DE154499C - - Google Patents
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- Publication number
- DE154499C DE154499C DENDAT154499D DE154499DA DE154499C DE 154499 C DE154499 C DE 154499C DE NDAT154499 D DENDAT154499 D DE NDAT154499D DE 154499D A DE154499D A DE 154499DA DE 154499 C DE154499 C DE 154499C
- Authority
- DE
- Germany
- Prior art keywords
- acid
- aldehydes
- water
- aldehyde
- pure
- 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.)
- Active
Links
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 8
- 150000003934 aromatic aldehydes Chemical class 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N Benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 7
- ZRSNZINYAWTAHE-UHFFFAOYSA-N 4-Anisaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-Nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 3
- 229940095076 benzaldehyde Drugs 0.000 description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L Chromic acid Chemical compound O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- SLAMLWHELXOEJZ-UHFFFAOYSA-N o-Nitrobenzoic acid Chemical compound OC(=O)C1=CC=CC=C1[N+]([O-])=O SLAMLWHELXOEJZ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- BWRBVBFLFQKBPT-UHFFFAOYSA-N (2-nitrophenyl)methanol Chemical compound OCC1=CC=CC=C1[N+]([O-])=O BWRBVBFLFQKBPT-UHFFFAOYSA-N 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N Anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000003935 benzaldehydes Chemical class 0.000 description 1
- 150000001622 bismuth compounds Chemical class 0.000 description 1
- -1 bisulfite compound Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative Effects 0.000 description 1
- 230000002035 prolonged Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C201/00—Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton
- C07C201/06—Preparation of nitro compounds
- C07C201/12—Preparation of nitro compounds by reactions not involving the formation of nitro groups
-
- 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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Das vorliegende Verfahren bezweckt die Reindarstellung von aromatischen Aldehyden mittels schwefliger Säure.The purpose of the present process is to prepare aromatic aldehydes in pure form by means of sulphurous acid.
Bertaguini (Annalen der Chemie und Pharmacie 85, 183) hat beobachtet, daß Benzaldehyd, welcher mit schwefliger Säure behandelt wird, nach Zusatz von Wasser in Lösung geht. Es wurde nun in diesem Anhalten ein treffliches Mittel gefunden, um aromatische Aldehyde von ihren Verunreinigungen zu trennen und so auf billigem Wege rein darzustellen. Diesbezügliche Versuche haben nämlich ergeben, daß schweflige Säure auf unreine Aldehyde eine selektive Wirkung ausübt in der Weise, daß die vorhandenen Fremdkörper im Wasser ungelöst bleiben, während die Aldehydschwefligsäureverbindung vom Wasser aufgenommen wird.Bertaguini (Annalen der Chemie und Pharmacie 85, 183) observed that benzaldehyde, which is treated with sulphurous acid, after adding water in Solution works. An excellent means has now been found in this halting to separate aromatic aldehydes from their impurities and so in a cheap way to portray pure. Experiments in this regard have shown that sulphurous acid exerts a selective effect on impure aldehydes in such a way that those present Foreign bodies remain undissolved in the water, while the aldehyde-sulfurous acid compound is absorbed by the water.
Bisher bediente man sich zum Ausziehen der Aldehyde aus Reaktionsgemischen ganz allgemein der Alkalibisulfite. Vor dieser Methode hat das vorliegende Verfahren den großen Vorzug der Billigkeit und Einfachheit. Die an sich schon wohlfeilere schweflige Säure wird nämlich hierbei quantitativ wiedergewonnen und kann somit in einfacher Weise stets wieder verwendet werden. Ein weiterer Vorzug des Verfahrens besteht darin, daß die nachteilige.. Einwirkung der zum Spalten der Bismutverbindungen angewendeten Mittel, seien sie nun alkalischer oder saurer Natur, vermieden wird. Die Erfindung gestattet, durch einfaches Erhitzen oder durch Lufteinblasen in die wäßrige Lösung daraus sowohl den reinen Aldehyd als auch die schweflige Säure zu gewinnen.So far, the aldehydes have been used entirely to extract the aldehydes from reaction mixtures generally the alkali bisulphites. Before this method, the present method has the great virtue of cheapness and simplicity. The sulphurous one, which is already cheaper in itself This is because acid is recovered quantitatively and can thus be easily recovered can be used over and over again. Another advantage of the method is that the adverse ... effect of the agents used to cleave the bismuth compounds, be they alkaline or acidic in nature, is avoided. The invention allows by simply heating or by blowing air into the aqueous solution therefrom both to obtain the pure aldehyde as well as the sulphurous acid.
Die Lösungen der Aldehyde in wäßriger schwefliger Säure geben beim Zusatz von Chloralkali Kristalle, die aus der Alkalibisulfitverbindung des betreffenden Aldehyds bestehen.The solutions of the aldehydes in aqueous sulphurous acid give with the addition of Chloralkali crystals, resulting from the alkali bisulfite compound of the aldehyde in question exist.
