DK158456B - Process for preparing trifluoroacetyl chloride - Google Patents
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- DK158456B DK158456B DK328281A DK328281A DK158456B DK 158456 B DK158456 B DK 158456B DK 328281 A DK328281 A DK 328281A DK 328281 A DK328281 A DK 328281A DK 158456 B DK158456 B DK 158456B
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- C—CHEMISTRY; METALLURGY
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- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
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DK 158456BDK 158456B
Opfindelsen angår en særlig fremgangsmåde til fremstilling af trifluoracetylchlorid ved omsætning af 1,1,1-tri-fluor-2,2,2-trichlorethan med svovltrioxid i nærvær af kviksølvsalte.The invention relates to a particular process for the preparation of trifluoroacetyl chloride by reacting 1,1,1-trifluoro-2,2,2-trichloroethane with sulfur trioxide in the presence of mercury salts.
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En sådan fremgangsmåde kendes fra US patentskrift nr.Such a method is known from U.S. Pat.
3 160 659. Ifølge dette kan perfluorcetylchlorid fremstilles ved, at der i trifluortrichlorethan, som er tilsat kviksølvsulfater som katalysatorer, ved tilbagesva-10 lingstemperaturen langsomt indføres oleum eller SOg, og denne blanding derpå holdes i længere tid under kogning med tilbagesvaling. Efter nogle timer begynder afdestil-lationen af trifluoracetylchloridet. Til fuldstændig omsætning kræves imidlertid flere dage.According to this, perfluoroacetyl chloride can be prepared by slowly introducing oleum or SOg into trifluorotrichlorethane, which is added to mercury sulfates as catalysts, at reflux temperature, and this mixture is then refluxed for a longer time. After a few hours, the distillation of the trifluoroacetyl chloride begins. For complete turnover, however, several days are required.
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Også fremstillingen af fluorholdige perhalogencarboxyl-syrer ved solvolyse bereder vanskeligheder. Relativt enkelt lykkes solvolysen af perchlorerede alifatiske forbindelser, som indeholder en eller flere CClg-grupper. De 20 kan ved hjælp af middelkoncentreret svovlsyre omdannes til carboxylsyrer med en eller flere carboxylgrupper, som f.eks. udført af H. Henecka i Houben Weyl, Methoden der Organischen Chemie, bd. 8, side 427. Hvis der i naboskab til den endestillede CClg-gruppe står et eller flere 25 fluoratomer, så finder en carboxylsyredannelse kun sted, hvis der anvendes SOg eller svovlsyre indeholdende frit SOg. Ved variation af svovlsyrens SOg-indhold, SOg-mæng-den i forhold til halogenalkanen, reaktionstemperaturen eller reaktionstiden er det allerede blevet forsøgt at 30 forbedre fremgangsmåden således, at en teknisk gennemførelse er mulig. Omsætningen gennemføres dels i fravær, dels i nærvær af katalysatorer, såsom kviksølvsulfater (US patentskrifterne nr. 2 396 076 og 3 102 139). Reaktionshastighederne af den kun diskontinuerligt gennemfør-35 bare fremgangsmåde er imidlertid stadig utilfredsstillende. En yderligere ulempe ved denne fremgangsmåde er den ofte omstændelige udvinding af syren fra reaktions-Also the preparation of fluorine-containing perhalogenic carboxylic acids by solvolysis causes difficulties. Relatively simple, the solvolysis of perchlorinated aliphatic compounds containing one or more CClg groups is successful. The 20 may be converted into carboxylic acids by one or more carboxylic groups, such as e.g. performed by H. Henecka in Houben Weyl, Methods der Organischen Chemie, bd. 8, page 427. If one or more 25 fluorine atoms are adjacent to the terminal CClg group, then a carboxylic acid formation occurs only if SOg or sulfuric acid containing free SOg is used. By varying the SOg content of the sulfuric acid, the SOg content in relation to the haloalkane, the reaction temperature or the reaction time, attempts have already been made to improve the process so that a technical implementation is possible. The reaction is carried out partly in the absence and partly in the presence of catalysts such as mercury sulphates (US Patent Nos. 2,396,076 and 3,102,139). However, the reaction rates of the only discontinuously practicable method are still unsatisfactory. A further disadvantage of this process is the often tedious recovery of the acid from the reaction mixture.
