CS276701B6 - Trimethoxystyrenes and their preparation - Google Patents

Trimethoxystyrenes and their preparation Download PDF

Info

Publication number
CS276701B6
CS276701B6 CS911111A CS111191A CS276701B6 CS 276701 B6 CS276701 B6 CS 276701B6 CS 911111 A CS911111 A CS 911111A CS 111191 A CS111191 A CS 111191A CS 276701 B6 CS276701 B6 CS 276701B6
Authority
CS
Czechoslovakia
Prior art keywords
general formula
trimethoxystyrenes
radicals
solvent
preparing
Prior art date
Application number
CS911111A
Other languages
Czech (cs)
Slovak (sk)
Other versions
CS111191A3 (en
Inventor
Juraj Ing Csc Zamocky
Marcel Rndr Zamocky
Anton Ing Ondrejkovic
Original Assignee
Chemicky Ustav Sav
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 Chemicky Ustav Sav filed Critical Chemicky Ustav Sav
Priority to CS911111A priority Critical patent/CS111191A3/en
Publication of CS276701B6 publication Critical patent/CS276701B6/en
Publication of CS111191A3 publication Critical patent/CS111191A3/en

Links

Landscapes

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

Abstract

Trimetoxystyrény všeobecného vzorca I sa · pripravujú intramolekulovou elimináciou vody z příslušného sekundárného trimetoxyf enyl- •efcylalkoholu všeobecného vzorca II, ktorý sa postupné přidává do refluxujúceho rozpúš-v ťadla za přítomnosti bezvodného síranu meďnatého připadne s prídavkom inhibítora polymerizácie, refluxuje sa do 5 hodin, nero-zpustná zložka sa oddělí, roztok zahustí a následné destiluje.Trimethoxystyrenes of general formula I are prepared by intramolecular elimination of water from the corresponding secondary trimethoxyphenyl- •cycloalcohol of general formula II, which is gradually added to a refluxing solvent in the presence of anhydrous copper sulfate and optionally with the addition of a polymerization inhibitor, refluxed for 5 hours, the insoluble component is separated, the solution is concentrated and subsequently distilled.

Description

•t' CS 276701 B 6

Vynález sa týká derivátov styrénu, charakterizovaných prítomnostou troch metoxylovýchskupin na benzénovom jádře a spósobu ich přípravy dehydratáciou příslušných trimetoxyfe-nyletylalkoholov.

Trimetoxystyrény substituované metoxylovýni radikálom v polohe 2,3,4 ako aj 2,4,5,neboli doteraz připravené. Analogické zlúčeniny boli připravené intramolekulovýni odštie-pením vody z příslušných trimetoxyf enylethylálkoholov. za přítomnosti kyslých katalyzátorov(Organic Syntheses, 5, 1955, C. G. Overberger, J. H. Saunders, "m-Chlorstyrene", Ed. JohnWiley et Sons, lne., New York, str. 204 až 206). Uvedený spósob sa nepodařilo reproduko-vat’ W. Kleebergovi a G. Suchardtovi (Naturwiss., 44, 1957, W. Kleeberg, G. Suchardt,"Beobachtungen uber den Verlauf der Dehydratisierung von Arylmethylcarbinolen", str. 584),ktorí naviac popierajú vhodnost’ používania kyslých katalyzátorov pri dehydratácii, nakolkoza takýchto podmienok dochádza k preferovanej tvorbě příslušných diaryléterov, čo platí ajv případe metoxylovaných styrénov.

Podstatou vynálezu sú trimetoxystyrény všeobecného vzorca I

kde radikály R^ a Rj sú rozdielne, predstavujú H alebo CH^O, pričom tiéto radikály R^ aR2 sú substituované v polohe 3, 5.

Ďalej jespočívá pódiaca II podstatou sposob přípravy trimetoxystyrénov všeobecného vzorca I, ktorývynálezu v tom, že na sekundárný trimetoxyfenyletylalkohol všeobecného vzor- CH,I 3

kde R^ a R2 majú už uvedený význam, sa působí refluxujúcim rozpúšťadlom o teplote varu140 až 174 °C za přítomnosti bezvodného síranu meďnatého, připadne s prídavkom inhibítorapolymerácie, refluxuje sa 15 minút až 4 hodiny, nerozpustná zložka sa oddělí, roztok za-hustí a následné destiluje pri tlaku 20 až 100 Pa. Ako refluxujúce rozpúšťadlo o teplotevaru medzi 151 až 174 °C sa použije nonán, propylbenzén alebo dekán.

