JP4466796B2 - Pentacyclotetradecane derivative and method for producing the same - Google Patents

Description

【０００８】
【化１０】

【０００９】
【化１１】

【００１０】
【化１２】

【００１１】
【化１３】

【００１２】
で表されるペンタシクロテトラデカン誘導体に関する。また、本発明は、式（６）
【００１３】
【化１４】

【００１４】
で表されるペンタシクロテトラデカジエンに酸化剤としてオスミウム化合物を反応させて式（１）または（２）で表される化合物を製造する事を特徴とするペンタシクロテトラデカン誘導体の製造方法、或いは酸化剤としてルテニウム化合物を反応させて式（５）の化合物を、また、式（１）又は（２）の化合物に酸触媒の存在下アセトン等を反応させて式（３）又は（４）の化合物を、更に、式（６）の化合物に酸化剤としてレニウム酸化物を反応させて式（７）または（８）
【００１５】
【化１５】

【００１６】
【化１６】

【００１７】
で表される化合物を製造することを特徴とするペンタシクロテトラデカン誘導体の製造方法に関する。
【００１８】
【発明の実施の形態】
以下、更に本発明を詳細に説明する。まずはじめに式（１）又は式（２）で表されるアルコール誘導体の製造方法について述べる。
式（６）
【００１９】
【化１７】

【００２０】
で表されるペンタシクロテトラデカジエンに酸化剤を反応させることにより式（１）又は式（２）のペンタシクロテトラデカン誘導体を製造することができる。用いる酸化剤としては通常オレフィンをジオールに変換できる酸化剤であればすべて可能であるが好ましくはオスミウム化合物（特にＫ₂ＯｓＯ₄）あるいはＡＤ−ｍｉｘ−α又はβ（商品名 アルドリッチ社）が良い。
【００２１】
ＡＤ−ｍｉｘ−βを使用するときは、使用する当量によって式（１）のジオール又は式（２）のテトラオールを別個にまたは混合物として合成できる。混合物として得られるときも蒸留等の操作によって分離することができる。反応溶媒としては不活性な溶媒であればすべて使用可能であるが、水−ｔ−ブタノールの混合系溶媒とするのがよい。反応温度は−３０℃〜溶媒の沸点まで可能であるが、好ましくは０℃〜３０℃である。反応時間はＴＬＣ，Ｇ．Ｃ．，等の分析法を用いて原料の消失及び生成物の確認によって決定されるが通常０．５〜４８時間である。
【００２２】
オスミウム酸化剤を使用するときは、通常酸化剤が高価であるため触媒量の使用とし助酸化剤を使用する。助酸化剤としてはＮ−メチルモルフォリン−Ｎ−オキシドが好ましい。反応溶媒としては不活性な溶媒であればすべて使用可能であるが、水−ｔ−ブタノール−アセトンの混合系溶媒とするのがよい。反応温度は−３０℃〜溶媒の沸点まで可能であるが、好ましくは０℃〜３０℃である。反応時間はＴＬＣ，Ｇ．Ｃ．，等の分析法を用いて原料の消失及び生成物の確認によって決定されるが通常０．５〜４８時間である。
【００２３】
このようにして得られた式（１）又は式（２）で表される化合物を酸触媒存在下でアセトンもしくはアセトンジメチルケタールと反応させることで式（３）又は式（４）で表される化合物を得ることができる。この際に用いる酸触媒としては通常ｐ−トルエンスルホン酸が好ましい。反応溶媒は不活性なものであればすべて可能であるが、通常アセトンおよびアセトンジメチルケタールを過剰に用いることで特に溶媒は必要としない。
【００２４】
反応温度は０℃〜溶媒の沸点まで可能であるが、好ましくは１０℃〜溶媒の沸点である。反応時間はＴＬＣ，Ｇ．Ｃ．，等の分析法を用いて原料の消失及び生成物の確認によって決定されるが通常０．５〜４８時間である。
【００２５】
次に式（５）で表される化合物の製造方法について述べる。式（６）で表されるペンタシクロテトラデカジエンに酸化剤を反応させることにより式（５）の化合物を製造することができる。用いる酸化剤としては通常オレフィンを開裂して酸化できる酸化剤であればすべて可能であるが好ましくはルテニウム化合物（特にＲｕＣｌ₃）が良い。
【００２６】
