DE874770C - Process for the preparation of esters of ª-chlorobutyric acid - Google Patents
Process for the preparation of esters of ª-chlorobutyric acidInfo
- Publication number
- DE874770C DE874770C DEB15853A DEB0015853A DE874770C DE 874770 C DE874770 C DE 874770C DE B15853 A DEB15853 A DE B15853A DE B0015853 A DEB0015853 A DE B0015853A DE 874770 C DE874770 C DE 874770C
- Authority
- DE
- Germany
- Prior art keywords
- esters
- chlorobutyric acid
- hydrogen chloride
- water
- preparation
- 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
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
Description
Verfahren zur Herstellung von Estern der y-Chlorbuttersäure Es ist bekannt, daß man bei der Umsetzung von ;,-Butvrolacton mit Chlorwasserstoff Gemische von ;,-Clllorbtittersäure und wechselnden Mengen eines e,sterartigen Kondensationsprodukts der -y-Clilorbuttersäure mit #,#-Oxybuttersäure der Formel CI-CH,-CH2-CH2-coo-CH.-CH2-CH2-COOH erhält. Führt man die Umsetzung in Gegenwart von Alkoholen oder Polvoxyverbiiidungen aus, so erhält man neben den einfachen 7,-Chlorbuttersäureestern dieser Oxyverbindungen auch Ester des genannten X-ondensationsproduktes.Process for the preparation of esters of γ-chlorobutyric acid It is known that, in the reaction of γ-butvrolactone with hydrogen chloride, mixtures of; of the formula CI-CH, -CH2-CH2-coo-CH.-CH2-CH2-COOH. If the reaction is carried out in the presence of alcohols or polyoxy compounds, in addition to the simple 7, chlorobutyric acid esters of these oxy compounds, esters of the X ondensation product mentioned are also obtained.
Es wurde nun gefunden, daß man einfache Ester der -y-Chlorbuttersä,ure in sehr guten Ausbeuten und unter Vermeidung unerwünschter Nebenprodukte erhält, wenn man ein Gemisch aus äquivalenten Mengen -y-Butyrolacton und einer Oxy- oder Poly-.oxvverbindun'- in Gegenwart eines Verdünniiiigsmittels, das mit Wasser azeotrop siedende Gemische bildet, unter Einleiten von Chlorwasserstoff derart erhitzt, dafl das gebildete Wasser laufend azeotrop entfernt wird.It has now been found that simple esters of -y-chlorobutyric acid can be used obtained in very good yields and avoiding undesired by-products, if you have a mixture of equivalent amounts -y-butyrolactone and an oxy- or Poly-.oxvverbindun'- in the presence of a diluent that azeotropes with water forms boiling mixtures, heated with the introduction of hydrogen chloride in such a way thatfl the water formed is continuously removed azeotropically.
Geeignete Verdünnungsmittel, die mit Wasser azeotrop siedende Gemische bilden, sind z. B. Methylerichlorid, Äthylenchlorid, Benzol oder Toltiol. Man führt die Verdünnungsmittel zweckmäßig nach Abscheidung des mit ihnen azeotrop übergegangenen Wassers wieder in das Reaktions-,gefäß zurück und arbeitet also in einem Kreislauf dieses Mittels. Als OxvverbindunIgen, die man in dieser Weise mit Z-Butyrolacton und Chlorwasserstoff umsetzen kann, seien z. B. genannt Hexanol, Äthylhexanol, Benzylalkohol, Hexandiol-(i, 6), Di- und Triäthylenglykol, Hexantriol-(j, 2, 4) oder Pentaerythrit.Suitable diluents which form azeotropically boiling mixtures with water are, for. B. methylene chloride, ethylene chloride, benzene or toltiol. The diluents are expediently returned to the reaction vessel after the water, which has passed over azeotropically with them, has been separated off, and this agent is therefore used in a cycle. As OxvverbindunIgen that can be reacted in this way with Z-butyrolactone and hydrogen chloride are, for. B. called hexanol, ethylhexanol, benzyl alcohol, hexanediol (i, 6), di- and triethylene glycol, hexanetriol (j, 2, 4) or pentaerythritol.