Podl’a vynálezu sa sekundárný trimetoxyfenyletylalkohol intramolekulovo dehydratuje,pričom sa reakcia l’ahko kontroluje stanovováním množstva vody v odlučovači. Výtažky súaž 75%né u 2,3,4-trimetoxystyrénu. Ak sa získané trimetoxystyrény nepoužijú do 48 hodinako medziprodukt, musia sa stabilizovat’ prídavkom inhibítora polymerizácie, od ktoréhosa dajú před použitím oddělit’ destiláciou při tlaku 20 až 100 Pa. Příklady realizovania vynálezu Příklad 1

Do 250 ml banky opatrenej mechanickým miešaním, prikvapkávacím lievikom s predíženou stonkou a odlučovačom vody so spatným chladičom, vloženej do laboratórneho vyhrievacieho hniezda sa vleje 100 ml děkanu a přidá 1,6 g bezvodného síranu meďnatého. Refluxuje sa 10 minút pri teplote varu dekánu 174 °C, počas ktorých sa cez odlučovač odstrání voda, ak síran meďnatý obsahuje stopy vody. Potom sa prikvapká 53 g (0,25 mol) 1-(2,3,4-tri-

• t 'CS 276701 B 6

The present invention relates to styrene derivatives characterized by the presence of three methoxy groups on the benzene core and a process for their preparation by dehydration of the corresponding trimethoxyphenylethyl alcohols.

Methoxylated substituted trimethoxystyrenes at 2,3,4 and 2,4,5 have not been prepared yet. Analogous compounds were prepared by intramolecular cleavage of water from the corresponding trimethoxyphenylethyl alcohols. in the presence of acidic catalysts (Organic Syntheses, 5, 1955, CG Overberger, JH Saunders, " m-Chlorstyrene ", Ed. JohnWiley et Sons, Inc., New York, pp. 204-206). This method could not be reproduced by W. Kleeberg and G. Suchardt (Naturwiss., 44, 1957, W. Kleeberg, G. Suchardt, "Beobachtungen uber den Verlauf der Dehydratisierung von Arylmethylcarbinolen", p. 584), who in addition deny the desirability of using acid catalysts in dehydration, since such conditions result in the preferred formation of the respective diaryl ethers, which also applies to the methoxylated styrenes.

The present invention provides trimethoxystyrenes of formula (I)

wherein the radicals R 1 and R 1 are different, represent H or CH 2 O, wherein these radicals R 1 and R 2 are substituted at the 3, 5 position.

Furthermore, the present invention is based on a process for preparing trimethoxystyrenes of the general formula (I) according to the invention in that the secondary trimethoxyphenylethyl alcohol of the general formula CH, I

where R 1 and R 2 are as defined above, refluxing solvent is applied at a temperature of 140 to 174 ° C in the presence of anhydrous copper sulfate, optionally with the addition of an inhibitor of polymerization, refluxing for 15 minutes to 4 hours, insoluble matter is separated, the solution is concentrated and subsequently distilled at a pressure of 20 to 100 Pa. A nonane, propylbenzene or decane is used as the refluxing solvent between 151-174 ° C.

According to the invention, the secondary trimethoxyphenylethyl alcohol is dehydrated intramolecularly, the reaction being readily controlled by determining the amount of water in the separator. Yields 75% for 2,3,4-trimethoxystyrene. If the trimethoxystyrenes obtained are not used as an intermediate within 48 hours, they must be stabilized by the addition of a polymerization inhibitor which can be separated before use by distillation at a pressure of 20 to 100 Pa. EXAMPLES Example 1

100 ml of decane is poured into a 250 ml flask equipped with mechanical stirring, a dropping funnel with a stalk and a water cooler with a cold condenser, added to a laboratory heating nest, and 1.6 g of anhydrous copper sulphate are added. Reflux for 10 minutes at decane temperature of 174 ° C, during which water is removed through the separator if copper sulfate contains traces of water. Then 53 g (0.25 mol) of 1- (2,3,4-tri-

Claims (3)

