CS209291B1 - Preparation method of 1-and 3-alkoxy-1-phenyl-propanes - Google Patents
Preparation method of 1-and 3-alkoxy-1-phenyl-propanes Download PDFInfo
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- CS209291B1 CS209291B1 CS707979A CS707979A CS209291B1 CS 209291 B1 CS209291 B1 CS 209291B1 CS 707979 A CS707979 A CS 707979A CS 707979 A CS707979 A CS 707979A CS 209291 B1 CS209291 B1 CS 209291B1
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- Prior art keywords
- phenyl
- alkoxy
- propene
- minutes
- yield
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- 238000002360 preparation method Methods 0.000 title claims 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- BYSMCAVFTNJCJC-UHFFFAOYSA-N 1-methoxyprop-2-enylbenzene Chemical compound COC(C=C)C1=CC=CC=C1 BYSMCAVFTNJCJC-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000002798 polar solvent Substances 0.000 claims description 3
- ANKVSZOYVTWLQO-UHFFFAOYSA-N 1-methoxypropylbenzene Chemical compound CCC(OC)C1=CC=CC=C1 ANKVSZOYVTWLQO-UHFFFAOYSA-N 0.000 claims description 2
- -1 1-phenyl-1-isobutyloxypropane Chemical compound 0.000 claims description 2
- FWJPBLZTIQGEGB-UHFFFAOYSA-N 3-methoxypropylbenzene Chemical compound COCCCC1=CC=CC=C1 FWJPBLZTIQGEGB-UHFFFAOYSA-N 0.000 claims 2
- XOURNDFHPYLQDJ-VMPITWQZSA-N [(e)-3-methoxyprop-1-enyl]benzene Chemical compound COC\C=C\C1=CC=CC=C1 XOURNDFHPYLQDJ-VMPITWQZSA-N 0.000 claims 2
- UUZKKBVIRZZQLN-UHFFFAOYSA-N 3-(2-methylpropoxy)prop-1-enylbenzene Chemical compound CC(C)COCC=CC1=CC=CC=C1 UUZKKBVIRZZQLN-UHFFFAOYSA-N 0.000 claims 1
- GWRNVSYKJMNFNM-UHFFFAOYSA-N 3-(2-methylpropoxy)propylbenzene Chemical compound CC(C)COCCCC1=CC=CC=C1 GWRNVSYKJMNFNM-UHFFFAOYSA-N 0.000 claims 1
- WDSFATLXYPBIRX-UHFFFAOYSA-N CC(C)COC(C=C)C1=CC=CC=C1 Chemical compound CC(C)COC(C=C)C1=CC=CC=C1 WDSFATLXYPBIRX-UHFFFAOYSA-N 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000000741 silica gel Substances 0.000 claims 1
- 229910002027 silica gel Inorganic materials 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 description 9
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical class CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- RCJRILMVFLGCJY-UHFFFAOYSA-N 4-phenyl-1,3-dioxane Chemical compound O1COCCC1C1=CC=CC=C1 RCJRILMVFLGCJY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- IWTYTFSSTWXZFU-QPJJXVBHSA-N [(e)-3-chloroprop-1-enyl]benzene Chemical compound ClC\C=C\C1=CC=CC=C1 IWTYTFSSTWXZFU-QPJJXVBHSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007327 hydrogenolysis reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
(54) Způsob přípravy 1- a 3-alkoxy-l-fenyIpropanů(54) A process for preparing 1- and 3-alkoxy-1-phenylpropanes
Vynález se týká způsobu přípravy 1- a 3-alkoxy- ; -1-fenylpropanů s 1 až 4 uhlíkovými atomy v alkoxyskupině. Nasycené ethery mají výborné vonné vlastnosti a mohou nalézt použití v parfumářském průmyslu.The invention relates to a process for preparing 1- and 3-alkoxy-; 1-phenylpropanes having 1 to 4 carbon atoms in the alkoxy group. Saturated ethers have excellent fragrance properties and can find use in the perfume industry.
