JP6434261B2 - Iodobenzamide type alcohol oxidation catalyst - Google Patents
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Description
本発明は、ヨードベンズアミド誘導体を触媒として用いるアルコール類の酸化方法に関するものである。 The present invention relates to a method for oxidizing alcohols using an iodobenzamide derivative as a catalyst.
近年、２−ヨード安息香酸を基礎とする超原子価ヨウ素酸化剤や１価のヨウ素触媒を用いるアルコール酸化反応の開発が盛ん行われている（非特許文献１）。高分子固定の反応剤のように他の機能を組み込んだ５価酸化剤（非特許文献２）や１価酸化触媒も開発されている（非特許文献３）。
一方、いくつかの２−ヨード安息香酸のエステルやアミドの５価類縁体が合成され、そのアルコール酸化剤としての反応性が示されている（非特許文献４、５）。
In recent years, an alcohol oxidation reaction using a hypervalent iodine oxidizer based on 2-iodobenzoic acid or a monovalent iodine catalyst has been actively developed (Non-patent Document 1). A pentavalent oxidant (non-patent document 2) and a monovalent oxidation catalyst incorporating other functions such as a polymer-fixed reactant have also been developed (non-patent document 3).
On the other hand, some pentavalent analogs of 2-iodobenzoic acid esters and amides have been synthesized, and their reactivity as alcohol oxidizing agents has been shown (Non-Patent Documents 4 and 5).
２−ヨード安息香酸やそのベンゼン環上に置換基を有するもの、あるいは２−ヨードスルホン酸など、従来用いられている触媒を、オキソン（過硫酸カリウムおよび硫酸水素カリウム、硫酸カリウムの混合物）存在下でアルコール類と７０度で加熱すると、第１級アルコールからは対応するアルデヒドが、第２級アルコールからは対応するケトンが得られている。これらの反応では、反応系中で５価のヨウ素種が発生しており、このものがアルコール類を酸化している。しかし、５価のヨウ素化合物は爆発性を持っているため、触媒量であっても、加熱条件下にさらすことは危険である。すなわち、本発明が解決しようという課題は、より低温で用いることが可能であるヨウ素触媒を開発することである。 In the presence of oxone (a mixture of potassium persulfate, potassium hydrogensulfate, and potassium sulfate), a conventionally used catalyst such as 2-iodobenzoic acid, one having a substituent on its benzene ring, or 2-iodosulfonic acid is used. When heated at 70 ° C. with alcohols, the corresponding aldehyde is obtained from the primary alcohol and the corresponding ketone is obtained from the secondary alcohol. In these reactions, pentavalent iodine species are generated in the reaction system, which oxidizes alcohols. However, since pentavalent iodine compounds have explosive properties, it is dangerous to expose them to heating conditions even in catalytic amounts. That is, the problem to be solved by the present invention is to develop an iodine catalyst that can be used at a lower temperature.
２−ヨード安息香酸は入手が容易である。そのため、そのカルボキシ基を調製容易なアルコールあるいはアミン類と縮合させれば、エステルあるいはアミドが容易に合成可能である。本発明者らは、様々なアルコールやアミンを用いて、エステル、アミドを合成してその触媒活性を検討した。その結果、低温（室温）で反応可能な触媒の創製に成功し本発明を完成させた。
以下、本発明を詳細に説明する。
2-Iodobenzoic acid is readily available. Therefore, an ester or amide can be easily synthesized by condensing the carboxy group with an easily prepared alcohol or amine. The present inventors have synthesized esters and amides using various alcohols and amines and studied their catalytic activities. As a result, the inventors succeeded in creating a catalyst capable of reacting at a low temperature (room temperature) and completed the present invention.
Hereinafter, the present invention will be described in detail.
本発明において、特に断らない限り、ハロゲン原子とは、フッ素原子、塩素原子、臭素原子、ヨウ素原子などを；アルキル基とは、メチル、エチル、n-プロピル、イソプロピル、ブチル、イソブチル、s-ブチル、t-ブチルなど直鎖状または分岐状のＣ1-6アルキル基を；アルキレンとは、メチレン、エチレン、プロピレンなど直鎖状または分岐状のＣ1-6アルキレン基を；アシル基とは、アセチル、プロピオニル、イソブチリルなど直鎖状または分岐状のＣ2-6アルキル−ＣＯ−基を；アシルオキシ基とは、アセチルオキシ、プロピオニルオキシ、イソブチリルオキシなど直鎖状または分岐状のＣ2-6アルキル−ＣＯ−Ｏ−基を；アルコキシ基とは、メトキシ、エトキシ、プロポキシなど直鎖状または分岐状のＣ1-6アルキル−Ｏ−基を；シクロアルキル基とは、シクロペンチル、シクロヘキシルなどのＣ2-7シクロアルキル基を；アリール基とは、フェニル、ナフチルなどの基を；アルキルスルホニル基とは、直鎖状または分岐状のＣ1-6アルキル−ＳＯ２−基を；アリールスルホニル基とは、アリール−ＳＯ２−基を、それぞれ意味する In the present invention, unless otherwise specified, a halogen atom is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc .; an alkyl group is methyl, ethyl, n-propyl, isopropyl, butyl, isobutyl, s-butyl A linear or branched C 1-6 alkyl group such as t-butyl; alkylene is a linear or branched C 1-6 alkylene group such as methylene, ethylene or propylene; an acyl group is A linear or branched C 2-6 alkyl-CO— group such as acetyl, propionyl, isobutyryl; etc .; an acyloxy group is a linear or branched C 2− group such as acetyloxy, propionyloxy, isobutyryloxy, etc. 6 alkyl -CO-O- groups; alkoxy groups include methoxy, ethoxy, propoxy etc. linear or branched C 1-6 alkyl -O- group; cycloalk The group, cyclopentyl, C 2-7 cycloalkyl groups such as cyclohexyl; and an aryl group, a phenyl, group a naphthyl; The alkylsulfonyl group, linear or branched C 1-6 alkyl A —SO 2 — group; an arylsulfonyl group means an aryl-SO 2 — group, respectively.
