WO1991011422A1 - Verfahren zur herstellung von 2-hydroxy-naphthalin-6-carbonsäure - Google Patents
Verfahren zur herstellung von 2-hydroxy-naphthalin-6-carbonsäure Download PDFInfo
- Publication number
- WO1991011422A1 WO1991011422A1 PCT/EP1991/000132 EP9100132W WO9111422A1 WO 1991011422 A1 WO1991011422 A1 WO 1991011422A1 EP 9100132 W EP9100132 W EP 9100132W WO 9111422 A1 WO9111422 A1 WO 9111422A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carboxylic acid
- potassium
- naphthalene
- hydroxy
- reaction
- Prior art date
Links
- KAUQJMHLAFIZDU-UHFFFAOYSA-N 6-Hydroxy-2-naphthoic acid Chemical compound C1=C(O)C=CC2=CC(C(=O)O)=CC=C21 KAUQJMHLAFIZDU-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000000034 method Methods 0.000 title claims description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 16
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims abstract description 15
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 8
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical class [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims abstract 3
- 238000006243 chemical reaction Methods 0.000 claims description 18
- NIXTUUCERQXALH-UHFFFAOYSA-M potassium;naphthalen-2-olate Chemical compound [K+].C1=CC=CC2=CC([O-])=CC=C21 NIXTUUCERQXALH-UHFFFAOYSA-M 0.000 claims description 13
- 239000003085 diluting agent Substances 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- ALKYHXVLJMQRLQ-UHFFFAOYSA-N 3-Hydroxy-2-naphthoate Chemical compound C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 ALKYHXVLJMQRLQ-UHFFFAOYSA-N 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract 1
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- -1 naphthol carboxylic acid Chemical class 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- TVBXXOVRWRDFMB-UHFFFAOYSA-N 3-hydroxynaphthalene-2,7-dicarboxylic acid Chemical compound C1=C(O)C(C(O)=O)=CC2=CC(C(=O)O)=CC=C21 TVBXXOVRWRDFMB-UHFFFAOYSA-N 0.000 description 1
- GHCWEHSPPCKWPM-UHFFFAOYSA-N 3-hydroxynaphthalene-2-carboxylic acid;potassium Chemical compound [K].[K].C1=CC=C2C=C(O)C(C(=O)O)=CC2=C1 GHCWEHSPPCKWPM-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 238000007065 Kolbe-Schmitt synthesis reaction Methods 0.000 description 1
- OIHCDFMMWBYGJN-UHFFFAOYSA-N OC1=CC2=CC=C(C=C2C=C1)C(=O)O.[K].[K] Chemical compound OC1=CC2=CC=C(C=C2C=C1)C(=O)O.[K].[K] OIHCDFMMWBYGJN-UHFFFAOYSA-N 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
Definitions
- the present invention is in the technical field of intermediates which can be used, for example, for the synthesis of azo dyes and polyester base materials.
- 2-Hydroxy-naphthalene-6-carboxylic acid is not only a valuable synthetic building block for pharmaceuticals, textile auxiliaries and dyes (see, for example, European Patent Application Publication No. 0 292 955A), but in particular also an important monomer for the production of liquid-crystalline high-performance plastics and fibers with superior properties (see U.S. Patent 4,393,191).
- Schmitt reaction ie by reacting the potassium salt of ⁇ -naphthol with carbon dioxide under pressure at 200-300 ° C (see, for example, US Pat. Nos. 1,593,816, 4,329,494 and 4,287,357).
- the procedures described in these publications have some technical disadvantages; this gives rise to considerable proportions of decomposition products, such as tars and resins, which, like the 2-hydroxy-naphthalene-3-carboxylic acid and 2-hydroxy-naphthalene-3,6-dicarboxylic acid formed in side reactions, are difficult to separate off.
