CS196930B1 - 2-brommethyl-3-/2-furyl/acrylic acid methylestere and process for preparing thereof - Google Patents
2-brommethyl-3-/2-furyl/acrylic acid methylestere and process for preparing thereof Download PDFInfo
- Publication number
- CS196930B1 CS196930B1 CS2278A CS2278A CS196930B1 CS 196930 B1 CS196930 B1 CS 196930B1 CS 2278 A CS2278 A CS 2278A CS 2278 A CS2278 A CS 2278A CS 196930 B1 CS196930 B1 CS 196930B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- acrylic acid
- furyl
- bromomethyl
- methyl ester
- acid methyl
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 title 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title 1
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 title 1
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 18
- DAQJLFCNVBLQJR-UHFFFAOYSA-N methyl 2-(bromomethyl)-3-(furan-2-yl)prop-2-enoate Chemical compound COC(=O)C(CBr)=CC1=CC=CO1 DAQJLFCNVBLQJR-UHFFFAOYSA-N 0.000 claims description 17
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical compound O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- -1 methyl 2-bromomethyl-3- (2-furyl) acrylic acid Chemical compound 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 238000002329 infrared spectrum Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229960002317 succinimide Drugs 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000031709 bromination Effects 0.000 claims description 3
- 238000005893 bromination reaction Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000000921 elemental analysis Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- PQDJYEQOELDLCP-UHFFFAOYSA-N trimethylsilane Chemical compound C[SiH](C)C PQDJYEQOELDLCP-UHFFFAOYSA-N 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims 1
- 239000001569 carbon dioxide Substances 0.000 claims 1
- WUWDAOLJZHBHPV-UHFFFAOYSA-N methyl 3-(furan-2-yl)-2-methylprop-2-enoate Chemical compound COC(=O)C(C)=CC1=CC=CO1 WUWDAOLJZHBHPV-UHFFFAOYSA-N 0.000 claims 1
- 238000004611 spectroscopical analysis Methods 0.000 claims 1
- 229940094989 trimethylsilane Drugs 0.000 claims 1
- 238000002360 preparation method Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000004071 biological effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- FVGQQMFIAJTLMJ-UHFFFAOYSA-N ethyl 3-(furan-2-yl)-2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=CC1=CC=CO1 FVGQQMFIAJTLMJ-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
ŽVAK VLADIMÍR ing. a KOVÁČ JAROSLAV prof. ing. DrSc., BRATISLAVA (54) Metylester kyseliny 2-brómmetyl-3-(2-furyl)akrylovéj a sposob jeho přípravyŽVAK VLADIMÍR ing. and KOVÁČ JAROSLAV prof. ing. DrSc., BRATISLAVA (54) 2-Bromomethyl-3- (2-furyl) acrylic acid methyl ester and process for its preparation
Vynález sa týká metylesteru kyseliny 2-brómmetyl-3-(2-furyl)akrylovéj a sposobu Jeho přípravy.The present invention relates to 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester and to a process for its preparation.
2-Halogénmetyl deriváty kyseliny 3-(2-furyl ) akrylovej sú vhodné ako východiskové produkty pre celý rad syntéz nových derivátov kyseliny 2-X-3-(5-nitro-2-furyl)akrylovej s předpokládanou biologickou účinnosťou, ktoré nie sú z dostupnej literatury známe.2-Halomethyl 3- (2-furyl) acrylic acid derivatives are suitable as starting products for a variety of syntheses of novel 2-X-3- (5-nitro-2-furyl) acrylic acid derivatives of expected biological activity that are not available literature.
Tieto nedostatky v podstatnej mlere odstraňuje vynález týkajúci sa metylesteru kyseliny 2-brómmetyl-3- (2-Turyl) akrylové j.The present invention concerning 2-bromomethyl-3- (2-Turyl) acrylic acid methyl ester, e.g.
Podstata sposobu přípravy metylesteru kyseliny 2-brómmetyl-3-(2-furyl)akrylovej podlá vynálezu spočívá v chemicky iniciovanej selektívnej bromácii metylu na dvojnej vázbe metylesteru kyseliny 2-metyl-3-(2-furyl)akrylove] N-brómsukcínimidom. Reakcia sa uskutočňuje v bezvodom chloride uhličitom za přítomnosti iniciátora a, a - azobisizobutyronitrilu pri teplote varu chloridu uhličitého.The process according to the invention for the preparation of 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester consists in chemically initiated selective bromination of methyl on the double bond of methyl 2-methyl-3- (2-furyl) acrylic acid N-bromosuccinimide. The reaction is carried out in anhydrous carbon tetrachloride in the presence of the initiator α, α-azobisisobutyronitrile at the boiling point of carbon tetrachloride.
Reakcia prebieha podlá schémy:The reaction proceeds according to the scheme:
CHt— G0.CH t -G0.
N—Br !ΗΜ-βΟΖ N — Br! Η Μ -βΟ Ζ
GHjtBrGHjtBr
GH-G^ XC00GMs GH-G ^ X C00GM p
Výhody sposobu přípravy metylesteru kyseliny 2-brómmetyl-3-(2-furyl)akrylovej pódia vynálezu spočívajú okrem iného v tom, že je jednoduchý, ekonomický a 1'ahko prevediteíný.The advantages of the process for the preparation of 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester according to the invention are, inter alia, that it is simple, economical and readily convertible.
Predmet vynálezu ilustruje, ale neobmedzuje nasledovný příklad prevedenia reakcie.The present invention illustrates, but does not limit, the following example.
