DE809808C - Process for the production of unsaturated aldehydes - Google Patents

Process for the production of unsaturated aldehydes

Info

Publication number
DE809808C
DE809808C DEP49205A DEP0049205A DE809808C DE 809808 C DE809808 C DE 809808C DE P49205 A DEP49205 A DE P49205A DE P0049205 A DEP0049205 A DE P0049205A DE 809808 C DE809808 C DE 809808C
Authority
DE
Germany
Prior art keywords
weight
parts
acid
water
unsaturated aldehydes
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
DEP49205A
Other languages
German (de)
Inventor
Alfred Max Dr Paquin
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.)
Individual
Original Assignee
Individual
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 Individual filed Critical Individual
Priority to DEP49205A priority Critical patent/DE809808C/en
Application granted granted Critical
Publication of DE809808C publication Critical patent/DE809808C/en
Expired legal-status Critical Current

Links

Classifications

    • 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
    • C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
    • C07C45/516—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of nitrogen-containing compounds to >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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic 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
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/562—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with nitrogen as the only hetero atom
    • 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
    • C07C45/65—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
    • C07C45/66—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 splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups by 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
    • C07C45/74—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
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/85—Separation; Purification; Stabilisation; Use of additives by treatment giving rise to a chemical modification

Landscapes

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

Description

Verfahren zur Herstellung von ungesättigten Aldehyden Es ist bekannt, Aldehyde mittels verdünnter Alkalien in ihre Aldole zu kondensieren und aus diesen durch Wasserabspaltung ungesättigte Aldehyde herzustellen. Es ist weiterhin bekanntgeworden, die gleiche Kondensation mit Hilfe der Salze sekundärer Amine oder sekundärer Aminosäuren (Sarkosin) durchzuführen.Process for the preparation of unsaturated aldehydes It is known To condense aldehydes into and out of their aldols by means of dilute alkalis to produce unsaturated aldehydes by splitting off water. It has also become known the same condensation with the help of the salts of secondary amines or secondary amino acids (Sarcosine).

Primäre Amine sind als Kondensationsmittel bisher nicht angewendet worden, da es auf der Hand zu liegen schien, daß sie sich für diesenZweck nicht eignen würden.Primary amines have so far not been used as condensation agents as it seemed obvious that they were not suitable for this purpose would suit.

Es wurde nun die überraschende Beobachtung gemacht, daß Salze primärer Amine in katalytischen Mengen nicht nur ebenfalls Aldolkondensation bewirken, sondern daß sie darüber hinaus sogar hesonders wirksame Aldolisierungsmittel sind, welche eine Aldolkondensation in erheblich kürzerer Zeit durchzuführen gestatten, als dies mit den bekannten Kondensationsmitteln der Fall ist. Ihre Wirkung ist so stark, äaß selbst die kleinen Mengen Aminsalz, die sich durch Neutralisation der in allen technischen Aldehyden enthaltenen Spuren von Säuren mit primären Aminen bilden, genügen, um schon in wenigen Minuten bei gering erhöhter Temperatur Aldolkondensation in Höhe von 6o bis 8o % der Aldehydmenge zu bewirken.The surprising observation has now been made that salts are more primary Amines in catalytic amounts not only cause aldol condensation, but that they are also particularly effective aldolizing agents, which allow an aldol condensation to be carried out in a considerably shorter time than this is the case with the known condensing agents. Your effect is so strong Ate even the small amounts of amine salt which were neutralized in all of them form traces of acids containing technical aldehydes with primary amines, suffice to cause aldol condensation in just a few minutes at a slightly elevated temperature to effect in the amount of 6o to 8o% of the amount of aldehyde.

