CH397635A - Process for the production of nitriles - Google Patents
Process for the production of nitrilesInfo
- Publication number
- CH397635A CH397635A CH740660A CH740660A CH397635A CH 397635 A CH397635 A CH 397635A CH 740660 A CH740660 A CH 740660A CH 740660 A CH740660 A CH 740660A CH 397635 A CH397635 A CH 397635A
- Authority
- CH
- Switzerland
- Prior art keywords
- sep
- aldehyde
- copper
- nitriles
- ammonia
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 15
- 150000002825 nitriles Chemical class 0.000 title claims description 11
- 238000004519 manufacturing process Methods 0.000 title description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 13
- 150000001299 aldehydes Chemical class 0.000 claims description 13
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 239000005749 Copper compound Substances 0.000 claims description 7
- 150000001880 copper compounds Chemical class 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- -1 heterocyclic aldehyde Chemical class 0.000 claims description 4
- 239000007800 oxidant agent Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- DMIYKWPEFRFTPY-UHFFFAOYSA-N 2,6-dichlorobenzaldehyde Chemical compound ClC1=CC=CC(Cl)=C1C=O DMIYKWPEFRFTPY-UHFFFAOYSA-N 0.000 claims description 3
- YDYNSAUGVGAOLO-UHFFFAOYSA-N 2,6-dibromobenzaldehyde Chemical compound BrC1=CC=CC(Br)=C1C=O YDYNSAUGVGAOLO-UHFFFAOYSA-N 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- NUGMENVSVAURGO-UHFFFAOYSA-N 2-bromo-6-chlorobenzaldehyde Chemical compound ClC1=CC=CC(Br)=C1C=O NUGMENVSVAURGO-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 150000003934 aromatic aldehydes Chemical class 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 230000001419 dependent effect Effects 0.000 claims 1
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 9
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 5
- 229910001868 water Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- KBLLYABRMLFXFZ-UHFFFAOYSA-N 2,6-dibromobenzonitrile Chemical compound BrC1=CC=CC(Br)=C1C#N KBLLYABRMLFXFZ-UHFFFAOYSA-N 0.000 description 2
- NVPXACXEVCJWCF-UHFFFAOYSA-N 2-bromo-6-chlorobenzonitrile Chemical compound ClC1=CC=CC(Br)=C1C#N NVPXACXEVCJWCF-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000003172 aldehyde group Chemical group 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 description 2
- SATCULPHIDQDRE-UHFFFAOYSA-N piperonal Chemical compound O=CC1=CC=C2OCOC2=C1 SATCULPHIDQDRE-UHFFFAOYSA-N 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKKHCCZLKYKUDN-UHFFFAOYSA-N (2,6-dichlorophenyl)methanol Chemical compound OCC1=C(Cl)C=CC=C1Cl WKKHCCZLKYKUDN-UHFFFAOYSA-N 0.000 description 1
- VUYRFIIFTJICNA-LKNRODPVSA-N (e)-n-[[(e)-benzylideneamino]-phenylmethyl]-1-phenylmethanimine Chemical compound C=1C=CC=CC=1/C=N/C(C=1C=CC=CC=1)\N=C\C1=CC=CC=C1 VUYRFIIFTJICNA-LKNRODPVSA-N 0.000 description 1
- FPYUJUBAXZAQNL-UHFFFAOYSA-N 2-chlorobenzaldehyde Chemical compound ClC1=CC=CC=C1C=O FPYUJUBAXZAQNL-UHFFFAOYSA-N 0.000 description 1
- YXDXXGXWFJCXEB-UHFFFAOYSA-N 2-furonitrile Chemical compound N#CC1=CC=CO1 YXDXXGXWFJCXEB-UHFFFAOYSA-N 0.000 description 1
- CMWKITSNTDAEDT-UHFFFAOYSA-N 2-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC=C1C=O CMWKITSNTDAEDT-UHFFFAOYSA-N 0.000 description 1