Nach bekannten Methoden wurde durch Oxydation von Toluol mittels Bleisuperoxyd und Schwefelsäure ein Rohprodukt gewonnen, welches neben 60 Prozent unveränderten Toluols etwa 40 Prozent Benzaldehyd enthielt. 100 kg dieses Produktes wurden bei 150 mit 400 1 Wasser innig verrührt und in die so gewonnene Emulsion 25 bis 30 kg schweflige Säure eingeleitet. Hierauf wurde das ungelöst gebliebene Toluol von der wäßrigen aldehydschwefligsauren Lösung getrennt und letztere behufs Gewinnung des Aldehyds allmählich auf ioo° erhitzt, wobei die schweflige Säure schon von etwa 300 ab entwich und sofort zu einem weiteren Ansatz Verwendung finden konnte. Nach dem Erkalten waren 36 bis 38 kg reinen Benzaldehyde ausgeschieden. Dadurch, daß man das vom Aldehyd getrennte Wasser wieder benutzt, wird die geringe Menge des im Wasser gelöst bleibenden Benzaldehyds beim nächsten Ansatz zurückgewonnen.According to known methods, by oxidizing toluene with lead peroxide and sulfuric acid, a crude product was obtained which, in addition to 60 percent unchanged toluene, contained about 40 percent benzaldehyde. 100 kg of this product were intimately stirred at 15 ° with 400 l of water and 25 to 30 kg of sulfurous acid were introduced into the emulsion obtained in this way. Thereupon, the undissolved toluene from the aqueous solution was separated and the latter aldehydschwefligsauren behufs recovery of the aldehyde gradually heated to ioo °, wherein the sulfurous acid escaped from and place immediately to another approach, use was already about 30 0th After cooling, 36 to 38 kg of pure benzaldehydes were excreted. By using the water separated from the aldehyde again, the small amount of the benzaldehyde remaining dissolved in the water is recovered in the next batch.
o-Nitrobenzylalkohol war durch saure Oxydation in einen Rohnitrobenzaldehyd vom Smp. 30/31° (Ep. 28,5°) verwandelt worden, der neben 80 Prozent reinen Aldehyds 13 Prozent Nitrobenzoesäure und 7,0 Prozent Harzo-Nitrobenzyl alcohol was by acidic oxidation has been converted into a crude nitrobenzaldehyde with a melting point of 30/31 ° (ep. 28.5 °), the 80 percent pure aldehyde, 13 percent nitrobenzoic acid and 7.0 percent resin
enthielt. ioo kg dieses o-Nitrobenzaldehyds wurden wie im Beispiel ι mit 400 1 Wasser verrührt und mit etwa 40 kg Schwefligsäuregas in Lösung gebracht. Das ungelöste Harz wurde durch ein Tierkohlefilter von der wäßrigen Lösung getrennt und mit der letzteren wie in Beispiel 1 verfahren. Nach dem vollständigen Verjagen der schwefligen Säure empfiehlt es sich, den ausgeschiedenen Aldehyd zur Entfernung beigemengter Nitrobenzoesäure mit verdünnter Sodalösung zu behandeln. Der so gewonnene o-Nitrobenzaldehyd ist nunmehr rein und zeigt den Smp. 45/460.contained. 100 kg of this o-nitrobenzaldehyde were stirred with 400 l of water as in Example 1 and brought into solution with about 40 kg of sulfuric acid gas. The undissolved resin was separated from the aqueous solution by an animal charcoal filter and the same procedure as in Example 1 was carried out with the latter. After the sulphurous acid has been chased away completely, it is advisable to treat the excreted aldehyde with a dilute soda solution to remove added nitrobenzoic acid. The o-nitrobenzaldehyde obtained in this way is now pure and has a melting point of 45/46 0 .
Anisol wurde mit Chromsäure oxydiertAnisole was oxidized with chromic acid
(vgl. Rössel, Ann. 151, 28) und so ein Rohanisaldehyd erhalten, der etwa 60 Prozent Anisaldehyd enthielt. 5 kg dieses Produktes wurden mit der zehnfachen Menge Wasser verrührt und mit schwefliger Säure gesättigt. Hierauf wurde bis zur vollständigen Klärung der wäßrigen Lösung längere Zeit bei 15 bis 20° stehen gelassen, von ungelösten Terpenen getrennt und zur Gewinnung des Aldehyds wie unter Beispiel 1 verfahren. Auf diese Weise wurden etwa 3 kg reinen Anisaldehyds gewonnen.(cf. Rössel, Ann. 151, 28) and so on Obtained crude anisaldehyde containing about 60 percent anisaldehyde. 5 kg of this product were stirred with ten times the amount of water and saturated with sulphurous acid. This was followed by a prolonged period of time at 15 ° until the aqueous solution was completely clear Left to stand up to 20 °, separated from undissolved terpenes and proceed as in Example 1 to obtain the aldehyde. on about 3 kg of pure anisaldehyde was obtained in this way.
Claims (1)
Publications (1)
Publication Number | Publication Date |
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DE154499C true DE154499C (en) |
Family
ID=421037
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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DENDAT154499D Active DE154499C (en) |
Country Status (1)
Country | Link |
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DE (1) | DE154499C (en) |
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- DE DENDAT154499D patent/DE154499C/de active Active
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