JP2008063314A - Environment-conscious hypervalent iodine reagent - Google Patents
Environment-conscious hypervalent iodine reagent Download PDFInfo
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Abstract
Description
本発明は超原子価ヨウ素化合物に関するもので，有機合成の属する分野，およびその他の分野で利用される環境調和型反応試剤に供するものである。 The present invention relates to a hypervalent iodine compound, and is used for an environmentally conscious reaction reagent used in the fields of organic synthesis and other fields.
超原子価ヨウ素化合物は，高い反応性と利用のしやすさから有機合成の多くの場面で利用されている。例えば，（ジアセトキシヨード）ベンゼンはＴＥＭＰＯと組み合わせて，アルコールをアルデヒドあるいはケトンに変換する際の酸化剤として用いられている。この反応は基質の分子内に二重結合が存在しても，それに影響を与えず進行する。また，［ヒドロキシ（トシルオキシ）ヨード］ベンゼンは，カルボニル化合物のα−トシル化剤として多用されている。得られたα−トシルカルボニル化合物のトシル基は種々の官能基に変換可能である。従って，カルボニル化合物のα−官能基化に有用である。 Hypervalent iodine compounds are used in many scenes of organic synthesis because of their high reactivity and ease of use. For example, (diacetoxyiodo) benzene is used in combination with TEMPO as an oxidant when converting alcohol to aldehyde or ketone. This reaction proceeds without affecting the presence of double bonds in the substrate molecule. [Hydroxy (tosyloxy) iodo] benzene is frequently used as an α-tosylating agent for carbonyl compounds. The tosyl group of the obtained α-tosylcarbonyl compound can be converted into various functional groups. Therefore, it is useful for α-functionalization of carbonyl compounds.
以上のように超原子価ヨウ素化合物は極めて有用な反応試剤として種々の反応に用いられている。一方，反応終了後，ヨードベンゼンの副生を避けることができず，このヨードベンゼンがしばしば目的物の単離の妨げとなる。この欠点を解消するため，超原子化ヨウ素化合物をポリマーに担持した，高分子担持型超原子価ヨウ素化合物が開発されている。例えばポリ［４−（ジアセトキシヨード）スチレン］を用いた反応では，反応終了後，ポリ（４−ヨードスチレン）を副生するが，これは多くの反応溶媒に不溶であるため，ろ過で簡単に取り除くことができる。また，回収したポリ（４−ヨードスチレン）は過酢酸で処理することによりポリ［４−（ジアセトキシヨード）スチレン］に再生することができ，再度利用することが可能である。 As described above, hypervalent iodine compounds are used in various reactions as extremely useful reaction reagents. On the other hand, after completion of the reaction, by-products of iodobenzene cannot be avoided, and this iodobenzene often hinders isolation of the target product. In order to eliminate this drawback, a polymer-supported hypervalent iodine compound in which a hyperatomized iodine compound is supported on a polymer has been developed. For example, in the reaction using poly [4- (diacetoxyiodo) styrene], poly (4-iodostyrene) is by-produced after the reaction is completed, but this is insoluble in many reaction solvents, so it can be easily filtered. Can be removed. The recovered poly (4-iodostyrene) can be regenerated into poly [4- (diacetoxyiodo) styrene] by treatment with peracetic acid and can be reused.