- SWBDKCMOLSUXRH-UHFFFAOYSA-N 2-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC=C1C#N SWBDKCMOLSUXRH-UHFFFAOYSA-N 0.000 description 1
- ZETIVVHRRQLWFW-UHFFFAOYSA-N 3-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=CC(C=O)=C1 ZETIVVHRRQLWFW-UHFFFAOYSA-N 0.000 description 1
- RUSAWEHOGCWOPG-UHFFFAOYSA-N 3-nitrobenzonitrile Chemical compound [O-][N+](=O)C1=CC=CC(C#N)=C1 RUSAWEHOGCWOPG-UHFFFAOYSA-N 0.000 description 1
- XDJAAZYHCCRJOK-UHFFFAOYSA-N 4-methoxybenzonitrile Chemical compound COC1=CC=C(C#N)C=C1 XDJAAZYHCCRJOK-UHFFFAOYSA-N 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PKRWWZCDLJSJIF-UHFFFAOYSA-N Piperonylonitrile Chemical compound N#CC1=CC=C2OCOC2=C1 PKRWWZCDLJSJIF-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- FXHGMKSSBGDXIY-UHFFFAOYSA-N heptanal Chemical compound CCCCCCC=O FXHGMKSSBGDXIY-UHFFFAOYSA-N 0.000 description 1
- SDAXRHHPNYTELL-UHFFFAOYSA-N heptanenitrile Chemical compound CCCCCCC#N SDAXRHHPNYTELL-UHFFFAOYSA-N 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 229940081310 piperonal Drugs 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/34—Nitriles
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
Verfahren zur Herstellung von Nitrilen
Die Erfindung bezieht sich auf ein neues Verfahren zur Herstellung von Nitrilen.
In der deutschen Patentschrift Nr. 832 147 ist ein Verfahren zur Herstellung von Nitrilen durch Umsetzung von Alkoholen oder Aldehyden mit Ammoniak in Gegenwart eines ZnS enthaltenden Katalysators bei Temperaturen von 350 bis 4750 C beschrieben. Die US-Patentschrift Nr. 2 525 818 betrifft ein Verfahren zur Herstellung von Nitrilen, wobei sekundäre und tertiäre Aldehyde bei Temperaturen von 260 bis 4500 C in Gegenwart eines Katalysators, bestehend aus metallischem Kupfer in Mischung mit einem Oxyd des Aluminiums oder Siliciums mit Ammoniak umgesetzt werden.
Diese Herstellungsverfahren finden in der Gasphase statt.
Die Erfindung betrifft ein Verfahren zur Herstellung von Nitrilen aus Aldehyden und Ammoniak, welches in der flüssigen Phase bei beträchtlich niedrigeren Temperaturen vor sich geht.
Erfindungsgemäss werden Nitrile durch Umsetzung eines Aldehyds mit Ammoniak in einem flüssigen alkalischen Medium in Gegenwart eines Oxydationsmittels unter dem Einfluss einer Kupferverbindung hergestellt.
Für das erfindungsgemässe Verfahren können als Ausgangsstoffe aromatische, heterocyclische oder aliphatische Aldehyde verwendet werden. Es kommen auch Aldehyde, die mehr als eine Aldehydgruppe aufweisen, z. B. Dialdehyde, in Betracht. Es kann grundsätzlich jeder Aldehyd verwendet werden, welcher mit Ammoniak ein Imin zu bilden vermag. Chelate bildende Aldehyde, z. B. diejenigen, welche ausser der Aldehydgruppe eine Hydroxygruppe enthalten, können jedoch zu Venvicklungen Anlass geben. Die als Ausgangsstoffe verwendeten Aldehyde können in situ durch Oxydation der entsprechenden Alkohole hergestellt werden.
Die folgenden Nitrile bilden sich sehr leicht:
Benzonitril aus Benzaldehyd,
2,6-Dichlorbenzonitril aus 2,6
Dichlorbenzaldehyd, 2,6-Dibrombenzonitril aus 2,6
Dibrombenzaldehyd,
2-Brom-6-chlorbenzonitril aus 2-Brom
6-chlorbenzaldehyd, p-Methoxybenzonitril aus Anisaldehyd, 3 ,4-Methylendioxybenzonitril aus Piperonal, Önanthonitril aus Önanthaldehyd.
