DE1077650B - Process for the preparation of phenylacetaldehyde dialkyl acetals - Google Patents
Process for the preparation of phenylacetaldehyde dialkyl acetalsInfo
- Publication number
- DE1077650B DE1077650B DEC18475A DEC0018475A DE1077650B DE 1077650 B DE1077650 B DE 1077650B DE C18475 A DEC18475 A DE C18475A DE C0018475 A DEC0018475 A DE C0018475A DE 1077650 B DE1077650 B DE 1077650B
- Authority
- DE
- Germany
- Prior art keywords
- phenylacetaldehyde
- weight
- preparation
- octadiene
- dialkyl acetals
- Prior art date
- Legal status (The legal status 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 status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 5
- 238000002360 preparation method Methods 0.000 title claims description 3
- DTUQWGWMVIHBKE-UHFFFAOYSA-N phenylacetaldehyde Chemical compound O=CCC1=CC=CC=C1 DTUQWGWMVIHBKE-UHFFFAOYSA-N 0.000 title description 16
- 229940100595 phenylacetaldehyde Drugs 0.000 title description 8
- 150000001241 acetals Chemical class 0.000 title description 7
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- SPEUIVXLLWOEMJ-UHFFFAOYSA-N 1,1-dimethoxyethane Chemical compound COC(C)OC SPEUIVXLLWOEMJ-UHFFFAOYSA-N 0.000 description 2
- WNJSKZBEWNVKGU-UHFFFAOYSA-N 2,2-dimethoxyethylbenzene Chemical compound COC(OC)CC1=CC=CC=C1 WNJSKZBEWNVKGU-UHFFFAOYSA-N 0.000 description 2
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000010626 work up procedure Methods 0.000 description 2
- FYERTDTXGGOMGT-UHFFFAOYSA-N 2,2-diethoxyethylbenzene Chemical compound CCOC(OCC)CC1=CC=CC=C1 FYERTDTXGGOMGT-UHFFFAOYSA-N 0.000 description 1
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical group CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000006136 alcoholysis reaction Methods 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KDUIUFJBNGTBMD-VXMYFEMYSA-N cyclooctatetraene Chemical compound C1=C\C=C/C=C\C=C1 KDUIUFJBNGTBMD-VXMYFEMYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/30—Compounds having groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Phenylacetaldehyddialkylacetalen Zur Herstellung des als Riechstoffkomponente vielfach verwendeten Phenylacetaldehyds und seiner Acetale sind bereits eine Anzahl Verfahren bekannt. So kann Phenylacetaldehyd bzw. dessen Dimethylacetal aus Cyclooctatetraen durch Behandeln mit molaren Mengen einer Quersilberverbindung in wäßriger oder methanolischer Lösung dargestellt werden. Weiterhin erhält man mit niedriger Ausbeute aus 7,8-Dichlor-bicyclo-(4,2,0)-octadien-2,4 durch Alkoholyse ein chlorhaltiges Phenylacetaldehyddimethylacetal, das schwierig zu reinigen ist. Nach einem anderen Verfahren kondensiert man Phenylacetylen in Gegenwart von alkalischen Mitteln bei 140° C mit Alkoholen. Als Nebenprodukt entsteht dabei co-Alkoxystyrol, das durch nochmalige Behandlung mit einem Alkohol in das Acetal übergeführt wird. Auch ist bekannt, Phenylacetaldehyd durch Isomerisierung von Styroloxyd zu gewinnen. Der nicht sehr beständige Phenylacetaldehyd muß dann in einer weiteren, mit Verlusten verbundenen Stufe in das Acetal übergeführt werden.Process for the preparation of phenylacetaldehyde dialkyl acetals Zur Production of phenylacetaldehyde, which is widely used as a fragrance component and its acetals, a number of processes are already known. So can phenylacetaldehyde or its dimethylacetal from cyclooctatetraene by treatment with molar amounts a cross silver compound in aqueous or methanolic solution. Furthermore, a low yield is obtained from 7,8-dichlorobicyclo- (4,2,0) -octadiene-2,4 by alcoholysis a chlorine-containing phenylacetaldehyde dimethylacetal that difficult is to be cleaned. Another method is to condense phenylacetylene in Presence of alkaline agents at 140 ° C with alcohols. Arises as a by-product thereby co-alkoxystyrene, which by repeated treatment with an alcohol in the Acetal is converted. Phenylacetaldehyde is also known to be produced by isomerization to win from styrene oxide. The not very stable phenylacetaldehyde must then be converted into the acetal in a further stage, which is associated with losses.