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2 blandingen. I almindelighed fortyndes denne med vand, og syren udvindes ved langvarige og bekostelige ekstraktionsprocesser. Ofte indtræder der nedbrydning af syren ved oparbejdningen, således at der også herved foregår en 5 formindskelse af udbyttet.2 mixture. Generally, this is diluted with water, and the acid is extracted by long and costly extraction processes. Often, degradation of the acid occurs during the work-up, so that there is also a decrease in the yield.
Ifølge DE patentskrift nr. 19 17 630 fremstilles fluor-holdige perhalogencarboxylsyrefluorider eller -chlorider ud fra fluorchloralkaner ved omsætning med SOg i nærvær 10 af katalytiske mængder af kviksølvsulfater. Denne fremgangsmåde egner sig til kontinuerlig drift, hvorved der opnås brugbare, men stadig ikke optimale rum-tids-udbytter.According to DE patent application 19 17 630, fluorine-containing perhalogenic carboxylic acid fluorides or chlorides are prepared from fluorochloroalkanes by reaction with SOg in the presence of 10 catalytic amounts of mercury sulfates. This approach is suitable for continuous operation, providing usable, but still not optimal, space-time yields.
15 Opfindelsens formål er at overvinde ulemperne ved teknikkens stade. Det har overraskende vist sig, at der kan opnås en fremskyndelse af reaktionen, især ved diskontinuerlig drift, når 1,l,l-trifluor-2,2,2-trichlorethan som ved den kendte teknik omsættes med svovltrioxid i 20 nærvær af kviksølvsalte, hvis omsætningen ifølge opfindelsen yderligere udføres i nærvær af borhalogenid BXg (X=F, Cl, Br, I) og/eller halogensul fonsyre HSOgY (Y=F, Cl, Br, I). Såvel for X som for Y er chlor eller brom det foretrukne halogen.The object of the invention is to overcome the disadvantages of the state of the art. Surprisingly, it has been found that an acceleration of the reaction can be achieved, especially in discontinuous operation, when 1,1,1-trifluoro-2,2,2-trichloroethane, as is known in the prior art, is reacted with sulfur trioxide in the presence of mercury salts. if the reaction of the invention is further carried out in the presence of boron halide BXg (X = F, Cl, Br, I) and / or halogen sulphonic acid HSOgY (Y = F, Cl, Br, I). For X as well as for Y, chlorine or bromine is the preferred halogen.
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En variant af fremgangsmåden ifølge opfindelsen består i kun at udføre reaktionen i yderligere nærvær af borhalogenid. 1 2 3 4 5 6One variant of the process of the invention consists in carrying out the reaction only in the further presence of boron halide. 1 2 3 4 5 6
Det er ganske vist kendt fra US patentskrift nr. 3 102 139 2 bl. a. at omsætte CFgCClg i nærvær af kviksølvsalte med 3 stabiliseret SOg. Men det som stabilisator nævnte boroxid 4 formår i dette system lige så lidt at medvirke til forbed 5 ring af reaktionen som det aluminiumtrichlorid, der udtryk- 6 keligt er betegnet som anvendelig katalysator. Det var derfor ikke nærliggende at foretage forsøg med borhalogenider på opfinderisk måde.It is admittedly known from U.S. Pat. a. Reacting CFgCClg in the presence of mercury salts with 3 stabilized SOg. However, in this system, boron oxide 4 mentioned as a stabilizer is able to contribute as little to the improvement of the reaction as the aluminum trichloride, which is explicitly designated as a useful catalyst. Therefore, it was not obvious to carry out experiments with boron halides in an inventive way.
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En foretrukken variant af fremgangsmåden ifølge opfindelsen består i at udføre reaktionen i yderligere nærvær af halogensulfonsyre. Denne arbejdsmåde er endog i modstrid med den i US patentskrift nr. 3 102 139 fremsatte lære, 5 hvorefter omsætningen af systemet fluorhalogen- alkan/svovltrioxid/katalysator skal foregå i fravær af forbindelser, som indeholder aktivt (Zerewitinoff) hydrogen.A preferred variant of the process of the invention consists in carrying out the reaction in the further presence of halogen sulfonic acid. This process is even contrary to the teachings of U.S. Patent No. 3,102,139, according to which the reaction of the fluorine-halo-alkane / sulfur trioxide / catalyst system is to occur in the absence of compounds containing active (Zerewitinoff) hydrogen.
