US3929864A - Process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters - Google Patents
Process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters Download PDFInfo
- Publication number
- US3929864A US3929864A US392097A US39209773A US3929864A US 3929864 A US3929864 A US 3929864A US 392097 A US392097 A US 392097A US 39209773 A US39209773 A US 39209773A US 3929864 A US3929864 A US 3929864A
- Authority
- US
- United States
- Prior art keywords
- hydroxy
- alkyl esters
- acid alkyl
- preparing
- nitration
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 15
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 14
- 229940090248 4-hydroxybenzoic acid Drugs 0.000 claims abstract description 12
- 238000006396 nitration reaction Methods 0.000 claims abstract description 11
- 150000002148 esters Chemical class 0.000 claims description 5
- QRYSWXFQLFLJTC-UHFFFAOYSA-N 616-82-0 Chemical compound OC(=O)C1=CC=C(O)C([N+]([O-])=O)=C1 QRYSWXFQLFLJTC-UHFFFAOYSA-N 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 4
- LXCFILQKKLGQFO-UHFFFAOYSA-N methylparaben Chemical compound COC(=O)C1=CC=C(O)C=C1 LXCFILQKKLGQFO-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 2
- 125000005907 alkyl ester group Chemical group 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- GNCWCTBHZCBXGL-UHFFFAOYSA-N methyl 4-hydroxy-3-nitrobenzoate Chemical compound COC(=O)C1=CC=C(O)C([N+]([O-])=O)=C1 GNCWCTBHZCBXGL-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WDMUXYQIMRDWRC-UHFFFAOYSA-N 2-hydroxy-3,4-dinitrobenzoic acid Chemical class OC(=O)C1=CC=C([N+]([O-])=O)C([N+]([O-])=O)=C1O WDMUXYQIMRDWRC-UHFFFAOYSA-N 0.000 description 1
- MRBKRZAPGUCWOS-UHFFFAOYSA-N 3-amino-4-hydroxybenzoic acid Chemical class NC1=CC(C(O)=O)=CC=C1O MRBKRZAPGUCWOS-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- RBXVOQPAMPBADW-UHFFFAOYSA-N nitrous acid;phenol Chemical class ON=O.OC1=CC=CC=C1 RBXVOQPAMPBADW-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
Definitions
- ABSTRACT A process for preparing 4-hydroxy-3 nitrobenzoic acid alkyl esters by nitration of 4-hydroxybenzoic acid alkyl esters with nitric acid, wherein nitration is carried out at about 0 to 60C with the aid of nitric acid having a strength of 30 to 62 which process represents a considerable improvement of the yield and wherein pure products are obtained.
- the present invention relates to an improved process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters, especially of the alkyl esters which contain 1 to 4 carbon atoms in the alkyl group, by nitration of the corresponding 4-hydroxy-benzoic acid alkyl esters with nitric acid. These compounds are suitable as intermediates for the preparation of optical brighteners or dyestuffs.
- 4-hydroxy-3-nitrobenzoic acid alkyl esters are obtained in a simple way and with excellent yeilds by nitration of 4-hydroxy-benzoic acid alkyl esters with nitric acid, if nitration is carried out at about 0 to 60C, preferably at about to 30C, by means of nitric acid having a strength of 30 to 62% by weight.
- the process is expediently carried out by introducing steadily the 4-hydroxy-benzoic acid alkyl ester, also possibly in form of a moist good, at about 20 to C into concentrated nitric acid and maintaining the temperature by external cooling at about 20 to 60C, preferably at about 20 to C. After stirring for one hour, the whole is diluted with water, suctionfiltered, washed until neutral and dried.
- the process claimed which is particularly suitable for preparing the lower alkyl esters, such as the methyl, ethyl, propyl or butyl ester of the 4- hydroxy-benzoic acid, a considerable improvement of the yield as well as pure products are obtained which are free from the initial ester and the impurities which are found, without exceptions, in the known processes as by-products such, for example, as dinitro-hydroxybenzoic acid esters, nitrophenols or polynitrophenols formed by saponification and decarboxylation processes. Therefore, the compounds obtained according to the process of the invention, can be used directly for further reactions, for example subjected to catalytical hydrogenation to give 4-hydroxy-3-aminobenzoic acid esters, without a previous purification being required.
- the lower alkyl esters such as the methyl, ethyl, propyl or butyl ester of the 4- hydroxy-benzoic acid
- the present process makes possible a simplified and less expensive preparation of 4-hydroxy-3-nitro-benzoic acid alkyl esters without using organic solvents and without any further purification processes and represents, thus, an essential addition to technical development.
