CH582145A5 - 2,2,6,6-Tetra-methyl-4-oxo-piperidine prepn. - from 2,2,4,4,6-penta-methyl-2,3,4,5-tetra-hydro-pyrimidine by heating in anhydrous medium - Google Patents
2,2,6,6-Tetra-methyl-4-oxo-piperidine prepn. - from 2,2,4,4,6-penta-methyl-2,3,4,5-tetra-hydro-pyrimidine by heating in anhydrous mediumInfo
- Publication number
- CH582145A5 CH582145A5 CH544074A CH544074A CH582145A5 CH 582145 A5 CH582145 A5 CH 582145A5 CH 544074 A CH544074 A CH 544074A CH 544074 A CH544074 A CH 544074A CH 582145 A5 CH582145 A5 CH 582145A5
- Authority
- CH
- Switzerland
- Prior art keywords
- reaction
- acetone
- carried out
- diacetone alcohol
- triacetonamine
- Prior art date
Links
- JWUXJYZVKZKLTJ-UHFFFAOYSA-N Triacetonamine Chemical compound CC1(C)CC(=O)CC(C)(C)N1 JWUXJYZVKZKLTJ-UHFFFAOYSA-N 0.000 title claims description 18
- PIFBMJMXJMZZRG-UHFFFAOYSA-N 2,2,4,6,6-pentamethyl-1,5-dihydropyrimidine Chemical compound CC1=NC(C)(C)NC(C)(C)C1 PIFBMJMXJMZZRG-UHFFFAOYSA-N 0.000 title claims description 13
- 238000010438 heat treatment Methods 0.000 title claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 33
- SWXVUIWOUIDPGS-UHFFFAOYSA-N diacetone alcohol Natural products CC(=O)CC(C)(C)O SWXVUIWOUIDPGS-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- CQTRUFMMCCOKTA-UHFFFAOYSA-N diacetoneamine hydrogen oxalate Natural products CC(=O)CC(C)(C)N CQTRUFMMCCOKTA-UHFFFAOYSA-N 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- FTVFPPFZRRKJIH-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidin-4-amine Chemical compound CC1(C)CC(N)CC(C)(C)N1 FTVFPPFZRRKJIH-UHFFFAOYSA-N 0.000 claims abstract description 8
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 claims abstract description 7
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 claims abstract description 7
- MTZWHHIREPJPTG-UHFFFAOYSA-N phorone Chemical compound CC(C)=CC(=O)C=C(C)C MTZWHHIREPJPTG-UHFFFAOYSA-N 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims abstract description 3
- 239000007859 condensation product Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 6
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 4
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 238000004508 fractional distillation Methods 0.000 claims description 4
- 238000004817 gas chromatography Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- VCUFZILGIRCDQQ-KRWDZBQOSA-N N-[[(5S)-2-oxo-3-(2-oxo-3H-1,3-benzoxazol-6-yl)-1,3-oxazolidin-5-yl]methyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C1O[C@H](CN1C1=CC2=C(NC(O2)=O)C=C1)CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F VCUFZILGIRCDQQ-KRWDZBQOSA-N 0.000 claims description 2
- 230000036571 hydration Effects 0.000 claims description 2
- 238000006703 hydration reaction Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000010626 work up procedure Methods 0.000 claims description 2
- QWOJMRHUQHTCJG-UHFFFAOYSA-N CC([CH2-])=O Chemical compound CC([CH2-])=O QWOJMRHUQHTCJG-UHFFFAOYSA-N 0.000 abstract 3
- 239000002904 solvent Substances 0.000 abstract 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 abstract 1
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- BCDGQXUMWHRQCB-UHFFFAOYSA-N glycine methyl ketone Natural products CC(=O)CN BCDGQXUMWHRQCB-UHFFFAOYSA-N 0.000 abstract 1
- 229930193351 phorone Natural products 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D211/00—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings
- C07D211/04—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D211/68—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D211/72—Heterocyclic compounds containing hydrogenated pyridine rings, not condensed with other rings with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D211/74—Oxygen atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
Abstract
acetonide is heated either (a) in an anhydrous medium or with less than an equimolar amt. of water based on amt. of acetonide and in the presence of acetone and/or diacetone alcohol or (b) at least an equimolar amt. of water. The reaction is pref. carried out in a solvent or mixt. of solvents e.g. acetone, diacetone alcohol, mesityl oxide, diacetone-amine, triacetone-diamine, phorone, a 1-4C alcohol, ethylene glycol monomethyl ether. It is pref. conducted at 1-30 atmos. press., partic. 1-3 atmos. The molar ratio of acetonide to water may be 1:1 to 1:5 in method (b) and this reaction is pref. carried out in the presence of acetone and/or diacetone-amine, triacetone-diamine and/or an acetone condensation prod. with an acid at 40-120 degrees C.