Werden erhöhte Mengen primären Aminsalzes (etwa 3 bis 5 % der Aldehydmenge) angewendet oder wird nach Zufügen von freiem primärem Amin die Möglichkeit zur Bildung desselben durch zusätzliehe ' freie Säure gegeben; so-lä$t-sich die Ausbeute an Produkten der Aldolstufe auf über 9b% erhöhen.Are increased amounts of primary amine salt (about 3 to 5% of the aldehyde amount) applied or is the possibility of formation after the addition of free primary amine the same by additional 'given free acid; so-can-be increase the yield of products of the aldol stage to over 9%.

Die Durchführung der Aldolkondensation kann je nach dem gewünschten-Produkt der Aldolstufe nach verschiedenen Mettiodcn erfolgen: Zu dem Aldehyd, dessen Säuregehalt gegebenenfalls durch Ansäuern erhöht worden ist, wird eingetragen: i. entweder gerade die Menge primären Amins, die zum Neutralisieren der freien Säure und für die Aldolkondensation erforderlich ist, man erhält in diesem Fall das übliche Aldolisierungsprodukt,_das durch Wasserabspaltung in den ungesättigten Aldehyd übergeht, 2. oder die Menge primären Amins, die sowohl zum Neutralisieren der freien Säure als auch zur Bildung der Schiff schen.Base des Aldehyds der Aldolstufe erforderlich ist. Für diese beiden Zwecke können auSh verschiedene primäre Amine nacheinander zur Anwendung kommen., Beispielsweise können für den zweiten Zweck aus -Diaminen doppelseitige Schiffsehe Basen hergestellt werden. Durch Hydrolyse der Schiffsehen Base mit verdünnter Mineralsäure erhält man den ungesättigten Aldehyd.The aldol condensation can be carried out depending on the desired product the aldol stage take place according to different mettiodine: To the aldehyde, its acidity if necessary increased by acidification, the following is entered: i. either straight the amount of primary amine required to neutralize the free acid and for the aldol condensation is required, in this case the usual aldolization product is obtained, _das passes into the unsaturated aldehyde by elimination of water, 2. or the amount primary amine, which both neutralizes the free acid and creates it the Schiff's base of the aldehyde of the aldol stage is required. For these two Various primary amines can be used one after the other., For example, double-sided marriages can be made from diamonds for the second purpose Bases are made. By hydrolysis of the ship's base with dilute mineral acid the unsaturated aldehyde is obtained.

Macht die Reinigung des ungesättigten Aldehyds etwa durch Destillation Schwierigkeiten, so kann diese über die Schiffsehe Base erfolgen. Die aus dem einsäurigen Salz eines Diamins gebildete einseitige Schiffsehe Base kann umkristallisiert werden, oder es kann auch nach Infreiheitsetzen der Schiffsehen Base mit einer freien Aminogruppe dieselbe durch Destillation gereinigt werden, da sie unter spontaner Umlagerung in das Tetrahydroimidazolderivat leicht destilliert, oder man bereitet die Oxäthylamin-Schiffsche Base, welche sich beim Erwärmen spontan in das leicht destillierende Oxazolidinderivat umlagert. Letzteres wie auch das Tetrahydroimidazolderivat lagern sich wieder in die Kettenform zurück, wenn zwecks hydrolytischer Spaltung der Schiffsehen Basen mit verdünnter Mineralsäure erhitzt wird.Does the purification of the unsaturated aldehyde, for example, by distillation Difficulties, this can be done via the ship's marriage base. The ones from the one-acid The unilateral ship's base formed by the salt of a diamine can be recrystallized or it can also after liberating the Schiff base with a free amino group the same can be purified by distillation, since it is under spontaneous rearrangement easily distilled into the tetrahydroimidazole derivative, or the Oxäthylamin-Schiffsche is prepared Base, which spontaneously turns into the easily distilling oxazolidine derivative when heated surrounded. The latter as well as the tetrahydroimidazole derivative are stored again in the chain form, if for the purpose of hydrolytic cleavage of the ships' bases is heated with dilute mineral acid.

