DE1237556B - Process for the production of perchloromethyl vinyl ketone - Google Patents
Process for the production of perchloromethyl vinyl ketoneInfo
- Publication number
- DE1237556B DE1237556B DE1965S0098109 DES0098109A DE1237556B DE 1237556 B DE1237556 B DE 1237556B DE 1965S0098109 DE1965S0098109 DE 1965S0098109 DE S0098109 A DES0098109 A DE S0098109A DE 1237556 B DE1237556 B DE 1237556B
- Authority
- DE
- Germany
- Prior art keywords
- perchloromethyl
- vinyl ketone
- production
- buten
- pentachloro
- 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.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/07—Aldehydes; Ketones
-
- 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
- C07C45/57—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
-
- 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
- C07C45/63—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 introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- 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
-
- 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
- C07C49/16—Saturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
-
- 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
- C07C49/227—Unsaturated compounds containing keto groups bound to acyclic carbon atoms containing halogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
DEUTSCHESGERMAN
PATENTAMTPATENT OFFICE
AUSLEGESCHRIFTEDITORIAL
Int. Cl.:Int. Cl .:
C07cC07c
Deutsche KL: 12 ο-19/02German KL: 12 o-19/02
Nummer: 1237556Number: 1237556
Aktenzeichen: S98109IVb/12oFile number: S98109IVb / 12o
Anmeldetag: 9. Juli 1965Filing date: July 9, 1965
Auslegetag: 30. März 1967Open date: March 30, 1967
Die Erfindung hat ein Verfahren zur Herstellung von Perchlormethylvinylketon zum Gegenstand, das dadurch gekennzeichnet ist, daß man /3,y3-bis-(Trichlormethyl)-/?-propiolacton in Gegenwart von Eisen(III)-halogenid in katalytisch wirksamer Menge bei Temperaturen von 60 bis 800C thermisch spaltet und das dabei erhaltene !,ljl^^-Pentachlor-S-buten-2-on in üblicher Weise chloriert und dehydrochloriert.The invention relates to a process for the preparation of perchloromethyl vinyl ketone, which is characterized in that / 3, y3-bis (trichloromethyl) - /? - propiolactone in the presence of iron (III) halide in a catalytically effective amount at temperatures of 60 to 80 0 C thermally and the resulting!, Ljl ^^ - pentachloro-S-buten-2-one chlorinated and dehydrochlorinated in the usual way.
Der erste Schritt des Verfahrens, die thermische Spaltung von jS^-bis-iTrichlormethyO-ß-propiolacton zu Kohlenmonoxyd, Chlorwasserstoff und 1,1,1,4, 4-Pentachlor-3-buten-2-on in Gegenwart eines Eisen(III)-halogenids als Katalysator stellt einen überraschenden Verlauf der Decarbonylierungsreaktion bei einem /?-Lacton dar, wie er bisher bei strukturanalogen Verbindungen noch nicht beobachtet wurde.The first step in the process, the thermal cleavage of jS ^ -bis-iTrichlormethyO-ß-propiolactone to carbon monoxide, hydrogen chloride and 1,1,1,4,4-pentachloro-3-buten-2-one in the presence of a Iron (III) halide as a catalyst represents a surprising course of the decarbonylation reaction in the case of a /? - lactone, which has not yet been observed in structurally analogous compounds.
Es wurde nämlich gefunden, daß das aus Trichloracetaldehyd und Keten (z. B. gemäß der deutschen Auslegeschrift 1136 323) erhältliche /3-Trichlormethyl-/?-propiolacton unter den Bedingungen des erfindungsgemäßen Verfahrens Polymerisationsprodukte ergibt, welche über eine ringöffnende Polyaddition entstanden sind, während das analog gebaute /3,/S-bis-(Trifluormethyl)-/?-propiolacton (bekannt aus Bull. Acad. Sc. USSR, 1960, S. 640) unter gleichen Bedingungen /?,/^bis-(Trifluormethyl)-acrylsäure bildet. Beide Reaktionen sind nicht vorbeschrieben.It has been found that the mixture of trichloroacetaldehyde and ketene (e.g. according to the German Auslegeschrift 1136 323) available / 3-trichloromethyl - /? - propiolactone results in polymerization products under the conditions of the process according to the invention, which were formed via a ring-opening polyaddition, while the analogously built / 3, / S-bis- (trifluoromethyl) - /? - propiolactone (known from Bull. Acad. Sc. USSR, 1960, p. 640) forms /?, / ^ bis (trifluoromethyl) acrylic acid under the same conditions. Both reactions are not described above.
