DE386619C - Process for the preparation of halogenated anhydrides of o-hydrocumaric acid (melilotic acid) - Google Patents

Process for the preparation of halogenated anhydrides of o-hydrocumaric acid (melilotic acid)

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Publication number
DE386619C
DE386619C DEC31309D DEC0031309D DE386619C DE 386619 C DE386619 C DE 386619C DE C31309 D DEC31309 D DE C31309D DE C0031309 D DEC0031309 D DE C0031309D DE 386619 C DE386619 C DE 386619C
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Germany
Prior art keywords
acid
hydrocumaric
preparation
melilotic
anhydrides
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Expired
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DEC31309D
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German (de)
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CHEMISCHE WERKE GRENZACH AG
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CHEMISCHE WERKE GRENZACH AG
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Priority to DEC31309D priority Critical patent/DE386619C/en
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Publication of DE386619C publication Critical patent/DE386619C/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/40—Unsaturated compounds
    • C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
    • C07C59/52—Unsaturated compounds containing hydroxy or O-metal groups a hydroxy or O-metal group being bound to a carbon atom of a six-membered aromatic ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)

Description

Verfahren zur Darstellung halogenierter Anhydride der o-Hydrocamarsäure (Melilotsäure). Es wurde gefunden, daß sich Halogencumarine bzw. Halogen-o-oxyzimmtsäuren durch Reduktionsmittel in die entsprechenden Halogen-o-hydrocumarsäuren überführen lassen. Aus den Halogen-o-hydrocumarsäuren werden deren Anhydride durch Erhitzen auf höhere Temperatur erhalten.Process for the preparation of halogenated anhydrides of o-hydrocamaric acid (Melilotic acid). It has been found that halocoumarins or halo-o-oxyzinntsäuren converted into the corresponding halogen-o-hydrocumaric acids by reducing agents permit. The halogen-o-hydrocumaric acids are converted into their anhydrides by heating obtained at higher temperature.

Eine glatte Durchführbarkeit dieser Reduktion war nicht vorauszusehen, da bei halo-,genierten Verbindungen die Halogengruppen bei der Reduktion sehr oft durch Wasserstoff substituiert werden (vgl. Ber. d. d. chem. Ges. 42 119091, S. 416o).A smooth implementation of this reduction could not be foreseen, since in halogenated compounds the halogen groups are very often substituted by hydrogen during the reduction (cf. Ber. Dd chem. Ges. 42 119091, p. 416o).

Die Halo,-en-o-hydrocumarsäureanhydride sollen als Mittel gegen Eingeweidewürmer therapeutische Verwendung finden. Beispiel i.The halo-en-o-hydrocumaric anhydrides are said to be used as a remedy against intestinal worms find therapeutic use. Example i.

3,5 -Dichlormelilotsäureanhydrid. 2o Teile 3,5-Dichloreunlarin (gewonnen durch Erhitzen von 3,5-Dichlorsalicylaldehyd mit Natriumacetat und Essigsäureanhydrid, Schmelzpunkt 1570) werden fein gepulvert, in 40o Teilen Wasser aufgeschlemmt und zu dieser Suspension allmählich unter Rühren 3oo Teile 4prozentiges Natriumamalgam zugegeben. Nach zwölfstündiger Einwirkung ist mit Ausnahme eines kleinen Restes alles in Lösung gegangen. Die filtrierte Lösung liefert beim Versetzen mit verdünnter Schwefelsäure die- 3,5-Dichlormelilotsäure vom Schmelzpunkt 122'. 3,5 -dichloromelilotic anhydride. 2o parts of 3,5-dichlorounlarin (obtained by heating 3,5-dichlorosalicylaldehyde with sodium acetate and acetic anhydride, melting point 1570) are finely powdered, suspended in 40o parts of water and 300 parts of 4% sodium amalgam are gradually added to this suspension with stirring. After twelve hours of exposure, everything went into solution with the exception of a small residue. When dilute sulfuric acid is added, the filtered solution gives 3,5-dichloromelilotic acid with a melting point of 122 '.

