CS269025B1 - Process for producing 3-ethyl-2-penten-4-yn-1-ol cia-isomer - Google Patents
Process for producing 3-ethyl-2-penten-4-yn-1-ol cia-isomer Download PDFInfo
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Abstract
Riešenie ee týká epBsobu výroby cis-lzoaéru 3-aetyl-2-pentón-4-in-l-oíu kyslo katalyzovanýa alylovýa prešaykoa 3-aetyl-l-pentén-4-in-3-olu. Prešayk sa uskutečni v pritoanjati slino kyelého aeniča katlónov v H cykle eko kyslého katalyzátore v heterogénnom kvape 1- noa systéme vodnej a organickej fázy, ktoru tvoři organická rozpúžladlo, medzl ktoré ea rozdelujú reakčné zlozky. Produkt ea aÓžo použil k výrobě retlnylacetátu. Riešenie sa aóže využil vo faraaceutlckoa priemyele pri výrobě vltealnu A-acetátu a v kozmetlke.The present invention relates to a process for the production of the cis-isoether of 3-acetyl-2-penten-4-yn-1-ol by acid-catalyzed allyl reaction of 3-acetyl-1-penten-4-yn-3-ol. The reaction is carried out in the presence of a salt of an acid catalyst in the H cycle of an acid catalyst in a heterogeneous liquid 1- or aqueous system of an organic phase, which is formed by an organic solvent, between which the reaction components are distributed. The product is also used to produce retinyl acetate. The solution is also used in the pharmaceutical industry in the production of retinyl A-acetate and in cosmetics.
Description
CS 269 025 81 1EN 269 025 81 1
Vynález es týká sposobu výroby cis-izomaru 3-aetyl-2-pentén-4-in-l-olu, ktorý sptrpoužívá k výrob· retinylacetétu, známého pod názvom Vitamin A-acetét.The invention relates to a process for the preparation of the cis-isomer of 3-ethyl-2-penten-4-yn-1-ol, which is useful in the production of retinylacetate, known as Vitamin A-Acetate.
Cis-izomér 3-metyl-2-pentén-4-in-l-ol sa vyréba alylovým preěmykom 3-metyl-l-pen-tén-4-in-3-olu v prltoanoati kyslého katalyzátore· Vznikajúci cie-izomér 3-metyl-2-pen-tén-4-in-l-olu sa Izoluje z reakčnej zaeel extrakciou organickým rozpúěfadlo·, alebodsstlláciou s vodnou parou, Zleka sa zmes cis- a trans- lzomérov 3-aetyl-2-pentén-4-in--l-olu, z ktorej ss cis-izomér zlska frakčnou rektiflkáciou pri znlženoa tlaku, Ako kys-lý katalyzátor sa v priemyselných podalenkach používejú silná minerálně kyseliny, na-příklad kyselina sírová, kyselina fosforečná /US patent 2 451 739/. Nevýhodou týchtopostupov Je, že při použiti silných minerálnych kyselin, ktorá sa použijú ako vodný roz-tok, vzniká pri výrobě značné množstvo odpsdných, chemicky znečistěných v6d, a vysokousolnosfou.The Cis-isomer of 3-methyl-2-penten-4-yn-1-ol is prepared by the allyl conversion of 3-methyl-1-penten-4-yn-3-ol in the acid catalyst catalyst. Methyl-2-pent-4-yn-1-ol is isolated from the reaction mixture by extraction with an organic solvent, but with water vapor depletion, and a mixture of cis- and trans-isomers of 3-ethyl-2-pentene-4-in is removed. The acidic catalyst used in the industrial formulations is a strong mineral acid, such as sulfuric acid, phosphoric acid (U.S. Pat. No. 2,451,739), and the cis-isomer is a fractionated rectification at reduced pressure. The disadvantage of these processes is that, when using strong mineral acids, which are used as aqueous solutions, a considerable amount of solvent, chemically contaminated v6d, and high salinity is produced.
Se tiež známa použitie slino kyelých aeničov kationov ako kyslých katalyzátorovpreSayku, Izomerizácia sa uskutočňuje vo vodnom, alebo vodno-alkohollckom prostřed! /SUpatent 126 227/,It is also known to use saline cyanide cation exchanger such as acid catalysts, isomerization is carried out in an aqueous or aqueous-alcoholic medium. SUpatent 126 227 /
Nevýhodou tohto postupu Je vysoká Specifická spotřeba ionomenlča, pretože počešreakcie sa znlžuje Jeho aktivita ab9orbciou vznlkajúcich produktov reakcle a dochádzak Jeho znehodnotenlu.The disadvantage of this process is the high specific consumption of the ion exchanger because its reaction decreases its activity and absorbs the decaying products of the reactor and becomes devalued.