10 En særlig foretrukken variant af fremgangsmåden ifølge opfindelsen består i at udføre reaktionen i yderligere nærvær af borhalogenid og halogensulfonsyre. Med denne fremgangsmådevariant opnås de bedste resultater.A particularly preferred variant of the process of the invention consists in carrying out the reaction in the further presence of boron halide and halogen sulfonic acid. This method variant achieves the best results.
15 I alle tilfælde, hvor reaktionen forløber i yderligere nærvær af borhalogenid, kan dette tilsættes reaktionsblandingen som sådant.In all cases where the reaction proceeds in the further presence of boron halide, this may be added to the reaction mixture as such.
Det er imidlertid ved en anden variant også muligt at 20 frembringe borhalogenidet in situ ud fra en egnet borforbindelse og et halogeneringsmiddel.However, in another variant it is also possible to generate the boron halide in situ from a suitable boron compound and a halogenating agent.
Blandt egnede borforbindelser forstås sådanne, der sammen med halogeneringsmidlet under de givne reaktionsbetingel-25 ser danner borhalogenid. Særligt egnede borforbindelser er oxygenholdige borforbindelser, f.eks. borsyre, boroxid eller natriumborat, hvorved natriumtetraborat er særligt egnet. 1 2 3 4 5 6Suitable boron compounds are those which, together with the halogenating agent under the given reaction conditions, form boron halide. Particularly suitable boron compounds are oxygen containing boron compounds, e.g. boric acid, boron oxide or sodium borate, making sodium tetraborate particularly suitable. 1 2 3 4 5 6
Som halogeneringsmiddel kommer sådanne på tale, der under 2 de givne reaktionsbetingelser danner borhalogenid med 3 borforbindelsen. Ifølge det foreliggende kendskab er alu- 4 miniumtrichlorid ikke virksomt som halogeneringsmiddel.As a halogenating agent, such are the ones which under the given reaction conditions form boron halide with the 3 boron compound. According to the present knowledge, aluminum trichloride is not effective as a halogenating agent.
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Der kan anvendes svovlhalogenider, svovloxyhalogenider, 6 phosphorhalogenider, phosphoroxyhalogenider og/eller ha-logensulfonsyrer. De sidstnævnte er særligt foretrukne, især også fordi reaktionen ved den særligt foretrukneSulfur halides, sulfur oxyhalides, 6 phosphorus halides, phosphorus oxyhalides and / or halogen sulfonic acids can be used. The latter are particularly preferred, especially because the reaction is particularly preferred
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4 variant af fremgangsmåden ifølge opfindelsen forløber i nærvær af både borhalogenidet og halogensulfonsyre. Hvis man altså til in situ dannelse af borhalogenidet tilsætter et i forhold til den borforbindelse, der skal haloge-5 neres, støkiometrisk overskud af halogensulfonsyre, så kommer man automatisk til den særligt foretrukne fremgangsmådevariant .4 variant of the process of the invention proceeds in the presence of both the boron halide and halogen sulfonic acid. Thus, if in situ formation of the boron halide, a stoichiometric excess of halogen sulfonic acid is added to the boron compound to be halogenated, then the particularly preferred process variant is automatically added.
I alle tilfælde, hvor reaktionen forløber i yderligere 10 nærvær af halogensulfonsyre, kan man sætte denne til reaktionsblandingen som sådan. Det er imidlertid også muligt at frembringe halogensulfonsyren på i sig selv kendt måde in situ i reaktionsblandingen. Særligt egnet til in situ fremstilling af halogensulfonsyre er omsætningen af 15 SOg med hydrogenhalogenid.In all cases where the reaction proceeds in an additional 10 presence of halogen sulfonic acid, it can be added to the reaction mixture as such. However, it is also possible to produce the halogen sulfonic acid in a manner known per se in situ in the reaction mixture. Particularly suitable for the in situ preparation of halogen sulfonic acid is the reaction of 15 SOg with hydrogen halide.
