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WO1998005630A1 - Procede de preparation de nitriles organiques - Google Patents

Procede de preparation de nitriles organiques Download PDF

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Publication number
WO1998005630A1
WO1998005630A1 PCT/US1997/013940 US9713940W WO9805630A1 WO 1998005630 A1 WO1998005630 A1 WO 1998005630A1 US 9713940 W US9713940 W US 9713940W WO 9805630 A1 WO9805630 A1 WO 9805630A1
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WO
WIPO (PCT)
Prior art keywords
oxime
aldoxime
fluorobenzaldehyde
acid salt
methoxybenzaldehyde
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.)
Ceased
Application number
PCT/US1997/013940
Other languages
English (en)
Inventor
Chempolil Thomas Mathew
Heng Su
Baihua Wu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell International Inc
Original Assignee
AlliedSignal Inc
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 AlliedSignal Inc filed Critical AlliedSignal Inc
Priority to AU38292/97A priority Critical patent/AU3829297A/en
Publication of WO1998005630A1 publication Critical patent/WO1998005630A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles

Definitions

  • the invention relates to the production of organic nitriles from the co ⁇ esrjonding aldoxime More particularly, the invention provides a process in which acid salts are used to convert an aldoxime to its corresponding nit ⁇ le, which process produces the nitrile in very high yield
  • Organic nitriles such as benzonitriles
  • 4-bromo- and 2-bromobenzon ⁇ t ⁇ le are used as intermediates in the production of pharmaceutical compounds
  • 2-Fluoro-4-hydroxybenzonit ⁇ le is used in the production of liquid crystal displays
  • 2-hydroxybenzorutnle is an intermediate in the synthesis of agricultural products such as fungicides
  • Acid dehydration catalysts are disadvantageous in that the acid may react violently and is corrosive. Additionally, the use of an acid dehydration catalyst results in formation of a significant amount of aldehyde byproduct. Finally, the use of an acid catalyst requires neutralization of the acid for reaction product purification.
  • the present invention provides a process for the production of organic nitriles that overcomes some of the disadvantages of the prior art reactions.
  • organic nitrile is meant nitriles of the formula R-CN wherein R is a substituted or unsubstituted alkyl of I to 15 carbon atoms, alkenyl of 1 to 15 carbon atoms, aryl, or aralkyl radical and wherein R may be substituted by one or more alkyl of 1 to 6 carbon atoms, alkoxy of 1 to 6 carbon atoms, alkylthio of 1 to 6 carbon atoms, nitro, halogen, or aryl radical.
  • the process of the invention comprises the steps of: (A) mixing an effective amount of an acid salt and an aldoxime to form a reaction mixture; and (B) heating the reaction mixture at a temperature and for a time sufficient to form a reaction product comprising an organic nitrile. It has been discovered that the process of the invention provides a simple, easily controlled method for producing organic nitriles in high yield and with decreased byproduct formation as compared to known processes.
  • R is substituted or unsubstituted aryl.
  • Illustrative useful aldoximes include, without limitation, undecylic aldehyde oxime, benzaldehyde oxime, 2-methoxybenzaldehyde oxime, 4- methoxybenzaldehyde oxime, 2,4-dimethoxybenzaldehyde oxime, 2,3- dimethoxybenzaldehyde oxime, 2,6-dimethoxybenzaldehyde oxime, 2- hydroxybenzaldehyde oxime, 4-hydroxybenzaldehyde oxime, 2,4,6- trimethylbenzaldehyde oxime, 2-chlorobenzaldehyde oxime, 3-chlorobenzaldehyde oxime, 4-chlorobenzaldehyde oxime, 2-bromobenzaldehyde oxime, 3- bromobenzaldehyde oxime, 4-bromobenzaldehyde oxime, 2-fluorobenzaldehyde oxi
  • the aldoxime is one of the above- listed bromo, chloro, or fluoro substituted benzaldoximes, methoxybenzaldoximes, hydroxybenzaldoximes, 4-phenylbenzaldoxime, or 2,4,6-trimethylbenzaldoxime
  • the aldoxime is 2-bromobenzaldehyde oxime, 4- bromobenzaldehyde oxime, or 2-fluoro-4-methoxybenzaldehyde oxime.
  • the aldoximes useful in the invention are commercially available Alternatively, the aldoximes may be prepared by reacting the corresponding aldehyde with hydroxylamine by any known process, for example as set forth in United States Patent No. 4,323,706, which is incorporated in its entirety herein by reference. The aldoximes produced by these processes may be used in this invention without purification. In the case of aldoximes prepared in the presence of a solvent, the solution of the oxime in the solvent also may be directly used in the process of the invention.
  • the acid salts useful in this invention generally, are salts of acids having a pKa of about 5 or less.
  • acid salts of mineral acids are used.
  • the preferred acid for use in the process of the invention is sulfuric acid.
  • the acid salt counterion may be ammonium or any alkali metal cation including without limitation, sodium or potassium.
  • the preferred cation is sodium.
  • the acid salts are commercially available.
  • the acid salts may be formed
  • the base suitable for acid neutralization will be readily determinable by one ordinarily skilled in the art depending on the acid selected.
  • an effective amount of the acid salt and the aldoxime are mixed together, in any order, to form a reaction mixture.
  • An effective amount of acid salt is an amount effective to catalyze the dehydration reaction.
  • the amount of acid salt used is from about 5 to about 100 weight percent based on the weight of the aldoxime. Preferably, from about 20 to about 50, more preferably from about 25 to about 35, weight percent is used.
  • the acid salt used may be in any form, but preferably is in the form of crystals.
  • the mixing of the acid salt and aldoxime occurs in the presence of any solvent that is chemically inert to the reactants.
  • the boiling point of the solvent is at least about 75° C. More preferably, the boiling point is from about 105° C to about 150° C at the operating pressure.
  • Any suitable solvent may be used including, without limitation, toluene, xylene, chlorobenzene, or dichlorobenzene.
  • step (B) of the process the reaction mixture is heated under conditions suitable to form the reaction product, which product contains the organic nitrile, unreacted starting material, solvent, and byproducts.
  • the reaction mixture is heated to a temperature from about 80 to about 200° C, preferably from about 100 to about 150° C, and maintained at that temperature for between about 10 minutes to about 10 hours, preferably from about 30 minutes to about three hours.
  • the time for which the reaction is maintained at the reaction temperature will depend on the structure of the aldoxime used.
  • the pressure at which the process is performed is not critical. Atmospheric pressure may be conveniently used.
  • the organic nitrile formed in step (B) may be recovered from the reaction product by filtering of the reaction product to remove the acid salt followed by removal of the solvent.
  • the acid salt may be removed by adding a sufficient amount of water to the reaction product to dissolve the salt followed by the separation of the aqueous solution of the salt.
  • the organic nitrile may be purified, in an optional step (D), to remove reaction byproducts and form purified organic nitrile by any convenient means including, without limitation, distillation or crystallization.
  • Example 1 To a 100 mL round-bottomed flask equipped with a heating mantle, a magnetic stirrer, a thermometer, and a Dean-Stark trap with condenser, were added 1.0 g of 2-chloro-6-fluorobenzaldoxime, 0.5 g sodium bisulfate, and 1 1.7 g of xylenes. The reaction mixture was heated under stirring to 143° C. The reaction was held at the same temperature until gas chromatography indicated that the dehydration reaction was complete, approximately 3 hours. After cooling to room temperature, the resulting mixture was filtered. The solid, sodium bisulfate, was washed with 2 x 10 mL xylene. The wash xylene was combined with the filtrate.
  • Example 2 To a 100 mL three-necked flask, fitted with a mechanical agitator, a thermometer, a heating mantle and a Dean-Stark trap with a condenser was charged 3.0 g of 98 % 2-methoxybenzaldoxime, 1 5 g potassium bisulfate, and 20 g xylenes. The reaction mixture was heated to 143° C at reflux for two hours and then cooled to room temperature. After removal of the potassium bisulfate by filtration, the filtrate was evaporated to afford 2.59 g of 98 4 % 2- methoxybenzonitrile, a yield of 96.4 % with a 99 6 % conversion. The product was identified by GC and ER spectrography.
  • Example 3 The procedure of Example 2 was used except that 3.0 g of 98 % mesitaldehyde oxime, 1.5 g sodium bisulfate, and 20 g xylenes were used. The reaction mixture was heated at reflux for one hour and cooled to room temperature. After removal of the sodium bisulfate, the filtrate was evaporated to provide 2.56 g of 95.5 % 2,4,6-trimethylbenzonitrile, mp 45 - 51° C, with 93 4 % yield and 100 % conversion.
  • Example 4 To a 1000 mL three-necked, round-bottomed flask equipped with a mechanical agitator, thermometer, heating mantle, and a dropping funnel were added a 547 6 g solution of crude 2-fluoro-4-methoxybenzaldehyde (FMBA) in xylenes containing 79 7 g (0.517 mol) of FMBA as 100 %, 328 g of 30 % hydroxylamine sulfate (0 6 mol). The reaction mixture was heated to 50° C and a 50 % by weight sodium hydroxide solution (96. Ig, 1 2 mol) was added through the dropping funnel over a period of 30 minutes while maintaining the temperature at 50° C.
  • FMBA 2-fluoro-4-methoxybenzaldehyde
  • FMBN 2-fluoro-4-methoxybenzonitrile
  • Example 5 To a three-necked flask equipped with a mechanical agitator, thermometer, heating mantle and Dean-Stark trap with condenser, were added 2.1 g of 99 2 % 4-bromobenzaldoxime, 1.05 g sodium bisulfate, and 20 g xylenes. The reaction mixture was heated to 1 12° C at reflux for 9 5 hours and then cooled to room temperature. GC analysis of the reaction indicated a 99 3 % conversion forming 96.9 % of the corresponding nitrile, 0.75 % of aldehyde, and 1.7 % of high boilers such as amide.
  • Example 5a In a comparative example to Example 5, a mixture of 3.0 g of 99 2 % 4- bromobenzaldoxime, 0.21 g 98 % sulfuric acid, and 20 g xylenes were heated at reflux for 2 hours and cooled to room temperature. GC analysis of the resulting mixture indicated a 99.8 % conversion forming 88.2 % of the corresponding nitrile, along with 5 6 % of the aldehyde and 5 7 % of the high boilers such as amide
  • Examples 5 and 5a demonstrate the superiority of the process of the invention to the prior art process that uses an acid dehydration catalyst.
  • the result of using an acid dehydration catalyst, as shown in Example 5a, is the formation of a large amount of byproducts including aidehdye.
  • the process of the invention, as exemplified in Example 5, using the acid salt results in minimization of byproduct formation.
  • Examples 6 - 20 For Examples 6 through 18, the procedure of Example 1 was used except that the reactants, reaction times, and products were as listed on Table I For Examples 6 - 10, 13 - 16, and 18 -20, 3 0 g aldoxime were used . 10 g aldoxime were used for Example 1 1 and 2.0 g were used for Examples 12 and 17 20 g solvent were used in all of the examples.
  • the process of the invention produces the desired organic nitrile in high yield. Additionally, the results on Table 1 demonstrate that the organic nitrile product is produced with only minimal formation of aldehyde byproduct.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention a pour objet un procédé de production de nitriles organiques à partir de l'aldoxime corrélative. Plus particulièrement, l'invention porte sur un procédé qui permet d'utiliser des sels acides pour transformer une aldoxime en nitrile corrélative, et de produire ledit nitrile en très grandes quantités.
PCT/US1997/013940 1996-08-08 1997-08-08 Procede de preparation de nitriles organiques Ceased WO1998005630A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU38292/97A AU3829297A (en) 1996-08-08 1997-08-08 Process for the preparation of organic nitriles