Die nach dem Verfahren dieses Patentes leicht durchführbare Aldolkondensation und Gewinnung der ungesättigten Aldehyde hat große technische Bedeutung, da die mannigfaltige Reaktionsfähigkeit der letzteren weitgehend für die verschiedensten Zwecke ausgenutzt werden kann. Beispiele i. Zu einer Mischung von 116 Gewichtsteilen Propionaldehyd, der 0,7 Gewichtsteile Propionsäure enthält, und 29 Gewichtsteilen Wässer werden unter Rühren 2,40 Gewichtsteile Eisessig zugegeben und danach 7,2o Gewichtsteile einer 25%igen wäßrigen Methylaminlösung, welche die Gesamtsäure neutralisiert, eingetragen. Dann wird i1/2 Stunden bei 40 bis 45° und i1/2 Stunden bei 5o bis 55° gerührt. Durch Destillation wird dann 2-:flethylpenten-(2)-al mit einer Ausbeute von 9i % erhalten.The aldol condensation and recovery of the unsaturated aldehydes, which can easily be carried out by the process of this patent, is of great technical importance, since the diverse reactivity of the latter can be used to a large extent for a wide variety of purposes. Examples i. To a mixture of 116 parts by weight of propionaldehyde containing 0.7 parts by weight of propionic acid and 29 parts by weight of water, 2.40 parts by weight of glacial acetic acid are added with stirring, and then 7.2o parts by weight of a 25% strength aqueous methylamine solution, which neutralizes the total acid, are added. The mixture is then stirred for 11/2 hours at 40 to 45 ° and for 11/2 hours at 50 to 55 °. 2-: Flethylpenten- (2) -al is then obtained by distillation in a yield of 91%.

2. Zu einer :Mischung von 144 Gewichtsteilen Butyraldehyd, der 1,2. Gewichtsteile Buttersäure enthält, und 36 Gewichtsteilen Wasser werden 2,i8 Gewichtsteile Eisessig unter Rühren zugefügt und dann 3,6$ Gewichtsteile Buty#lämin eingefrägen, das die Gesamtsäure neutralisiert. Danach wird i1/2 Stunden bei 4o bis 45 ° und i1/2 Stunden bei 5o bis 55 ° gerührt. -Durch Destillation wird 2-ÄthylheXen-(2)-al mit einer Ausbeute von89%gewonnen.2. To a: mixture of 144 parts by weight of butyraldehyde, the 1.2. Contains parts by weight of butyric acid, and 36 parts by weight of water become 2.18 parts by weight Glacial acetic acid was added with stirring and then 3.6 parts by weight of buty lämin were imprinted, which neutralizes the total acid. Then i1 / 2 hours at 4o to 45 ° and Stirred i1 / 2 hours at 50 to 55 °. -Distillation becomes 2-ÄthylheXen- (2) -al obtained with a yield of 89%.

3. Zu einer Mischung von 144 Gewichtsteilen Isobutyraldehyd, der o,9 Gewichtsteile Isobuttersäure enthält, und 36 Gewichtsteilen Wasser werden 2,38 Gewichtsteile Eisessig unter Rühren zugefügt und dann-3,65 Gewichtsteile Isobutylamin eingetragen, das -die Gesamtsäure neutralisiert. Danach wird 1112 Stunden bei 4o bis 45° und i1/2 Stunden bei 5o bis 55° gerührt. Dann wird bei 5o° unter vermindertem Druck entwässert, und es hinterbleibt Isobut.,raldol mit einer Ausbeute von 870/0.3. To a mixture of 144 parts by weight of isobutyraldehyde, the o, 9 Parts by weight of isobutyric acid contains, and 36 parts by weight of water becomes 2.38 parts by weight Glacial acetic acid was added with stirring and then -3.65 parts by weight of isobutylamine were added, that neutralizes the total acid. Then 1112 hours at 4o to 45 ° and Stirred i1 / 2 hours at 50 to 55 °. Then at 5o ° under reduced pressure dehydrated, and there remains isobut., raldol with a yield of 870/0.

