CH513902A - Prepn of 2-(1'-halogenoalkyl)-oxazolines - Google Patents
Prepn of 2-(1'-halogenoalkyl)-oxazolinesInfo
- Publication number
- CH513902A CH513902A CH1079269A CH1079269A CH513902A CH 513902 A CH513902 A CH 513902A CH 1079269 A CH1079269 A CH 1079269A CH 1079269 A CH1079269 A CH 1079269A CH 513902 A CH513902 A CH 513902A
- Authority
- CH
- Switzerland
- Prior art keywords
- reaction
- oxazolines
- ethanolamine
- halogenoalkyl
- prepn
- Prior art date
Links
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 150000008282 halocarbons Chemical class 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 5
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000000460 chlorine Chemical group 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 239000003085 diluting agent Substances 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 3
- 239000012442 inert solvent Substances 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- HTHNTJCVPNKCPZ-UHFFFAOYSA-N 2-chloro-1,1-difluoroethene Chemical group FC(F)=CCl HTHNTJCVPNKCPZ-UHFFFAOYSA-N 0.000 description 1
- SZIFAVKTNFCBPC-UHFFFAOYSA-N 2-chloroethanol Chemical compound OCCCl SZIFAVKTNFCBPC-UHFFFAOYSA-N 0.000 description 1
- JQDXZJYAUSVHDH-UHFFFAOYSA-N 3-chloropropanamide Chemical class NC(=O)CCCl JQDXZJYAUSVHDH-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- QDGONURINHVBEW-UHFFFAOYSA-N dichlorodifluoroethylene Chemical group FC(F)=C(Cl)Cl QDGONURINHVBEW-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- -1 for example Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 150000002463 imidates Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 150000004965 peroxy acids Chemical class 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009183 running Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Prepn of 2-(1'-halogenoalkyl)-DELTA2oxazolines.. Of general formula (I):- (where R is H, F or Cl or F3C-(CF2)n-where n is 0-10 and X is F or Cl) comprises reacting R-CX=CF2 with ethanolamine. Heat of reaction is pref. removed using an inert solvent esp. lower halogenated hydrocarbons. The reaction is generally performed at 0-120 degrees C pref. about 20-100 degrees C esp. 35-45 degrees C.
Description
Verfahren zur Herstellung von 2-(1'-ll.Halogenalkyi)-A2-oxazolinen
Die vorliegende Erfindung betrifft ein Verfahren zur Herstellung von 2-(l'-H-Halogenalkyl)-A2-oxazo- linen der Fonnel I
EMI1.1
in welcher R ein Wasserstoff-, Chlor- oder Fluoratom oder eine Gruppe der Formel CFS-(CF2)n, in welcher n für 0 der eine ganze Zahl von 1-10 steht, und X ein Fluor- oder Chloratom bedeuten, das dadurch gekennzeichnet ist, dass man Olefine der Formel II R-CX=CF2 II mit AthanoIamin umsetzt.
Es ist bereits bekannt, in 2-Stellung substituierte A2-Oxazoline aus Carbonsäuren bzw. deren Derivaten durch Umsetzung mit Äthanolamin herzustellen (Seeliger, Angew. Chem. 78 cm966) 913). Als einfachstes Syntheseprinzip wird hier die Gasphasendehydrierung der aus Äthanolamin und der Carbonsäure bzw.
dem Carbonsäureester erhaltenen ss-Hydroxyäthylcarbonsäureamide an einem Alumlnzumoxyd-Kontakt bei Temperaturen von 32N575 C und einem Druck von 0,5-20 Torr beschrieben.
2-Perfluoralkyl-A2-oxazoline wurden bereits durch Kondensation von Perfluoralkylnitrilen mit 2-Chloräthanol in Gegenwart von überschüssigem Tri methylarnin hergestellt (H. C. Brown und Ch. R. Wetzel, J. org. Chem. 30 (1965) 3729). Es wird jedohe hierbei ausgeführt, dass die gebildeten Oxazoline thermisch nur wenig stabiler als die intermediär gebildeten Imidoester sind und leicht in die entsprechenden N-Vinyl- carbonamide umgewandelt werden.
Aus der britischen Patentschrift 1 123 671 ist weiterhin ein Verfahren zur Herstellung von 2-Fluoralkyl A2-oxazolinen aus den entsprechenden ss-Chloräthylcarbonsäureamiden mit Hilfe von Basen bekannt.
Alle diese bekannten Verfahren sind relativ umständlich bzw. erfordern Ausgangsprodukte, die nicht ohne weiteres zugänglich sind. Demgegenüber stellt das erfindungsgemässe Verfahren eine einfache und vieIseitige Reaktion dar, deren Ausgangsmaterialien leicht zugänglich sind.