ルテニウム酸化剤を使用するときは、通常酸化剤が高価であるため触媒量の使用とし助酸化剤を使用する。助酸化剤としては過ヨウ素酸ナトリウムが好ましい。通常基質に対して２〜２０当量用いる。反応溶媒は不活性なものであればすべて可能であるが、通常四塩化炭素、アセトニトリル、水等の混合溶媒を用いる。反応温度は０℃〜溶媒の沸点まで可能であるが、好ましくは０℃〜５０℃である。反応時間はＴＬＣ，Ｇ．Ｃ．，等の分析法を用いて原料の消失及び生成物の確認によって決定されるが通常０．５〜４８時間である。
【００２７】
また式（２）で表される化合物を原料として用いて同様に反応させても式（５）の化合物を製造することができる。
次に式（７）又は式（８）で表される化合物の製造方法について述べる。これらの化合物は文献に公知の物質であるが以下の製造方法は公知の製造方法より収率、純度等の点で優れた製造方法である。
【００２８】
すなわち式（６）で表されるペンタシクロテトラデカジエンにメチルトリオキソレニウムを触媒量用い、過酸化水素を必要当量加えて反応させることで式（７）又は式（８）で表される化合物を製造することができる。
反応溶媒は不活性なものであればすべて可能であるが、通常ニトロメタン、ジクロロメタン等の溶媒を用いる。また添加剤としてピリジンを加えることが好ましい。反応温度は０℃〜溶媒の沸点まで可能であるが、好ましくは０℃〜５０℃である。反応時間はＴＬＣ，Ｇ．Ｃ．，等の分析法を用いて原料の消失及び生成物の確認によって決定されるが通常０．５〜４８時間である。反応生成物の単離方法は特に限定されず、通常用いられる蒸留、カラムクロマトグラフィー、再結晶などにより精製することができる。
【００２９】
これらの方法によって得られたペンタシクロテトラデカン誘導体には立体異性体が存在するが、当然すべての異性体が本方法に含まれるものである。
また上記で述べたような酸化方法を駆使することによって式（９）や式（１０）で表される化合物の製造についてもできるものと考えられる。
【００３０】
【化１８】

【００３１】
【化１９】

【００３２】
【実施例】
次に実施例を挙げ本発明の内容を具体的に説明するが、本発明はこれらに限定されるものではない。
実施例１（式（１）、式（２）、式（３）又は式（４）の化合物の製造）
磁気回転子を入れた容量１００ｍｌの２つ口反応瓶に、式（６）の純度９６％のペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカ−４，１１−ジエン（ＰＣＴＤ）３７２ｍｇ（ＰＣＴＤとして１．９４ ｍｍｏｌ）をいれ、ｔ−ブチルアルコール２０ｍｌおよび水２０ｍｌの混合溶液に溶解した後、不斉ジヒドロキシル化試薬ＡＤ−ｍｉｘ−β（商品名 アルドリッチ社）５．６ｇ（オレフィン４．０ｍｍｏｌを酸化するのに必要な量、２．１当量）を加え、室温で２４時間撹拌した。氷冷後反応溶液に亜硫酸ナトリウム６．０ｇを加え、室温に戻した後１時間撹拌後、固体をろ過により除去した。ろ液から酢酸エチル４０ｍｌで１回、２０ｍｌで３回抽出し、この酢酸エチル溶液に硫酸ナトリウムを加えて乾燥した。減圧下、酢酸エチルを留去すると、白色固体が得られた。
【００３３】
これは、式（１）のジオール（１１，１２−ジヒドロキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデセン−４）と式（２）のテトラオール（４，５，１１，１２−テトラヒドロキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカン）の混合物である。
【００３４】
この白色固体に、アセトン４ｍｌ、２，２−ジメトキシプロパン５ｍｌ、ｐ−トルエンスルホン酸６０ｍｇを加えた懸濁液を、室温で１時間撹拌し、均一になった溶液に炭酸水素ナトリウム水溶液１０ｍｌおよびヘキサン１０ｍｌを加えた。ヘキサン層を分離した後、水層をヘキサン５ｍｌで２回抽出し、これもヘキサン層に加えた。硫酸ナトリウムを加えて乾燥した後、減圧下で溶媒を留去した。分取高速液体クロマトグラフィーより分離し、式（３）のジオールのアセタール化物１１４ｍｇ（０．４４ｍｍｏｌ、収率２３％）および式（４）のテトラオールのジアセタール化物２３８ｍｇ（０．７２ｍｍｏｌ、収率３７％）を得た。
ジオールは、ジオールとテトラオールの混合物をキューゲルロール蒸留することによっても単離できた。
【００３５】
実施例２（式（２）の化合物の製造）
磁気回転子を入れた容量２０ｍｌの２つ口フラスコに、式（６）の純度９６％のペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカ−４，１１−ジエン（ＰＣＴＤ）２７９ｍｇ（ＰＣＴＤとして１．４５ｍｍｏｌ）をいれ、ｔ−ブチルアルコール１．０ｍｌ、水１．０ｍｌ、アセトン２．０ｍｌの混合溶液に溶解した後、Ｎ−メチルモルホリン−Ｎ−オキシド０．７８ｇ（７．７ｍｍｏｌ、５．３当量）およびオスミウム酸カリウム１１．１ｍｇ（０．０３３ｍｍｏｌ、２．３ｍｏｌ％）を加え、室温で２４時間撹拌し、生成した白色固体をろ別し洗浄すると、式（２）の粗テトラオール（４，５，１１，１２−テトラヒドロキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカン）２３７ｍｇ（０．９４ｍｍｏｌ、粗収率６５％）が得られた。
【００３６】
この白色固体１６５ｍｇを、磁気回転子を入れた容量２０ｍｌの２つ口フラスコにいれ、アセトン４ｍｌ、２，２−ジメトキシプロパン５ｍｌ、ｐ−トルエンスルホン酸６０ｍｇを加えた懸濁液を、室温で１時間撹拌し、均一になった溶液に炭酸水素ナトリウム水溶液１０ｍｌおよびヘキサン１０ｍｌを加えた。ヘキサン層を分離した後、水層をヘキサン５ｍｌで２回抽出し、これもヘキサン層に加えた。硫酸ナトリウムを加えて乾燥した後、減圧下で溶媒を留去し、キューゲルロール蒸留（１３０℃／１．５ｍｍＨｇ）により精製し、式（４）の無色固体ジアセタール化生成物を単離した。これを磁気回転子を入れた容量５０ｍｌの２つ口フラスコにいれ、酢酸８ｍｌおよび水２ｍｌの混合溶媒に溶解し、６０℃で１．５時間撹拌し、放冷後、反応液をトルエン２０ｍｌで希釈した後、溶媒を減圧留去することにより純粋な式（２）のテトラオールを得た。
【００３７】
実施例３（式（５）の化合物の製造方法）
磁気回転子を入れた容量２００ｍｌの２つ口反応瓶に、式（６）の純度９６ ％のペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカ−４，１１−ジエン（ＰＣＴＤ）１．０５ ｇ（ＰＣＴＤとして５．５ｍｍｏｌ）をいれ、四塩化炭素２４ｍｌ、アセトニトリル２４ｍｌ、水３６ｍｌの混合溶液に溶解した後、過ヨウ素酸ナトリウム１１．７ｇ（５５ｍｍｏｌ、１０当量）、三塩化ルテニウム三水和物６３ ｍｇ（０．２４ｍｍｏｌ、４．４ｍｏｌ％）を加え、室温で２時間撹拌した。油層を除去した後、水層に濃塩酸を加えてｐＨ１とし、塩化メチレン５０ｍｌで３回抽出した後、硫酸ナトリウムを加えて乾燥させた。溶媒留去後、ジエチルエーテルで洗浄すると、式（５）の白色固体５，７−ジオキサ−４，８−ジオキソペンタシクロ［７．６．０．０^2,6．０^3,14．０^11,15］ペンタデカン−１３−カルボン酸２１１ｍｇ（０．７６ｍｍｏｌ、収率１４％）が得られた。メタノールから再結晶することにより、純粋なものが得られた。
【００３８】
実施例４（式（２）の化合物から式（５）の化合物の製造）
磁気回転子を入れた容量５０ｍｌの２つ口反応瓶に、式（２）のテトラオール（４，５，１１，１２−テトラヒドロキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカン）５０５ｍｇ（２．０ｍｍｏｌ）、三塩化ルテニウム三水和物２０ｍｇ（０．０７６ｍｍｏｌ、３．８ｍｏｌ％）、過ヨウ素酸ナトリウム２．０ｇ（９．４ｍｍｏｌ、４．７当量）をいれ、四塩化炭素８．０ｍｌ、アセトニトリル８．０ｍｌ、水１２ｍｌを加えて懸濁させた後、室温で４時間撹拌した。油層を除去した後、水層に濃塩酸を加えてｐＨ１とし、塩化メチレン１５ｍｌで３回抽出した後、硫酸ナトリウムを加えて乾燥させた。溶媒留去後、ジエチルエーテルで洗浄すると、式（５）の白色固体５，７−ジオキサ−４，８−ジオキソペンタシクロ［７．６．０．０^2,6．０^3,14．０^11,15］ペンタデカン−１３−カルボン酸１７３ｍｇ（０．６２ｍｍｏｌ、収率３１％）が得られた。
【００３９】
参考例１（式（７）又は式（８）の化合物の製造）
磁気回転子を入れた容量２０ｍｌの２つ口フラスコに、式（６）の純度９６％のペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカ−４，１１−ジエン（ＰＣＴＤ）３７０ｍｇ（ＰＣＴＤとして１．９３ｍｍｏｌ）をいれ、ニトロメタン２ｍｌを加えて溶解した後、メチルトリオキソレニウム５．９ｍｇ（１．２ｍｏｌ％）、ピリジン０．０３９ｍｌ（２４ｍｏｌ％）、３０％過酸化水素水０．２１ｍｌ（２．１ｍｍｏｌ、１．１当量）を加え、室温で２時間撹拌した。反応溶液のガスクロマトグラフィー分析より、式（７）のモノエポキシド収率６５％、式（８）のジエポキシド収率２０％であった。油層を分離した後、水層をジエチルエーテル５ｍｌで３回抽出し、これも油層に加えた。硫酸ナトリウムを加えて乾燥した後、減圧下で溶媒を留去し、キューゲルロール蒸留（１４０℃／１．３ｍｍＨｇ）した後、分取高速液体クロマトグラフィーを用いて分離することにより純粋な式（７）の４，５−エポキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデセン−４が得られた。
【００４０】
実施例６（式（８）の化合物の製造）
磁気回転子を入れた容量５０ｍｌの２つ口反応瓶に、式（６）の純度９６％のペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカ−４，１１−ジエン（ＰＣＴＤ）１．６９ｇ（ＰＣＴＤとして８．８ｍｍｏｌ）をいれ、塩化メチレン１０ｍｌを加えて溶解した後、メチルトリオキソレニウム２３ｍｇ（１．０ｍｏｌ％）、ピリジン０．２０ｍｌ（２４ｍｏｌ％）、３０％過酸化水素水３．１ｍｌ（３０ｍｍｏｌ、３．４当量）を加え、室温で２時間撹拌した。油層を分離した後、水層をジエチルエーテル５ｍｌで３回抽出し、これも油層に加えた。硫酸ナトリウムを加えて乾燥した後、減圧下で溶媒を留去し、キューゲルロール蒸留（１４０℃／１．３ｍｍＨｇ）により精製し、式（８）の無色の結晶４，５：１１，１２−ジエポキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデカン１．７２ｇ（７．９５ｍｍｏｌ、収率９０％）を得た。
次に各化合物の物性について記載する。
【００４１】
式（１）の化合物
１１，１２−ジヒドロキシペンタシクロ［６．６．０．０^2,6．０^3,13．０^10,14］テトラデセン−４
無色固体
MS(m/z): 218(M⁺)
IR(KBr) : 3412,3035,2936,2894,1364,1357,1262,1223,1095,1076,1057,1036,792cm^-1．
¹H NMR(400 MHz,CDCl₃):δ5.65(dd,1H,11-H or 12-H,J=5.4,2.2 Hz),5.52(dd,1H,11-H or 12-H,J=5.4,2.2 Hz),4.21(br s,1H,4-H),3.99(br s,1H,5-H),3.41(m,3H,2-,13- and1 4-H),3.18(br t,1H,6-H,J=8.3 Hz),2.89(q,1H,1-H,J=9.3 Hz),2.72(td,1H,3-H,J=10.7,4.9 Hz),2.44(m,1H,8-H),2.36(ddd,1H,10-H,J=10.8,9.3,8.3 Hz),2.21(d,1H,OH,J=3.5 Hz),2.10(d,1H,OH,J=6.4 Hz),1.81(ddd,1H,7-exo-H,J=13.2,9.3,7.8 Hz),1.72(dt,1H,9-H,J=12.7,8.3 Hz),1.66(d,1H,7-endo-H,J=13.2 Hz),1.01(dt,1H,9-H,J=12.7,11.2 Hz).
¹³C NMR(100MHz,CDCl₃):δ 136.7 and 129.8(C11 and C12),80.3(C5),76.5(C4),58.1(C2,C13 or C14),57.1(C3),56.5(C2,C13 or C14),56.1(C1),53.3(C2,C13 or C14),52.6(C6),52.5(C10),47.8(C8),36.0(C7),35.4(C9).