本発明は、以下の一般式［１］ので表されるヨードベンズアミド型触媒。
一般式
General formula
本発明のより具体的なヨードベンズアミド型触媒として以下のものが挙げられる。
「上記の一般式［１ａ］〜［１ｄ］の式中、Ｒ１は、水素原子もしくはハロゲン原子またはアルキル、アルコキシ、アシル、アシルオキシもしくはニトロから選ばれる基を；Ｒ２ａは、保護されていてもよいカルボキシル基もしくはアシルオキシ基で置換されていてもよいアルキル基またはシクロアルキル基を、Ｒ４は、アルキル基またはアリール基を、Ｒ５は、アルキル基を、Ｒ６は、カルボキシル基または１,１−ジフェニルヒドロキシメチル基、Ａはアルキレン基を、それぞれ意味する。」 “In the formulas [1a] to [1d], R 1 represents a hydrogen atom or a halogen atom or a group selected from alkyl, alkoxy, acyl, acyloxy or nitro; R 2a may be protected. R 4 is an alkyl group or an aryl group, R 5 is an alkyl group, R 6 is a carboxyl group or 1,1 -Diphenylhydroxymethyl group, A means an alkylene group respectively. "
また、本発明は、上記の一般式［１］で表されるヨードベンズアミド型触媒の存在に、共酸化剤を用いてアルコール類を酸化する方法である。 The present invention is also a method for oxidizing alcohols using a cooxidant in the presence of the iodobenzamide type catalyst represented by the above general formula [1].
ここで用いる共酸化剤としてペルオキシ一硫酸カリウムなどの無機酸化剤またはｍ−クロロ過安息香酸などの有機酸化剤が挙げられ、オキソン（過硫酸カリウムおよび硫酸水素カリウム、硫酸カリウムの混合物）が好ましい。
共酸化剤、の使用量は、原料のアルコールに対して１〜５当量であればよい。
Examples of the co-oxidant used here include inorganic oxidants such as potassium peroxymonosulfate and organic oxidants such as m-chloroperbenzoic acid, and oxone (a mixture of potassium persulfate, potassium hydrogensulfate and potassium sulfate) is preferred.
The usage-amount of a co-oxidant should just be 1-5 equivalent with respect to alcohol of a raw material.
ここで用いる溶媒は、反応に悪影響を及ぼさない限り特に限定されないが、例えば、ニトロメタン・水、酢酸エチル・水、クロロホルム・水などの混合溶媒が挙げられる。 The solvent used here is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include mixed solvents such as nitromethane / water, ethyl acetate / water, chloroform / water.
ここで用いる一般式［１］で表されるヨードベンズアミド型化合物の量は、触媒量でよいが、例えば、原料のアルコール類に対して、０.０５〜０.５当量、好ましくは、０.０５〜０.３当量であればよい。 The amount of the iodobenzamide type compound represented by the general formula [1] used here may be a catalytic amount, but is, for example, 0.05 to 0.5 equivalent, preferably 0.5 to the starting alcohol. What is necessary is just 0.5-0.3 equivalent.
また、本発明の酸化方法おいて、テトラブチルアンモニウム硫酸水素塩などのイオン対試薬を用いてもよい。イオン対試薬の使用量は、原料のアルコール類に対して０.１〜３.０当量、好ましくは、０.１〜１.０当量であればよい。 In the oxidation method of the present invention, an ion pair reagent such as tetrabutylammonium hydrogen sulfate may be used. The amount of the ion pair reagent used may be 0.1 to 3.0 equivalents, preferably 0.1 to 1.0 equivalents, relative to the starting alcohol.
本発明の、２−ヨード安息香酸アミド型触媒と共酸化剤の存在下に行うアルコール類の酸化により、室温といった低温下に、第１級アルコール類からカルボン酸類、第２級アルコール類からケトン類を効率よく製造することができる。 Oxidation of alcohols in the present invention in the presence of a 2-iodobenzoic acid amide type catalyst and a co-oxidant causes primary alcohols to carboxylic acids and secondary alcohols to ketones at a low temperature such as room temperature. Can be manufactured efficiently.
本発明のヨードベンズアミド型触媒は、例えば、以下の方法で製造することができる。 The iodobenzamide type catalyst of the present invention can be produced, for example, by the following method.
＜製造法１＞
「式中、Ｒ１は、水素原子もしくはハロゲン原子またはアルキル、アルコキシ、アシル、アシルオキシもしくはニトロから選ばれる基を；Ｒ２およびＲ３は、同一または異なって水素原子、置換されていてもよいアルキル、シクロアルキル、アルキルスルホニルもしくアリールスルホニル基または一緒になって置換されていてもよいアルキレン基を、Ｘは、塩素原子などのハロゲン原子を。それぞれ意味する。」 “In the formula, R 1 represents a hydrogen atom or a halogen atom or a group selected from alkyl, alkoxy, acyl, acyloxy or nitro; R 2 and R 3 are the same or different and each represents a hydrogen atom or an optionally substituted alkyl. , Cycloalkyl, alkylsulfonyl or arylsulfonyl group, or an alkylene group which may be substituted together, X represents a halogen atom such as a chlorine atom.