Description
Gegenstand des Hauptpatentes Nr. 574413 ist ein Verfahren zur Herstellung von 2,2,6,6-Tetramethyl-4-oxopiperidin, dadurch gekennzeichnet, dass man 2,2,4,4,6-Pentamethyl- -2,3,4,5-tetrahydropiperidin oder dessen Hydrat erwärmt. Vorteilhaft wird die Reaktion in Gegenwart von Aceton durchgeführt.
Die vorliegende Erfindung ist eine Abänderung des oben erwähnten Verfahrens, das dadurch gekennzeichnet ist, dass man in Gegenwart von Diacetonamin, Triacetondiamin und/oder einem sauren Kondensationsprodukt von Aceton und gegebenenfalls Aceton erwärmt.
Ein saures Kondensationsprodukt von Aceton ist z.B. Phoron und Mesityloxid und insbesondere Diacetonalkohol.
Die Umsetzung wird bei erhöhter Temperatur durchgeführt, beispielsweise zwischen 40 und 120"C, insbesondere zwischen 40 und 95"C, in Gegenwart von Diacetonalkohol oder Mesityloxid 80 - 1000C.
Die Reaktionszeit beträgt bevorzugt 1/2 - 15, insbesondere 1 - 12 Stunden, mit Diacetonalkohol als Coreaktant bevorzugt 1/2 - 2, insbesondere 1 - 1V2 Stunden.
Die zu verwendende Menge Diacetonamin, Triacetondiamin bzw. Kondensationsprodukt liegt zweckmässig bei mindestens 1,5 Molen pro Mol Pyrimidin-Ausgangsmaterial, kann aber bis zu 10 Molen betragen. Aus praktischen Gründen beträgt der bevorzugte Bereich 2 bis 6 Mole, insbesondere 3 bis 4 Mole. Es können aber auch mit Vorteil weniger als 1,5 Mol verwendet werden.
Besonders geeignet ist die Verwendung von Diacetonalkohol als Coreaktant, da eine schnellere Durchführung der Reaktion wegen der Möglichkeit erhöhter Reaktionstemperatur gegeben ist. Gegebenenfalls kann man bei Anwesenheit von Aceton dieses während der Reaktion abdestillieren, um die Temperatur zu erhöhen.
Die Aufarbeitung erfolgt auf die im Hauptpatent Nummer 274413 beschriebene Weise.
Es ist vorteilhaft, bei der erfindungsgemässen Reaktion etwas Wasser zu verwenden, entweder als Pyrimidin-Hydratwasser und/oder als kleine Menge zugesetztes Wasser.
Die vorliegende Erfindung wird durch folgende Beispiele illustriert.
Beispiel 1
10 gAcetoninhydrat und 10 g Diacetonalkohol werden auf ca. 1000 erwärmt. In regelmässigen Zeitabständen wird der Gehalt des Reaktionsgemisches an Acetonin bzw. Triacetonamin gaschromatographisch bestimmt. Nach 2 Stunden Reaktionsdauer bei 90 - 100" sind weniger als 3% der ursprünglichen Acetoninmenge nachweisbar. Der Rest ist zu Triacetonamin umgelagert. das durch fraktionierte Destillation isoliert wird.
Beispiel 2
10 g wasserfreies Acetonin und 10 g Diacetonalkohol werden auf ca. 100" erwärmt. In regelmässigen Zeitabständen wird der Gehalt des Reaktionsgemisches an Acetonin bzw.
Triacetonamin gaschromatographisch bestimmt. Nach 4 Stunden Reaktionsdauer bei 90 - 100" sind weniger als 5% der ursprünglichen Acetoninmenge nachweisbar. Der Rest ist weitgehend zu Triacetonamin umgelagert, das durch fraktionierte Destillation isoliert wird.