高分子担持型超原子価ヨウ素化合物は反応後の処理が簡便であり，再利用可能な有用な反応試剤であるが，ポリマーであるが故，ポリマーへの超原子化ヨウ素の定量的導入とその評価に限界がある。また，対応する小分子型試剤と比べ，反応性が劣るという欠点を有している。これに対し，近年，下記構造式で示される溶媒に難溶性の小分子型超原子価ヨウ素化合物，１，３，５，７−テトラキス［４−（ジアセトキシヨード）フェニル］アダマンタン，１，３，５，７−テトラキス［４−［ヒドロキシ（トシルオキシ）ヨード］フェニル］アダマンタン，テトラキス［４−（ジアセトキシヨード）フェニル］メタン，テトラキス［４−［ヒドロキシ（トシルオキシ）ヨード］フェニル］メタンが開発され，その有用性が報告されている。 The polymer-supported hypervalent iodine compound is a useful reaction reagent that can be easily processed after the reaction and can be reused. However, since it is a polymer, quantitative introduction of hyperatomic iodine into the polymer and its There is a limit to evaluation. In addition, it has the disadvantage that the reactivity is inferior to the corresponding small molecule type reagent. On the other hand, in recent years, a small molecule hypervalent iodine compound which is hardly soluble in a solvent represented by the following structural formula, 1,3,5,7-tetrakis [4- (diacetoxyiodo) phenyl] adamantane, 1,3 , 5,7-tetrakis [4- [hydroxy (tosyloxy) iodo] phenyl] adamantane, tetrakis [4- (diacetoxyiodo) phenyl] methane, tetrakis [4- [hydroxy (tosyloxy) iodo] phenyl] methane have been developed. , Its usefulness has been reported.
これらの小分子型超原子価ヨウ素化合物，および反応後副生する４−ヨード体は極性溶媒に難溶であり，ろ過により回収，超原子価ヨウ素化合物の原料として再利用することができる。さらにその反応性は（ジアセトキシヨード）ベンゼン，［ヒドロキシ（トシルオキシ）ヨード］ベンゼンと同等，またはそれ以上である。 These small-molecule hypervalent iodine compounds and 4-iodo form by-produced after the reaction are hardly soluble in polar solvents, and can be recovered by filtration and reused as raw materials for hypervalent iodine compounds. Furthermore, its reactivity is equivalent to or higher than (diacetoxyiodo) benzene and [hydroxy (tosyloxy) iodo] benzene.
上記のように１，３，５，７−テトラキス［４−（ジアセトキシヨード）フェニル］アダマンタン，１，３，５，７−テトラキス［４−［ヒドロキシ（トシルオキシ）ヨード］フェニル］アダマンタン，テトラキス［４−（ジアセトキシヨード）フェニル］メタン，テトラキス［４−［ヒドロキシ（トシルオキシ）ヨード］フェニル］メタンは副生物の回収，原料として再利用可能な環境調和型超原子価ヨウ素化合物である。しかしながら，原料である１，３，５，７−テトラフェニルアダマンタンは入手困難であり，その合成は頻雑である。また，テトラフェニルメタンは高価な化合物である。より入手しやすい安価な原料から合成可能な環境調和型超原子価ヨウ素化合物が求められている。 1,3,5,7-tetrakis [4- (diacetoxyiodo) phenyl] adamantane, 1,3,5,7-tetrakis [4- [hydroxy (tosyloxy) iodo] phenyl] adamantane, tetrakis [ 4- (diacetoxyiodo) phenyl] methane and tetrakis [4- [hydroxy (tosyloxy) iodo] phenyl] methane are environment-friendly hypervalent iodine compounds that can be recovered as by-products and reused as raw materials. However, the raw material 1,3,5,7-tetraphenyladamantane is difficult to obtain and its synthesis is complicated. Tetraphenylmethane is an expensive compound. There is a need for an environmentally harmonious hypervalent iodine compound that can be synthesized from cheaper raw materials that are more readily available.