一般式［２］の化合物と一般式［３］の化合物を、溶媒中で反応させることにより一般式［１］の化合物を製造することができる。 The compound of general formula [1] can be produced by reacting the compound of general formula [2] with the compound of general formula [3] in a solvent.
この反応に用いる溶媒は、反応に悪影響を及ぼさないものであれば、特に限定されないが、例えば、塩化メチレン、クロロホルムおよびジクロロエタンなどのハロゲン化炭化水素類が挙げられ、溶媒を一種または二種以上混合して使用してもよい。
この反応は、２０℃〜６０℃で、３０分〜１２時間行えばよい。
The solvent used in this reaction is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include halogenated hydrocarbons such as methylene chloride, chloroform and dichloroethane. One or a mixture of two or more solvents can be used. May be used.
This reaction may be performed at 20 ° C. to 60 ° C. for 30 minutes to 12 hours.
一般式［２］の化合物は、市販品を購入するか、または公知方法に準じて製造すればよい。また、一般式［１］の化合物は、例えば、以下に示すように別の一般式［１］へ誘導することもできる。 The compound of the general formula [2] may be purchased commercially or manufactured according to a known method. Moreover, the compound of general formula [1] can also be derived into another general formula [1] as shown below, for example.
＜製造法２＞
「式中、Ｒ１は、水素原子もしくはハロゲン原子またはアルキル、アルコキシ、アシル、アシルオキシもしくはニトロから選ばれる基を；Ｒ５は、アルキル基を、Ａはアルキレン基を、それぞれ意味する。」 “Wherein R 1 represents a hydrogen atom or a halogen atom or a group selected from alkyl, alkoxy, acyl, acyloxy or nitro; R 5 represents an alkyl group, and A represents an alkylene group.
一般式［１ｄ］の化合物と一般式［４］の化合物を、反応させることにより一般式［１ｃ］の化合物を製造することができる。この反応は、製造法１で説明したと同様に行えばよい。 The compound of general formula [1c] can be produced by reacting the compound of general formula [1d] with the compound of general formula [4]. This reaction may be performed in the same manner as described in Production Method 1.
以下に、実施例により本発明をさらに具体的に説明するが、本発明はそれらに限定されるものではない。 EXAMPLES The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.
実施例１
＜触媒の合成＞
<Catalyst synthesis>
２−ヨードベンゾイルクロリド（799mg, 3mmol）の塩化メチレン（3mL）溶液をイソプロピルアミン（213mg, 3.6mmol）とトリエチルアミン（911mg, 9mmol）の塩化メチレン（7mL）溶液に0℃で加え、その後室温で1時間撹拌した。反応液を酢酸エチル（50mL）で希釈し、10%塩酸、飽和炭酸水素ナトリウム水溶液、水、飽和食塩水で洗浄後、乾燥し濃縮した。残渣を酢酸エチル−ヘキサンで再結晶して無色針状の２−ヨード−Ｎ−イソプロピルベンズアミド[化合物1]（580mg, 67%）を得た。
融点：134〜135℃
同様にして以下の化合物を得た。
A solution of 2-iodobenzoyl chloride (799 mg, 3 mmol) in methylene chloride (3 mL) was added to a solution of isopropylamine (213 mg, 3.6 mmol) and triethylamine (911 mg, 9 mmol) in methylene chloride (7 mL) at 0 ° C. and then at room temperature. Stir for hours. The reaction mixture was diluted with ethyl acetate (50 mL), washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried and concentrated. The residue was recrystallized from ethyl acetate-hexane to obtain colorless needle-like 2-iodo-N-isopropylbenzamide [Compound 1] (580 mg, 67%).
Melting point: 134-135 ° C
Similarly, the following compounds were obtained.
・N-ethyl-2-iodobenzamide [化合物2]
・N-tert-butyl-2-iodobenzamide [化合物3]
・2-iodo-N-tert-pentylbenzamide [化合物4]
・2-iodo-N-(1-methylhexyl)benzamide [化合物5]
・N-cyclohexyl-2-iodobenzamide [化合物6]
・2-iodo-N-phenethylbenzamide [化合物7]
・2-(2-iodobenzamido)ethyl acetate [化合物8]
・methyl 2-(2-iodobenzamido)acetate [化合物9]
・methyl 2-(2-iodobenzamido)propanoate [化合物10]
・2-iodo-N-(methylsulfonyl)benzamide [化合物11]
・2-iodo-N-(phenylsulfonyl)benzamide [化合物12]
実施例２
＜触媒の合成２＞
<Catalyst synthesis 2>
２−ヨードベンゾイルクロリド（799mg, 3mmol）の塩化メチレン（3mL）溶液を２−アミノ−２−メチルプロパン酸塩酸塩（553mg, 3.6mmol）とトリエチルアミン（911mg, 9mmol）の塩化メチレン（7mL）溶液に0℃で加え、その後室温で1時間撹拌した。反応液を酢酸エチル（50mL）で希釈し、10％塩酸，飽和炭酸水素ナトリウム水溶液、水、飽和食塩水で洗浄後、乾燥し濃縮した。残渣をシリカゲルカラムクロマトグラフィーで精製してメチル２−（２−イソベンズアミド−２−メチルプロパネート [化合物13]（889mg, 85%）を得た。
無色針状結晶(再結晶溶媒：酢酸エチル−ヘキサン)。
融点：125〜127℃
A solution of 2-iodobenzoyl chloride (799 mg, 3 mmol) in methylene chloride (3 mL) was added to a solution of 2-amino-2-methylpropanoic acid hydrochloride (553 mg, 3.6 mmol) and triethylamine (911 mg, 9 mmol) in methylene chloride (7 mL). The mixture was added at 0 ° C. and then stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate (50 mL), washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried and concentrated. The residue was purified by silica gel column chromatography to obtain methyl 2- (2-isobenzamido-2-methylpropanoate [Compound 13] (889 mg, 85%).