Omsætningen af trifluortrichlorethan med SOg til tri-fluoracetylchlorid ved fremgangsmåden ifølge opfindelsen lader sig gennemføre ved atmosfæretryk i temperaturområ-20 det 0-120 °C, hvorved det foretrukne temperaturområde er 20-80 °C. Men det er også absolut muligt at lade reaktionen forløbe ved temperaturer over 120 °C og/eller ved tryk over atmosfæretryk, men dette kræver yderligere teknisk udstyr.The reaction of trifluorotrichloroethane with SOg to trifluoroacetyl chloride in the process of the invention is carried out at atmospheric pressure in the temperature range of 0-120 ° C, whereby the preferred temperature range is 20-80 ° C. But it is also absolutely possible to allow the reaction to proceed at temperatures above 120 ° C and / or at atmospheric pressure, but this requires additional technical equipment.
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Fremgangsmåden kan gennemføres charge-vis, halvkontinuerligt eller kontinuerligt. Ved charge-vis drift kan borhalogenidet og/eller halogensulfonsyren eller de til fremstilling af denne eller disse forbindelser anvendte ud-30 gangsforbindelser sættes til den i reaktionsbeholderen indførte reaktionsblanding (CFgCClg+ S0g+ kviksølvsalt) bagefter. Rækkefølgen af tilsætningerne spiller imidlertid ingen væsentlig rolle, således at den også kan ændres. Reaktionshastigheden aftager under reaktionens 35 forløb ved forbruget af udgangskomponenterne. For at opnå en kvantitativ omsætning af trifluortrichlorethanet anvendes S03 i overskud, hvorved der opnås gunstige rum-The process can be carried out charge-wise, semi-continuously or continuously. In charge-driven operation, the boron halide and / or halogen sulfonic acid or the starting compounds used to prepare this or these compounds may be added to the reaction mixture (CFgCClg + SOg + mercury salt) introduced afterwards. However, the order of the additives plays no significant role, so that it can also be changed. The rate of the reaction decreases during the course of the reaction with the consumption of the starting components. In order to obtain a quantitative reaction of the trifluorotrichloroethane, SO3 is used in excess to obtain favorable space.
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5 tids-udbytter, når der står 1-10 mol, fortrinsvis 1-5 mol, SOg til rådighed pr. mol CF^CCl^· Et højere SO^-indhold i reaktionsblandingen har ingen væsentlig indflydelse på reaktionshastigheden og udbyttet.5 time yields when 1-10 moles are present, preferably 1-5 moles, SO · A higher SO 2 content in the reaction mixture has no significant influence on the reaction rate and the yield.
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En indflydelse fra mængden af borhalogenid og/eller halo-gensulfonsyre på reaktionen med hensyn til udbyttet og reaktionshastigheden kan kun fastslås i begrænset grad.An influence of the amount of boron halide and / or halogen sulfonic acid on the reaction with respect to the yield and reaction rate can only be ascertained to a limited extent.
Et gunstigt reaktionsforløb opnås ved borindhold på 0,01-10 0,30 mol, fortrinsvis 0,01-0,10 mol, pr. mol anvendt fluorchloralkan. Mængden af halogensulfonsyre udgør med fordel 0,03-1,40 mol, især 0,03-0,50 mol pr. mol anvendt fluorchloralkan. Højere indhold af borhalogenid og/eller halogensulfonsyre forbedrer kun reaktionshastigheden i 15 ringe grad.A favorable reaction course is obtained at a boron content of 0.01-10 0.30 mol, preferably 0.01-0.10 mol, per liter. mole of fluorochloroalkane used. Advantageously, the amount of halogen sulfonic acid is 0.03-1.40 moles, especially 0.03-0.50 moles per mole. mole of fluorochloroalkane used. Higher boron halide and / or halogen sulfonic acid content only improves the reaction rate to 15 degrees.
Det ved reaktionen dannede trifluoracetylchlorid fås enten direkte kvantitativt eller omsættes til andre tri-fluoracetylforbindelser på i sig selv kendt måde. Således 20 kan det f.eks. indledes i ethanol og omsættes til tri-fluoreddikesyreethylester. I stedet for ethanol kan der også anvendes andre alifatiske eller aromatiske alkoholer. Det er ligeledes muligt at foretage omsætninger med andre forbindelser, som på kendt måde kan indgå en reak-25 tion med syrechlorider, som f.eks. ammoniak, aminer, vand, keten osv. På denne måde når man til værdifulde trifluoracetylforbindelser, som kan anvendes inden for mange af teknikkens områder, f.eks. indenfor lægemiddel-eller plantebeskyttelsessektoren.The trifluoroacetyl chloride formed by the reaction is either obtained directly quantitatively or is converted to other trifluoroacetyl compounds in a manner known per se. Thus, e.g. is introduced into ethanol and converted to trifluoroacetic acid ethyl ester. Instead of ethanol, other aliphatic or aromatic alcohols may also be used. It is also possible to make reactions with other compounds which in a known manner can react with acid chlorides, such as e.g. ammonia, amines, water, chain, etc. In this way, valuable trifluoroacetyl compounds can be obtained which can be used in many areas of the art, e.g. within the pharmaceutical or plant protection sector.