PříkladExample
Příprava metylesteru 2-brómmetyl-3-(2-furyl )akrylovej kyseliny.Preparation of 2-Bromomethyl-3- (2-furyl) acrylic acid methyl ester.
Zmes 17,6 g (0,1 mol) ihetylesteru kyseliny 2-metyl-3-( 2-furyl) akrylovej, 17,9 g (0,1 mol) N-brómsukcínimidu v 400 ml bezv. chloridu uhličitého sa zahřeje do varu. Do vrúceho chloridu uhličitého sa přidá 200 mg iniciátoru chemickej radikálovej bromácie a, «‘-azobisizobutyronitrilu. Ukončenie reákcie indikuje plávanie sukclnimidu na povrchu reakčnej zmesi (N-brómsukcínimid je na začiatku reakcie na dne reakčnej banky). Sukcinimid sa za horúca odfiltruje, chlorid uhličitý sa vákuovo oddestiluje a metylester kyseliny 2-brómmetyl-3-(2-furyl) akrylovej sa prekryštallzuje z petroléteru. Výťažok 19,9 g, t.j. 81,4%.A mixture of 17.6 g (0.1 mol) of 2-methyl-3- (2-furyl) acrylic acid ethyl ester, 17.9 g (0.1 mol) of N-bromosuccinimide in 400 ml of colorless salt. of carbon tetrachloride is heated to boiling. 200 mg of chemical radical bromination initiator and .beta.-azobisisobutyronitrile are added to boiling carbon tetrachloride. The completion of the reaction indicates that succinimide is floating on the surface of the reaction mixture (N-bromosuccinimide is at the beginning of the reaction at the bottom of the reaction flask). The succinimide is filtered off while hot, the carbon tetrachloride is distilled off in vacuo, and 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester is recrystallized from petroleum ether. Yield 19.9 g, i. 81.4%.
Metylester kyseliny 2-brómmetyl-3-(2-furyl)akrylovej podía vynálezu je zlúčenina vzorca zCHa.Bi·The 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester according to the invention is a compound of the formula zCHa.Bi ·
-CH-C ^GOOCHs-CH-C 1 GOOCH 3
Sumárny vzorec zlúčeniny je C9H9BrO3. Molekulová hmotnost je 245,075 a t. t. 50,5 až 52,0 °C.The general formula of the compound is C 9 H 9 BrO 3. The molecular weight is 245.075 and t. t. 50.5-52.0 ° C.
Elementárna analýzaElemental analysis
Štruktúra metylesteru kyseliny 2-brómmetyl-3-(2-furyl)akrylovej bola dokázaná IČ a NMR spektroskopiou. IČ spektrá boli namerané na spektrofotometr! (UR-20 fy Zeiss jena) v chloroforme (koncentrácia 10’2 mol). IČ spektrum metylesteru 2-brómmetyl-3-( 2-furyl )akrylovej kyseliny vykazuje tieto charakteristické pásy:The structure of 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester was shown by IR and NMR spectroscopy. IR spectra were recorded on a spectrophotometer. (UR-20 from Zeiss jena) in chloroform (10 -2 mol concentration). The IR spectrum of 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester shows the following characteristic bands:
XH NMR spektrum bolo namerané na spektrometri (BS-487C fy Tesla Brno). X H-NMR spectrum is taken to the MS (BS-487C Tesla Brno f).
XH NMR spektrum bolo získané meraním látky v deuterovanom chloroforme za použitia trimetylsilánu ako interného standartu. The 1 H NMR spectrum was obtained by measuring the substance in deuterated chloroform using trimethylsilane as an internal standard.
R — metyl = C—CH2R-methyl = C-CH 2
ΗβΗβ
Hshs
H4H4
H5 singlet 3,85 singlet 4,71 singlet 7,49 dublet 6,84 dublet dubletu 6,55 dublet 7,65H5 singlet 3.85 singlet 4.71 singlet 7.49 doublet 6.84 doublet doublet 6.55 doublet 7.65
Metylester kyseliny 2-brómmetyl-3-( 2-f uryl) akrylovej podía vynálezu je látka dobré rozpustná v organických rozpúšťadlách a velmi reaktívna voči nukleofilným činidlám. Metylester kyseliny 2-brómmetyl-3-(2-furyl)akrylovej může byť použitý pre syntézu nových 5-nitro-2-ťuryletylénových zlúčenín s očakávanou biologickou účinnosťou. Metylester kyseliny 2-brómmetyl-3-( 2-f uryl) akrylovej podía vynálezu sprístupňuje syntézy uvedených látok.The 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester of the invention is well soluble in organic solvents and very reactive to nucleophilic agents. 2-Bromomethyl-3- (2-furyl) acrylic acid methyl ester can be used to synthesize novel 5-nitro-2-turylethylene compounds with expected biological activity. The 2-bromomethyl-3- (2-furyl) acrylic acid methyl ester of the invention provides for the synthesis of said compounds.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS2278A CS196930B1 (en) | 1978-01-02 | 1978-01-02 | 2-brommethyl-3-/2-furyl/acrylic acid methylestere and process for preparing thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS2278A CS196930B1 (en) | 1978-01-02 | 1978-01-02 | 2-brommethyl-3-/2-furyl/acrylic acid methylestere and process for preparing thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196930B1 true CS196930B1 (en) | 1980-04-30 |
Family
ID=5331657
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS2278A CS196930B1 (en) | 1978-01-02 | 1978-01-02 | 2-brommethyl-3-/2-furyl/acrylic acid methylestere and process for preparing thereof |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196930B1 (en) |
-
1978
- 1978-01-02 CS CS2278A patent/CS196930B1/en unknown
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