Andere Beispiele für Reaktionen, welche erfindungsgemäss durchgeführt werden können, sind die Herstellung von:
Benzonitril aus Benzylalkohol,
2, 6-Dichlorbenzonitril aus 2, 6-Dichlorbenzyl alkohol, o- und m-Nitrobenzonitril aus o- und m
Nitrobenzaldehyd,
2-Cyanfuran aus Furfurol,
Benzonitril aus Hydrobenzamid (gebildet aus
Benzaldehyd und Ammoniak).
Das beim erfindungsgemässen Verfahren zu verwendende flüssige alkalische Medium ist vorzugsweise ein organisches Lösungsmittel, welches eine starke Base enthält. Es werden mit einer Lösung von Natriummethylat (oder Natriumhydroxyd) in Methanol sehr gute Ergebnisse erhalten.
Die erfindungsgemäss zu verwendende Kupferverbindung ist vorzugsweise eine anorganische Kupfer (II)-verbindung. Es werden sehr günstige Ergebnisse erzielt, wenn als Kupferverbindung Kupfer(II)-chlorid verwendet wird. Gegebenenfalls kann dieses in Form des Hydrats CuCl2 2H2O zugegeben werden. Es können auch viele andere Kupfersalze verwendet werden, und insbesondere sind Kupfer(II)-bromid, Kupfer(II)-acetat, Kupfer(II)-nitrat und Kupfer(11)- sulfat sehr geeignete Kupferverbindungen. Kupfer(II)oxyd und Kupfer(II)-hydroxyd sind nicht bevorzugt, sie können jedoch beim erfindungsgemässen Verfahren verwendet werden.
Die Reaktion wird im allgemeinen bei Atmosphärendmck und Temperaturen von 0 bis 1000 C durchgeführt. Manchmal sind niedrigere Temperaturen geeignet, um Nebenreaktionen zu verlangsamen. Gegen die Verwendung von höheren Drücken ist nichts einzuwenden, dies bringt jedoch keine besonderen Vorteile mit sich. Die Reaktion geht im allgemeinen bei Temperaturen von 20 bis 400 C sehr leicht vonstatten.
Vorteilhaft wird ein leicht verfügbares Oxydationsmittel, wie Sauerstoff bzw. ein Sauerstoff enthaltendes Gas, z. B. Luft, verwendet und mit den übrigen Reaktionspartnern in innige Berührung gebracht, z. B. durch Durchleiten des Gases durch die Flüssigkeit unter Rühren.
Bei Bildung des Aldehyds in situ aus einem Alkohol spielen sich insgesamt folgende Reaktionen ab:
EMI2.1
<tb> <SEP> 02
<tb> A. <SEP> RCH20H <SEP> > <SEP> RCHO <SEP> durch <SEP> die <SEP> Kupferverbindung <SEP> katalysierte <SEP> Oxydation
<tb> <SEP> NH
<tb> B. <SEP> RCHO <SEP> t <SEP> RCH <SEP> = <SEP> NH <SEP> + <SEP> H20 <SEP> : <SEP> t <SEP> Kondensationsprodukte
<tb> C. <SEP> RCH <SEP> = <SEP> NH <SEP> + <SEP> CH30 <SEP> / <SEP> oder <SEP> OH(-) <SEP> / <SEP> ruf <SEP> RCH <SEP> = <SEP> N(-) <SEP> + <SEP> CH3OH <SEP> (oder <SEP> H2O)
<tb> <SEP> Cu-Ammoniakkomplex
<tb> D. <SEP> RCH=N(- > <SEP> RCN+H2O
<tb> <SEP> +02
<tb>
Verschiedene der erwähnten Nitrile, z. B. 2,6 Dichlorbenzonitril, 2,6-Dibrombenzonitril und 2 Brom-6-chlorbenzonitril zeigen eine beträchtliche herbicide Wirksamkeit.
