JPH03865B2 - - Google Patents
Info
- Publication number
- JPH03865B2 JPH03865B2 JP174583A JP174583A JPH03865B2 JP H03865 B2 JPH03865 B2 JP H03865B2 JP 174583 A JP174583 A JP 174583A JP 174583 A JP174583 A JP 174583A JP H03865 B2 JPH03865 B2 JP H03865B2
- Authority
- JP
- Japan
- Prior art keywords
- aminoisoxazole
- reaction
- alkali metal
- hydroxylamine
- methanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- RHFWLPWDOYJEAL-UHFFFAOYSA-N 1,2-oxazol-3-amine Chemical compound NC=1C=CON=1 RHFWLPWDOYJEAL-UHFFFAOYSA-N 0.000 claims description 16
- -1 alkali metal alkoxide Chemical class 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 10
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 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 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- IPCRTSDORDQHRO-DUXPYHPUSA-N (e)-3-methoxyprop-2-enenitrile Chemical compound CO\C=C\C#N IPCRTSDORDQHRO-DUXPYHPUSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- PBZUAIHRZUBBAJ-UHFFFAOYSA-N Hydroxyiminoacetic acid Natural products ON=CC(O)=O PBZUAIHRZUBBAJ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000001340 alkali metals Chemical group 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- LNDJVIYUJOJFSO-UHFFFAOYSA-N cyanoacetylene Chemical group C#CC#N LNDJVIYUJOJFSO-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- DKFAYHWIVQDPCC-OWOJBTEDSA-N (e)-3-chloroprop-2-enenitrile Chemical compound Cl\C=C\C#N DKFAYHWIVQDPCC-OWOJBTEDSA-N 0.000 description 1
- HUPVIAINOSTNBJ-HWKANZROSA-N (e)-3-ethoxyprop-2-enenitrile Chemical compound CCO\C=C\C#N HUPVIAINOSTNBJ-HWKANZROSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- LBLYYCQCTBFVLH-UHFFFAOYSA-M 2-methylbenzenesulfonate Chemical compound CC1=CC=CC=C1S([O-])(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-M 0.000 description 1
- LBLTWXAKZNCZLY-UHFFFAOYSA-N 3-propoxyprop-2-enenitrile Chemical compound CCCOC=CC#N LBLTWXAKZNCZLY-UHFFFAOYSA-N 0.000 description 1
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZYBWTEQKHIADDQ-UHFFFAOYSA-N ethanol;methanol Chemical compound OC.CCO ZYBWTEQKHIADDQ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Chemical group 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- RCOSUMRTSQULBK-UHFFFAOYSA-N sodium;propan-1-olate Chemical compound [Na+].CCC[O-] RCOSUMRTSQULBK-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Description
【発明の詳細な説明】
本発明は、３−アミノイソオキサゾールの新規
な製法に関するものである。さらに詳しくは、３
−アルコキシアクリロニトリルとヒドロキシルア
ミンを、アルカリ金属アルコキシドの存在下に反
応させる３−アミノイソオキサゾールの新規な製
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 3-aminoisoxazole. For more details, see 3.
This invention relates to a novel method for producing 3-aminoisoxazole in which alkoxyacrylonitrile and hydroxylamine are reacted in the presence of an alkali metal alkoxide.
３−アミノイソオキサゾールは、例えば医薬、
農薬などの原料として有用な化合物であり、以前
からその製法について種々の提案がなされてい
る。 3-Aminoisoxazole can be used, for example, in pharmaceuticals,
It is a compound that is useful as a raw material for agricultural chemicals, and various proposals have been made for its production methods.
例えば特公昭45−34132号公報には、３−クロ
ルアクリロニトリルとヒドロキシイミノ酢酸エス
テルをナトリウムエトキシドの存在下に反応さ
せ、得られる３−（アルコキシメチルメチレンア
ミノオキシ）アクリロニトリルを酸性条件下で環
化させることによる、３−アミノイソオキサゾー
ルの製法が提案されている。この方法は、反応に
２工程を要するのみでなく、原料のヒドロキシイ
ミノ酢酸エステルが極めて高価であるなど、必ず
しも工業的に満足できるものではない。 For example, in Japanese Patent Publication No. 45-34132, 3-chloroacrylonitrile and hydroxyiminoacetic acid ester are reacted in the presence of sodium ethoxide, and the resulting 3-(alkoxymethylmethyleneaminooxy)acrylonitrile is cyclized under acidic conditions. A method for producing 3-aminoisoxazole has been proposed. This method not only requires two steps for the reaction, but also the raw material hydroxyiminoacetic acid ester is extremely expensive, so it is not necessarily industrially satisfactory.