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Fremgangsmåden ifølge opfindelsen belyses nærmere ved de efterfølgende eksempler, hvor de i eksempel 1.-7 opnåede udbytter af trifluoracetylchlorid i % af det teoretiske udbytte beregnet på trifluorchlorethan er angivet i tabel 35 li afhængighed af reaktionstiden.The process of the invention is further illustrated by the following Examples, in which the yields of Trifluoroacetyl Chloride obtained in Examples 1-7 in% of the theoretical yield of Trifluoro Chloroethane are given in Table 35 l depending on the reaction time.
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i 6 EKSEMPEL 1 1 en 250 ml trehalset glaskolbe med påsat tilbagesvaler, der holdes termostateret ved 0 °C, indføres 1 g HgS04 og 5 1 g H2S04. Til denne blanding sættes en opløsning af 93,7 g (0,5 mol) CFgCClg og 162 g (2,0 mol) SOg. Efter yderligere tilsætning af 17,5 g (0,18 mol) HSOgF omrøres blandingen ved stuetemperatur, og i .denne opløsning indledes 2 g BFg (0,03 mol). Derpå opvarmes kolbens indhold, hvor-10 ved der ved 30 °C indtræder en livlig CFgCOCl-udvikling.EXAMPLE 1 In a 250 ml three-neck glass flask with reflux mounted on a thermostat at 0 ° C, 1 g of HgSO 4 and 5 1 g of H2 SO4 are introduced. To this mixture is added a solution of 93.7 g (0.5 mol) of CFgCClg and 162 g (2.0 mol) of SOg. After further addition of 17.5 g (0.18 mol) of HSOgF, the mixture is stirred at room temperature and in this solution 2 g of BFg (0.03 mol) is initiated. Then, the contents of the flask are heated, at which a lively CFgCOCl evolution occurs at 30 ° C.
Trifluoracetylchloridet gennemstrømmer tilbagesvaleren, passerer en HgSO^vasker for at fraskille medrevet SOg og udkondenseres i 2 efterfølgende kølefælder ved -78 °C.The trifluoroacetyl chloride flows through the reflux condenser, passes an HgSO4 washer to separate entrained SOg and is condensed in 2 subsequent cooling traps at -78 ° C.
Under reaktionens forløb stiger temperaturen i kolben fra 15 30 °C til 59 °C.During the course of the reaction, the temperature of the flask rises from 30 ° C to 59 ° C.
EKSEMPEL 2 I det i eksempel 1 beskrevne forsøgsapparatrur indføres 20 93,7 g CFgCClg og tilsættes 2 g HgS04· Opslæmningen omrø res ved 20 °C. Derefter inddryppes en opløsning af 162,0 g SOg, 17,5 g HSOgF og 2 g BFg. En intensiv reaktion indtræder ved 38 °C. Sluttemperaturen i reaktionsbeholderen udgjorde 56 °C.EXAMPLE 2 In the test apparatus described in Example 1, 20 93.7 g of CFgCClg are introduced and 2 g of HgSO4 is added. The slurry is stirred at 20 ° C. Then, a solution of 162.0 g of SOg, 17.5 g of HSOgF and 2 g of BFg is instilled. An intense reaction occurs at 38 ° C. The final temperature in the reaction vessel was 56 ° C.
25 EKSEMPEL 3 I kolberne til det i eksempel 1 beskrevne forsøgsapparatur indvejes 4 g HgBOg og 2 g HgS04. Dertil sættes fra en 30 tildrypningstragt en blanding af 93,7 g CFgCClg, 162 g S0g og 17,5 g HSOgCl. Reaktionsblandingen opvarmes under stærk gasudvikling til 35 °C.EXAMPLE 3 4 g of HgBOg and 2 g of HgSO4 are weighed into the flasks of the test apparatus described in Example 1. To this is added a mixture of 93.7 g CFgCClg, 162 g SOg and 17.5 g HSOgCl from a drip funnel. The reaction mixture is heated to 35 ° C under strong gas evolution.
