DE937058C - Process for the preparation of low molecular weight trialkylamine oxides and their hydrates - Google Patents
Process for the preparation of low molecular weight trialkylamine oxides and their hydratesInfo
- Publication number
- DE937058C DE937058C DEB22743A DEB0022743A DE937058C DE 937058 C DE937058 C DE 937058C DE B22743 A DEB22743 A DE B22743A DE B0022743 A DEB0022743 A DE B0022743A DE 937058 C DE937058 C DE 937058C
- Authority
- DE
- Germany
- Prior art keywords
- molecular weight
- low molecular
- hydrates
- preparation
- hydrogen peroxide
- 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
- 125000005270 trialkylamine group Chemical group 0.000 title claims description 10
- 238000000034 method Methods 0.000 title claims description 6
- 150000004677 hydrates Chemical class 0.000 title claims 2
- 238000002360 preparation method Methods 0.000 title claims 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010533 azeotropic distillation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000011541 reaction mixture Substances 0.000 claims 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 10
- UYPYRKYUKCHHIB-UHFFFAOYSA-N trimethylamine N-oxide Chemical compound C[N+](C)(C)[O-] UYPYRKYUKCHHIB-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- DJEQZVQFEPKLOY-UHFFFAOYSA-N N,N-dimethylbutylamine Chemical compound CCCCN(C)C DJEQZVQFEPKLOY-UHFFFAOYSA-N 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 239000012458 free base 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
- 239000000203 mixture Substances 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- NHLUVTZJQOJKCC-UHFFFAOYSA-N n,n-dimethylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)C NHLUVTZJQOJKCC-UHFFFAOYSA-N 0.000 description 1
- PGFPZGKEDZGJQZ-UHFFFAOYSA-N n,n-dimethylmethanamine oxide;dihydrate Chemical compound O.O.C[N+](C)(C)[O-] PGFPZGKEDZGJQZ-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/04—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds containing amino-oxide bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
AUSGEGEBEN AM 29. DEZEMBER 1955ISSUED DECEMBER 29, 1955
B 22743 IVb J12 qB 22743 IVb J12 q
Es ist bekannt, Trialkylaminoxyde der allgemeinen Formel (CnH2n + J3NO durch Behandlung von Trialkylaminen mit Wasserstoffperoxyd zu gewinnen. Hierbei wurde mit verdünnten wäßrigen Lösungen von Wasserstoffperoxyd bei Zimmertemperatur gearbeitet. Trimethylaminoxyd stellt man z. B. her, indem man eine wäßrige Lösung von Trimethylamin mit der äquivalenten Menge einer 3°/oigen Wasserstoffperoxydlösung vermischt und das Gemisch 24 Stunden bei Zimmertemperatur stehenläßt. Hierauf wird das Wasser im Vakuum bis auf eine geringe Menge entfernt und der Rückstand mit Chlorwasserstoff versetzt, wobei das Hydrochlorid des Trimethylaminoxyds in Kristallform ausfällt. Dieses wird mit der äquivalenten Menge Silberoxyd zur freien Base bzw. ihrem Dihydrat umgesetzt. Die lange Umsetzungsdauer, die Notwendigkeit der Entfernung der verhältnismäßig großen Wassermenge, ferner der Umweg über das Hydrochlorid und schließlich die schwankende, zum Teil sehr niedrige Ausbeute gestalten das Verfahren recht ungünstig.It is known that trialkylamine oxides of the general formula (C n H 2n + J 3 NO) can be obtained by treating trialkylamines with hydrogen peroxide. In this case, dilute aqueous solutions of hydrogen peroxide are used at room temperature aqueous solution of trimethylamine is mixed with the equivalent amount of a 3% hydrogen peroxide solution and the mixture is left to stand for 24 hours at room temperature, the water is then removed in vacuo except for a small amount and the residue is treated with hydrogen chloride, the hydrochloride of trimethylamine oxide in crystal form This is converted with the equivalent amount of silver oxide to the free base or its dihydrate.The long reaction time, the need to remove the relatively large amount of water, the detour via the hydrochloride and finally the fluctuating, sometimes very low yield make the process quite un cheap.