Das 2,6-Dichlorbenzonitril ist äusserst wirksam und kann in Unkrautvertilgungsmitteln verwendet werden.
Die Erfindung wird anhand der folgenden Beispiele näher erläutert.
Beispiel 1
Es wurden in einer Lösung von 0,77 Gewichtsteilen CuCl2-2H20, 1,82 Gewichtsteilen NaOCH3 und 7,65 Gewichtsteilen Ammoniak in 77,9 Gewichtsteilen Methanol 11,8 Gewichtsteile Benzaldehyd gelöst.
Es wurde mit der Lösung während 23 Stunden unter kräftigem Rühren bei einer Temperatur von 300 C und unter Atmosphärendruck Sauerstoff in Berührung gebracht. Die Mischung wurde dann in einen 5fachen Überschuss von Wasser eingegossen.
Das Nitril (79%, bezogen auf den Aldehyd) wurde mit Äther extrahiert und destilliert. Der Siedebereich des entstandenen Benzonitrüs betrug 185 bis 1880 C.
Beispiel 2
Es wurden in einer Lösung von 0,84 Gewichtsteilen CuCl2 2H2O, 2 Gewichtsteilen NaOCH3 und 8,4 Gewichtsteilen Ammoniak in 86,2 Gewichtsteilen Methanol 2,47 Gewichtsteile 2, 6-Dichlorbenzaldehyd gelöst.
Es wurde mit der Lösung während 4 Stunden unter kräftigem Rühren bei einer Temperatur von 300 C und unter Atmosphärendruck Sauerstoff in Berührung gebracht. Die Mischung wurde dann in einen Sfachen Überschuss von Wasser eingegossen. Das ausgefallene 2,6-Dichlorbenzonitril (76%, bezogen auf den Aldehyd) wurde abfiltriert und war im wesentlichen rein (Schmelzpunkt: 142 bis 1430 C). Aus dem Filtrat wurde durch Ansäuern und Extrahieren mit Äther eine weniger reine Fraktion erhalten.
Process for the production of nitriles
The invention relates to a new process for the production of nitriles.
German Patent No. 832 147 describes a process for the preparation of nitriles by reacting alcohols or aldehydes with ammonia in the presence of a ZnS-containing catalyst at temperatures from 350 to 4750.degree. US Pat. No. 2,525,818 relates to a process for the production of nitriles, wherein secondary and tertiary aldehydes are reacted with ammonia at temperatures of 260 to 4500 ° C. in the presence of a catalyst consisting of metallic copper mixed with an oxide of aluminum or silicon will.
These manufacturing processes take place in the gas phase.
The invention relates to a process for the preparation of nitriles from aldehydes and ammonia, which takes place in the liquid phase at considerably lower temperatures.
According to the invention, nitriles are produced by reacting an aldehyde with ammonia in a liquid alkaline medium in the presence of an oxidizing agent under the influence of a copper compound.
For the process according to the invention, aromatic, heterocyclic or aliphatic aldehydes can be used as starting materials. There are also aldehydes which have more than one aldehyde group, e.g. B. dialdehydes, into consideration. In principle, any aldehyde which can form an imine with ammonia can be used. Chelating aldehydes, e.g. B. those which contain a hydroxyl group in addition to the aldehyde group, however, can give rise to developments. The aldehydes used as starting materials can be prepared in situ by oxidation of the corresponding alcohols.
The following nitriles form very easily:
Benzonitrile from benzaldehyde,
2,6-dichlorobenzonitrile from 2,6
Dichlorobenzaldehyde, 2,6-dibromobenzonitrile from 2,6
Dibromobenzaldehyde,
2-bromo-6-chlorobenzonitrile from 2-bromine
6-chlorobenzaldehyde, p-methoxybenzonitrile from anisaldehyde, 3, 4-methylenedioxybenzonitrile from piperonal, enanthonitrile from enanthaldehyde.