PATENTANSPRUCH
Verfahren gemäss Patentanspruch des Hauptpatentes zur Herstellung von 2,2,6,6-Tetramethyl-4-oxopiperidin, dadurch gekennzeichnet, dass man in Gegenwart von Diacetonamin, Triacetondiamin und/oder einem sauren Kondensationsprodukt von Aceton erwärmt.
UNTERANSPRÜCHE
1. Verfahren gemäss dem Patentanspruch, dadurch gekennzeichnet, dass man Diacetonalkohol verwendet.
2. Verfahren gemäss dem Patentanspruch, dadurch gekennzeichnet, dass man Phoron verwendet.
3. Verfahren gemäss dem Patentanspruch, dadurch gekennzeichnet, dass man Mesityloxid verwendet.
4. Verfahren gemäss dem Patentanspruch, dadurch gekennzeichnet, dass man die Reaktion bei einer Temperatur von 80-1000C durchführt.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
The main patent no. 574413 is a process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine, characterized in that 2,2,4,4,6-pentamethyl-2,3,4, 5-tetrahydropiperidine or its hydrate is heated. The reaction is advantageously carried out in the presence of acetone.
The present invention is a modification of the above-mentioned process, which is characterized in that heating is carried out in the presence of diacetonamine, triacetonediamine and / or an acidic condensation product of acetone and optionally acetone.
An acid condensation product of acetone is e.g. Phoron and mesityl oxide and especially diacetone alcohol.
The reaction is carried out at an elevated temperature, for example between 40 and 120.degree. C., in particular between 40 and 95.degree. C., in the presence of diacetone alcohol or mesityl oxide 80-1000.degree.
The reaction time is preferably 1/2-15, in particular 1-12 hours, with diacetone alcohol as the coreactant, preferably 1/2-2, in particular 1-12 hours.
The amount of diacetonamine, triacetonediamine or condensation product to be used is expediently at least 1.5 moles per mole of pyrimidine starting material, but can be up to 10 moles. As a practical matter, the preferred range is 2 to 6 moles, especially 3 to 4 moles. However, less than 1.5 mol can also be used with advantage.
The use of diacetone alcohol as a coreactant is particularly suitable, since the reaction can be carried out more quickly because of the possibility of increased reaction temperature. If appropriate, if acetone is present, it can be distilled off during the reaction in order to increase the temperature.
The work-up is carried out in the manner described in main patent number 274413.
It is advantageous to use some water in the reaction according to the invention, either as pyrimidine hydration water and / or as a small amount of added water.
The present invention is illustrated by the following examples.
example 1
10 g acetonin hydrate and 10 g diacetone alcohol are heated to approx. 1000. The acetonine or triacetonamine content of the reaction mixture is determined by gas chromatography at regular intervals. After a reaction time of 2 hours at 90-100 ", less than 3% of the original amount of acetonin can be detected. The remainder has been rearranged to triacetonamine, which is isolated by fractional distillation.
Example 2
10 g of anhydrous acetonine and 10 g of diacetone alcohol are heated to approx. 100 ". The content of the reaction mixture in terms of acetonine or alcohol is measured at regular intervals.
Triacetonamine determined by gas chromatography. After a reaction time of 4 hours at 90-100 ", less than 5% of the original amount of acetonin can be detected. The remainder has largely been rearranged to triacetonamine, which is isolated by fractional distillation.
PATENT CLAIM
Process according to claim of the main patent for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine, characterized in that heating is carried out in the presence of diacetonamine, triacetonediamine and / or an acidic condensation product of acetone.
