CH313549A - Process for the preparation of carboxylic acid halides - Google Patents
Process for the preparation of carboxylic acid halidesInfo
- Publication number
- CH313549A CH313549A CH313549DA CH313549A CH 313549 A CH313549 A CH 313549A CH 313549D A CH313549D A CH 313549DA CH 313549 A CH313549 A CH 313549A
- Authority
- CH
- Switzerland
- Prior art keywords
- carboxylic acid
- halides
- parts
- preparation
- acid halides
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 10
- -1 carboxylic acid halides Chemical class 0.000 title claims description 9
- 238000002360 preparation method Methods 0.000 title description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 6
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 claims description 5
- 150000004820 halides Chemical class 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 230000002140 halogenating effect Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910001507 metal halide Inorganic materials 0.000 claims description 2
- 150000005309 metal halides Chemical class 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 3
- 229910001508 alkali metal halide Inorganic materials 0.000 claims 1
- 150000008045 alkali metal halides Chemical class 0.000 claims 1
- 229910001615 alkaline earth metal halide Inorganic materials 0.000 claims 1
- 150000004678 hydrides Chemical class 0.000 claims 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 6
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 5
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 5
- 239000012346 acetyl chloride Substances 0.000 description 5
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 5
- 239000001110 calcium chloride Substances 0.000 description 5
- 229910001628 calcium chloride Inorganic materials 0.000 description 5
- 235000011148 calcium chloride Nutrition 0.000 description 5
- 229910015900 BF3 Inorganic materials 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910001622 calcium bromide Inorganic materials 0.000 description 3
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- 101100326791 Caenorhabditis elegans cap-2 gene Proteins 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- FXXACINHVKSMDR-UHFFFAOYSA-N acetyl bromide Chemical compound CC(Br)=O FXXACINHVKSMDR-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- MBXXQYJBFRRFCK-UHFFFAOYSA-N benzyl fluoride Chemical compound FCC1=CC=CC=C1 MBXXQYJBFRRFCK-UHFFFAOYSA-N 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Carbonsäurehalogeniden
Die bisher bekannten Methoden zur Darstellung von Carbonsäurehalogeniden, insbesondere von Acetylhalogeniden, sind alle dadurch gekennzeichnet, dass sie als ILalogen- lieferanten wertvolle Stoffe verwenden. Solche sind die Halogene selbst, Phosphor-oder Sehwefelhalogenide, gasförmige oder flüssige Halogenwasserstoffe, Phosgen oder andere organische Halogenverbindungen, wie Benzylfluorid und-chlorid, Benzotrifluorid und -chlorid, Benzolsulfonsäurechlorid, p-Toluolsulfonsäurechlorid und andere.
Es wurde nun ein Verfahren gefunden, wonach für die Herstellung der Carbonsäure- halogenide die billigen, leicht zugängliehen Alkali-und Erdalkalihalogenide als Halogenlieferanten verwendet werden können. So steht, wie gefunden wurde, beispielsweise im technischen Abfallprodukt Kalziumchlorid ein sehr reaktionsfähiger Chlorlieferant zur Verfiigung, der sich z. B. mit Essigsäureanhy- drid in Gegenwart von Katalysatoren, wie z. B. Bortrifluo. rid oder Aluminiumehlorid, nach der Gleichung
EMI1.1
zum Acetylchlorid umsetzt.
In ähnlieher Weise setzen sich u. a. auch NaCl, KC1, CaP2, CaBr2, MgCl2 mit Carbonsäureanhydriden um. Die Reaktion setzt in vielen Fällen bereits in der Kälte ein und wird durch Erhitzen der Realitionspartner stark gefördert, wobei allenfalls das entstehende Säurehalogenid überdestilliert werden kann.
Die Erfindung betrifft somit ein Verfah- ren zur Herstellung von Carbonsä, urehalo- geniden aus Carbonsäureanhydriden und Halogenierungsmitteln, das dadurch gekennzeichnet ist, dass man Metallhalogenide mit Carbonsaureanhydriden, insbesondere Essig säureanhydrid, in Gegenwart von catalysa- toren umsetzt. Als Katalysatoren kommen vor allem Halogenide dreiwertiger Metalle, insbesondere Bortrifluorid oder Aluminiumchlorid, in Betracht.
Betsptele
1. 55 Gewichtsteile CaCl2, bei 220 C im Trockenschrank getrocknet, werden gepulvert in eine Mischung von 500 Volumenteile Aeetanhydrid und 17 Volumenteile BF3 Ätherat (45%ig) eingetragen. Es wird zunächst etwa % Stunde bei Zimmertempe- ratur gerührt, dann unter fortwährendem intensivem Umrühren das Olbad auf 180 bis 200 C aufgewärmt, wobei über einer Kolonne mit Raschigringen das Acetylehlorid abdestilliert.
Die Ausbeute an Acetylchlorid, bezogen auf die eingewogene Menge CaCl2, beträgt 80 /o.
2. 58 Gewichtsteile NaCl werden bei 220 C im Trockenschrank getrocknet, mit 500 Vo Lumenteilen Acetanhydrid und 10 Volumenteilen BF3-Ätherat (45%ig) versetzt ; es wird erst bei Zimmertemperatur 1zj Stunde umge riihrt, dann das Ölbad auf 180 bis 200 C aufgeheizt. Es destilliert über der Kolonne das Acetylchlorid ab.