【００４２】
式（２）の化合物
４，５，１１，１２−テトラヒドロキシペンタシクロ［６．６．０．０^2,6．０^{3 ,13}．０^10,14］テトラデカン
無色固体
IR(KBr) : 3468,3283,2943,2930,2859,1463,1349,1116,1100,1072,1059,1035,1018cm^-1．
¹HNMR(400 MHz,DMSO-d₆):δ4.29(d,2H,OH,J=4.4 Hz),4.18(d,2H,OH,J=5.4 Hz),3.99(br d,2H,4- and 12-H,J=3.4 Hz),3.87(br d,2H,5- and 11-H,J=3.9 Hz),3.19(q,2H,2- and 14-H,J=9.8 Hz),2.80(q,1H,1-H,J=9.8 Hz),2.53(m,3H,3-,8- and 13-H),2.31(m,2H,6- and 10-H),1.86(dt,2H,7-exo- and 9-exo-H,J=13.7,9.3 Hz),1.32(dt,2H,7-endo- and 9-endo-H,J=13.7,5.9 Hz).
¹³CNMR(75 MHz,DMSO-d₆):δ80.2 and 75.2(C4,C5,C11 and C12),57.2(C2 and C14 or C3 and C13),56.2(C1),52.3(C2 and C14 or C3 and C13),52.3(C6 and C10),47.4(C8),36.6(C7 and C9).
【００４３】
式（３）の化合物
１４，１４−ジメチル−１３，１５−ジオキサヘキサシクロ［９．６．０．０^2,9．０^3,7．０^4,17．０^12,16］ヘプタデセン−５
無色固体, 融点 57〜58.5℃
MS(m/z):258(M⁺)
IR(KBr) : 3034,2979,2949,2923,2905,2851,1375,1370,1264,1259,1224,1160,1053,1045,870,733,707cm^-1．
¹H NMR(400MHz,CDCl₃):δ5.69(dd,1H,11-H or 12-H,J=5.4,2.0 Hz),5.49(dd,1H,11-H or 12-H,J=5.4,2.0 Hz),4.67(d,1H,4-H,J=4.9 Hz),4.34(d,1H,5-H,J=4.9 Hz),3.42(q,1H,2-H,J=9.3 Hz),3.41(tt,1H,13-H,J=9.3,2.0 Hz),3.31(dt,1H,14-H,J=10.3,8.8 Hz),3.18(tt,1H,10-H,J=8.1,2.0 Hz),3.02(t,1H,3-H,J=9.3 Hz),2.92(dt,1H,1-H,J=10.3,9.3 Hz),2.55(dt,1H,6-H,J=11.2,9.3 Hz),2.45(m,1H,8-H),1.77(dt,1H,7-H,J=13.7,9.3 Hz),1.74(m,2H,9-H),1.31(dt,1H,7-H,J=13.7,11.2 Hz),1.44(s,3H,Me),1.26(s,3H,Me).
¹³C NMR(100MHz,CDCl₃):δ138.4 and 129.4(C11 and C12),108.9(CMe₂),88.8(C5),85.3(C4),59.4(C3),57.0(C14),56.9(C1),56.6(C2),53.7(C13),52.9(C6),52.3(C10),47.9(C8),36.4(C7),35.8(C9),27.3(Me),24.8(Me).
【００４４】
式（４）の化合物
６，６，１６，１６−テトラメチル−５，７，１５，１７−テトラオキサヘプタシクロ［９．９．０．０^2,9．０^3,19．０^4,8．０^13,20．０^14,18］イコサン
無色固体 融点 106〜108℃
MS(m/z):317(M⁺-15)
元素分析値：分子式 C₂₀H₂₈O₄：計算値：C, 72.26; H, 8.49.;測定値:C,72.16 ; H, 8.29.
IR(KBr): 2979,2952,2933,2901,2883,2855,1381,1371,1263,1255,1215,1210,1161,1056,1041,873cm^-1．
¹H NMR(400 MHz,CDCl₃):δ4.61(d,2H,4- and 12-H or 5- and 11-H,J=5.2 Hz),4.50(d,2H,4- and 12-H or 5- and 11-H,J=5.2 Hz),3.33(q,2H,2- and 14-H,J=9.3 Hz),2.86(br d,2H,3- and 13-H,J=9.3 Hz),2.83(q,1H,1-H,J=9.3 Hz),2.69(td,2H,6,and10-H,J=9.3,6.8 Hz),2.40(qt,1H,8-H,J=9.3,6.8 Hz),1.96(dt,2H,J=14.2,9.3 Hz),1.23(dt,2H,J=14.2,6.8 Hz),1.41(s,6H,Me),1.24(s,6H,Me).
¹³C NMR(100MHz,CDCl₃):δ109.3,90.6 and 85.7(C4,C5,C11 and C12),57.8(C1,C2 and C14),56.7(C3 and C13),52.2(C6 and C10),47.5(C8),36.9(C7 and C9),27.2(Me),24.4(Me).
【００４５】
式（５）の化合物
５，７−ジオキサ−４，８−ジオキソペンタシクロ［７．６．０．０^2,6．０^3,14．０^11,15］ペンタデカン−１３−カルボン酸
無色固体
元素分析値：分子式 C₁₄H₁₄O₆：計算値： C,60.43;H,5.07.;測定値: C,60.10;H,5.15.
IR(KBr):3433,2963,1783,1752,1707,1701,1691,1261,1124,1000,803cm^-1．
¹H NMR(400 MHz,DMSO-ｄ₆):δ11.7(br,1H,CO₂H),6.32(d,1H,4-H,J=6.6 Hz),3.56(dd,1H,13-H,J=10.3,8.8 Hz),3.35(td,1H,3-H,J=10.3,6.6 Hz),3.27(td,1H,10-H,J=10.3,7.3 Hz),3.20(dt,1H,1-H,J=11.0,8.8 Hz),3.07(dt,1H,6-H,J=13.2,8.8 Hz),3.00(td,1H,14-H,J=8.8,7.3 Hz),2.91(dt,1H,2-H,J=10.3,8.8 Hz),2.66(m,1H,8-H),2.29(dt,1H,7-H,J=13.9,8.8 Hz),2.12(dt,1H,9-H,J=13.2,10.3 Hz),1.56(ddd,1H,9-H,J=13.2,10.3,5.5 Hz),1.30(dt,1H,7-H,J=13.9,13.2 Hz).
¹³CNMR(100MHz,DMSO-d₆):δ174.4(CO),174.0(CO),170.3(CO),99.8(C4,J_C-H=186Hz),59.1(C1),48.8(C13),48.0(C14),47.8(C10),45.0(C6),42.5(C2),41.4(C3),40.7(C8),38.3(C7),33.2(C9).
ナンバーリングはＰＣＴＤに準ずる。
【００４６】
【発明の効果】
本発明は反応性に富んだ官能基を有するペンタシクロテトラデカン誘導体およびその製造法に関するものであり、機能性ポリマー原料や生理活性化合物材料として有用な化合物である。[0001]
[Industrial application fields]
The present invention relates to a novel pentacyclotetradecane derivative useful as a functional polymer monomer and as a raw material for medical agrochemicals, perfumes and the like, and a method for producing the same.
[0002]
[Prior art]
Conventionally, many aromatic compounds have been developed as polymer monomers, but as a polymer using them, problems remain in coloring, weather resistance and heat resistance. Therefore, in recent years, alicyclic compounds that can overcome these problems, particularly polycyclic aliphatic compounds, have attracted attention.
[0003]
The synthesis of pentacyclotetradecadiene (PCTD), which can be produced relatively inexpensively as one of polycyclic aliphatic compounds, has been reported in Journal of Chemical Society, Chemical Communication, 1994, 435.
These derivatives are reported in Journal of Chemical Society, Perkin Trans. 1, 1998, 1095, JP-A-8-245456 and JP-A-9-67286.
[0004]
[Problems to be solved by the invention]
Only a limited number of compounds having a functional group rich in reactivity imparted from pentacyclotetradecadiene are reported as reported in the above-mentioned literatures. Therefore, if various reactive functional groups can be further imparted to these compounds, their uses can be greatly expanded as polymer raw materials and bioactive compound raw materials.
[0005]
[Means for Solving the Problems]
In order to solve these problems, the present inventors have conducted intensive studies. As a result, by reacting an oxidant with pentacyclotetradecadiene, it is possible to introduce a highly reactive hydroxyl group, ketal, carboxylic acid or lactone. The present invention has been completed.
[0006]
The present invention relates to formula (1), formula (2), formula (3), formula (4) or formula (5).
[0007]
[Chemical 9]

[0008]
[Chemical Formula 10]

[0009]
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[0010]
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[0011]
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[0012]
It is related with the pentacyclotetradecane derivative represented by these. Further, the present invention provides the formula (6)
[0013]
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[0014]
A process for producing a pentacyclotetradecane derivative characterized in that a compound represented by formula (1) or (2) is produced by reacting an osmium compound as an oxidizing agent with pentacyclotetradecadiene represented by the formula: The compound of formula (5) is reacted with a ruthenium compound as an agent, and the compound of formula (3) or (4) is reacted with acetone or the like in the presence of an acid catalyst with the compound of formula (1) or (2). Is further reacted with a rhenium oxide as an oxidant to the compound of formula (6) to give a compound of formula (7) or (8)
[0015]
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[0016]
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[0017]
And a method for producing a pentacyclotetradecane derivative, which comprises producing a compound represented by the formula:
[0018]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be further described in detail. First, a method for producing an alcohol derivative represented by formula (1) or formula (2) will be described.
