DE675659C - Process for the production of low molecular weight, unsaturated aliphatic carboxylic acid nitriles - Google Patents
Process for the production of low molecular weight, unsaturated aliphatic carboxylic acid nitrilesInfo
- Publication number
- DE675659C DE675659C DEI50512D DEI0050512D DE675659C DE 675659 C DE675659 C DE 675659C DE I50512 D DEI50512 D DE I50512D DE I0050512 D DEI0050512 D DE I0050512D DE 675659 C DE675659 C DE 675659C
- Authority
- DE
- Germany
- Prior art keywords
- molecular weight
- low molecular
- carboxylic acid
- aliphatic carboxylic
- acid nitriles
- 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
- -1 aliphatic carboxylic acid nitriles Chemical class 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 7
- 238000004519 manufacturing process Methods 0.000 title description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 150000004653 carbonic acids Chemical class 0.000 claims description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 2
- 239000012433 hydrogen halide Substances 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 150000002825 nitriles Chemical class 0.000 description 4
- AMAFFZUDKROYAJ-UHFFFAOYSA-N 2-chloro-2-methylpropanenitrile Chemical compound CC(C)(Cl)C#N AMAFFZUDKROYAJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- MYCXCBCDXVFXNE-UHFFFAOYSA-N 2-chloro-2-methylpropanoic acid Chemical compound CC(C)(Cl)C(O)=O MYCXCBCDXVFXNE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- WLAMNBDJUVNPJU-UHFFFAOYSA-N 2-methylbutyric acid Chemical class CCC(C)C(O)=O WLAMNBDJUVNPJU-UHFFFAOYSA-N 0.000 description 1
- INUNLMUAPJVRME-UHFFFAOYSA-N 3-chloropropanoyl chloride Chemical compound ClCCC(Cl)=O INUNLMUAPJVRME-UHFFFAOYSA-N 0.000 description 1
- QDHHCQZDFGDHMP-UHFFFAOYSA-N Chloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 1
- 241000861718 Chloris <Aves> Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical class CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- GBUDNGCDDQUCJV-UHFFFAOYSA-N prop-2-enoic acid;silver Chemical compound [Ag].OC(=O)C=C GBUDNGCDDQUCJV-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Verfahren zur Herstellung niedrigmolekularer ungesättiger aliphatischer Carbonsäurenitrile Es wurde gefunden, daß man in technisch einfacher Weise niedrigmolekulaxe ungesättigte aliphatische Carbo.nsäurenitrile erhalten kann, wenn man aus niedrigmolekularen, Halogen @enthaltenden gesättigten aliphatischen Carbonsäurenitrilen durch Überleiten über Katalysatoren ioder basisch wirkende Stoffe bei erhöhter Temperatur Haliogenw.asserstofabspaltet. Man arbeitet z. B. in der Weise, daß man die genannten Halog:encarbonsäurenitrile, vorteilhaft in Gegenwart von Ammoniak, über basisch wirkende Stoffe, wie Alkalien, leitet. Geeignete Katalysatoren, die an Stelle der basisch wirkenden Stoffe benutzt werden können, sind z. B. Kieselsäuregel, Tittandioxyd, Aluminiumoxyd, Bariumchlorid ,oder aktive Kohle. Zweckmäßig arbeitet main bei Temperaturen oberhalb ioo°, vorteilhaft zwischen 300 und ¢5o°. Das Verfahren läßt sich .auch unter vermindertem Druck ausführen.Process for the preparation of low molecular weight unsaturated aliphatic carboxylic acid nitriles It has been found that low molecular weight unsaturated aliphatic carboxylic acid nitriles can be obtained in a technically simple manner if halogenated or basic substances are obtained from low molecular weight, halogenated saturated aliphatic carboxylic acid nitriles by passing them over catalysts at elevated temperature. split off hydrogen. One works z. B. in such a way that the said halo: encarboxylic acid nitrile, advantageously in the presence of ammonia, over basic substances, such as alkalis, passes. Suitable catalysts that can be used in place of the basic substances are, for. B. silica gel, titanium dioxide, aluminum oxide, barium chloride, or active charcoal. Mainly works at temperatures above 100 °, advantageously between 300 and 50 °. The process can also be carried out under reduced pressure.
Für das Verfahren geeignete niedrigmolekulare, Halogen @enthaltende gesättigte aliphatische Carbonsäurenitrile sind nach an sich bekannten Verfahren .erhältlich. Man kann sie z. B. herstellen, indem man niedrigmolekulare gesättigte .aliphatische Carbonsäuren durch Behandeln mit Ammoniak in Gegenwart von Katalysatoren in die entsprechenden Carbonsäurenitrile überführt und diese dann halogeniert.Low molecular weight halogen containing compounds suitable for the process Saturated aliphatic carboxylic acid nitriles are produced by processes known per se .available. You can z. B. produce by adding low molecular weight saturated .aliphatic carboxylic acids by treatment with ammonia in the presence of catalysts converted into the corresponding carboxonitriles and then halogenated.
Es ist bekannt, ;aus (3-Dichlorpr,opionsäure-.esber bzw. (3-Chlorpropionylchlorid durch Abspaltung von Chlorwasserstoff die @entsprechenden Acrylsäureesber bzw. Acrylsäurechlorid herzustellen. Hieraus konnte jedoch nicht hergeleitet werden, daß die Abspaltung von Halogenwasserstioff aus niedrigm@olekularen, Halogen ,enthalteagden gesättigten aliphatischen-Carbansäurenitrilen glatt verlaufen würde, vielmehr war zu erwarten, daß sich die gebildeten ungesättigten Nitrile infolge der Anwesenheit von Haliogenwassersboff miteinander kondensieren und polymerisieren würden. Beispiel i Man leitet bei 380° in der Stunde i2o Gewichtsteile einer Chlorisobuttersäure (hergestellt durch Chlorieren von Isobuttersä@ure bei 6o°) zusammen mit q.o Gewichtsteilen Ammoniak über 3oo Gewichtsteile eines Kieselsäuregelkatalys.ators. In der gekühlten Vorlage bilden sich zwei Schichten, von denen die obere nach dem Trocknen und Destillieren in einer Ausbeute von über 6o % Methacrylsäureinitril vom Siedepunkt go bis g i ° liefert. Das bei der Reaktion gebildete Chlorammonium scheidet sich in den kühleren Teilen der Vorlage :ab und kann laufend entfernt werden.It is known that; from (3-dichloropr, opionic acid .esber or (3-chloropropionyl chloride by splitting off hydrogen chloride, the corresponding acrylic acid silver or acrylic acid chloride to manufacture. However, it could not be deduced from this that the split of hydrogen halide from low molecular weight, halogen, containing agents saturated aliphatic carbanoic acid nitriles would run smoothly, rather it was to be expected that the unsaturated nitriles formed are due to the presence of Haliogenwassersboff would condense and polymerize with one another. Example i One conducts at 380 ° per hour i2o parts by weight of a chloroisobutyric acid (produced by chlorination of isobutyric acid at 60 °) together with q.o parts by weight of ammonia over 300 parts by weight of a silica gel catalyst. Two layers form in the cooled template, of which the upper after drying and distilling in a yield of over 60% methacrylic acid nitrile from boiling point g to g i ° supplies. That with the reaction formed chlorammonium separates into the cooler ones Share the Template: from and can be removed continuously.
An Stelle der Chlorisobuttersäure kann, man auch eine chlorierte Methyläthylessig- , säure als Ausgangsstoff verwenden, wobei= ,ein entsprechendes ungesättigtes Carb@onsäüie,-nitril verhalten wird.Instead of chloroisobutyric acid, one can also use a chlorinated methylethyl acetic acid , acid as starting material, where =, a corresponding unsaturated carbonic acid, nitrile will behave.
Beispiel 2 Chloriertes Isobutyronitril (iiergellt durch Chlorieren von Isobutyronit'ril bei 6o bis 65') wird unter vermindertem Druck bei etwa. qoo bis q.50° über Titandioxyd geleitet. In der stark gekühlten Vorlage scheidet sich ein Gemisch :aus Methacrylsäurenitril und Chloris,obutyronitril :ab, aus dem durch fraktionierte Destillation in einer Ausbeute von etwa 7o bis 8o% reines M.eth:acry1säurenitril vom Siedepunkt 9o bis 9i° erhalten wird.Example 2 Chlorinated isobutyronitrile (gelified by chlorination of Isobutyronit'ril at 6o to 65 ') is under reduced pressure at about. qoo up to q.50 ° passed over titanium dioxide. Separates in the strongly cooled template a mixture: of methacrylic acid nitrile and chloris, obutyronitrile: from, from which through fractional distillation in a yield of about 7o to 8o% pure M.eth: acry1säurenitril is obtained from the boiling point 9o to 9i °.
