DE634501C - Process for the production of ª ‡ -methylacrolein - Google Patents
Process for the production of ª ‡ -methylacroleinInfo
- Publication number
- DE634501C DE634501C DER93387D DER0093387D DE634501C DE 634501 C DE634501 C DE 634501C DE R93387 D DER93387 D DE R93387D DE R0093387 D DER0093387 D DE R0093387D DE 634501 C DE634501 C DE 634501C
- Authority
- DE
- Germany
- Prior art keywords
- parts
- alcohol
- methylacrolein
- production
- selenium
- 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.)
- Expired
Links
- 238000000034 method Methods 0.000 title claims description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 12
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 3
- 239000011669 selenium Substances 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 claims 1
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 3
- 229940000207 selenious acid Drugs 0.000 description 3
- MCAHWIHFGHIESP-UHFFFAOYSA-N selenous acid Chemical compound O[Se](O)=O MCAHWIHFGHIESP-UHFFFAOYSA-N 0.000 description 3
- -1 unsaturated aliphatic alcohols Chemical class 0.000 description 3
- WCASXYBKJHWFMY-UHFFFAOYSA-N crotyl alcohol Chemical compound CC=CCO WCASXYBKJHWFMY-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 230000029142 excretion Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von a-Methylaerolein Es wurde gefunden, daß ungesättigte aliphatische Alkohole im Gegensatz zu den gesättigten aliphatischen Alkoholen, und zwar insbesondere der a-Methylallylalkohol, durch Selendioxyd oder selenige Säure in flüssiger Phase zu dem betreffenden ungesättigten Aldehyd mit gutem Erfolg oxydiert werden. Bei dieser Umsetzung können Lösungsmittel, wie gesättigte Alkohole, z. B. Hexylalkohol, als auch geeignete Äther oder auch Dioxan, mitverwendet werden. In den beiden letzterwähnten Lösungsmitteln ist jedoch Selendioxyd nur beschränkt löslich. Es wird deshalb vorzugsweise so gearbeitet, daß das Selendioxyd durch ein Rührwerk in Suspension gehalten wird.Process for the preparation of a-methyl aerolein It has been found that unsaturated aliphatic alcohols in contrast to the saturated aliphatic Alcohols, in particular the a-methylallyl alcohol, by selenium dioxide or selenious acid in the liquid phase to the unsaturated aldehyde in question to be oxidized with good success. In this reaction, solvents such as saturated Alcohols e.g. B. hexyl alcohol, as well as suitable ethers or dioxane, are also used will. However, selenium dioxide is only limited in the last two solvents mentioned soluble. It is therefore preferably worked so that the selenium dioxide by a Stirrer is kept in suspension.
Das Verfahren wird besonders zweckmäßig so durchgeführt, daß der gebildete Aldehyd sofort nach seiner Entstehung aus der Reaktionszone abgeführt wird, wobei der umzusetzende Alkohol in gleichem Maße der Reaktionsmasse zugeführt wird.The method is particularly expediently carried out so that the formed Aldehyde is removed from the reaction zone immediately after its formation, wherein the alcohol to be converted is fed to the reaction mass to the same extent.
Beispiele i. 2o Teile reines kristallisiertes Selendioxyd werden in 5o Teile Hexylalkohol unter gelindem Erwärmen aufgelöst und in einen Kessel eingebracht, der mit einer gut wirkenden, mit Rückflußkühler versehenen Fraktionierkolonne verbunden ist. Im Laufe i Stunde -werden 26 Teile ac-Methylallylalkohol in den Kessel, dessen Inhalt erhitzt wird, eintropfen gelassen. Es tritt dabei eine Ausscheidung von dunkelbraunem metallischem Selen ein. Die Temperatur wird so gehalten, daß am Kopfe der Fraktionierkolonne ein Destillat übergeht, das zwischen 63 bis 70° siedet. Es werden 15 Teile eines Rohproduktes erhalten, das bei einer wiederholten Fraktionierung 13 Teile u-Methylacrolein (Kp760 68 bis 69°) ergibt. Die Ausbeute an Aldehyd beträgt somit 51,30/0.Examples i. 2o parts of pure crystallized selenium dioxide are in Dissolve 5o parts of hexyl alcohol with gentle heating and pour it into a kettle, connected to a well-functioning fractionating column equipped with a reflux condenser is. In the course of one hour, 26 parts of ac-methylallyl alcohol are added to the kettle, its Contents are heated, allowed to drop in. There is an excretion of dark brown metallic selenium. The temperature is maintained at the top of the fractionating column a distillate passes that boils between 63 and 70 °. There will be 15 parts of one Obtained crude product which, in repeated fractionation, 13 parts of u-methylacrolein (Kp760 68 to 69 °) results. The yield of aldehyde is thus 51.30 / 0.