Other examples of reactions which can be carried out according to the invention are the preparation of:
Benzonitrile from benzyl alcohol,
2,6-dichlorobenzonitrile from 2,6-dichlorobenzyl alcohol, o- and m-nitrobenzonitrile from o- and m
Nitrobenzaldehyde,
2-cyanfuran from furfural,
Benzonitrile from hydrobenzamide (formed from
Benzaldehyde and ammonia).
The liquid alkaline medium to be used in the process according to the invention is preferably an organic solvent which contains a strong base. Very good results are obtained with a solution of sodium methylate (or sodium hydroxide) in methanol.
The copper compound to be used in the present invention is preferably an inorganic copper (II) compound. Very favorable results are achieved when copper (II) chloride is used as the copper compound. If necessary, this can be added in the form of the hydrate CuCl2 2H2O. Many other copper salts can also be used and in particular copper (II) bromide, copper (II) acetate, copper (II) nitrate and copper (II) sulfate are very suitable copper compounds. Copper (II) oxide and copper (II) hydroxide are not preferred, but they can be used in the process of the present invention.
The reaction is generally carried out at atmospheric pressure and temperatures from 0 to 1000.degree. Sometimes lower temperatures are suitable to slow down side reactions. There is no objection to the use of higher pressures, but this does not have any particular advantages. The reaction generally proceeds very easily at temperatures from 20 to 400.degree.
A readily available oxidizing agent, such as oxygen or an oxygen-containing gas, e.g. B. air, used and brought into intimate contact with the other reactants, e.g. B. by passing the gas through the liquid with stirring.
When the aldehyde is formed in situ from an alcohol, the following reactions take place:
EMI2.1
<tb> <SEP> 02
<tb> A. <SEP> RCH20H <SEP>> <SEP> RCHO <SEP> by <SEP> the <SEP> copper compound <SEP> catalyzed <SEP> oxidation
<tb> <SEP> NH
<tb> B. <SEP> RCHO <SEP> t <SEP> RCH <SEP> = <SEP> NH <SEP> + <SEP> H20 <SEP>: <SEP> t <SEP> condensation products
<tb> C. <SEP> RCH <SEP> = <SEP> NH <SEP> + <SEP> CH30 <SEP> / <SEP> or <SEP> OH (-) <SEP> / <SEP> call <SEP > RCH <SEP> = <SEP> N (-) <SEP> + <SEP> CH3OH <SEP> (or <SEP> H2O)
<tb> <SEP> Cu ammonia complex
<tb> D. <SEP> RCH = N (-> <SEP> RCN + H2O
<tb> <SEP> +02
<tb>
Various of the nitriles mentioned, e.g. B. 2,6 dichlorobenzonitrile, 2,6-dibromobenzonitrile and 2 bromo-6-chlorobenzonitrile show considerable herbicidal activity.
The 2,6-dichlorobenzonitrile is extremely effective and can be used in herbicides.
The invention is explained in more detail by means of the following examples.
example 1
11.8 parts by weight of benzaldehyde were dissolved in a solution of 0.77 parts by weight of CuCl2-2H20, 1.82 parts by weight of NaOCH3 and 7.65 parts by weight of ammonia in 77.9 parts by weight of methanol.
Oxygen was brought into contact with the solution for 23 hours with vigorous stirring at a temperature of 300 ° C. and under atmospheric pressure. The mixture was then poured into a 5-fold excess of water.
The nitrile (79% based on the aldehyde) was extracted with ether and distilled. The boiling range of the resulting benzonitrus was 185 to 1880 C.
Example 2
2.47 parts by weight of 2,6-dichlorobenzaldehyde were dissolved in a solution of 0.84 parts by weight of CuCl2 2H2O, 2 parts by weight of NaOCH3 and 8.4 parts by weight of ammonia in 86.2 parts by weight of methanol.
