JP6425980B2 - Process for producing corresponding ketone compounds from ketoxime alkali metal salts or ketoxime alkaline earth metal salts - Google Patents
Process for producing corresponding ketone compounds from ketoxime alkali metal salts or ketoxime alkaline earth metal salts Download PDFInfo
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- -1 ketone compounds Chemical class 0.000 title claims description 73
- 229910052784 alkaline earth metal Inorganic materials 0.000 title claims description 35
- 229910052783 alkali metal Inorganic materials 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 23
- 150000001875 compounds Chemical class 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 14
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 239000003799 water insoluble solvent Substances 0.000 claims description 7
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 230000003301 hydrolyzing effect Effects 0.000 claims description 4
- 125000003944 tolyl group Chemical group 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- 125000003831 tetrazolyl group Chemical group 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000002904 solvent Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000844 anti-bacterial effect Effects 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000006460 hydrolysis reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000007062 hydrolysis Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 4
- 229910001617 alkaline earth metal chloride Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003021 water soluble solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000001747 exhibiting effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 238000006146 oximation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DFOFVBAIHWDCNO-UHFFFAOYSA-N (1-methyltetrazol-5-yl)-phenylmethanone Chemical compound CN1N=NN=C1C(=O)C1=CC=CC=C1 DFOFVBAIHWDCNO-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Description
本発明はケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩から対応するケトン化合物を高効率で製造する方法に関する。 The present invention relates to a process for the highly efficient preparation of the corresponding ketone compounds from ketoxime alkali metal salts or ketoxime alkaline earth metal salts.
一部のケトキシム化合物は高い殺菌効果を示す。係るケトキシム化合物を有効成分とする植物病害防除剤が提案されている（特許文献１）。
特許文献１などに開示されているケトキシム化合物にはＥ体とＺ体の二種の異性体が存在する。いずれの異性体も殺菌効果を有するが、一方の異性体が他方の異性体より殺菌効果が高いこともある。そのような場合、効果の低い方の異性体を除去して、効果の高い方の異性体だけを分取することが行われる。例えば、特許文献１においては、晶析によってＺ体を析出させて、析出物を分取している。
Some ketoxime compounds exhibit high bactericidal effects. There has been proposed a plant disease control agent comprising such a ketoxime compound as an active ingredient (Patent Document 1).
In the ketoxime compounds disclosed in Patent Document 1 and the like, two isomers of an E form and a Z form exist. Either isomer has a bactericidal effect, but one isomer may be more bactericidal than the other. In such a case, the less effective isomer is removed and only the more effective isomer is fractionated. For example, in Patent Document 1, the Z-form is precipitated by crystallization to separate the precipitate.
分取後の残渣には効果の低い方の異性体と分取しきれなかった若干量の効果の高い方の異性体が含まれている。このようなケトキシム異性体混合物から所望の化合物を回収して目的異性体の製造に再利用することが、製造コストの低減のために望まれる。 The residue after the separation contains the less effective isomer and a small amount of the more potent isomer that could not be separated. Recovering the desired compound from such a ketoxime isomer mixture and reusing it for the production of the desired isomer is desirable for reducing the production cost.
回収の方法として、(1)ケトキシム異性体混合物をアルカリ金属塩化若しくはアルカリ土類金属塩化してケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩の異性体混合物を得、 (2)晶析によって難溶性のケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩異性体を易溶性のケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩異性体から分離し、 (3)易溶性のケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩異性体を加水分解してケトン化合物を得、 (4)得られたケトン化合物をオキシム化することを含むものがある。 As a method of recovery, (1) alkali metal chloride or alkaline earth metal chloride of ketoxime isomer mixture to obtain an isomer mixture of ketoxime alkali metal salt or ketoxime alkaline earth metal salt, (2) by crystallization A poorly soluble ketoxime alkali metal salt or ketoxime alkaline earth metal salt isomer is separated from a readily soluble ketoxime alkali metal salt or ketoxime alkaline earth metal salt isomer, and (3) a readily soluble ketoxime alkali There is one including hydrolysis of a metal salt or ketoxime alkaline earth metal salt isomer to obtain a ketone compound, and (4) oximation of the obtained ketone compound.