そこで，発明者らは鋭意研究を重ね，本発明を完成するに至った。すなわち，本発明は下記構造式 Thus, the inventors have conducted extensive research and have completed the present invention. That is, the present invention has the following structural formula:
（式中，Ｒ１，Ｒ２はアセトキシ基，トリフルオロアセトキシ基，水酸基，トシル基から選択され，ｎは０以上の整数から選ばれる。ただし，Ｒ１，Ｒ２のいずれか一方が水酸基の場合，他方はトシル基で，Ｒ１，Ｒ２のいずれか一方がアセトキシ基の場合，他方はアセトキシ基かトリフルオロアセトキシ基で，Ｒ１，Ｒ２のいずれか一方がトリフルオロアセトキシ基の場合，他方はアセトキシ基かトリフルオロアセトキシ基で，Ｒ１，Ｒ２が同一でアセトキシ基，トリフルオロアセトキシ基の場合，ｎは１以上の整数から選ばれる。）で示される新規超原子価ヨウ素化合物，及び下記構造式(In the formula, R 1 and R 2 are selected from an acetoxy group, a trifluoroacetoxy group, a hydroxyl group, and a tosyl group, and n is selected from an integer of 0 or more, provided that either R 1 or R 2 is a hydroxyl group. In this case, the other is a tosyl group, and one of R 1 and R 2 is an acetoxy group, the other is an acetoxy group or a trifluoroacetoxy group, and one of R 1 and R 2 is a trifluoroacetoxy group , The other is an acetoxy group or a trifluoroacetoxy group, and when R 1 and R 2 are the same and are an acetoxy group or a trifluoroacetoxy group, n is selected from an integer of 1 or more.) , And the following structural formula
（式中，Ｒ１，Ｒ２はアセトキシ基，トリフルオロアセトキシ基，水酸基，トシル基から選択され，Ｒ３はハロゲン，水素から選択され，ｎは０以上の整数から選ばれる。ただし，Ｒ１，Ｒ２のいずれか一方が水酸基の場合，他方はトシル基で，Ｒ１，Ｒ２のいずれか一方がアセトキシ基の場合，他方はアセトキシ基かトリフルオロアセトキシ基で，Ｒ１，Ｒ２のいずれか一方がトリフルオロアセトキシ基の場合，他方はアセトキシ基かトリフルオロアセトキシ基で，Ｒ３が塩素，水素の場合，ｎは１以上の整数から選ばれる）で示される新規超原子価ヨウ素化合物に関するものである。(Wherein R 1 and R 2 are selected from an acetoxy group, a trifluoroacetoxy group, a hydroxyl group, and a tosyl group, R 3 is selected from halogen and hydrogen, and n is selected from an integer of 0 or more, provided that R 1 , R 2 is a hydroxyl group, the other is a tosyl group, and one of R 1 , R 2 is an acetoxy group, the other is an acetoxy group or a trifluoroacetoxy group, and R 1 , R 2 A novel hypervalent iodine compound represented by any one of which is a trifluoroacetoxy group, the other is an acetoxy group or a trifluoroacetoxy group, and R 3 is chlorine or hydrogen, n is selected from an integer of 1 or more) It is about.
以下に本発明の代表例として下記構造式１〜３で示される新規超原子価ヨウ素化合物を取り上げ本発明の有用性を明らかにする。 Hereinafter, as representative examples of the present invention, novel hypervalent iodine compounds represented by the following structural formulas 1 to 3 are taken up to clarify the usefulness of the present invention.
本発明の代表例である構造式１〜４で示される４，４”−ビス（ジアセトキシヨード）−ｐ−ターフェニル（１），４−ブロモ−４”−（ジアセトキシヨード）ビフェニル（２），４−ブロモ−４”−［ヒドロキシ（トシルオキシ）ヨード］ビフェニル（３）は文献未載の新規化合物で下記反応式に従って容易に合成することができる。これは例示であり変形可能なことは当業者には明らかであろう。 4,4 ″ -bis (diacetoxyiodo) -p-terphenyl (1), 4-bromo-4 ″-(diacetoxyiodo) biphenyl (2) represented by structural formulas 1 to 4 which are representative examples of the present invention. ), 4-bromo-4 "-[hydroxy (tosyloxy) iodo] biphenyl (3) is a novel compound not yet published in the literature and can be easily synthesized according to the following reaction formula. It will be apparent to those skilled in the art.