Výchozí nenasycené ethery lze nejsnáze připravit reakcí l-fenyl-3-chlor-l-propenu (cinnámyl-, chloridu) s alkoholy, katalyzovanou bázemi, jak je uvedeno v čs. autorském osvědčení č. 198 325. Je-li jako katalyzátor použit alkalický hydroxid, vznikají vždy 3-alkoxy-l-fenyl-l-propeny, pri použití slabších bází, například uhličitanu sodného nebo draselného, vznikají směsi 3-alkoxy-1-fenylpropenů s odpovídajícími 3-alkoxy-3-fenyl-l-propeny. Tyto směsi lze destilačně snadno dělit na oba nenasycené ethery.The starting unsaturated ethers are most readily prepared by reacting 1-phenyl-3-chloro-1-propene (cinnamyl-, chloride) with base-catalyzed alcohols as disclosed in U.S. Pat. No. 198 325. When an alkali hydroxide is used as the catalyst, 3-alkoxy-1-phenyl-1-propenes are always formed, and using weaker bases, for example sodium or potassium carbonate, results in mixtures of 3-alkoxy-1-phenylpropenes with the corresponding 3-alkoxy-3-phenyl-1-propenes. These mixtures can be easily separated into the two unsaturated ethers by distillation.
Výchozí l-fenyl-3-chlor-l-propen je možno připravit například reakcí 4-fenyl-l,3-dioxanu s kyselinou chlorovodíkovou podle čs. autorského osvědčení č. 198 326, přičemž pro reakci s alkoholy je možno vedle čistého produktu použít i surové reakční směsi; 4-fenyl-l,3-dioxan je možno připravit kysele katalyzovanou reakcí styrenu s formaldehydem, jak je uvedeno například v práci Beetse M. G. J. v Rec. Trav. Chim. Pays-Bas 70,20 (1951) nebo Červeného, L., Marhoula A., Železného M. a Růžičky V. v Chem. Prům. 26, 519 (1976).The starting 1-phenyl-3-chloro-1-propene can be prepared, for example, by reacting 4-phenyl-1,3-dioxane with hydrochloric acid according to U.S. Pat. No. 198,326, wherein crude reaction mixtures may be used in addition to the pure product to react with alcohols; 4-Phenyl-1,3-dioxane can be prepared by the acid-catalyzed reaction of styrene with formaldehyde, as described, for example, in Beets M. G. J. in Rec. Trav. Chim. Pays-Bas 70, 20 (1951) or Red, L., Marhoula A., Zelezny M. and Ruzicky V. in Chem. Avg. 26, 519 (1976).
i Oba typy popsaných nenasycených etherů mají i výborné vonné vlastnosti. V důsledku přítomností j dvojné vazby v jejich molekule je však jejich ; stálost určitým způsobem omezena, což se projevuje žloutnutím při dlouhodobém stání na vzduchu.Both types of the described unsaturated ethers have excellent aromatic properties. However, due to the presence of the j bond in their molecule is their; stability is somewhat limited, which is manifested by yellowing during long standing in the air.
Uvedené nedostatky odstraňuje podle vynálezu způsob přípravy 1- a 3-alkoxy-l-fenylpropanů s 1 až 4 uhlíkovými atomy v alkoxyskupině. Jeho podstata spočívá v tom,,že se 3-alkoxy-3-fenyl-l-propeny a 3-alkoxy-l-fenyl-l-propeny s 1 až 4 uhlíkovými atomy v alkoxyskupině podrobí katalytické hydrogenaci za přítomnosti platinových nebo paladiových katalyzátorů, nejlépe v prostředí polárních rozpouštědel, například alkoholů, s výhodou při teplotě místnosti a atmosférickém ; tlaku.According to the invention, these processes are overcome by a process for preparing 1- and 3-alkoxy-1-phenylpropanes having 1 to 4 carbon atoms in the alkoxy group. It consists in subjecting 3-alkoxy-3-phenyl-1-propenes and 3-alkoxy-1-phenyl-1-propenes having 1 to 4 carbon atoms in the alkoxy group to undergo catalytic hydrogenation in the presence of platinum or palladium catalysts, preferably in an environment of polar solvents, for example alcohols, preferably at room temperature and atmospheric ; pressure.
Výhoda vynálezu spočívá v tom, že převedením j na nasycené ethery, jsou tyto podstatně stabilnější, změní se i vonný charakter, vonné vlastnosti ; nasycených etherů jsou však opět výborné a díky větší stabilitě mají i universálnější použití než ethery nenasycené. Hydrogenace s použitím rozpouštědel probíhá mnohem rychleji než v substanci, z hlediska reakční rychlosti i selektivity tvorby nasycených etherů pak je: výhodné pracovat v polárních rozpouštědlech, především v alkoholech.The advantage of the invention is that by converting j to saturated ethers, these are substantially more stable; however, saturated ethers are again excellent and, due to their greater stability, have a more versatile use than unsaturated ethers. Hydrogenation using solvents proceeds much faster than in the substance, in terms of reaction rate and selectivity of formation of saturated ethers it is advantageous to work in polar solvents, especially in alcohols.
