WO2000035553A1 - Procede de separation d'un compose metallique du groupe iii ou iv - Google Patents

Procede de separation d'un compose metallique du groupe iii ou iv Download PDF

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Publication number
WO2000035553A1
WO2000035553A1 PCT/JP1999/007044 JP9907044W WO0035553A1 WO 2000035553 A1 WO2000035553 A1 WO 2000035553A1 JP 9907044 W JP9907044 W JP 9907044W WO 0035553 A1 WO0035553 A1 WO 0035553A1
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WO
WIPO (PCT)
Prior art keywords
compound
acid
group
metal
alkoxide
Prior art date
Application number
PCT/JP1999/007044
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English (en)
Japanese (ja)
Inventor
Hideo Hashimoto
Tadashi Fukui
Tadashi Hanaoka
Original Assignee
Takeda Chemical Industries, Ltd.
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 Takeda Chemical Industries, Ltd. filed Critical Takeda Chemical Industries, Ltd.
Priority to AU16862/00A priority Critical patent/AU1686200A/en
Publication of WO2000035553A1 publication Critical patent/WO2000035553A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles

Definitions

  • the present invention relates to a method for separating an organic compound exhibiting lipophilicity at a pH region higher than PH2 and a metal compound belonging to Group III or IV, and is particularly applied to the separation and purification of a target compound in the field of synthesis of organic compounds. Things. Background art
  • Alkoxides of Group II or Group IV metals in the short-periodic periodic table are often used in organic synthesis reactions. However, at the end of the reaction, an operation of decomposing with addition of water is performed in order to invalidate the effect.
  • the metal compound formed by this decomposition is soluble in water under strongly acidic conditions of less than pH 2, but is generally insoluble in both water and organic solvents under conditions of pH 2 or more.
  • some of the target compounds in the chemical reaction show lipophilicity in the pH range higher than any pH of 2 or more, but show hydrophilicity or non-hydrophilicity under strongly acidic conditions below any pH. Some are stable.
  • the solvent is used as an extraction solvent under conditions of pH 2 or more. Addition of an oily organic solvent is performed.
  • the compound of the metal formed by the decomposition of the metal alkoxide cannot be separated by liquid separation because it is present as fine particles in both the aqueous layer and the lipophilic organic solvent layer, and the separation by filtration requires a long time. It was very disadvantageous industrially. Disclosure of the invention
  • the present invention provides an industrially advantageous method for separating a target compound from a Group II, Group IV metal compound under a condition of pH 2 or more.
  • any organic compound having a pH of 2 or more can be obtained by an organic synthesis reaction using an alkoxide of a Group III or Group IV metal in the short periodic table.
  • an organic compound exhibiting lipophilicity in the pH range higher than the above value is synthesized, at the end of the reaction, the pH of the aqueous layer together with the lipophilic organic solvent for extraction and water is adjusted to the pH within the range where the target compound exhibits lipophilicity.
  • a polybasic carboxylic acid a carboxylic acid having a plurality of carboxylic acid groups
  • it is insoluble in both water and lipophilic organic solvents, even when the liquidity is pH 2 or higher. It was found that the target compound was distributed to the organic layer, and the Group III and Group IV metal compounds were distributed to the aqueous layer, thereby completing the present invention.
  • solution II A solution containing an organic compound exhibiting lipophilicity in a pH range higher than pH 2 and an alkoxide of a Group III or Group IV metal in the short-periodic periodic table (hereinafter referred to as “solution II”).
  • lipophilic organic solvent 4 a lipophilic organic solvent (hereinafter referred to as lipophilic organic solvent 4) is further added during mixing.
  • the lipophilic organic solvent 4 is a halogenated hydrocarbon having 1 to 2 carbon atoms, an ether having 2 to 6 carbon atoms, a lower alkyl ester of a lower aliphatic carboxylic acid, or an aromatic carbonization having 6 to 8 carbon atoms. Hydrogens, aliphatic hydrocarbons having 5 to 7 carbon atoms, alicyclic hydrocarbons having 5 to 7 carbon atoms, a mixed solvent of two or more of these, or a mixture of these solvents and other solvents.
  • Polybasic carboxylic acid 3 is oxalic acid, malonic acid, konoic acid, oxalic acid, daltaric acid, adipic acid, maleic acid, fumaric acid, fumaric acid, isophthalic acid, terephthalic acid, citric acid Or the method according to the above (1), which is a mixture of two or more of these,
  • Ar represents a phenyl group optionally substituted with halogen
  • X represents a lower alkylene group
  • (R) represents a steric configuration
  • the alkoxide of a Group II or Group IV metal in the short-periodic table is an alkoxide of titanium
  • the polybasic carboxylic acid 3 is a di- or tricarboxylic acid having 2 to 8 carbon atoms.
  • the lipophilic organic solvent ⁇ is a lower alkyl ester of a lower aliphatic carboxylic acid
  • solution I A solution containing an organic compound exhibiting lipophilicity and an alkoxide of a Group III or Group IV metal in the short-periodic periodic table (hereinafter referred to as solution I) is mixed with water II and polybasic rubonic acid 3.
  • a method for separating the organic compound and the metal compound wherein the method comprises transferring the metal compound to an aqueous layer;
  • a reaction mixture containing the compound represented by the formula, water2, a di- or tricarboxylic acid having 28 carbon atoms and a lipophilic organic solvent4 are mixed, and the titanium compound is transferred to an aqueous layer.
  • a method for producing the compound represented by (I) is described in detail below.
  • titanium alkoxide is titanium (IV) methoxide, titanium (IV) ethoxide, titanium (IV) propoxide, titanium (IV) isopropoxide or titanium (IV) butoxide.
  • the lipophilic organic compound is an organic compound that is more soluble in a lipophilic organic solvent than in water. Whether the organic compound is more soluble in water or the lipophilic organic solvent is determined by adding the organic compound to an equal volume of water and the lipophilic organic solvent, mixing the mixture, and then allowing the mixture to stand. Can be determined by measuring the amount of the organic compound contained in each of the above. In this case, the conditions such as the temperature may be adjusted to the conditions for actually implementing the present invention.
  • the above-mentioned organic compound exhibiting lipophilicity in a pH region higher than pH 2 is a compound which is more soluble in a lipophilic organic solvent than water in a pH region higher than an arbitrary pH value higher than 2 in water.
  • Lipophilic organic solvent in the pH range below any pH value Ricoh refers to an organic compound that is soluble in water in large quantities or decomposed partly or entirely.
  • examples of such a compound include organic compounds having a basic substituent, for example, an amino group which may be substituted (eg, an alkylamino group such as methylamino, ethylamino, propylamino, and butylamino, and an acylamino group such as acetylamino, propioamino, and propylamino).
  • a heterocyclic group having an optionally substituted nitrogen atom eg, optionally substituted pyridyl, pyrimidinyl, triazinyl, pyrrolyl, diazolyl, triazolyl, oxazolyl, oxaziazolyl, imidazolyl, imidazolidinyl, etc.
  • an organic compound having the following group eg, an organic compound having the following group.
  • the compound represented by the formula (I) is also an example.
  • (2R, 3R) -2- (2,4-difluorophenyl) -3- [N- (2-hydroxyethyl) amino]- 1- (1H-1,2,4-triazol-1-yl) -2-butanol is lipophilic above pH 3 and hydrophilic below pH 3.
  • Alkoxides of Group III or Group IV metals in the short-periodic table include, for example, Group III metals such as aluminum, scandium and gallium or Group IV metals such as titanium, germanium, zirconium, tin and namari.
  • Alkoxides of metals for example, alkoxides having 1 to 5 carbon atoms such as methoxide, ethoxide, propoxide, isopropoxide, butoxide, isobutoxide, t-butoxide, sec-butoxide).
  • alkoxides of titanium, zirconium or aluminum are preferred.
  • titanium alkoxides such as, for example, titanium (IV) methoxide, titanium (IV) butoxide, titanium diisopropoxide bis (2,4-pentanedionate), and titanium (IV).
  • titanium (IV) methoxide titanium (IV) butoxide
  • titanium diisopropoxide bis (2,4-pentanedionate) titanium (IV).
  • Ethoxide titanium (IV) 2-ethylhexoxide
  • titanium (IV) isopropoxide titanium (IV) propoxide and the like.
  • the solution 1 may contain other substances in addition to the organic compound and the metal alkoxide.
  • This solution is usually a reaction mixture in organic synthesis, which contains the organic compound and the alkoxide of the metal, as well as unreacted raw materials, catalyst, ⁇ (J products, decomposition products, organic solvents, etc.) .
  • the amount of water used is not particularly limited.
  • the amount is usually 0.1 to 100 L (liter), preferably 0.5 to 50 L (liter), per 1 mol of the alkoxide of the Group IV metal.
  • Polybasic liponic acid 3 refers to liponic acid having a plurality of lipoxyl groups in one molecule. Specific examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. Dicarboxylic acid having 2 to 8 carbon atoms such as maleic acid, fumaric acid, fumaric acid, isofluoric acid, terephthalic acid, and tricarboxylic acid having 6 to 10 carbon atoms such as citric acid. Among them, di- or tricarboxylic acids having 2 to 8 carbon atoms such as oxalic acid and citric acid are preferred. Also, a mixture of two or more of these may be used.
  • the amount of the polybasic carboxylic acid 3 used is usually 0.2 to 20 mol, preferably 0.5 to 0.5 mol, per mol of the alkoxide of the Group III or Group IV metal in the short-periodic periodic table. Is a mole.
  • the lipophilic organic solvent must be contained in the mixture when the metal compound is transferred to the aqueous layer.
  • solution (1) already contains lipophilic organic solvent (2), only water (2) and polybasic carboxylic acid (3) need to be added, but solution (2) contains lipophilic organic solvent (2). If not, you need to add it.
  • the lipophilic organic solvent 4 may be any solvent which can be separated from water, for example, halogenated hydrocarbons having 1 to 2 carbon atoms such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, etc.
  • C2-C6 ethers such as getyl ether, diisopropyl ether, dimethylene glycol dimethyl ether, and diethylene glycol getyl ether; C1-C3 lower aliphatic carboxylic acids such as methyl acetate, ethyl acetate, propyl acetate, and butyl acetate C1-C4 lower alkyl esters of acids, C6-C8 aromatic hydrocarbons such as benzene, toluene and xylene; C5-C7 alicyclic hydrocarbons such as cyclohexane, pentane Solvents such as aliphatic hydrocarbons having 5 to 7 carbon atoms, such as hexane, hexane and heptane.
  • Lower alkyl esters of lower aliphatic carboxylic acids are preferred.
  • Preferred specific examples of the lipophilic organic solvent include benzene, chloroform, carbon tetrachloride, dichloroethane, dichloromethane, dimethyl ether, diisopropyl ether, ethyl acetate, hexane, pentane, toluene and xylene.
  • a mixed solvent of two or more of these, or a mixed solvent of these solvents and other solvents may be used.
  • the amount of the lipophilic organic solvent to be used is not particularly limited, but is from 0.01 to: L 0 0 L (liter) per mole of the alkoxide of the Group II or Group IV metal in the short-periodic periodic table. Preferably, it is 0.1 to 50 L (liter).
  • L 0 0 L (liter) per mole of the alkoxide of the Group II or Group IV metal in the short-periodic periodic table Preferably, it is 0.1 to 50 L (liter).
  • an alkoxide of a Group II or Group IV metal in the short-periodic table is decomposed by contact with water. Due to this decomposition, the alkoxide of the Group II or Group IV metal in the Short Periodic Table is probably an oxide of the Group II or Group IV metal in the Short Periodic Table. In the present invention, this refers to a compound of a Group II or Group IV metal in the short-periodic periodic table. In the separation method of the present invention, the order of mixing these may be any order.
  • a lipophilic organic solvent is newly mixed, for example, a solution is mixed with water and water, and then a polybasic carboxylic acid and lipophilic organic solvent are sequentially mixed.
  • a mixture of solution 2, lipoic acid 3 and lipophilic organic solvent 2 with water ⁇ , a mixture of solution 1 and lipophilic organic solvent 2 with water 2 and polybasic A method of mixing a part of the carboxylic acid 3 and then sequentially mixing the water 2 and the rest of the polybasic carboxylic acid 3 can be mentioned.
  • an organic compound which exhibits hydrophilicity at an arbitrary pH lower than an arbitrary pH higher than pH 2 is used, but is intended to separate an unstable organic compound at an arbitrary pH lower than the arbitrary pH.
  • the amount of polybasic ruponic acid 3 is p The range is such that H does not fall below the arbitrary pH.
  • a basic compound may be used together with the polybasic force ruponic acid 3 to maintain the pH of the aqueous layer at a pH at which the target compound shows lipophilicity.
  • an inorganic base such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, or the like, or an organic base such as triethylamine or pyridine may be added.
  • an organic base such as triethylamine or pyridine
  • the pH of the solution containing the target compound was high, and even if the required amount of polybasic liponic acid 3 was added, it was not necessary to add these if the target compound had a lipophilic pH.
  • the pH when the purpose is to separate an organic compound that is stable but hydrophilic under a condition of an arbitrary pH value higher than pH 2 but lower than pH 2, the pH temporarily decreases during mixing. After mixing, the pH may be set to a pH region higher than the arbitrary pH value.
  • the organic compound is stirred for a while in the ⁇ region where the organic compound exhibits lipophilicity in the ⁇ region higher than the ⁇ value of the above, the compound of the metal, which is a decomposition product of the alkoxide of the metal, migrates to the aqueous layer if left standing.
  • a lipophilic organic solvent layer containing an organic compound showing lipophilicity in a pH region higher than any pH value higher than ⁇ 2, and an aqueous layer containing a decomposition product of the above-mentioned metal alkoxide.
  • ⁇ and the amount of the lipophilic organic solvent are small, they may not separate into two layers. In this case, add both water and / or the lipophilic organic solvent, stir and allow to stand. It can be separated into layers. If the alkoxide decomposition product remains as an insoluble material, polybasic carboxylic acid 3 may be added. When fine particles of the metal compound remain in the lipophilic organic solvent layer, the same operation may be repeated by further adding water (2) and polybasic carboxylic acid (3).