EKSEMPEL 4 35 I det i eksempel 1 beskrevne forsøgsapparatur indføres 11 g HgS04, 1 g BgOg og 93,7 g CFgCClg. Fra en tildrypnings- 7EXAMPLE 4 35 In the test apparatus described in Example 1, 11 g of HgSO 4, 1 g of BgOg and 93.7 g of CFgCClg are introduced. From a drip 7
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tragt tilsættes en opløsning af 162 g SO^, 20 g HSO^Cl og 1 g BFg. Derved stiger temperaturen i reaktionsbeholderen til 37 °C.funnel is added a solution of 162 g SO 2, 20 g HSO 2 Cl and 1 g BFg. Thereby, the temperature of the reaction vessel rises to 37 ° C.
5 EKSEMPEL 5 I det i eksempel 1 beskrevne forsøgsapparatur indføres 2 g HgSO^ og 10 g BBr^. Der tildryppes en opløsning af 93,7 g CFgCClg, 162 g SOg og 4 g H2S04* Trifluoracetylchlori-10 det, som forlader tilbagesvaleren, ledes igennem en vaskeflaske H2S04 og indføres i en reaktionsbeholder med ethanol. Herved dannes trifluoreddikesyreethylester.EXAMPLE 5 In the test apparatus described in Example 1, 2 g of HgSO 4 and 10 g of BBr 2 are introduced. A solution of 93.7 g of CFgCClg, 162 g of SOg and 4 g of H2 SO4 * leaving the reflux acetylchloride is passed through a wash bottle of H2 SO4 and introduced into a reaction vessel with ethanol. Hereby trifluoroacetic acid ethyl ester is formed.
EKSEMPEL 6 15 1 det i eksempel 1 beskrevne forsøgsapparatur indføres en blanding af 1 g HgS04, 1 g Hg2S04, 93,7 g CF^CClg, 162 g SO3 og 17,5 g HSO^Cl. Derpå opvarmes reaktionsblandingen under omrøring til 38 °C. Under reaktionens forløb stiger 20 reaktionstemperaturen til 67 °C. Efter 12 timer ophører gasudviklingen.EXAMPLE 6 In the test apparatus described in Example 1, a mixture of 1 g of HgSO 4, 1 g of Hg 2 SO 4, 93.7 g of CF 2 CClg, 162 g of SO 3 and 17.5 g of HSO 3 Cl is introduced. Then, the reaction mixture is heated to 38 ° C with stirring. During the course of the reaction, the reaction temperature rises to 67 ° C. After 12 hours gas evolution ceases.
EKSEMPEL 7 25 I kolberne til det i eksempel 1 beskrevne forsøgsapparatur indvejes 5 g Na2B40^‘10 H20 og 4 g HgS04. Fra en til-drypningstragt tilsættes en blanding af 93,7 g CF^CClg, 162 g SOg og 20 g HSO^Cl, hvorved der under opvarmning indtræder en kraftig gasudvikling. Begyndelsestemperatu-30 ren 32 °C i kolberne stiger efter 6 timers opvarmning under tilbagesvaling til 74 °C.EXAMPLE 7 In the flasks of the test apparatus described in Example 1, weigh 5 g of Na 2 B 4 O 10 H 2 O and 4 g of HgSO 4. From a drip funnel is added a mixture of 93.7 g of CF 2 CClg, 162 g of SOg and 20 g of HSO 2 Cl, whereby vigorous gas evolution occurs during heating. The initial temperature of 32 ° C in the flasks rises to reflux to 74 ° C after 6 hours of heating.
