210 to 220"C with adjustment of a pressure of 20 to 23 bar. After 1 hour the pressure of the autoclave was released at 2000C in order to remove the water formed from the reaction equilibrium. A further 200 g of gaseous dimethylamine were introduced into the autoclave and the reaction mixture was again heated to 2100C. The mixture was maintained at this temperature for 1 hour and thereafter the pressure was again released. After depressurisation of the autoclave a further 100 g of gaseous dimethyl amine were introduced and the mixture was maintained for 1 hour at 210 C. The reaction mixture solidified at room temperature and contained 76% of the theory of 3-dimethylaminophenol, which could be worked up in the manner described in
Example 3.
WHAT WE CLAIM IS:
1. A process for the manufacture of a m-aminophenol, which comprises reacting resorcinol with ammonia or a primary or secondary amine in the presence of a catalytic amount of phosphoric acid or a salt thereof, the amount of phosphoric acid or salt thereof being at most 0.05 mol per mol of resorcinol.
2. A process as claimed in claim 1, wherein the phosphoric acid or salt there of is used in an amount of from 0.001 to 0.02 mol per mol of resorcinol.
3. A process as claimed in claim 1 or claim 2, wherein a phosphoric acid salt is a salt of phosphoric acid with a weak base.
4. A process as claimed in claim 3, wherein a phosphoric acid salt is a salt of phosphoric acid with ammonia or a primary or secondary amine.
5. A process as claimed in any one of claims 1 to 4, wheren a phosphoric acid oligomer or polyphosphoric acid, or a salt thereof, is used as catalyst.
6. A process as claimed in any one of claims 1 to 5, wherein the amine is a primary or secondary, aliphatic, aromatic, araliphatic or heterocyclic amine.
7. A process as claimed in claim 6, wherein the amine is any one of those specifically mentioned herein.
8. A process as claimed in claim 7, wherein resorcinol is reacted with dimethyl amine.
9. A process as claimed in any one of claims 1 to 8, wherein the reaction is carried out at a temperature in the range of from 1500 to 250"C.
10. A process as claimed in claim 1, conducted substantially as described herein.
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (13)
- **WARNING** start of CLMS field may overlap end of DESC **.Example 2560 g of resorcinol (98.9% strength), 642 g of p-toluidine and 4 g of phosphoric acid (85% strength) were heated as described in Example 1. After the separation of 90 ml of water, the product was distilled under reduced pressure. At 0.5 torr first unreacted p-toluidine distilled over. 880 g of 3-hydroxy-4'-methyldiphenylamine of the formulawere then obtained at a sump temperature of 192" to 230"C and a head temperature of 185 to 1950C. Yield: 88.4% of the theory.Example 3 In a 2 litre steel autoclave with. electrical heating 667 9 of resorcinol (98.9% strength), 462 g of aqueous dimethyl amine solution (60% strength and 5 g of phosphoric acid (85% strength) were heated to 2000C during the course of 1 hour and maintained at that room temperature for about 12 hours. The pressure decreased from initially about 20 kg/cm2 to 14 kg/cm2. After completion of the reaction, the unreacted dimethyl amine and the water were distilled off and the oily/waxy reaction product was subjected to a vacuum distillation. At a sump temperature of 135 to 140"C and a head temperature of 132" to 1340C there were obtained at about 3 torr 687 g of 3-dimethylaminophenol of the formulasolidifying in the form of light crystals and having a content of pure substance of 83%, corresponding to a yield of about 69% of the theory, calculated on the resorcinol.If the 3-dimethylaminophenol prepared as described above is used for the manufacture of phenoxazin dyes according to' German Offenlegungsschrift No. 2,458,347, its purification by vacuum distillation can be dispensed with and the crude product, freed from dimethyl amine and water, can be directly subjected to the nitrosation.Example 4 In an autoclave fitted with a stirrer, temperature measurement and gas inlet, 1,320 g of resorcinol (98.9% strength) 10 g of phosphoric acid (85% strength) and 300 g of gaseous dimethyl amine were heated to 140"C while stirring. Heating was then discontinued.Thereafter the temperature rose automatically to 210 to 220"C with adjustment of a pressure of 20 to 23 bar. After 1 hour the pressure of the autoclave was released at 2000C in order to remove the water formed from the reaction equilibrium. A further 200 g of gaseous dimethylamine were introduced into the autoclave and the reaction mixture was again heated to 2100C. The mixture was maintained at this temperature for 1 hour and thereafter the pressure was again released. After depressurisation of the autoclave a further 100 g of gaseous dimethyl amine were introduced and the mixture was maintained for 1 hour at 210 C. The reaction mixture solidified at room temperature and contained 76% of the theory of 3-dimethylaminophenol, which could be worked up in the manner described in Example 3.WHAT WE CLAIM IS: 1. A process for the manufacture of a m-aminophenol, which comprises reacting resorcinol with ammonia or a primary or secondary amine in the presence of a catalytic amount of phosphoric acid or a salt thereof, the amount of phosphoric acid or salt thereof being at most 0.05 mol per mol of resorcinol.