  • the target compound containing no or almost no fine particles of the metal compound (the lipophilicity in a pH region higher than ⁇ 2) is obtained.
  • the target compound can be obtained from the lipophilic organic solvent layer containing the target compound by a usual method, for example, separation, concentration, distillation, crystallization, or a combination thereof. Can be.
  • the present invention is generally applied to separation and purification of a target compound at the end of an organic synthesis reaction.
  • a compound represented by the formula (I) as a target compound is prepared from a reaction solution obtained by reacting a compound represented by the formula (II) with a compound represented by the formula (III) in the presence of a titanium alkoxide. It can be used for separation and purification. This reaction is usually performed in a solvent-free or organic solvent.
  • the phenyl group which may be substituted by the octogen represented by Ar may be substituted by, for example, one or two of fluorine, chlorine, bromine, iodine and the like.
  • examples thereof include 2,4-difluorophenyl, 2,4-dichlorophenyl, 4-chlorophenyl, 4-fluorophenyl, 2-chlorophenyl, 2-fluorophenyl, and 2-fluorophenyl.
  • Preferable phenyl, 2-chloro-4-fluorophenyl, 4-bromophenyl and the like are preferable, and among them, 2-fluorophenyl and 2,4-difluorophenyl are particularly preferable.
  • examples of the lower alkylene represented by X include a methylene chain having 1 to 4 carbon atoms such as methylene, ethylene and propylene.
  • organic solvent examples include methanol, ethanol (including various denatured ethanols), 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, Alcohols such as -methyl-2-propanol, ethylene glycol, methylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, halogens such as dichloromethane, chloroform, carbon tetrachloride, dichloroethylene, etc.
  • Hydrocarbons such as tetrahydrofuran, dioxane, geethylether, diisopropyl ether, dimethyleneglycoldimethylether, and dimethyleneglycolether, aromatic hydrocarbons such as benzene, toluene, and xylene Hydrogens, ketones such as acetone and ethyl methyl ketone, nitriles such as acetonitrile and benzonitrile, hydrocarbons such as cyclohexane, hexane, heptane and pentane, dimethylformamide, dimethylsulfoxide, dimethyla Aprotic polar solvents such as cetamide and hexamethylphosphoric triamide; and nitrogen-containing aromatics such as pyridine.
  • a mixed solvent of two or more of these, or a mixture of these solvents and other solvents May be used as a mixed solvent.
  • a solvent-free solution may be used. There is no particular limitation on the amount
  • reaction temperature is suitably about 40 to 200 ° C, preferably about 70 to 180 ° C. Reaction times of about 1 to 80 hours are suitable, and about 5 to 50 hours are preferred.
  • the compound represented by the formula (III) is used in a larger amount than the compound represented by the formula (I) to increase the reaction rate. Therefore, the reaction mixture contains the unreacted compound represented by the formula (III) and is basic, and in this case, it may not be necessary to add a base. To this is added a di- or tricarboxylic acid having 2 to 8 carbon atoms and a lipophilic organic solvent 4.
  • a di- or tricarboxylic acid having 2 to 8 carbon atoms and a lipophilic organic solvent 4.
  • the target compound and the metal compound can be separated only by a simple liquid separation operation, which is advantageous for industrially producing the target compound.
  • the precipitated particulate compound was removed by filtration (using a filter paper on which a filter aid was placed), and washed with 1 Oml of ethyl acetate. The filtrate and the washing were separated. 25 ml of saturated aqueous sodium hydrogen carbonate was added to the organic layer. The precipitated fine particles of the compound were removed by filtration (using a filter paper on which a filter aid was placed), and washed with 10 ml of ethyl acetate. The filtrate and the washing were separated. 25 ml of a 0.001 N aqueous sodium hydroxide solution was added to the organic layer.
  • the precipitated particulate compound was filtered off (using a filter paper on which a filter aid was placed), and washed with ethyl acetate 1 Om1. The filtrate and the washing were separated. 25 ml of a 0.001N aqueous sodium hydroxide solution was added to the organic layer. The precipitated particulate compound was filtered off (using a filter paper on which a filter aid was placed) and washed with 10 ml of ethyl acetate. The filtrate and the washing were separated. 25 ml of a 0.001N aqueous sodium hydroxide solution was added to the organic layer, and the mixture was separated. The organic layer was washed with 25 ml of water.
  • the decomposition of the alkoxide of a Group III or Group IV metal with water in the short-periodic periodic table can be separated from the organic compound by a simple liquid separation operation, which is advantageous for industrially producing the target compound. is there.