Die Reaktion verläuft stark exotherm. Da die 2 Halogenalkyl-A2-oxazoline bei thermischer Beanspruchung mehr oder weniger leicht in die entsprechenden N-Vinylcarbonsäureamlide übergehen, wird die Reaktionswärme bevorzugt mit Hilfe eines inerten Lösungsmittels abgeführt. Die Reaktionstemperatur richtet sich deshalb auch nach der Stabilität des Produktes.
Als inerte Lösungsmittel kommen in erster Linie niedere halogenierte Kohlenwasserstoffe in Frage, wie beispielsweise Methylenchlorid, Chloroform, Tetrachlorkohlenstoff, 1,2-Dichloräthan, Trichloräthylen oder Tetrachloräthylen. Es ist auch möglich, das eingesetze Äthanolamin oder - wenn der Siedepunkt es erlaubt - das eingesetzte Fluorolefin im Überschuss zur Abführung der Reaktionswärme heranzuziehen. Das im Einzelfalle zweckmässigste Lösungs- bzw. Verdünnungsmittel wählt man nach der thermischen Stabilität des Endproduktes und der Abtrennbarkeit des Produk tes vom Reaktionsmedium. Im Zweifelsfalle lässt sich das günstigste Reaktionsmedium anhand von Vorversuchen leicht ermitteln.
Aufgrund des niedrigen Siedepunktes und der damit verbundenen leichten Abtrennbarkeit hat sich vor allem Methylenchlorid als Lösungsmittel besonders bewährt.
Die Verfahrensprodukte sind zum Teil bekannte Verbindungen. Die 2-(1'-H-Fluoralkyl)-2-oxazoline sind leicht mit Persäuren polymerisierbar und liefern Polymerisate, die zur Hydro- und Olephobierung von Fasermaterialien geeignet sind.
Beispiel 1
233 g (1,55 Mol) Perfluorpropylen werden im Verlauf von 5 Stunden unter heftigem Rühren in eine Lösung von 368 g (6 Mol) Äthanolamin in 1000ml Methylenchlorid eingeleitet. Die Innentemperatur steigt, bis das Lösungsmittel unter Rückfluss siedet.
Die Einleitungsgeschwindigkeit wird so bemessen, dass an einem mit Aceton/CO2 beschickten Kühlfinger ein möglichst geringer Rückfluss auftritt. Die erhaltene Reaktionsmischung wird viermal mit je 200 ml Wasser ausgeschüttelt und die organische Phase fraktioniert.
Man erhält nach Ab destillieren des Methylenchlorids 9,7 g Vorlauf, Kp30 25-540 C und 185 g (69,8 /o) 2 (1'-H-Perfluoräthyl)-A2-oxazolin, Kp30 54-56,5" C.
Das Spektrum zeigt eine starke Bande bei 1670 cmt (-C=N-). Bei der Hydrolyse entsteht quantitativ
EMI2.1
C5H7NO2F4 (189,11)
Gefunden: C 31,75 H 3,73 F 40,2 O/o
Berechnet: C 31,9 H 3,8 F 40,2 O/o
Beispiel 2
In eine Mischung von 100g (1,64 Mol) Äthanolamin und 500ml Methylenchlorid werden unter starkem Rühren 100 g (0,286 Mol) Perfluorhepten-1 innerhalb 2 Stunden zugetropft. Die Mischung wird erst mit Wasser, dann mit Natriumcarbonatlösung (5 /o) und wieder mit Wasser ausgeschüttelt. Die organische Phase wird destilliert.
Ausbeute: 67,75 g (64 /o) 2-(1-H'-Perfluorheptyl) A2-oxazolin, Kp125 78-81 C.
Beispiel 3
245 g (2,5 Mol) 1,1-Difluor-2-chlor-äthylen werden, wie unter Beispiel 1 beschrieben, mit Athanolamin (300 g; 5 Mol) umgesetzt.
Man erhält 215 g (70 /o) 2-Chlormethyl-A2-oxazo- lin, Kp9 680 C.
Beispiel 4 264 g (2 Mol) 1,1-Difluor-2,2-dichloräthylen werden, wie unter Beispiel 1 beschrieben, mit Äthanolamin (183 g; 3 Mol) umgesetzt.
Man erhält 192 g (62 /o) 2-Dichlormethyl-n2-oxa- zolin, Kpl7 930 C.
Process for the preparation of 2- (1'-ll.Halogenalkyi) -A2-oxazolines
The present invention relates to a process for the preparation of 2- (1'-H-haloalkyl) -A2-oxazolines of formula I.
EMI1.1
in which R is a hydrogen, chlorine or fluorine atom or a group of the formula CFS- (CF2) n, in which n is 0 or an integer from 1-10, and X is a fluorine or chlorine atom, which is characterized is that olefins of the formula II R-CX = CF2 II are reacted with AthanoIamin.
It is already known that A2-oxazolines which are substituted in the 2-position can be prepared from carboxylic acids or their derivatives by reaction with ethanolamine (Seeliger, Angew. Chem. 78 cm966) 913). The simplest synthesis principle is the gas phase dehydrogenation of the ethanolamine and the carboxylic acid or
the ß-Hydroxyäthylcarbonsäureamide obtained the carboxylic acid ester on an aluminum oxide contact at temperatures of 32N575 C and a pressure of 0.5-20 Torr.