Zur Gewinnung des 3,5-Dichlormelilotsäureanhydrids wird die Säure allmählich auf 2-io' erhitzt Durch Destillation des entstandenen Anhydrits unter 25 mm Druck bei 2o4' im Vakuum erhält man es rein vom Schmelzpunkt 107'. Beispiel :2. 5- Chlormelilotsäureanhydrid. 4o Teile 5-Chlorctimarin (gewonnen durch Erhitzen von 5-Chlorsalicylaldehyd mit Natriumacetat und Essigsäureanhydrid, Schmelzpunkt 165') werden in Wasser suspendiert und mit 5oo Teilen 4prozentigem Natriumamalgarn reduziert. Nach Beendigung der Reaktion wird vom Quecksilber abgegossen und aus der filtrierten Lösung die entstandene 5-Chlormelilotsäure mit verdünnter Schwefelsäure ausgefällt; Schmelzpunkt 142'. Die 5-Chlormelilotsäure wird durch Erhitzen im Ölbad in das Anhydrid verwandelt, welches durch Destillation im Vakuum unter 2,o mm Druck bei ig:2' rein vom Schmelzpunkt iog,' gewonnen wird. Beispiel 3. 5 Teile 3,5-Dichlorcumarsäure werden in 8o Teilen Alkohol gelöst und dazu in kleinen Anteilen :2oo Teile 4prozentiges Natriumamalgam und so viel Eisessig gegeben, daß die Lösung neutral oder schwach sauer reagiert. Nach Beendigung der Reaktion wird vom Quecksilber abgetrennt, der Alkohol abdestilFiert und der Destillationsrückstand in Wasser gegossen. Beim Ansäuern mit Mineralsäure fällt die gebildete 3,5-Dichlormelilotsäure aus, welche, wie im Beispiel i beschrieben, in das Anhydrid übergeführt wird.To obtain the 3,5-dichloromelilotic anhydride, the acid is gradually heated to 2o '. Distillation of the anhydrite formed under 25 mm pressure at 2o4' in vacuo gives it purely with a melting point of 107 '. Example: 2. 5- chloromelilotic anhydride. 40 parts of 5-chloroctimarin (obtained by heating 5-chlorosalicylaldehyde with sodium acetate and acetic anhydride, melting point 165 ') are suspended in water and reduced with 500 parts of 4% sodium amalgarn. After the reaction has ended, the mercury is poured off and the 5-chloromelilotic acid formed is precipitated from the filtered solution with dilute sulfuric acid; Melting point 142 '. The 5-chloromelilotic acid is converted into the anhydride by heating in an oil bath, which is obtained by distillation in vacuo under 2.0 mm pressure at ig: 2 'pure from the melting point iog'. Example 3. 5 parts of 3,5-dichlorocumaric acid are dissolved in 80 parts of alcohol and, in small proportions: 200 parts of 4 percent sodium amalgam and enough glacial acetic acid are added so that the solution is neutral or slightly acidic. When the reaction has ended, the mercury is separated off, the alcohol is distilled off and the distillation residue is poured into water. On acidification with mineral acid, the 3,5-dichloromelilotic acid formed precipitates, which, as described in Example i, is converted into the anhydride.

Claims (1)

PATENT-ANSPRUCH: Verfahren zur Darstellung halogenierter Anhydride der o-Hydrocurnarsäure (Melilotsäure), dadurch gekennzeichnet, daß man Halogencumarine oder Halogeno-cumarsäuren mit Reduktionsmitteln bebandelt und die so entstandenen Halogeno-hydrocuinarsäuren durch Erhitzen in die Anhydride überführt.PATENT CLAIM: Process for the preparation of halogenated anhydrides o-hydrocurnaric acid (melilotic acid), characterized in that one halocoumarins or halogeno-cumaric acids treated with reducing agents and the resulting Halogeno-hydrocuinaric acids converted into the anhydrides by heating.
DEC31309D 1921-11-01 1921-11-01 Process for the preparation of halogenated anhydrides of o-hydrocumaric acid (melilotic acid) Expired DE386619C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEC31309D DE386619C (en) 1921-11-01 1921-11-01 Process for the preparation of halogenated anhydrides of o-hydrocumaric acid (melilotic acid)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEC31309D DE386619C (en) 1921-11-01 1921-11-01 Process for the preparation of halogenated anhydrides of o-hydrocumaric acid (melilotic acid)

Publications (1)

Publication Number Publication Date
DE386619C true DE386619C (en) 1923-12-13

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEC31309D Expired DE386619C (en) 1921-11-01 1921-11-01 Process for the preparation of halogenated anhydrides of o-hydrocumaric acid (melilotic acid)

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DE (1) DE386619C (en)

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