CS232394B1 - Processing of 1-phenyl-1,3-propandiol - Google Patents
Processing of 1-phenyl-1,3-propandiol Download PDFInfo
- Publication number
- CS232394B1 CS232394B1 CS834170A CS417083A CS232394B1 CS 232394 B1 CS232394 B1 CS 232394B1 CS 834170 A CS834170 A CS 834170A CS 417083 A CS417083 A CS 417083A CS 232394 B1 CS232394 B1 CS 232394B1
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- Czechoslovakia
- Prior art keywords
- phenyl
- propanediol
- methanol
- reaction
- diacetate
- Prior art date
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- RRVFYOSEKOTFOG-UHFFFAOYSA-N 1-phenylpropane-1,3-diol Chemical compound OCCC(O)C1=CC=CC=C1 RRVFYOSEKOTFOG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 12
- SBOBOTARPDBQPK-UHFFFAOYSA-N (3-acetyloxy-3-phenylpropyl) acetate Chemical compound CC(=O)OCCC(OC(C)=O)C1=CC=CC=C1 SBOBOTARPDBQPK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 6
- 238000005809 transesterification reaction Methods 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 5
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 230000002940 repellent Effects 0.000 abstract description 2
- 239000005871 repellent Substances 0.000 abstract description 2
- 150000001241 acetals Chemical class 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- RCJRILMVFLGCJY-UHFFFAOYSA-N 4-phenyl-1,3-dioxane Chemical compound O1COCCC1C1=CC=CC=C1 RCJRILMVFLGCJY-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MMOXZBCLCQITDF-UHFFFAOYSA-N N,N-diethyl-m-toluamide Chemical compound CCN(CC)C(=O)C1=CC=CC(C)=C1 MMOXZBCLCQITDF-UHFFFAOYSA-N 0.000 description 1
- 238000010478 Prins reaction Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229960001673 diethyltoluamide Drugs 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Vynález se týká přípravy 1-fenyl1,3-propandiolu transesterifikaci l-fsnyl-l,3-propandioldiacetátu metanolem. Jako katalyzátor transesterifikace se použije uhličitan draselný v množství 1 gramu až 50 gramů na kilogram výchozího l-fenyl-l,3-propandiolacstátu. Oblast použití je v parfumářské výrobě, kde slouží jako meziprodukt pro výrýbu vonných acetalů a má repelentni účinky.The present invention relates to the preparation of 1-phenyl-1,3-propanediol transesterification 1-Phenyl-1,3-propanediol diacetate with methanol. The transesterification catalyst is using potassium carbonate in an amount 1 gram to 50 grams per kilogram of starting 1-phenyl-1,3-propanediolate. Field of application is in perfumery production, where it serves as an intermediate for debarking fragrant acetals and has a repellent effects.
Description
Vynález se týká způsobu'přípravy l-±‘enyl-l,3-propandiolu.The invention relates to a process for the preparation of 1- (4-phenyl) -1,3-propanediol.
Přímá hydrolýza 4-fenyl-l,3-dioxanu na l-fenyl-l,3-propandiol není možná. Dioxan je v alkalickém prostředí stálý, v kyselém prostředí vzhledem k velmi snadné dehydrataci diolu a následné polymer izac i vede hydrolýza maximálně k polymerním produktům. Z těchto důvodů se zatím prováděla dvojstupňové, přičemž v prvním stupni byl reakci dioxanu s acetanhydridem získán l-fenyl-l,3-propandioldiacetát, který ve druhém stupni reakcí s metanolem poskytl l-fenyl-l,3-propandiol a metylacetát. Tato reakce byla dosud katalyzována pouze kovovým sodíkem, který v reakční směsi přecházel na metanolát sodný, jak je popsáno v práci Heslinga A.·: Hec. trav. chim. Pays-Bas 78, 474 /1979/. Reakce mela dobrý výtěžek, nesla ovšem s sebou všechny nevýhody, dané pro provoz ne příliš vnodným katalyzátorem. Šorygina v Ž. obšč. chim. 26, 1460 /1956/ použila pro transesteri±‘ikaci 16% roztok hydroxidu sodného v etanolu, výtěžky však Dyly pouze 58 až 65 %.Direct hydrolysis of 4-phenyl-1,3-dioxane to 1-phenyl-1,3-propanediol is not possible. Dioxane is stable in an alkaline medium, in an acidic medium due to the very easy dehydration of the diol, and subsequent polymerization leads to hydrolysis to maximum polymeric products. For these reasons, the two-stage process has so far been carried out, whereby in the first step the reaction of dioxane with acetic anhydride gives 1-phenyl-1,3-propanediol diacetate which in the second step reacts with methanol to give 1-phenyl-1,3-propanediol and methyl acetate. So far, this reaction has been catalyzed only by sodium metal, which in the reaction mixture has been converted to sodium methoxide, as described in Hesling A. Hec. trav. chim. Pays-Bas 78, 474 (1979). The reaction had a good yield but carried all the disadvantages of a not very aqueous catalyst. Šorygina v Ž. obšč. chim. 26, 1460 (1956) used a 16% solution of sodium hydroxide in ethanol for transesterification, but the yields of Dyly were only 58-65%.