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(0 io 'tf cn <N io IS(0 io 'tf cn <N io IS
H 00 CO ^ 'tf 'tf Φ---H 00 CO ^ 'tf' tf Φ ---
PP
PP
>ι Ό> ι Ό
J3 HJ3 H
Ό PΌ P
ίΟ CDίΟ CD
C ^ ·· OÆHMOO'tfWOæc^C ^ ·· OÆHMOO'tfWOæc ^
ri ·Η Hri · Η H
PP
J a: u (0 m o)J a: u (0 m o)
< K<K
^ -- 9^ - 9
DK 158456BDK 158456B
EKSEMPEL 8 (sammenligningseksempel) I det i eksempel 1 beskrevne forsøgsapparatur opvarmes en blanding af 93,7 g CF^CClg, 621 g SO^, 5 g fint pulveri-5 seret vandfrit aluminiumchlorid og 2 g HgS04 i et tidsrum på 4 timer. I kolben indstilller sig ved god tilbagesvaling en vedvarende temperatur på 38 °C. En gasudvikling finder ikke sted, og der opnås ikke trifluoracetylchlo-rid.EXAMPLE 8 (Comparative Example) In the test apparatus described in Example 1, a mixture of 93.7 g of CF 2 CClg, 621 g of SO 2, 5 g of finely powdered anhydrous aluminum chloride and 2 g of HgSO 4 is heated for a period of 4 hours. At the reflux flask, a sustained temperature of 38 ° C is set. Gas evolution does not take place and trifluoroacetyl chloride is not obtained.
10 15 20 25 1 3510 15 20 25 1 35
Claims (10)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2947376 | 1979-11-24 | ||
| DE19792947376 DE2947376A1 (en) | 1979-11-24 | 1979-11-24 | METHOD FOR PRODUCING TRIFLUOROACETIC DERIVATIVES |
| EP8000134 | 1980-11-21 | ||
| PCT/EP1980/000134 WO1981001406A1 (en) | 1979-11-24 | 1980-11-21 | Process for the preparation of trifluoroacetic acid derivatives |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK328281A DK328281A (en) | 1981-07-23 |
| DK158456B true DK158456B (en) | 1990-05-21 |
| DK158456C DK158456C (en) | 1990-10-08 |
Family
ID=6086764
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK328281A DK158456C (en) | 1979-11-24 | 1981-07-23 | PROCEDURE FOR PREPARING TRIFLUORACETYL CHLORIDE |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0029591B1 (en) |
| JP (1) | JPS6348256B2 (en) |
| AT (1) | ATE1279T1 (en) |
| DE (2) | DE2947376A1 (en) |
| DK (1) | DK158456C (en) |
| WO (1) | WO1981001406A1 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4411843A (en) * | 1980-12-15 | 1983-10-25 | Allied Corporation | Conversion of 1,1,1-trichloroperhaloalkanes into perhaloalkanoyl chlorides |
| JPS60197635A (en) * | 1984-03-21 | 1985-10-07 | Central Glass Co Ltd | Preparation of trifluoroacetic acid derivative |
| DE4313793A1 (en) * | 1993-04-27 | 1994-11-03 | Solvay Fluor & Derivate | Production of carboxylic acid halides and carboxylate salts |
| JPH07220573A (en) * | 1994-01-31 | 1995-08-18 | Nec Corp | Operation button structure |
| US8591457B2 (en) | 2005-08-10 | 2013-11-26 | Alza Corporation | Method for making a needle-free jet injection drug delivery device |
-
1979
- 1979-11-24 DE DE19792947376 patent/DE2947376A1/en not_active Ceased
-
1980
- 1980-11-21 WO PCT/EP1980/000134 patent/WO1981001406A1/en unknown
- 1980-11-21 AT AT80107265T patent/ATE1279T1/en active
- 1980-11-21 EP EP80107265A patent/EP0029591B1/en not_active Expired
- 1980-11-21 DE DE8080107265T patent/DE3060636D1/en not_active Expired
- 1980-11-21 JP JP55502632A patent/JPS6348256B2/ja not_active Expired
-
1981
- 1981-07-23 DK DK328281A patent/DK158456C/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| EP0029591B1 (en) | 1982-06-30 |
| ATE1279T1 (en) | 1982-07-15 |
| WO1981001406A1 (en) | 1981-05-28 |
| DE2947376A1 (en) | 1981-06-11 |
| DK328281A (en) | 1981-07-23 |
| EP0029591A1 (en) | 1981-06-03 |
| JPS56501649A (en) | 1981-11-12 |
| JPS6348256B2 (en) | 1988-09-28 |
| DE3060636D1 (en) | 1982-08-19 |
| DK158456C (en) | 1990-10-08 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PBP | Patent lapsed |