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WO2003066566A1 - Procede de production d'esters d'acide trans-3,3-dimethyl-2-formylcyclopropane carboxylique - Google Patents

Procede de production d'esters d'acide trans-3,3-dimethyl-2-formylcyclopropane carboxylique Download PDF

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Publication number
WO2003066566A1
WO2003066566A1 PCT/JP2003/000954 JP0300954W WO03066566A1 WO 2003066566 A1 WO2003066566 A1 WO 2003066566A1 JP 0300954 W JP0300954 W JP 0300954W WO 03066566 A1 WO03066566 A1 WO 03066566A1
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Prior art keywords
compound
dimethyl
methyl
hydroperoxy
formula
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PCT/JP2003/000954
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English (en)
Inventor
Naoyuki Takano
Koji Hagiya
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Sumitomo Chemical Company, Limited
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Priority to AU2003206131A priority Critical patent/AU2003206131A1/en
Publication of WO2003066566A1 publication Critical patent/WO2003066566A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/04—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom being acyclic
    • C07C409/06—Compounds containing rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to a process for the production of an aldehyde.
  • R is substituted or unsubstituted alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aralkyl, are very important compounds as the intermediates for the synthesis of pyrethroid-type household agents for epidemic prevention, pesticides, or the like (see, e.g., JP-B 46- 24695).
  • olefin compounds of formula (4) there have been known a process in which olefin compounds of formula (4):
  • R is as defined above
  • osmium te- troxide catalyst see, e.g., J. Labelled Compounds and Radiopharmaceuticals, 13, 561 (1977)
  • ozone-oxidized see, e.g., JP-B 46-24695.
  • osmium tetroxide is highly toxic, and the ozone oxidation method requires special equipment taking into account fire prevention; therefore, both cannot be said to be a fully satisfactory production process from an industrial point of view.
  • R is substituted or unsaturated alkyl, substituted or unsaturated aryl, or substituted or unsaturated aralkyl, in an industrially more advantageous manner, and have found the aldehyde of formula (2) can be obtained by reacting a diol compound of formula (1):
  • R is as defined above, without using highly toxic reagents or special equipment, thereby completing the present invention.
  • R is substituted or unsaturated alkyl, substituted or unsaturated aryl, or substituted or unsaturated aralkyl, which process comprises reacting a diol compound of formula (1):
  • R is as defined above, with an oxidizing agent selected from a periodic acid compound, a hypohalogenous acid compound, a bismuth compound, or an activated manganese dioxide.
  • diol (1) wherein R is substituted or unsaturated alkyl, substituted or unsaturated aryl, or substituted or unsaturated aralkyl.
  • R represents substituted or unsaturated alkyl, substituted or unsaturated aryl, or substituted or unsaturated aralkyl.
  • the substituted or unsaturated alkyl may include straight or branched chain, or cyclic alkyl groups of 1 to 20 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexa- decyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, cyclopropyl, 2,2-di- methylcyclopropyl, cyclopentyl, cyclohexyl, and menthyl, and alkyl groups substituted with
  • the substituted or unsubstituted aryl may include phenyl and naph- thyl groups, and phenyl and naphthyl groups substituted with a substi- tuent(s), such as the above-mentioned substituted or unsubstituted alkyl, aryl (e.g., phenyl or naphthyl), above-mentioned alkoxy, aralkyl (e.g., phen- ylalkyl such as benzyl or naphthylalkyl such as naphthylmethyl), the above- mentioned aryloxy, the above-mentioned aralkyloxy, and the above-mentioned halogen.
  • Specific examples of the substituted phenyl and naphthyl groups include, for example, 2-methylphenyl, 4-chlorophenyl, 4-methyl- phenyl, 4-methoxyphenyl, and 3-phenoxyphenyl.
  • the substituted or unsubstituted aralkyl may include those which are composed of the above-mentioned substituted or unsubstituted aryl group and the above-mentioned substituted or unsubstituted alkyl group, such as benzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-methoxybenzyl, 3-phen- oxybenzyl, 2,3,5,6-tetrafluorobenzyl, 2,3,5,6-tetrafruoro-4-methylbenzyl, 2,3,5,6-tetrafluoro-4-methoxybenzyl, and 2,3,5,6-tetrafluoro-4-methoxy- methylbenzyl.
  • Preferred is the unsubstituted alkyl.
