CH346558A - Process for the production of new intermediate products of the naphthalene series - Google Patents
Process for the production of new intermediate products of the naphthalene seriesInfo
- Publication number
- CH346558A CH346558A CH346558DA CH346558A CH 346558 A CH346558 A CH 346558A CH 346558D A CH346558D A CH 346558DA CH 346558 A CH346558 A CH 346558A
- Authority
- CH
- Switzerland
- Prior art keywords
- formula
- hydroxy
- naphthalene
- parts
- production
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- 239000013067 intermediate product Substances 0.000 title claims description 3
- 150000002790 naphthalenes Chemical class 0.000 title description 3
- 238000004519 manufacturing process Methods 0.000 title description 2
- HMNPDEGBVWDHAR-UHFFFAOYSA-N 8-aminonaphthalen-1-ol Chemical compound C1=CC(O)=C2C(N)=CC=CC2=C1 HMNPDEGBVWDHAR-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000008707 rearrangement Effects 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000007513 acids Chemical class 0.000 claims description 3
- XMZQTLHPSDAPBB-UHFFFAOYSA-N 2-chloro-n-(8-hydroxynaphthalen-1-yl)acetamide Chemical compound C1=CC(NC(=O)CCl)=C2C(O)=CC=CC2=C1 XMZQTLHPSDAPBB-UHFFFAOYSA-N 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims 1
- 239000002609 medium Substances 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- -1 fatty acid halides Chemical class 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- FECNOIODIVNEKI-UHFFFAOYSA-N 2-[(2-aminobenzoyl)amino]benzoic acid Chemical class NC1=CC=CC=C1C(=O)NC1=CC=CC=C1C(O)=O FECNOIODIVNEKI-UHFFFAOYSA-N 0.000 description 1
- PUPDISBRKNJGKV-UHFFFAOYSA-N 4-[(2-chloroacetyl)amino]-5-hydroxynaphthalene-2,7-disulfonic acid Chemical compound OS(=O)(=O)C1=CC(NC(=O)CCl)=C2C(O)=CC(S(O)(=O)=O)=CC2=C1 PUPDISBRKNJGKV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical class [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical group 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/45—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton
- C07C309/49—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms
- C07C309/50—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing nitrogen atoms, not being part of nitro or nitroso groups, bound to the carbon skeleton the carbon skeleton being further substituted by singly-bound oxygen atoms having at least one of the sulfo groups bound to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung neuer Zwischenprodukte der Naphthalinreihe
Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung wertvoller 1 -Carboxyalk- oxy-8-amino-naphthaline oder deren Mono- oder Disulfonsäuren, welches dadurch gekennzeichnet ist, dass man Abkömmlinge des 1-Hydroxy-8-aminonaphthalins der Formel
EMI1.1
worin n die Zahl 0, 1 oder 2, X ein Halogenatom und R einen aliphatischen Kohlenwasserstoffrest bedeuten, mit alkalischen Mitteln behandelt.
Die als Ausgangsstoffe verwendeten Abkömmlinge des 1-Hydroxy-8-amino-naphthalins der Formel (II) lassen sich durch Acylieren des l-Hydroxy-8amino-naphthalins selbst oder dessen Mono- oder Disulfonsäuren mit Halogenfettsäurehalogeniden, vorzugsweise mit dem Chloracetylchlorid, herstellen.
Die Behandlung der Abkömmlinge des 1 -Hy- droxy-8-amino-naphthalins der Formel (II) mit alkalischen Mitteln bewirkt deren Umlagerung in 1 -Carb- oxyalkoxy-8- amino- naphthalinverbindungen. Diese Umlagerung erfolgt vermutlich stufenweise über einen inneren Acylaminoäther der Formel
EMI1.2
worin n und R die obengenannten Bedeutungen besitzen. In einigen Fällen gelingt es, diesen inneren Acylaminoäther, der weder diazotierbar noch kupplungsfähig ist, zu isolieren.
Die erste Stufe, die Cyclisierung, erfolgt schon in schwach alkalischer Lösung bei pE-Werten von 7,5 bis 10 und bei Temperaturen von 20 bis 100 C. Als alkalische Mittel eignen sich zum Beispiel Alkali metallhydroxyde, -carbonate, -bicarbonate und -borate, Erdalkalimetalloxyde, -hydroxyde und -carbo- nate, die sekundären und tertiären Phosphate der Alkali- und Erdalkalimetalle sowie Ammoniak und organische Basen, vorzugsweise jedoch Natrium- oder Kaliumbicarbonat.
Für die zweite Reaktionsstufe, die Aufspaltung der -CO-NH-Bindung, ist im allgemeinen eine stärkere Alkalinität als in der ersten Stufe nötig.