Colorless needle crystals (recrystallization solvent: ethyl acetate-hexane).
Melting point: 125-127 ° C
化合物13（889mg, 2.56mmol）と水酸化リチウム１水和物（430mg, 10.24mmol）をテトラヒドロフラン・メタノール・水（25:8:8）の混合溶媒（28mL）に溶かし室温で30分間撹拌した。反応液を水（60mL)で希釈し、10％塩酸で酸性にした。酢酸エチルで抽出した。抽出液を乾燥し濃縮して２−（２−イソベンズアミド−２−メチルプロパン酸[化合物14]（836mg, 98%）を得た。
無色針状結晶(再結晶溶媒：酢酸エチル−ヘキサン)
融点：206〜207℃。
Compound 13 (889 mg, 2.56 mmol) and lithium hydroxide monohydrate (430 mg, 10.24 mmol) were dissolved in a mixed solvent (28 mL) of tetrahydrofuran / methanol / water (25: 8: 8) and stirred at room temperature for 30 minutes. The reaction was diluted with water (60 mL) and acidified with 10% hydrochloric acid. Extracted with ethyl acetate. The extract was dried and concentrated to give 2- (2-isobenzamido-2-methylpropanoic acid [Compound 14] (836 mg, 98%).
Colorless needle crystal (recrystallization solvent: ethyl acetate-hexane)
Melting point: 206-207 ° C.
化合物14（836mg, 2.51mmol）と塩化チオニル（3.1mL）に加え，2時間加熱還流した後、濃縮して、2-(2-iodobenzamido)-2-methylpropanoyl chloride [14a]得た。
化合物14aの塩化メチレン（8mL）溶液にブチルアミン（220mg, 3.01mmol）とトリエチルアミン（762mg, 7.53mmol）を0℃で加え，室温で1時間撹拌した。反応液を酢酸エチル（50mL）で希釈し、10%塩酸、飽和炭酸水素ナトリウム水溶液、飽和食塩水で洗浄後、乾燥し濃縮した。残渣を酢酸エチル−ヘキサンで再結晶して無色針状のN-(1-ブチルカルバモイル-1-メチルエチル)-2-ヨードベンズアミド [化合物15]（788mg, 80%）を得た。
融点134〜135℃。
In addition to compound 14 (836 mg, 2.51 mmol) and thionyl chloride (3.1 mL), the mixture was heated to reflux for 2 hours and then concentrated to give 2- (2-iodobenzamido) -2-methylpropanoyl chloride [14a].
Butylamine (220 mg, 3.01 mmol) and triethylamine (762 mg, 7.53 mmol) were added to a solution of compound 14a in methylene chloride (8 mL) at 0 ° C., and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate (50 mL), washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried and concentrated. The residue was recrystallized from ethyl acetate-hexane to obtain colorless needle-like N- (1-butylcarbamoyl-1-methylethyl) -2-iodobenzamide [Compound 15] (788 mg, 80%).
Melting point 134-135 ° C.
＜触媒の合成３＞
実施例３
Example 3
2-ヨード-5-メトキシ安息香酸（471mg, 1.69mmol）を塩化チオニル（2.1mL）に加え、2時間加熱還流した後、濃縮して、2-ヨード-5-メトキシベンゾイルクロリドを得た。次いで、2-ヨード-5-メトキシベンゾイルクロリドの塩化メチレン（5.6mL）溶液にイソプロピルアミン（120mg, 2.03mmol）とトリエチルアミン（513mg, 5.07mmol）を0℃で加え、室温で1時間撹拌した。反応液を酢酸エチル（50mL）で希釈し、10%塩酸、飽和炭酸水素ナトリウム水溶液、水、飽和食塩水で洗浄後、乾燥し濃縮した。残渣をクロロホルム−ヘキサンで再結晶して無色針状の2-ヨード-N-イソプロピル-5-メトキシベンズアミド[化合物16]（402mg, 75%）を得た。 2-Iodo-5-methoxybenzoic acid (471 mg, 1.69 mmol) was added to thionyl chloride (2.1 mL), heated under reflux for 2 hours, and then concentrated to obtain 2-iodo-5-methoxybenzoyl chloride. Next, isopropylamine (120 mg, 2.03 mmol) and triethylamine (513 mg, 5.07 mmol) were added to a solution of 2-iodo-5-methoxybenzoyl chloride in methylene chloride (5.6 mL) at 0 ° C., and the mixture was stirred at room temperature for 1 hour. The reaction mixture was diluted with ethyl acetate (50 mL), washed with 10% hydrochloric acid, saturated aqueous sodium hydrogen carbonate solution, water and saturated brine, dried and concentrated. The residue was recrystallized from chloroform-hexane to obtain colorless needle-like 2-iodo-N-isopropyl-5-methoxybenzamide [Compound 16] (402 mg, 75%).
融点：147〜148.5℃
1H-NMR (400 MHz, CDCl3) δ: 7.68(1H,d,J=8.7Hz),6.96(1H,d,J=3.2Hz),6.68(1H,dd,J=8.7,3.2Hz), 5.59(1H,brd, J=6.4Hz),4.29(1H,m), 3.80(3H,s),1.29(6H,d,J=6.9Hz).