特公昭45−33890号公報には、シアノアセチレ
ンとシクロヘキサノンオキシムを、エタノール溶
媒中Ｎ−メチルモルホリンの存在下に反応させ
る、３−アミノイソオキサゾールの製法につき提
案がなされている。この方法は、反応が完結する
まで長時間を要するうえに、原料のシアノアセチ
レンがやはり高価であり、経済的に満足できる方
法とは言い難い。 Japanese Patent Publication No. 45-33890 proposes a method for producing 3-aminoisoxazole in which cyanoacetylene and cyclohexanone oxime are reacted in the presence of N-methylmorpholine in an ethanol solvent. This method requires a long time to complete the reaction, and the raw material cyanoacetylene is also expensive, so it cannot be said to be an economically satisfactory method.
またオランダ特許第6408919号明細書には、α，
β−ジクロロプロピオニトリルとカルバミルヒド
ロキシルアミンとの反応による、３−アミノイソ
オキサゾールの製法につき提案されている。しか
しこの方法は、目的物の収率が極めて低いという
欠点を有している。 In addition, Dutch Patent No. 6408919 describes α,
A method for producing 3-aminoisoxazole by reaction of β-dichloropropionitrile and carbamylhydroxylamine has been proposed. However, this method has the drawback that the yield of the target product is extremely low.
本発明者らは、３−アミノイソオキサゾールの
工業的有利な製法を開発することを目的とし、鋭
意研究を行つた。その結果、安価に容易に入手で
きる３−アルコキシアクリロニトリルとヒドロキ
ルアミンを、アルカリ金属アルコキシドの存在下
に反応させれば、一段でしかも高収率にて３−ア
ミノイソオキサゾールを合成できることを見い出
し、本発明を完成するに到つた。 The present inventors conducted extensive research with the aim of developing an industrially advantageous manufacturing method for 3-aminoisoxazole. As a result, they discovered that 3-aminoisoxazole could be synthesized in a single step and in high yield by reacting 3-alkoxyacrylonitrile, which is easily available at low cost, with hydroxylamine in the presence of an alkali metal alkoxide. He has completed his invention.
本発明の原料である３−アルコキシアクリロニ
トリルは、一般にROCH＝CHCNで示すことが
できる。該式において、Ｒはメチル、エチル、ｎ
−プロピル、ｉ−プロピル、ｎ−ブチル，ｉ−ブ
チル、sec−ブチル、tert−ブチル、ｎ−ペンチ
ル、ｎ−ヘキシル、ｎ−ヘプチル、ｎ−オクチル
などの如き炭素数１〜８を有するアルキル基を挙
げることができる。これらのアルキル基には、反
応を阻額害しない置換基、例えばアルコキシ基、
ハロゲン原子などの置換基を有すこともできる。 3-alkoxyacrylonitrile, which is a raw material of the present invention, can generally be represented by ROCH=CHCN. In this formula, R is methyl, ethyl, n
- Alkyl groups having 1 to 8 carbon atoms such as propyl, i-propyl, n-butyl, i-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, etc. can be mentioned. These alkyl groups may contain substituents that do not inhibit the reaction, such as alkoxy groups,
It can also have a substituent such as a halogen atom.
本発明のもう一つの原料であるヒドロキシルア
ミンは、それ自体でもよいが、通常硫酸塩、塩酸
塩、硝酸塩、リン酸塩、酢酸塩あるいはトルエン
スルホン酸塩などの塩の形で使用に供される。そ
の使用量は、３−アルコキシアクリロニトリル１
モルに対して0.1〜10モル、好ましくは0.5〜５モ
ルである。 Hydroxylamine, which is another raw material of the present invention, may be used as such, but is usually used in the form of a salt such as sulfate, hydrochloride, nitrate, phosphate, acetate, or toluenesulfonate. . The amount used is 3-alkoxyacrylonitrile 1
The amount is 0.1 to 10 mol, preferably 0.5 to 5 mol.
