DE849242C - Process for the preparation of diadipic acid - Google Patents

Process for the preparation of diadipic acid

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Publication number
DE849242C
DE849242C DED4359D DED0004359D DE849242C DE 849242 C DE849242 C DE 849242C DE D4359 D DED4359 D DE D4359D DE D0004359 D DED0004359 D DE D0004359D DE 849242 C DE849242 C DE 849242C
Authority
DE
Germany
Prior art keywords
acid
preparation
diadipic
oxidation
nitric acid
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
DED4359D
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German (de)
Inventor
Winfried Dr Hentrich
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.)
Deutsche Hydrierwerke AG
Original Assignee
Deutsche Hydrierwerke 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 Deutsche Hydrierwerke AG filed Critical Deutsche Hydrierwerke AG
Priority to DED4359D priority Critical patent/DE849242C/en
Application granted granted Critical
Publication of DE849242C publication Critical patent/DE849242C/en
Expired legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C55/00—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms
    • C07C55/24—Saturated compounds having more than one carboxyl group bound to acyclic carbon atoms containing more than three carboxyl groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/316—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with oxides of nitrogen or nitrogen-containing mineral acids

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

Verfahren zur Herstellung von Diadipinsäure Es wurde gefunden, daß man zu einer neuen verzweigtkettigen aliphatischen Tetracarbonsäure, der 1)ia(lil)irisäure, gelangt, wenn man das ,@, . -f)ioxydicyclohexyl der Oxydation mit Salpetersäure, zweckmäßig in Gegenwart von Oxydationskatalysatoren, unterwirft. Die Oxydation verläuft nach folgendem Reaktionsschema: Das 4, 4'-Dioxydicyclohexyl erhält man beispielsweise dadurch, daß man 4, 4'-Diaminodiphenyl diazotiert und verkocht und das gebildete 4, 4 -Dioxydiphenyl anschließend perhydriert. Man verwendet bei der Oxydation in.. der Regel' 6o%ige Salpetersäure, kann aber auch mit geringer oder höher konzentrierter Säure arbeiten, also in einem Bereich von etwa 5o. bis 8o %> -,Als .K:atalysatoren verwendet man bekannte Oxy'datiönskätalysatoren, vorzugsweise Vanadin- oder Molybdänsalze. Die Temperaturen, bei denen die Oxydation erfolgt, liegen oberhalb 25°, am günstigsten sind Temperaturen von etwa 3o bis 5o°, jedoch sind auch höhere Temperaturen anwendbar. Die Aufarbeitung der Tetracarbonsäure erfolgt in übIkdier Weise. Man kann die Säure den üblichen Verwendungszwecken für mehrbasische aliphatische Car= Bonsäuren zuführen und sie beispielsweise ,in Mischung mit Carbonaten oder stcaxböriateii' zur-Herstellung von Kohlensäure entwickelnden Pulvern oder Täbletten verwenden- -- - - -.,., -. . .Process for the preparation of diadipic acid It has been found that a new branched-chain aliphatic tetracarboxylic acid, 1) ia (lil) iric acid, is obtained if the, @,. -f) ioxydicyclohexyl subjected to oxidation with nitric acid, expediently in the presence of oxidation catalysts. The oxidation proceeds according to the following reaction scheme: 4,4'-Dioxydicyclohexyl is obtained, for example, by diazotizing 4,4'-diaminodiphenyl and boiling it off and then perhydrating the 4,4'-dioxydiphenyl formed. As a rule, 60% nitric acid is used for the oxidation, but it is also possible to work with less or more concentrated acid, that is to say in a range of about 50. Up to 80%> -, As .K: atalysatoren one uses known Oxy'datiönskätalysatoren, preferably vanadium or molybdenum salts. The temperatures at which the oxidation takes place are above 25 °, temperatures of about 30 to 50 ° are most favorable, but higher temperatures can also be used. The tetracarboxylic acid is worked up in the usual way. You can use the acid for the usual purposes for polybasic aliphatic carboxylic acids and use them, for example, in a mixture with carbonates or stcaxböriateii 'for the production of powders or tablets that develop carbon dioxide - - - -.,., -. . .

