CH516527A - Omega-aminoalkane nitriles - Google Patents
Omega-aminoalkane nitrilesInfo
- Publication number
- CH516527A CH516527A CH1709370A CH1709370A CH516527A CH 516527 A CH516527 A CH 516527A CH 1709370 A CH1709370 A CH 1709370A CH 1709370 A CH1709370 A CH 1709370A CH 516527 A CH516527 A CH 516527A
- Authority
- CH
- Switzerland
- Prior art keywords
- catalyst
- omega
- preparation
- fluorine
- fluorinated
- Prior art date
Links
- 150000002825 nitriles Chemical class 0.000 title abstract description 3
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000003951 lactams Chemical class 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 239000011575 calcium Substances 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 11
- 239000011737 fluorine Substances 0.000 claims description 11
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 150000004985 diamines Chemical class 0.000 claims description 3
- 238000005984 hydrogenation reaction Methods 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000011949 solid catalyst Substances 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims 1
- 150000004760 silicates Chemical class 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- 239000000543 intermediate Substances 0.000 abstract description 2
- -1 omega-aminododecanoic acid nitrile Chemical class 0.000 abstract description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 239000004411 aluminium Substances 0.000 abstract 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical class [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 abstract 1
- PBLZLIFKVPJDCO-UHFFFAOYSA-N omega-Aminododecanoic acid Natural products NCCCCCCCCCCCC(O)=O PBLZLIFKVPJDCO-UHFFFAOYSA-N 0.000 abstract 1
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 description 3
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SLXKOJJOQWFEFD-UHFFFAOYSA-N 6-aminohexanoic acid Chemical compound NCCCCCC(O)=O SLXKOJJOQWFEFD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- XUWHAWMETYGRKB-UHFFFAOYSA-N piperidin-2-one Chemical compound O=C1CCCCN1 XUWHAWMETYGRKB-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(A) Improved preparation of omega-aminoalkane nitriles, wherein a suitable lactam is treated with an excess of ammonia at between 280 and 400 deg.C, preferably between 300 and 360 deg.C in the presence of a catalyst. Suitable catalysts for the reaction are titanium dioxide, either natural or synthetic on a base of fluorinated aluminium oxide, fluorinated magnesium silicate or the fluorinated silicates of calcium, zinc, aluminium, manganese or iron. - (B) omega-aminododecanoic acid nitrile - Intermediates. - The use of improved catalysts gives improved yields of the product.
Description
Verfahren zur Herstellung von w-Aminoalkannitrilen Die Erfindung bezieht sich auf ein verbessertes Ver fahren zur Herstellung von w-Aminoalkannitrilen durch Umsetzung entsprechender Lactame mit überschüssigem Ammoniak bei erhöhter Temperatur in der Gasphase über einen Feststoffkatalysator. Während bisher für diese Umsetzung z.B. Kupfer auf Silicagel, Kaolin, Alumi niumoxid oder Aluminiumphosphat oder Phosphorsäure auf einem Träger als Katalysator verwendet wird,
ist das Verfahren der Erfindung durch die Verwendung von Fluor enthaltendem Aluminiumoxid oder Fluor enthal tendem Magnesium-, Calcium-, Zink-, Aluminium-, Man gan- oder Eisensilikat als Katalysator gekennzeichnet.
Während die bisher verwendeten Katalysatoren ent weder nur geringe Ausbeuten an Nitrilen liefern oder nur geringe Aktivität besitzen oder sehr sauerstoffemp findlich sind, besitzen die erfindungsgemäss zu verwen denden Katalysatoren diese Nachteile nicht.
Die Fluor enthaltenden Silikate können dadurch er halten werden, dass man die Silikate mit Flusssäure oder mit deren neutralen oder sauren Salzen oder mit kom plexen fluorhaltigen Säuren oder deren Salzen oder mit Fluor enthaltenden Gasen behandelt. Auch kann man die Silikate aus einer fluorhaltigen Lösung fällen. Nach dem Trocknen können die Katalysatoren gegebenenfalls zwi schen etwa 100 und 600 C calciniert werden.
Der Fluor- gehalt kann in weiten Grenzen schwanken, er liegt zweck- mässig zwischen etwa 0,1 und etwa 10 Gew.-%.
Die genannten Katalysatoren können für sich allein, in Mischung und bzw. oder Verbindung miteinander mit oder ohne Träger verwendet werden.
Die Umsetzung der Lactame mit dem Ammoniak wird zweckmässig unter normalem Druck im Temperaturbe reich von etwa 280 bis etwa 400 C, vorzugsweise zwi schen etwa 300 und etwa 360 C, durchgeführt.
Die Berührungszeit des Gasgemisches mit dem Kata lysator soll mit Vorteil zwischen etwa 0,1 und etwa 10 sek liegen. Die Ammoniakmenge beträgt zweckmässig mehr als 5 Mol, vorzugsweise etwa 10 bis etwa 20 Mol/Mol Lac- tam.
Die Katalysatoren können als Festbett- oder als Wir belschichtkatalysator verwendet werden.