Es wurde nun gefunden, daß diese Nachteile vermieden werden können und daß man Trialkylaminoxyde in sehr vorteilhafter Weise gewinnen kann, wenn man von unverdünnten oder mit nicht mehr als der gleichen Menge an Lösungsmittel verdünnten niedrigmolekularen Trialkylaminen und hochprozentigen Wasserstoffperoxydlösungen ausgeht und bei sehr niedriger, zweckmäßig o° nicht wesentlich überschreitender, vorteilhaft wesentlich darunterliegender Temperatur arbeitet. Wird z. B. unver-It has now been found that these disadvantages can be avoided and that trialkylamine oxides can gain in a very advantageous manner if one of them is undiluted or with no more as the same amount of solvent diluted low molecular weight trialkylamines and high percentage Hydrogen peroxide solutions run out and at very low, expedient o ° not essential exceeding, advantageously substantially below temperature works. Is z. B. un-
dünntes Trimethylamin bei —io bis —500 einer ebenfalls stark gekühlten 30°/oigen Wasserstoffperoxydlösung (eventuell in kleinen Portionen oder langsam kontinuierlich) zugesetzt, so tritt unter Temperaturanstieg sofort praktisch quantitative Umsetzung zum gewünschten Trimethylaminoxyd ein. Nach kurzer Eindickung der bei normaler Temperatur bereits sirupösen Flüssigkeit auf dem Wasserbade — gegebenenfalls im Vakuum — oder teilweiser Entfernung des Wassers durch azeotrope Destillation kristallisiert das Dihydrat des Trimethylaminoxyds unmittelbar aus. Man kann das Trimethylamin auch gasförmig in die stark gekühlte, hochprozentige Wasserstoffperoxydlösung, gegebenenfalls unter dauernder Kühlung, einleiten. Man hat hochprozentiges Wasserstoffperoxyd bereits zur Überführung eines sehr hochmolekularen Trialkylamins, nämlich des Hexadecyldimethylamins, in das betreffende Aminoxyd verwendet (vgl, die schweizerische Patentschrift 177 456). Dabei erhitzte man in Gegenwart großer Mengen eines nicht wäßrigen Lösungsmittels 36 Stunden auf 45 bis 500. Es war daher unerwartet, daß man niedrigmolekulare Trialkylamine im unverdünnten, oder mit weniger als der gleichen Menge Lösungsmittel verdünntem Zustand mit hochprozentigem Wasserstoff peroxyd schon bei o° nahezu augenblicklich in die Aminoxyde umwandeln kann.Diluted with trimethylamine -io to -50 0 of an also strongly cooled 30 ° / o hydrogen peroxide (possibly slowly and continuously in small portions or) is added, under temperature rise occurs immediately virtually quantitative conversion to the desired trimethylamine oxide a. After briefly thickening the liquid, which is already syrupy at normal temperature, on the water bath - if necessary in vacuo - or after partial removal of the water by azeotropic distillation, the dihydrate of trimethylamine oxide crystallizes out immediately. The trimethylamine can also be introduced in gaseous form into the strongly cooled, high-percentage hydrogen peroxide solution, optionally with continuous cooling. High-percentage hydrogen peroxide has already been used to convert a very high molecular weight trialkylamine, namely hexadecyldimethylamine, into the amine oxide in question (cf. Swiss Patent 177 456). In this case, one large quantities heated in the presence of a non-aqueous solvent to 36 hours 45 to 50 0th It was therefore unexpected that low molecular weight trialkylamines in the undiluted state or in a state diluted with less than the same amount of solvent can be converted into the amine oxides almost instantaneously with high percentage hydrogen peroxide at 0 °.
520 Gewichtsteile reines Trimethylamin werden in einem Tiefkühlgefäß kondensiert und auf etwa —400 gebracht. Diese Menge fügt man langsam zu 1000 Gewichtsteilen 30°/oiger Wasserstoffperoxyd-, lösung, die gleichfalls auf etwa —40° gekühlt wurde. Unter Temperaturanstieg bis auf etwa + 6o° tritt augenblicklich die Umsetzung zu Trimethylaminoxyd ein. Die sirupöse Flüssigkeit kann entweder sofort in einem offenen Gefäß bis zum Auskristallisieren auf dem Wasserbad eingedickt oder nach Zusatz von Benzol durch azeotrope Destillation vom Wasser befreit werden. Man erhält 1010 bis 1020 Gewichtsteile einer feuchten, schwachgelblichen Kristallmasse, die aus absolutem Methanol oder Äthanol zum reinen Trimethylaminoxyd-dihydrat umkristallisiert werden kann. Die Ausbeute ist praktisch quantitativ.520 parts by weight of pure trimethylamine are condensed in a freezer vessel and brought to about -40 0th This amount is slowly added to 1000 parts by weight of 30% hydrogen peroxide solution, which has also been cooled to about -40 °. When the temperature rises to about + 60 °, the conversion to trimethylamine oxide occurs immediately. The syrupy liquid can either be thickened immediately in an open vessel until it crystallizes out on the water bath or, after adding benzene, it can be freed from the water by azeotropic distillation. 1010 to 1020 parts by weight of a moist, pale yellowish crystal mass are obtained which can be recrystallized from absolute methanol or ethanol to give pure trimethylamine oxide dihydrate. The yield is practically quantitative.
In analoger Weise verfährt man, wenn man statt des Trimethylamins Dimethyläthylamin, Triäthylamin, Dimethylbutylamin oder andere niedrigmolekulare Trialkylamine verwendet.The procedure is analogous if, instead of trimethylamine, dimethylethylamine, triethylamine, Dimethylbutylamine or other low molecular weight trialkylamines are used.
Claims (3)
Schweizerische Patentschrift Nr. 177 456.Referred publications:
Swiss patent specification No. 177 456.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB22743A DE937058C (en) | 1952-11-04 | 1952-11-04 | Process for the preparation of low molecular weight trialkylamine oxides and their hydrates |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB22743A DE937058C (en) | 1952-11-04 | 1952-11-04 | Process for the preparation of low molecular weight trialkylamine oxides and their hydrates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE937058C true DE937058C (en) | 1955-12-29 |
Family
ID=6960989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB22743A Expired DE937058C (en) | 1952-11-04 | 1952-11-04 | Process for the preparation of low molecular weight trialkylamine oxides and their hydrates |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE937058C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2557456A1 (en) * | 1974-12-19 | 1976-06-24 | Albright & Wilson | PROCESS FOR THE PRODUCTION OF AMINOXIDES |
| EP0401503A3 (en) * | 1989-04-26 | 1991-07-17 | Albemarle Corporation | Solid non-hygroscopic trialkylamine oxides |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH177456A (en) * | 1934-02-16 | 1935-05-31 | Chem Ind Basel | Process for the preparation of an amine oxide. |
-
1952
- 1952-11-04 DE DEB22743A patent/DE937058C/en not_active Expired
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH177456A (en) * | 1934-02-16 | 1935-05-31 | Chem Ind Basel | Process for the preparation of an amine oxide. |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2557456A1 (en) * | 1974-12-19 | 1976-06-24 | Albright & Wilson | PROCESS FOR THE PRODUCTION OF AMINOXIDES |
| EP0401503A3 (en) * | 1989-04-26 | 1991-07-17 | Albemarle Corporation | Solid non-hygroscopic trialkylamine oxides |
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