また本発明におけるアルカリ金属アルコキシド
としては、メタノール、エタノール、ｎ−プロパ
ノール、ｉ−プロパノール、ｎ−ブタノール、ｉ
−ブタノール、sec−ブタノール、tert−ブタノ
ール、ｎ−アミルアルコール、ｎ−ヘキサノー
ル、ｎ−ヘプタノールあるいはｎ−オクタノール
などの炭素数１〜８を有するアルコールの水酸基
の水素を、ナトリウム、カリウム、リチウムなど
の如きアルカリ金属で置換したものが有用であ
る。その使用量は、ヒドロキシルアミン１モルに
対して0.1〜10モル、好ましくは0.5〜５モルであ
る。これらアルカリ金属アルコキシドは、通常、
前記アルコール類にアルカリ金属を溶解させる
か、あるいはアルコール類にアルカリ金属の水酸
化物を混合した後脱水することによつて、容易に
調整することができる。 Further, examples of the alkali metal alkoxide in the present invention include methanol, ethanol, n-propanol, i-propanol, n-butanol, i
- Hydrogen of the hydroxyl group of an alcohol having 1 to 8 carbon atoms such as butanol, sec-butanol, tert-butanol, n-amyl alcohol, n-hexanol, n-heptanol or n-octanol is replaced with sodium, potassium, lithium, etc. Those substituted with alkali metals such as the like are useful. The amount used is 0.1 to 10 mol, preferably 0.5 to 5 mol, per 1 mol of hydroxylamine. These alkali metal alkoxides are usually
It can be easily adjusted by dissolving an alkali metal in the alcohol, or by mixing an alkali metal hydroxide with the alcohol and then dehydrating the mixture.
本発明の反応は、原料をよく溶かし反応を阻害
しない溶媒中で行われる。その溶媒としては、例
えばメタノール、エタノールなどの前記アルカリ
金属アルコキシドの調製に使用されるアルコール
類、あるいはジオキサン、アセトニトリル、ジメ
チルホルムアミドなどを例示することができ、こ
れらは単独で使用してもよく併用することもでき
る。このようにアルコール類が溶媒として有用で
あるため、前記の方法で調製されたアルカリ金属
アルコキシドを含むアルコール溶液から、アルカ
リ金属アルコキシドを単離することなく、その系
に３−アルコキシアクリロニトリルとヒドロキシ
ルアミンとを添加して、反応を行うこともでき
る。 The reaction of the present invention is carried out in a solvent that dissolves the raw materials well and does not inhibit the reaction. Examples of the solvent include alcohols used in the preparation of the alkali metal alkoxides such as methanol and ethanol, dioxane, acetonitrile, and dimethylformamide, which may be used alone or in combination. You can also do that. Since alcohols are useful as solvents, it is possible to add 3-alkoxyacrylonitrile and hydroxylamine to the alcohol solution containing the alkali metal alkoxide prepared by the above method without isolating the alkali metal alkoxide. The reaction can also be carried out by adding .
本発明の反応は、室温程度の温和な条件でも反
応は進行するが、加熱によつて反応速度を高める
こともできる。通常、反応は10〜150℃の温度で
0.5〜10時間行うことによつて、完結する。 Although the reaction of the present invention proceeds under mild conditions at about room temperature, the reaction rate can also be increased by heating. Usually the reaction is carried out at a temperature of 10-150℃
It can be completed by doing it for 0.5 to 10 hours.
反応後、蒸留、過、抽出あるいはクロマトグ
ラフイーなどの操作を適宜行うことにより、目的
物の３−アミノイソオキサゾールを単離、取得す
ることができる。 After the reaction, the target product, 3-aminoisoxazole, can be isolated and obtained by appropriately performing operations such as distillation, filtration, extraction, or chromatography.
次に、本発明の実施例を挙げる。 Next, examples of the present invention will be given.
実施例 １
還流冷却器をつけた内容積100mlの三ツ口フラ
スコに、メタノール70mlを入れた後、金属ナトリ
ウムの小片2.7gを加え、金属ナトリウムを完全に
反応させ、エタノールメトキシドのメタノール溶
液を調製した。該溶液に、ヒドロキシルアミン塩
酸塩4.20gを加えて10分間撹拌した後、３−メト
キシアクリロニトリル4.43gを加え、撹拌下に５
時間加熱還流を行つた。次いで、減圧下でメタノ
ールを留去し、残液に水50mlを加えた後、酢酸エ
チルで抽出した。酢酸エチル層を無水硫酸ナトリ
ウムで乾燥した後、減圧下で酢酸エチルを留去し
2.58gの油状物を得た。該油状物は、Ｈ−NMR，
IR，MSスペクトルより３−アミノイソオキサゾ
ールであることを確認した。Example 1 After putting 70 ml of methanol into a 100 ml three-necked flask equipped with a reflux condenser, 2.7 g of small pieces of metallic sodium were added to completely react the metallic sodium to prepare a methanol solution of ethanol methoxide. . After adding 4.20 g of hydroxylamine hydrochloride to the solution and stirring for 10 minutes, 4.43 g of 3-methoxyacrylonitrile was added and the mixture was stirred for 5 minutes.
