CS254933B1 - Method of 2-bromoacrylic acids preparation - Google Patents
Method of 2-bromoacrylic acids preparation Download PDFInfo
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- CS254933B1 CS254933B1 CS862258A CS225886A CS254933B1 CS 254933 B1 CS254933 B1 CS 254933B1 CS 862258 A CS862258 A CS 862258A CS 225886 A CS225886 A CS 225886A CS 254933 B1 CS254933 B1 CS 254933B1
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Abstract
Riešenie sa týká sposobu přípravy 2-brómakrylových kyselin obecného vzorca I, kde Ar je fenyl, nítrofenyl, 2-nltrofuryl, 2-nitrotienyl, 2-brómfuryl, 2-brómtienyl, furyl, tienyl. Jeho podstata spočívá v tom, že na akryl- alebo heteroarylidénmalónové kyseliny sa působí brómom v prostředí organických rozpúšťadiel, vo vodě, alebo ich zmesiach pri teplote 5 až 150 °C.The present invention relates to a process for preparing 2-bromoacrylic acids of the formula I wherein Ar is phenyl, nitrophenyl, 2-nltrofuryl, 2-nitrocenyl, 2-bromofuryl, 2-bromothienyl, furyl, thienyl. Its essence lies in the fact that or heteroarylidene malonic acids is treated with bromine in an organic environment solvents, in water, or mixtures thereof at a temperature of 5 to 150 ° C.
Description
Halogenačné a dehalogenačné metódy pripravy vyžadujú prácnu minimálně trojaž pStstupňovú syntézu, kde výtažky sú do 60—70 %. Wittigové metódy vyžadujú činidlá, ako sú organofosfořové zlůčeniny (hlavně trifenylfosfénť a dávajú výtažky do 60 až 75 % esterov kyselin, pričom třeba finálně zlůčeniny prácne čistit od triíenylfosfánoxidu a následné hydrolyzovať. Keďže organofosforečné činidlá sú vysoko toxické lát ky, uvedená metoda je nevhodná pre přípravu látok s možným použitím v humánnej resp. veterinárnej medicíně.The halogenation and dehalogenation methods of preparation require a minimum of three to three steps of synthesis where yields are up to 60-70%. Wittig methods require reagents such as organophosphorus compounds (mainly triphenylphosphate and yields up to 60-75% acid esters, with the final need to laboriously purify the triphenylphosphine oxide and then hydrolyse them. Since the organophosphorus reagents are highly toxic, this method is unsuitable for preparation substances with possible use in human or veterinary medicine.
Podstata spósobu přípravy 2-brómakrylových kyselin podfa vynálezu spočívá v tom, že na aryl- alebo heteroarylidénmalónové kyseliny obecného vzorca IIThe process for the preparation of 2-bromoacrylic acids according to the invention consists in that on aryl or heteroarylidene malonic acids of the general formula II
COOHCOOH
Ar—CH= -CAr = CH = -C
2-brómfuryl2-brómfuryl
COOH (Π)COOH (Π)
2-brómtienyl2-bromothienyl
kde Ar má hoře uvedený význam, sa pósobí brómom v prostředí organických rozpúšťadiel zo skupiny halogénovaných uhlovodíkov, organických kyselin, sírouhlíka, N,N-dimetylformamidu a vo vodě alebo v ich zmesiach pri teplote 5 až 150 °C.wherein Ar is as defined above, is treated with bromine in an environment of organic solvents from the group of halogenated hydrocarbons, organic acids, carbon disulphide, N, N-dimethylformamide and in water or mixtures thereof at a temperature of 5 to 150 ° C.
Reakcia prebieha podlá nasledujúcej schémy:The reaction proceeds according to the following scheme:
Br ·Br ·
S ' furylS 'furyl
O 'ABOUT '
COOH /COOH /
Ar—CH=C \Ar — CH = C \
COOHCOOH
COOH /COOH /
+ Βγζ -> Ar—CH=C+ Βγζ -> Ar — CH = C
Br tienylBr thienyl
2-brómakrylové kyseliny sú důležité chemické medziprodukty pre syntézu acetylénov, polymérov, 2-amínokyselín atď. Ich přípravy sa uskutočňujú róznymi hlavně halogenačnými a dehalogenačnými reakciami2-Bromoacrylic acids are important chemical intermediates for the synthesis of acetylenes, polymers, 2-amino acids, etc. Their preparation is carried out by various mainly halogenation and dehalogenation reactions
pričom Ar má hoře uvedený význam.wherein Ar is as defined above.