  • the diol (1) may include methyl 3,3-dimethyl-2-(2-methyl-l,2-dihy- droxypropyl)cyclopropanecarboxylate, ethyl 3,3-dimethyl-2-(2-methyl-l,2-di- hydroxypropyl)cyclopropanecarboxylate, isopropyl 3,3-dimethyl-2-(2-methyl- l,2-dihydroxypropyl)cyclopropanecarboxylate, tert-butyl 3,3-dimethyl-2-(2- methyl- l,2-dihydroxypropyl)cyclopropanecarboxylate, cyclohexyl 3,3-di- methyl-2-(2-methyl-l,2-dihydroxypropyl)cyclopropanecarboxylate, menthyl 3,3-dimethyl-2-(2-methyl-l,2-dihydroxypropyl)cyclopropanecarboxylate, benzyl 3,3-dimethyl-2-
  • the diol (1) may exist in cis-form where the group of -CO 2 R and the 2-methyl-l,2-dihydroxypropyl group are present on the same side, relative to the cyclopropane ring plane, or in trans-form where these groups are present on the opposite sides, and either any one of them or a mixture of them may be used in the present invention. Further, the diol (1) contains asymmetric carbon atoms in the molecule and has optical isomers, and either individuals or mixtures of the optical isomers may be used in the present invention.
  • the diol (1) can be obtained, for example, by reacting a hydroperoxy compound of formula (3):
  • hydroperoxy compound (3) wherein R is as defined above; and one of X and Y is hydroxyl and the other is hydroperoxy, with the reducing agent as described below.
  • the hydroperoxy compound (3) may include methyl 3,3-dimethyl-2-
  • the hydroperoxy compound (3) contains asymmetric carbon atoms in the molecule and has optical isomers, and either individuals or mixtures of the optical isomers may be used in the present invention.
  • the reducing agent may include an inorganic reducing agent such as sodium thiosulfate, sodium borohydride, and sodium hydrosulfide; organic reducing agents such as dimethyl sulfide, diethyl sulfide, thiodiglycol, 2- mercaptoethanol, 2-(ethylthio)ethanol, and triphenylphosphine; and hydrogen/palladium catalyst, with the organic reducing agent being preferred.
  • the amount of reducing agent that may be suitably used is usually 1 mole, per mol of the hydroperoxy compound (3), and there is no particular upper limit thereof.
  • the amount of reducing agent that may be suitably used is usually not more than 5 moles, per mol of the hydroperoxy compound (3).
  • the reaction conditions such as reaction temperatures and reaction solvents in the reaction of the hydroperoxy compound (3) with a reducing agent may be suitably selected depending on the kind of reducing agent.
  • the reaction mixture may be subjected to concentration or column chromatography to isolate the diol (1) from the reaction mixture, and the isolated diol (1) may be used in the reaction with an oxidizing agent as described below.
  • water and/or a water-immiscible organic solvent may be added to the reaction mixture, followed by extraction, and the resulting organic layer containing the diol (1) may be used as such, or after concentration, in the reaction with an oxidizing agent as described below.
  • the reaction mixture obtained may also be used as such in the reaction with an oxidizing agent as described below.
  • the isolated diol (1) may be purified by ordinary means of purification, such as distillation and column chromatography, before use in the reaction with an oxidizing agent as described below.
  • the hydroperoxy compound (3) in trans-form is used, the diol in trans-form is obtained.
  • the hydroperoxy compound in cis-form is used, the diol in cis-form is obtained.
  • the optically active hydroperoxy compound is used, the optically active diol is obtained.
  • aldehyde (2) wherein R is as defined above, by oxidizing the diol (1).
  • the diol (1) obtained by reacting the above-mentioned hydroperoxy compound (3) with a reducing agent may be isolated from the reaction mixture obtained in the above reaction, or the reaction mixture may also be used as such.
  • the reducing agent remains in the reaction mixture, it is necessary to use an oxidizing agent in an sufficient amount to oxidize the remaining reducing agent. Therefore, it is preferred from an economical point of view that the diol (1) is separated or isolated from the reaction mixture for use in the present step or the reaction mixture is used after removal of the remaining reducing agent.
  • the oxidizing agent may include a periodic acid compound, a hypohalogenous acid compound, a bismuth compound, and activated manganese dioxide.
  • the periodic acid compound may include periodic acid and periodic acid alkali metal salts such as sodium periodate and potassium periodate.
  • the hypohalogenous acid compound may include hypohalogenous acid; hy- pohalogenous acid alkaline earth metal salts such as calcium hypochlorite; and hypohalogenous acid alkali metal salts such as sodium hypochlorite.
  • the bismuth compound may include pentavalent bismuth compounds such as triphenylbismuth carbonate, triphenyldichlorobismuth, ⁇ -oxobis(chloro- triphenylbismuth), and sodium bismuthate.
  • the activated manganese di- oxide can be obtained according to the known method in which manganese sulfate is reacted with potassium permanganate.
  • the amount of oxidizing agent that may be suitably used is usually 1 to 5 moles, preferably 1 to 3 moles, per mol of the diol (1).
  • the reaction mixture containing the diol (1) is used as such, and the reducing agent that may remain in the reaction mixture is usually oxidized with a sufficient amount of oxidizing agent.
  • the oxidizing agent may be used as such, or for example, as an aqueous solution.
  • the reaction of the diol (1) with the oxidizing agent is usually carried out by contacting and mixing both of them.
  • the reaction temperature is usually -10 to 100°C.
  • the present reaction is usually carried out in a solvent which dissolves the diol (1).
  • the solvent may include water; alcohol solvents such as methanol, ethanol, and tert-butyl alcohol; nitrile solvents such as acetonitrile and propionitrile; ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydro- furan; ester solvents such as ethyl acetate; aromatic hydrocarbon solvents such as toluene and xylene; and halogenated hydrocarbon solvents such as dichloromethane, dichloroe thane, chloroform, carbon tetrachloride, chloro- benzene, and dichlorobenzene.
  • the amounts for their use are not particu- larly limited. These solvents may be used alone or in combination.
  • the reaction mixture is subjected as such, or if necessary, after removal of insoluble matter by filtration, to concentration and/or column chromatography, if necessary, to isolate the aldehyde (2) from the reaction mixture.
  • water and/or the above-mentioned water-immiscible organic solvent is added to the reaction mixture, followed by extraction, and the resulting organic layer is subjected to concentration to isolate the aldehyde (2).
  • the isolated aldehyde (2) can be purified by means such as distillation and/or column chromatography.
  • the aldehyde (2) thus obtained may include methyl 3,3-dimethyl-2- formylcyclopropanecarboxylate, ethyl 3,3-dimethyl-2-formylcyclopropanecar- boxylate, isopropyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, tert-butyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2- formylcyclopropanecarboxylate, menthyl 3,3-dimethyl-2-formylcyclopro- panecarboxylate, benzyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, 4- chlorobenzyl 3,3-dimethyl-2-formylcyclopropanecarboxylate, 2,3,5,6-tetrafluorobenzyl 3,3-dimethyl-2-formylcyclopropanecarboxy
  • the hydroperoxy compound (3) can be obtained, for example, by reacting an olefin compound of formula (4):
  • olefin (4) wherein R is as defined above, with hydrogen peroxide in the presence of a metal oxide catalyst obtained by reacting at least one selected from the group consisting of tungsten metal, molybdenum metal; tungsten compounds comprising tungsten and an element of Group Illb, INb, Nb, or Nib; and molybdenum compounds comprising molybdenum and an element of Group Illb, INb, Nb, or Nib, with hydrogen peroxide.
  • a metal oxide catalyst obtained by reacting at least one selected from the group consisting of tungsten metal, molybdenum metal; tungsten compounds comprising tungsten and an element of Group Illb, INb, Nb, or Nib; and molybdenum compounds comprising molybdenum and an element of Group Illb, INb, Nb, or Nib, with hydrogen peroxide.
  • the olefin (4) may include methyl 3,3-dimethyl-2-(2-methyl-l-pro- penyl)cyclopropanecarboxylate, ethyl 3,3-dimethyl-2-(2-methyl-l-propenyl)- cyclopropanecarboxylate, isopropyl 3,3-dimethyl-2-(2-methyl-l-propenyl)- cyclopropanecarboxylate, tert-butyl 3,3-dimethyl-2-(2-methyl-l-propenyl)- cyclopropanecarboxylate, cyclohexyl 3,3-dimethyl-2-(2-methyl-l-propenyl)- cyclopropanecarboxylate, menthyl 3,3-dimethyl-2-(2-methyl-l-propenyl)- cyclopropanecarboxylate, benzyl 3,3-dimethyl-2-(2-methyl-l-propenyl)cyclo- propanecarbox
  • the olefin (4) may exist in cis-form where the group of-CO 2 R and the 2-methyl-l-propenyl group are present on the same side, relative to the cyclopropane ring plane, or in trans-form where these groups are present on the opposite sides, and either any one of them or a mixture of them may be used in the present invention. Further, the olefin (4) contains asymmetric carbon atoms in the molecule and has optical isomers, and either individuals or mixtures of the optical isomers may be used in the present invention.