Hat die Aktivität des Katalysators nachgelassen, so kann man diese durch Erhitzen des Katalysators mit Sauerstoff bzw. Luft wieder herstellen.
Für das erfindungsgemässe Verfahren geeignete Lac- tame sind z.B. Butyrolactam, Valerolactam, Onanthlac- tam und Laurinlactam, von technisch überwiegender Be deutung ist jedoch die Überführung des e-Caprolactams in das e-Aminocapronitril. Man kann auch das durch Depolymerisation von Polycaprolactam gewonnene, so genannte Spaltlactam verwenden.
Die w-Aminoalkannitrile haben als Zwischenprodukte zur Herstellung z.B. der entsprechenden Diamine durch Hydrieren oder zur Herstellung von Schädlingsbekämp fungsmitteln Bedeutung.
<I>Beispiel</I> 100 g aktives Aluminiumoxid (y-A1-03) von 0,5 1 mm Körnung und einer spezifischen Oberfläche vor etwa 108 m /g werden mit einer Lösung von 50 NH,HF, in 150 ml Wasser getränkt und 16 h lang be: Raumtemperatur unter Wasserstrahlvakuum aufbewahrt Dann wird die Flüssigkeit dekantiert und der Feststoff bei 120 C getrocknet. Der Fluorgehalt des so erhaltener. Katalysators beträgt 5,3 Gew.-%.
Über 70 g dieses Katalysators werden bei 340 C wäh. rend 20 h 278g Caprolactam und stündlich 401 Ammo. niak geleitet. Das Reaktionsprodukt enthält noch einer. Teil der Ausgangsstoffe sowie e-Aminocapronsäurenitri und Nebenprodukte. Der organische Anteil besteht au; 49,6 Gew.-% e-Aminocapronsäurenitril, 49;8 Gew.- j Lactam und 0,6 Gew.-% Nebenprodukten.
Verwendet man dagegen das aktive Aluminiumoxid, welches kein Fluor enthält, so erhält man unter den glei chen Versuchsbedingungen ein Reaktionsprodukt, dessen organischer Anteil aus 38,3 Gew.-% Lactam, 52,6 Gew.-% E-Aminocapronsäurenitril, aber 9,1 Gew.-% Ne benprodukten besteht.
Das w-Aminododecansäurenitril ist bisher nicht be- schrieben und besonders wertvoll, weil man damit über die Hydrierung zum Diamin und dessen Umsetzung mit Dicarbonsäuren zu Polyamiden mit besonders günstigen Eigenschaften kommen kann.
Process for the preparation of w-aminoalkanenitriles The invention relates to an improved process for the preparation of w-aminoalkanenitriles by reacting corresponding lactams with excess ammonia at elevated temperature in the gas phase over a solid catalyst. While so far for this implementation e.g. Copper on silica gel, kaolin, aluminum oxide or aluminum phosphate or phosphoric acid on a carrier is used as a catalyst,
the method of the invention is characterized by the use of fluorine-containing aluminum oxide or fluorine-containing magnesium, calcium, zinc, aluminum, manganese or iron silicate as a catalyst.
While the catalysts used hitherto provide only low yields of nitriles or have only low activity or are very sensitive to oxygen, the catalysts to be used according to the invention do not have these disadvantages.
The fluorine-containing silicates can be obtained by treating the silicates with hydrofluoric acid or with its neutral or acidic salts or with complex fluorine-containing acids or their salts or with fluorine-containing gases. The silicates can also be precipitated from a fluorine-containing solution. After drying, the catalysts can optionally be calcined between about 100 and 600.degree.
The fluorine content can vary within wide limits; it is expediently between about 0.1 and about 10% by weight.
The catalysts mentioned can be used alone, in a mixture and / or in combination with one another, with or without a carrier.
The reaction of the lactams with the ammonia is expediently carried out under normal pressure in the temperature range from about 280 to about 400.degree. C., preferably between about 300 and about 360.degree.
The contact time of the gas mixture with the catalyst should advantageously be between about 0.1 and about 10 seconds. The amount of ammonia is suitably more than 5 mol, preferably about 10 to about 20 mol / mol lactam.
The catalysts can be used as a fixed bed or as a fluidized bed catalyst.
If the activity of the catalyst has decreased, this can be restored by heating the catalyst with oxygen or air.
Lactames suitable for the method according to the invention are e.g. Butyrolactam, valerolactam, onanthlactam and laurolactam, but of major technical importance is the conversion of e-caprolactam into e-aminocapronitrile. One can also use the so-called split lactam obtained by depolymerization of polycaprolactam.
The w-aminoalkanenitriles have been used as intermediates for the preparation of e.g. importance of the corresponding diamines by hydrogenation or for the production of pesticides.
<I> Example </I> 100 g of active aluminum oxide (y-A1-03) with a grain size of 0.5 1 mm and a specific surface area of about 108 m / g are mixed with a solution of 50 NH, HF, in 150 ml water soaked and stored for 16 h at room temperature under a water jet vacuum. The liquid is then decanted and the solid is dried at 120.degree. The fluorine content of the so obtained. Catalyst is 5.3% by weight.
