CS254933B1 - Preparation of 2-bromoacrylic acids - Google Patents

Preparation of 2-bromoacrylic acids Download PDF

Info

Publication number
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
Authority
CS
Czechoslovakia
Prior art keywords
acids
preparation
bromoacrylic
cooh
bromine
Prior art date
Application number
CS862258A
Other languages
Czech (cs)
Slovak (sk)
Other versions
CS225886A1 (en
Inventor
Daniel Vegh
Jaroslav Kovac
Miloslava Dandarova
Original Assignee
Daniel Vegh
Jaroslav Kovac
Miloslava Dandarova
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daniel Vegh, Jaroslav Kovac, Miloslava Dandarova filed Critical Daniel Vegh
Priority to CS862258A priority Critical patent/CS254933B1/en
Publication of CS225886A1 publication Critical patent/CS225886A1/en
Publication of CS254933B1 publication Critical patent/CS254933B1/en

Links

Landscapes

  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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 solution relates to the method of preparation of 2-bromoacrylic acids of general formula I, where Ar is phenyl, nitrophenyl, 2-nitrofuryl, 2-nitrothienyl, 2-bromofuryl, 2-bromothienyl, furyl, thienyl. Its essence is that acrylic or heteroarylidenemalonic acids are treated with bromine in an environment of organic solvents, in water, or in their mixtures 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)

PREDMETSUBJECT Spésob přípravy 2-brómakrylových kyselin obecného vzorca IProcess for the preparation of 2-bromoacrylic acids of general formula (I) COOH /COOH / Ar—CH=C \Ar — CH = C \ Br (I) kde Ar je fenyl, ο-, m-, p-nitrofenyl, 2-nitrofuryl, 2-nitrotienyl, 2-brómfuryl, 2-brómtienyl, furyl, tienyl, vyznačujúci sa tým, že na aryl- alebo heteroarylidénmalónové kyseliny obecného vzorca IIBr (I) wherein Ar is phenyl, ο-, m-, p-nitrophenyl, 2-nitrofuryl, 2-nitrophenyl, 2-bromofuryl, 2-bromothienyl, furyl, thienyl, characterized in that they are aryl or heteroarylidenemalonic acids of formula II COOH /COOH / Ar—CH=C \Ar — CH = C \ COOH (Π) kde Ar má hoře uvedený význam, sa pósobí brómom v prostředí organických rozpúšťadiel zo skupiny halogénovaných uhíovodíkov, organických kyselin, sírouhlíka, N,N-dimetylformamidu a vo vodě alebo v ich zmesiach pri teplote 5 až 150 °C.COOH (Π) where Ar is as defined above, is treated with bromine in the 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.
CS862258A 1986-04-01 1986-04-01 Preparation of 2-bromoacrylic acids CS254933B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CS862258A CS254933B1 (en) 1986-04-01 1986-04-01 Preparation of 2-bromoacrylic acids

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CS862258A CS254933B1 (en) 1986-04-01 1986-04-01 Preparation of 2-bromoacrylic acids

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 Preparation of 2-bromoacrylic acids

Country Status (1)

Country Link
CS (1) CS254933B1 (en)

Also Published As

Publication number Publication date
CS225886A1 (en) 1987-06-11

Similar Documents

Publication Publication Date Title
JPS6019908B2 (en) 1,3-dioxolen-2-one derivative
FI105402B (en) Process for Preparation of 2 ', 3' '- Didehydro-2', 3'-Dideoxynucleosides on a Large Scale
Wang et al. [3+ 2] Cycloaddition reactions of β-diazo-α, α-difluoromethylphosphonates with α, β-unsaturated esters
US4812585A (en) Process for producing 2-aceylfuran derivatives
EP0597329A2 (en) Process for the preparation of alpha-fluor-beta dicarbonyle compounds
CS254933B1 (en) Preparation of 2-bromoacrylic acids
CN116947709B (en) Synthesis method of beta-arylvinyl sulfonyl fluoride compound
Huffman et al. Syntheses of halogenated phenanthrene amino alcohols as antimalarials
HRP980419A2 (en) A process for the preparation of cyclopropylacetylene
Sidler et al. Toward a Scalable Synthesis and Process for EMA401, Part II: Development and Scale-Up of a Pyridine-and Piperidine-Free Knoevenagel–Doebner Condensation
Wennerberg et al. Development of a practical and reliable synthesis of laquinimod
JPH01290662A (en) Method for producing pyrazole carboxylic acid chlorides
CN103288806A (en) Synthesis method of troxacitabine
CN105017188B (en) A method of synthesis 3- halogen methyl -2,3- Dihydrobenzofuranes class compound
ES2211919T3 (en) METHOD FOR PREPARING ESTERES OF HALONICOTINIC ACIDS.
Ugurchieva et al. Synthesis of (±)-4-alkanolides from pent-4-enoic acid
CN109320554B (en) Novel method for synthesizing practical acetaminoacrylate compound
Deng et al. The first nucleophilic substitution reaction of organoindium reagents with sulfonyl chlorides: a facile method for preparation of vinyl sulfones
SU740779A1 (en) Method of preparing alpha-nitroderivatives of thiophene series alpha,beta-unsaturated ketones
JPS5888361A (en) 3-amino-1,4-bis(alkoxycarbonyl)maleimide compound and its preparation
Moriwake et al. Heterocycles. III. Syntheses of N-tosyl-3-carbomethoxy-3-methyl-4-oxo-1, 2, 3, 4-tetrahydroquinoline and N-tosyl-3-cyano-3-methyl-4-oxo-1, 2, 3, 4-tetrahydroquinoline
JP2005068036A (en) Method for producing substituted pyridones, raw material compound thereof and method for producing the same
JPH0262845A (en) Method for producing carboxylic acid phenyl esters
SU398542A1 (en) Method of producing derivatives of 3,3'-dithienylsulfonyl
JP2640822B2 (en) Method for producing isoxazolidines