- the following Examples serve to illustrate the process.
- EXAMPLE 1 183.8 Parts by weight of a moist 4-hydroxybenzoic acid methyl ester having a degree of purity of 82.7% (prepared by esterification of 4-hydroxybenzoic acid with dimethyl sulfate at a pH-value of 5) were steadily introduced, in the course of one hour, while stirring at 20-25C, into 304 parts by weight of a 62% nitric acid. The whole was stirred for about one hour, the ester was precipitated by addition of 300 parts of water, suctionfiltered, washed with water until neutral and dried at 60C. 177.3 Parts by weight of 3-nitro-4-hydroxy-benzoic acid methyl ester having a degree of purity of greater than 99% and a melting point of 73C were obtained which corresponds to a yield of of thecry.
- a process for preparing a pure 4-hydroxy-3- nitrobenzoic acid alkyl ester by nitration of 4-hydroxybenzoic acid alkyl esters with nitric acid wherein nitration is carried out at about 0 to 60C with the aid of nitric acid having a strength of 30 to 62%.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters by nitration of 4-hydroxybenzoic acid alkyl esters with nitric acid, wherein nitration is carried out at about 0 to 60*C with the aid of nitric acid having a strength of 30 to 62 %, which process represents a considerable improvement of the yield and wherein pure products are obtained.
Description
United States Patent Papent'uss PROCESS FOR PREPARING 4-HYDROXY-3-NITROBENZOIC ACID ALKYL ESTERS Theodor Papenfuss, Frankfurt am Main, Germany Hoechst Aktiengesellschaft, Frankfurt, Germany Filed: Aug. 27, 1973 Appl. No.: 392,097
Inventor:
Assignee:
References Cited UNITED STATES PATENTS 5/1970 Prosser 260/471 R 3,636,037 1/1972 Do'nninger et al. 260/471 R Primary Examiner-Lorraine A. Weinberger Assistant ExaminerL. A. Thaxton Attorney, Agent, or Firm-Connolly and Hutz [57] ABSTRACT A process for preparing 4-hydroxy-3 nitrobenzoic acid alkyl esters by nitration of 4-hydroxybenzoic acid alkyl esters with nitric acid, wherein nitration is carried out at about 0 to 60C with the aid of nitric acid having a strength of 30 to 62 which process represents a considerable improvement of the yield and wherein pure products are obtained.
3 Claims, No Drawings PROCESS FOR PREPARING 4-HYDROXY-3-NITROBENZOIC ACID ALKYL ESTERS The present invention relates to an improved process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters, especially of the alkyl esters which contain 1 to 4 carbon atoms in the alkyl group, by nitration of the corresponding 4-hydroxy-benzoic acid alkyl esters with nitric acid. These compounds are suitable as intermediates for the preparation of optical brighteners or dyestuffs.
It is known that by treating 4-hydroxy-benzoic acid alkyl esters with diluted, about nitric acid at an elevated temperature, for example at the temperature of water baths, 4-hydroxy-3-nitrobenzoic acid alkyl esters are obtained (cf. Berichte der Deutschen Chemischen Gesellschaft Vol. 30, p. 991 (1897), and Journal fur praktische Chemie [2] 43, p. 453 1891 However, according to this process, impure 4- hydroxy-3-nitrobenzoic acid esters are obtained which have to be subjected to a subsequent purification pro- -cess. Furthermore, by treating 4-hydroxybenzoic acid methyl ester with fuming nitric acid in glacial acetic acid at 45C, the 4-hydroxy-3-nitrobenzoic acid methyl ester is obtained in a yield of 68% (cf. US. Pat. No. 2,647,053). However, this process is not satisfying, neither with regard to yield nor to purity. Furthermore, when the process is carried out on an industrial scale, working with glacial acetic acid causes problems with regard to regeneration and purification of the waste water.
It has now been found that 4-hydroxy-3-nitrobenzoic acid alkyl esters are obtained in a simple way and with excellent yeilds by nitration of 4-hydroxy-benzoic acid alkyl esters with nitric acid, if nitration is carried out at about 0 to 60C, preferably at about to 30C, by means of nitric acid having a strength of 30 to 62% by weight.
The process is expediently carried out by introducing steadily the 4-hydroxy-benzoic acid alkyl ester, also possibly in form of a moist good, at about 20 to C into concentrated nitric acid and maintaining the temperature by external cooling at about 20 to 60C, preferably at about 20 to C. After stirring for one hour, the whole is diluted with water, suctionfiltered, washed until neutral and dried.
