DE540534C - Process for the preparation of alkoxy derivatives of 2-oxynaphthalene-3-carboxylic acid - Google Patents
Process for the preparation of alkoxy derivatives of 2-oxynaphthalene-3-carboxylic acidInfo
- Publication number
- DE540534C DE540534C DE1930540534D DE540534DD DE540534C DE 540534 C DE540534 C DE 540534C DE 1930540534 D DE1930540534 D DE 1930540534D DE 540534D D DE540534D D DE 540534DD DE 540534 C DE540534 C DE 540534C
- Authority
- DE
- Germany
- Prior art keywords
- carboxylic acid
- oxynaphthalene
- preparation
- acid
- alkoxy derivatives
- 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
- 125000003545 alkoxy group Chemical group 0.000 title claims description 3
- 238000000034 method Methods 0.000 title claims description 3
- 238000002360 preparation method Methods 0.000 title claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 229940100198 alkylating agent Drugs 0.000 claims 1
- 239000002168 alkylating agent Substances 0.000 claims 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 1
- 239000002253 acid Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012670 alkaline solution Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- VJWFFRAUKLEPHS-UHFFFAOYSA-N methyl hydrogen sulfate;sodium Chemical compound [Na].COS(O)(=O)=O VJWFFRAUKLEPHS-UHFFFAOYSA-N 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940045681 other alkylating agent in atc Drugs 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
- C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
Verfahren zur Darstellung von Alkoxyderivaten der 2-Oxynaphthalin-3-carbonsäure Die Hydroxylgruppen solcher Dioxynaphthaline, die in beiden Kernen je eine Hydroxy bgruppe enthalten. lassen sich leicht schon durch Alkohol und Säure veräthern. Man erhält deshalb bei der Behandlung, beispielsweise des 2, 6-Dioxynaphthalins, mit Alkohol und Säure 2, 6-Dialkoxynaphthalin (Annalen 257 [189o], Seite -.2; Berichte 36 [1903a, Seite 27o).Process for the preparation of alkoxy derivatives of 2-oxynaphthalene-3-carboxylic acid The hydroxyl groups of such dioxynaphthalenes, which have a hydroxyl in each of the two nuclei bgroup included. can easily be etherified by alcohol and acid. Man therefore receives in the treatment, for example of 2,6-dioxynaphthalene, with Alcohol and acid 2, 6-dialkoxynaphthalene (Annalen 257 [189o], page -.2; reports 36 [1903a, page 27o).
Es wurde nun gefunden, daß im Gegensatz hierzu in den Dioxynaphthalin-3-carbonsäuren, bei denen eine Hydroxylgruppe in 2-Stellung und die andere im nicht carboxylierten Kern steht, nur die Hydroxylgruppe, die im nicht carboxylierten Kern steht, sich leicht durch Alkohol und Säure veräthern läßt. -Man erhält beispielsweise bei der Behandlung der 2, 6-Dioxynaphthaän-3-carbonsäure mit Alkohol und Säure 6-Alkoxy-2-oxynaphthalin-3-carbonsäuren neben 6-Alkoxy-2-oxynaphthalin-3-carbonsäureestern, die durch Behandeln mit Alkalien leicht in die entsprechenden Alkoxyoxynaphthalincarbonsäuren übergehen.It has now been found that, in contrast to this, in the dioxynaphthalene-3-carboxylic acids, with one hydroxyl group in the 2-position and the other in the non-carboxylated Core, only the hydroxyl group that is in the non-carboxylated core, itself can be easily etherified by alcohol and acid. -You get for example at the Treatment of 2,6-dioxynaphthaene-3-carboxylic acid with alcohol and acid 6-alkoxy-2-oxynaphthalene-3-carboxylic acids in addition to 6-alkoxy-2-oxynaphthalene-3-carboxylic acid esters, which are obtained by treatment with alkalis easily convert into the corresponding alkoxyoxynaphthalenecarboxylic acids.