  • the catalyst used in the reaction of olefin (4) with hydrogen peroxide is a metal oxide catalyst obtained by reacting at least one (hereinafter abbreviated the metal compound(s)) selected from the group consisting of tungsten metal, molybdenum metal; a tungsten compound comprising tungsten and an element of Group Illb, INb, Nb, or Nib; and a molybdenum compound comprising molybdenum and an element of Group Illb, INb, Nb, or Nib, with hydrogen peroxide.
  • the tungsten compound comprising tungsten and an element of Group Illb may include tungsten boride.
  • the tungsten compound comprising tungsten and an element of Group INb may include tungsten carbide and tungsten suicide.
  • the tungsten compound comprising tungsten and an element of Group Nb may include tungsten nitride and tungsten phosphide.
  • the tungsten compound comprising tungsten and an element of Group Nib may include tungsten oxide, tungstic acid, sodium tungstate, and tungsten sulfide.
  • the molybdenum compound comprising molybdenum and an element of Group Illb may include molybdenum boride.
  • the molybdenum compound comprising molybdenum and an element of Group INb may include molybdenum carbide and molybdenum suicide.
  • the molybdenum compound comprising molybdenum and an element of Group Nb may include molybdenum nitride and molybdenum phosphide.
  • the molybdenum compound comprising molybdenum and an element of Group Nib may include molybdenum oxide, molybdic acid, and molybdenum sulfide.
  • tungsten metal molybdenum metal, tungsten boride, molybdenum boride, tungsten sulfide, and molybdenum sulfide are preferred. These metal compounds may be used alone or in combination. The use of a metal compound of a fine particle is preferred in that it makes easier the preparation of a metal compound catalyst as a catalyst.
  • the hydrogen peroxide to be reacted with such metal or metal compound is usually used as an aqueous solution, but it may also be used as an organic solvent solution. From the viewpoint of easy handling, the use of an aqueous hydrogen peroxide solution is preferred.
  • the concentration of hydrogen peroxide in an aqueous solution or an organic solvent solution of hydrogen peroxide is not particularly limited, but taking into account volume efficiency and safety, it is usually 1 to 60 wt.%.
  • the aqueous hydrogen peroxide solution may usually be used as such a commercially available product, or if necessary, after concentration adjustment by dilution or concentration.
  • the organic solvent solution of hydrogen peroxide can be prepared, for example, by means such as extraction of an aqueous hydrogen peroxide solution with an organic solvent, or distillation in the presence of an organic solvent.
  • the reaction of the metal or metal compound with hydrogen peroxide is usually carried out in an aqueous solution.
  • an organic solvent such as an ether solvent (e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran), an ester solvent (e.g., ethyl acetate), an alcohol solvent (e.g., methanol, ethanol, tert-butanol), or a nitrile solvent (e.g., acetonitrile, propionitrile), or in a mixed solvent of such an organic solvent and water.
  • an ether solvent e.g., diethyl ether, methyl tert-butyl ether, tetrahydrofuran
  • an ester solvent e.g., ethyl acetate
  • an alcohol solvent e.g., methanol, ethanol, tert-butanol
  • a nitrile solvent e.g., acetonitrile, propionitrile
  • the amount of hydrogen peroxide that may be used in the preparation of the metal oxide catalyst is usually not less than 3 moles, preferably not less than 5 moles, per mol of the metal or metal compound, and there is no particular limit thereof.
  • the reaction of the metal or metal compound with hydrogen peroxide is usually carried out by mixing both of them, and to improve the contact efficiency of the metal or metal compound and hydrogen peroxide, the reaction is preferably carried out while stirring so that the metal or metal compound can sufficiently disperse in the solution for the preparation of the metal oxide catalyst. From the viewpoints of an increase in the contact efficiency of the metal or metal compound and hydrogen peroxide and easier control in the preparation of the metal oxide catalyst, it is preferred to use the metal or metal compound with a fine particle diameter, such as a powdered metal or metal compound.
  • the temperature in the preparation of the metal oxide catalyst is usually -10°C to 100°C.
  • the reaction of the metal or the metal compound with hydrogen per- oxide in water or in an organic solvent makes all or some of the metal or metal compound dissolved, so that a uniform solution or suspension containing the metal oxide catalyst can be prepared.
  • the metal oxide catalyst may be isolated from the solution for the preparation, for example, by concentration, and used as a catalyst, or the solution for the preparation may be used as a catalyst solution without treatment.
  • the reaction of olefin (4) with hydrogen peroxide in the presence of the metal oxide catalyst thus obtained gives hydroperoxy compound (3).
  • the amount of metal oxide catalyst used as a catalyst is usually not less than 0.001 mole, per mol of the olefin (4), and there is no particular upper limit thereof. From an economical point of view, the amount of metal oxide catalyst used is not more than 1 mole, per mol of the olefin (4).
  • the hydrogen peroxide is usually used as an aqueous solution.
  • an organic solvent solution of hydrogen peroxide may be used.
  • concentration of hydrogen peroxide in an aqueous solution or an organic solvent solution of hydrogen peroxide is not particularly limited, but taking into account volume efficiency and safety, it is usually 1 to 60 wt.%.
  • the aqueous hydrogen peroxide solution may usually be used as such a com- shoutally available product, or if necessary, after concentration adjustment by dilution or concentration.
  • the organic solvent solution of hydrogen peroxide can be prepared, for example, by means such as extraction of an aqueous hydrogen peroxide solution with an organic solvent, or distillation in the presence of an organic solvent.
  • the amount of hydrogen peroxide used is usually not less than 1 mole, per mol of the olefin (4), and there is no particular upper limit thereof. From an economical point of view, the amount of hydrogen peroxide used is usually not more than 10 moles, per mol of the olefin (4).
  • the amount of hydrogen peroxide used may be set in addition to the amount of hydrogen peroxide contained in the solution for the preparation.
  • the reaction of the olefin (4) with hydrogen peroxide is usually carried out in an aqueous solvent or in an organic solvent.
  • the organic solvent may include ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran; ester solvents such as ethyl acetate; alcohol solvents such as methanol, ethanol, and tert-butanol; and nitrile solvents such as acetonitrile and propionitrile.
  • the amount of aqueous or organic solvent used is not particularly limited, but taking into account volume efficiency, it is not more than 100 parts by weight, per 1 part by weight of the olefin (4).
  • the reaction of olefin (4) with hydrogen peroxide gives the hydroperoxy compound (3), but in addition to the hydroperoxy compound (3), for example, the products as the further oxidized hydroperoxy compound (3) are also formed as minor by-products.
  • Lower water content in the reaction system has a tendency to selectively provide the hydroperoxy compound (3), and therefore, it is preferred that the reaction is carried out under the conditions that the water content in the reaction system is low.
  • the method for carrying out the reaction under low water content conditions may include coexistence with a desiccant in the reaction system.
  • the desiccant may include anhydrous magnesium sulfate, anhydrous sodium sulfate, anhydrous boric acid, and polyphosphoric acid.
  • Too high reaction temperature increases the formation of the further oxidized hydroperoxy compound (3) as by-products, and therefore, for selectively obtaining the hydroperoxy compound (3), it is preferred that the reaction is carried out in the range of 0°C to 65°C, while monitoring the conversion of the olefin (4).
  • reaction of olefin (4) with hydrogen peroxide is usually carried out under normal pressure conditions, but it may also be carried out under pressurized conditions
  • the reaction mixture is subjected, for example, to extraction, phase separation and/or concentration, and column chromatog- raphy, if necessary, so that the hydroperoxy compound (3) can be isolated from the reaction mixture.
  • water and/or a water-immiscible organic solvent is added to the reaction mixture, followed by extraction, and the resulting organic layer is subjected to concentration, so that the hydroperoxy compound (3) can also isolated.
  • the isolated hydroperoxy compound (3) can be purified by ordinary means of purification, such as distillation.
  • the water-immiscible organic solvent may include aromatic hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon sol- vents such as dichloromethane, chloroform, and chlorobenzene; ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran; and ester solvents such as ethyl acetate.
  • aromatic hydrocarbon solvents such as toluene and xylene
  • halogenated hydrocarbon sol- vents such as dichloromethane, chloroform, and chlorobenzene
  • ether solvents such as diethyl ether, methyl tert-butyl ether, and tetrahydrofuran
  • ester solvents such as ethyl acetate.
  • the amount for their use are not particularly limited.