代表例１あるいは２は，それぞれ酸化剤の存在下，４，４”−ジヨード−ｐ−ターフェニルあるいは４−ブロモ−４”−ヨードビフェニルに酢酸を作用させることで得られる。酸化剤としては過ホウ酸ナトリウム，ｍ−クロロ過安息香酸，過酸化水素などから適宜選択される。また，過酢酸を用いてもよい。反応温度は使用する酸化剤などにより異なり，０℃から酢酸の還流温度までの間で選択されるが，好ましくは室温付近である。反応に要する時間は使用する酸化剤，反応温度により異なるが，１時間から４８時間の間で適宜選択される。
代表例３は酸化剤の存在下，４−ブロモ−４”−ヨードビフェニルにｐ−トルエンスルホン酸を作用させることで得られる。酸化剤としては過ホウ酸ナトリウム，ｍ−クロロ過安息香酸，過酸化水素などから適宜選択される。また，２にｐ−トルエンスルホン酸を反応させることで３を得ることができる。反応温度は０℃から１００℃までの間で選択されるが，好ましくは室温付近である。反応に要する時間は使用する酸化剤，反応温度により異なるが，１時間から４８時間の間で適宜選択される。Representative example 1 or 2 can be obtained by allowing acetic acid to act on 4,4 ″ -diiodo-p-terphenyl or 4-bromo-4 ″ -iodobiphenyl in the presence of an oxidizing agent, respectively. The oxidizing agent is appropriately selected from sodium perborate, m-chloroperbenzoic acid, hydrogen peroxide, and the like. Peracetic acid may also be used. The reaction temperature varies depending on the oxidizing agent used and is selected between 0 ° C. and the reflux temperature of acetic acid, but is preferably around room temperature. The time required for the reaction varies depending on the oxidizing agent used and the reaction temperature, but is appropriately selected from 1 hour to 48 hours.
Representative example 3 is obtained by reacting 4-bromo-4 "-iodobiphenyl with p-toluenesulfonic acid in the presence of an oxidizing agent. Examples of the oxidizing agent include sodium perborate, m-chloroperbenzoic acid, peroxysulfonic acid. It is appropriately selected from hydrogen oxide, etc. Further, 3 can be obtained by reacting p-toluenesulfonic acid with 2. The reaction temperature is selected between 0 ° C. and 100 ° C., preferably room temperature. The time required for the reaction varies depending on the oxidizing agent used and the reaction temperature, but is appropriately selected from 1 hour to 48 hours.
以上のように本発明化合物は簡便に合成することができる。以下に本発明化合物を反応試剤として用いた参考例を示し，本発明化合物の有用性を明らかにする。これは例示でありこれに限定されるものではない。
参考例１桂皮アルコールの酸化 As described above, the compound of the present invention can be easily synthesized. Reference examples using the compounds of the present invention as reaction reagents are shown below to clarify the usefulness of the compounds of the present invention. This is an example, and the present invention is not limited to this.
Reference Example 1 Oxidation of cinnamon alcohol
通常の小分子型超原子価ヨウ素である４−（ジアセトキシヨード）トルエンを比較対照例として用いた。上記のように触媒量のＴＥＭＰＯの存在下，室温で反応させたところ，どの反応試剤でも高収率で桂皮アルデヒドが得られた。本発明化合物１，２を用いた場合は反応終了後，アルコールを加えることにより，４，４”−ジヨード−ｐ−ターフェニル，４−ブロモ−４”−ヨードビフェニルが沈殿し，ろ過により回収することができた。回収したヨウ素化合物を酸化剤の存在下，酢酸を作用させることにより，１，２を再生することができた。比較対照例の副生物であるヨードトルエンは反応終了後，回収することができなかった。
参考例２ケトンのα−トシルオキシ化 4- (diacetoxyiodo) toluene, which is a normal small molecule type hypervalent iodine, was used as a comparative example. As described above, when reaction was carried out at room temperature in the presence of a catalytic amount of TEMPO, cinnamaldehyde was obtained in high yield with any reaction reagent. When the compounds 1 and 2 of the present invention are used, 4,4 ″ -diiodo-p-terphenyl and 4-bromo-4 ″ -iodobiphenyl are precipitated by addition of alcohol after the reaction is completed and recovered by filtration. I was able to. The recovered iodine compound was regenerated by allowing acetic acid to act in the presence of an oxidizing agent. Iodotoluene, a by-product of the comparative control example, could not be recovered after the reaction was completed.
Reference Example 2 α-Tosyloxylation of ketone
通常の小分子型超原子価ヨウ素である４−［ヒドロキシ（トシルオキン）ヨード］トルエンを比較対照例として用いた。上記のようにアセトニトリル中，還流条件下で反応させたところ，どちらの反応試剤でも高収率で対応するα−トシルオキシケトンが得られた。３を用いた場合は反応終了後，アルコールを加えることにより，４−ブロモ−４”−ヨードビフェニルが沈殿するので，ろ過で回収することができる。回収した４−ブロモ−４”−ヨードビフェニルを再酸化することにより，３を再生することができる。比較対照例の副生物であるヨードトルエンは反応終了後，カラムクロマトグラフィーを用いることにより，回収できたが，ごく低収率であった。 4- [Hydroxy (tosylokine) iodo] toluene, a normal small molecule hypervalent iodine, was used as a comparative control. When the reaction was carried out in acetonitrile under reflux conditions as described above, the corresponding α-tosyloxyketone was obtained in high yield with either reaction reagent. When 3 is used, 4-bromo-4 "-iodobiphenyl is precipitated by adding alcohol after completion of the reaction, and can be recovered by filtration. The recovered 4-bromo-4" -iodobiphenyl is recovered. 3 can be regenerated by reoxidation. Although iodotoluene, a by-product of the comparative control example, was recovered by using column chromatography after the reaction was completed, the yield was very low.
以上のように，本発明化合物である新規低分子型超原子価ヨウ素化合物は，安価で入手しやすいオリゴフェニル化合物を原料として利用することができ，反応性も従来の低分子型超原子価ヨウ素化合物と比べて遜色ない。さらに反応終了後，回収，再酸化することにより，再生することができ，反応試剤として再利用可能である。このことから，本発明化合物は，極めて有用な環境調和型超原子価ヨウ素化合物といえる。 As described above, the novel low molecular weight hypervalent iodine compound which is the compound of the present invention can use an oligophenyl compound which is inexpensive and easily available as a raw material, and the reactivity is also low compared with the conventional low molecular weight hypervalent iodine compound. Compared to compounds. Furthermore, after the reaction is completed, it can be regenerated by recovery and reoxidation, and can be reused as a reaction reagent. From this, it can be said that the compound of the present invention is a very useful environment-friendly hypervalent iodine compound.
以下に本発明の好ましい実施例を記載するが，これは例示の目的であり，本発明を制限するものではない。本発明の範囲内では変形が可能なことは当業者には明らかであろう。 In the following, preferred embodiments of the present invention will be described, but this is for illustrative purposes and is not intended to limit the present invention. It will be apparent to those skilled in the art that variations are possible within the scope of the invention.