- the formate serving as solvent (diluent) is used in at least the same molar amount as the potassium ⁇ -naphtholate starting product; the amount of potassium formate used is not critical and can vary within wide limits. However, it is advantageous to use potassium formate in a larger amount as a solvent (diluent), for example in 2.5 to 18 times, preferably in 6 to 15 times, the amount by weight of the potassium ⁇ -naphtholate used, by one the best possible mixing of the reactants dissolved in potassium formate potassium- ⁇ -naphtholate and potassium carbonate and the gaseous
- the potassium formate used as a solvent (diluent) not only brings about a high selectivity of the reaction with the formation of the potassium salt of 2-hydroxy-naphthalene-6-carboxylic acid, but it also has the advantage that it is not a foreign product in the reaction mixture, but is identical to the by-product of the implementation.
- the potassium formate can therefore be completely replaced in later Reactions are used, or else carbon monoxide is obtained from the excess of this product by heating with concentrated sulfuric acid, which can be recycled into a later reaction.
- the potassium carbonate likewise used in the process according to the invention is used in the reaction in at least the same molar amount as the potassium ⁇ -naphtholate.
- the molar ratio of potassium ⁇ -naphtholate to potassium carbonate is between 1: 1 and 1: 1.5.
- the batch can be worked up in various ways and the 2-naphthol-6-carboxylic acid formed is isolated.
- One way is that
- the fine cleaning is carried out analogously to known procedures, for example by pressure redissolving in water or by cleaning with 1,4-dioxane (see, for example, German Offenlegungsschrift 38 00 989).
- the reaction mixture is then cooled, the autoclave is depressurized, the reaction product is dissolved in water, the pH is adjusted to 7 with concentrated sulfuric acid, and the precipitated, unreacted ⁇ -naphthol is filtered off, and the filtrate is adjusted to a pH of 1 using sulfuric acid and the now precipitated 2-hydroxy-naphthalene-6-carboxylic acid is isolated.
- the 2-naphthol-6-carboxylic acid can be separated from the by-products from the crude product in a conventional manner and thus be obtained in pure form. Yield: 34% of theory, based on the ⁇ -naphthol as
- Example 1 The procedure of Example 1 is followed, with the difference that the reaction is carried out at 300 ° C. and with 125 parts of potassium formate. You get that
- EXAMPLE 3 The procedure described in the examples above is carried out at a carbon monoxide pressure of 100 bar and a temperature of 320 ° C. for about 5 hours Use of 10 parts of potassium ⁇ -naphtholate, 7, 6 parts of potassium carbonate and 75 parts of potassium formate. After working up the reaction mixture, 2-hydroxy-naphthalene-6-carboxylic acid is obtained in a yield of 37.5% of theory. Th. in addition to 5.7% 2-naphthol-3-carboxylic acid.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE59103290T DE59103290D1 (de) | 1990-02-02 | 1991-01-24 | Verfahren zur herstellung von 2-hydroxy-naphthalin-6-carbonsäure. |
| EP91902673A EP0513053B1 (de) | 1990-02-02 | 1991-01-24 | Verfahren zur herstellung von 2-hydroxy-naphthalin-6-carbonsäure |
| US07/917,049 US5312976A (en) | 1990-02-02 | 1991-01-24 | Process for the preparation of 2-hydroxy-naphthalene-6-carboxylic acid |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4003043.1 | 1990-02-02 | ||
| DE4003043A DE4003043A1 (de) | 1990-02-02 | 1990-02-02 | Verfahren zur herstellung von 2-hydroxy-naphthalin-6-carbonsaeure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1991011422A1 true WO1991011422A1 (de) | 1991-08-08 |
Family