ケトキシム異性体混合物から所望の化合物を回収するための過程の中間においてケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩から対応するケトン化合物に転化する(step(3))必要がある。
本発明の課題は、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩から対応するケトン化合物を効率的に製造する方法を提供することである。
It is necessary to convert the ketoxime alkali metal salt or ketoxime alkaline earth metal salt to the corresponding ketone compound (step (3)) in the middle of the process for recovering the desired compound from the ketoxime isomer mixture.
An object of the present invention is to provide a method for efficiently producing the corresponding ketone compound from ketoxime alkali metal salt or ketoxime alkaline earth metal salt.
上記課題を解決すべく、鋭意検討した結果、以下の形態を包含する本発明を完成するに至った。 As a result of earnestly examining in order to solve the said subject, it came to complete this invention including the following form.
〔１〕 塩酸の存在下、非水溶性溶媒中にて、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩を、加水分解することを含む、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩から対応するケトン化合物を製造する方法。 [1] A ketoxime alkali metal salt or ketoxime alkaline earth metal comprising hydrolyzing a ketoxime alkali metal salt or ketoxime alkaline earth metal salt in a non-aqueous solvent in the presence of hydrochloric acid Process for the preparation of the corresponding ketone compounds from salts.
〔２〕 非水溶性溶媒がトルエンまたはクロロホルムである〔１〕に記載の製造方法。
〔３〕 ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩が、式（Ｚ１）で表される化合物および／または式（Ｅ１）で表される化合物である、〔１〕または〔２〕に記載の製造方法。
[2] The process according to [1], wherein the water-insoluble solvent is toluene or chloroform.
[3] to [1] or [2], wherein the ketoxime alkali metal salt or ketoxime alkaline earth metal salt is a compound represented by the formula (Z1) and / or a compound represented by the formula (E1) Manufacturing method described.
（式（Ｅ１）および（Ｚ１）中、ＡおよびＢは相異なる置換基である。Ｍはアルカリ金属若しくはアルカリ土類金属である。ｍはＭの価数に対応する整数（１または２）である。）
(In the formulas (E1) and (Z1), A and B are different substituents. M is an alkali metal or alkaline earth metal. M is an integer (1 or 2) corresponding to the valence of M. is there.)
〔４〕Ａが無置換の若しくは置換基を有するアリール基であり、
Ｂが無置換の若しくは置換基を有するテトラゾリル基である、〔３〕に記載の製造方法。
〔５〕Ｍがナトリウムである、〔３〕または〔４〕に記載の製造方法。
[4] A is an unsubstituted or substituted aryl group,
The production method according to [3], wherein B is a substituted or unsubstituted tetrazolyl group.
[5] The method according to [3] or [4], wherein M is sodium.
本発明の製造方法によれば、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩から対応するケトン化合物を効率的に製造することができる。 According to the production method of the present invention, the corresponding ketone compound can be efficiently produced from ketoxime alkali metal salt or ketoxime alkaline earth metal salt.
本発明に係る、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩から対応するケトン化合物を製造する方法は、塩酸の存在下、非水溶性溶媒中にて、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩を、加水分解することを含むものである。 The method for producing the corresponding ketone compound from ketoxime alkali metal salt or ketoxime alkaline earth metal salt according to the present invention comprises the steps of: ketoxime alkali metal salt or ketoxime in the presence of hydrochloric acid in a water-insoluble solvent It comprises hydrolyzing an alkaline earth metal salt.