４，４”−ビス（ジアセトキシヨード）−ｐ−ターフェニルの合成
４，４”−ジヨード−ｐ−ターフェニル９６４ｍｇ（２ｍｍｏｌ），ｍＣＰＢＡ２．０８ｇ（１２ｍｍｏｌ）をクロロホルム３００ｍｌ，酢酸４０ｍｌに入れ，室温にて２４時間撹拌した後，エバポレーターでクロロホルムを減圧回収した。酢酸残渣にヘキサンを加え２〜４時間撹拌し，析出した結晶をろ取後，酢酸にて再結晶し，４，４”−ビス（ジアセトキシヨード）−ｐ−ターフェニル１．４１ｇ（収率９８％）を得た。
以下に得られた４，４”−ビス（ジアセトキシヨード）−ｐ−ターフェニルの物性値を示す。
ｍｐ：２１４℃（ｄｅｃｏｍｐ．）
ＩＲ（ＫＢｒ）２３６０，１５６０，１３９０，１０００，８００ｃｍ−１；１Ｈ ＮＭＲ（ＣＤＣｌ３）δ＝２．０４（１２Ｈ，ｓ），７．７１（４Ｈ，ｓ），７．７３（４Ｈ，ｄ，Ｊ＝８．５Ｈｚ），８．１９（４Ｈ，ｄ，Ｊ＝８．５Ｈｚ））；Ｅｌｅｍｅｎｔａｌ ａｎａｌｙｓｉｓ：ｃａｌｃｄ．ｆｏｒ Ｃ２６Ｈ２４Ｉ２Ｏ８・３ＣＨ３ＣＯ２Ｈ Ｃ４２．７８，Ｈ４．４，Ｉ２８．２５；ｆｏｕｎｄ Ｃ４２．６７，Ｈ４．２４，Ｉ２８．３０ Synthesis of 4,4 " -bis (diacetoxyiodo) -p -terphenyl 964 mg (2 mmol) of 4,4" -diiodo-p-terphenyl and 2.08 g (12 mmol) of mCPBA were placed in 300 ml of chloroform and 40 ml of acetic acid at room temperature. After stirring for 24 hours, chloroform was recovered under reduced pressure using an evaporator. Hexane was added to the acetic acid residue and stirred for 2 to 4 hours. The precipitated crystals were collected by filtration and recrystallized with acetic acid to give 1.41 g of 4,4 ″ -bis (diacetoxyiodo) -p-terphenyl (yield). 98%).
The physical properties of 4,4 ″ -bis (diacetoxyiodo) -p-terphenyl obtained are shown below.
mp: 214 ° C. (decomp.)
IR (KBr) 2360, 1560, 1390, 1000, 800 cm −1 ; 1 H NMR (CDCl 3 ) δ = 2.04 (12H, s), 7.71 (4H, s), 7.73 (4H, d , J = 8.5 Hz), 8.19 (4H, d, J = 8.5 Hz)); Elemental analysis: calcd. for C 26 H 24 I 2 O 8 · 3CH 3 CO 2 H C42.78, H4.4, I28.25; found C42.67, H4.24, I28.30
４，４’−ビス［ヒドロキシ（トシルオキシ）ヨード］ビフェニルの合成
４，４’−ジヨードビフェニル２．０３ｇ（５ｍｍｏｌ），ＴｓＯＨ・Ｈ２Ｏ ２ｇ（１１ｍｍｏｌ），ｍＣＰＢＡ２．１ｇ（１１ｍｍｏｌ）をクロロホルム６０ｍｌに入れ，室温で４時間撹拌した後，エーテルを加え析出した結晶をろ取，乾燥し４，４’−ビス［ヒドロキシ（トシルオキシ）ヨード］ビフェニル３．３２ｇ（収率８５％）を得た。
以下に得られた４，４’−ビス［ヒドロキシ（トシルオキシ）ヨード］ビフェニルの物性値を示す。
ｍｐ：１０４℃（ｄｅｃｏｍｐ．）
ＩＲ（ＫＢｒ）３７００−３２００，１４７０，１１９０，１１３０，１０４０，８００，６００ｃｍ−１；１Ｈ ＮＭＲ（ＣＤＣｌ３＋３ｄｒｏｐｓ ｏｆ ＣＦ３ＣＯ２Ｈ）δ＝２．４５（６Ｈ，ｓ），７．３３（４Ｈ，ｇ，Ｊ＝８．２Ｈｚ），７．７２（４Ｈ，ｄ，Ｊ＝８．２Ｈｚ），７．８１（４Ｈ，ｄ，Ｊ＝８．７Ｈｚ），８３７（４Ｈ，ｄ，Ｊ＝８．７Ｈｚ） Synthesis of 4,4′ -bis [hydroxy (tosyloxy) iodo] biphenyl 2.04 g (5 mmol) of 4,4′-diiodobiphenyl, 2 g (11 mmol) of TsOH · H 2 O, 2.1 g (11 mmol) of mCPBA, 60 ml of chloroform After stirring at room temperature for 4 hours, ether was added and the precipitated crystals were collected by filtration and dried to obtain 3.32 g (yield 85%) of 4,4′-bis [hydroxy (tosyloxy) iodo] biphenyl.
