CS196006B1 - Process for preparing mixture of esters of 1-phenyl-1,3-propandiole and acetic and formic acid - Google Patents
Process for preparing mixture of esters of 1-phenyl-1,3-propandiole and acetic and formic acid Download PDFInfo
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- CS196006B1 CS196006B1 CS432477A CS432477A CS196006B1 CS 196006 B1 CS196006 B1 CS 196006B1 CS 432477 A CS432477 A CS 432477A CS 432477 A CS432477 A CS 432477A CS 196006 B1 CS196006 B1 CS 196006B1
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- Prior art keywords
- phenyl
- acetic
- formic acid
- mixture
- esters
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- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 title claims description 18
- 239000000203 mixture Substances 0.000 title claims description 13
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 title claims description 9
- 235000019253 formic acid Nutrition 0.000 title claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title description 12
- 150000002148 esters Chemical class 0.000 title description 2
- 238000004519 manufacturing process Methods 0.000 title description 2
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 18
- -1 1-acetoxy-3-phenyl-3-formyloxypropane Chemical compound 0.000 claims description 8
- RRVFYOSEKOTFOG-UHFFFAOYSA-N 1-phenylpropane-1,3-diol Chemical compound OCCC(O)C1=CC=CC=C1 RRVFYOSEKOTFOG-UHFFFAOYSA-N 0.000 claims description 6
- RCJRILMVFLGCJY-UHFFFAOYSA-N 4-phenyl-1,3-dioxane Chemical compound O1COCCC1C1=CC=CC=C1 RCJRILMVFLGCJY-UHFFFAOYSA-N 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- RDCASYVPNQBLPI-UHFFFAOYSA-N (3-formyloxy-3-phenylpropyl) formate Chemical compound O=COCCC(OC=O)C1=CC=CC=C1 RDCASYVPNQBLPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- ADJVISPITYOIPF-UHFFFAOYSA-N (5-acetyloxy-5-propylcyclohexa-1,3-dien-1-yl) acetate Chemical compound C(C)(=O)OC=1CC(OC(C)=O)(C=CC1)CCC ADJVISPITYOIPF-UHFFFAOYSA-N 0.000 claims 1
- 235000019439 ethyl acetate Nutrition 0.000 claims 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- 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 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 238000010478 Prins reaction Methods 0.000 description 1
- VXHHJEOCFONIIR-UHFFFAOYSA-N [3-(acetyloxymethoxy)-3-phenylpropyl] acetate Chemical compound CC(=O)OCCC(OCOC(C)=O)C1=CC=CC=C1 VXHHJEOCFONIIR-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- 244000285940 beete Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Vynález se týká způsobu přípravy směsi esterů l-fenyl-l,3-propandiolu a kyseliny mravenčí a octové. Uvedenou směs tvoří L,3-diacetoxyl-l-fenylpropan /1/, 1-acetoxy-3-fenyl-3-formyloxypropan /11/, l-acetoxy-l-fenyl-3-formyloxypropan /111/ a 1-fenyl-1,3-diformyloxypropan /IV/sThe present invention relates to a process for preparing a mixture of 1-phenyl-1,3-propanediol esters and formic and acetic acid. Said mixture consists of 1,3-diacethoxy-1-phenylpropane (1), 1-acetoxy-3-phenyl-3-formyloxypropane (11), 1-acetoxy-1-phenyl-3-formyloxypropane (111) and 1-phenyl- 1,3-diformyloxypropane (IV) s
Uvedené látky nacházejí použití především v parfumářském průmyslu. Výchozí látkou pro je-jich syntézu je 4-fenyl-l,3-dioxan, který lze snadno získat Prinsovou reakcí formaldehydu se styrenem, která je popsána v řadě prací, například v Org. Syntheses 33. 72 (1953), Beete M.O.J. v Rec. Trav. Chim. Paya-Bas 70, 20 (1951), Isaguljans V.J., Rachmaňkulov D.L. a Saferov M.O. v Z. prikl. chim. 43, 2703 (1970).These substances are mainly used in the perfumery industry. The starting material for their synthesis is 4-phenyl-1,3-dioxane, which is readily obtainable by the Prins reaction of formaldehyde with styrene, which is described in many works, for example in Org. Syntheses 33, 72 (1953), Beete M.O.J. in Rec. Trav. Chim. Paya-Bas 70, 20 (1951), Isaguljans VJ, Rachmanuklov D.L. and Saferov M.O. in Z. Example. chim. 43, 2703 (1970).