According to the process claimed, which is particularly suitable for preparing the lower alkyl esters, such as the methyl, ethyl, propyl or butyl ester of the 4- hydroxy-benzoic acid, a considerable improvement of the yield as well as pure products are obtained which are free from the initial ester and the impurities which are found, without exceptions, in the known processes as by-products such, for example, as dinitro-hydroxybenzoic acid esters, nitrophenols or polynitrophenols formed by saponification and decarboxylation processes. Therefore, the compounds obtained according to the process of the invention, can be used directly for further reactions, for example subjected to catalytical hydrogenation to give 4-hydroxy-3-aminobenzoic acid esters, without a previous purification being required.
The present process makes possible a simplified and less expensive preparation of 4-hydroxy-3-nitro-benzoic acid alkyl esters without using organic solvents and without any further purification processes and represents, thus, an essential addition to technical development. The following Examples serve to illustrate the process.
EXAMPLE 1 183.8 Parts by weight of a moist 4-hydroxybenzoic acid methyl ester having a degree of purity of 82.7% (prepared by esterification of 4-hydroxybenzoic acid with dimethyl sulfate at a pH-value of 5) were steadily introduced, in the course of one hour, while stirring at 20-25C, into 304 parts by weight of a 62% nitric acid. The whole was stirred for about one hour, the ester was precipitated by addition of 300 parts of water, suctionfiltered, washed with water until neutral and dried at 60C. 177.3 Parts by weight of 3-nitro-4-hydroxy-benzoic acid methyl ester having a degree of purity of greater than 99% and a melting point of 73C were obtained which corresponds to a yield of of thecry.
The following compounds listed in the Table l were prepared in analogy to Example 1.
1. A process for preparing a pure 4-hydroxy-3- nitrobenzoic acid alkyl ester by nitration of 4-hydroxybenzoic acid alkyl esters with nitric acid, wherein nitration is carried out at about 0 to 60C with the aid of nitric acid having a strength of 30 to 62%.
2. A process as claimed in claim 1, which is conducted at a temperature of from about 20 to 30C.
3. A process as claimed in claim 1, wherein 4- hydroxy-benzoic acid alkyl ester having 1 to 4 carbon atoms in the alkyl radicals, are prepared.
Claims (3)
1. A PROCESS FOR PREPARING A PURE 4-HYDROXY-3-NITROBENZOIC ACID ALKYL ESTER BY NITRATION OF 4-HYDROXYBENZOIC ACID ALKYL ESTERS WITH NITRIC ACID, WHEREIN NITRATION IS CARRIED OUT AT ABOUT 0* TO 60*C WITH THE AID OF NITRIC ACID HAVING A STRENGTH OF 30 TO 62%.
2. A process as claimed in claim 1, which is conducted at a temperature of from about 20* to 30*C.
3. A process as claimed in claim 1, wherein 4-hydroxy-benzoic acid alkyl ester having 1 to 4 carbon atoms in the alkyl radicals, are prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US392097A US3929864A (en) | 1973-08-27 | 1973-08-27 | Process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US392097A US3929864A (en) | 1973-08-27 | 1973-08-27 | Process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3929864A true US3929864A (en) | 1975-12-30 |
Family
ID=23549239
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US392097A Expired - Lifetime US3929864A (en) | 1973-08-27 | 1973-08-27 | Process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3929864A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206635A1 (en) | 1985-06-26 | 1986-12-30 | The Dow Chemical Company | Preparation of 3-amino-4-hydroxybenzoic acids |
| US4835306A (en) * | 1986-02-10 | 1989-05-30 | The Dow Chemical Company | Preparation of 3-amino-4-hydroxybenzoic acids |
| US4959492A (en) * | 1989-07-14 | 1990-09-25 | The Dow Chemical Company | Process to synthesize AB-PBO monomer and phosphate salts thereof |
| US5068384A (en) * | 1989-07-14 | 1991-11-26 | The Dow Chemical Company | Phosphate salts of AB-polybenzoxazole monomer |