Dieselbe Reaktion kann man in geeigneter Weise mit anderen alkylierenden Mitteln, wie methylschwefelsaurem -Natrium, ausführen.The same reaction can be conveniently carried out with other alkylating agents Carry out agents such as sodium methylsulfuric acid.
Die erhaltenen Verbindungen färben sich in wäßriger Lösung beim Behandeln mit Eisenchlorid intensiv blau, zeigen also die Reaktion einer o-Oxvcarbonsäure. Es folgt daraus, daß die neuen Säuren die freie Hy droxylgruppe in 2-Stellung besitzen, daß ihnen also die Konstitution einer 6-Alkoxy-2-oxynaphthaän-3-carbonsäure zukommt. Beispiele 1. 1 Gewichtsteil 2, 6-Dioxynaphthalin-3-carbonsäure wird mit 5 Gewichtsteilen methylalhoholischer Schwefelsäure (1oo;o) 2,1 'Stunden gekocht. -Nach dem Erkalten wird die auskristallisierte Substanz abgesaugt und mit etwas kaltem Methylalkohol gewaschen. Das Filtrat enthält das unveränderte Ausgangsmaterial, das leichter in Alkohol löslich ist als das monomethylierte Produkt, und kann für einen neuen Ansatz verwertet werden. Der Rückstand löst sich zum Teil in Natriumcarbonatlösung, der Rest in verdünnter Natronlauge. Die natronalkalische Lösung wird zur Verseifung des Carbonsäureesters kurz aufgekocht und mit der sodaalkalischen Lösung vereinigt. Die Lösung wird mit Schwefelsäure angesäuert und die erhaltene 6-Methoxy-2-oxynaphthalin-3-carbonsäure abgesaugt. Durch Umkristallisieren aus Alkohol läßt sich die Säure leicht reinigen. Sie kristallisiert in gelben Nadeln vom Schmelzpunkt 233°.The compounds obtained change color in aqueous solution on treatment intensely blue with ferric chloride, thus showing the reaction of an o-oxycarboxylic acid. It follows from this that the new acids have the free hydroxyl group in the 2-position, that they have the constitution of a 6-alkoxy-2-oxynaphthaene-3-carboxylic acid. Examples 1. 1 part by weight of 2,6-dioxynaphthalene-3-carboxylic acid is mixed with 5 parts by weight methyl alcoholic sulfuric acid (100; o) boiled for 2.1 'hours. -After cooling down the crystallized substance is suctioned off and washed with a little cold methyl alcohol washed. The filtrate contains the unchanged starting material, which is more easily converted into Alcohol is more soluble than the monomethylated product, and can be used for a new approach be recycled. The residue partially dissolves in sodium carbonate solution, the Remainder in dilute sodium hydroxide solution. The sodium-alkaline solution is used for saponification of the carboxylic acid ester briefly boiled and combined with the soda-alkaline solution. The solution is acidified with sulfuric acid and the 6-methoxy-2-oxynaphthalene-3-carboxylic acid obtained sucked off. The acid can be easily purified by recrystallization from alcohol. It crystallizes in yellow needles with a melting point of 233 °.
2. 7 .1 Gewichtsteile 2, 6-Dioxynaphthalin-3-carbonsäure, 70 Gewichtsteile methylschwefelsaures Natrium. 55 Gewichtsteile Natronlauge (.1o° Be), 23o Teile Wasser «-erden zum Sieden erhitzt. Nach kurzem Kochen scheidet sich das Natriumsalz der 6-'lethoxv-2-oxynaphthaliti-3-carbonsäure aus. das in Wasser schwerer löslich ist als das Natüumsalz des Ausgangsmaterials. Nach dem Erkalten wird abgesaugt und ,mit etwas Natriumchloridlösung ausgewaschen. Das erhaltene Natriumsalz kann durch Umkristallisieren aus Wasser noch weitergereinigt werden. Die freie Säure ist identisch mit der im Beispiel i beschriebenen.2.7.1 parts by weight of 2,6-dioxynaphthalene-3-carboxylic acid, 70 parts by weight of sodium methylsulfuric acid. 55 parts by weight of caustic soda (.1o ° Be), 23o parts of water "earths heated to boiling. After a short boil, the sodium salt of 6-'lethoxv-2-oxynaphthaliti-3-carboxylic acid separates out. which is less soluble in water than the natural salt of the starting material. After cooling, it is suctioned off and washed out with a little sodium chloride solution. The sodium salt obtained can be further purified by recrystallization from water. The free acid is identical to that described in Example i.