Nevýhody doterajěich postupov sa dajú odstránif spSsobom pódia vynálezu, pričomsa postupuje tak, že cis-izomér 3-aetyl-2-pentén-4-in-l-olu sa připraví alylovým preě-mykom 3-metyl-l-pentén-4-in-3-olu katalyzovaným, slino kyslým meničom kationov, v H+ cyk-le, v heterogénnom kvapalnom prostředí vodnej a organickej fázy, ktorú tvor! organickérozpúěfadlo, medzi ktoré fázy sa rozdelia reakčné zložky. Výhodné sa použijú slino kyelé neniče katiúnov na báze syntetických živic typufenolických polykondenzátov, alebo kopolyméry styrén-divinylbenzénového typu, v ktorýchsú funkční sulfoskupiny -SO^H naviazané bu3 na benzénové Jádro priamo, alebo cez mety-lénovu skupinu. Takými sú například komerčně dostupné slino kyslé neniče kationov ivofo-tit KS-10, Ostion KS, katex KU-2, Amberlit R-120. Pri postupné sa použijú lonoaeničev H* cykle, výhodné naboptnaló vodou. Výhodný hmotnostný poměr 3-metyl-l-pentén-4-ln--3-olu ku katsxu v naboptnalom stave Je 1 i O, 01 až 1,0.The drawbacks of the prior art can be avoided by the process of the invention wherein the cis-isomer of 3-ethyl-2-penten-4-yn-1-ol is prepared by the allyl precursor 3-methyl-1-pentene-4-one -3-ol catalysed, saline acidic cation exchanger, in H + cycles, in the heterogeneous liquid medium of the aqueous and organic phases that the creatine. an organic solvent, between which phases the reactants are separated. Preference is given to the use of slime yellow non-cationic synthetic resin-type phenol polycondensates, or styrene-divinylbenzene-type copolymers in which the functional sulfo-groups are bonded either to the benzene core directly or via the methyl-group. Such are, for example, commercially available slino acid non-cationic KS-10, Ostion KS, KU-2 cation exchange resin, Amberlite R-120. In the sequential step, H @ + cycles are used, preferably water. The preferred weight ratio of 3-methyl-1-penten-4-yn-3-ol to katsx in the charcoal state is 1 to 0.1 to 1.0.
Ako organické rozpúěfadlo sa výhodné použijú aromatické uhlovodíky, ako benzén,alebo deriváty benzénu, v ktorých sú substituované atomy vodika skupinami alifatickýchuhlovodlkov, ako například toluen, xylény.As the organic solvent, aromatic hydrocarbons such as benzene or benzene derivatives in which hydrogen atoms are substituted by aliphatic hydrocarbon groups such as toluene, xylenes are preferred.
Ako organické rozpúěfadlo Je Sálej výhodné použif halogénové deriváty alifatickýchuhíovodlkov, výhodné nízkých alkánov a alkénov s počtom atómov uhlika 1 až 6, ako na-příklad dlchlárnetán, chloroform, chlorid uhličitý, dlchlórstány, dlchlóretény a tri-chlóratény. Množstvo použitého rozpúěfadla Je limitované iba vzéjomnou rozpustnosfouzložiek reakčnej znesi 3-metyl-l-pantón-4-ln-3-olu, vody a rozpúžfadla tak, že pri tep-loto reakcie tvorla heterogénny kvapalný systém dvoch féz. Výhodný Je hmotnostný pomarpoužitých zložiek 3-metyl-l-pentén-4-in-3-olu, k vodě a k organickému rozpúšfadlu 1 : 0,1až 3,0 J 0,1 až 20,0.As the organic solvent, it is still preferable to use halogen derivatives of aliphatic hydrocarbons, preferably low alkanes and alkenes having carbon numbers of 1 to 6, such as, for example, dichloromethane, chloroform, carbon tetrachloride, dlchlorstanes, dlchloretenes and trichlorotenes. Amount of solvent used It is limited solely by the solubility of the reaction mixture of 3-methyl-1-pantone-4-yn-3-ol, water and solvent so that it forms a heterogeneous two-phase liquid system in the reaction. Preference is given to the weight of the 3-methyl-1-penten-4-yn-3-ol components used, to water and to the organic solvent 1: 0.1 to 3.0 J 0.1 to 20.0.
Reakcla sa vedle tek, že k roztoku 3-metyl-l-pentón-4-in-3-olu v organickém rozpúě-fadle sa za oleěania přidá vo vodo naboptnalý měnič kationov, Reakčné zmes sa mleěav atmosféře duslka pri teploto 15 až 90 °C, výhodné v intervale teplat 30 až 70 °C podobu 2 až 10 hodin. Potom aa reakčné zmes ochladl na teplotu 20 °C, odfilruje sa ionoroe-nič. Z filtrátu sa oddělí organická fáze, Ionomenič sa premyje čistým organickým roz-púěfadlom, filtrétom sa extrahuje vodné oddálená fáza, organický extrakt sa oddali aorganické fázy sa spoje. Z roztoku sa oddestlluja organické rozpúěfadlo, pričom je vý-hodné postupná znižovaf tlak v systéme tak, že teplota na hlav· kolúny neprevýěl 50 °C.In addition to the solution of 3-methyl-1-penton-4-yn-3-ol in the organic solvent, the reaction mixture was added to the water-cationic cation exchanger under acidification. The reaction mixture was milled at 15 to 90 ° C in a nitrogen atmosphere. C, preferably in the range of 30 to 70 ° C for 2 to 10 hours. Thereafter, the reaction mixture was cooled to 20 ° C, the ionoroel was filtered off. The organic phase is separated from the filtrate, the ionomer is washed with pure organic solvent, the aqueous phase is extracted with a filter, the organic extract is separated and the organic phases are separated. The organic solvent is removed from the solution, with a gradual reduction in system pressure such that the temperature at the head of the column does not exceed 50 ° C.
Zo zvyšku sa frakčnou rektiflkáciou oddali nezreagovaný 3-metyl-l-pentén-4-in-3-ol přitlaku 16 až 1,2 kPa. Frakcia s obaahom cis-izoméru 3-metyl-2-pentén-4-in-l-olu sa odo- CS 269 025 B1 2 berle prl tlaku 1,5 až 0,13 kPa. Zo zvyšku je možné při Salšej rektiflkácii odebralfrakclu a obeahoa trane- izoméru 3-aatyl-2-pentén-4-in-l-olu· Cis-izoaér 3-metyl-2-pen-tén-4-in-l-olu sa takto zisk* vo výlažku výše 50 %, při atupnl konverzie do 70 %. Zlakaaa produkt o čistota nad 95 haot. %.From the residue, unreacted 3-methyl-1-penten-4-yn-3-ol was withdrawn from the residue by a pressure of 16 to 1.2 kPa. The fraction containing the cis-isomer of 3-methyl-2-penten-4-in-1-ol is crushed with a pressure of 1.5 to 0.13 kPa. From the remainder, the distillation and obeahoa trane isomer of 3-aatyl-2-penten-4-yn-1-ol · Cis-isoaer of 3-methyl-2-penten-4-in-1-ol can be removed in in this way, the gain * in the plant is 50%, at the conversion rate up to 70%. Zlakaaa product with purity above 95 haot. %.
Novosi poplašného rlešenia spočívá v to*, že lzoaarlzácia 3-mstyl-l-pentén-4-in-3-olu aa uskutečni katalýzou slino kyslým meničom katiúnov v proatradí heterogénneho kve-palného systému vodnej a organickej fázy, či* aa dosahuje zachovanle aktivity lonomenl-ča po dobu reakcie· Dosahuje aa stupeň premeny okolo 70 % prl selektivita premeny výíe75 % e znlženle Speciflekej epotreby ionomeničs.The novelty is that the polarization of 3-methyl-1-penten-4-yn-3-ol and by catalysis with an acidic cathode transducer is essentially a heterogeneous water system of the aqueous and organic phases, and maintains activity. lonomenl-c during the reaction · It achieves aa degree of conversion of about 70% of the selectivity of the conversion of over 75% of the specific ion exchange rate.
SpSsoboa podle vynálezu sa Sálej zvyšuje efektivnost lzolácie produktu reakčnej zasal a tekaer úplné sa odetraňujú z procesu výroby odpady chealoky znečistěných a zasole-ných vSd.According to the present invention, the efficiency of the reaction product product is increased and the liquid is completely removed from the production process by the waste of polluted and salted waste.