Dazu verwendet man beispielsweise ein Alkali- oder Erdalkalimetallhydroxyd, vorzugsweise Natrium- oder Kaliumhydroxyd, ein Alkalimetallcarbonat im Über- schuss über die stöchiometrische Menge oder auch eine starke organische Base.
Als Lösungs- oder Verdünnungsmittel für die beiden Stufen der Umlagerung kommen zum Beispiel Alkohole, Äther, Ätheralkohole, Ketone, tertiäre Amine sowie wässerig-organische Gemische und ganz besonders Wasser in Betracht.
Die neuen Zwischenprodukte der Naphthalinreihe lassen sich leicht diazotieren; ihre Diazoverbindungen kuppeln mit den verschiedensten Azokomponenten zu Farbstoffen oder Farbstoffzwischenprodukten.
In den folgenden Beispielen bedeuten die Teile Gewichtsteile, die Prozente Gewichtsprozente. Die Temperaturen sind in Celsiusgraden angegeben.
Beispiel 1
39,6 Teile 1 -Hydroxy- 8-chloracetylamino-naph- thalin-3,6-disulfonsäure werden in 300 Teilen Was ser und 11 Teilen wasserfreier Soda bei 60700 gelöst. Nun versetzt man die Lösung mit 14 Teilen Natriumbicarbonat und erwärmt sie während 20 Minuten auf 950. Der p-Wert liegt zwischen 7,5 und 8,5. Anschliessend giesst man in die Lösung 21 Teile 300/oiger Natronlauge und erwärmt diese während weiteren 60 Minuten auf 950. Hierauf kühlt man das Reaktionsgemisch auf Zimmertemperatur, versetzt es mit so viel 360/obiger Salzsäure, dass eine Probe auf Kongopapier deutliche Blaufärbung erzeugt, und kühlt es unter Rühren auf 2-5" ab.
Dabei kristallisiert das Mononatriumsalz der 1-Carboxymethoxy-8amino-naphthalin-3,6-disulfonsäure aus; es wird abfiltriert und getrocknet. Die neue Verbindung ist ein hellgraues Pulver, das sich diazotieren lässt.
Beispiel 2
Man versetzt die Lösung aus 31,6 Teilen 1-Hy droxy-8- chloracetylamino- naphthalin-5-sulfonsäure, 500 Teilen Wasser und 13,5 Teilen 300/obiger Natronlauge mit 15 Teilen Natriumbicarbonat, erwärmt sie auf 90o und rührt sie noch während 30 Minuten bei dieser Temperatur. Anschliessend lässt man sie unter Rühren erkalten. Das dabei auskristallisierte Reaktionsprodukt, dem vermutlich die Formel
EMI2.1
zukommt, wird durch Abnutschen isoliert.
Man suspendiert die feuchte Paste in 195 Teilen 1 /oiger Natronlauge und erwärmt das Ganze auf 800, wobei klare Lösung eintritt. Man rührt die Lösung 30 Minuten lang bei 80 , kühlt sie dann auf 600 ab und versetzt sie mit 16 Teilen Kochsalz.
Das schön kristallin ausgefällte Natriumsalz der 1 Carboxymethoxy -8- amino-naphthalin -5- sulfonsäure wird in der Kälte abgesaugt, gewaschen und getrocknet. Die neue Verbindung ist schwach grau gefärbt und lässt sich auf übliche Art diazotieren.
Beispiel 3
23 Teile 1 -Hydroxy- 8-chloracetylamino-naphtha- lin werden in 700 Teilen 20/oiger Natriumbicarbonatlösung angerührt. Man erwärmt die Suspension in nerhalb von 15 Minuten auf 900, rührt sie während 45 Minuten bei 90o und versetzt sie dann mit 236 Teilen 300/oiger Natronlauge. Es entsteht nach kurzer Zeit eine klare Lösung, die während weiteren 25 Minuten bei 90o gerührt wird. Anschliessend lässt man die Lösung unter Rühren erkalten, kühlt sie noch auf 50 ab, saugt das abgeschiedene Natriumsalz des 1-Carboxy-methoxy-8-amino-naphthalins ab und trocknet es. Es ist ein heligraues, in Wasser klar lösliches Pulver, welches sich auf übliche Art diazotieren lässt.
Process for the production of new intermediate products of the naphthalene series
The present invention relates to a process for the preparation of valuable 1-carboxyalkoxy-8-amino-naphthalenes or their mono- or disulphonic acids, which is characterized in that derivatives of 1-hydroxy-8-aminonaphthalene of the formula
EMI1.1
where n is the number 0, 1 or 2, X is a halogen atom and R is an aliphatic hydrocarbon radical, treated with alkaline agents.