3. i Teil 2, 6-Dioxynaphthalin-3-carbonsäure wird mit i o Gewichtsteilen ioprozentiden e r ' 'ithylallzoholischer gekocht. Durch Einrühren Schwefelsäure von Natrium- :!4 Stuncarbonat wird die Lösung alkalisch gestellt und der Alkohol abdestilliert. Der Rückstand löst sich bis auf geringe Mengen Carbonsäureester beim Erwärmen mit Wasser auf. Aus der wäßrigen Lösung läßt sich das gebildete 6-i:ithoxy-2-oxvnaphtbalin-3-carbonsaure Natrium durch Versetzen mit Natriumchloridlösung ausfällen. Die freie Säure kristallisiert aus Xylol in schönen reingelben Nadeln vom Schmelzpunkt 2i9`.3. Part 2, 6-dioxynaphthalene-3-carboxylic acid is boiled in a more alcoholic manner with 10 parts by weight of ioprozentiden er ''. The solution is made alkaline by stirring in sulfuric acid and sodium carbonate:! 4 stun carbonate and the alcohol is distilled off. Except for small amounts of carboxylic acid ester, the residue dissolves on warming with water. The 6-i: ithoxy-2-oxynaphthalene-3-carboxylic acid sodium formed can be precipitated from the aqueous solution by adding sodium chloride solution. The free acid crystallizes from xylene in beautiful, pure yellow needles with a melting point of 219 '.
.1. 2o Gewichtsteile 2, 8-Dioxynaphthalin-3-carbonsäure werden in Zoo Gewichtsteilen Methylalkohol gelöst und mit 6o Gewichtsteilen Oleum, _oprozentig. versetzt. Die Mischung wird 2.1 Stunden zum Sieden erhitzt. Der gebildete 8 -'letlioxy-2-oxynaphthalin-3-carbonsäuremethi-lester scheidet sich aus. Er wird abgesaugt und durch Kochen mit Natriumcarbonatlösung verseift. Beim Ansäuern der sodaalkalischen Lösung fällt die 8-1lethoxy-2-oxynaphthalin-3-carbonsäure aus, die nach dem Umkristallisieren aus Alkohol bei 248' schmilzt..1. 2o parts by weight of 2, 8-Dioxynaphthalin-3-carboxylic acid are in Zoo parts by weight of methyl alcohol dissolved and 60 parts by weight of oleum, _op%. offset. The mixture is heated to boiling for 2.1 hours. The 8 -'letlioxy-2-oxynaphthalene-3-carboxylic acid methyl ester formed is eliminated. It is suctioned off and boiled with sodium carbonate solution saponified. When the soda-alkaline solution is acidified, the 8-1lethoxy-2-oxynaphthalene-3-carboxylic acid falls which, after recrystallization from alcohol, melts at 248 '.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE540534T | 1930-08-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE540534C true DE540534C (en) | 1931-12-21 |
Family
ID=6558964
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1930540534D Expired DE540534C (en) | 1930-08-02 | 1930-08-02 | Process for the preparation of alkoxy derivatives of 2-oxynaphthalene-3-carboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE540534C (en) |
-
1930
- 1930-08-02 DE DE1930540534D patent/DE540534C/en not_active Expired
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