3-alkoxy-l-fenyl-l-propeny se hydrogenují na platinových & palachových katalyzátorech tak, že vedle 3-alkoxy-l-fenylpropanů vzniká vedlejší hydrogenolytickou reakcí propylbenzen a příslušný alkohol; 3-alkoxy-l-fenyl-l-propany jsou za podmínek hydrogenace stabilní,The 3-alkoxy-1-phenyl-1-propenes are hydrogenated on platinum & palach catalysts such that, besides the 3-alkoxy-1-phenylpropanes, propylbenzene and the corresponding alcohol are formed by side hydrogenolytic reaction; 3-alkoxy-1-phenyl-1-propanes are stable under hydrogenation conditions,
3-alkoxy-3-fenyl-l-propeny poskytují hydroge- í nací 1-alkoxy-l-fenylprppany, které ovšem za podmínek hydrogenace podléhají následné hydrogenolýze na propylbenzen a příslušný alkohol.3-Alkoxy-3-phenyl-1-propenes provide hydrogenation of 1-alkoxy-1-phenylpropanes, which, however, are subjected to subsequent hydrogenolysis to propylbenzene and the corresponding alcohol under hydrogenation conditions.
K tvorbě těchto vedlejších produktů dochází na páladiových katalyzátorech vedle následné hydrogenolýzy nasyceného etheru také vedlejší reakcí přímo ze 3-alkoxy-3-fenyl-l-propenů.The formation of these by-products occurs on the palladium catalysts in addition to the subsequent hydrogenolysis of the saturated ether, also by side reaction directly from the 3-alkoxy-3-phenyl-1-propenes.
Pro hydrogenaci 3-alkoxy-3-fenyl-l-propenů je ; výhodnější použít platinový katalyzátor, pro hyd- ί rogenaci 3-alkoxy-l-fenyl-l-propenů paladiový katalyzátor. Za optimálních podmínek probíhá hydrogenace 3-alkoxy-3-fenyl-l-propenů selektivněji.For the hydrogenation of 3-alkoxy-3-phenyl-1-propenes is; more preferably a platinum catalyst is used, for the hydrogenation of 3-alkoxy-1-phenyl-1-propenes a palladium catalyst. Under optimal conditions, hydrogenation of 3-alkoxy-3-phenyl-1-propenes is more selective.
Vynález je dále blíže popsán na několika příkladech provedení.The invention is described in more detail below with reference to several exemplary embodiments.
Příklad 1Example 1
Do hydrogenačního skleněného dokonale míchaného reaktoru bylo předloženo 10 ml metanolu, 1 ml 3-fenyl-3-metoxy-l-propenu a 0,05 g katalyzátoru 10% Pd/aktivním uhlí. Hydrogenace byla provedena při 20 °C a atmosférickém tlaku. To 12 minutách došlo k úplnému zreagování i 3-fenyl-3-metoxy-l-propenu, který se přeměnil ze 66 % na 1-fenyl-l-metoxypropan, zbytek na propylbenzen a metanol.10 ml of methanol, 1 ml of 3-phenyl-3-methoxy-1-propene and 0.05 g of 10% Pd / activated carbon catalyst were charged to a hydrogenated glass thoroughly stirred reactor. Hydrogenation was performed at 20 ° C and atmospheric pressure. After 12 minutes, 3-phenyl-3-methoxy-1-propene was also reacted completely, which was converted from 66% to 1-phenyl-1-methoxypropane, the remainder to propylbenzene and methanol.
Příklad 2Example 2
Bylo postupováno stejně jako v příkladu 1 š tím iThe procedure of Example 1 was followed
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS707979A CS209291B1 (en) | 1979-10-18 | 1979-10-18 | Preparation method of 1-and 3-alkoxy-1-phenyl-propanes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS707979A CS209291B1 (en) | 1979-10-18 | 1979-10-18 | Preparation method of 1-and 3-alkoxy-1-phenyl-propanes |
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| Publication Number | Publication Date |
|---|---|
| CS209291B1 true CS209291B1 (en) | 1981-11-30 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS707979A CS209291B1 (en) | 1979-10-18 | 1979-10-18 | Preparation method of 1-and 3-alkoxy-1-phenyl-propanes |
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| Country | Link |
|---|---|
| CS (1) | CS209291B1 (en) |
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1979
- 1979-10-18 CS CS707979A patent/CS209291B1/en unknown
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