Man hat bereits durch Einwirkung heißer konzentrierter Salpetersäure auf -4, 4 -Dioxydicyclohexylmethan in etwa 3o%iger Ausbeute eine als ß, ß'-Methylendiadipinsäure bezeichnete Tetracarbonsäure erhalten (Ber.d.Dtsch.Chem.Gesellsch.64, S. 2623). Es war jedoch nicht zu efwarten'däß das 4, 4 -Dioxydicyclohexyl bei der Oxydation ohne weitgehenden. Molekülabbau zu der - neuen Tetracarbonsäure führen würde, dazu in sehr guter Ausbeute von 6o bis. 70 0/0.-Be- ispie--1 -In einen 2-Liter-Kolben werden 4oo Gewichtsteile 6o%ige Salpetersäure, 44 Gewichtsteile Wasset in:;g;4;:,(eiclitsteile Ammonvanadat vorgejegt,.. In die Salpetersäure gibt man unter Rühren in kleinen Anteilen 65 Gewichtsteile 4, 4 -Dioxydi-,cyelo'he-xy-1,-wobei-Ydie .Temperatur unter sc'hwac'her Kühlung zwischen 3o bis 38° gehalten wird. Nachdem alles zugegeben ist, rührt man noch 5 Stunden bei 35° nach. Die ausgeschiedene, fast farbloge' Diadipinsäure wird nach längerem Stehen (-xelttuell unter Eiskühlung) abgesaugt und mit eiskaltem Wasser gewaschen. Aus der Mutterlaugeerhält man durch Einengung noch eine weitere Menge Diadipinsäure.One already has the action of hot concentrated nitric acid on -4, 4 -dioxydicyclohexylmethane in about 3o% yield as ß, ß'-methylenediadipic acid designated tetracarboxylic acid obtained (Ber.d.Dtsch.Chem.Gesellsch.64, p. 2623). However, it was not to be expected that the 4,4-dioxydicyclohexyl was oxidized without extensive. Molecular degradation to the - new tetracarboxylic acid would lead to this in very good yield from 6o to. 70 0/0 Example - 1 - Into a 2 liter flask 400 parts by weight of 60% nitric acid, 44 parts by weight of water in:; g; 4;:, (eiclitsteile Ammonvanadate is used, .. In the nitric acid you add little ones while stirring Portions 65 parts by weight 4, 4 -Dioxydi-, cyelo'he-xy-1, -Wobei-Ydie .Temperature below slow cooling is kept between 3o to 38 °. After all is admitted The mixture is stirred for a further 5 hours at 35 °. The excreted, almost colorless, diadipic acid is sucked off after standing for a long time (-xelttuell under ice cooling) and with ice cold Water washed. A further one is obtained from the mother liquor by concentration Amount of diadipic acid.

- Das Rohprodukt wird aus Wasser unter Zusatz von Aktivkohle umkristallisiert. Die Diadipinsätire'.falr in :zei isomeren Formen an mit den Schmelzpunkten 195 bis i96° und 203 bis 2o5°.- The crude product is recrystallized from water with the addition of activated charcoal. The Diadipinsätire'.falr in: two isomeric forms with the melting points 195 to 96 ° and 203 to 205 °.

-höher -schmelzende Form ist leichter wasserlösliqh," so daß man das Gemisch durch fraktioriierte Krisfalligation trennen kann. iBeide Isomeren erhält man in Form rein weißer Kristalle. Gesamtausbeute = 7o bis 75 0/0. Analyse: _ C12 H18 08 gef. C = 49,25 %, H = 6,11 % . .. .. . ber. C = 4955 %, H = 6,31 0/0 VZ. des Tetraäthylesters gef. 553, her. 557. The higher-melting form is more readily water-soluble, "so that the mixture can be separated by fractional crystal ligation. Both isomers are obtained in the form of pure white crystals. Total yield = 70 to 75%. Analysis: _ C12 H18 08 found. C = 49.25%, H = 6.11% . .. ... calcd. C = 4955%, H = 6.31 0/0 VZ. of the tetraethyl ester found. 553, her. 557

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von Diadipinsäure; dadurch gekennzeichnet, daß man 4, 4 -Dioxydicyclohexyl, zweckmäßig in Gegenwärt von Oxydationskatalysatoren, der Ox@@-dation mit Salpetersäure unterwirft.PATENT CLAIM: Process for the production of diadipic acid; through this characterized in that 4, 4-dioxydicyclohexyl, expediently in the presence of oxidation catalysts, subject to ox @@ - dation with nitric acid.
DED4359D 1944-04-22 1944-04-22 Process for the preparation of diadipic acid Expired DE849242C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DED4359D DE849242C (en) 1944-04-22 1944-04-22 Process for the preparation of diadipic acid

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DED4359D DE849242C (en) 1944-04-22 1944-04-22 Process for the preparation of diadipic acid

Publications (1)

Publication Number Publication Date
DE849242C true DE849242C (en) 1952-09-11

Family

ID=7030970

Family Applications (1)

Application Number Title Priority Date Filing Date
DED4359D Expired DE849242C (en) 1944-04-22 1944-04-22 Process for the preparation of diadipic acid

Country Status (1)

Country Link
DE (1) DE849242C (en)

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