Over 70 g of this catalyst are at 340 ° C. rend 20 h 278g caprolactam and hourly 401 ammo. niak headed. The reaction product contains another one. Part of the starting materials as well as e-aminocaproic acid and by-products. The organic part consists of; 49.6% by weight of e-aminocaproic acid nitrile, 49; 8% by weight of lactam and 0.6% by weight of by-products.
If, on the other hand, the active aluminum oxide, which does not contain fluorine, is used, a reaction product is obtained under the same test conditions, the organic content of which consists of 38.3% by weight of lactam, 52.6% by weight of E-aminocapronitrile, but 9 1 wt .-% by-products.
The w-aminododecanoic acid nitrile has not yet been described and is particularly valuable because it can be used to produce polyamides with particularly favorable properties via hydrogenation to the diamine and its reaction with dicarboxylic acids.
Claims (1)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEF0052884 | 1967-07-07 | ||
| DEF0053776 | 1967-10-14 | ||
| DEF0053775 | 1967-10-14 | ||
| CH1009268A CH516526A (en) | 1967-07-07 | 1968-07-05 | Process for the preparation of w-aminoalkanenitriles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH516527A true CH516527A (en) | 1971-12-15 |
Family
ID=27429267
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH406971A CH516528A (en) | 1967-07-07 | 1968-07-05 | Process for the preparation of w-aminoalkanenitriles |
| CH1709370A CH516527A (en) | 1967-07-07 | 1968-07-05 | Omega-aminoalkane nitriles |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH406971A CH516528A (en) | 1967-07-07 | 1968-07-05 | Process for the preparation of w-aminoalkanenitriles |
Country Status (1)
| Country | Link |
|---|---|
| CH (2) | CH516528A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602538A (en) * | 2020-12-08 | 2022-06-10 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, and preparation method and application thereof |
| CN117756667A (en) * | 2023-12-18 | 2024-03-26 | 江苏扬农化工集团有限公司 | A method for producing aminododeconitrile from laurellactam |
-
1968
- 1968-07-05 CH CH406971A patent/CH516528A/en not_active IP Right Cessation
- 1968-07-05 CH CH1709370A patent/CH516527A/en not_active IP Right Cessation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114602538A (en) * | 2020-12-08 | 2022-06-10 | 中国科学院大连化学物理研究所 | Molecular sieve catalyst, and preparation method and application thereof |
| CN117756667A (en) * | 2023-12-18 | 2024-03-26 | 江苏扬农化工集团有限公司 | A method for producing aminododeconitrile from laurellactam |
| CN117756667B (en) * | 2023-12-18 | 2026-03-17 | 江苏扬农化工集团有限公司 | A method for producing aminododeconitrile from laurolactam |
Also Published As
| Publication number | Publication date |
|---|---|
| CH516528A (en) | 1971-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US2166150A (en) | Catalytic hydrogenation of dinitriles to diamines | |
| CH516527A (en) | Omega-aminoalkane nitriles | |
| US2166151A (en) | Catalytic hydrogenation of adiponitriles to produce hexamethylene diamines | |
| DE954416C (en) | Process for the production of aminonitriles and diamines | |
| US3256311A (en) | Production of nitriles from n-formylated primary amino compounds in contact with acatalyst | |
| DE1643370C3 (en) | Process for the preparation of omega-aminoalkanenitriles | |
| DE4319134A1 (en) | Process for the preparation of caprolactam | |
| DE19500040A1 (en) | Process for the preparation of aliphatic alpha, omega-aminonitriles in the gas phase | |
| DE1643369A1 (en) | Process for the preparation of omega-aminoalkanenitriles | |
| DE1545789A1 (en) | Process for producing lactams | |
| DE69106677T2 (en) | Process for the preparation of orthophenylenediamine. | |
| DE743967C (en) | Process for the preparation of dinitriles | |
| DE1117121B (en) | Process for the preparation of carboxylic acid nitriles | |
| DE1643369C3 (en) | Process for the preparation of omega-aminoalkanenitriles | |
| CH391681A (en) | Process for the production of nitriles | |
| CN116272969B (en) | Catalyst for synthesizing hexamethylenediamine and preparation method thereof | |
| US3689479A (en) | Process for oxidizing an alpha-hydroxylaminolactam to the corresponding alpha-oximinolactam | |
| DE910294C (en) | Process for the production of substituted formamides | |
| SU312417A1 (en) | ||
| DE740638C (en) | Process for the preparation of pyridines in addition to nitriles, etc. | |
| CH692506A5 (en) | A process for producing aminocyanoacetamide. | |
| CH349593A (en) | Process for the preparation of alkenene nitriles | |
| US3592853A (en) | Process for manufacture of amines | |
| DE875524C (en) | Process for the production of peptides or their anhydrides | |
| DE528897C (en) | Process for the production of nitrogen-containing condensation products |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PL | Patent ceased |