Tyto nevýhody spolehlivě odstraňuje postup podle tohoto vynálezu, podle něhož se připraví l-fenyl-l,3-propandiol transestenfixací l-í’enyl-±,3-propandioldiacetátu metanolem, přičemž se jako katalyzátor přeestenfikace použije uhličitan draselný v množství 1 gram az 50 gramů na kilogram výchozího l-fenyl-1,3-propandioldiacetátu. Směs 1-fenyl-l,3-propandiolaiacetátu s metanolem a uhličitanem draselným se zahřívá k varu, přičemž se postupně oddestilovavá vznikající metylacetát. Po skončení reakce se vydestiluje nezreagovaný přebytečný metanol a poté se za vakua předestiluje l-renyl-l,3-propandiol.These drawbacks are reliably overcome by the process of the present invention, which is prepared by 1-phenyl-1,3-propanediol by transestenfixing 1-phenyl-1,3-propanediol diacetate with methanol, using potassium carbonate in an amount of 1 gram to 50% grams per kilogram of starting 1-phenyl-1,3-propanediol diacetate. A mixture of 1-phenyl-1,3-propanediol diacetate with methanol and potassium carbonate is heated to boiling while gradually distilling off the methyl acetate formed. After completion of the reaction, unreacted excess methanol is distilled off and then 1-renyl-1,3-propanediol is distilled under vacuum.
l-Penyl-l,3-propandioldiacetat se získává acidolýzou 4-fenyl-1,5-dioxanu acetanhydridem, katalyzovanou například chloridem1-Penyl-1,3-propanediol diacetate is obtained by acidolysis of 4-phenyl-1,5-dioxane with acetic anhydride, catalyzed by, for example, chloride
- 2 232 394 železitým dle čs. autor, osvědčení 185 517. 4-Fenyl-l,3-dioxan se získá snadno. Prinsovou reakcí formaldehydu se styrenem, která je popsána v řadě prací, například v Org. Syntheses 33, 72 /1953/, Beets M.G.J. v Rec. trav. chim. Pays-Bas 70, 20 /1951/, Isaguljans V.J., Rachmankulov D.L. a Safarov M.G„ v Ž. prikl. chim. 43,- 2 232 394 ferric according to MS. 4-Phenyl-1,3-dioxane is readily obtained. The prins reaction of formaldehyde with styrene is described in a number of works, for example in Org. Syntheses 33, 72 (1953), Beets M.G.J. in Rec. trav. chim. Pays-Bas 70, 20 (1951), Isaguljans V.J., Rachmankulov D.L. and Safarov M.G. prikl. chim. 43,
2703 /1970/ a jinde.2703 (1970) and elsewhere.
Způsobem přípravy 1-feny1-1,3-propandiolu podle vynálezu se dosahuje vysokých výtěžků získaného produktu v množství minimálně 85 %.The process for preparing 1-phenyl-1,3-propanediol according to the invention achieves high yields of the product obtained in an amount of at least 85%.