2-Perfluoroalkyl-A2-oxazolines have already been prepared by condensing perfluoroalkylnitriles with 2-chloroethanol in the presence of excess tri-methylamine (H. C. Brown and Ch. R. Wetzel, J. org. Chem. 30 (1965) 3729). However, it is stated here that the oxazolines formed are only slightly more thermally stable than the imidoesters formed as intermediates and are easily converted into the corresponding N-vinyl carbonamides.
British Patent 1,123,671 also discloses a process for the preparation of 2-fluoroalkyl A2-oxazolines from the corresponding β-chloroethylcarboxamides with the aid of bases.
All of these known processes are relatively cumbersome or require starting products that are not readily available. In contrast, the process according to the invention represents a simple and versatile reaction, the starting materials of which are easily accessible.
The reaction is strongly exothermic. Since the 2 haloalkyl-A2-oxazolines are more or less easily converted into the corresponding N-vinylcarboxamlides under thermal stress, the heat of reaction is preferably dissipated with the aid of an inert solvent. The reaction temperature therefore also depends on the stability of the product.
Lower halogenated hydrocarbons such as, for example, methylene chloride, chloroform, carbon tetrachloride, 1,2-dichloroethane, trichlorethylene or tetrachlorethylene, are primarily suitable as inert solvents. It is also possible to use the ethanolamine used or - if the boiling point permits - the fluoroolefin used in excess to dissipate the heat of reaction. The most expedient solvent or diluent in the individual case is chosen according to the thermal stability of the end product and the ability of the product to be separated from the reaction medium. In case of doubt, the most favorable reaction medium can easily be determined on the basis of preliminary tests.
Due to the low boiling point and the associated easy separability, methylene chloride in particular has proven to be particularly useful as a solvent.
Some of the products of the process are known compounds. The 2- (1'-H-fluoroalkyl) -2-oxazolines are easy to polymerize with peracids and provide polymers which are suitable for the hydrophobization and oleophobic treatment of fiber materials.
example 1
233 g (1.55 mol) of perfluoropropylene are introduced into a solution of 368 g (6 mol) of ethanolamine in 1000 ml of methylene chloride in the course of 5 hours with vigorous stirring. The internal temperature rises until the solvent boils under reflux.
The rate of introduction is such that the lowest possible reflux occurs on a cold finger charged with acetone / CO2. The reaction mixture obtained is extracted four times with 200 ml of water each time and the organic phase is fractionated.
After the methylene chloride has been distilled off, 9.7 g of first runnings, boiling point 25-540 ° C. and 185 g (69.8 / o) 2 (1'-H-perfluoroethyl) -A2-oxazoline, boiling point 54-56.5 ° C. are obtained .
The spectrum shows a strong band at 1670 cmt (-C = N-). During hydrolysis, it is produced quantitatively
EMI2.1
C5H7NO2F4 (189.11)
Found: C 31.75 H 3.73 F 40.2 O / o
Calculated: C 31.9 H 3.8 F 40.2 O / o
Example 2
100 g (0.286 mol) of perfluorohepten-1 are added dropwise to a mixture of 100 g (1.64 mol) of ethanolamine and 500 ml of methylene chloride over the course of 2 hours, with vigorous stirring. The mixture is extracted first with water, then with sodium carbonate solution (5 / o) and again with water. The organic phase is distilled.
Yield: 67.75 g (64 / o) 2- (1-H'-Perfluoroheptyl) A2-oxazoline, boiling point 125 78-81 C.
Example 3
245 g (2.5 mol) of 1,1-difluoro-2-chloroethylene are, as described in Example 1, reacted with ethanolamine (300 g; 5 mol).
This gives 215 g (70 / o) 2-chloromethyl-A2-oxazoline, boiling point 9,680 C.
Example 4 264 g (2 mol) of 1,1-difluoro-2,2-dichloroethylene are reacted, as described under Example 1, with ethanolamine (183 g; 3 mol).
192 g (62 / o) 2-dichloromethyl-n2-oxazoline, Kpl7 930 C. are obtained.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1079269A CH513902A (en) | 1969-07-14 | 1969-07-14 | Prepn of 2-(1'-halogenoalkyl)-oxazolines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1079269A CH513902A (en) | 1969-07-14 | 1969-07-14 | Prepn of 2-(1'-halogenoalkyl)-oxazolines |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH513902A true CH513902A (en) | 1971-10-15 |
Family
ID=4366914
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1079269A CH513902A (en) | 1969-07-14 | 1969-07-14 | Prepn of 2-(1'-halogenoalkyl)-oxazolines |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH513902A (en) |
-
1969
- 1969-07-14 CH CH1079269A patent/CH513902A/en not_active IP Right Cessation
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| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |