WO2000040534A1 - Salicylaldoximes et methode d'obtention - Google Patents

Salicylaldoximes et methode d'obtention Download PDF

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Publication number
WO2000040534A1
WO2000040534A1 PCT/IB1998/002136 IB9802136W WO0040534A1 WO 2000040534 A1 WO2000040534 A1 WO 2000040534A1 IB 9802136 W IB9802136 W IB 9802136W WO 0040534 A1 WO0040534 A1 WO 0040534A1
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WO
WIPO (PCT)
Prior art keywords
aryloxy
group
formula
compound
magnesium
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Application number
PCT/IB1998/002136
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English (en)
Inventor
Jeffrey H. Dimmit
Mark A. Kearns
William H. Chambless
Original Assignee
Cognis Deutschland Gmbh
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.)
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Publication date
Application filed by Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Priority to PCT/IB1998/002136 priority Critical patent/WO2000040534A1/fr
Priority to AU17768/99A priority patent/AU1776899A/en
Publication of WO2000040534A1 publication Critical patent/WO2000040534A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
    • C07C249/08—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes by reaction of hydroxylamines with carbonyl compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/64—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring
    • C07C37/66—Preparation of O-metal compounds with O-metal group bound to a carbon atom belonging to a six-membered aromatic ring by conversion of hydroxy groups to O-metal groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

Definitions

  • the present invention relates to an oxime of the formula IV, a process for making an oxime of the formula IV, an aryloxy magnesium salt of the formula II, a process for making an aryloxy magnesium salt of the formula II and a process for making an aldehyde of the formula III
  • each of R R 5 is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms with the proviso that one of R R 5 is hydrogen with magnesium alkoxide to form an aryloxy magnesium compound: (2) reacting the aryloxy magnesium compound with a compound capable of forming a non-aryloxy anion X to form a compound of the formula II wherein X is a non-aryloxy anion selected from the group consisting of chloride, acetate, sulfate, nitrate, sulfonate, hydroxide, oxide, carboxylate, formate; N is an integer having a value of 1 or 2; each of R R 5 is defined as above to form an aryloxy magnesium salt of the formula II;
  • each of R R 5 is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms with magnesium alkoxide to form an aryloxy magnesium compound; (2) reacting the aryloxy magnesium compound with a compound capable of forming a non-aryloxy anion X wherein X is a non-aryloxy anion selected from the group consisting of chloride, acetate, sulfate, nitrate, sulfonate, hydroxide, oxide, carboxylate, formate; N is an integer having a value of 1 or 2; and each of R R 5 is defined as above.
  • the process for making an aldehyde of the formula III comprises (1) reacting a compound of the formula I
  • each of R r R 5 is defined as above with magnesium alkoxide to form an aryloxy magnesium salt of the formula II;
  • step (3) above can be carried out in the presence of water.
  • each of R 2 - R 5 is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms.
  • R 3 is a dodecyl group or a nonyl group and each of R 2 , R 4 and R 5 is hydrogen.
  • aryloxy magnesium salts according to the invention are those of the formula II
  • each of R 2 - R 5 is hydrogen, a halogen, an alkyl or cycloalkyl group having from 1 to 36 carbon atoms, an aryl or alkaryl group having from 1 to 36 carbon atoms, an alkoxy or an aryloxy group having from 1 to 30 carbon atoms, an acyl group having from 1 to 24 carbon atoms.
  • the aryloxy magnesium salts are useful as intermediates in the production of the aldehydes of formula III and the oximes of formula IV as disclosed herein.
  • the preferred aryloxy magnesium salts are those in which R 3 is a dodecyl or a nonyl group; R 3 is a dodecyl group and each of R 2 , R 4 and R 5 hydrogen; R 3 is a nonyl group, each of R 2 , R 4 and R 5 hydrogen and X is an acetate ion or a chloride ion.
  • the processes according to the invention begin with the formation of the aryloxy magnesium salt of the formula II. This compound can be made by reacting a phenolic compound of the formula I wherein at least one of the ortho positions, i.e. the 2- and/or 6-positions of the aromatic ring with respect to the carbon carrying the phenolic hydroxyl group, are free.
  • the other four positions in the aromatic nucleus may carry substituents which are inert under the reaction conditions.
  • substituents include one or more of hydrogen atoms; halogen atoms; alkyl, cycloalkyl, and alicyclic groups, aryl groups, alkaryl groups, aralkyl groups having 1-36 carbon atoms; alkoxy groups, aryloxy groups which have from 1-30 carbon atoms; acyl groups which have from 1- 24 carbon atoms; and any combinations thereof.
  • substituents include one or more of hydrogen atoms; halogen atoms; alkyl, cycloalkyl, and alicyclic groups, aryl groups, alkaryl groups, aralkyl groups having 1-36 carbon atoms; alkoxy groups, aryloxy groups which have from 1-30 carbon atoms; acyl groups which have from 1- 24 carbon atoms; and any combinations thereof.
  • Such compounds can be prepared by any of the methods known to those skilled in the art.
  • the aryloxy magnesium salt of the formula II is made from an arlyoxy magnesium intermediate.
  • the arlyoxy magnesium intermediate can be prepared by any of the methods known to those skilled in the art. Such methods include, for example, reacting magnesium in the form of its alkoxide, e.g. methoxide, with a reactant capable of providing the aryloxy group, i.e. a phenolic compound, such as e.g. para-nonyi phenol, in the presence of a non-polar solvent such as e.g. benzene, toluene, xylene or cyclohexane optionally in the presence of a polar co-solvent.
  • a reactant capable of providing the aryloxy group i.e. a phenolic compound, such as e.g. para-nonyi phenol
  • a non-polar solvent such as e.g. benzene, toluene, xylene or cyclohexane optional
  • polar cosolvents examples include one or more of: lower C1-C4 alcohols such as, e.g., methanol and ethanol; amines such as e.g. triethylamine or pyridine; amides such as, e.g., dimethylformamide and N, N-dimethylacetamide; sulfoxides such as, e.g., dimethyl sulfoxide; mono-glyme, di-glyme and tri-glyme; and ethers such as, e.g., diethyl ether, diphenyl ether and tetrahydrofuran.
  • the reaction mixture is heated to reflux to allow the magnesium to dissolve.
  • the phenolic compound e.g.
  • nonyl phenol is then added to this solution of magnesium alkoxide in a non-polar solvent with agitation to ensure good mixing of the reactants.
  • the mixture is suitably heated for a period to facilitate completion of the reaction.
  • the temperature for this step is preferably within the range from 25°C to the boiling point of the reaction mixture.
  • the reaction is preferably run at or near the boiling point of the solvent used for the reaction. For example, if toluene is used as the solvent and magnesium methoxide is the alkoxide, the reaction mixture is preferably run at a temperature of about 65°C.
  • the duration of the reaction is generally in the range from about 30 minutes to several hours depending upon the reaction temperature employed. In general, lower temperatures which require longer reaction times to complete the conversion.
  • the relative mole ratios of the phenolic compound to the magnesium alkoxide is suitably in the range from about 0.9:1 to about 1. 1 : 1 , and is preferably about 1 : 1.
  • the non-polar solvent and the polar co-solvent are then removed as an azeotrope from the reaction mixture by fractional distillation.
  • the reaction may be carried out at ambient or under reduced pressure, the latter being used to facilitate the removal of volatile by-products of the reaction.
  • the resultant aryloxy magnesium compound is then reacted with a compound capable of providing the desired non aryloxy anion such as e.g.
  • aryloxy magnesium compound an oxide, a hydroxide, a carboxylate, sulphate or a nitrate anion to form the aryloxy magnesium salt of the formula II.
  • An example of a compound capable of providing a carboxylate anion is glacial acetic acid which provides an acetate anion.
  • the relative mole ratios of the aryloxy magnesium compound to the compound capable of giving rise to the non-aryloxy anion is suitably in the range from about 0.9:1 to about 1.1 :1 , and is preferably about 1 :1.
  • the addition of the compound capable of giving rise to the non-aryloxy anion is suitably carried out over a short duration e.g.
  • the desired aryloxy magnesium salt is generated and is ready for the next stage of the reaction.
  • the final aryloxy magnesium salt so formed is substantially free of any aryloxymagnesium alkoxide.
  • the addition of the formaldehyde reactant to the aryloxy magnesium salt can then be commenced.
  • the relative mole ratios of the aryloxy magnesium salt to the (para)formaldehyde for this stage of the reaction is suitably in the range from about 2 to 3.5, preferably from about 2.5 to 3.
  • This stage of the reaction is carried out at a temperature in the range suitably from 40° to 120°C, and preferably from 45-100°C.
  • the formaldehyde may be added as a gas, a solid or as a solution of solid paraformaldehyde in an anhydrous solvent over a duration, e.g., of 1 to 10 hours and during this addition the reaction temperature is suitably in the range of 60-90°C. Whichever form is used, the reaction mixture and the added reactants, with the exception of paraformaldehyde, are substantially anhydrous.
  • any volatile reaction by-products formed are removed continually from the reaction mixture by distillation.
  • the reaction temperature is suitably raised to about 70-100°C and maintained at that temperature for a further duration, e.g., 2-5 hours, preferably about 3 hours.
  • a strong acid solution such as e.g. a 10% aqueous solution of sulfuric acid, is added to the reaction mixture and stirred for a duration, e.g., 1 hour and the reaction mixture is then allowed to undergo phase separation.
  • the organic phase is washed several times with water, the organic phase dried and rendered free of any solvents.
  • the residual product is crude 2-hydroxy arylaldehyde. Where para-nonyl phenol is used, the crude product will be 5- nonylsalicylaldehyde.
  • the crude product can be purified by methods known to those skilled in the art such as, e.g., distillation under reduced pressure, especially if the product aldehyde is of a relatively higher molecular weight.
  • the 2-hydroxyarylaldehydes so formed are very useful compounds. They can, for instance, be converted to the corresponding oximes and used as metal extractants. It can also be used in the pharmaceutical industry, in the production of perfumes and agrochemicals.
  • a feature of the present invention is its ability to tolerate the presence of water.
  • the oximes according to the invention can be made from the aldehydes according to the invention by any method known to those skilled in the art.
  • the oximes are made by reacting the appropriate aldehyde with hydroxylamine sulfate in an aqueous solution in a pH of from about 7 to about 10, preferably in the range between 7 and 9.
  • the pH adjustment is preferably made using aqueous NaOH.
  • the oximation can be carried out a temperature of from about 25°C to about 100°C, preferably from about 70°C to about 75°C.
  • the oxime can be purified by fractional distillation as described in Example 5. The following are examples which are meant to illustrate but not to limit the invention.
  • Example 1 A 2-liter round-bottomed flask was charged with magnesium (12 g, 0.49 mol), methanol (285 ml), toluene (120 ml) and magnesium methoxide (10 ml solution of 7.4% by weight magnesium methoxide in methanol). The reaction mixture was heated to reflux and the magnesium dissolved. Para- nonyl phenol (112.4 g) was added in one portion to the reaction mixture. The flask was then rigged for a fractional vacuum distillation and an azeotrope of methanol/toluene was distilled off to an internal temperature of 70°C at a pressure of 350 nun Hg.
  • Glacial acetic acid (28.5 ml, 0.5 mole) was added to the reaction mixture over a 1 hour period while maintaining the reaction temperature at 70°C and the pressure at 350 mm Hg.
  • glacial acetic acid solid paraformaldehyde (46 g, a commercial sample containing 5-7% by weight water) was added over a 105 minute period.
  • the reaction mixture was maintained at a temperature of 65°C and a pressure of 350 mm Hg.
  • the addition of paraformaldehyde and the volatile reaction by-products were continually removed.
  • the reaction temperature was increased to 75°C and maintained at that temperature for an additional 3 hours.
  • Para- nonyl phenol 112.4 g was added in one portion to the reaction mixture.
  • the flask was then rigged for a fractional vacuum distillation and an azeotrope of methanol/toluene was distilled off to an internal temperature of 70°C at a pressure of 350 mm Hg.
  • Glacial acetic acid (28.5 ml, 0.5 mole) was added to the reaction mixture over a 1 hour period while maintaining the reaction temperature at 70°C and the pressure at 350 mm Hg.
  • pyridine 79 ml
  • toluene 250 ml
  • reaction temperature was then cooled to 70°C and sulfuric acid (300 ml, 10% w/w) was added to the reaction mixture, which was then stirred for 30 minutes. After phase separation, the organic phase was washed twice with 200 ml portions of water. The washed organic phase was then separated, dried and rendered free of the solvent to yield crude 5-nonyl salicylaldehyde. A 62% yield was obtained.
  • a 2 liter round-bottomed flask was charged with magnesium turnings (12.2 g, 0.50 mole), methanol (13 3 ml), toluene (60 ml), and magnesium methoxide solution (10 ml of an 8 weight % solution of magnesium methoxide in methanol).
  • the reaction mixture was heated to 45°C at which point the magnesium dissolution became vigorous.
  • the temperature of the reaction mixture was maintained between 45 and 55°C.
  • Para-dodecyl phenol (128.0 g, 0.50 mole) dissolved in toluene (125 ml) was added in one portion to the reaction mixture which was then maintained at 65°C for one hour.
  • Glacial acetic acid (30.1 g, 0.50 mole) was added over a 1 hour period, while maintaining the reaction mixture at reflux (65-66°). The reaction flask was then rigged for fractional distillation and the methanol/toluene azeotrope was distilled off until an internal temperature of 85 °C. A total of 117 g of distillate, assaying 65% methanol and 35% toluene, was collected. Toluene (130 g) was added to the reaction mixture in one portion. Paraformaldehyde (45.0 g) slurried in toluene (90 g) was then added over a 90 " minute period.
  • reaction mixture was maintained at a temperature of 85-90°C allowing a continuous distillation of the volatile reaction by-products.
  • the reaction mixture was maintained at 90°C for an additional 90 minutes.
  • the reaction mass was then cooled to 35°C and 500 ml of 20 vol% sulfuric acid was added.
  • the hydrolysis mass was then stirred for an additional 45 minutes.
  • phase separation the organic phase was washed twice with 200 ml portions of water. The washed organic phase was then separated, dried and rendered free of the solvent to yield crude 5-dodecyl salicylaldehyde. A 65% yield was obtained.
  • 2-hydroxy-5-nonylbenzaldehyde (5-nonyl salicylaldehyde) obtained from a preparation similar to that set forth in Examples 1-3 was fractionally distilled prior to use in this example.
  • the 2-hydroxy-5- nonylbenzaldehyde used was a combination of a first fraction boiling at 178°C and at 17 mm Hg and a second fraction boiling at 175°C and at 18 mm Hg. Each fraction contained about 87% 2-hydroxy-5-nonylbenzaldehyde as determined by titration with 0.1N NaOH of the HCL produced by the reaction of the substituted benzaldehyde with excess hydroxylamine hydrochloride.
  • the organic phase (containing the oxime) was washed twice with 100 ml portions of deionized water and the washed phase stripped under vacuum to remove the toluene and any residual water.
  • a 54 gram portion of the isolated dried 2-hydroxy-5-nonylbenzadloxime was blended with 20 grams of EXAL® 13, a trademark product of Exxon Corp., which is C 13 alcohol, 26 grams of ESCADE® 100, a trademark product of Exxon Corp., which is a liquid hydrocarbon diluent.

Abstract

Cette invention concerne des oximes représentés par la formule (IV), dans laquelle chacun de R2-R5 est un groupe hydrogène, halogène, alkyle ou cycloalkyle avec 1 à 36 atomes de carbone, un groupe aryle ou alkaryle avec 1 à 36 atomes de carbone, un groupe alkoxy ou aryloxy avec 1 à 30 atomes de carbone, un groupe acyle avec 1 à 24 atomes de carbone, ainsi que des produits intermédiaires (II). X est un anion non-aryloxy pris dans le groupe composé de chlorure, d'acétate, de sulfate, de nitrate, de sulfonate, d'hydroxyde, d'oxyde, de carboxylate et de formate ; N est un entier compris entre 1 et 2 et (III) conduit à l'obtention des composés selon l'invention.
PCT/IB1998/002136 1998-12-30 1998-12-30 Salicylaldoximes et methode d'obtention WO2000040534A1 (fr)

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PCT/IB1998/002136 WO2000040534A1 (fr) 1998-12-30 1998-12-30 Salicylaldoximes et methode d'obtention
AU17768/99A AU1776899A (en) 1998-12-30 1998-12-30 Salicylaldoximes and method of preparation

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PCT/IB1998/002136 WO2000040534A1 (fr) 1998-12-30 1998-12-30 Salicylaldoximes et methode d'obtention

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103476837A (zh) * 2011-01-19 2013-12-25 巴斯夫欧洲公司 制备复合材料的方法
CN104230748A (zh) * 2014-11-04 2014-12-24 洛阳市三诺化工有限公司 一种铜萃取剂5-壬基水杨醛肟的合成工艺
CN104356025A (zh) * 2014-11-25 2015-02-18 泰兴市凌飞化工有限公司 一种5-壬基水杨醛肟的合成方法
CN104230748B (zh) * 2014-11-04 2017-01-04 洛阳市三诺化工有限公司 一种铜萃取剂5-壬基水杨醛肟的合成工艺

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5354920A (en) * 1992-08-20 1994-10-11 Zeneca Limited Chemical process for the preparation of a 2-hydroxyarylaldehyde
US5763675A (en) * 1993-07-08 1998-06-09 Zeneca Limited Process for the preparation of 2-hydroxyarylaldehydes under reduced pressure
US5856583A (en) * 1997-05-21 1999-01-05 Allco Chemical Corp. Synthesis of 2-hydroxyarylaldehydes

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5354920A (en) * 1992-08-20 1994-10-11 Zeneca Limited Chemical process for the preparation of a 2-hydroxyarylaldehyde
US5763675A (en) * 1993-07-08 1998-06-09 Zeneca Limited Process for the preparation of 2-hydroxyarylaldehydes under reduced pressure
US5856583A (en) * 1997-05-21 1999-01-05 Allco Chemical Corp. Synthesis of 2-hydroxyarylaldehydes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
ROBERT ALDRED ET AL.: "Magnesium-mediated ortho-Specific Formylation and Formaldoximation of Phenols", JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1, 1994 - 7 July 1994 (1994-07-07), CHEMICAL SOCIETY. LETCHWORTH., GB, pages 1823 - 1831, XP002110000 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103476837A (zh) * 2011-01-19 2013-12-25 巴斯夫欧洲公司 制备复合材料的方法
CN104230748A (zh) * 2014-11-04 2014-12-24 洛阳市三诺化工有限公司 一种铜萃取剂5-壬基水杨醛肟的合成工艺
CN104230748B (zh) * 2014-11-04 2017-01-04 洛阳市三诺化工有限公司 一种铜萃取剂5-壬基水杨醛肟的合成工艺
CN104356025A (zh) * 2014-11-25 2015-02-18 泰兴市凌飞化工有限公司 一种5-壬基水杨醛肟的合成方法

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