Uvedený způsob pripravy je energeticky nenáročný, pričom vznikajú produkty o vysokej čistotě a vysokých výťažkoch prakticky kvantitativných.Said method of preparation is energy-efficient and produces products of high purity and high yields of practically quantitative yield.
5 4 55 4 5
Vedíajšími produktami reakcie sú oxid uhličitý a brómovodík, ktoré sú za daných podmienok v plynnom stave.The by-products of the reaction are carbon dioxide and hydrogen bromide, which are gaseous under the given conditions.
Příklad 1 g 4-nitrobenzilidén-malónovej kyseliny sa rozpustí v 200 ml kyseliny octovej a přidá sa naraz k 20 g brómu v 100 ml kyseliny octovej. Reakčná zmes sa zahrieva pri teplote varu 2 h. Po oddestilovaní rozpúšťadla sa získal 25 g 2-bróm-3- (4-nitrofenyl jakrylovej kyseliny o teplote topenia 213 až 215 °C.Example 1 g of 4-nitrobenzilidene-malonic acid is dissolved in 200 ml of acetic acid and added to 20 g of bromine in 100 ml of acetic acid at the same time. The reaction mixture is heated at boiling for 2 h. After distilling off the solvent, 25 g of 2-bromo-3- (4-nitrophenyl) acrylic acid of melting point 213 DEG-215 DEG C. were obtained.
Příklad 2Example 2
25,5 g 5-nitro-2-tienylidénmalónovej kyse33 líny sa suspenduje do 200 ml chloroformu a přidá sa k 20 g brómu v 200 ml chloroformu. Po 2 h. zahrievania pri teplote varu rozpúšťadlo sa oddestiluje za vákua. Získalo sa 27 g 2-bróm-3-(5-nitro-2-tienyl)-akrylovej kyseliny o teplote topenia 255—256 stupňov Celzia.25.5 g of 5-nitro-2-thienylidene-malonic acid are suspended in 200 ml of chloroform and added to 20 g of bromine in 200 ml of chloroform. After 2 h. heating at the boiling point the solvent is distilled off under vacuum. 27 g of 2-bromo-3- (5-nitro-2-thienyl) -acrylic acid of melting point 255-256 degrees Celsius were obtained.
Příklad 3 g 5-nitro-2-furylidén-malónovej kyseliny sa suspenduje do 100 ml 1,2-dichlóretánu a přidá sa k 20 g brómu v 100 ml 1,2-dichlóretánu. Po 2 h. zahrievania pri teplote varu rozpúšťadlo sa oddestiluje za vákua. Získalo sa 25 g 2-bróm-3-(5-nitro-2-furyl )akrylovej kyseliny o t. t. 190—196 °C.Example 3 g of 5-nitro-2-furylidene-malonic acid is suspended in 100 ml of 1,2-dichloroethane and added to 20 g of bromine in 100 ml of 1,2-dichloroethane. After 2 h. heating at the boiling point the solvent is distilled off under vacuum. 25 g of 2-bromo-3- (5-nitro-2-furyl) acrylic acid of m.p. t. 190-196 ° C.
PREDMETSUBJECT
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS862258A CS254933B1 (en) | 1986-04-01 | 1986-04-01 | Method of 2-bromoacrylic acids preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS862258A CS254933B1 (en) | 1986-04-01 | 1986-04-01 | Method of 2-bromoacrylic acids preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS225886A1 CS225886A1 (en) | 1987-06-11 |
| CS254933B1 true CS254933B1 (en) | 1988-02-15 |
Family
ID=5359185
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS862258A CS254933B1 (en) | 1986-04-01 | 1986-04-01 | Method of 2-bromoacrylic acids preparation |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS254933B1 (en) |
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1986
- 1986-04-01 CS CS862258A patent/CS254933B1/en unknown
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| Publication number | Publication date |
|---|---|
| CS225886A1 (en) | 1987-06-11 |
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