同様にして以下の化合物を得た。
Melting point: 147-148.5 ° C
1 H-NMR (400 MHz, CDCl 3 ) δ: 7.68 (1H, d, J = 8.7Hz), 6.96 (1H, d, J = 3.2Hz), 6.68 (1H, dd, J = 8.7,3.2Hz) , 5.59 (1H, brd, J = 6.4Hz), 4.29 (1H, m), 3.80 (3H, s), 1.29 (6H, d, J = 6.9Hz).
Similarly, the following compounds were obtained.
・5-chloro-2-iodo-N-isopropylbenzamide [化合物17]
無色針状晶(再結晶溶媒：クロロホルム−ヘキサン)、 融点：160.5〜162℃
1H-NMR (400 MHz, CDCl3) δ: 7.76(1H,d,J=8.2Hz),7.37(1H,d,J=2.3Hz),7.08(1H,dd,J= 8.2,2.3Hz),5.54(1H,brs),4.29(1H,m),1.29(6H,d,J=6.4Hz).
Colorless needle crystal (recrystallization solvent: chloroform-hexane), melting point: 160.5-162 ° C
1 H-NMR (400 MHz, CDCl 3 ) δ: 7.76 (1H, d, J = 8.2Hz), 7.37 (1H, d, J = 2.3Hz), 7.08 (1H, dd, J = 8.2,2.3Hz) , 5.54 (1H, brs), 4.29 (1H, m), 1.29 (6H, d, J = 6.4Hz).
・2-iodo-N-isopropyl-5-methylbenzamide [化合物18]
無色針状晶(再結晶溶媒：クロロホルム−ヘキサン)、 融点：147〜149℃
1H-NMR (400 MHz, CDCl3) δ: 7.69(1H,d,J=7.8Hz),7.21(1H,d,J=1.8Hz),6.90(1H,dd,J= 7.8,1.8Hz),5.57(1H,brd,J=4.6Hz),4.29(1H,m),2.31(3H,s),1.28(6H,d,J=6.4Hz).
Colorless needle crystals (recrystallization solvent: chloroform-hexane), melting point: 147-149 ° C
1 H-NMR (400 MHz, CDCl 3 ) δ: 7.69 (1H, d, J = 7.8Hz), 7.21 (1H, d, J = 1.8Hz), 6.90 (1H, dd, J = 7.8,1.8Hz) , 5.57 (1H, brd, J = 4.6Hz), 4.29 (1H, m), 2.31 (3H, s), 1.28 (6H, d, J = 6.4Hz).
・methyl 4-iodo-3-(isopropylcarbamoyl)benzoate [化合物19]
無色柱状晶(再結晶溶媒：クロロホルム−ヘキサン)、 融点：170〜171.5℃
1H-NMR (400 MHz, CDCl3) δ: 8.49(1H,d,J=1.4Hz),8.01(1H,dd,J=7.8,1.4Hz),7.42(1H, d,J=7.8Hz),5.64(1H,brd,J=7.3Hz),4.30(1H,m),3.93(3H,s),1.30(6H,d,J=6.4Hz).
Colorless columnar crystals (recrystallization solvent: chloroform-hexane), melting point: 170-171.5 ° C.
1 H-NMR (400 MHz, CDCl 3 ) δ: 8.49 (1H, d, J = 1.4Hz), 8.01 (1H, dd, J = 7.8,1.4Hz), 7.42 (1H, d, J = 7.8Hz) , 5.64 (1H, brd, J = 7.3Hz), 4.30 (1H, m), 3.93 (3H, s), 1.30 (6H, d, J = 6.4Hz).
・2-iodo-N-isopropyl-5-nitrobenzamide [化合物20]
無色針状晶(再結晶溶媒：クロロホルム−ヘキサン)、 融点：196〜198℃
1H-NMR (400 MHz, CDCl3) δ: 8.19(1H,d,J=2.7Hz),8.07(1H,d,J=8.7Hz),7.92(1H,dd,J =8.7,2.7Hz),5.64(1H,brd,J=4.6Hz),4.33(1H,m),1.32(6H,d,J=6.4Hz).
Colorless needle crystals (recrystallization solvent: chloroform-hexane), melting point: 196-198 ° C
1 H-NMR (400 MHz, CDCl 3 ) δ: 8.19 (1H, d, J = 2.7Hz), 8.07 (1H, d, J = 8.7Hz), 7.92 (1H, dd, J = 8.7,2.7Hz) , 5.64 (1H, brd, J = 4.6Hz), 4.33 (1H, m), 1.32 (6H, d, J = 6.4Hz).
・2-iodo-N-isopropyl-4-methoxybenzamide [化合物21]
無色針状晶(再結晶溶媒：クロロホルム−ヘキサン)、 融点：132.5〜135℃
1H-NMR (400 MHz, CDCl3) δ:7.37(1H,d,J=2.7Hz),7.35(1H,d,J=8.2Hz),6.89(1H,dd,J= 8.2,2.7Hz),5.58(1H,brd,J=5.0Hz),4.28(1H,m),3.80(3H,s),1.28(6H,d,J=6.4Hz).
Colorless needle crystals (recrystallization solvent: chloroform-hexane), melting point: 132.5-135 ° C
1 H-NMR (400 MHz, CDCl 3 ) δ: 7.37 (1H, d, J = 2.7Hz), 7.35 (1H, d, J = 8.2Hz), 6.89 (1H, dd, J = 8.2,2.7Hz) , 5.58 (1H, brd, J = 5.0Hz), 4.28 (1H, m), 3.80 (3H, s), 1.28 (6H, d, J = 6.4Hz).
