DE932793C - Process for the preparation of aromatic nitrocarbonyl compounds - Google Patents

Process for the preparation of aromatic nitrocarbonyl compounds

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Publication number
DE932793C
DE932793C DER13054A DER0013054A DE932793C DE 932793 C DE932793 C DE 932793C DE R13054 A DER13054 A DE R13054A DE R0013054 A DER0013054 A DE R0013054A DE 932793 C DE932793 C DE 932793C
Authority
DE
Germany
Prior art keywords
compounds
nitrocarbonyl
para
aromatic
methanol
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
Application number
DER13054A
Other languages
German (de)
Inventor
Karl Dr Faltings
Heinrich Mueller
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell Riedel de Haen AG
Original Assignee
Riedel de Haen AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Riedel de Haen AG filed Critical Riedel de Haen AG
Priority to DER13054A priority Critical patent/DE932793C/en
Application granted granted Critical
Publication of DE932793C publication Critical patent/DE932793C/en
Expired legal-status Critical Current

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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
    • 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
    • C07C201/14—Preparation of nitro compounds by formation of nitro groups together with reactions not involving the formation of nitro groups

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

Description

Verfahren zur Herstellung von aromatischen Nitrocarbonylverbindungen Aromatische Nitrocarbonylverbindungen können bekanntlich hergestellt werden, indem man aromatische Carbonylverbindungen nitriert. Diese Reaktion führt jedoch nahezu ausschließlich zu meta-Nitroverbindungen und nur in ganz untergeordnetem Maße zu den entsprechenden para- und ortho-Derivaten. Process for the preparation of aromatic nitrocarbonyl compounds Aromatic As is known, nitrocarbonyl compounds can be prepared by adding aromatic Carbonyl compounds nitrated. However, this reaction leads almost exclusively to meta-nitro compounds and only to a very subordinate extent to the corresponding ones para and ortho derivatives.

Es ist möglich, die para- und ortho-Nitrocarbonylverbindungen durch Oxydation von geeigneten Nitrokohlenwasserstoffen, Nitroalkoholen oder Halogeniden von Nitroverbindungen zu erhalten. So gewinnt man beispielsweise para-Nitrobenzaldehyd durch Oxydation von para-Nitrobenzylchlorid und para-Nitroacetophenon durch Oxydation von para-Nitroäthylbenzol. Diese Verfahrensweise - Oxydation aromatischer Nitroverbindungen - ist jedoch häufig umständlich und nur unter größerem technischem Aufwand, insbesondere unter Einsatz ganz bestimmter Oxydationsmittel, durchführbar. It is possible to use the para- and ortho-nitrocarbonyl compounds Oxidation of suitable nitro hydrocarbons, nitro alcohols or halides from nitro compounds. For example, para-nitrobenzaldehyde is obtained in this way by oxidation of para-nitrobenzyl chloride and para-nitroacetophenone by oxidation of para-nitroethylbenzene. This procedure - oxidation of aromatic nitro compounds - However, it is often cumbersome and only requires a great deal of technical effort, in particular using very specific oxidizing agents, feasible.

Es wurde nun gefunden, daß man auf relativ einfache Weise in guter Ausbeute aromatische Nitrocarbonylverbindungen herstellen kann, die die Nitrogruppe vornehmlich in para- und ortho-Stellung zur Carbonylgruppe enthalten, wenn man Aralkylalkohole bei tiefen Temperaturen, vorzugsweise unter oO, mit Nitriersäure in Salpetersäureester der Nitroalkohole überführt und diese Ester dann durch langsame Zugabe einer berechneten Menge wasserfreier alkoholischer Ätzalkalilaugen oder alkoholischer Metall-Alkoholat-Lösungen in die Nitrocarbonylverbindungen spaltet. It has now been found that in a relatively simple manner in good Yield aromatic nitrocarbonyl compounds containing the nitro group mainly in the para and ortho position to the carbonyl group when using aralkyl alcohols at low temperatures, preferably below oO, with nitrating acid in nitric acid ester of nitro alcohols and then these esters by slowly adding a calculated Amount of anhydrous alcoholic caustic alkali solutions or alcoholic metal alcoholate solutions splits into the nitrocarbonyl compounds.

Beispiele I. Zu einer Mischung aus 500 g Schwefelsäure (960/cit) und 250 g Salpetersäure (6o0/oig) läßt man bei -I50 Io8 g Benzylalkohol in 2 Stunden zufließen. Die Reaktionsmischung wird. nach weiteren 30 Minuten mit einer Mischung aus 500 g Eis und 500 g Wasser zerlegt. Die ölige Schicht wird durch Absaugen oder Abschleudern gereinigt. Das kristallisierte para- Nitrobenzylnitrat wird aus Methanol umkristallisiert. Ausbeute: 105 g, das sind 54°/o der Theorie. Examples I. To a mixture of 500 g of sulfuric acid (960 / cit) and 250 g of nitric acid (6o0 / oig) are left at -I50 Io8 g of benzyl alcohol in 2 hours flow in. The reaction mixture will. after another 30 minutes with a mixture broken down from 500 g of ice and 500 g of water. The oily layer is removed by suction or Spin cleaned. The crystallized para-nitrobenzyl nitrate is made from methanol recrystallized. Yield: 105 g, that is 54% of theory.