Die Abspaltung des Chlorwasserstoffs aus dem Chlorisobutyronitril kann auch erfolgen, indem man das Chlorisobutyronitril zusammen mit Ammoniak in Dampfform bei etwa Zoo bis 25o° über Katalysatoren, z. B. Kieselgel, führt.The elimination of the hydrogen chloride from the chloroisobutyronitrile can also be done by adding the chloroisobutyronitrile together with ammonia in Form of vapor at about zoo to 25o ° over catalysts, z. B. silica gel leads.
Beispiel 3 123o Gewichtsteile Chlorisobutyronitrilwerden bei 44o° in einem Röhr .aus V2A-Stahl über 14.5o Gewichtsteile Calciumoxyd geleitet, , das durch Glühen von Marmor gewonnen wurde. Man erhält hierbei in einer Ausbeute von über 75% rohes Methylacrylsäurenitril, das nach einmaligem Destillieren ,ein Methylacrylsäurenitril vom Siedepunkt =88 bis 96° vergibt, das durch nochmalige 'Tb#stillatian weiter gereinigt werden kann.Example 3 123o parts by weight of chloroisobutyronitrile become at 44o ° in a tube made of V2A steel passed over 14.5o parts by weight of calcium oxide, that obtained by annealing marble. This is obtained in a yield of over 75% crude methylacrylic acid nitrile, which after a single distillation, a methylacrylic acid nitrile from boiling point = 88 to 96 °, which is further purified by repeated 'Tb # stillatian can be.
Man kann auch im durchlaufenden Betrieb arbeiten, indem man dem Reaktionsgefäß nach Maßgabe der Mengen der Reaktionsteilnehmer Calciumoxyd zusetzt, das die gebildete Salzsäure bindet. An Stelle von Calci.umoxyd kann man auch Magnesiuinoxyd verwenden.You can also work in continuous operation by opening the reaction vessel according to the amounts of the reactants adding calcium oxide, the formed Hydrochloric acid binds. Magnesium oxide can also be used in place of calcium oxide.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI50512D DE675659C (en) | 1934-09-05 | 1934-09-05 | Process for the production of low molecular weight, unsaturated aliphatic carboxylic acid nitriles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEI50512D DE675659C (en) | 1934-09-05 | 1934-09-05 | Process for the production of low molecular weight, unsaturated aliphatic carboxylic acid nitriles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE675659C true DE675659C (en) | 1939-05-19 |
Family
ID=7192850
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEI50512D Expired DE675659C (en) | 1934-09-05 | 1934-09-05 | Process for the production of low molecular weight, unsaturated aliphatic carboxylic acid nitriles |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE675659C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE854798C (en) * | 1942-02-08 | 1952-11-06 | Roehm & Haas G M B H | Process for the production of methacrylic acid nitrile |
| DE752481C (en) * | 1939-09-01 | 1952-11-10 | Ig Farbenindustrie Ag | Process for the preparation of acrylic acid amides |
| DE1104947B (en) * | 1958-02-27 | 1961-04-20 | Basf Ag | Process for the preparation of unsaturated carboxylic acid nitriles by splitting off hydrogen halide from halogenated saturated carboxylic acid nitriles |
-
1934
- 1934-09-05 DE DEI50512D patent/DE675659C/en not_active Expired
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE752481C (en) * | 1939-09-01 | 1952-11-10 | Ig Farbenindustrie Ag | Process for the preparation of acrylic acid amides |
| DE854798C (en) * | 1942-02-08 | 1952-11-06 | Roehm & Haas G M B H | Process for the production of methacrylic acid nitrile |
| DE1104947B (en) * | 1958-02-27 | 1961-04-20 | Basf Ag | Process for the preparation of unsaturated carboxylic acid nitriles by splitting off hydrogen halide from halogenated saturated carboxylic acid nitriles |
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