Spdsob výroby podle vynálezu je ilustrovaný naaledovnýai přikladši prevedenla, kto-rá ho však v žiednom případe neobaedzujú. Přiklad 1 K zaesl pozoatávajúcej z 90,55 g /0,940 mol/ 99,8 %-ného 3-mstyl-l-pentén-4-ín-3-olu a 77,5 g chloridu uhličitého sa za niešenia přidá 28,0 g vo vods naboptnaláho slinekysláho aenlča katiónov Wofetit KS-10. Zaes sa Intenzivně aleéa v etaosfára dusika podobu 4 hodin prl teplote 62 °C> Reakčná zaea aa ochladl na teplotu 20 °C, přefiltruje asa cez fritu a z filtrátu se oddělí v dellacoa llevlku organická fáza· lonoaenič aa presyje na frlte s 30 sl chloridu uhličitého, filtrátoa sa extrahuje oddá-lená vodná fáza a roztoky chloridu uhličitého sa spoje·- Roztok chloridu obsahuje podle 'analýzy plynovou chromatograflout 36,9 g 3-aetyl-l-pentén-4-in-3-olu, 41.7 g cls-lzoaéru 3-metyl-2-pentén-4-ín-l-olu a 11.7 g trens-izoeéru 3-aetyl-2-pentén-4-in-l-olu.The process of the invention is illustrated by the following examples, which, however, are not omitted in any case. Example 1 To a mixture consisting of 90.55 g (0.940 mol) of 99.8% 3-methyl-1-penten-4-yn-3-ol and 77.5 g of carbon tetrachloride, 28.0 g were added under agitation. in the water of the Wofetit KS-10. After 4 hours at 62 [deg.] C. in an atmosphere of nitrogen for 4 hours, the reaction mixture was cooled to 20 [deg.] C., filtered through a sintered glass funnel and the organic phase was separated from the filtrate and washed with 30 [mu] l of carbon tetrachloride. , the filtrate is extracted with the separated aqueous phase and the carbon tetrachloride solutions are combined. - The chloride solution contains 36.9 g of 3-ethyl-1-penten-4-yn-3-ol, 41.7 g of cls-lzoaer by gas chromatography. Of 3-methyl-2-penten-4-yn-1-ol and 11.7 g of 3-ethyl-2-penten-4-yn-1-ol trensyl isomer.
Stanovené anožstvá látok zodpovsdajú 46,1 %-nému výtažku a selektivita preaeny 3-metyl-l-pentén-4-in-3-olu 78 %. K roztoku se přidá 0,9 g hydrochinónu a prl postupné znižovanoa tlaku do 16 kPa saoddestiluje chlorid uhličitý· Rektifikáclou při postupné znižovanoa tlaku v intervaleod 16 do 0,87 kPa se zleka frakcia 38 g 96 haot· %-ného 3-aetyl-l-pentén-4-in-2-olus 2,5 haot. % cis-lzonéru 3-aetyl-2-pantén-4-in-l-olu. Balšou rektifikáciou pri tlaku0,87 až 0,65 kPa sa ziska frakcia a teplotou varu 45 °C o celkovej hmotnosti 37,4 gs obeahoa 98,1 haot. % cie-izoaéru 3-metyl-2-pentén-4-in-l-olu a 1,2 hmot. % trsns-izo-méru 3-aetyl-2-pentón-4-in-l-olu. Rektifikáciou prl znlženoa tlaku 0,65 až 0,20 kPasa’3alsj zlaka frakcia s intervaloa teplSt varu 45 až 55 °C o hmotnosti 7,37 g, a ob.-,9ahoa 55 hmot· % cis-izoméru a 44 haot. % trans-izoméru 3-aetyl-2-pentén-4-ln-l-olu.Oestllačný zvyáok hmotnosti 8,45 g představuje tmevočervenú olejovltú hmotu* Přiklad 2 K roztoku 89,0 g /0,924 mol/ 99,8 %-ného 3-oetyl-l-pentén-4-in-2-olu e 136,6 gchloridu uhličitého sa za oieSanla přidá 19,4 vodou naboptnaláho ke taxu Wofetit KS-10.Znee sa intenzivně mieSa pod ataosférou dusika po dobu 4 hodin při teplote 62 °G. Bel-áim postupom ako v přiklade 1. sa získá roztok chloridu uhličitého s obsahoai 30,6 g 3-metyl-l-pentén-4-in-3-olu, 45,4 g cla-izonéru 3-metyl-2-pentén-4-in-l-olu a 12,3 g trans-izoméru 3-metyl-2-pentén-4-ín-l-olu, čo zodpovedá 51,7 %-nému výtažkureakcie a selektivitě premeny 3-metyl-l-pentén-4-in-2-olu 78 %.The determined yields corresponded to a yield of 46.1% and the selectivity of the preaene of 3-methyl-1-penten-4-yn-3-ol was 78%. 