Abstract

L'invention concerne un procédé qui comporte l'étape consistant à mélanger (1) une solution contenant un composé organique oléophile à des pH supérieurs à 2, et un alcoxyde d'un métal du groupe III ou IV de la classification périodique simplifiée des éléments, avec (2) de l'eau et (3) un acide carboxylique polybasique afin de transférer le composé métallique vers la couche aqueuse. De cette manière, le composé métallique peut être facilement séparé du composé organique. Ce procédé est avantageux d'un point de vue industriel.
PCT/JP1999/007044 1998-12-16 1999-12-15 Procede de separation d'un compose metallique du groupe iii ou iv WO2000035553A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU16862/00A AU1686200A (en) 1998-12-16 1999-12-15 Method of separating compound of group iii or iv metal

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP35811398 1998-12-16
JP10/358113 1998-12-16

Publications (1)

Publication Number Publication Date
WO2000035553A1 true WO2000035553A1 (fr) 2000-06-22

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WO (1) WO2000035553A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002006159A1 (fr) * 2000-07-17 2002-01-24 Industrial Research Limited Materiaux contenant du titane

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0558997A (ja) * 1991-09-04 1993-03-09 Mitsubishi Kasei Corp チオカルバモイルアセトニトリル誘導体
JPH09201501A (ja) * 1995-11-01 1997-08-05 Union Carbide Chem & Plast Technol Corp 液状炭化水素からの重金属アルコキシド化合物の除去方法
JPH1036357A (ja) * 1996-07-25 1998-02-10 Mitsubishi Kagaku Kk トリアゾール誘導体並びにそれを含有する農園芸用殺菌剤

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0558997A (ja) * 1991-09-04 1993-03-09 Mitsubishi Kasei Corp チオカルバモイルアセトニトリル誘導体
JPH09201501A (ja) * 1995-11-01 1997-08-05 Union Carbide Chem & Plast Technol Corp 液状炭化水素からの重金属アルコキシド化合物の除去方法
JPH1036357A (ja) * 1996-07-25 1998-02-10 Mitsubishi Kagaku Kk トリアゾール誘導体並びにそれを含有する農園芸用殺菌剤

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002006159A1 (fr) * 2000-07-17 2002-01-24 Industrial Research Limited Materiaux contenant du titane

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