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US69404996A 1996-08-08 1996-08-08
US08/694,049 1996-08-08

Publications (1)

Publication Number Publication Date
WO1998005630A1 true WO1998005630A1 (fr) 1998-02-12

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AU (1) AU3829297A (fr)
WO (1) WO1998005630A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0943604A1 (fr) * 1998-03-19 1999-09-22 Lonza A.G. Procédé pour la préparation de malononitrile
EP1057807A1 (fr) * 1999-06-02 2000-12-06 Kao Corporation Procédé pour la préparation de nitriles
WO2005123661A1 (fr) * 2004-06-19 2005-12-29 Archimica Gmbh Procede pour produire des nitriles par elimination d'eau d'aldehydoximes avec des anhydrides d'acide d'alkylphosphone
JPWO2013176088A1 (ja) * 2012-05-21 2016-01-14 高砂香料工業株式会社 ニトリルの製造方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD117872A1 (fr) * 1974-11-06 1976-02-05
EP0080700A1 (fr) * 1981-12-02 1983-06-08 Sumitomo Chemical Company, Limited Procédé pour la production de nitriles
EP0609179A1 (fr) * 1993-01-28 1994-08-03 Ciba-Geigy Ag Procédé de préparation de nitriles aromatiques
EP0731086A1 (fr) * 1995-03-09 1996-09-11 Ciba-Geigy Ag Procédé de préparation de nitriles aromatiques
EP0790234A1 (fr) * 1996-02-15 1997-08-20 Ciba Spezialitätenchemie Holding AG (Ciba Spécialités Chimiques Holding SA) (Ciba Specialty Chemicals Holding Inc.) Procédé de préparation de nitriles aromatiques

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DD117872A1 (fr) * 1974-11-06 1976-02-05
EP0080700A1 (fr) * 1981-12-02 1983-06-08 Sumitomo Chemical Company, Limited Procédé pour la production de nitriles
US4456562A (en) * 1981-12-02 1984-06-26 Sumitomo Chemical Company, Limited Process for producing nitriles
EP0609179A1 (fr) * 1993-01-28 1994-08-03 Ciba-Geigy Ag Procédé de préparation de nitriles aromatiques
EP0731086A1 (fr) * 1995-03-09 1996-09-11 Ciba-Geigy Ag Procédé de préparation de nitriles aromatiques
EP0790234A1 (fr) * 1996-02-15 1997-08-20 Ciba Spezialitätenchemie Holding AG (Ciba Spécialités Chimiques Holding SA) (Ciba Specialty Chemicals Holding Inc.) Procédé de préparation de nitriles aromatiques

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0943604A1 (fr) * 1998-03-19 1999-09-22 Lonza A.G. Procédé pour la préparation de malononitrile
EP1057807A1 (fr) * 1999-06-02 2000-12-06 Kao Corporation Procédé pour la préparation de nitriles
US6320067B1 (en) 1999-06-02 2001-11-20 Kao Corporation Process for producing nitrile
WO2005123661A1 (fr) * 2004-06-19 2005-12-29 Archimica Gmbh Procede pour produire des nitriles par elimination d'eau d'aldehydoximes avec des anhydrides d'acide d'alkylphosphone
US7405318B2 (en) 2004-06-19 2008-07-29 Archimica Gmbh Method for producing nitriles by elimination of water from aldehyde oximes with alkylphosphonic anhydrides
JPWO2013176088A1 (ja) * 2012-05-21 2016-01-14 高砂香料工業株式会社 ニトリルの製造方法
EP2853526A4 (fr) * 2012-05-21 2016-02-10 Takasago Perfumery Co Ltd Procédé de fabrication d'un nitrile

Also Published As

Publication number Publication date
AU3829297A (en) 1998-02-25

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