4. Zu der nach Beispiel 3 erhaltenen noch nicht entwässerter Reaktionsflüssigkeit werden unter Rührei bei 45 bis 50° innerhalb '/2 Stunde 146 Gewichtsteile Isobutylämin eingetragen und '/2Stunde bei dieser Temperatur nachgerührt. Es entsteht bei gleichzeitiger Wasserabspaltung aus dem Aldol die Schiffsehe #Base 2, 2, 4-Trimethylpenten- (3) -isobutylamin, welche mit 13o Gewichtsteilen Wasser und 265 Gewichtsteilen Salzsäure 37% versetzt und unter Rühren 3/4 Stunden am Rückflußkühler am Sieden gehalten wird. Nach Abziehen der wäßrigen Schicht, Waschen bis zur neutralen Reaktion und Trocknen bei 50' unter vermindertem Druck erhält man 2, 2, 4-Trimethylpenten-(3)-al mit einer Aubbeute von 82()/0.4. 146 parts by weight of isobutylamine are added within 1/2 hour to the not yet dehydrated reaction liquid obtained according to Example 3, while stirring eggs at 45 to 50 °, and stirring is continued for 1/2 hour at this temperature. With simultaneous elimination of water from the aldol, the Schiffsehe #Base 2, 2, 4-trimethylpentene- (3) -isobutylamine is formed, which is mixed with 130 parts by weight of water and 265 parts by weight of 37% hydrochloric acid and kept at the boil for 3/4 hours on the reflux condenser with stirring will. After peeling off the aqueous layer, washing until neutral and drying at 50 ' under reduced pressure, 2,2,4-trimethylpentene- (3) -al is obtained in a yield of 82 () / 0.

5. Zu der nach Beispiel 3 erhaltenen wäßrigen Reaktionsflüssigkeit werden 62,5 Gewichtsteile Äthylendiamin 96%, das mit der gleichen Menge Wasser verdünnt ist, bei 35 bis 4o° unter Rühren eilgetragen und '/2 Stunde bei 40 bis 45° nachgerührt. Man erhält rohes Äthylendi-(2, 2, 4-Trimethylpenten-(3) )-amin, welches durch Abdestillieren des flüchtigen Anteils unter vermindertem Druck bei einer Temperatur bis zu ioo° weitgehend gereinigt wird. Die Hydrolyse erfolgt dann durch Zugabe von 264 Gewichtsteilen Wasser und 6oo Gewichtsteilen Salzsäure 37% und 3/4stündigem Kochen am Rückflußkühler. Nach Abziehen der wäßrigen Schicht wird 2, 2, 4-Trimethylpenten-(3)-al in beschriebener Weise gewonnen. Ausbeute über 8o %.5. To the aqueous reaction liquid obtained in Example 3 62.5 parts by weight of ethylenediamine 96%, which is diluted with the same amount of water is carried at 35 to 40 ° with stirring and stirred for 1/2 hour at 40 to 45 °. Crude ethylenedi- (2, 2, 4-trimethylpentene- (3)) amine is obtained, which is obtained by distilling off of the volatile component under reduced pressure at a temperature of up to 100 ° is largely cleaned. The hydrolysis is then carried out by adding 264 parts by weight Water and 600 parts by weight of 37% hydrochloric acid and reflux for 3/4 hours. After peeling off the aqueous layer, 2, 2, 4-trimethylpentene- (3) -al is described in Way won. Yield over 80%.

