CH526506A - 3-amino-azacycloheptan-2-one - Google Patents
3-amino-azacycloheptan-2-oneInfo
- Publication number
- CH526506A CH526506A CH784570A CH784570A CH526506A CH 526506 A CH526506 A CH 526506A CH 784570 A CH784570 A CH 784570A CH 784570 A CH784570 A CH 784570A CH 526506 A CH526506 A CH 526506A
- Authority
- CH
- Switzerland
- Prior art keywords
- hydrogen bromide
- bromomethyl
- pentaerythritol
- bis
- mixture
- Prior art date
Links
- BOWUOGIPSRVRSJ-UHFFFAOYSA-N 2-aminohexano-6-lactam Chemical compound NC1CCCCNC1=O BOWUOGIPSRVRSJ-UHFFFAOYSA-N 0.000 title abstract 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 40
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- 229910000042 hydrogen bromide Inorganic materials 0.000 claims description 20
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 16
- 125000005997 bromomethyl group Chemical group 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 230000000397 acetylating effect Effects 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 2
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 2
- WDNXKYRHRFUEKA-UHFFFAOYSA-N BrCC(C(O)O)(C)CBr Chemical compound BrCC(C(O)O)(C)CBr WDNXKYRHRFUEKA-UHFFFAOYSA-N 0.000 claims description 2
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 239000003063 flame retardant Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000013067 intermediate product Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- MFMLHXQPFVVJNK-UHFFFAOYSA-N 3-nitro-2-oxoazepane-1-carbaldehyde Chemical compound [O-][N+](=O)C1CCCCN(C=O)C1=O MFMLHXQPFVVJNK-UHFFFAOYSA-N 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000007868 Raney catalyst Substances 0.000 abstract 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 abstract 1
- 229910000564 Raney nickel Inorganic materials 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/02—Esters of acyclic saturated monocarboxylic acids having the carboxyl group bound to an acyclic carbon atom or to hydrogen
- C07C69/12—Acetic acid esters
- C07C69/16—Acetic acid esters of dihydroxylic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
3-Amino-azacycloheptan-2-one is prepared by the reduction of 1-formyl-3-nitro-azacycloheptan-2-one with hydrogen. The starting material is dissolved in ammoniacal lower alkanol solution and the reaction performed at 50-150 degrees C under a pressure of 20-200 atmos. in the presence of a catalyst e.g. Raney nickel.
Description
Verfahren zur Herstellung von 2,2-Bis-(brommethyl)-propandiol-1,3-diacetat
Es ist bekannt, 2,2-Bis-(brommethyl)-propandioi- 1,3- -diacetat durch Erhitzen von Pentaerythrit mit konzentriert wässeriger Bromwasserstoffsäure in Eisessig herzustellen, wobei aber ein Überschuss von 100% Bromwasserstoff eingesetzt werden muss.
Es wurde nun gefunden, dass man 2.2-Bis-(brom- methyl) -propandiol- 1,3 -diacetat in guter Ausbeute und unter Anwendung von Essigsäureanhydrid und von nahezu stöchiometrischen Mengen Bromwasserstoffsäure auf wirtschaftliche Weise herstellen kann.
Gegenstand der Erfindung ist also ein Verfahren zur Herstellung von 2,2-Bis-(brommethyl)-propandiol- 1,3-di- acetat durch Acetylieren und Bromieren von Pentaerythrit, das dadurch gekennzeichnet ist, dass man Pentaerythrit mit einer wässerigen Bromwasserstofflösung, der eine dem anwesenden Wasser äquimolare Menge Essigsäureanhydrid zugegeben wird, bei erhöhter Temperatur umsetzt.
Man verwendet vorteilhaft konzentrierte wässerige Bromwasserstofflösungen, z.B. 40-66%ige Lösungen.
Vorzugsweise wird einer Mischung aus 1 Mol Pentaerythrit und einer konzentrierten wässerigen Lösung von 2-2,2 Mol Bromwasserstoff bei Raumtemperatur und unter Kühlung Essigsäureanhydrid in einer Menge zugegeben, die geradezu ausreicht, um das durch die Zugabe der wässerigen Bromwasserstofflösung zugegebene Wasser chemisch zu binden.