SUBCLAIMS
1. The method according to claim, characterized in that diacetone alcohol is used.
2. The method according to the patent claim, characterized in that Phoron is used.
3. The method according to the patent claim, characterized in that mesityl oxide is used.
4. The method according to the patent claim, characterized in that the reaction is carried out at a temperature of 80-1000C.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (27)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AR254315A AR208393A1 (en) | 1973-06-29 | 1974-01-01 | PROCEDURE FOR THE PREPARATION OF 2,2,6,6-TETRAMETHYL-4-OXOPIPERIDINE |
| CH544074A CH582145A5 (en) | 1974-04-19 | 1974-04-19 | 2,2,6,6-Tetra-methyl-4-oxo-piperidine prepn. - from 2,2,4,4,6-penta-methyl-2,3,4,5-tetra-hydro-pyrimidine by heating in anhydrous medium |
| NO742233A NO742233L (en) | 1973-06-29 | 1974-06-19 | |
| SE7408173A SE7408173L (en) | 1973-06-29 | 1974-06-20 | |
| DK330974AA DK140406B (en) | 1973-06-29 | 1974-06-20 | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine. |
| FI1906/74A FI190674A7 (en) | 1973-06-29 | 1974-06-20 | |
| IT24296/74A IT1021055B (en) | 1973-06-29 | 1974-06-21 | PROCEDURE FOR THE PREPARATION OF 2 2 6 6 TETRAMETHYL 4 OSSOPIPERIDINE |
| AT517874A AT338263B (en) | 1973-06-29 | 1974-06-21 | PROCESS FOR THE PREPARATION OF 2,2,6,6-TETRAMETHYL-4-OXOPIPERIDINE |
| AU70337/74A AU487861B2 (en) | 1973-06-29 | 1974-06-21 | Process forthe preparation of 2, 2, 6, 6-tetra-methyl-4-oxopiperidine |
| CA203,061A CA1027952A (en) | 1973-06-29 | 1974-06-21 | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine |
| RO7479252A RO67193A (en) | 1973-06-29 | 1974-06-21 | PROCESS FOR THE PREPARATION OF 2,2,6,6-TETRAMETHYL-4-PIPERYDONE |
| IL45092A IL45092A (en) | 1973-06-29 | 1974-06-21 | Preparation of 2,2,6,6-tetra-methyl-4 oxopiperidine |
| DD179371A DD112444A5 (en) | 1973-06-29 | 1974-06-21 | |
| BG027041A BG27081A3 (en) | 1973-06-29 | 1974-06-21 | METHOD FOR OBTAINING 2,2,6,6-TETRAMETHYL-4-OXYPIPERIDINE |
| GB2760274A GB1461701A (en) | 1973-06-29 | 1974-06-21 | Process for the preparation of 2,2,6,6-tetra-methyl-4-oxopiper idine |
| JP49071217A JPS5036474A (en) | 1973-06-29 | 1974-06-21 | |
| US05/481,935 US3960875A (en) | 1973-06-29 | 1974-06-21 | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine |
| NL7408411A NL7408411A (en) | 1973-06-29 | 1974-06-21 | |
| CS744395A CS200467B2 (en) | 1973-06-29 | 1974-06-21 | Process for preparing 2,2,6,6-tetramethyl-4-oxopiperidine |
| HUCI1484A HU169841B (en) | 1973-06-29 | 1974-06-21 | |
| FR7421685A FR2235118B1 (en) | 1973-06-29 | 1974-06-21 | |
| DE2429935A DE2429935C3 (en) | 1973-06-29 | 1974-06-21 | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine |
| IE1300/74A IE39521B1 (en) | 1973-06-29 | 1974-06-21 | Process for the preparation of 2,2,6,6,-tetramethyl-4-oxopiperidine |
| LU70388*A LU70388A1 (en) | 1973-06-29 | 1974-06-21 | |
| ES427548A ES427548A1 (en) | 1973-06-29 | 1974-06-21 | Process for the preparation of 2,2,6,6-tetramethyl-4-oxopiperidine |
| BR5080/74A BR7405080D0 (en) | 1973-06-29 | 1974-06-21 | PROCESS FOR THE PREPARATION OF 2 2 6 6-TETRAMETHIL-4-OXOPIPERIDINE |
| EG242/74A EG11230A (en) | 1973-06-29 | 1974-06-24 | Process for preparation of 2,2,6,6 tetramethyl-4 oxopiperidine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH544074A CH582145A5 (en) | 1974-04-19 | 1974-04-19 | 2,2,6,6-Tetra-methyl-4-oxo-piperidine prepn. - from 2,2,4,4,6-penta-methyl-2,3,4,5-tetra-hydro-pyrimidine by heating in anhydrous medium |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH582145A5 true CH582145A5 (en) | 1976-11-30 |
Family
ID=4293625
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH544074A CH582145A5 (en) | 1973-06-29 | 1974-04-19 | 2,2,6,6-Tetra-methyl-4-oxo-piperidine prepn. - from 2,2,4,4,6-penta-methyl-2,3,4,5-tetra-hydro-pyrimidine by heating in anhydrous medium |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH582145A5 (en) |
-
1974
- 1974-04-19 CH CH544074A patent/CH582145A5/en not_active IP Right Cessation
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|---|---|---|---|
| PL | Patent ceased | ||
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