Es wurde gefunden, daß bereits Mengen von weniger als 0,1 Gewichtsprozent an Eisen(III)-halogenid, bezogen auf die eingesetzte Menge /5,/3-bis-(Trichlormethyl)-/9-propiolacton, ausreichen, um die Reaktion in Gang zu setzen, jedoch verwendet man zweckmäßigerweise etwas größere Mengen. Als Eisen(III)-halogenid kommt vor allem das Eisen(III)-chlorid in Betracht.It has been found that amounts of less than 0.1 percent by weight of iron (III) halide, based on the amount used / 5, / 3-bis- (trichloromethyl) - / 9-propiolactone, sufficient to set the reaction in motion, but it is convenient to use slightly larger amounts. Iron (III) chloride is the main iron (III) halide Consideration.
Die Reaktionstemperatur liegt oberhalb des Schmelzpunktes des halogenierten Lactons (5O0C), im Bereich zwischen 60 und 8O0C. Die Reaktion, welche unter äquimolarer Abspaltung von Kohlenmonoxyd und Chlorwasserstoff verläuft, kann an Hand der Gasentwicklung verfolgt und gesteuert werden.The reaction temperature is above the melting point of the halogenated lactone (5O 0 C), in the range between 60 and 8O 0 C. The reaction, which proceeds with equimolar elimination of carbon monoxide and hydrogen chloride, can be followed with reference to the gas evolution and to be controlled.
Das nahezu quantitativ anfallende 1,1,1,4,4-Pentachlor-3-buten-2-on wird dann unmittelbar oder nach Rektifizieren im Vakuum zum 1,1,1,3,4,4,4-Heptachlor-2-butanon chloriert. Die Chlorierung erfolgt auf übliche Weise und führt in quantitativer Ausbeute zu einem Produkt mit einem Reinheitsgrad von mehr als 99%.The almost quantitatively obtained 1,1,1,4,4-pentachloro-3-buten-2-one becomes 1,1,1,3,4,4,4-heptachloro-2-butanone immediately or after rectification in vacuo chlorinated. The chlorination takes place in the usual way and results in quantitative yield to a product with a purity of more than 99%.
Die Dehydrochlorierung erfolgt ebenfalls auf übliche Weise, z. B. mit Hilfe von tertiären Basen, die
aus dem Heptachlorbutanon leicht Chlorwasserstoff abspalten und das gesuchte perchlorierte Methyl-Verfahren
zur Herstellung von
PerchlormethylvinylketonThe dehydrochlorination is also carried out in a conventional manner, e.g. B. with the help of tertiary bases that easily split off hydrogen chloride from the heptachlorobutanone and the sought-after perchlorinated methyl process for the production of
Perchloromethyl vinyl ketone
Anmelder:Applicant:
Shell Internationale Research
Maatschappij N. V., Den HaagShell International Research
Maatschappij NV, The Hague
Vertreter:Representative:
Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Puls
und Dr. E. Frhr. v. Pechmann, Patentanwälte,
München 90, Schweigerstr. 2Dr.-Ing. F. Wuesthoff, Dipl.-Ing. G. Pulse
and Dr. E. Frhr. v. Pechmann, patent attorneys,
Munich 90, Schweigerstr. 2
Als Erfinder benannt:Named as inventor:
Hans Hellmut Wilhelm Ohse,Hans Hellmut Wilhelm Ohse,
Oberdollendorf/Rhein;Oberdollendorf / Rhine;
Kurt Hans Gerhard Pilgram, Bonn-DransdorfKurt Hans Gerhard Pilgram, Bonn-Dransdorf
vinylketon in praktisch quantitativer Ausbeute liefern. Als tertiäre Basen kommen vor allem die Trialkylamine, insbesondere das Triäthylamin, in Frage. Die Chlorwasserstoffabspaltung wird bevorzugt in einem inerten Lösungsmittel bei Temperaturen zwischen 0 und 20°C durchgeführt.Provide vinyl ketone in practically quantitative yield. The trialkylamines are mainly used as tertiary bases, especially triethylamine, in question. The elimination of hydrogen chloride is preferred in one go inert solvent carried out at temperatures between 0 and 20 ° C.