  • Example 1 The present invention will hereinafter be further illustrated by the following Examples; however, the present invention is not limited to these Examples.
  • the analysis was carried out by gas chromatography (herein- after abbreviated as GC) and high-pressure liquid chromatography (hereinafter abbreviated as LC).
  • GC gas chromatography
  • LC high-pressure liquid chromatography
  • the reaction mixture was concentrated under reduced pressure conditions to give about 90 g of concentrated residue.
  • To the concentrated residue was added 40 g of toluene and then added dropwise 70 g of 15 wt.% aqueous sodium periodate solution at an internal temperature of 0°C over 10 minutes. After stirring at the same temperature for 1 hour and holding to effect reaction, insoluble matter was removed by filtration. The resulting filtrate was subjected to phase separation to give 140 g of the organic layer containing methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate. The content for methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate: 5 wt.%.
  • a 300-mL flask equipped with a stirrer and a reflux condenser was charged with 15 g of water and 2 g of tungsten metal powder, to which 7.4 g of 60 wt.% aqueous hydrogen peroxide solution was added dropwise at an internal temperature of 40°C while stirring over 20 minutes, followed by stirring at the same temperature for 1 hour to effect reaction, giving a uniform solution.
  • To the solution was added 1.4 g of boric acid, and the mixture was stirred at an internal temperature of 40°C for 1 hour and held, followed by cooling to room temperature and addition of 76 g of tert-butyl alcohol and 2 g of 60 wt.% aqueous hydrogen peroxide solution.
  • LC corrected percentage area for the total of methyl trans-3,3-dimethyl-2-(l- hydroxy-2-hydroperoxy-2-methylpropyl)cyclopropanecarboxylate and methyl trans-3,3-dimethyl-2-(2-hydroxy-l-hydroperoxy-2-methylpropylcyclopro- panecarboxylate was 78%.
  • methyl trans-3,3-di- methyl-2-(l,2-dihydroxy-2-methylpropyl)cyclopropanecarboxylate was contained at 17% (the value of LC corrected percentage area).
  • the resulting filtrate was subjected to phase separation to give 147 g of the organic layer containing methyl trans-3,3-dimethyl-2-formylcyclopropanecarboxylate.
  • the GC analysis of the organic layer showed that the content for methyl trans-3,3-di- methyl-2-formylcyclopropanecarboxylate was 5.2 wt.% and the yield of methyl trans-3,3-diemthyl-2-formylcyclopropanecarboxylate on the basis of methyl trans-3,3-dimethyl-2-(2-methyl-l-propenyl)cyclopropanecarboxylate was 89%.

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Abstract

L'invention concerne un procédé de production d'un aldéhyde de formule (2), dans laquelle R représente un alkyle substitué ou non substitué, un aryle substitué ou non substitué, ou un aralkyle substitué ou non substitué. Ce procédé consiste à faire réagir un composé diol de formule (1), dans laquelle R est tel que défini ci-dessus, avec un agent oxydant choisi parmi un composé d'acide iodique, un composé d'acide hypohalogène, un composé de bismuth ou un dioxyde de manganèse activé.
PCT/JP2003/000954 2002-02-08 2003-01-31 Procede de production d'esters d'acide trans-3,3-dimethyl-2-formylcyclopropane carboxylique WO2003066566A1 (fr)

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AU2003206131A AU2003206131A1 (en) 2002-02-08 2003-01-31 Process for the production of trans-3,3-dimethyl-2-formlcyclopropane carboxylic acid esters

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004087633A1 (fr) * 2003-03-31 2004-10-14 Sumitomo Chemical Company, Limited Procede de production d'un compose aldehyde
EP1609776A1 (fr) * 2003-03-31 2005-12-28 Sumitomo Chemical Company, Limited Proc d de production de compos s carbonyle

Citations (4)

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Publication number Priority date Publication date Assignee Title
WO2004087633A1 (fr) * 2003-03-31 2004-10-14 Sumitomo Chemical Company, Limited Procede de production d'un compose aldehyde
EP1609776A1 (fr) * 2003-03-31 2005-12-28 Sumitomo Chemical Company, Limited Proc d de production de compos s carbonyle
EP1609776A4 (fr) * 2003-03-31 2006-09-06 Sumitomo Chemical Co Proc d de production de compos s carbonyle
US7304185B2 (en) 2003-03-31 2007-12-04 Sumitomo Chemical Company, Limited Process for production of carbonyl compounds

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