Das para-Nitrobenzylnitrat wird in 500 g Methanol gelöst und durch Zugabe einer Lösung von 20 g Ätznatron in 300 g Methanol in einer halben Stunde unter Sieden gespalten. Durch Zugabe von Wasser wird der gebildete para-Nitrobenzaldehyd ausgefällt. Nach Absaugen und Trocknen erhält man 6I g para-Nitrobenzaldehyd vom Schmelzpunkt Io60. The para-nitrobenzyl nitrate is dissolved in 500 g of methanol and washed through Addition of a solution of 20 g of caustic soda in 300 g of methanol in half an hour split under boiling. The para-nitrobenzaldehyde is formed by adding water failed. After filtering off with suction and drying, 61 g of para-nitrobenzaldehyde are obtained Melting point Io60.

2. I22 g alpha-Phenyläthylalkohol läßt man bei 150 während 2 Stunden zu einer Mischung aus 500 g Schwefelsäure (960/oig) und 250 g Salpetersäure (600/zig) fließen. Nach einer halben Stunde wird die Reaktionsmischung mit einer Mischung aus 500 g Eis und 500 g Wasser zerlegt. Aus der öligen Schicht gewinnt man durch Absaugen und Umkristallisieren aus Methanol 95 g para-Nitrophenyläthylnitrat. 2. I22 g of alpha-phenylethyl alcohol are left at 150 for 2 hours to a mixture of 500 g sulfuric acid (960 per cent) and 250 g nitric acid (600 per cent) flow. After half an hour, the reaction mixture becomes with a mixture broken down from 500 g of ice and 500 g of water. One wins through from the oily layer Suction and recrystallization from methanol 95 g of para-nitrophenylethyl nitrate.

Claims (1)

Das para-Nitrophenyläthylnitrat wird in 300 g Methanol gelöst und unter Sieden mit einer Lösung von IO g Natrium in 200 g Methanol in einer halben Stunde gespalten. Die Lösung wird mit Wasser verdünnt. Das ausgeschiedene para-Nitroacetophenon wiegt nach dem Trocknen 55 g und hat einen Schmelzpunkt von So PATENTANSPRUCH: Verfahren zur Herstellung von aromatischen Nitrocarbonylverbindungen, dadurch gekennzeichnet, daß man Aralkylalkohole bei tiefen Temperaturen, vorzugsweise unter oO, mit Nitriersäure in Salpetersäureester der Nitroalkohole überführt und diese Ester dann mit wasserfreien alkoholischen Ätzalkalilaugen oder alkoholischen Metall-Alkoholat-Lösungen in die Nitrocarbonylverbindungen spaltet. The para-nitrophenylethyl nitrate is dissolved in 300 g of methanol and while boiling with a solution of IO g of sodium in 200 g of methanol in half Split hour. The solution is diluted with water. The excreted para-nitroacetophenone weighs 55 g after drying and has a melting point of So. PATENT CLAIM: Process for the production of aromatic nitrocarbonyl compounds, characterized in that that aralkyl alcohols at low temperatures, preferably below oO, with nitrating acid converted into nitric acid esters of the nitro alcohols and these esters then with anhydrous alcoholic caustic alkali solutions or alcoholic metal alcoholate solutions in the Cleaves nitrocarbonyl compounds.
DER13054A 1953-11-28 1953-11-28 Process for the preparation of aromatic nitrocarbonyl compounds Expired DE932793C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DER13054A DE932793C (en) 1953-11-28 1953-11-28 Process for the preparation of aromatic nitrocarbonyl compounds

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DER13054A DE932793C (en) 1953-11-28 1953-11-28 Process for the preparation of aromatic nitrocarbonyl compounds

Publications (1)

Publication Number Publication Date
DE932793C true DE932793C (en) 1955-09-08

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DER13054A Expired DE932793C (en) 1953-11-28 1953-11-28 Process for the preparation of aromatic nitrocarbonyl compounds

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DE (1) DE932793C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1194839B (en) * 1960-02-09 1965-06-16 Ministerul Ind Petrolului Process for the preparation of p-nitroacetophenone oxime
WO2001028975A2 (en) * 1999-10-19 2001-04-26 Alpharma-Isis Gmbh & Co. Kg Method for production of 3-nitryloxy-2,2-bis(nitryloxymethyl)-propanal

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1194839B (en) * 1960-02-09 1965-06-16 Ministerul Ind Petrolului Process for the preparation of p-nitroacetophenone oxime
WO2001028975A2 (en) * 1999-10-19 2001-04-26 Alpharma-Isis Gmbh & Co. Kg Method for production of 3-nitryloxy-2,2-bis(nitryloxymethyl)-propanal
WO2001028975A3 (en) * 1999-10-19 2002-02-28 Alpharma Isis Gmbh & Co Kg Method for production of 3-nitryloxy-2,2-bis(nitryloxymethyl)-propanal

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