Bei Anwendung von hochkonzentrierter Bromwasserstofflösung kann man durch Zusatz von Eisessig der Verflüchtigung von HBr bei der Reaktionstemperatur vorbeugen.
Die Mischung wird nun erwärmt und bei erhöhter Temperatur vorzugsweise zwischen 900C und der Siedetemperatur der Mischung umgesetzt. Unter diesen Bedingungen verläuft die Reaktion in einigen Stunden, zum Beispiel bei 1100C 8-10 Stunden.
Das bei der Reaktion entstehende Wasser kann durch langsame Destillation zusammen mit überschüssigem Eisessig abdestilliert werden.
Das erfindungsgemäss hergestellte 2,2-Bis-(bromme thyl)-propandiol-1,3-diacetat dient z.B. zur Herstellung von 2,2-Bis-(brommethyl)-propan-1,3-diol und findet daher Verwendung z.B. als Zwischenprodukt für die Herstellung flammfester Polymere.
Im folgenden Beispiel bedeuten die Teile Gewichtsteile und die Prozente Gewichtsprozente. Die Temperaturen sind in Celsiusgraden angegeben.
Beispiel
Zu einer Mischung von 13,6 Teilen Pentaerythrit und 26,5 Teilen einer 63%igen wässerigen Bromwasserstoffsäurelösung lässt man bei Raumtemperatur und unter äusserer Kühlung 55,5 Teile Essigsäureanhydrid langsam zulaufen. Nach beendeter Zugabe erwärmt man die Mischung auf 1100 und hält sie unter Rühren 8-10 Stunden bei dieser Temperatur, wobei man langsam ein Gemisch aus Wasser und Eisessig abdestillieren lässt. Anschliessend destilliert man zunächst Eisessig ab, danach gewinnt man bei 1400/1 mm Hg etwa 31 Teile 2,2-Bis (brommethyl)-propandiol-1,3-diacetat (ca. 90% d.Th.).
Analyse für C5H14Br2O4:
Berechnet: C 31,2 H 4,1 Br. 46,2
Gefunden: C 31,6 H 4,2 Br. 46,2
PATENTANSPRUCH
Verfahren zur Herstellung von 2,2-Bis-(brommethyl) -propandiol-1,3-diacetat durch Acetylieren und Bromieren von Pentaerythrit, dadurch gekennzeichnet, dass man Pentaerythrit mit einer wässerigen Bromwasserstofflösw sung, der eine dem anwesenden Wasser äquimolare Menge Essigsäureanhydrid zugegeben wird, bei erhöhter Temperatur umsetzt.
UNTERANSPRüCHE
1. Verfahren nach Patentanspruch, dadurch gekennzeichnet, dass man auf 1 Mol Pentaerythrit 2 bis 2,2 Mol Bromwasserstoff einsetzt und die Umsetzung bei Temperaturen zwischen 900C und der Siedetemperatur des Reaktionsgemisches durchführt.
2. Verfahren nach Patentanspruch und Unteranspruch 1, dadurch gekennzeichnet, dass man wässerige, 40-66%ige Bromwasserstofflösung verwendet.
**WARNUNG** Ende DESC Feld konnte Anfang CLMS uberlappen**.
Process for the preparation of 2,2-bis- (bromomethyl) -propanediol-1,3-diacetate
It is known that 2,2-bis (bromomethyl) propanedioi- 1,3- diacetate can be prepared by heating pentaerythritol with concentrated aqueous hydrobromic acid in glacial acetic acid, but using an excess of 100% hydrogen bromide.
It has now been found that 2,2-bis- (bromomethyl) -propanediol-1,3-diacetate can be produced economically in good yield and using acetic anhydride and almost stoichiometric amounts of hydrobromic acid.
The invention therefore relates to a process for the preparation of 2,2-bis (bromomethyl) propanediol 1,3-di-acetate by acetylating and brominating pentaerythritol, which is characterized in that pentaerythritol is treated with an aqueous hydrogen bromide solution, the an equimolar amount of acetic anhydride is added to the water present, is reacted at an elevated temperature.
