DE580981C - Process for the production of aromatic oxyaldehydes - Google Patents

Process for the production of aromatic oxyaldehydes

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Publication number
DE580981C
DE580981C DEH131837D DEH0131837D DE580981C DE 580981 C DE580981 C DE 580981C DE H131837 D DEH131837 D DE H131837D DE H0131837 D DEH0131837 D DE H0131837D DE 580981 C DE580981 C DE 580981C
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parts
production
oxyaldehydes
added
aromatic
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Expired
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DEH131837D
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German (de)
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HOFFMANNI LA ROCHE and CO AKT GE
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HOFFMANNI LA ROCHE and CO AKT GE
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Priority to DEH131837D priority Critical patent/DE580981C/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung aromatischer Oxyaldehyde Nach dem - Verfahren des Hauptpatents 578 037 gelingt es, Phenole, die in Ortho-oder Parastellung zur Hydroxylgruppe Propenylreste enthalten, in wässerig-alkalischer Lösung mit Hilfe von Nitroarylsulfosäuren - oder Nitroarylcarbonsäuren zu den -entsprechenden Aldehyden zu oxydieren.Process for the production of aromatic oxyaldehydes According to the process of main patent 578 037 it is possible to oxidize phenols which contain propenyl radicals in ortho- or para-position to the hydroxyl group in aqueous-alkaline solution with the help of nitroarylsulfonic acids - or nitroarylcarboxylic acids to the corresponding aldehydes.

Es wurde nun gefunden, daß Phenole, die statt der Propenylreste die Carbinolgruppe enthalten, also Oxybenzylalkohole, ebenfalls - in wässerig-alkalischer Lösung mit den gleichen Oxydationsmitteln oxydiert werden können. Werden die Oxybenzylalkohole in bekannter Weise durch Kondensation von Formaldehyd mit Phenolen - in alkalischer Lösung gewonnen, - so genügt nachheriges Kochen des Kondensationsansatzes unter Zusatz von z- B. nitrobenzolsulfosaurem Natrium; utn die Oxyaldehyde zu gewinnen. Es gelingt auch auf diesem Wege, Oxybenzylalkohole, welche zwei Carbinolgruppen enthalten, z. B. Dimetlivlol-p-Kresol, in die entsprechenden Dialdehyde zu überführen. Beispiel i 15 Teile Vanillinalkoholwerden in i2o Teilcn ioo/aiger Natronlauge gelöst, 25 Teile ni-tiitrobenzolsulfosaures Natrium zugefügt w@d 4 Stunden am Rückflußkühler gekocht. Dann wird mit Schwefelsäure angesäuert und ausgeäthert. Dem Äther entzieht Bisulfitlauge das in sehr guter Ausbeute entstandene Vanillin. Beispiel e 45 Volumteile einer verdünnten Nitrobenzolsulfurierung (enthaltend 34,2 % Nitrobenzolsulfosäure) werden mit 48 Volumteilen 2oo%oiger Natronlauge neutralisiert und noch weitere 70 Volumteile 20 01" Natronlauge zugefügt. Unter Erwärmen auf dem Wasserbade werden. 13,6 Teile Guajacoltrichlormethylcarbinol eingetragen und hierauf noch 14 Stunden am Rückflußkühler gekocht. Der dann angesäuerten Flüssigkeit werden die Oxydationsprodukte mit Äther entzogen und das gebildete Vanillin durch Umkristallisieren aus Benzol und Wasser ven nebenher entstandener 4-Oxy-3-metlioxybenzoylcarbonsäure getrennt. Beispiel 3 9,.4 Teile Phenol werden in 150 Volumteilen 3,3°/oiger Natronlauge gelöst und 8,5 GewichtstQile 4ooloiger Formaldehyd zugefügt. Nach längerem Stehen werden in der Flüssigkeit log Ätznatron aufgelöst, 12 g nitrobenzolsulfosaures Natrium zugefügt und z'/2 Stunden am Rückflußkühler gekocht. Die angesäuerte Reaktionsflüssigkeit wird mit Äther extrahiert, dem die gebildeten Aldehyde durch Bisulfitlösung entzogen werden. Im Äther bleibt unverändertes Phenot, während bei der Aufarbeitung der Bisulfitlösung neben etwas Salicylaldehyd hauptsächlich p-Oxybenzaldehyd gewonnen wird.It has now been found that phenols which contain the carbinol group instead of the propenyl radicals, ie oxybenzyl alcohols, can also be oxidized in aqueous-alkaline solution with the same oxidizing agents. If the oxybenzyl alcohols are obtained in a known manner by condensation of formaldehyde with phenols - in an alkaline solution - then it is sufficient to boil the condensation mixture with the addition of, for example, sodium nitrobenzenesulfonic acid; utn to extract the oxyaldehydes. It is also possible in this way to obtain oxybenzyl alcohols which contain two carbinol groups, e.g. B. Dimetlivlol-p-cresol to convert into the corresponding dialdehydes. EXAMPLE I 15 parts of vanilla alcohol are dissolved in 120 parts of 100% sodium hydroxide solution, 25 parts of sodium nitrobenzenesulfonate are added for 4 hours and the mixture is refluxed for 4 hours. It is then acidified with sulfuric acid and extracted with ether. Bisulphite liquor removes the vanillin, which is produced in very good yield, from the ether. Example e 45 parts by volume of a dilute nitrobenzenesulfurization (containing 34.2 % nitrobenzenesulfonic acid) are neutralized with 48 parts by volume of 2oo% sodium hydroxide solution and a further 70 parts by volume of 20 01 "sodium hydroxide solution are added. While warming on the water bath, 13.6 parts of guaiacol trichloromethyl carbinol are added and then added The oxidation products are then removed from the acidified liquid with ether and the vanillin formed is separated by recrystallization from benzene and water from the 4-oxy-3-metlioxybenzoylcarboxylic acid formed at the same time. Example 3 9, .4 parts of phenol are separated in 1 50 parts by volume of 3.3% sodium hydroxide solution and 8.5 parts by weight of 4oolo formaldehyde are added Ether extracted from which the aldehydes formed removed by bisulfite solution. Unchanged phenol remains in the ether, while when working up the bisulfite solution, in addition to some salicylaldehyde, mainly p-oxybenzaldehyde is obtained.

Beispie14 4 Teile Dimethylol-p=Kresol werden in 4o Teilen io°;oiger Natronlauge gelöst. ioTeile m-nitrobenzolsulfosaures Natrium zugefügt und a Stunden im Dampfbad erhitzt. Dabei fällt das Natriumsalz des gebildeten 4-Oxyuvitinaldehyds aus. Dasselbe wird abgesaugt und gibt beim Zersetzen mit Säuren reinen 4-Oxyuvitinaldehyd vom F. i33° (vgl. Berichte der Deutschen chem. Ges. 42, igog, Bd. II, S. a545)Example 4 parts of dimethylol-p = cresol are dissolved in 40 parts of 10% Sodium hydroxide solution dissolved. 10 parts of sodium m-nitrobenzenesulfonate were added and the mixture was added for a hour heated in the steam bath. The sodium salt of the 4-oxyuvitaldehyde formed falls in the process the end. It is sucked off and, when decomposed with acids, gives pure 4-oxyuvitaldehyde vom F. i33 ° (see reports of the Deutsche chem. Ges. 42, igog, vol. II, p. a545)

Claims (1)

PATENTANSPRUCH: Abänderung des Verfahrens des-Hauptpatents 578037 zur Herstellung von aromatischen Oxyaldehyden, dadurch gekennzeichnet, daß man an Stelle der Phenole, die in der Ortho- oder der Parastellung eine Propenylgruppe enthalten, die entsprechenden Oxybenzylalkohole in wässerig-alkalischer Lösung mit Nitroverbindungen oxydiert; die infolge ihres Gehaltes an S 03H- oder C O O H-Gruppen ig alkalihaltigem Wasser löslich sind. PATENT CLAIM: Modification of the process of the main patent 578037 for the production of aromatic oxyaldehydes, characterized in that instead of the phenols which contain a propenyl group in the ortho or para position, the corresponding oxybenzyl alcohols are oxidized in an aqueous alkaline solution with nitro compounds; which are soluble in alkaline water due to their content of S 03H or COO H groups.
DEH131837D 1932-05-19 1932-05-19 Process for the production of aromatic oxyaldehydes Expired DE580981C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEH131837D DE580981C (en) 1932-05-19 1932-05-19 Process for the production of aromatic oxyaldehydes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEH131837D DE580981C (en) 1932-05-19 1932-05-19 Process for the production of aromatic oxyaldehydes

Publications (1)

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DE580981C true DE580981C (en) 1933-07-19

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Family Applications (1)

Application Number Title Priority Date Filing Date
DEH131837D Expired DE580981C (en) 1932-05-19 1932-05-19 Process for the production of aromatic oxyaldehydes

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DE (1) DE580981C (en)

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