CS253435B1 - Process for preparing 2-chloracrylic acid - Google Patents
Process for preparing 2-chloracrylic acid Download PDFInfo
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- CS253435B1 CS253435B1 CS862312A CS231286A CS253435B1 CS 253435 B1 CS253435 B1 CS 253435B1 CS 862312 A CS862312 A CS 862312A CS 231286 A CS231286 A CS 231286A CS 253435 B1 CS253435 B1 CS 253435B1
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- SZTBMYHIYNGYIA-UHFFFAOYSA-N 2-chloroacrylic acid Chemical compound OC(=O)C(Cl)=C SZTBMYHIYNGYIA-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract 3
- -1 2-nitrofuryl Chemical group 0.000 claims abstract description 13
- 239000000460 chlorine Substances 0.000 claims abstract description 9
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 6
- 125000003118 aryl group Chemical group 0.000 claims abstract description 3
- 125000002541 furyl group Chemical group 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000001544 thienyl group Chemical group 0.000 claims abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 4
- DIKBFYAXUHHXCS-UHFFFAOYSA-N bromoform Chemical compound BrC(Br)Br DIKBFYAXUHHXCS-UHFFFAOYSA-N 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 229950005228 bromoform Drugs 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 150000002691 malonic acids Chemical class 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LVABDEFBDPWHJL-UHFFFAOYSA-N 2-(4-nitrophenyl)prop-2-enoic acid Chemical compound OC(=O)C(=C)C1=CC=C([N+]([O-])=O)C=C1 LVABDEFBDPWHJL-UHFFFAOYSA-N 0.000 description 1
- RHOXTLQEQOIWMH-UHFFFAOYSA-N 2-[(5-nitrofuran-2-yl)methylidene]propanedioic acid Chemical compound OC(=O)C(C(O)=O)=CC1=CC=C([N+]([O-])=O)O1 RHOXTLQEQOIWMH-UHFFFAOYSA-N 0.000 description 1
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- 238000003476 Darzens condensation reaction Methods 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000007239 Wittig reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 125000002534 ethynyl group Chemical class [H]C#C* 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Riešenie sa týká spůsobu přípravy 2-chlórakrylových kyselin obecného vzorce Ar—CH=CC1—-COOH kde Ar je fenyl, o-, m-, p-nitrofenyl, 2-nitrofuryl, 2-nitrotienyl, 2-bróinfuryl, 2-brómtienyl, furyl, tienyl. Jeho podstata spočívá v tom, že na aryl alebo heteroacylidénmalónové kyseliny sa působí chlórom 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-chloroacrylic acids of the formula Ar-CH = CCl-COOH where Ar is phenyl, o-, m-, p-nitrophenyl, 2-nitrofuryl, 2-nitrocenyl, 2-bromo-furyl, 2-bromothienyl, furyl, thienyl. Its essence lies in the fact that the aryl or heteroacylidenemalonic acid is chlorine in organic solvents in water or mixtures thereof temperature of 5 to 150 ° C.
Description
Vynález sa týká spůsobu přípravy 2-chlórakrylových kyselin vzorca IThe invention relates to a process for the preparation of 2-chloroacrylic acids of the formula I
COOHCOOH
ZFROM
Ar—CH=C \Ar — CH = C \
Cl 1 (I) kdeCl 1 (I) wherein
Ar je fenyl, o-, m-, p-nitrofenyl (Newman M. S.: Org. React 5, 426 /1949/]. Podstata spůsobu přípravy 2-chlórakrylových kyselin podl'a vynálezu spočívá v tom, že na aryl alebo heteroarylidenmalónové kyseliny vzorca IIAr is phenyl, o-, m-, p-nitrophenyl (Newman MS: Org. React 5, 426 (1949)). The essence of the process for the preparation of 2-chloroacrylic acids according to the invention is based on the aryl or heteroarylidenemalonic acids of the formula II
COOHCOOH
ZFROM
Ar—CH=C \Ar — CH = C \
COOH (Π) kdeCOOH (Π) where
2-nitrofuryl2-nitrofuryl
2-nitrotienyl2-nitrotienyl
O,WAr má hoře uvedený význam sa působí chlórom v prostředí organických rozpúšťadiel zo skupiny halogenovaných uhlOvodíkov ako dichlórmetán, chloroform, tetrachlórmetán, 1,2-dichlóretán, 1.1,2,2-tetrachlóretán, brómoform, organických kyselin ako kyselina octová, propionová, ďalej v sírouhlíku, Ν,Ν-dimetylformamide a vo vodě alebo v ich zmesiach pri teplote 5 až 150 °C.O, WAr as defined above is treated with chlorine in the environment of organic solvents from the group of halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, bromoform, organic acids such as acetic acid, propionic acid, in carbon disulphide, Ν, Ν-dimethylformamide and in water or mixtures thereof at a temperature of 5 to 150 ° C.