Acidolýzou 4-fenyl-l,3-dioxan acetanhydridem, provedenou podle čs. autoíkého osvědčení č. 185517 vzniká ve vysokém výtěžku 1,3-diacetoxy-l-fenylpropan. Selektivní průběh.táto reakce umožňuje vhodný katalyzátor, kterým je v daném případě chlorid železitý, zinečnatý, nebo jejich smés. Š použitím jiných kyselých katalyzátorů, například kyseliny sírové nebo chlorovodíkůvé vzniká směs 1,3-diacetoxy-l-fenylpropanu sAcidolysis of 4-phenyl-1,3-dioxane with acetic anhydride according to U.S. Pat. No. 185517 is produced in high yield of 1,3-diacetoxy-1-phenylpropane. The selective course of this reaction allows a suitable catalyst, which in the present case is iron (III) chloride, zinc chloride, or mixtures thereof. The use of other acid catalysts such as sulfuric acid or hydrochloric acid results in a mixture of 1,3-diacetoxy-1-phenylpropane with
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196 008196 008
1,5-diacstoxy-3-fenyl-2-oxapentanem, jak popsali Červený L.,Marhoul A., železný M. a Růžička V. v Chem. prům. 28, 519 (1976). Přítomnost l,5-diacetoxy-3-fenyl-2-oxapentanu vždy značně omezuje použitelnost l,3-diacstoxy-l-fsnylpropanu, nebol se částečně rozkládá za vzniku formaldehydu. ’1,5-diacstoxy-3-phenyl-2-oxapentane as described by Red L., Marhoul A., Iron M. and Ruzicka V. in Chem. Avg. 28, 519 (1976). The presence of 1,5-diacetoxy-3-phenyl-2-oxapentane always greatly limits the usefulness of 1,3-diacstoxy-1-phenylpropane, since it does not partially decompose to form formaldehyde. ’
K výše uvedené směsi esterů l-fenyl-l,3-propandiolu a kyselinou mravenčí a octovou je možno dospět eeterifikací l-fenyl-l,3-propandiolu. l-Fenyl-l,3-propandiol však nepatří mezi snadno dostupné látky, nejčastěji se získává právě alkalickou hydrolýzou,popřípadě trensesterifikací 1,3-diacetoxy-l-fenylpropanu, jak je popsáno například v pracech šóriginy N.V. v Ž.oběČ. chim. 26, 1460 /1956/ a Heslingy A. v Reo. Trav. Chim. Pays-Bae 78, 474 /1959/. ,The above mixture of 1-phenyl-1,3-propanediol esters and formic and acetic acid can be obtained by etherification of 1-phenyl-1,3-propanediol. 1-Phenyl-1,3-propanediol, however, is not readily available, most often it is obtained by alkaline hydrolysis or trensesterification of 1,3-diacetoxy-1-phenylpropane, as described, for example, in the work of N.V. v Ž.oběČ. chim. 26, 1460 (1956) and Heslingy A. in Reo. Trav. Chim. Pays-Bae 78, 474 (1959). ,
Uvedená nevýhoda je odstraněna postupem podle vynálezu, jehož podstata spočívá v tom, že se 4-'enyl-l,3-dioxan podrobí acidolýze acetanhydridem za přítomnosti kyseliny mravenčí a chloridu železitého jako katalyzátoru.This disadvantage is overcome by the process according to the invention, which comprises subjecting 4-phenyl-1,3-dioxane to acidolysis with acetic anhydride in the presence of formic acid and ferric chloride as a catalyst.