Formula (6)
[0019]
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[0020]
A pentacyclotetradecane derivative represented by the formula (1) or the formula (2) can be produced by reacting an oxidant with the pentacyclotetradecadiene represented by the formula: As the oxidizing agent to be used, any oxidizing agent capable of converting an olefin into a diol can be used, but preferably an osmium compound (particularly K ₂ OsO ₄ ), AD-mix-α or β (trade name: Aldrich).
[0021]
When AD-mix-β is used, the diol of formula (1) or the tetraol of formula (2) can be synthesized separately or as a mixture, depending on the equivalents used. Even when it is obtained as a mixture, it can be separated by an operation such as distillation. Any inert solvent can be used as long as it is an inert solvent, but a mixed solvent of water-t-butanol is preferred. The reaction temperature can be from −30 ° C. to the boiling point of the solvent, but is preferably 0 ° C. to 30 ° C. The reaction time is TLC, G.M. C. It is usually 0.5 to 48 hours although it is determined by disappearance of raw materials and confirmation of the product using an analytical method such as.
[0022]
When an osmium oxidant is used, since an oxidizer is usually expensive, a catalytic amount is used and a co-oxidizer is used. As the co-oxidant, N-methylmorpholine-N-oxide is preferable. Any inert solvent can be used as long as it is an inert solvent, but a mixed solvent of water-t-butanol-acetone is preferred. The reaction temperature can be from −30 ° C. to the boiling point of the solvent, but is preferably 0 ° C. to 30 ° C. The reaction time is TLC, G.M. C. It is usually 0.5 to 48 hours although it is determined by disappearance of raw materials and confirmation of the product using an analytical method such as.
[0023]
The compound represented by formula (1) or formula (2) thus obtained is reacted with acetone or acetone dimethyl ketal in the presence of an acid catalyst, and is represented by formula (3) or formula (4). A compound can be obtained. As the acid catalyst used in this case, p-toluenesulfonic acid is usually preferred. Any inert solvent can be used as long as it is inert, but usually no excess solvent is required by using acetone and acetone dimethyl ketal in excess.
[0024]
The reaction temperature can be from 0 ° C. to the boiling point of the solvent, but is preferably from 10 ° C. to the boiling point of the solvent. The reaction time is TLC, G.M. C. It is usually 0.5 to 48 hours although it is determined by disappearance of raw materials and confirmation of the product using an analytical method such as.
[0025]
Next, the manufacturing method of the compound represented by Formula (5) is described. A compound of formula (5) can be produced by reacting an oxidant with pentacyclotetradecadiene represented by formula (6). As the oxidizing agent to be used, any oxidizing agent that can be oxidized by cleaving an olefin can be used, but a ruthenium compound (particularly RuCl ₃ ) is preferable.
[0026]
When a ruthenium oxidant is used, since an oxidant is usually expensive, a catalytic amount is used and a co-oxidant is used. As a co-oxidant, sodium periodate is preferred. Usually, 2 to 20 equivalents are used relative to the substrate. Any reaction solvent can be used as long as it is inert, but usually a mixed solvent such as carbon tetrachloride, acetonitrile, water or the like is used. The reaction temperature can be from 0 ° C to the boiling point of the solvent, but is preferably 0 ° C to 50 ° C. The reaction time is TLC, G.M. C. It is usually 0.5 to 48 hours although it is determined by disappearance of raw materials and confirmation of the product using an analytical method such as.
[0027]
The compound of formula (5) can also be produced by reacting in the same manner using the compound represented by formula (2) as a raw material.
Next, the manufacturing method of the compound represented by Formula (7) or Formula (8) is described. These compounds are known in the literature, but the following production methods are superior to the known production methods in terms of yield, purity and the like.
[0028]
That is, a compound represented by formula (7) or formula (8) by reacting pentacyclotetradecadiene represented by formula (6) with a catalytic amount of methyltrioxorhenium and adding a required equivalent amount of hydrogen peroxide. Can be manufactured.