The physical property values of 4,4′-bis [hydroxy (tosyloxy) iodo] biphenyl obtained are shown below.
mp: 104 ° C. (decomp.)
IR (KBr) 3700-3200, 1470, 1190, 1130, 1040, 800, 600 cm −1 ; 1 H NMR (CDCl 3 +3 drops of CF 3 CO 2 H) δ = 2.45 (6H, s), 7.33 (4H, g, J = 8.2 Hz), 7.72 (4H, d, J = 8.2 Hz), 7.81 (4H, d, J = 8.7 Hz), 837 (4H, d, J = (8.7Hz)
４−ブロモ−４’−（ジアセトキシヨード）ビフェニルの合成
４−ブロモ−４’−ヨードビフェニル２．７ｇ（７．５ｍｍｏｌ），ＮａＢＯ３・４Ｈ２Ｏ ５．８ｇ（３７．５ｍｍｏｌ）を酢酸３００ｍｌに加え，５０℃で１時間攪拌した後，さらにＮａＢＯ３・４Ｈ２Ｏ ５．８ｇ（３７．５ｍｍｏｌ）を加え，５０℃で２４時間攪拌した。反応後，ろ過し，ろ液をクロロホルムと水で分液し，硫酸ナトリウムで乾燥した。ろ過後，エバポレータで濃縮し，４−ブロモ−４’−（ジアセトキシヨード）ビフェニル３．５３ｇ（収率９９％）を得た。
以下に得られた４−ブロモ−４’−（ジアセトキシヨード）ビフェニルの物性値を示す。
ｍｐ：１７１℃
ＩＲ（ＫＢｒ）２４００−２３００，１５６０，１４１０，１０００，８００ｃｍ−１；１Ｈ ＮＭＲ（ＣＤＣｌ３）δ＝２．０３（６Ｈ，ｓ），７．４５（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），７．６２（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），７．６５（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ），８．１５（２Ｈ，ｄ，Ｊ＝８．５Ｈｚ）；１３ＣＮＭＲ（ＣＤＣｌ３）δ＝２０．５２（ｐ），１２０．５４（ｑ），１２３．２３（ｑ），１２８．９９（ｔ），１２９．４９（ｔ），１３２．３９（ｔ），１３５．６８（ｔ），１３８．１５（ｑ），１４３．８４（ｑ），１７６．６１（ｑ）；Ｅｌｅｍｅｎｔａｌ ａｎａｌｙｓｉｓ：ｃａｌｃｄ．ｆｏｒ Ｃ１６Ｈ１４ＢｒＩＯ４Ｃ４０．２８，Ｈ２．９６；ｆｏｕｎｄ Ｃ４０．２５，Ｈ３．０６Synthesis of 4- bromo-4 ′-(diacetoxyiodo) biphenyl 2.7 g (7.5 mmol) of 4-bromo-4′-iodobiphenyl and 5.8 g (37.5 mmol) of NaBO 3 .4H 2 O were mixed with 300 ml of acetic acid. After stirring at 50 ° C. for 1 hour, 5.8 g (37.5 mmol) of NaBO 3 .4H 2 O was further added and stirred at 50 ° C. for 24 hours. After the reaction, the mixture was filtered, and the filtrate was partitioned between chloroform and water and dried over sodium sulfate. After filtration, the filtrate was concentrated with an evaporator to obtain 3.53 g (yield 99%) of 4-bromo-4 ′-(diacetoxyiodo) biphenyl.