ID=6399256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/EP1991/000132 WO1991011422A1 (de) | 1990-02-02 | 1991-01-24 | Verfahren zur herstellung von 2-hydroxy-naphthalin-6-carbonsäure |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US5312976A (OSRAM) |
| EP (1) | EP0513053B1 (OSRAM) |
| JP (1) | JPH05504346A (OSRAM) |
| CA (1) | CA2075197A1 (OSRAM) |
| DE (2) | DE4003043A1 (OSRAM) |
| IN (1) | IN170980B (OSRAM) |
| WO (1) | WO1991011422A1 (OSRAM) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643494A (en) * | 1993-05-21 | 1997-07-01 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic hydroxy carboxylic acids |
| US5808142A (en) * | 1993-05-21 | 1998-09-15 | Hoechst Aktiengesellschaft | Process for the preparation of 2-hydroxynaphthalene-6-carboxylic acid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3197905B2 (ja) * | 1996-10-21 | 2001-08-13 | 株式会社上野製薬応用研究所 | ２―ヒドロキシナフタレン―３，６―ジカルボン酸の製造方法 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE955599C (de) * | 1955-05-15 | 1957-01-03 | Fabricacion Nac De Colorantes | Verfahren zur Herstellung von 2-Oxynaphthalin-3-carbonsaeure |
| US3769326A (en) * | 1971-03-26 | 1973-10-30 | Monsanto Co | Production of carboxylic acids and esters |
| US4345094A (en) * | 1980-03-06 | 1982-08-17 | American Cyanamid Company | Process for the production of 6-hydroxy-2-naphthoic acid |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1593816A (en) * | 1924-08-16 | 1926-07-27 | Grasselli Dyestuffs Corp | Making 2-hydroxy-naphthalene-6-carboxylic acid |
| DE1643537B2 (de) * | 1966-08-16 | 1976-09-16 | Toray Industries, Inc., Tokio | Verfahren zur herstellung von metallsalzen aromatischer hydroxycarbonsaeuren oder deren freie saeuren |
| US4287357A (en) * | 1980-03-06 | 1981-09-01 | American Cyanamid Company | Process for the production of 6-hydroxy-2-naphthoic acid |
| US4345095A (en) * | 1980-03-06 | 1982-08-17 | American Cyanamid Company | Process for the production of 6-hydroxy-2-naphthoic acid |
| US4329494A (en) * | 1981-07-22 | 1982-05-11 | American Cyanamid Company | Recycling techniques in the production of 6-hydroxy-2-naphthoic acid |
-
1990
- 1990-02-02 DE DE4003043A patent/DE4003043A1/de not_active Withdrawn
-
1991
- 1991-01-22 IN IN61/CAL/91A patent/IN170980B/en unknown
- 1991-01-24 US US07/917,049 patent/US5312976A/en not_active Expired - Fee Related
- 1991-01-24 WO PCT/EP1991/000132 patent/WO1991011422A1/de active IP Right Grant
- 1991-01-24 JP JP3502541A patent/JPH05504346A/ja active Pending
- 1991-01-24 EP EP91902673A patent/EP0513053B1/de not_active Expired - Lifetime
- 1991-01-24 CA CA002075197A patent/CA2075197A1/en not_active Abandoned
- 1991-01-24 DE DE59103290T patent/DE59103290D1/de not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE955599C (de) * | 1955-05-15 | 1957-01-03 | Fabricacion Nac De Colorantes | Verfahren zur Herstellung von 2-Oxynaphthalin-3-carbonsaeure |
| US3769326A (en) * | 1971-03-26 | 1973-10-30 | Monsanto Co | Production of carboxylic acids and esters |
| US4345094A (en) * | 1980-03-06 | 1982-08-17 | American Cyanamid Company | Process for the production of 6-hydroxy-2-naphthoic acid |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5643494A (en) * | 1993-05-21 | 1997-07-01 | Hoechst Aktiengesellschaft | Process for the preparation of aromatic hydroxy carboxylic acids |
| US5808142A (en) * | 1993-05-21 | 1998-09-15 | Hoechst Aktiengesellschaft | Process for the preparation of 2-hydroxynaphthalene-6-carboxylic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| US5312976A (en) | 1994-05-17 |
| CA2075197A1 (en) | 1991-08-03 |
| IN170980B (OSRAM) | 1992-06-27 |
| JPH05504346A (ja) | 1993-07-08 |
| DE4003043A1 (de) | 1991-08-08 |
| DE59103290D1 (de) | 1994-11-24 |
| EP0513053B1 (de) | 1994-10-19 |
| EP0513053A1 (de) | 1992-11-19 |
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