Es wurde nun gefunden, daß man Phenylacetaldehyddialkylacetale in einfacher Weise herstellen kann, wenn man 7,8-Dialkoxybicyclo-(4,2;0)-octadiene-2,4 in Gegenwart von sauren Katalysatoren mit Alkoholen umsetzt.It has now been found that phenylacetaldehyde dialkyl acetals can be used in can be produced in a simple manner if 7,8-dialkoxybicyclo- (4,2; 0) -octadiene-2,4 Reacts with alcohols in the presence of acidic catalysts.
Die Reaktion verläuft nach dem folgenden Schema:- Hierin bedeuten I ein 7,8-Dialkoxybicyclo-(4,2,0)-octadien-2,4, II und III Zwischenstufen, die nicht isoliert werden, und IV ein PhenylacetaIdehyddialkylacetal. Als Ausgangsmaterial eignen sich 7,8-Dialkoxybicyclo- (4,2,0) -octadiene-2,4, z. B. 7,8-Dimethoxybicyclo-(4,2,0)-octadien-2,4 oder 7,8-Diisopropoxybicyclo-(4,2,0)-octadien-2,4, die man durch Isomerisierung der bei der Hydrierung von 1,8-Dialkoxyoctadien-1,7-diinen-3,5 anfallenden 1,8-Dialkoxyoctatetraene-1,3,5,7 erhält.The reaction proceeds according to the following scheme: - Herein, I denote a 7,8-dialkoxybicyclo- (4,2,0) -octadiene-2,4, II and III intermediates which are not isolated, and IV a phenylacetaldehyde dialkyl acetal. 7,8-Dialkoxybicyclo- (4,2,0) -octadiene-2,4, z. B. 7,8-dimethoxybicyclo- (4,2,0) -octadiene-2,4 or 7,8-diisopropoxybicyclo- (4,2,0) -octadiene-2,4, which can be obtained by isomerizing in the hydrogenation 1,8-dialkoxyoctatetraene-1,3,5,7 obtained from 1,8-dialkoxyoctadiene-1,7-diynes-3,5.
Die Umsetzung führt man in der Weise durch, daß man das 7,8-Dialkoxybicyclo-(4,2,0)-octadien-2,4 in der 3- bis 5fachen Menge eines Alkohols löst und nach Zugabe des Katalysators und eines Stabilisators 3 bis 5 Stunden unter Rückfluß kocht.The reaction is carried out in such a way that the 7,8-dialkoxybicyclo- (4,2,0) -octadiene-2,4 dissolves in 3 to 5 times the amount of an alcohol and after adding the catalyst and a stabilizer is refluxed for 3 to 5 hours.
Für die Umsetzung eignen sich besonders niedrigmolekulare Alkohole, wie Methanol, Äthanol oder Butanol. Diese dienen gleichzeitig als Verdünnungsmittel. Als Stabilisatoren kommen Hydrochinon, tertiär-Butylbrenzkatechin, Thiazin oder auch Methylenblau in Frage, die man in Mengen von 0,01 bis 211/o, auf das Ausgangsmaterial bezogen, einsetzt. Als Katalysatoren eignen sich geringe Mengen von starken Säuren, wie z. B. Chlorwasserstoff, Schwefelsäure, Borfluorid oder auch p-Toluol-sulfochlorid, die am besten wasserfrei in Mengen von 2 bis 5o/11, bezogen auf das eingesetzte Dialkoxybicyclooctadien, angewandt werden.Low molecular weight alcohols are particularly suitable for the implementation, such as methanol, ethanol or butanol. These also serve as diluents. The stabilizers used are hydroquinone, tert-butyl pyrocatechol, thiazine or also methylene blue in question, which can be used in amounts of 0.01 to 211 / o, on the starting material related, uses. Small amounts of strong acids are suitable as catalysts, such as B. hydrogen chloride, sulfuric acid, boron fluoride or p-toluene sulfochloride, the best anhydrous in amounts of 2 to 5o / 11, based on the used Dialkoxybicyclooctadiene, can be used.
Die Aufarbeitung wird in der Weise vorgenommen, daß man die Säure durch Zugabe eines Alkalihydroxyds neutralisiert und das Lösungsmittel abdestilliert. Phenylacetaldehyddialkylacetal wird anschließend durch Vakuumdestillation in reiner Form erhalten. Zuweilen ist es von Vorteil, das durch Neutralisation gebildete Salz vor der Destillation durch Herauslösen mit Wasser, gegebenenfalls unter Zugabe von Äther, zu entfernen. Beispiel 1.The work-up is carried out in such a way that the acid neutralized by adding an alkali hydroxide and the solvent is distilled off. Phenylacetaldehyddialkylacetal is then purified by vacuum distillation Maintain shape. Sometimes it is advantageous to use the salt formed by neutralization before the distillation by dissolving out with water, optionally with the addition of Ether, remove. Example 1.