The physical property values of 4-bromo-4 ′-(diacetoxyiodo) biphenyl obtained are shown below.
mp: 171 ° C
IR (KBr) 2400-2300, 1560, 1410, 1000, 800 cm −1 ; 1 H NMR (CDCl 3 ) δ = 2.03 (6H, s), 7.45 (2H, d, J = 8.5 Hz) , 7.62 (2H, d, J = 8.5 Hz), 7.65 (2H, d, J = 8.5 Hz), 8.15 (2H, d, J = 8.5 Hz); 13 C NMR (CDCl 3 ) δ = 20.52 (p), 120.54 (q), 123.23 (q), 128.99 (t), 129.49 (t), 132.39 (t), 135.68 ( t), 138.15 (q), 143.84 (q), 176.61 (q); Elemental analysis: calcd. for C 16 H 14 BrIO 4 C40.28, H2.96; found C40.25, H3.06
４−ブロモ−４’−［ヒドロキシ（トシルオキシ）ヨード］ビフェニルの合成
４−ブロモ−４’−ヨードビフェニル１．８ｇ（５ｍｍｏｌ），ＴｓＯＨ・Ｈ２Ｏ １．１ｇ（６ｍｍｏｌ），ｍＣＰＢＡ１．１５ｇ（６ｍｍｏｌ）をクロロホルム１５ｍｌに入れ，室温で４時間撹拌した後，エーテルを加え析出した結晶をろ取，乾燥し４−ブロモ−４’−［ヒドロキシ（トシルオキシ）ヨード］ビフェニル２．３８ｇ（収率８７％）を得た。
以下に得られた４−ブロモ−４’−［ヒドロキシ（トシルオキシ）ヨード］ビフェニルの物性値を示す。
ｍｐ：９８−１００℃
ＩＲ（ＫＢｒ）３７００−３２００，１４８０，１３９０，１１９０，１１３０，１０４０，１０００，８００，６００ｃｍ−１；１Ｈ ＮＭＲ（ＣＤＣｌ３＋３ｄｒｏｐｓ ｏｆ ＣＦ３ＣＯ２Ｈ）δ＝２．４５（３Ｈ，ｓ），７．３５（２Ｈ，ｄ，Ｊ＝８．２Ｈｚ），７．４８（２Ｈ，ｄ，Ｊ＝８．７Ｈｚ），７．６６（２Ｈ，ｄ，Ｊ＝８．７Ｈｚ），７．７３（２Ｈ，ｄ，Ｊ＝８．２Ｈｚ），７．７７（２Ｈ，ｄ，Ｊ＝８．７Ｈｚ），８．２９（２Ｈ，ｄ，Ｊ＝８．７Ｈｚ）Synthesis of 4- bromo-4 ′-[hydroxy (tosyloxy) iodo] biphenyl 4-bromo-4′-iodobiphenyl 1.8 g (5 mmol), TsOH · H 2 O 1.1 g (6 mmol), mCPBA 1.15 g (6 mmol) Was added to chloroform (15 ml) and stirred at room temperature for 4 hours. Ether was added and the precipitated crystals were collected by filtration and dried to give 2.38 g of 4-bromo-4 ′-[hydroxy (tosyloxy) iodo] biphenyl (yield 87%). )
The physical property values of 4-bromo-4 ′-[hydroxy (tosyloxy) iodo] biphenyl obtained are shown below.
mp: 98-100 ° C
IR (KBr) 3700-3200, 1480, 1390, 1190, 1130, 1040, 1000, 800, 600 cm −1 ; 1 H NMR (CDCl 3 +3 drops of CF 3 CO 2 H) δ = 2.45 (3H, s) 7.35 (2H, d, J = 8.2 Hz), 7.48 (2H, d, J = 8.7 Hz), 7.66 (2H, d, J = 8.7 Hz), 7.73 ( 2H, d, J = 8.2 Hz), 7.77 (2H, d, J = 8.7 Hz), 8.29 (2H, d, J = 8.7 Hz)
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