Die nach dem Verfahren der Erfindung erhältlichen drei neuen, bisher noch nicht beschriebenen halogenierten Ketone, das l,l,l,4,4-Pentachlor-3-buten-2-on, das l,l,l,3,4,4,4-Heptachlor-2-butanon sowie das Perchlorvinylmethylketen (l,l,l,3,4,4-Hexachlor-3-buten-2-on), finden Verwendung als flammenhemmende Zusätze zu Kunstharzen und dienen darüber hinaus als Ausgangsstoffe zur Herstellung von Schädlingsbekämpfungsmitteln .The three new halogenated compounds not previously described which can be obtained by the process of the invention Ketones, l, l, l, 4,4-pentachloro-3-buten-2-one, l, l, l, 3,4,4,4-heptachloro-2-butanone and perchlorovinylmethyl ketene (l, l, l, 3,4,4-hexachloro-3-buten-2-one), are used as flame-retardant additives to synthetic resins and are also used as starting materials for the manufacture of pesticides .
102,3 g (0,33 Mol) /3,/?-bis-(Trichlormethyl)-i3-propiolacton werden mit 0,5 g wasserfreiem Eisen(III)-chlorid in einem Kolben, welcher mit Steigrohr, Thermometer und Rührer versehen ist, auf 700C erhitzt. Bereits bei der Schmelztemperatur (50° C) setzt Gasentwicklung ein, und das Reaktionsgemisch färbt sich grün. Das entweichende Gasgemisch besteht aus äquimolaren Mengen Kohlenmonoxyd und Chlorwasserstoff. 102.3 g (0.33 mol) / 3, /? - bis (trichloromethyl) -i3-propiolactone are combined with 0.5 g of anhydrous iron (III) chloride in a flask equipped with a riser tube, thermometer and stirrer is heated to 70 ° C. Gas evolution begins at the melting temperature (50 ° C) and the reaction mixture turns green. The escaping gas mixture consists of equimolar amounts of carbon monoxide and hydrogen chloride.
Die Reaktion ist nach ungefähr 7 Stunden beendet, erkenntlich am Aufhören der Gasentwicklung. Durch anschließende Vakuumdestillation kann das 1,1,1,4, 4-Pentachlor-3-buten-2-on als schwach gelbgefärbteThe reaction is over after about 7 hours, recognizable by the cessation of gas evolution. By subsequent vacuum distillation can produce the 1,1,1,4,4-pentachloro-3-buten-2-one as a pale yellow color
709 547/427709 547/427
Flüssigkeit rein erhalten werden. Die Ausbeute beträgt 79,2 g, entsprechend 98,3 % der Theorie.Liquid can be kept pure. The yield is 79.2 g, corresponding to 98.3% of theory.
Kp.13mm = 95 bis 96°C; nl° = 1,5423; dzo = 1,6493. IR-Absorption: 5,8 μ (C = O) und 6,2 μ (C = C). Bp 13mm = 95 to 96 ° C; nl ° = 1.5423; d zo = 1.6493. IR absorption: 5.8 µ (C = O) and 6.2 µ (C = C).
Analyse: Cl5C4HO:Analysis: Cl 5 C 4 HO:
Berechnet ... C 19,8, H 0,4, Cl 73,2;
gefunden ... C 19,7, H 0,5, Cl 73,4.Calculated ... C 19.8, H 0.4, Cl 73.2;
Found ... C 19.7, H 0.5, Cl 73.4.
400 g l,l,l,4,4-Pentachlor-3-buten-2-on werden auf 0°C abgekühlt. Unter Rühren und UV-Bestrahlung mittels eines Quarzbrenners wird so lange Chlor eingeleitet, bis die Gewichtszunahme 105 bis 120 g beträgt. Die Chlorierung ist nach ungefähr 3 Stunden beendet. Darauf wird überschüssiges Chlor durch Einleiten von Luft oder im Vakuum entfernt. Es werden 505 g eines farblosen Produktes erhalten, dessen Reinheitsgrad über 99% liegt. Die Vakuumdestillation liefert 485 g an 1,1,1,3,4,4,4-Heptachlor-2-butanon, entsprechend 97,8 °/„ der Theorie. ao400 g of l, l, l, 4,4-pentachloro-3-buten-2-one are cooled to 0 ° C. With stirring and UV irradiation using a quartz burner, chlorine is passed in until the increase in weight is 105 to 120 g amounts to. The chlorination is over after about 3 hours. Excess chlorine is then used Introducing air or removed in vacuo. 505 g of a colorless product are obtained, whose degree of purity is over 99%. The vacuum distillation provides 485 g of 1,1,1,3,4,4,4-heptachloro-2-butanone, corresponding to 97.8% of the theory. ao
Kp.emm = 1100C; Schmp. 16°C; «2 0° = 1,5271; <P» = 1,7561.. Emm Kp = 110 0 C; M.p. 16 ° C; « 2 0 ° = 1.5271; <P »= 1.7561.