2. .35 Teile selenige Säure werden in 8o Teilen Dioxan unter Erwärmen eingetragen und die nicht gelöste selenige Säure durch einen Rührer in Suspension gehalten. In die auf 9o° .erwärmte Lösung werden im Laufe von 2 Stunden 45,5 Teile ä-Methylallylalkohol eingetropft. Es tritt Ausscheidung von hochrotem metallischem Selen ein. Am Kopf der Fraktionierkolonne werden 3o Teile eines Rohproduktes (Kp.63 bis 70°) erhalten, das bei wiederholter Fraktionierung 26-Teile a-Methylacrolein (Kp760 68 bis 69°) ergibt. Die Ausbeute an ungesättigtem Aldehyd beträgt 59%.2. 35 parts of selenious acid are dissolved in 80 parts of dioxane with heating entered and the undissolved selenious acid by a stirrer in suspension held. 45.5 parts are added to the solution heated to 90 ° in the course of 2 hours ä-Methylallyl alcohol was added dropwise. There occurs excretion of crimson metallic Selenium a. At the top of the fractionating column, 3o parts of a crude product (boiling point 63 up to 70 °) obtained that with repeated fractionation 26 parts of a-methylacrolein (Kp760 68 to 69 °) results. The yield of unsaturated aldehyde is 59%.
3. In einen mit einem Rührwerk und einer Fraktionierkolonne versehenen Kessel werden 5 Teile Methylallylalkohol gegeben, der Alkohol auf 50° .erwärmt, und im Laufe von i1/2 Stunden werden 32 Teile Selendioxyd in kleinen Portionen zugegeben. Gleichzeitig werden 37 Teile Methylallylalkohol in den Kessel eingetropft. Der Kesselinhalt wird etwa auf 9o° gehalten. Am Kopf der Kolonne werden 27 Teile rohes Methylacrolein abgezogen, die bei wiederholt-er Fraktionierung 25,4 Teile reines a-Methylacrolein ergeben. Die Ausbeute beträgt 62% der Theorie.3. In one equipped with a stirrer and a fractionating column 5 parts of methyl allyl alcohol are added to the kettle, the alcohol is warmed to 50 °, and 32 parts of selenium dioxide are added in small portions over the course of one and a half hours. At the same time, 37 parts of methyl allyl alcohol are added dropwise to the kettle. The contents of the kettle is held at about 90 °. At the head of the column will be 27 parts raw methylacrolein withdrawn, which with repeated fractionation 25.4 parts result in pure α-methylacrolein. The yield is 62% of theory.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER93387D DE634501C (en) | 1935-05-19 | 1935-05-19 | Process for the production of ª ‡ -methylacrolein |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DER93387D DE634501C (en) | 1935-05-19 | 1935-05-19 | Process for the production of ª ‡ -methylacrolein |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE634501C true DE634501C (en) | 1936-08-28 |
Family
ID=7418961
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DER93387D Expired DE634501C (en) | 1935-05-19 | 1935-05-19 | Process for the production of ª ‡ -methylacrolein |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE634501C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1025859B (en) * | 1955-09-26 | 1958-03-13 | Dr Hans P Kaufmann | Process for the production of fatty aldehydes |
| DE1028111B (en) * | 1956-06-30 | 1958-04-17 | Ravensberg G M B H Chem Fab | Process for the preparation of basic diarylaldehydes |
-
1935
- 1935-05-19 DE DER93387D patent/DE634501C/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1025859B (en) * | 1955-09-26 | 1958-03-13 | Dr Hans P Kaufmann | Process for the production of fatty aldehydes |
| DE1028111B (en) * | 1956-06-30 | 1958-04-17 | Ravensberg G M B H Chem Fab | Process for the preparation of basic diarylaldehydes |
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