- 2. A process as claimed in claim 1, wherein the phosphoric acid or salt there of is used in an amount of from 0.001 to 0.02 mol per mol of resorcinol.
- 3. A process as claimed in claim 1 or claim 2, wherein a phosphoric acid salt is a salt of phosphoric acid with a weak base.
- 4. A process as claimed in claim 3, wherein a phosphoric acid salt is a salt of phosphoric acid with ammonia or a primary or secondary amine.
- 5. A process as claimed in any one of claims 1 to 4, wheren a phosphoric acid oligomer or polyphosphoric acid, or a salt thereof, is used as catalyst.
- 6. A process as claimed in any one of claims 1 to 5, wherein the amine is a primary or secondary, aliphatic, aromatic, araliphatic or heterocyclic amine.
- 7. A process as claimed in claim 6, wherein the amine is any one of those specifically mentioned herein.
- 8. A process as claimed in claim 7, wherein resorcinol is reacted with dimethyl amine.
- 9. A process as claimed in any one of claims 1 to 8, wherein the reaction is carried out at a temperature in the range of from 1500 to 250"C.
- 10. A process as claimed in claim 1, conducted substantially as described herein.
- 11. A process as claimed in claim 1, conducted substantially as described in any one ofthe Examples.
- 12. A m-aminophenol whenever prepared by a process as claimed in any one of claims 1 to 11.
- 13. A process for preparing an oxazine dyestuff, wherein a m-aminophenol as claimed in claim 12, is treated, without intermediate purification, with nitrous acid to introduce a nitroso group and the product is condensed with a m-phenylene diamine.-14. A process for preparing a xanthene dyestuff, wherein a m-aminophenol as claimed in claim 12 is condensed, without intermediate purification, with a 2-hydroxy-4 dialkylamino-benzophenone-2'-carboxylic acid.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19772714255 DE2714255A1 (en) | 1977-03-31 | 1977-03-31 | METHOD FOR PRODUCING M-AMINOPHENOLS AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1575860A true GB1575860A (en) | 1980-10-01 |
Family
ID=6005182
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB1265778A Expired GB1575860A (en) | 1977-03-31 | 1978-03-31 | Process for the manufacture of m-aminophenols |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS53121728A (en) |
| DE (1) | DE2714255A1 (en) |
| FR (1) | FR2385683A1 (en) |
| GB (1) | GB1575860A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2245563A (en) * | 1990-06-23 | 1992-01-08 | Basf Ag | Preparation of 3-dialkylaminophenols |
| CN102924304A (en) * | 2012-10-26 | 2013-02-13 | 大连市旅顺口区江西化工工业总公司 | Preparation method of m-dimethylaminophenol |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4116830A1 (en) * | 1991-05-23 | 1992-11-26 | Basf Ag | METHOD FOR PRODUCING N, N-DISUBSTITUTED M-AMINOPHENOLS |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2238320A (en) * | 1938-05-28 | 1941-04-15 | Wingfoot Corp | Process for preparing secondary amines |
| US2376112A (en) * | 1942-04-21 | 1945-05-15 | Eastman Kodak Co | Amination of dihydric phenols |
| GB619877A (en) * | 1946-06-13 | 1949-03-16 | Stanley Francis Birch | Improvements in or relating to the production of aromatic amines |
| ZA77333B (en) * | 1976-02-24 | 1977-11-30 | Goodrich Co B F | Manufacture of diarylamines |
-
1977
- 1977-03-31 DE DE19772714255 patent/DE2714255A1/en not_active Withdrawn
-
1978
- 1978-03-30 JP JP3619478A patent/JPS53121728A/en active Pending
- 1978-03-31 FR FR7809514A patent/FR2385683A1/en not_active Withdrawn
- 1978-03-31 GB GB1265778A patent/GB1575860A/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2245563A (en) * | 1990-06-23 | 1992-01-08 | Basf Ag | Preparation of 3-dialkylaminophenols |
| GB2245563B (en) * | 1990-06-23 | 1993-12-22 | Basf Ag | Preparation of 3-dialkylaminophenols |
| CN102924304A (en) * | 2012-10-26 | 2013-02-13 | 大连市旅顺口区江西化工工业总公司 | Preparation method of m-dimethylaminophenol |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2385683A1 (en) | 1978-10-27 |
| DE2714255A1 (en) | 1978-10-05 |
| JPS53121728A (en) | 1978-10-24 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed | ||
| PCNP | Patent ceased through non-payment of renewal fee |