| US5380345A (en) * | 1993-12-03 | 1995-01-10 | Chevron Research And Technology Company | Polyalkyl nitro and amino aromatic esters and fuel compositions containing the same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3510527A (en) * | 1967-05-18 | 1970-05-05 | Hercules Inc | Preparation of p-nitrophenols |
| US3636037A (en) * | 1968-06-04 | 1972-01-18 | Shell Oil Co | Carbonic esters of 4-nitrophenol |
-
1973
- 1973-08-27 US US392097A patent/US3929864A/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3510527A (en) * | 1967-05-18 | 1970-05-05 | Hercules Inc | Preparation of p-nitrophenols |
| US3636037A (en) * | 1968-06-04 | 1972-01-18 | Shell Oil Co | Carbonic esters of 4-nitrophenol |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0206635A1 (en) | 1985-06-26 | 1986-12-30 | The Dow Chemical Company | Preparation of 3-amino-4-hydroxybenzoic acids |
| JPS6212750A (en) * | 1985-06-26 | 1987-01-21 | ザ ダウ ケミカル カンパニ− | Method for producing 3-amino-4-hydroxybenzoic acid |
| JPH0811745B2 (en) | 1985-06-26 | 1996-02-07 | ザ ダウ ケミカル カンパニ− | Method for producing 3-amino-4-hydroxybenzoic acid |
| US4835306A (en) * | 1986-02-10 | 1989-05-30 | The Dow Chemical Company | Preparation of 3-amino-4-hydroxybenzoic acids |
| US4959492A (en) * | 1989-07-14 | 1990-09-25 | The Dow Chemical Company | Process to synthesize AB-PBO monomer and phosphate salts thereof |
| WO1991001304A1 (en) * | 1989-07-14 | 1991-02-07 | The Dow Chemical Company | Process to synthesize ab-pbo monomer and phosphate salts thereof |
| US5068384A (en) * | 1989-07-14 | 1991-11-26 | The Dow Chemical Company | Phosphate salts of AB-polybenzoxazole monomer |
| US5380345A (en) * | 1993-12-03 | 1995-01-10 | Chevron Research And Technology Company | Polyalkyl nitro and amino aromatic esters and fuel compositions containing the same |
| WO1995015366A1 (en) * | 1993-12-03 | 1995-06-08 | Chevron Chemical Company | Polyalkyl nitro and amino aromatic esters and fuel compositions containing the same |
| AU690183B2 (en) * | 1993-12-03 | 1998-04-23 | Chevron Chemical Company | Polyalkyl nitro and amino aromatic esters and fuel compositions containing the same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3929864A (en) | Process for preparing 4-hydroxy-3-nitrobenzoic acid alkyl esters | |
| US3890376A (en) | Process for the manufacture of perfluoroalkyl esters | |
| DE2258985C2 (en) | Process for the preparation of 2- (3-benzoylphenyl) propionic acid | |
| US2447998A (en) | Preparation of substituted acylanilides | |
| US4159991A (en) | Acyloxy-N,N'-diacylmalonamides and methods for their preparation | |
| EP0665212B1 (en) | Process for the preparation of 2,4,6-trimethylphenylacetic acid | |
| US4506089A (en) | Preparation of methyl m-nitrobenzoate | |
| US3739009A (en) | Production of aromatic o-aminonitriles | |
| EP0348464B1 (en) | 2-neopentylanthraquinone | |
| JPH05194341A (en) | Process for producing alkyl 3-chloroanthranilate | |
| US2394520A (en) | Nitriles and method of making the same | |
| DE2517918C3 (en) | Process for the preparation of 1,4-diaminoanthraquinone-2-carboxylic acid esters | |
| DE69426006T2 (en) | Process for the preparation of cephalosporins | |
| US3862209A (en) | Process of making nitro phenoxybenzoic acid esters | |
| EP0397048B1 (en) | Process for the preparation of 2-mercapto-4-methyl-1,3-thiazol-5-yl acetic acid and its esters | |
| CH390271A (en) | Process for the preparation of diarylaminoaromatic dicarboxylic acids | |
| US3274261A (en) | Process of producing ortho-formic acid methyl ester | |
| US2052881A (en) | Purification of alcohols | |
| US3492337A (en) | Process for the preparation of alkyl 4-ketoalkanoates | |
| EP0498847A1 (en) | PROCESS FOR PRODUCING 1,4-bis-(4-HYDROXYBENZOYL)BENZOL. | |
| US2339789A (en) | Process for producing beta-(1-naphthoyl) propionic acid | |
| DE2242512C3 (en) | Process for the preparation of 4-hydroxy-3-nitrobenzoic acid alkyl esters | |
| US3884943A (en) | Preparation and separation of 1,5- and 1,8-dihydroxyanthraquinone | |
| US3836546A (en) | Process for the production of 1-nitroanthraquinones | |
| US3652648A (en) | Production of 4 5-benztropone-2 7-dicarboxylic esters |