Ausbeute, bezogen auf das eingewogene NaCl : 15 /o.
3. 55 Gewiehtsteile fein gepulvertes CaCl2, das im Schrank bei 220 C getrocknet worden ist, wird zusammen mit 5 Gewichtsteilen Aval3 in 250 Volumteilen Acetanhydrid eingetragen. Es wird erst 1/2 Stunde kalt gerührt, dann das Bad auf 180 bis 200 C aufgeheizt, wobei das Acetylchlorid über der Kolonne abdestilliert.
Die Ausbeute, bezogen auf das eingewogene CaCl2, beträgt 35 %.
4. 100 Gewichtsteile CaBr2 werden bei 220 C getrocknet und fein pulverisiert in 500 Volumenteile Acetanhydrid eingetragen ; als Katalysator fügt man 10 Volumenteile BF3-Ätherat (45%ig) bei. Dann wird 3/4 Stunden bei Zimmertemperatur gerührt und schliesslich das Ba. d auf 180 bis 200 C auf gewärmt.
Uber der Kolonne destilliert das Acetyl- bromid über.
Die Ausbeute, bezogen auf das eingewogene CaBr2, beträgt 25 %.
Process for the preparation of carboxylic acid halides
The previously known methods for the preparation of carboxylic acid halides, in particular acetyl halides, are all characterized in that they use valuable substances as suppliers of Ialogens. Such are the halogens themselves, phosphorus or sulfur halides, gaseous or liquid hydrogen halides, phosgene or other organic halogen compounds, such as benzyl fluoride and chloride, benzotrifluoride and chloride, benzenesulphonic acid chloride, p-toluenesulphonic acid chloride and others.
A process has now been found according to which the cheap, easily accessible alkali and alkaline earth halides can be used as halogen suppliers for the production of the carboxylic acid halides. As has been found, for example in the technical waste product calcium chloride a very reactive chlorine supplier is available. B. with acetic anhydride in the presence of catalysts such. B. Borotrifluo. rid or aluminum chloride, according to the equation
EMI1.1
converts to acetyl chloride.
In a similar way, u. a. also NaCl, KC1, CaP2, CaBr2, MgCl2 with carboxylic acid anhydrides. In many cases, the reaction begins even when it is cold and is strongly promoted by heating the reaction partners, with the acid halide formed being able to be distilled over if necessary.
The invention thus relates to a process for the production of carboxylic acid, acid halides from carboxylic acid anhydrides and halogenating agents, which is characterized in that metal halides are reacted with carboxylic acid anhydrides, in particular acetic acid anhydride, in the presence of catalysts. Particularly suitable catalysts are halides of trivalent metals, in particular boron trifluoride or aluminum chloride.
Betsptele
1. 55 parts by weight of CaCl2, dried at 220 ° C. in a drying cabinet, are powdered into a mixture of 500 parts by volume of acetal anhydride and 17 parts by volume of BF3 etherate (45%). The mixture is first stirred for about ½ hour at room temperature, then the oil bath is warmed up to 180 to 200 ° C. with continued intensive stirring, the acetyl chloride being distilled off over a column with Raschig rings.
The yield of acetyl chloride, based on the weighed amount of CaCl2, is 80 / o.
2. 58 parts by weight of NaCl are dried at 220 ° C. in a drying cabinet, and 500 parts by volume of acetic anhydride and 10 parts by volume of BF3 etherate (45%) are added; The mixture is first stirred at room temperature for an hour and a half, then the oil bath is heated to 180 to 200 C. The acetyl chloride is distilled off over the column.
Yield, based on the NaCl weighed in: 15 / o.
3. 55 parts by weight of finely powdered CaCl2, which has been dried in a cupboard at 220 C, is added to 250 parts by volume of acetic anhydride together with 5 parts by weight of Aval3. It is first stirred for 1/2 hour while cold, then the bath is heated to 180 to 200 ° C., the acetyl chloride being distilled off over the column.
The yield, based on the weighed CaCl2, is 35%.
4. 100 parts by weight of CaBr2 are dried at 220 C and finely pulverized and added to 500 parts by volume of acetic anhydride; 10 parts by volume of BF3 etherate (45%) are added as a catalyst. The mixture is then stirred for 3/4 hours at room temperature and finally the Ba. d warmed to 180 to 200 C.
The acetyl bromide distills over the column.
The yield, based on the weighed CaBr2, is 25%.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH313549T | 1952-05-23 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH313549A true CH313549A (en) | 1956-04-30 |
Family
ID=4495241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH313549D CH313549A (en) | 1952-05-23 | 1952-05-23 | Process for the preparation of carboxylic acid halides |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH313549A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623577A1 (en) * | 1993-04-27 | 1994-11-09 | Solvay Fluor und Derivate GmbH | Preparation of halogenides and salts of carboxylic acids |
-
1952
- 1952-05-23 CH CH313549D patent/CH313549A/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0623577A1 (en) * | 1993-04-27 | 1994-11-09 | Solvay Fluor und Derivate GmbH | Preparation of halogenides and salts of carboxylic acids |
| US5532411A (en) * | 1993-04-27 | 1996-07-02 | Solvay Fluor Und Derivate Gmbh | Production of carboxylic acid halides and carboxylate salts |
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