・2-iodo-N-isopropyl-3-methoxybenzamide [化合物22]
無色柱状晶(再結晶溶媒：クロロホルム−ヘキサン)、 融点：136〜137.5℃
1H-NMR (400 MHz, CDCl3) δ: 7.31(1H,t,J=7.8Hz),6.96(1H,d,J=7.8Hz),6.83(1H,d,J= 7.8Hz),5.54(1H,brd,J=5.5Hz),4.30(1H,m),3.90(3H,s),1.28(6H,d,J=6.4Hz).
Colorless columnar crystals (recrystallization solvent: chloroform-hexane), melting point: 136-137.5 ° C
1 H-NMR (400 MHz, CDCl 3 ) δ: 7.31 (1H, t, J = 7.8Hz), 6.96 (1H, d, J = 7.8Hz), 6.83 (1H, d, J = 7.8Hz), 5.54 (1H, brd, J = 5.5Hz), 4.30 (1H, m), 3.90 (3H, s), 1.28 (6H, d, J = 6.4Hz).
実施例４
＜第１級アルコールの酸化＞
<Oxidation of primary alcohol>
３−フェニルプロパノール（68mg, 0.5mmol）を２−ヨード−Ｎ−イソプロピルベンズアミド[化合物1]（43mg, 0.15mmol）とテトラブチルアンモニウム硫酸水素塩（170mg, 0.5mmol）のニトロメタン（1.6mL）・水（0.6mL）の混合液に加え、ついでオキソン（768mg，1.25mmol）を室温（25℃）で加えた。20時間後反応液を酢酸エチル（（50mL）、水（10mL）および飽和チオ硫酸ナトリウム水溶液（15mL）で希釈した。二層に分離後、酢酸エチル希釈層を飽和炭酸水素ナトリウム水溶液で抽出した。抽出液を10％塩酸で酸性にした後、酢酸エチルで抽出した。抽出液を飽和食塩水で洗浄した後、無水硫酸マグネシウムで乾燥し溶媒を減圧留去し、フェニルプロピオン酸（68mg, 90%）を得た。一方、酢酸エチル希釈層を飽和食塩水で洗浄後，無水硫酸マグネシウムで乾燥し、溶媒を減圧留去して、２-ヨード−Ｎ−イソプロピルベンズアミド（39mg, 91%）を回収した。 3-Phenylpropanol (68 mg, 0.5 mmol) was added to 2-iodo-N-isopropylbenzamide [Compound 1] (43 mg, 0.15 mmol) and tetrabutylammonium hydrogen sulfate (170 mg, 0.5 mmol) in nitromethane (1.6 mL) and water (0.6 mL) was added to the mixture followed by oxone (768 mg, 1.25 mmol) at room temperature (25 ° C.). After 20 hours, the reaction mixture was diluted with ethyl acetate ((50 mL), water (10 mL) and saturated aqueous sodium thiosulfate solution (15 mL). After separation into two layers, the ethyl acetate diluted layer was extracted with saturated aqueous sodium bicarbonate solution. The extract was acidified with 10% hydrochloric acid and extracted with ethyl acetate, washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to remove phenylpropionic acid (68 mg, 90% On the other hand, the ethyl acetate diluted layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to recover 2-iodo-N-isopropylbenzamide (39 mg, 91%). did.
実施例５
実施例４の３−フェニルプロパノールの代わりにtetradecan-1-ol用い、酸化反応を24時間行って、tetradecanoic acidを収率82%で得た。
Example 5
Tetradecan-1-ol was used in place of 3-phenylpropanol in Example 4 and an oxidation reaction was performed for 24 hours to obtain tetradecanoic acid in a yield of 82%.
実施例６
実施例４の３−フェニルプロパノールの代わりに(4-nitrophenyl)methanol用い、酸化反応を24時間行って、4-nitrobenzoic acidを収率82%で得た。
Example 6
Instead of 3-phenylpropanol in Example 4, (4-nitrophenyl) methanol was used and the oxidation reaction was carried out for 24 hours to obtain 4-nitrobenzoic acid in a yield of 82%.
実施例７
実施例４の３−フェニルプロパノールの代わりに(4-chlorophenyl)methanol用い、酸化反応を24時間行って、4-chlorobenzoic acidを収率74%で得た。
Example 7
Instead of 3-phenylpropanol in Example 4, (4-chlorophenyl) methanol was used and the oxidation reaction was carried out for 24 hours to obtain 4-chlorobenzoic acid in a yield of 74%.
実施例９
３−フェニルプロパノール（68mg, 0.5mmol）をＮ−（１−ブチルカルバモイル−１−メチルエチル）−２−ヨードベンズアミド[化合物15]（43mg, 0.15mmol）とテトラブチルアンモニウム硫酸水素塩（170mg, 0.5mmol）のニトロメタン（1.6mL）・水（0.6mL）の混合液に加え、ついでオキソン（768 mg, 1.25mmol）を室温（25℃）で加えた。20時間後、反応液を酢酸エチル（50mL）、水（10mL）および飽和チオ硫酸ナトリウム水溶液（15mL）で希釈した。二層に分離後、酢酸エチル希釈層を、飽和炭酸水素ナトリウム水溶液で抽出した。抽出液を10％塩酸で酸性にした後、酢酸エチルで抽出し、抽出液を無水硫酸マグネシウムで乾燥し、溶媒を減圧留去して、フェニルプロピオン酸（66mg, 90%）を得た。一方，酢酸エチル希釈層を飽和食塩水で洗浄後，無水硫酸マグネシウムで乾燥し、溶媒を減圧留去して、Ｎ−（１−ブチルカルバモイル−１−メチルエチル）−２−ヨードベンズアミド（40mg, 93%）を回収した。 3-phenylpropanol (68 mg, 0.5 mmol) was added to N- (1-butylcarbamoyl-1-methylethyl) -2-iodobenzamide [compound 15] (43 mg, 0.15 mmol) and tetrabutylammonium hydrogen sulfate (170 mg, 0.5 mmol). mmol) of nitromethane (1.6 mL) / water (0.6 mL), and then oxone (768 mg, 1.25 mmol) was added at room temperature (25 ° C.). After 20 hours, the reaction was diluted with ethyl acetate (50 mL), water (10 mL) and saturated aqueous sodium thiosulfate (15 mL). After separation into two layers, the ethyl acetate diluted layer was extracted with a saturated aqueous sodium bicarbonate solution. The extract was acidified with 10% hydrochloric acid and extracted with ethyl acetate, the extract was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to obtain phenylpropionic acid (66 mg, 90%). On the other hand, the ethyl acetate diluted layer was washed with saturated brine and dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure to give N- (1-butylcarbamoyl-1-methylethyl) -2-iodobenzamide (40 mg, 93%) was recovered.