Postup přípravy 1-feny1-1,3-propandiolu podle vynálezu je zře jiný z následujících příkladů konkrétního provedení.The process for preparing 1-phenyl-1,3-propanediol according to the invention is obvious from another of the following examples of a specific embodiment.
Přiklad 1Example 1
Směs 236,3 g /1 mol/ l-fenyl-l,3-propandioldiacetátu, 320 g /10 ml/ metanolu a 4,1 g /0,03 mol/ uhličitanu draselného byla zahřívána po dobu 4 hodin pod refluxem. Reakční buňka byla opatřena destilační kolonkou, naplněnou nerezovými spirálkami /5x5 mm/ o účinnosti asi 8 TP. V průběhu reakce byl oddestilováván vznikající metylacetát /b.v. 57,3 °C/. Po skončení reakce byl oddestilován přebytečný metanol /b.v. 64 °C/ a za vakua byl předestilován l-fenyl-l,3-propandiol /b.v. 163 °C/0,258 kPa/, který byl zísxán ve výtěžku 88,7 % theor.A mixture of 236.3 g (1 mol) of 1-phenyl-1,3-propanediol diacetate, 320 g (10 ml) of methanol and 4.1 g (0.03 mol) of potassium carbonate was heated under reflux for 4 hours. The reaction cell was equipped with a distillation column packed with stainless steel coils (5x5 mm) having an efficiency of about 8 TP. The resulting methyl acetate / bv was distilled off during the reaction. 57.3 ° C. After completion of the reaction, excess methanol / bv was distilled off. 64 ° C) and 1-phenyl-1,3-propanediol was distilled under vacuum. 163 DEG C. (0.258 kPa) which was obtained in a yield of 88.7% of theor.
Příklad 2Example 2
Byl proveden analogickým způsobem jako příklad 1 s tím rozdílem, že bylo použito poloviční množství metanolu, množství uhličitanu draselného bylo 3 g. Reakce byla UKončena po 3 hodinách. Reakční rychlost byla vyšěí v důsledku vyšší teploty /85 °C/ v destilační baňce /proti předchozímu postupu, kde byla asi 70 °C/. Bylo to dáno tím, že v tomto pokusu byla většina metanolu v destilační koloně. Výtěžek 1-fenyl-1,3-propandiolu byl 91 %.It was carried out in an analogous manner to Example 1 except that half the amount of methanol was used, the amount of potassium carbonate was 3 g. The reaction was terminated after 3 hours. The reaction rate was higher due to the higher temperature (85 ° C) in the distillation flask (versus the previous procedure, where it was about 70 ° C). This was because in this experiment most of the methanol was in the distillation column. The yield of 1-phenyl-1,3-propanediol was 91%.
l-Fenyl-l,3-propandiol patří mezi poměrně xěžko dostupné látky. Jeho použití by mohlo být velmi široké. Má repelentní účinky, které zvláště vynikají v Kombinaci s dietyltoluamidem, Kde vyká- 5 232 394 zuje synergický účinek. Je aále vhodnou látkou pro přípravu ace talů s nejrůznějšími aldehydy, z nichž řada má vyhxkající vonné vlastnosti.1-Phenyl-1,3-propanediol is one of the relatively poorly available substances. Its use could be very wide. It has repellent effects, which excel especially in combination with diethyltoluamide, where it shows 5 232 394 a synergistic effect. It is also a suitable substance for the preparation of talc with various aldehydes, many of which have scented aromatic properties.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS834170A CS232394B1 (en) | 1983-06-09 | 1983-06-09 | Processing of 1-phenyl-1,3-propandiol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS834170A CS232394B1 (en) | 1983-06-09 | 1983-06-09 | Processing of 1-phenyl-1,3-propandiol |
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| Publication Number | Publication Date |
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| CS417083A1 CS417083A1 (en) | 1984-06-18 |
| CS232394B1 true CS232394B1 (en) | 1985-01-16 |
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| CS834170A CS232394B1 (en) | 1983-06-09 | 1983-06-09 | Processing of 1-phenyl-1,3-propandiol |
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1983
- 1983-06-09 CS CS834170A patent/CS232394B1/en unknown
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| CS417083A1 (en) | 1984-06-18 |
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