The derivatives of the 1-hydroxy-8-amino-naphthalene of the formula (II) used as starting materials can be prepared by acylating the l-hydroxy-8-amino-naphthalene itself or its mono- or disulphonic acids with halogenated fatty acid halides, preferably with the chloroacetyl chloride.
Treatment of the derivatives of 1-hydroxy-8-aminonaphthalene of the formula (II) with alkaline agents causes them to be rearranged into 1-carboxyalkoxy-8-aminonaphthalene compounds. This rearrangement probably takes place in stages via an internal acylamino ether of the formula
EMI1.2
wherein n and R have the meanings given above. In some cases it is possible to isolate this inner acylamino ether, which is neither diazotizable nor capable of coupling.
The first stage, the cyclization, takes place in a weakly alkaline solution at pE values of 7.5 to 10 and at temperatures of 20 to 100 C. Suitable alkaline agents are, for example, alkali metal hydroxides, carbonates, bicarbonates and borates , Alkaline earth metal oxides, hydroxides and carbonates, the secondary and tertiary phosphates of the alkali and alkaline earth metals, and ammonia and organic bases, but preferably sodium or potassium bicarbonate.
For the second reaction stage, the cleavage of the —CO — NH bond, a stronger alkalinity is generally required than in the first stage.
For this purpose, for example, an alkali or alkaline earth metal hydroxide, preferably sodium or potassium hydroxide, an alkali metal carbonate in excess of the stoichiometric amount or a strong organic base is used.
Suitable solvents or diluents for the two stages of the rearrangement are, for example, alcohols, ethers, ether alcohols, ketones, tertiary amines, and aqueous-organic mixtures and very particularly water.
The new intermediates of the naphthalene series can be easily diazotized; their diazo compounds couple with a wide variety of azo components to form dyes or dye intermediates.
In the following examples, the parts are parts by weight and the percentages are percentages by weight. The temperatures are given in degrees Celsius.
example 1
39.6 parts of 1-hydroxy-8-chloroacetylamino-naphthalene-3,6-disulfonic acid are dissolved in 300 parts of water and 11 parts of anhydrous soda at 60700. The solution is then mixed with 14 parts of sodium bicarbonate and heated to 950 for 20 minutes. The p-value is between 7.5 and 8.5. Subsequently, 21 parts of 300% sodium hydroxide solution are poured into the solution and heated to 950 for a further 60 minutes. The reaction mixture is then cooled to room temperature, and so much 360% of the above hydrochloric acid is added that a sample on Congo paper produces a clear blue color, and cool it down to 2-5 "while stirring.
The monosodium salt of 1-carboxymethoxy-8amino-naphthalene-3,6-disulfonic acid crystallizes out; it is filtered off and dried. The new compound is a light gray powder that can be diazotized.
Example 2
The solution of 31.6 parts of 1-hydroxy-8-chloroacetylamino-naphthalene-5-sulfonic acid, 500 parts of water and 13.5 parts of 300 / above sodium hydroxide solution is mixed with 15 parts of sodium bicarbonate, heated to 90o and stirred while it is still 30 minutes at this temperature. They are then left to cool while stirring. The reaction product which crystallized out in the process, presumably the formula
EMI2.1
is isolated by suction.
The moist paste is suspended in 195 parts of 1 / o sodium hydroxide solution and the whole is heated to 800, during which a clear solution occurs. The solution is stirred for 30 minutes at 80, then cooled to 600 and mixed with 16 parts of common salt.
The nicely crystalline precipitated sodium salt of 1-carboxymethoxy-8-amino-naphthalene -5-sulfonic acid is filtered off with suction in the cold, washed and dried. The new compound is pale gray in color and can be diazotized in the usual way.
Example 3
23 parts of 1-hydroxy-8-chloroacetylamino-naphthalin are mixed in 700 parts of 20% sodium bicarbonate solution. The suspension is heated to 900 within 15 minutes, stirred for 45 minutes at 90 ° and then admixed with 236 parts of 300% sodium hydroxide solution. A clear solution is formed after a short time, which is stirred at 90 ° for a further 25 minutes. The solution is then allowed to cool while stirring, it is still cooled to 50, the precipitated sodium salt of 1-carboxy-methoxy-8-amino-naphthalene is filtered off with suction and dried. It is a light-gray powder that is clearly soluble in water and can be diazotized in the usual way.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH346558T | 1956-06-22 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH346558A true CH346558A (en) | 1960-05-31 |
Family
ID=4507664
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH346558D CH346558A (en) | 1956-06-22 | 1956-06-22 | Process for the production of new intermediate products of the naphthalene series |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH346558A (en) |
-
1956
- 1956-06-22 CH CH346558D patent/CH346558A/en unknown
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