In eine Lösung von 50 Gewichtsteilen- 7,8-Dimethoxybicyclo-(4,2,0)-octadien-2,4 in 200 Gewichtsteilen Methanol gibt man 1 Gewichtsteil konzentrierte Schwefelsäure sowie 0,1 Gewichtsteil tertiär-Butylbrenzkatechin und kocht 5 Stunden unter RückfluB. Nach dem Abkühlen neutralisiert man mit 2 Gewichtsteilen Kaliumhydroxyd und destilliert das Lösungsmittel ab. Den Rückstand schüttelt man unter Zugabe von wenig Wasser mit Äther aus und destilliert im Vakuum. Man erhält 41 Gewichtsteile Phenylacetaldehyddimethylacetal vom KP-7 = 87 bis 90° C, entsprechend 820% der Theorie; nö0 =1,494; d' =1,005. Beispiel 2 In der im Beispiel 1 angegebenen Weise kocht man eine Lösung von 50 Gewichtsteilen 7,8-Dimethoxybicyclo- (4,2,0) -octadien-2,4 in 200 Gewichtsteilen Äthanol, 1 Gewichtsteil konzentrierter Schwefelsäure und 0,1 Gewichtsteilen tertiär-Butylbrenzkatechin 5 Stunden unter Rückfluh. Nach der im Beispiel 1 angegebenen Aufarbeitung erhält man 45 Gewichtsteile Phenylacetaldehyddiäthylacetal vom KP-7 = 100 bis 105° C, entsprechend einer Ausbeute von 770/a der Theorie.In a solution of 50 parts by weight 7,8-dimethoxybicyclo- (4,2,0) -octadiene-2,4 1 part by weight of concentrated sulfuric acid is added to 200 parts by weight of methanol and 0.1 part by weight of tert-butyl pyrocatechol and refluxed for 5 hours. After cooling, the mixture is neutralized with 2 parts by weight of potassium hydroxide and distilled the solvent off. The residue is shaken while adding a little water with ether and distilled in vacuo. 41 parts by weight of phenylacetaldehyde dimethylacetal are obtained vom KP-7 = 87 to 90 ° C, corresponding to 820% of theory; no0 = 1.494; d '= 1.005. example 2 In the manner indicated in Example 1, a solution of 50 parts by weight is boiled 7,8-Dimethoxybicyclo- (4,2,0) -octadiene-2,4 in 200 parts by weight of ethanol, 1 part by weight concentrated sulfuric acid and 0.1 part by weight of tertiary butyl pyrocatechol 5 Hours under reflux. After the work-up indicated in Example 1, one obtains 45 parts by weight of phenylacetaldehyde diethylacetal from KP-7 = 100 to 105 ° C, accordingly a yield of 770 / a of theory.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC18475A DE1077650B (en) | 1959-02-25 | 1959-02-25 | Process for the preparation of phenylacetaldehyde dialkyl acetals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEC18475A DE1077650B (en) | 1959-02-25 | 1959-02-25 | Process for the preparation of phenylacetaldehyde dialkyl acetals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1077650B true DE1077650B (en) | 1960-03-17 |
Family
ID=7016442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEC18475A Pending DE1077650B (en) | 1959-02-25 | 1959-02-25 | Process for the preparation of phenylacetaldehyde dialkyl acetals |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1077650B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0403841A1 (en) * | 1989-06-19 | 1990-12-27 | Hüls Aktiengesellschaft | Process for the production of arylacetaldehyde-dialkylacetals |
| US5202500A (en) * | 1989-06-19 | 1993-04-13 | Huels Aktiengesellschaft | Process for the preparation of arylacetaldehyde-dialkylacetals |
-
1959
- 1959-02-25 DE DEC18475A patent/DE1077650B/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0403841A1 (en) * | 1989-06-19 | 1990-12-27 | Hüls Aktiengesellschaft | Process for the production of arylacetaldehyde-dialkylacetals |
| US5202500A (en) * | 1989-06-19 | 1993-04-13 | Huels Aktiengesellschaft | Process for the preparation of arylacetaldehyde-dialkylacetals |
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