Die auf die beschriebene Weise erhältlichen Ester sind wertvolle Zwischenprodukte; sie eignen sich auch als Weichmacher für Kunststoffe.The esters obtainable in the manner described are valuable intermediates; they are also suitable as plasticizers for plastics.
Die im Beispiel genannten Teile sind Gewichtsteile. Beispiel In einem Rührkessel, der mit einer Rücklaufkolonne versehen ist, bringt man ein Gemisch von 344 Teilen technischem -y-Butyrolacton, 236 Teilen Hexandiol-(i, 6) und i5oo Teilen Toluol derart zum Sieden, daß stündlich etwa i:2oo bis 16oo Teile Toluol überdestillieren und über einen Wasserabscheider und Siphon wieder in den Kessel zurückfließen. Sobald sich dieser Toluolkreislauf eingestellt hat, leitet man in den Kessel einen Strom von trockenem Chlorwasserstoff ein. Dabei geht mit dem Toluol das gebildete Wasser über, das im Abscheider laufend entfernt wird, bevor das Toluol wieder in den Kessel zurückläuft. Sobald kein Wasser mehr übergeht, unterbricht man das Einleiten von Chlorwasserstoff und das Erhitzen. Der Kesselinhalt wird zur Entfernung gelösten überschüssigen Chlorwasserstoffs mehrfach mit Wasser gewaschen, mit Kohle entf ärbt, filtriert und bei vermindertem Druck vom Toluol befreit. Als Rückstand verbleiben etwa 575 Teile (# 88 1/o der Theorie) ein-es schwach bräunlichen Öles mit einem Chlorgehalt von 20,3 % (für den Bis--y-chlorbuttersäureester des Hexandiols-(i, 6) berechnet sich ein Chlorgehalt von :21,7'/0); ioccm des Öles verbrauchen 0,3ccm n-Natronlauge.The parts mentioned in the example are parts by weight. EXAMPLE A mixture of 344 parts of technical-γ-butyrolactone, 236 parts of hexanediol ( 1.6) and 1500 parts of toluene is brought to the boil in a stirred kettle equipped with a reflux column in such a way that about 1: 2oo to 1,6oo per hour Distill over parts of toluene and flow back into the kettle via a water separator and siphon. As soon as this toluene cycle has established itself, a stream of dry hydrogen chloride is passed into the boiler. The water formed passes over with the toluene and is continuously removed in the separator before the toluene runs back into the boiler. As soon as no more water passes over, the introduction of hydrogen chloride and the heating are interrupted. To remove dissolved excess hydrogen chloride, the contents of the kettle are washed several times with water, decolorized with charcoal, filtered and freed from toluene under reduced pressure. About 575 parts (# 88 1 / o of theory) of a slightly brownish oil with a chlorine content of 20.3% remain as residue (the chlorine content is calculated for the bis-γ-chlorobutyric acid ester of hexanediol- (1.6 ) from: 21.7 '/ 0); 1 ounce of the oil consume 0.3ccm of sodium hydroxide solution.
Polyvinylchloridfolien, die mit diesem 01 weichgemacht sind, zeigen eine hervorragende Kältefestigkeit.Polyvinyl chloride films that are plasticized with this 01 show excellent resistance to cold.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB15853A DE874770C (en) | 1951-07-14 | 1951-07-14 | Process for the preparation of esters of ª-chlorobutyric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB15853A DE874770C (en) | 1951-07-14 | 1951-07-14 | Process for the preparation of esters of ª-chlorobutyric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE874770C true DE874770C (en) | 1953-04-27 |
Family
ID=6958644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB15853A Expired DE874770C (en) | 1951-07-14 | 1951-07-14 | Process for the preparation of esters of ª-chlorobutyric acid |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE874770C (en) |
-
1951
- 1951-07-14 DE DEB15853A patent/DE874770C/en not_active Expired
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