PATENTOVÉ NÁROKYPATENT CLAIMS 1. Trimetoxystyrény všeobecného vzorca I cii=ch2 R2 ooh3 kde radikály R^ a R2 sú rozdielne, predstavujú H alebo CH^O, pričom tieto radikály1. Trimethoxystyrenes of the general formula I cii=ch 2 R 2 ooh 3 where the radicals R^ and R 2 are different, represent H or CH^O, these radicals being R| a R2 sú substituované v polohe 3,5.R 1 and R 2 are substituted at the 3,5 position. 2. Spósob přípravy trimetoxystyrénov všeobecného vzorca I podl’a bodu 1, vyznačujúci sa tým, že na trimetoxyfenyletylalkohol všeobecného vzorca II2. A method for preparing trimethoxystyrenes of general formula I according to point 1, characterized in that trimethoxyphenylethyl alcohol of general formula II CS 276701 B 6CS 276701 B 6 CH3 CH 3 CH-OHCH-OH kde a R£ majú už uvedený význam, sa působí refluxujúcim rozpúšťadlom o teplote varu 151 až 174 °C za přítomnosti bezvodného síranu meďnatého, připadne s přídavkem inhibítora polymerácie, refluxuje sa 15 minút až 4 hodiny, nerozpustná zložka sa oddělí, roztok zahustí a následné destiluje při tlaku 20 až 100 Pa.where and R£ have the meanings already given, is treated with a refluxing solvent with a boiling point of 151 to 174 °C in the presence of anhydrous copper sulfate, optionally with the addition of a polymerization inhibitor, refluxed for 15 minutes to 4 hours, the insoluble component is separated, the solution is concentrated and subsequently distilled at a pressure of 20 to 100 Pa. 3. Spůsob přípravy trimetoxystyrenov všeobecného vzorce I podlá bodu 2, vyznačujúci sa tým, že refluxujúcim rozpúšťadlom je rozpúšťadlo o teplote varu 151 až 174 °C s výhodou nonán, propylbenzén alebo dekán.3. A method for preparing trimethoxystyrenes of general formula I according to item 2, characterized in that the refluxing solvent is a solvent with a boiling point of 151 to 174 °C, preferably nonane, propylbenzene or decane.
CS911111A 1991-04-19 1991-04-19 Trimethoxystyrenes and process for preparing thereof CS111191A3 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CS911111A CS111191A3 (en) 1991-04-19 1991-04-19 Trimethoxystyrenes and process for preparing thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CS911111A CS111191A3 (en) 1991-04-19 1991-04-19 Trimethoxystyrenes and process for preparing thereof

Publications (2)

Publication Number Publication Date
CS276701B6 true CS276701B6 (en) 1992-07-15
CS111191A3 CS111191A3 (en) 1992-07-15

Family

ID=5344647

Family Applications (1)

Application Number Title Priority Date Filing Date
CS911111A CS111191A3 (en) 1991-04-19 1991-04-19 Trimethoxystyrenes and process for preparing thereof

Country Status (1)

Country Link
CS (1) CS111191A3 (en)

Also Published As

Publication number Publication date
CS111191A3 (en) 1992-07-15

Similar Documents

Publication Publication Date Title
DE69000467T2 (en) BIS-AZA-BICYCLIC ANXIOLYTICA AND ANTIDEPRESSIVA.
DE69520312T2 (en) Group III A organometallic derivatives and process for their preparation
DE3888756T2 (en) Carbamoylpyrrolidone derivatives, their use and preparation.
DE69932620T2 (en) HYDRATFORMS OF SODIUM SALT OF ALENDRONATE, METHOD FOR THE PRODUCTION THEREOF AND PHARMACEUTICAL COMPOSITIONS CONTAINING THEREOF
DE3141256C2 (en) Spiro-quaternary ammonium halides, a process for the preparation of these compounds and a process for the further processing of these compounds to give N- (2-pyrimidinyl) -piperazinylalkyl-azaspiroalkanediones
SU1660579A3 (en) Method for obtaining derivatives of isoindolinone or their salts
DE60202782T2 (en) COMPOUNDS INHIBITING THE RELEASE OF CYTOKINES
DE2149249A1 (en) 6-aryl pyrimidines
DE69328962T2 (en) METHOD FOR PRODUCING CYANO-METHOXYIMINOMETHYL DERIVATIVES
EP0167121B1 (en) Substituted phenylpiperazinyl propanols, process for their preparation, their use, and compositions containing these compounds
DE1470004A1 (en) New piperazines and processes for their preparation
CH649084A5 (en) N - ((4- (3-SUBSTITUTED-PYRIDYL) -PIPERAZINO) -ALKYL) -AZA-SPIRODECANDIONE.
DE69104842T2 (en) INTERMEDIATE PRODUCTS FOR CHELATE-MAKING ACTIVE SUBSTANCES WITH PRE-DETERMINED SYMMETRY AND METHOD FOR THE PRODUCTION THEREOF.
CS276701B6 (en) Trimethoxystyrenes and their preparation
DE2628570B2 (en)
DE1645964A1 (en) Oxazepines and thiazepines
EP0178587A3 (en) Benzyloxyalkyl azoles and fungicides containing them
DD202712A5 (en) PROCESS FOR THE PREPARATION OF (THIENYL-2) AND (THIENYL-3) -2-AETHYLAMINE DERIVATIVES
SU1145932A3 (en) Method of obtaining derivatives of 2,3,6,7-tetrahydrothiazolo (3,2-a) pyrimidine-5-on
DE2661028C2 (en)
DE2429515A1 (en) 3-AMINO- (1) -BENZOPYRANO- AND -BENZOTHIOPYRANO- (4,3,2-DE) PHTHALAZINE
DE1620044B2 (en) Process for the preparation of substituted aminomethylphosphinic acids
DE19612828C1 (en) Cyano-naphthyl-substd. phenyl-ethene or -acrylic acid derivs. prodn.
EP0439796B1 (en) Indolylpropanols, process for their preparation, and their use and preparations containing them
DE1570013B1 (en) 1,4-bis (phenoxyacetyl) piperazine derivatives and processes for their preparation