It is advantageous to use concentrated aqueous hydrogen bromide solutions, e.g. 40-66% solutions.
Preferably, acetic anhydride is added to a mixture of 1 mole of pentaerythritol and a concentrated aqueous solution of 2-2.2 moles of hydrogen bromide at room temperature and with cooling in an amount that is almost sufficient to chemically bind the water added by the addition of the aqueous hydrogen bromide solution.
When using a highly concentrated hydrogen bromide solution, the addition of glacial acetic acid can prevent the volatilization of HBr at the reaction temperature.
The mixture is then heated and reacted at an elevated temperature, preferably between 90 ° C. and the boiling point of the mixture. Under these conditions the reaction takes a few hours, for example 8-10 hours at 110.degree.
The water formed during the reaction can be removed by slow distillation together with excess glacial acetic acid.
The 2,2-bis (bromomethyl) propanediol-1,3-diacetate prepared according to the invention is used e.g. for the production of 2,2-bis- (bromomethyl) -propane-1,3-diol and is therefore used e.g. as an intermediate product for the production of flame-retardant polymers.
In the following example, parts are parts by weight and percentages are percentages by weight. The temperatures are given in degrees Celsius.
example
55.5 parts of acetic anhydride are slowly run in at room temperature and with external cooling to a mixture of 13.6 parts of pentaerythritol and 26.5 parts of a 63% strength aqueous hydrobromic acid solution. When the addition is complete, the mixture is heated to 1100 and kept at this temperature for 8-10 hours while stirring, a mixture of water and glacial acetic acid being slowly distilled off. Glacial acetic acid is then distilled off, after which about 31 parts of 2,2-bis (bromomethyl) propanediol-1,3-diacetate (about 90% of theory) are obtained at 1400/1 mm Hg.
Analysis for C5H14Br2O4:
Calculated: C 31.2 H 4.1 Br. 46.2
Found: C 31.6 H 4.2 Br. 46.2
PATENT CLAIM
Process for the preparation of 2,2-bis- (bromomethyl) -propanediol-1,3-diacetate by acetylating and brominating pentaerythritol, characterized in that pentaerythritol is added with an aqueous hydrogen bromide solution to which an amount of acetic anhydride equimolar to the water present is added , reacts at elevated temperature.
SUBCLAIMS
1. The method according to claim, characterized in that 2 to 2.2 moles of hydrogen bromide are used per mole of pentaerythritol and the reaction is carried out at temperatures between 90 ° C. and the boiling point of the reaction mixture.
2. The method according to claim and dependent claim 1, characterized in that aqueous, 40-66% strength hydrogen bromide solution is used.
** WARNING ** End of DESC field could overlap beginning of CLMS **.
Claims (1)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH784570A CH526506A (en) | 1970-05-27 | 1970-05-27 | 3-amino-azacycloheptan-2-one |
| BE753930D BE753930A (en) | 1970-05-27 | 1970-07-24 | PROCESS FOR THE PREPARATION OF 2,2-BIS- (BROMOMETHYL) -PROPANEDIOL-1,3 DIACETATE |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH784570A CH526506A (en) | 1970-05-27 | 1970-05-27 | 3-amino-azacycloheptan-2-one |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH526506A true CH526506A (en) | 1972-08-15 |
Family
ID=4331276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH784570A CH526506A (en) | 1970-05-27 | 1970-05-27 | 3-amino-azacycloheptan-2-one |
Country Status (2)
| Country | Link |
|---|---|
| BE (1) | BE753930A (en) |
| CH (1) | CH526506A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1994014778A1 (en) * | 1992-12-18 | 1994-07-07 | Pola Chemical Industries, Inc. | Optically active 2-nitroimidazole derivative, process for producing the same, and intermediate for producing the same |
-
1970
- 1970-05-27 CH CH784570A patent/CH526506A/en not_active IP Right Cessation
- 1970-07-24 BE BE753930D patent/BE753930A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BE753930A (en) | 1970-12-31 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |