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WO1998033767A1 - Procede de preparation de cyanoarylmethylamine - Google Patents

Procede de preparation de cyanoarylmethylamine Download PDF

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Publication number
WO1998033767A1
WO1998033767A1 PCT/JP1998/000464 JP9800464W WO9833767A1 WO 1998033767 A1 WO1998033767 A1 WO 1998033767A1 JP 9800464 W JP9800464 W JP 9800464W WO 9833767 A1 WO9833767 A1 WO 9833767A1
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WO
WIPO (PCT)
Prior art keywords
catalyst
raney
aromatic
hydrogen
dinitrile
Prior art date
Application number
PCT/JP1998/000464
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English (en)
Japanese (ja)
Inventor
Motoo Miura
Yuseki Suyama
Hideyuki Kondo
Kouhei Morikawa
Original Assignee
Showa Denko K.K.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Showa Denko K.K. filed Critical Showa Denko K.K.
Priority to IL12644398A priority Critical patent/IL126443A/xx
Priority to AU57799/98A priority patent/AU5779998A/en
Priority to EP98901507A priority patent/EP0908447B1/fr
Priority to PCT/JP1998/000464 priority patent/WO1998033767A1/fr
Priority to US09/155,450 priority patent/US6114277A/en
Priority to CA002250770A priority patent/CA2250770C/fr
Priority to JP53272998A priority patent/JP3528970B2/ja
Priority to DE69837423T priority patent/DE69837423T2/de
Publication of WO1998033767A1 publication Critical patent/WO1998033767A1/fr
Priority to NO19984622A priority patent/NO319399B1/no
Priority to NO20053066A priority patent/NO20053066D0/no

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Classifications

    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J25/00—Catalysts of the Raney type
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J25/00—Catalysts of the Raney type
    • B01J25/04—Regeneration or reactivation
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a method for producing a cyano group-containing aromatic methylamine, and more particularly to a method for efficiently converting aromatic dinitrile under a low temperature and a low pressure using a small amount of a catalyst.
  • the present invention relates to a method for producing a cyano group-containing aromatic methylamine at a high yield.
  • Aromatic methylamine containing a cyano group is a useful substance as a raw material and intermediate for pharmaceuticals, agricultural chemicals, polymer additives, and other organic compounds. For example, hydrolyzes -m- or p-cyanobenzylamine By doing so, the corresponding useful m- or p-aminomethylbenzoic acid can be easily obtained.
  • a method for obtaining an aromatic methylamine containing a cyano group by adding hydrogen to only one of the two nitrile groups of the aromatic dinitrile is disclosed in, for example, Japanese Patent Application Laid-Open No. -There is a method described in 85041. This method requires the use of a catalyst in which palladium is supported on a carrier as the catalyst, and the addition of liquid ammonia and inorganic alkali is essential, and the reaction pressure is as high as 20 O kg 7 cm 2 .
  • Japanese Patent Application Laid-Open No. 6-5070909 discloses that one of aliphatic dinitrile using Raney nickel or Ranekobalt as a catalyst is used.
  • a method for producing an aminonitrile by hydrogenating only the lil group is disclosed. In this method, there is no description about aromatic dinitrile, and there was a drawback that when the conversion of aliphatic dinitrile was increased, the selectivity to aminonitrile was reduced.
  • JP-T-Hei 7-520020 proposes a method for producing amimononitrile by partial hydrogenation of a ditolyl compound having two or more ditolyl groups.
  • Raney nickel pretreated with an alkanolate such as sodium methoxide is used as a catalyst.
  • an alkanolate such as sodium methoxide
  • the pressure must be as high as 70 atm, and relatively expensive and inconvenient alkanolates must be used. There is a problem that it must not.
  • aromatic dinitrile can be highly converted even when a conventional Raney catalyst containing nickel, Z or cobalt is used as it is. It has been difficult to produce only aromatic cyanoamine-containing aromatic compounds in high yield by hydrogenation reaction at a high yield.
  • the present inventors have conducted intensive research to find a catalyst that can react aromatic dinitrile at a high conversion rate and produce a cyano group-containing aromatic methylamine in high yield.
  • it is effective to use a Raney catalyst that has been subjected to a specific treatment, and have completed the present invention.
  • the present invention is intended to solve the above-described problems associated with the prior art, and hydrogenates only one of two ditolyl groups of an aromatic dinitrile to obtain a cyano group-containing aromatic compound.
  • a reaction with a small amount of catalyst at a low temperature and a low pressure allows the aromatic dinitrile to undergo a hydrogenation reaction at a high conversion rate, thereby achieving a high yield of the aromatic dinitrile.
  • the catalyst when producing a cyano group-containing aromatic methylamine from an aromatic dinitrile, the catalyst is activated by contact with hydrogen in a solvent and activated by a Raney-catalyst (activation-treated Raney catalyst). (A catalyst).
  • the Raney catalyst used in producing the cyano group-containing aromatic methylamine from the aromatic dinitrile is regenerated by contacting with hydrogen in a solvent in the presence of alkali. Also aromatic dinitrate It is characterized in that this regenerated catalyst (regenerated Raney catalyst) is used when producing a cyano group-containing aromatic methylamine from lilyl.
  • the activated Raney catalyst and / or the regenerated Raney catalyst are used in an amount of 0.1 to 10% by weight, preferably 0.1% by weight of the aromatic dinitrile in the activated Raney catalyst. It is desirable to use it in an amount of 5 to 5% by weight, in a regenerated Raney catalyst, 0.1 to 50% by weight, preferably 0.5 to 20% by weight.
  • the activation of the Raney catalyst is preferably carried out by subjecting the Raney catalyst to a temperature ranging from room temperature to 200 ° C. and a hydrogen partial pressure of 0.1 to 5 O kg / cm 2 .
  • the regeneration is carried out by contacting with hydrogen.
  • the regeneration of the Raney catalyst is carried out at room temperature to 200 ° C. in the co-presence of 0.1 to 100% by weight of the alkaline catalyst to be regenerated. It is desirable that the Raney catalyst be brought into contact with hydrogen under the condition of a hydrogen partial pressure of 0.1 to 50 kg / cm 2 at the above temperature.
  • iron and iron oxide are used together with the activated Raney catalyst and Z or the regenerated Raney catalyst. It is desirable that at least one of iron hydroxide and iron hydroxide coexist.
  • At least one of the above-mentioned iron, iron oxide and iron hydroxide is used, and the total amount thereof is 0.1 to 100% by weight of the Raney catalyst. It is desirable to use it.
  • the Raney catalyst is preferably a Raney catalyst containing nickel and Z or cobalt, and more preferably a Raney nickel or modified Raney nickel.
  • the solvent contains an alcohol. It is desirable for W et al. To use the above-mentioned solvent and methanol.
  • the aromatic dinitrile is phthalonitrile, isophthalonitrile, or terephthalonitrile.
  • a cyano group-containing aromatic methylamine According to such a method for producing a cyano group-containing aromatic methylamine according to the present invention, only one of the two ditolyl groups (N ⁇ C-) in the aromatic dinitrile is hydrogenated, In the production of aromatic methylamine containing a cyano group, an aromatic dinitrile is subjected to a hydrogenation reaction at a high conversion rate with a smaller amount of catalyst and a lower temperature and lower pressure than before. Thus, a cyano group-containing aromatic methylamine can be produced from an aromatic dinitrile in a high yield.
  • Raney catalyst activated by contact with hydrogen in a solvent (hereinafter also referred to as an activated Raney catalyst);
  • Raney catalyst that is used to produce a cyano-containing aromatic methylamine from aromatic dinitrile by regenerating the Raney catalyst by contacting it with hydrogen in a solvent. )), At least one of them is used, and in a preferred embodiment, in the activated Raney catalyst, 0.1 to 10 times the aromatic dinitrile is used. %, Preferably 0.5 to 5% by weight, and in the case of a regenerated Raney catalyst, 0.1 to 50% by weight of the aromatic dinitrile, preferably 0.5 to 20% by weight. Used in the amount of
  • the “Raney catalyst” that is activated by contacting with hydrogen in a solvent is an alloy of two or more metals, one of which is included in the alloy. This is a porous metal catalyst with a large specific surface area, which is obtained by removing some components.
  • metals that are insoluble in alkali and / or acid eg, nickel and / or phenol
  • metals that are soluble in alkali and / or acid eg, aluminum and silicon
  • Raney catalysts containing nickel or cobalt or both are preferred, and Raney catalysts containing nickel are more preferably used.
  • a modified Raney catalyst that has been modified in the presence of a metal or metal oxide other than nickel and cobalt can also be used.
  • a modified Raney catalyst include modified Raney nickel modified with iron and Z or chromium.
  • such activation of the Raney catalyst is preferably performed by treating the Raney catalyst in a solvent under a hydrogen atmosphere.
  • the Raney catalyst that is regenerated by bringing it into contact with hydrogen in a solvent is the above-mentioned activated Raney catalyst, which is obtained from aromatic dinitrile It is a Raney catalyst that was used and then recovered when producing cyano group-containing methylamine.
  • such regeneration of the Raney catalyst is preferably performed by treating the above Raney catalyst in a solvent in the presence of alkali and in a hydrogen atmosphere.
  • the hydrogen partial pressure during these activation and regeneration treatments is usually 0.05 to 100 kg Z cm 2 , preferably 0.1 to 50 kg Z cm 2 .
  • the temperature is usually from 0 to 250 ° C, preferably from room temperature [ie from 15 to 25 ° C] to 200 ° C. If the hydrogen partial pressure is less than 0.1 kgs cm 2, especially less than 0.05 kg Z cm 2 or if the temperature is below room temperature, especially below 0 ° C, activation (hydrogen treatment) The effect is reduced, when the hydrogen partial pressure exceeds 50 kg Z cm 2 , especially when it exceeds 100 kg cm 2, and when the temperature exceeds 200 ° C, especially when it exceeds 250 ° C.
  • the two ditolyl groups in the aromatic dinitrile are both hydrogenated with a large amount of diamine, and the activity of the catalyst is reduced, resulting in an aromatic compound containing a cyano group.
  • the yield of trimethylamine may decrease.
  • an alkali preferably an inorganic alkali, for example, a hydroxide of an alkali metal is used in order to exhibit the effect of the regeneration.
  • carbonate, alkali earth metal hydroxide or carbonate, or ammonia is added at the time of regeneration treatment.
  • the addition amount of this force is a force depending on the regeneration conditions, usually 0.01 to 200% by weight, preferably 0.1 to 100% by weight of the catalyst amount.
  • activation treatment and regeneration treatment of the Raney-catalyst are system-based. It may be carried out continuously while introducing hydrogen gas or a hydrogen-containing mixed gas under pressure, or may be carried out by a batch system in a system into which hydrogen gas is injected.
  • the solvent examples include alcohol solvents, ether solvents of aliphatic and alicyclic hydrocarbons, saturated aliphatic and alicyclic hydrocarbon solvents, and water. These solvents can be used alone or in combination of two or more.Furthermore, any one of these solvents or two or more solvents and a solvent other than these can be used. It is also possible to use as a mixed solvent containing the above solvent. Of these, preferred solvents include solvents containing alcoholic solvents (eg, solvents containing methanol), and particularly preferred is methanol. . The amount of the solvent used is not particularly limited, but the solvent is usually used in an amount of 1 to 100 parts by weight, preferably 2 to 500 parts by weight, per 1 part by weight of the Raney catalyst. Used in
  • the time required to activate or regenerate the Raney catalyst can be reduced by increasing the pressure (hydrogen partial pressure), and tends to increase as the pressure decreases.
  • pressure 5 0 kg Z cm about 2, 1 0 min, 1 kg Z cm at tens
  • the kind of Raney catalysts have with activation to be reproduced, conditions, and La reproduction In the treatment, it varies depending on the type and amount of the added alkali.
  • the aromatic dinitrile used in the present invention is a compound in which two of the hydrogen atoms bonded to the aromatic ring are substituted with a ditolyl group (N ⁇ C—).
  • the aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring.
  • One or more of these aromatic rings are bonded in a chain (eg, biphenyl).
  • the remaining hydrogen atoms bonded to the aromatic ring may be halogen atoms, alkyl groups (preferably having about 1 to 5 carbon atoms), alkoxy groups (preferably carbon atoms). About 1 to 5) may be substituted.
  • aromatic dinitrile preferably, aromatic dinitrile having one benzene ring or naphthalene ring is mentioned, and more preferably, substituted dinitrile is substituted.
  • Discyanbenzene and discianonaphthalene having only two 2-tolyl groups as a group are exemplified.
  • aromatic dinitrile examples include dicyanobenzenes such as phthalonitrile, isophthalonitrile, and terephthalonitrile;
  • the phthalanolinoles, isophthalonitriles and terephthalonitriles of the dicyanobenzenes are particularly preferred.
  • the aromatic dinitrile is the same as the above two ditolyl groups.
  • halogen atoms such as fluorine and chlorine; alkyl groups such as methyl and ethyl groups (preferably having about 1 to 5 carbon atoms); and alkoxy groups such as methoxy and ethoxy groups.
  • a group preferably having about 1 to 5 carbon atoms); such as, for example, 2-chloroterinol, 2-nitrochloro, Row 4 — Methino Rey Soft Roni Tril etc. can be used.
  • the Raney catalyst at least one of the above-mentioned activated Raney catalysts and regenerated Raney catalysts is used.
  • the activated Raney catalysts are aromatic dihydrogenated (hydrogenated) catalysts. 0.1 to 10% by weight, preferably 0.5 to 5% by weight of the tolyl, and the regenerated Raney catalyst is 0.1 to 50% by weight, preferably 0 to 5% by weight. Used in amounts of 5 to 20% by weight.
  • an activated Raney catalyst and Z or a regenerated Raney catalyst are used.
  • at least one of iron, iron oxide and iron hydroxide can coexist.
  • Such iron, iron oxide, or iron hydroxide is preferably, for example, electrolytic iron, reduced iron, ferrous oxide, ferric oxide, iron hydroxide oxide, iron supported on a carrier, or the like. (Eg, iron supported on alumina, iron supported on silica, etc.).
  • the total amount of coexisting iron, iron oxide or iron hydroxide is usually from 0.01 to 200% by weight of the Raney catalyst amount (in terms of iron content in the case of iron supported on a carrier), preferably. Or 0.1 to 100% by weight.
  • Solvents can be used.
  • Preferred examples of such a solvent include alcohol solvents, ether solvents of aliphatic and alicyclic hydrocarbons, and saturated aliphatic and alicyclic hydrocarbon solvents.
  • solvents can be used alone, or can be used as a mixed solvent containing any of them.
  • Preferred examples of the solvent include an alcohol-based solvent and a mixed solvent containing an alcohol-based solvent, and particularly preferably, methanol is used.
  • the solvent for the hydrogenation reaction of the aromatic dinitrile is not necessarily the same as the solvent used for the activation (hydrotreatment) or regeneration of the Raney monocatalyst. However, if the activation or regeneration of the catalyst and the hydrogenation reaction of aromatic dinitrile are carried out in the same solvent, there is a great advantage in that no solvent replacement is required.
  • Such a solvent is generally used in an amount of 1 to 30 parts by weight, preferably 1.5 to 10 parts by weight, per 1 part by weight of the hydrogenated substance (aromatic dinitrile).
  • an alkali preferably an inorganic alkali, for example, a hydroxide of an alkali metal is used to suppress side reactions and improve selectivity.
  • a carbonate, an alkali earth metal hydroxide or a carbonate, or ammonia can be added during the hydrogenation reaction.
  • the amount of addition depends on the reaction conditions. For example, in the case of an alkali metal hydroxide, the amount is usually 0.01 to 200% by weight of the catalyst amount.
  • the hydrogenation reaction of the aromatic dinitrile is usually carried out at room temperature (15 to 25 ° C) to 200 ° C, preferably 50 to 130 ° C. line ⁇ d. If the temperature is lower than room temperature, a sufficient hydrogenation rate cannot be obtained,
  • the pressure at the time of the hydrogenation reaction is usually a partial pressure of hydrogen, and is preferably in the range of 1 to L 0 kg Z cm 2 , preferably 2 to 30 kg Z cm 2 .
  • the hydrogen gas used in this reaction need not be of high purity, and may contain other gases as long as it does not significantly affect the hydrogenation reaction. Etc. may be contained.
  • the hydrogenation reaction can be terminated when the reaction system has absorbed about the theoretical amount of hydrogen, that is, 100 to 120% of the theoretical amount, or preferably 100 to 110% of the theoretical amount. Desirable.
  • H 2 N-H 2 C — (aminomethyl group), which is a cyano group-containing aromatic methylamine having one nitrile group and one aminomethyl group. Is obtained.
  • the conversion of such an aromatic dinitrile depends on the type of the catalyst and the like and is not determined unconditionally, but is usually 90 mol% or more, preferably 95 mol% or more.
  • the yield of a cyano group-containing aromatic methylamine is usually 70% or more, preferably 75% or more.
  • an activated Raney catalyst preferably nickel and / or cobalt activated under a hydrogen atmosphere in a solvent
  • Raney catalysts preferably Raney catalysts containing nickel and / or cobalt regenerated under a hydrogen atmosphere in the presence of alcohol in a solvent
  • At least one of them is preferably 0.1 to 10% by weight, more preferably 0.5 to 0.5% by weight of the aromatic ditolyl in the case of the activated treated catalyst.
  • -5% by weight preferably 0.1-50% by weight, more preferably 0.5-20% by weight, in the case of the regenerated radiating catalyst, particularly preferably 0.5-20% by weight.
  • Aromatic by co-existing at least one of iron, iron oxide and iron hydroxide in an amount of 0.1 to 100% by weight of the Raney catalyst with the Raney catalyst.
  • aromatic dinitrile can be reacted at high conversion under low temperature and low pressure.
  • only one ditolyl group was hydrogenated while suppressing the formation of diamine, in which two ditolyl groups of aromatic dinitrile were both hydrogenated.
  • Aromatic methylamine containing a cyano group can be produced in high yield.
  • a 500 ml autoclave was charged with 180 ml of methanol and 2.0 g of Raney Nickel catalyst R—240 (W.R. Grace), and the temperature was kept at room temperature. (2 4 ° C) at a hydrogen pressure of 5 K g Z cm 2 (gauge pressure. below the Then, stirring and heating of the contents of the auto crepe were started and the temperature was kept at 100 ° C. for 2 hours. The maximum pressure during this heating was 9 kg / cm 2 . Next, the obtained autoclave contents were cooled to room temperature, and then the catalyst was settled to recover the catalyst.
  • the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography-an internal standard method, and the conversion of terephthalonitrile was determined.
  • the yield was over 99% by mole, the yield of p-cyanobenzylamine was 80%, and the yield of p-xylylenediamine was 5%.
  • Example 2 the catalyst was regenerated under the same conditions as in Example 2, except that sodium hydroxide was not charged.
  • a hydrogenation reaction of telephthalonitrile was carried out in the presence of the above catalyst under the same conditions as in Example 2, and after cooling to room temperature, the catalyst was filtered, and the obtained reaction solution was subjected to gas chromatography.
  • the analysis showed that the conversion of terephthalonitrile was over 99 mol%, the yield of p-cyanobenzylamine was 63%, and the yield of ⁇ -xylylenediamine was 100%. The rate was 6%.
  • the catalyst was separated by filtration and removed, and the obtained reaction solution was analyzed by gas chromatography internal standard method, and terephthalonitrile was obtained.
  • the conversion of this was not less than 99 mol%, the yield of p-cyanobenzylamine was 79%, and the yield of p-xylylenediamine was 5%.
  • Example 1 together with 1.0 g of the activated Raney-nickel catalyst, 0.2 g of reduced iron, 50 g of terephthalonitrile, and 0.2 g of sodium hydroxide were used. After adding hydrogen, the hydrogenation reaction of placeonitrile was performed under the same conditions as in Example 1, and after cooling to room temperature, the catalyst and reduced iron were filtered, and the obtained reaction solution was subjected to gas chromatography. According to the analysis by the graphite internal standard method, the conversion of terephthalonitrile was more than 99 mol%, the yield of p-cyanobenzylamine was 85%, and p-xylylamine was obtained. The yield of Ndamine was 4%. WO 98/33767 ] [g PCT / JP98 / 00464
  • terephthalonitrile 50 g was added to a 500 m1 autoclave containing the above regenerated catalyst, and the hydrogenation reaction of terephthalonitrile was carried out under the same conditions as in Example 1. After cooling to room temperature, the catalyst and reduced iron were filtered, and the resulting reaction solution was analyzed by gas chromatography internal standard method. The conversion of terephthalonitrile was found to be 99 mol%. Thus, the yield of p-cyanobenzylamine was 83%, and the yield of p-xylylenediamine was 5%.
  • Example 1 the catalyst was activated under the same conditions as in Example 1 except that the methanol used in activating the catalyst was changed to ethanol. ⁇ Hydrogenation reaction>
  • Example 1 terephthalonitrile was produced under the same conditions as in Example 1. After cooling to room temperature, the catalyst was filtered, and the resulting reaction solution was analyzed by gas chromatography-internal standard method to find that the conversion of terephthalonitrile was 99%. The yield of p-cyanobenzylamine was 77%, and the yield of p-xylylenediamine was 5%.
  • Example 1 the hydrogenation reaction of isophthalonitrile was performed under the same conditions as in Example 1 except that terephthalonitrile was replaced with isophthalonitrile, and then cooled to room temperature. The catalyst was filtered, and the obtained reaction mixture was analyzed by gas chromatography internal standard method. The conversion of isophthalonitrile was more than 99 monole%, and m-cyanobenziruyl The yield of min was 82% and the yield of m-xylylenediamine was 6%.
  • Example 1 a hydrogenation reaction of terephthalone nitrile was performed under the same conditions as in Example 1 except that the amount of the catalyst was changed to 1.5 g.After cooling to room temperature, the catalyst was filtered. When the obtained reaction mixture was analyzed by gas chromatography-internal standard method, the conversion of telephthalonitrile was confirmed. The ratio was 9.9 mol% or more, the yield of ⁇ -cyanobenzylamine was 79%, and the yield of ⁇ -xylylenediamine was 5%.
  • the catalyst was separated and removed by filtration, and the obtained reaction solution was analyzed by gas chromatography internal standard method.
  • the conversion was more than 99 mol%, the yield of p-cyanobenzylamine was 58%, and the yield of p-xylylenediamine was 3%.
  • Example 1 terephthalonitrile was prepared in the same manner as in Example 1 except that the amount of the catalyst was changed to 0.02 g and the amount of sodium hydroxide was changed to 0.05 g. A hydrogenation reaction was performed, but there was almost no absorption of hydrogen. The conversion of terephthalic evening Roni Application Benefits Le was Tsu der less than 1 mole 0/6. [Reference Example 3]
  • Example 1 The same conditions as in Example 1 except that the amount of the catalyst was changed to 10 g, the reaction pressure (hydrogen pressure) was changed to 5.0 kg Zcm 2 , and the reaction temperature was changed to 60 ° C in Example 1. The hydrogenation reaction of terephthalonitrile was carried out.
  • the catalyst was filtered and the obtained reaction solution was analyzed by gas chromatography internal standard method.
  • the conversion of telephthalonitrile was 99 mol. %
  • the yield of p-cyanobenzilamin was 73%
  • the yield of p-xylylenediamine was 17%.

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  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

La présente invention concerne un procédé de préparation de cyanoarylméthylamine par hydrogénation de l'un uniquement des groupes cyano d'un dinitrile aromatique, ce qui permet la préparation de l'amine recherché avec un rendement élevé par réaction du dinitrile en conversion haute avec utilisation d'une petite quantité d'un catalyseur dans des conditions de réaction de basse température et de basse pression. Selon ce procédé, on n'utilise comme catalyseur pour la préparation de cyanoarylméthylamine à partir d'un dinitrile aromatique, qu'un seul des catalyseurs activés de Raney préparés par traitement de catalyseurs de Raney avec de l'hydrogène dans des solvants et des catalyseurs de Raney régénérés préparés par traitement de catalyseurs de Raney avec de l'hydrogène en présence d'alcalis dans des solvants. La quantité de catalyseurs de Raney activés à utiliser représente de préférence de 0,1 à 10 % de la masse, et de préférence de 0,5 à 5 % de la masse de dinitrile aromatique, la quantité de catalyseurs de Raney régénérés à utiliser représentant de préférence de 0,1 à 50 % de la masse, et de préférence de 0,5 à 20 % de la masse de dinitrile aromatique. Le catalyseur de Raney activé est de préférence du type contenant du nickel et/ou du cobalt et préparé par activation dans un solvant sous atmosphère d'hydrogène, le catalyseur de Raney régénéré étant de préférence d'un type préparé en soumettant à régénération au moyen d'hydrogène dans un solvant en présence d'un alcali un catalyseur de Raney qui a été utilisé pour la préparation de cyanoarylméthylamine à partir d'un dinitrile aromatique.
PCT/JP1998/000464 1997-02-04 1998-02-04 Procede de preparation de cyanoarylmethylamine WO1998033767A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
IL12644398A IL126443A (en) 1997-02-04 1998-02-04 Process for preparing cyano group containing aromatic methylamines
AU57799/98A AU5779998A (en) 1998-02-04 1998-02-04 Process for the preparation of cyanoarylmethylamine
EP98901507A EP0908447B1 (fr) 1997-02-04 1998-02-04 Procede de preparation de cyanoarylmethylamine
PCT/JP1998/000464 WO1998033767A1 (fr) 1997-02-04 1998-02-04 Procede de preparation de cyanoarylmethylamine
US09/155,450 US6114277A (en) 1997-02-04 1998-02-04 Process for preparing cyano group-containing aromatic methylamines
CA002250770A CA2250770C (fr) 1997-02-04 1998-02-04 Procede de preparation d'un groupement cyano contenant des methylamines aromatiques
JP53272998A JP3528970B2 (ja) 1997-02-04 1998-02-04 シアノ基含有芳香族メチルアミンの製造方法
DE69837423T DE69837423T2 (de) 1997-02-04 1998-02-04 Verfahren zur herstellung von cyanoarylmethylamin
NO19984622A NO319399B1 (no) 1997-02-04 1998-10-02 Fremgangsmate ved fremstilling av cyanogruppe-inneholdende aromatiske metylaminer
NO20053066A NO20053066D0 (no) 1997-02-04 2005-06-22 Fremgangsmate ved regenerering av en Rayney-katalysator.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
USPCT/JP97/00270 1997-02-04
PCT/JP1998/000464 WO1998033767A1 (fr) 1997-02-04 1998-02-04 Procede de preparation de cyanoarylmethylamine

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7227036B2 (en) * 2002-05-22 2007-06-05 Showa Denko K.K. Production process of aminomethyl group-containing benzamide compound
EP1900428A1 (fr) 2006-08-09 2008-03-19 Mitsubishi Gas Chemical Company, Inc. Procédé de production d'amines primaires et catalyseurs pour produire des amines primaires
JP2008063326A (ja) * 2006-08-09 2008-03-21 Mitsubishi Gas Chem Co Inc 一級アミンの製造方法および一級アミン製造用触媒
CN103408480A (zh) * 2013-07-17 2013-11-27 张家港威胜生物医药有限公司 4-苯基-吡咯烷酮的合成工艺

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US7227036B2 (en) * 2002-05-22 2007-06-05 Showa Denko K.K. Production process of aminomethyl group-containing benzamide compound
EP1900428A1 (fr) 2006-08-09 2008-03-19 Mitsubishi Gas Chemical Company, Inc. Procédé de production d'amines primaires et catalyseurs pour produire des amines primaires
JP2008063326A (ja) * 2006-08-09 2008-03-21 Mitsubishi Gas Chem Co Inc 一級アミンの製造方法および一級アミン製造用触媒
US7767859B2 (en) 2006-08-09 2010-08-03 Mitsubishi Gas Chemical Company, Inc. Production method of primary amines and catalysts for producing primary amines
US8119556B2 (en) 2006-08-09 2012-02-21 Mitsubishi Gas Chemical Company, Inc. Production method of primary amines and catalysts for producing primary amines
CN103408480A (zh) * 2013-07-17 2013-11-27 张家港威胜生物医药有限公司 4-苯基-吡咯烷酮的合成工艺

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