IR-Absorption: 5,7 μ (C = O).IR absorption: 5.7 µ (C = O).
Analyse: Cl7C4HO (313,5): a5 Analysis: Cl 7 C 4 HO (313.5): a 5
Berechnet ... C 15,3, H 0,3, Cl 79,2;
gefunden ... C 15,5, H 0,4, Cl 79,1.Calculated ... C 15.3, H 0.3, Cl 79.2;
Found ... C 15.5, H 0.4, Cl 79.1.
Zu einer auf 5 bis 15 0C gekühlten Lösung von 313,5 g (lMol) l,l,l,3,4,4,4-Heptachlor-2-butanon in 21 trockenem Äther läßt man unter Rühren eine Lösung von 101 g (1 Mol) Triäthylamin in 100 ml Äther langsam zutropfen. Die Abscheidung von Triäthylammoniumchlorid erfolgt spontan. Nach vollendeter Zugabe wird noch 10 Minuten bei Raumtemperatur gerührt, darauf vom salzsauren Triäthylamin abgesaugt und der Niederschlag mit Äther gewaschen. Nach Entfernen des Äthers am Rotationsverdampfer erhält man ein rötlichgefärbtes Rohprodukt, welches durch Vakuumdestillation gereinigt wird. Perchlormethylvinylketon stellt eine schwach grüngelbgefärbte Flüssigkeit dar, welche angenehm riecht. Die Ausbeute beträgt 267,4 g, entsprechend 96,5% der Theorie.To a 0 to 15 C, cooled to 5 solution of 313.5 g (lmole) l, l, l, 3,4,4,4-heptachlor-2-butanone in 21 dry ether is allowed with stirring, a solution of 101 g Slowly add dropwise (1 mol) of triethylamine in 100 ml of ether. The separation of triethylammonium chloride takes place spontaneously. After the addition is complete, the mixture is stirred for a further 10 minutes at room temperature, then the hydrochloric acid triethylamine is filtered off with suction and the precipitate is washed with ether. After removing the ether on a rotary evaporator, a reddish-colored crude product is obtained, which is purified by vacuum distillation. Perchloromethyl vinyl ketone is a pale greenish-yellow liquid that has a pleasant smell. The yield is 267.4 g, corresponding to 96.5% of theory.
Kp.ooimm = 340C; «f? = 1,5300; d™ = 1,6979.
IR-Absorption: 5,7 μ (C = O) und 6,2 μ (C = C).. Ooimm Kp = 34 0 C; «F? = 1.5300; d ™ = 1.6979.
IR absorption: 5.7 µ (C = O) and 6.2 µ (C = C).
Analyse: Cl6C4O (277,0):
Berechnet ... C 17,3, H 0, Cl 76,9;
gefunden ... C 17,7, Cl 77,3.Analysis: Cl 6 C 4 O (277.0):
Calculated ... C 17.3, H 0, Cl 76.9;
found ... C 17.7, Cl 77.3.
Claims (1)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1965S0098109 DE1237556B (en) | 1965-07-09 | 1965-07-09 | Process for the production of perchloromethyl vinyl ketone |
| GB3048866A GB1100576A (en) | 1965-07-09 | 1966-07-07 | Polychlorobutanones and butenones |
| FR68540A FR1486109A (en) | 1965-07-09 | 1966-07-07 | Process for preparing perchloromethylvinyl ketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE1965S0098109 DE1237556B (en) | 1965-07-09 | 1965-07-09 | Process for the production of perchloromethyl vinyl ketone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1237556B true DE1237556B (en) | 1967-03-30 |
Family
ID=7521227
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE1965S0098109 Pending DE1237556B (en) | 1965-07-09 | 1965-07-09 | Process for the production of perchloromethyl vinyl ketone |
Country Status (2)
| Country | Link |
|---|---|
| DE (1) | DE1237556B (en) |
| GB (1) | GB1100576A (en) |
-
1965
- 1965-07-09 DE DE1965S0098109 patent/DE1237556B/en active Pending
-
1966
- 1966-07-07 GB GB3048866A patent/GB1100576A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1100576A (en) | 1968-01-24 |
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