DE965402C - Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(1,2) - Google Patents

Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(1,2)

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Publication number
DE965402C
DE965402C DER12278A DER0012278A DE965402C DE 965402 C DE965402 C DE 965402C DE R12278 A DER12278 A DE R12278A DE R0012278 A DER0012278 A DE R0012278A DE 965402 C DE965402 C DE 965402C
Authority
DE
Germany
Prior art keywords
ketobutene
methylol
water
preparation
formaldehyde
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
DER12278A
Other languages
English (en)
Inventor
Dipl-Chem Dr Walter Grimme
Dipl-Chem Dr Johannes Woellner
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.)
Rheinpreussen AG fuer Bergbau und Chemie
Original Assignee
Rheinpreussen AG fuer Bergbau und Chemie
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 Rheinpreussen AG fuer Bergbau und Chemie filed Critical Rheinpreussen AG fuer Bergbau und Chemie
Priority to DER12278A priority Critical patent/DE965402C/de
Application granted granted Critical
Publication of DE965402C publication Critical patent/DE965402C/de
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/17—Saturated compounds containing keto groups bound to acyclic carbon atoms containing hydroxy 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
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/74—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups combined with dehydration
    • 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
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
    • C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
    • C07C45/75—Reactions with formaldehyde
    • 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
    • C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
    • C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
    • 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
    • C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/04—Saturated compounds containing keto groups bound to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C49/00—Ketones; Ketenes; Dimeric ketenes; Ketonic chelates
    • C07C49/20—Unsaturated compounds containing keto groups bound to acyclic carbon atoms
    • C07C49/203—Unsaturated compounds containing keto groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation

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

Description

BUNDESREPUBLIK DEUTSCHLAND
AUSGEGEBEN AM 6. JUNI 1957
DEUTSCHES PATENTAMT
PATENTSCHRIFT
KLASSE 12 o GRUPPE 19o3 INTERNAT. KLASSE C07c
R 12278 IVb112 ο
Dipl.-Chem. Dr. Walter Grimme, Utfort über Moers,
und Dipl.-Chem. Dr. Johannes Wöllner, Moers
sind als Erfinder genannt worden
Rheinpreussen Aktiengesellschaft für Bergbau und Chemie,
Homberg (Ndrh.)
Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(l,2)
Patentiert im Gebiet der Bundesrepublik Deutschland vom 4. August 1953 an
Patentanmeldung bekanntgemacht am 6. Dezember 1956
Patenterteilung bekanntgemacht am 23. Mai 1957
Es ist bekannt, den ungesättigten Ketoalkohol 2-Methyk>l-3~ketobuten-(i, 2) durch Wasserabspal- 15 tung aus 3, 3-Dimethylolaceton herzustellen.
CH3 -CO-CH (CH2OH)2 > CH3 -CO-C (CH2OH) = CH2 + H2O
Die Herstellung des 3, 3-Dimethylolacetons ist technisch nur mit kleinen Ausbeuten durchzuführen. Es wurde nun gefunden, daß man dias 2-Metbylol-
zeitige Abspaltung von ι MoI Formaldehyd und ι Mol Wasser aus 3,3, 3-Trimethylolaceton herstellen kann:
3-ketobuten-(i, 2) in hoher Ausbeute durch gleich-
CH3 - CO - C (CH2OH) > CH3 -CO-C (CH2OH) = CH2 + CH2O + H2O .
Die Abspaltung von Formaldehyd und Wasser aus dem 3, 3, 3-Trimethylolaceton erfolgt in Gegenwart von wasserabspaltenden Mitteln, wie Phosphorsäure, Schwefelsäure, Tohiolsuilfonsäiure, Bimsstein, Aluminiumhydroxyd:, Aluminiumhydrosilicate od. dgl. Die Wasserabspaltung beginnt bei Temperaturen oberhalb ioo°. Als Zweckmäßig haben sich Temperaturen von 120 bis 2500 erwiesen. Die
709 532'287
Abspaltungsreaktion wird durch Anwendung von Vakuum begünstigt.
Das bei der Umsetzung verwendete 3, 3, 3-Trimethylolaceton kann nach dem Verfahren des Patents 959 643 durch Umsatz von Aceton und Formaldehyd in einem Molverhältnis von weniger als ι: 3 in wäßrigem alkalischem Medium bei Temperaturen unterhalb 50°, vorzugsweise unterhalb 20°, in Gegenwart von etwa 1000 ecm Wasser pro Mol Aceton hergestellt werden.
Das nach dem erfindungsgemäßen Verfahren hergestellte 2-Methylol-3-ketobu.ten-(i, 2) dient unter anderem zur Herstellung von glasklaren Polymerisationskunstharzen als Lösungsmittel sowie als Zwischenprodukt für die pharmazeutische Industrie.
Beispiel
100 g kristallisiertes 3, 3, 3-Trimethylolaceton und 4 g feingepulverter Bimsstein werden in einem Mörser innig gemischt. Beim allmählichen Erhitzen dieser Mischung in Vakuum der Wasserstrahlpumpe durch ein Ölbad auf 180 bis 2100 tritt die Wasserabspaltung ein. Nachdem zunächst vorwiegend Wasser übergegangen ist, steigt die Destillationstemperatur auf 80 bis 95 ° bei 18 mm Hg, wobei 66 g 2-Methylol-3-ketobuten-(i, 2), d. h. 99% der Theorie, erhalten werden, welches durch nochmalige Fraktionierung weitergereinigt werden kann.

Claims (2)

Patentansprüche:
1. Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(i, 2), dadurch gekennzeichnet, daß man aus 3,3,3-Trimethylolaceton in Gegenwart wasserabspaltender Mittel bei Temperaturen oberhalb ioo°, zweckmäßig bei 120 bis 250°, ι Mol Formaldehyd und 1 Mol Wasser abspaltet.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die Abspaltung von Formaldehyd und Wasser im Vakuum erfolgt.
In Betracht gezogene Druckschriften:
Deutsche Patentschrift Nr. 577 256;
britische Patentschrift Nr. 509 348.
© 609 710/363 11.56 (709 532/287 5. 57)
DER12278A 1953-08-04 1953-08-04 Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(1,2) Expired DE965402C (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DER12278A DE965402C (de) 1953-08-04 1953-08-04 Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(1,2)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DER12278A DE965402C (de) 1953-08-04 1953-08-04 Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(1,2)

Publications (1)

Publication Number Publication Date
DE965402C true DE965402C (de) 1957-06-06

Family

ID=7398762

Family Applications (1)

Application Number Title Priority Date Filing Date
DER12278A Expired DE965402C (de) 1953-08-04 1953-08-04 Verfahren zur Herstellung von 2-Methylol-3-ketobuten-(1,2)

Country Status (1)

Country Link
DE (1) DE965402C (de)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE577256C (de) * 1931-05-16 1933-06-01 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von ungesaettigten Ketonalkoholen
GB509348A (en) * 1938-02-25 1939-07-14 George William Johnson Improvements in the manufacture and production of 2-methyl-butanediol-1.3

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE577256C (de) * 1931-05-16 1933-06-01 I G Farbenindustrie Akt Ges Verfahren zur Darstellung von ungesaettigten Ketonalkoholen
GB509348A (en) * 1938-02-25 1939-07-14 George William Johnson Improvements in the manufacture and production of 2-methyl-butanediol-1.3

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