6. Zu der nach Beispiel 3 erhaltenen noch wasserhaltigen Reaktionsflüssigkeit werden 128 Gewichtsteile Äthanolamin 96% unter Rühren bei 35 bis 4o 1 eingetragen, mit halbstündlichem Nachrühren bei 4o°. Nach .dem. Entwässern unter vermindertem Druck bei 5o° wird die viskose Schiffsehe Base unter vermindertemDruck fraktioniert. Die wasserdünne, im Gegensatz zur Schiffsehen Base wasserunlösliche Hauptfraktion, die aus i, i, 3-Trimethylbuten-(2)-oxazolidin besteht, wird in beschriebener Weise.mit 12%iger Salzsäure zunächst wieder in die Kettenform zurückgelagert und durch Hydrolyse in 2, 2, 4-Trimethylpenten-(3>-al gespalten. Ausbeute über 8o %.6. 128 parts by weight of ethanolamine 96% are added to the still water-containing reaction liquid obtained according to Example 3, with stirring at 35 to 4o 1 , with stirring every half hour at 40 °. After this. Dehydrating under reduced pressure at 50 °, the viscous Schiff base is fractionated under reduced pressure. The water-thin main fraction, which is insoluble in water in contrast to Schiffsee's base and which consists of i, i, 3-trimethylbutene- (2) -oxazolidine, is initially stored back into the chain form with 12% hydrochloric acid and by hydrolysis in 2, 2,4-Trimethylpentene (3> -al cleaved. Yield over 80%.

7. Zu einer Lösung von 193- Gewichtsteilen Äthylendiaminmonochlorhydrat in 193 Gewichtsteilen Wasser wird die nach Beispiel 3 erhaltene noch wasserhaltige Reaktionsflüssigkeit bei 35 bis 4o° unter Rühren in 20 Minuten eingetragen und 1/2 Stunde bei dieser Temperatur nachgerührt. Nach Abtreiben der flüchtigen Anteile bei 5o° unter vermindertem Druck erhält man 2, 2, 4-Trimethylpenten-(3)-äthylendiaminchlorhydrat als amorphe :lasse, die allmählich kristallinisch erstarrt. Nach Umkristallisieren aus Äthanol 96% wird die Verbindung in reiner Form erhalten.7. To a solution of 193 parts by weight of ethylenediamine monochlorohydrate in 193 parts by weight of water, the still water-containing reaction liquid obtained according to Example 3 is added at 35 to 40 ° with stirring in 20 minutes and stirred for 1/2 hour at this temperature. After the volatile constituents have been stripped off at 50 ° under reduced pressure, 2,2,4-trimethylpentene (3) ethylenediamine chlorohydrate is obtained as an amorphous lasse which gradually solidifies in a crystalline form. After recrystallization from ethanol 96%, the compound is obtained in pure form.

Die Aufarbeitung kann aber auch folgendermaßen erfolgen: das Chlorhydrat wird in Wasser aufgenommen, mit Natronlauge alkalisch gemacht und die freie ölige Base in Äther aufgenommen. Die getrocknete Base wird im Stickstoffstrome im guten Vakuum fraktioniert, was nach der spontan erfolgenden Umlagerung in 1, 1, 3-Trimethylbuten-(2)-hexahvdroimidazol leicht vonstatten geht. Hieraus wird in üblicher Weise mit 12%iger Salzsäure nach der Rücklagerung in das salzsaure Salz der Schiffschen Base und hydrolytischer Spaltung 2, 2, 4-Trimethylpenten-(3)-al gewonnen.However, work-up can also be carried out as follows: the hydrochloride is taken up in water, made alkaline with caustic soda and the free oily Base taken up in ether. The dried base is in good condition in the nitrogen stream Vacuum fractionated, which occurs after the spontaneous rearrangement in 1, 1, 3-trimethylbutene- (2) -hexahvdroimidazole goes easily. This is followed up in the usual way with 12% hydrochloric acid the return to the hydrochloric acid salt of the Schiff base and hydrolytic cleavage 2, 2, 4-trimethylpentene- (3) -al obtained.