Reakcia prebieha podl'a nasledujúcej schémy:The reaction proceeds according to the following scheme:
COOHCOOH
2-brómfuryl2-brómfuryl
Ar—CH=C + Cl2 \Ar — CH = C + Cl2 \
COOHCOOH
2-brómtienyl2-bromothienyl
S ' furylS 'furyl
2-chlórakrylové kyseliny sú důležité chemické medziprodukty pre syntézu acetylénov, polymérov, 2-aminokyselín atd. Ich přípravy sa uskutočňujú různými hlavně halogenačnými a dehalogenačnými reakciami (Houben-Weyl, Methoden der Organischen Chemie, Band V/4, Stuttgart 1960), ako aj kondenzačnými, ako napr. Wittigovou reakciou (Johnson A. W. Ylid Chemistry, Acad. Press, NY and London /1966/). Pri Darzenovej syntéze vznikajú ako vedfajSie produkty2-chloroacrylic 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 (Houben-Weyl, Methoden der Organischen Chemie, Band V / 4, Stuttgart 1960) as well as by condensation, such as e.g. Wittig reaction (Johnson A.W. Ylid Chemistry, Acad. Press, NY and London (1966)). In Darzen's synthesis, they are formed as by-products
COOHCOOH
ZFROM
-»Ar—CH=C \- »Ar — CH = C \
ClCl
... / / + CO ř HCý.... / / + CO HC HCý.
pričom Ar má hoře uvedený význam.wherein Ar is as defined above.
Uvedený spůsob přípravy 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 virtually quantitative yields.
Vedfajšími produktami reakcie sú oxid uhličitý a chlorovodík, ktoré sú za daných podmienok v plynnom stave.The by-products of the reaction are carbon dioxide and hydrogen chloride, which are gaseous under the given conditions.
Přikladl g 4-nitrobenzilidén malónovej kyseliny sa rozpustilo v 200 ml kyseliny octovej a přidalo sa naraz k 10 g chlóru v 100 ml kyseliny octovej. Reakčná zmes sa zahríala pri teplote varu 2 h. Po oddestilovaní rozpúšťadla sa získal 23 g 2-chlór-3-(4-nitrofenyljakrylovej kyseliny o t. t. 197 — 202 °C. Příklad 2Example 1 g of 4-nitrobenzilidene malonic acid was dissolved in 200 ml of acetic acid and added simultaneously to 10 g of chlorine in 100 ml of acetic acid. The reaction mixture was heated at boiling for 2 h. After distilling off the solvent, 23 g of 2-chloro-3- (4-nitrophenylacrylic acid, m.p. 197-202 ° C) were obtained.
25,5 g 5-nitro-2-tienylidénmalónovej kyše253435 líny sa suspendovalo do 200 ml chloroformu a přidalo sa k 10 g chlóru v 200 ml chloroformu. Po 2 hod. zahrievania pri teplote varu rozpúšt'adlo sa oddestilovalo za vakua. Získalo sa 27 g 2-chlór-3-(5-nitro-2-tie.nyí j-akrylovej kyseliny o t. t. 252 — 254 °C.25.5 g of 5-nitro-2-thienylidenemalone acid were suspended in 200 ml of chloroform and added to 10 g of chlorine in 200 ml of chloroform. After 2 hours heating at boiling point the solvent was distilled off under vacuum. 27 g of 2-chloro-3- (5-nitro-2-thienyl) -acrylic acid of m.p. 252-254 ° C were obtained.
Příklad 3 g 5-nltro-2-furfurylidén malónovej kyseliny sa suspendovalo do 100 ml 1,2-dichlóretánu a přidalo sa k 10 g chlóru v 100 ml 1,2-dichlóretánu. Po 2 hod. zahrievania prí teplote varu rozpúšťadlo sa oddestilovalo za vákua. Získalo sa 25 g 2-chlór-3-(5-nitro-2-furyl)akrylovéj kyseliny o t. t. 252 — 254 stupňov Celzia.Example 3 g of 5-nitro-2-furfurylidene malonic acid was suspended in 100 ml of 1,2-dichloroethane and added to 10 g of chlorine in 100 ml of 1,2-dichloroethane. After 2 hours heating at boiling point the solvent was distilled off under vacuum. 25 g of 2-chloro-3- (5-nitro-2-furyl) acrylic acid of m.p. t. 252 - 254 degrees Celsius.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS862312A CS253435B1 (en) | 1986-04-01 | 1986-04-01 | Process for preparing 2-chloracrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS862312A CS253435B1 (en) | 1986-04-01 | 1986-04-01 | Process for preparing 2-chloracrylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS231286A1 CS231286A1 (en) | 1987-03-12 |
| CS253435B1 true CS253435B1 (en) | 1987-11-12 |
Family
ID=5359890
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS862312A CS253435B1 (en) | 1986-04-01 | 1986-04-01 | Process for preparing 2-chloracrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS253435B1 (en) |
-
1986
- 1986-04-01 CS CS862312A patent/CS253435B1/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CS231286A1 (en) | 1987-03-12 |
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