実施例１０
＜第２級アルコールの酸化＞
<Oxidation of secondary alcohol>
ジフェニルメタノール（100mg, 0.54mmol）を２−ヨード−Ｎ−イソプロピルベンズアミド[化合物1]（47mg, 0.16mmol）とテトラブチルアンモニウム硫酸水素塩（184mg, 0.54mmol）のニトロメタン（1.6mL）・水（0.6mL）の混合液に加え、ついでオキソン（835mg，1.36mmol）を室温（25 ℃）で加えた。12時間後反応液を酢酸エチル（50mL）で希釈し、水、飽和チオ硫酸ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄後、無水硫酸マグネシウムで乾燥し、溶媒を減圧留去した。残渣をシリカゲルカラムクロマトグラフィーで精製してベンゾフェノン（93mg, 94%）を得た。また、２−ヨード−Ｎ−イソプロピルベンズアミド（42mg, 89%）を回収した。 Diphenylmethanol (100 mg, 0.54 mmol) was added to 2-iodo-N-isopropylbenzamide [Compound 1] (47 mg, 0.16 mmol) and tetrabutylammonium hydrogensulfate (184 mg, 0.54 mmol) in nitromethane (1.6 mL) and water (0.6 mL) and then oxone (835 mg, 1.36 mmol) was added at room temperature (25 ° C.). After 12 hours, the reaction solution was diluted with ethyl acetate (50 mL), washed successively with water, saturated aqueous sodium thiosulfate solution, saturated aqueous sodium hydrogen carbonate solution and saturated brine, and then dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. . The residue was purified by silica gel column chromatography to obtain benzophenone (93 mg, 94%). In addition, 2-iodo-N-isopropylbenzamide (42 mg, 89%) was recovered.
実施例１１
実施例１０のジフェニルメタノールの代わりに用い、1-フェニルエタノールを用い、酸化反応を14時間行って、アセトフェノンを収率70%で得た。
Example 11
The acetophenone was obtained in a yield of 70% by using 1-phenylethanol in place of diphenylmethanol of Example 10 and carrying out an oxidation reaction for 14 hours.
実施例１２
実施例１０のジフェニルメタノールの代わりに用い、4-phenylbutan-2-olを用い、酸化反応を30時間行って、4-phenylbutan-2-oneを収率70%で得た。
Example 12
Using 4-phenylbutan-2-ol in place of diphenylmethanol of Example 10 and carrying out an oxidation reaction for 30 hours, 4-phenylbutan-2-one was obtained in a yield of 70%.
実施例１３
ジフェニルメタノール（92mg, 0.5mmol）をＮ−（１−ブチルカルバモイル−１−メチルエチル）−２−ヨードベンズアミド[化合物15]（58mg, 0.15mmol）とテトラブチルアンモニウム硫酸水素塩（170mg, 0.5mmol）のニトロメタン（1.6mL）・水（0.6mL）の混合液に加え、ついでオキソン（765mg，1.25mmol）を室温（25℃）で加えた。13時間後、反応液を酢酸エチル（50mL）で希釈し、水、飽和チオ硫酸ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩水で順次洗浄後、無水硫酸マグネシウムで乾燥し、溶媒を減圧留去した。残渣をシリカゲルカラムクロマトグラフィーで精製してベンゾフェノン（89mg, 98%）を得た。また、Ｎ−（１−ブチルカルバモイル−１−メチルエチル）−２−ヨードベンズアミド（44mg, 76%）を回収した。 Diphenylmethanol (92 mg, 0.5 mmol) was added to N- (1-butylcarbamoyl-1-methylethyl) -2-iodobenzamide [Compound 15] (58 mg, 0.15 mmol) and tetrabutylammonium hydrogensulfate (170 mg, 0.5 mmol). Was added to a mixture of nitromethane (1.6 mL) and water (0.6 mL), followed by oxone (765 mg, 1.25 mmol) at room temperature (25 ° C.). After 13 hours, the reaction mixture was diluted with ethyl acetate (50 mL), washed successively with water, saturated aqueous sodium thiosulfate solution, saturated aqueous sodium bicarbonate solution, and saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure. did. The residue was purified by silica gel column chromatography to obtain benzophenone (89 mg, 98%). In addition, N- (1-butylcarbamoyl-1-methylethyl) -2-iodobenzamide (44 mg, 76%) was recovered.
実施例１４
実施例１０の化合物1(0.3等量)の代わりに化合物3(0.1等量)用い、酸化反応を34時間行って、ベンゾフェノンを収率98%で得た。
Example 14
Compound 3 (0.1 equivalent) was used in place of compound 1 (0.3 equivalent) in Example 10, and the oxidation reaction was performed for 34 hours to obtain benzophenone in a yield of 98%.