Claims (1)

PATENTANSPRUCH: Verfahren zur Herstellung von ungesättigten Aldehyden, dadurch gekennzeichnet, daB Aldehyde mit Lösungen von Salzen primärer Amine oder wäBrige, freie Säure enthaltende Aldehydlösungen mit primären Aminen bei Temperaturen zwischen o und ioo° behandelt werden,, so daB nach Neutralisation der Säure o,5 bis 6% an Aminsalzen, berechnet auf den Aldehyd, bei der Reaktion zugegen sind, worauf die gebildeten Aldole oder die daraus direkt entstandenen Schiffschen Basen der ungesättigten Aldehyde, gegebenenfalls nach ihrer Fraktionierung, hydrolytisch gespalten werden. PATENT CLAIM: Process for the production of unsaturated aldehydes, characterized in that aldehydes are treated with solutions of salts of primary amines or aqueous aldehyde solutions containing free acid with primary amines at temperatures between 0 and 100 °, so that after neutralization of the acid 0.5 up to 6% of amine salts, calculated on the aldehyde, are present in the reaction, whereupon the aldols formed or the Schiff bases of the unsaturated aldehydes directly resulting therefrom are hydrolytically cleaved, optionally after their fractionation.
DEP49205A 1949-07-19 1949-07-19 Process for the production of unsaturated aldehydes Expired DE809808C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DEP49205A DE809808C (en) 1949-07-19 1949-07-19 Process for the production of unsaturated aldehydes

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEP49205A DE809808C (en) 1949-07-19 1949-07-19 Process for the production of unsaturated aldehydes

Publications (1)

Publication Number Publication Date
DE809808C true DE809808C (en) 1951-08-02

Family

ID=7383604

Family Applications (1)

Application Number Title Priority Date Filing Date
DEP49205A Expired DE809808C (en) 1949-07-19 1949-07-19 Process for the production of unsaturated aldehydes

Country Status (1)

Country Link
DE (1) DE809808C (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1043314B (en) * 1953-03-09 1958-11-13 Union Carbide Corp Process for the production of straight-chain ª ‡, ª ‰ -unsaturated aldehydes

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1043314B (en) * 1953-03-09 1958-11-13 Union Carbide Corp Process for the production of straight-chain ª ‡, ª ‰ -unsaturated aldehydes

Similar Documents

Publication Publication Date Title
DE2240665A1 (en) PROCESS FOR THE PRODUCTION OF N, N'-DISUBSTITUTED CYCLIC DIAMINES
DE1618528B1 (en) New alfa-methylene-aldehydes
DE809808C (en) Process for the production of unsaturated aldehydes
DE2407675A1 (en) PROCESS FOR THE SEPARATION AND RECOVERY OF 3-METHYL-3-BUTEN-1-OL
DE617596C (en) Process for the preparation of secondary and tertiary unsaturated amines
DE1937526B2 (en) PROCESS FOR PRODUCING SUBSTITUTED PHENYLAMINE
DE545398C (en) Process for the preparation of fragrances
DE2605650A1 (en) PROCESS FOR THE PRODUCTION OF PARA-ISOBUTYL-PHENYL ACID DERIVATIVES
DE960813C (en) Process for the production of unsaturated ª † and ª € lactones
DE744756C (en) Process for the preparation of 6-isoamylamino-2-methylheptane
DE563398C (en) Process for the preparation of organic nitrogenous compounds
DE422098C (en) Process for the preparation of aminoketones
AT208837B (en) Process for the preparation of γ-aminocaprylic acid and its esters
DEP0049205DA (en) Process for the production of unsaturated aldehydes.
DE835738C (en) Process for the production of unsaturated aldehydes
DE912212C (en) Process for the preparation of stable dehydroabietic acid esters
DE1567046A1 (en) Parasiticides, especially fungicides
DE528270C (en) Process for the preparation of ephedrine derivatives
DE1618570C3 (en) Process for purifying adipic dinitrile
DE916055C (en) Process for the preparation of amino compounds
DE671841C (en) Process for the preparation of N-alkyl and N-aralkyl compounds of aminoethylphedrine
DE582245C (en) Process for the preparation of basic particles of catechol
CH366554A (en) Process for the preparation of @ -amino-caprylic acid and its esters
DE1002337C2 (en) Process for the preparation of hydrophenanthrylcarboxylic acids
DE854956C (en) Method of making a pteridine bead