The mixture was heated under reflux for an hour. Next, methanol was distilled off under reduced pressure, and 50 ml of water was added to the residual liquid, followed by extraction with ethyl acetate. After drying the ethyl acetate layer over anhydrous sodium sulfate, ethyl acetate was distilled off under reduced pressure.
2.58g of oil was obtained. The oily substance was analyzed by H-NMR,
It was confirmed from IR and MS spectra that it was 3-aminoisoxazole.
実施例 ２
ヒドロキシルアミン塩酸塩に代えて、ヒドロキ
シルアミン硫酸塩4.95gを用いた他は、実施例１
と同様の操作で実験を行つた。その結果、３−ア
ミノイソオキサゾール2.51gの生成が認められた。Example 2 Example 1 except that 4.95 g of hydroxylamine sulfate was used instead of hydroxylamine hydrochloride.
The experiment was carried out using the same procedure. As a result, production of 2.51 g of 3-aminoisoxazole was observed.
実施例 ３
メタノールに代えてエタノール70mlを用い、実
施例１と同様の操作でナトリウムのエタノール溶
液を調製した。次いで、該容液に３−エトキシア
クリロニトリル5.14gを加え、その後の操作は実
施例１と同様に行つた。その結果、３−アミノイ
ソオキサゾールが油状物として2.43g得られた。Example 3 An ethanol solution of sodium was prepared in the same manner as in Example 1, using 70 ml of ethanol instead of methanol. Next, 5.14 g of 3-ethoxyacrylonitrile was added to the liquid, and the subsequent operations were carried out in the same manner as in Example 1. As a result, 2.43 g of 3-aminoisoxazole was obtained as an oily substance.
実施例 ４
メタノールに代えてｎ−プロパノール70mlを用
い、実施例１と同様の操作でナトリウムｎ−プロ
ポキシドのｎ−プロパノール溶液を調製した。次
いで、該溶液に３−ｎ−プロポキシアクリロニト
リル5.55gを加え、その後の操作は実施例１と同
様に行つた。その結果、３−アミノイソオキサゾ
ールが2.38g生成していた。Example 4 An n-propanol solution of sodium n-propoxide was prepared in the same manner as in Example 1, using 70 ml of n-propanol instead of methanol. Next, 5.55 g of 3-n-propoxyacrylonitrile was added to the solution, and the subsequent operations were carried out in the same manner as in Example 1. As a result, 2.38g of 3-aminoisoxazole was produced.
実施例 ５
ナトリウムメトキシドのメタノール溶液に代え
て、カリウムメトキシド8.40gを含むメタノール
溶液75mlを用いた他は、実施例１と同様の操作で
実験を行つた。その結果、３−アミノイソオキサ
ゾール2.20gの生成が認められた。Example 5 An experiment was carried out in the same manner as in Example 1, except that 75 ml of a methanol solution containing 8.40 g of potassium methoxide was used instead of the methanol solution of sodium methoxide. As a result, production of 2.20 g of 3-aminoisoxazole was observed.
実施例 ６
３−メトキシアクリロニトリルとヒドロキシル
アミン塩酸塩の反応条件を、50℃で８時間に変え
た他は、実施例１と同様の操作で実験を行つた。
その結果、３−アミノイソオキサゾール2.30gの
生成が認められた。Example 6 An experiment was carried out in the same manner as in Example 1, except that the reaction conditions for 3-methoxyacrylonitrile and hydroxylamine hydrochloride were changed to 8 hours at 50°C.
As a result, production of 2.30 g of 3-aminoisoxazole was observed.
Claims (1)
シルアミンを、アルカリ金属アルコキシドの存在
下に反応させることを特徴とする３−アミノイソ
オキサゾールの製法。1. A method for producing 3-aminoisoxazole, which comprises reacting 3-alkoxyacrylonitrile and hydroxylamine in the presence of an alkali metal alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP174583A JPS59128378A (en) | 1983-01-11 | 1983-01-11 | Preparation of 3-aminoisoxazole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP174583A JPS59128378A (en) | 1983-01-11 | 1983-01-11 | Preparation of 3-aminoisoxazole |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59128378A JPS59128378A (en) | 1984-07-24 |
| JPH03865B2 true JPH03865B2 (en) | 1991-01-09 |
Family
ID=11510096
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP174583A Granted JPS59128378A (en) | 1983-01-11 | 1983-01-11 | Preparation of 3-aminoisoxazole |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59128378A (en) |
-
1983
- 1983-01-11 JP JP174583A patent/JPS59128378A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59128378A (en) | 1984-07-24 |
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