実施例１５
実施例１０の化合物1(0.3等量)の代わりに化合物13(0.3等量)用い、酸化反応を16時間行って、ベンゾフェノンを収率97%で得た。
Example 15
Compound 13 (0.3 equivalent) was used instead of compound 1 (0.3 equivalent) in Example 10 and the oxidation reaction was carried out for 16 hours to obtain benzophenone in a yield of 97%.
実施例１６
＜第２級アルコールの酸化２＞
<Oxidation of secondary alcohol 2>
ジフェニルメタノール（92mg, 0.5mmol）を2-ヨード-N-イソプロピル-5-メトキシベンズアミド[化合物16]（48mg, 0.15mmol）とテトラブチルアンモニウム硫酸水素塩（170mg, 0.5mmol）のニトロメタン（1.6mL）−水（0.6mL）に加え、次いでオキソン（768mg, 1.25mmol）を室温（25 ℃）で加えた。6時間後反応液を酢酸エチル（50mL）で希釈し、水、飽和チオ硫酸ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液で順次洗浄後、無水硫酸マグネシウムで乾燥し、溶媒を減圧留去した。残渣をシリカゲルカラムクロマトグラフィーで精製してベンゾフェノン（88mg, 97%）を得た。また、2-ヨード-N-イソプロピル-5-メトキシベンズアミド（41mg, 85%）を回収した。 Diphenylmethanol (92 mg, 0.5 mmol) with 2-iodo-N-isopropyl-5-methoxybenzamide [Compound 16] (48 mg, 0.15 mmol) and tetrabutylammonium hydrogen sulfate (170 mg, 0.5 mmol) in nitromethane (1.6 mL) -Added to water (0.6 mL) followed by Oxone (768 mg, 1.25 mmol) at room temperature (25 ° C). After 6 hours, the reaction solution was diluted with ethyl acetate (50 mL), washed successively with water, saturated aqueous sodium thiosulfate solution, and saturated aqueous sodium hydrogen carbonate solution, and dried over anhydrous magnesium sulfate, and the solvent was evaporated under reduced pressure. The residue was purified by silica gel column chromatography to obtain benzophenone (88 mg, 97%). In addition, 2-iodo-N-isopropyl-5-methoxybenzamide (41 mg, 85%) was recovered.
実施例１７
実施例１６の化合物16(0.3等量)の代わりに化合物17(0.3等量)用い、酸化反応を18時間行って、ベンゾフェノンを収率98%で得た。
Example 17
Compound 17 (0.3 equivalent) was used instead of compound 16 (0.3 equivalent) in Example 16, and the oxidation reaction was performed for 18 hours to obtain benzophenone in a yield of 98%.
実施例１８
実施例１６の化合物16(0.3等量)の代わりに化合物18(0.3等量)用い、酸化反応を10時間行って、ベンゾフェノンを収率98%で得た。
Example 18
Compound 18 (0.3 equivalent) was used instead of compound 16 (0.3 equivalent) in Example 16, and the oxidation reaction was carried out for 10 hours to obtain benzophenone in a yield of 98%.
実施例１９
実施例１６の化合物16(0.3等量)の代わりに化合物19(0.3等量)用い、酸化反応を23時間行って、ベンゾフェノンを収率96%で得た。
Example 19
Compound 19 (0.3 equivalent) was used in place of compound 16 (0.3 equivalent) in Example 16, and an oxidation reaction was performed for 23 hours to obtain benzophenone in a yield of 96%.
実施例２０
実施例１６の化合物16(0.3等量)の代わりに化合物20(0.3等量)用い、酸化反応を46時間行って、ベンゾフェノンを収率98%で得た。
Example 20
Compound 20 (0.3 equivalent) was used instead of compound 16 (0.3 equivalent) in Example 16, and the oxidation reaction was carried out for 46 hours to obtain benzophenone in a yield of 98%.
実施例２１
実施例１６の化合物16(0.3等量)の代わりに化合物21(0.3等量)用い、酸化反応を13時間行って、ベンゾフェノンを収率98%で得た。
Example 21
Compound 21 (0.3 equivalent) was used in place of compound 16 (0.3 equivalent) in Example 16, and the oxidation reaction was carried out for 13 hours to obtain benzophenone in a yield of 98%.
実施例２２
実施例１６の化合物16(0.3等量)の代わりに化合物22(0.3等量)用い、酸化反応を23時間行って、ベンゾフェノンを収率99%で得た。
Example 22
Compound 22 (0.3 equivalent) was used in place of compound 16 (0.3 equivalent) in Example 16, and an oxidation reaction was performed for 23 hours to obtain benzophenone in a yield of 99%.
本発明の２−ヨード安息香酸アミド型触媒は、医薬品や農薬などのファインケミカル製造において、アルコール類の酸化工程に利用することができ、廃棄物の少ないグリーンな工業プラントの構築が達成できる。 The 2-iodobenzoic acid amide type catalyst of the present invention can be used in the oxidation process of alcohols in the production of fine chemicals such as pharmaceuticals and agricultural chemicals, and can achieve the construction of a green industrial plant with little waste.
Claims (4)
で表されるヨードベンズアミド型触媒と共酸化剤とを用いることを特徴とするアルコール類の酸化方法。 General formula
A method for oxidizing alcohols, characterized by using an iodobenzamide type catalyst represented by the formula (1) and a cooxidant.
The method for oxidizing an alcohol according to any one of claims 1 to 3 , wherein R 2 of the iodobenzamide type catalyst is a hydrogen atom, and R 3 is an optionally substituted alkyl, cycloalkyl, alkylsulfonyl, or arylsulfonyl group.
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