本発明に用いられるケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩としては、式（Ｅ１）で表される化合物、式（Ｚ１）で表される化合物またはそれらの混合物を挙げることができる。ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩はケトキシムを公知の方法でアルカリ金属塩化若しくはアルカリ土類金属塩化することによって得られる。アルカリ金属塩化若しくはアルカリ土類金属塩化においては、アルカリ金属アルコキシド、アルカリ金属水酸化物、アルカリ土類金属アルコキシド、アルカリ土類金属水酸化物などを用いることができる。 Examples of the ketoxime alkali metal salt or ketoxime alkaline earth metal salt used in the present invention include a compound represented by Formula (E1), a compound represented by Formula (Z1), or a mixture thereof. Ketoxime alkali metal salts or ketoxime alkaline earth metal salts are obtained by alkali metal chlorides or alkaline earth metal chlorides of ketoximes in a known manner. In the alkali metal chloride or alkaline earth metal chloride, alkali metal alkoxide, alkali metal hydroxide, alkaline earth metal alkoxide, alkaline earth metal hydroxide and the like can be used.
式（Ｅ１）および（Ｚ１）中のＡおよびＢは相異なる置換基である。係る置換基は特に制限されないが、本発明においては、Ａが無置換の若しくは置換基を有するアリール基であり、Ｂが無置換の若しくは置換基を有するテトラゾリル基であるものが好ましく用いられる。
式（Ｅ１）および（Ｚ１）中のＭはアルカリ金属若しくはアルカリ土類金属である。アルカリ金属としては、ナトリウム、カリウム、リチウムなどを挙げることができる。アルカリ土類金属としては、マグネシウム、カルシウムなどを挙げることができる。これらのうち、ナトリウムまたはカリウムが好ましく、ナトリウムが最も好ましい。ｍはＭの価数に対応する整数（１または２）である。
A and B in formulas (E1) and (Z1) are different substituents. Such a substituent is not particularly limited, but in the present invention, it is preferable to use one in which A is an unsubstituted or substituted aryl group and B is an unsubstituted or substituted tetrazolyl group.
M in formulas (E1) and (Z1) is an alkali metal or an alkaline earth metal. As the alkali metal, sodium, potassium, lithium and the like can be mentioned. Examples of alkaline earth metals include magnesium and calcium. Of these, sodium or potassium is preferred, and sodium is most preferred. m is an integer (1 or 2) corresponding to the valence of M.
本発明においては、反応原料として、テトラゾリルアリールケトキシムアルカリ金属塩若しくはテトラゾリルアリールケトキシムアルカリ土類金属塩（例えば、式（１）などで表される化合物）が好ましく用いられる。
In the present invention, as a reaction raw material, Tetorazori luer Lee Luque Toki shim alkali metal salt or Tetorazori luer Lee Luque Toki shim alkaline earth metal salt (e.g., a compound represented by such formula (1)) is preferably used.
テトラゾリルアリールケトキシムアルカリ金属塩若しくはテトラゾリルアリールケトキシムアルカリ土類金属塩は、特許文献１などに記載のテトラゾリルアリールケトキシムをアルカリ金属塩化若しくはアルカリ土類金属塩化することによって得られる。
Tetorazori luer Lee Luque Toki shim alkali metal salt or Tetorazori luer Lee Luque Toki shim alkaline earth metal salts are obtained by Tetorazori luer Lee Luque Tokishimu alkali metal chloride or alkaline earth metal chloride such as described in Patent Document 1 .
ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩が、式（Ｅ１）で表される化合物と式（Ｚ１）で表される化合物との混合物であり、且つ式（Ｅ１）で表される化合物と式（Ｚ１）で表される化合物とのうち一方が他方に比べて高い殺菌活性を示す場合、高い殺菌活性を示す化合物が難溶性になり、且つ低い殺菌活性を示す化合物が易溶性になるような溶媒を選択して、高い殺菌活性を示す化合物を公知の固液分離法で固体として回収することが好ましい。このような分離のために使用する溶媒としては、トルエン、キシレンなどの芳香族炭化水素系溶媒；四塩化炭素、クロロホルムなどのハロゲン化炭化水素系溶媒などが挙げられる。係る溶媒は１種単独で若しくは２種以上を組み合わせて用いることができる。さらに溶解性の調整などのために、必要に応じて、メタノール、エタノールなどの低級アルコール系溶媒、水などを前述の溶媒と併用することができる。 The ketoxime alkali metal salt or ketoxime alkaline earth metal salt is a mixture of the compound represented by the formula (E1) and the compound represented by the formula (Z1), and the compound represented by the formula (E1) And when one of the compounds represented by the formula (Z1) exhibits higher bactericidal activity than the other, the compound exhibiting high bactericidal activity becomes poorly soluble, and the compound exhibiting low bactericidal activity becomes readily soluble It is preferable to select such a solvent and recover a compound exhibiting high bactericidal activity as a solid by a known solid-liquid separation method. Examples of the solvent used for such separation include aromatic hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as carbon tetrachloride and chloroform. Such solvents can be used singly or in combination of two or more. Furthermore, for the purpose of adjusting the solubility, if necessary, a lower alcohol solvent such as methanol or ethanol, water or the like can be used in combination with the above-mentioned solvent.
このような固液分離法で得られた残液には易溶性の化合物が主に含まれている。本発明においては、この残液を反応原料であるケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩として好ましく用いることができる。 The residual liquid obtained by such a solid-liquid separation method mainly contains easily soluble compounds. In the present invention, this residue can be preferably used as a ketoxime alkali metal salt or ketoxime alkaline earth metal salt as a reaction raw material.
本発明においては、ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩の加水分解を、塩酸の存在下に行う。塩酸の量は、加水分解を促進できる量であれば、特に制限されない。該加水分解においては、塩酸以外の酸が本発明の効果を阻害しない範囲で反応系に併存してもよい。他の酸として、例えば硫酸、硝酸、リン酸などの塩酸以外の無機酸；酢酸、トリフルオロ酢酸などの有機酸が挙げられる。これらの酸は１種単独で若しくは２種以上を組み合わせて用いることができる。 In the present invention, the hydrolysis of the ketoxime alkali metal salt or ketoxime alkaline earth metal salt is carried out in the presence of hydrochloric acid. The amount of hydrochloric acid is not particularly limited as long as it can promote hydrolysis. In the hydrolysis, an acid other than hydrochloric acid may coexist in the reaction system as long as the effect of the present invention is not inhibited. Examples of other acids include inorganic acids other than hydrochloric acid such as sulfuric acid, nitric acid and phosphoric acid; and organic acids such as acetic acid and trifluoroacetic acid. These acids can be used singly or in combination of two or more.
ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩の加水分解は、非水溶性溶媒中にて行う。「非水溶性溶媒」とは水に対する溶解度が１０ｇ／１００ｇ−Ｈ2Ｏ以下のものをいう。非水溶性溶媒の具体例としては、トルエン、キシレンなどの芳香族炭化水素系溶媒、四塩化炭素、クロロホルムなどのハロゲン化炭化水素系溶媒などが挙げられる。これらのうちトルエン、クロロホルムが好ましい。これら非水溶性溶媒は１種単独で若しくは２種以上を組み合わせて用いることができる。
ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩の加水分解においては、水溶性溶媒が本発明の効果を阻害しない範囲で反応系に併存してもよい。水溶性溶媒としては、例えば、メタノール、エタノールなどの低級アルコール系溶媒などが挙げられる。これら水溶性溶媒は１種単独で若しくは２種以上を組み合わせて用いることができる。
The hydrolysis of the ketoxime alkali metal salt or ketoxime alkaline earth metal salt is carried out in a water insoluble solvent. The "non-water soluble solvent" refers to one having a solubility in water of 10 g / 100 g H 2 O or less. Specific examples of the water-insoluble solvent include aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as carbon tetrachloride and chloroform, and the like. Among these, toluene and chloroform are preferred. These water-insoluble solvents can be used singly or in combination of two or more.
In the hydrolysis of ketoxime alkali metal salt or ketoxime alkaline earth metal salt, a water-soluble solvent may coexist in the reaction system as long as the effect of the present invention is not inhibited. Examples of the water-soluble solvent include lower alcohol solvents such as methanol and ethanol. These water-soluble solvents can be used singly or in combination of two or more.
ケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩の加水分解反応は、通常、室温〜溶媒還流温度、好ましくは５０〜６０℃にて行う。また、係る加水分解反応は、反応装置や反応規模にもよるが、転化率が所望の範囲内に入るまでの時間で行うことができる。 The hydrolysis reaction of ketoxime alkali metal salt or ketoxime alkaline earth metal salt is usually carried out at room temperature to solvent reflux temperature, preferably at 50 to 60 ° C. In addition, such a hydrolysis reaction can be performed in a time until the conversion falls within a desired range, although it depends on the reactor and the reaction scale.
なお、本発明の製造方法における、反応原料であるケトキシムアルカリ金属塩若しくはケトキシムアルカリ土類金属塩、および反応生成物であるケトン化合物は、化学的に許容される、水和物、結晶多形などの形態を成していてもよい。 In the production method of the present invention, ketoxime alkali metal salt or ketoxime alkaline earth metal salt which is a reaction raw material, and ketone compound which is a reaction product are chemically acceptable, hydrate, crystal multiple. It may be in a form such as a shape.
次に、実施例を挙げて本発明をさらに詳細に説明する。但し、本発明は以下の実施例に何ら限定されるものではない。 Next, the present invention will be described in more detail by way of examples. However, the present invention is not limited to the following examples.
実施例１
（１−メチル−１Ｈ−テトラゾル−５−イル）（フェニル）メタノンオキシムナトリウム塩（以下、ＴＺＯＸＮａと表記する。 Ｚ体／Ｅ体の質量比：２．３／７．３）を含む液９．４ｇを用意した。該液をエバポレータで残渣２．３ｇにまで濃縮した。濃縮物をトルエン２４．６ｇで希釈した。
該希釈液に３５％塩酸１５．２ｇを添加した。その後、温水バスにて約６０℃にて３．５時間加水分解反応させて（１−メチル−１Ｈ−テトラゾル−５−イル）（フェニル）メタノン（以下、ＴＺと表記する。）に転化させた。その後、反応液を冷却し、分液操作を行った。ＨＰＬＣにより有機層を定量分析した。ＴＺが収率９０モル％で得られた。
Example 1
Liquid 9 containing (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone oxime sodium salt (hereinafter referred to as TZOXNa. Mass ratio of Z form / E form: 2.3 / 7.3) We prepared .4g. The liquid was concentrated by an evaporator to a residue of 2.3 g. The concentrate was diluted with 24.6 g of toluene.
To the diluted solution was added 15.2 g of 35% hydrochloric acid. Thereafter, the mixture was hydrolyzed in a hot water bath at about 60 ° C. for 3.5 hours to convert it into (1-methyl-1H-tetrazol-5-yl) (phenyl) methanone (hereinafter referred to as TZ). . Thereafter, the reaction solution was cooled and liquid separation operation was performed. The organic layer was quantitatively analyzed by HPLC. TZ was obtained in a yield of 90 mol%.
実施例２
トルエンをクロロホルムに置き換え、反応時間４時間に変えた以外は実施例１と同じ操作を行った。ＨＰＬＣにより有機層を定量分析した。ＴＺが収率３４モル％で得られた。
Example 2
The same operation as in Example 1 was carried out except that toluene was replaced with chloroform and the reaction time was changed to 4 hours. The organic layer was quantitatively analyzed by HPLC. TZ was obtained in a yield of 34 mol%.
比較例１
３５％塩酸１５．２ｇを希硫酸（９８％硫酸７．３ｇ＋水７．２ｇ）１４．５ｇに置き換え、反応時間４時間に変えた以外は実施例１と同じ操作を行った。ＨＰＬＣにより有機層を定量分析した。ＴＺが収率２２モル％で得られた。
Comparative Example 1
The same operation as in Example 1 was performed except that 15.2 g of 35% hydrochloric acid was replaced with 14.5 g of dilute sulfuric acid (7.3 g of 98% sulfuric acid + 7.2 g of water) and the reaction time was changed to 4 hours. The organic layer was quantitatively analyzed by HPLC. TZ was obtained in a yield of 22 mol%.