Oxygen was brought into contact with the solution for 4 hours with vigorous stirring at a temperature of 300 ° C. and under atmospheric pressure. The mixture was then poured into a five-fold excess of water. The precipitated 2,6-dichlorobenzonitrile (76%, based on the aldehyde) was filtered off and was essentially pure (melting point: 142 to 1430 ° C.). A less pure fraction was obtained from the filtrate by acidification and extraction with ether.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL240848 | 1959-07-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH397635A true CH397635A (en) | 1965-08-31 |
Family
ID=19751808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH740660A CH397635A (en) | 1959-07-02 | 1960-06-30 | Process for the production of nitriles |
Country Status (2)
| Country | Link |
|---|---|
| CH (1) | CH397635A (en) |
| GB (1) | GB920987A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044002A1 (en) * | 1980-07-16 | 1982-01-20 | Bayer Ag | Process for preparing 3-bromo-4-fluorobenzaldehyde (-acetals),3-bromo- 4-fluoro-benzoic acid nitrile and its preparation |
| EP0097839A1 (en) * | 1982-06-16 | 1984-01-11 | Gruppo Lepetit S.P.A. | Process for preparing 2-amino-2-arylacetonitriles |
-
1960
- 1960-06-30 GB GB2292360A patent/GB920987A/en not_active Expired
- 1960-06-30 CH CH740660A patent/CH397635A/en unknown
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0044002A1 (en) * | 1980-07-16 | 1982-01-20 | Bayer Ag | Process for preparing 3-bromo-4-fluorobenzaldehyde (-acetals),3-bromo- 4-fluoro-benzoic acid nitrile and its preparation |
| US4383949A (en) | 1980-07-16 | 1983-05-17 | Bayer Aktiengesellschaft | Preparation of 3-bromo-4-fluorobenzaldehyde and its acetals |
| EP0097839A1 (en) * | 1982-06-16 | 1984-01-11 | Gruppo Lepetit S.P.A. | Process for preparing 2-amino-2-arylacetonitriles |
Also Published As
| Publication number | Publication date |
|---|---|
| GB920987A (en) | 1963-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| DE1195754B (en) | Process for the preparation of alkali salts of carboxylic acids by oxidation of aldehydes | |
| EP0190617B1 (en) | Process for producing a catalyst containing copper and silicium oxide | |
| DE1244151B (en) | Process for the production of saturated alpha-di- or trimethylol fatty acids | |
| EP0039828B1 (en) | Process for producing 4-methyl imidazoles | |
| CH397635A (en) | Process for the production of nitriles | |
| DE2027995A1 (en) | ||
| DE1169937B (en) | Process for the production of carboxylic acid nitriles | |
| DE1593127A1 (en) | Catalyst and process for the production of nitriles | |
| AT233549B (en) | Process for the production of epoxy carboxylic acids | |
| DE855254C (en) | Process for the preparation of oximes | |
| DE2344604A1 (en) | METHOD OF MANUFACTURING AZINES | |
| DE69132997T2 (en) | Process for the preparation of aminoanthraquinone derivatives | |
| AT219575B (en) | Process for the preparation of α-β, δ-ε unsaturated carboxyl compounds | |
| DE950286C (en) | Process for the preparation of a hydrazone of isonicotinic acid hydrazide | |
| DE2513678C3 (en) | Process for the production of acetic acid which is practically free of formic acid | |
| DE938786C (en) | Process for the preparation of cycloalkanone oximes | |
| DE441433C (en) | Process for the production of organic compounds by catalytic gas reactions | |
| DE550121C (en) | Process for the production of formaldehyde | |
| DE1917658C3 (en) | Hydroxycarboxylic acid nitriles | |
| DE764047C (en) | Process for the production of solid, liquid and easily liquefiable aliphatic hydrocarbons from gases containing carbon dioxide and hydrogen | |
| DE719829C (en) | Process for the preparation of olefin oxides | |
| DE915813C (en) | Process for the preparation of hydrazones | |
| DE870840C (en) | Process for the preparation of acetals of acetylacetaldehyde | |
| DE924386C (en) | Process for the preparation of ª ‡, ª ‡ '-Dicyan-ª ‰ -alkylglutaric acids | |
| DE1813013C3 (en) | Process for the preparation of 2,4,5-trichlorobenzoic acid |