Reakce ae provádí při teplotě okolo 80 °C, za normálního tlaku, přičemž je důležitá pořadí míšení jednotlivých komponent reakční směsi. Největší Výtěžnost poskytne, způsob, kdy je ke směsi 4-fenyl-l,3-dioxanu, kyseliny mravenčí a katalyzátoru postupně přidáván acetanhydrid. Poatup je zřejmý z následujících příkladů konkrétního provedení.Reaction ae is carried out at a temperature of about 80 ° C, under normal pressure, the order of mixing of the individual components of the reaction mixture being important. The greatest yield will be provided by a process in which acetic anhydride is gradually added to the mixture of 4-phenyl-1,3-dioxane, formic acid and catalyst. The procedure is apparent from the following examples of a particular embodiment.
Příklad 1Example 1
Do skleněného míchaného reaktoru bylo předloženo 16,4 g 4-fenyl-l,3-dioxanu,ll,5 g 99,8%ní kyseliny mravenčí a 0,4 g bezvodého chloridu železitého. Směe bylej vyhřátá na 80 načež byl postupně přidáván acetanhydrid takovou rychlostí, aby teplota reakční směsi nepřestoupila 85 °C. Po nadávkování 20 g acetanhydridu byla směs udržována při dané teplotě ještě 30 minut. Chromatografickou analýzou bylo zjištěno, že směs esterů l-fenyl-1,3-propandiolu s kyselinou mravenčí a octovou,25,3 % l-acetoxy-l-fenyl-3-foř'myloxypropanu,16.4 g of 4-phenyl-1,3-dioxane, 11.5 g of 99.8% formic acid and 0.4 g of anhydrous ferric chloride were introduced into a glass stirred reactor. The mixture was heated to 80 and acetic anhydride was gradually added at such a rate that the temperature of the reaction mixture did not exceed 85 ° C. After the addition of 20 g of acetic anhydride, the mixture was kept at that temperature for a further 30 minutes. Chromatographic analysis revealed that a mixture of 1-phenyl-1,3-propanediol esters of formic and acetic acid, 25.3% of 1-acetoxy-1-phenyl-3-formyl-oxypropane,
19,7 % Í-acetoxy-3-fenyl-3-formyloxypropanu a 42,5 J 1,3-diacetoxy-l-fenylpropanu.19.7% 1-acetoxy-3-phenyl-3-formyloxypropane and 42.5 J 1,3-diacetoxy-1-phenylpropane.
Příklad 2Example 2
Pokus byl proveden analogicky jako v příkladu l,e tím rozdílem,že bylo použito dvojnásobného množství kyseliny mravenčí. Získané směs esterů měla následující složení:The experiment was carried out in analogy to Example 1, except that twice the formic acid was used. The mixture of esters obtained had the following composition:
37,1 % hmot. l-fenyl-l,3-diformyloxypropanu, 31,0 % l-acetoxy-l-fenyl-3-formyloxypropanu,37.1 wt. 1-phenyl-1,3-diformyloxypropane, 31.0% 1-acetoxy-1-phenyl-3-formyloxypropane,
1-8,0 % l-acetoxy-3-fenyl-3-formyloxypropanu a 13,9 % 1,3-diacetoxy-l-fenylpropanu.1-8.0% 1-acetoxy-3-phenyl-3-formyloxypropane and 13.9% 1,3-diacetoxy-1-phenylpropane.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS432477A CS196006B1 (en) | 1977-06-30 | 1977-06-30 | Process for preparing mixture of esters of 1-phenyl-1,3-propandiole and acetic and formic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS432477A CS196006B1 (en) | 1977-06-30 | 1977-06-30 | Process for preparing mixture of esters of 1-phenyl-1,3-propandiole and acetic and formic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196006B1 true CS196006B1 (en) | 1980-02-29 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS432477A CS196006B1 (en) | 1977-06-30 | 1977-06-30 | Process for preparing mixture of esters of 1-phenyl-1,3-propandiole and acetic and formic acid |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196006B1 (en) |
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1977
- 1977-06-30 CS CS432477A patent/CS196006B1/en unknown
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