比較例２
トルエンをメタノールに置き換え、反応時間４時間に変えた以外は実施例１と同じ操作を行った。ＨＰＬＣにより有機層を定量分析した。ＴＺが収率９モル％で得られた。
Comparative example 2
The same operation as in Example 1 was performed except that toluene was replaced with methanol and the reaction time was changed to 4 hours. The organic layer was quantitatively analyzed by HPLC. TZ was obtained in 9 mol% yield.
実施例１と比較例１との対比から、塩酸の存在下において加水分解を行うと、高効率でケトン化合物に転化できることがわかる。また、実施例１または実施例２と比較例２との対比から、トルエンやクロロホルムなどの非水溶性溶媒を用いると、高効率でケトン化合物に転化できることがわかる。 From the comparison between Example 1 and Comparative Example 1, it is understood that when the hydrolysis is performed in the presence of hydrochloric acid, it can be converted to the ketone compound with high efficiency. Further, from the comparison between Example 1 or Example 2 and Comparative Example 2, it is understood that conversion to a ketone compound can be performed with high efficiency by using a water-insoluble solvent such as toluene or chloroform.
本発明の方法で得られたケトン化合物をオキシム化して、上記に示す回収方法を繰り返すことによって、殺菌活性が低いと思われるケトキシム異性体を殺菌活性が高いと思われるケトキシム異性体に変換することができる。このようにして、植物病害防除剤の有効成分の製造収率を高くすることができる。 Converting a ketoxime isomer which is considered to be low in bactericidal activity into a ketoxime isomer which is considered to be high in bactericidal activity by oximation of the ketone compound obtained by the method of the present invention and repeating the recovery method shown above Can. Thus, the production yield of the active ingredient of the plant disease control agent can be increased.
Claims (5)
The presence of hydrochloric acid, in a non-aqueous solvent, the Tetorazori luer Lee Luque Toki shim alkali metal salt or Tetorazori luer Lee Luque Toki shim alkaline earth metal salt, which comprises hydrolyzing, Tetorazori luer Lee Luque Toki shim alkali how to produce the corresponding ketone compound of a metal salt or Tetorazori luer Lee Luque Toki shim alkaline earth metal salts.
（式（１）中、
Ｒ1は、それぞれ独立に、ハロゲノ基、アルキル基、アルコキシ基、アミノ基、シアノ基、またはフェニル基であり、
Ｒ2は、水素原子、ハロゲノ基、アルキル基、アルコキシ基、アミノ基、またはシアノ基であり、
ｎ１は、Ｒ1の数を示し且つ０〜５のいずれかの整数であり、
Ｍは、アルカリ金属若しくはアルカリ土類金属であり、
ｍは、Ｍの価数に対応する整数（１または２）である。）
Tetorazori luer Lee Luque Toki shim alkali metal salt or Tetorazori luer Lee Luque Toki shim alkaline earth metal salt is a compound represented by the formula (1), The process according to claim 1.
(In the formula (1),
Each R 1 is independently a halogeno group, an alkyl group, an alkoxy group, an amino group, a cyano group or a phenyl group,
R 2 is a hydrogen atom, a halogeno group, an alkyl group, an alkoxy group, an amino group or a cyano group,
n1 represents the number of R 1 and is an integer of 0 to 5,
M is an alkali metal or alkaline earth metal,
m is an integer (1 or 2) corresponding to the valence of M. )
（式（Ｅ１）および（Ｚ１）中、
Ａは、無置換の若しくは置換基を有するアリール基であり、
Ｂは、無置換の若しくは置換基を有するテトラゾリル基であり、
Ｍは、アルカリ金属若しくはアルカリ土類金属であり、且つ
ｍは、Ｍの価数に対応する整数（１または２）である。） A compound of Formula (Z1) comprising hydrolyzing a compound of Formula (Z1) and / or a compound of Formula (E1) in a non-aqueous solvent in the presence of hydrochloric acid And / or a method of producing the corresponding ketone compound from the compound represented by the formula (E1) .
(In the formulas (E1) and (Z1),
A is an unsubstituted or substituted aryl group,
B is a substituted or unsubstituted tetrazolyl group,
M is Ri alkali metal or alkaline earth metal der, and m is an integer (1 or 2) corresponding to the valence of M. )
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