0.9 g of hydroquinone is added to the solution, and the pressure is gradually reduced to 16 kPa and the carbon tetrachloride is distilled off. By rectifying the pressure of 38 to 96% by weight of 3-aethyl-1, the fraction of 38 g of 96 ha of sodium is removed. -pentene-4-in-2-olus 2.5 haot. 3-ethyl-2-panthen-4-yn-1-ol cis-ester. The fractional rectification at 0.87 to 0.65 kPa yields a fraction and boiling point of 45 ° C with a total weight of 37.4 g with obeahoa of 98.1 ha. % of the iso-isolator of 3-methyl-2-penten-4-yn-1-ol and 1.2 wt. 3% ethyl-2-penton-4-yn-1-ol tris-isomer. By rectification, the pressure drop of 0.65 to 0.20 kPasa'3also is the fraction with a boiling interval of 45 to 55 ° C weighing 7.37 g, and 55% by weight of the cis isomer and 44 ha. % of the trans-isomer of 3-ethyl-2-penten-4-yn-1-ol. A residual residue of 8.45 g is a dark red oil-yellow mass * Example 2 To a solution of 89.0 g / 0.924 mol / 99.8% by weight 3-acetyl-1-penten-4-yn-2-ol, 136.6 g of carbon tetrachloride, was added with water (19.4%) to the Wofetit KS-10 taxane. 62 ° G. By the same procedure as in Example 1, a solution of carbon tetrachloride is obtained containing 30.6 g of 3-methyl-1-penten-4-yn-3-ol, 45.4 g of isomer-3-methyl-2-pentene 4-in-1-ol and 12.3 g of the 3-methyl-2-penten-4-yn-1-ol trans isomer, corresponding to a 51.7% yield and selectivity of the conversion of 3-methyl-1-ol % penten-4-yn-2-ol.
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| CS884138A CS269025B1 (en) | 1988-06-15 | 1988-06-15 | Process for producing 3-ethyl-2-penten-4-yn-1-ol cia-isomer |
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| CS884138A CS269025B1 (en) | 1988-06-15 | 1988-06-15 | Process for producing 3-ethyl-2-penten-4-yn-1-ol cia-isomer |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1167331A3 (en) * | 2000-06-30 | 2003-05-07 | F. Hoffmann-La Roche Ag | Isomerization of a pentol |
| WO2008095724A1 (en) * | 2007-02-09 | 2008-08-14 | Dsm Ip Assets B.V. | Process for isomerizing a pent-1-en-3-ol |
| EP2128120A1 (en) | 2008-05-30 | 2009-12-02 | DSM IP Assets B.V. | Process for the rearrangement of allyl alcohols |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113943210B (en) * | 2021-11-02 | 2024-05-03 | 厦门金达威维生素有限公司 | Non-translocated six-carbon alcohol translocation method |
-
1988
- 1988-06-15 CS CS884138A patent/CS269025B1/en unknown
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1167331A3 (en) * | 2000-06-30 | 2003-05-07 | F. Hoffmann-La Roche Ag | Isomerization of a pentol |
| WO2008095724A1 (en) * | 2007-02-09 | 2008-08-14 | Dsm Ip Assets B.V. | Process for isomerizing a pent-1-en-3-ol |
| EP2128120A1 (en) | 2008-05-30 | 2009-12-02 | DSM IP Assets B.V. | Process for the rearrangement of allyl alcohols |
| WO2009144328A1 (en) * | 2008-05-30 | 2009-12-03 | Dsm Ip Assets B.V. | Process for the rearrangement of allyl alcohols |
| CN102046571A (en) * | 2008-05-30 | 2011-05-04 | 帝斯曼知识产权资产管理有限公司 | Process for the rearrangement of allyl alcohols |
| CN102046571B (en) * | 2008-05-30 | 2015-04-29 | 帝斯曼知识产权资产管理有限公司 | Process for the rearrangement of allyl alcohols |
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| Publication number | Publication date |
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| CS413888A1 (en) | 1989-08-14 |
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