Any inert solvent can be used as long as it is inert, but usually a solvent such as nitromethane or dichloromethane is used. It is preferable to add pyridine as an additive. The reaction temperature can be from 0 ° C to the boiling point of the solvent, but is preferably 0 ° C to 50 ° C. The reaction time is TLC, G.M. C. It is usually 0.5 to 48 hours although it is determined by disappearance of raw materials and confirmation of the product using an analytical method such as. The isolation method of the reaction product is not particularly limited, and it can be purified by commonly used distillation, column chromatography, recrystallization and the like.
[0029]
The pentacyclotetradecane derivatives obtained by these methods have stereoisomers, but naturally all isomers are included in this method.
It is also considered that the compounds represented by formula (9) and formula (10) can be produced by making full use of the oxidation method as described above.
[0030]
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[0031]
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[0032]
【Example】
Next, the content of the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
Example 1 (Production of compound of formula (1), formula (2), formula (3) or formula (4))
In a 100 ml two-necked reaction bottle containing a magnetic rotor, pentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14] tetradec-4,11-put diene (PCTD) 372mg (1.94 mmol as PCTD), was dissolved in a mixed solution of t- butyl alcohol 20ml and water 20ml, asymmetric dihydroxylation reagent AD -Mix-β (trade name: Aldrich) 5.6 g (amount required to oxidize 4.0 mmol of olefin, 2.1 equivalents) was added and stirred at room temperature for 24 hours. After cooling with ice, 6.0 g of sodium sulfite was added to the reaction solution, the mixture was returned to room temperature, stirred for 1 hour, and the solid was removed by filtration. The filtrate was extracted once with 40 ml of ethyl acetate and three times with 20 ml, and sodium sulfate was added to the ethyl acetate solution and dried. When ethyl acetate was distilled off under reduced pressure, a white solid was obtained.
[0033]
This is because the diol of formula (1) (11,12-dihydroxypentacyclo [6.6.0.0 ^2,6 0.0 ^3,13 .0 ^10,14 ] tetradecene-4) and tetra of formula (2) ol (4,5,11,12- tetrahydroxy penta cyclo [6.6.0.0 ^2,6 .0 ^3,13 .0 ^10,14] tetradecane) mixtures.
[0034]
A suspension obtained by adding 4 ml of acetone, 5 ml of 2,2-dimethoxypropane and 60 mg of p-toluenesulfonic acid to this white solid was stirred at room temperature for 1 hour, and 10 ml of aqueous sodium hydrogen carbonate solution and hexane were added to the uniform solution. 10 ml was added. After separating the hexane layer, the aqueous layer was extracted twice with 5 ml of hexane, and this was also added to the hexane layer. After adding sodium sulfate and drying, the solvent was distilled off under reduced pressure. Separated from preparative high-performance liquid chromatography, 114 mg (0.44 mmol, yield 23%) of the diol acetal of formula (3) and 238 mg (0.72 mmol, yield 37) of the tetraol diacetal of formula (4) %).
The diol could also be isolated by kuegel roll distillation of a mixture of diol and tetraol.
[0035]
Example 2 (Production of compound of formula (2))
Into a 20 ml two-necked flask containing a magnetic rotator, pentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14] tetradec-4,11-put diene (PCTD) 279mg (1.45mmol as PCTD), t- butyl alcohol 1.0 ml, water 1.0 ml, was dissolved in a mixed solution of acetone 2.0ml , N-methylmorpholine-N-oxide 0.78 g (7.7 mmol, 5.3 eq) and potassium osmate 11.1 mg (0.033 mmol, 2.3 mol%) were added and stirred at room temperature for 24 hours to form When the white solid is filtered and washed, crude tetraol of formula (2) (4,5,11,12- tetrahydroxy penta cyclo [6.6.0.0 ^2,6 .0 ^3,13 .0 ^{10 , 14} ] tetradecane) 237 mg (0.94 mmol, crude yield 65%) was obtained.
[0036]
165 mg of this white solid was placed in a 20-ml two-necked flask containing a magnetic rotator, and a suspension containing 4 ml of acetone, 5 ml of 2,2-dimethoxypropane and 60 mg of p-toluenesulfonic acid was added at room temperature to 1 ml. The mixture was stirred for an hour, and 10 ml of an aqueous sodium hydrogen carbonate solution and 10 ml of hexane were added to the homogenized solution. After separating the hexane layer, the aqueous layer was extracted twice with 5 ml of hexane, and this was also added to the hexane layer. After adding sodium sulfate and drying, the solvent was distilled off under reduced pressure, and the residue was purified by Kugelrohr distillation (130 ° C./1.5 mmHg) to isolate the colorless solid diacetalized product of formula (4). This was placed in a 50 ml two-necked flask containing a magnetic rotor, dissolved in a mixed solvent of 8 ml of acetic acid and 2 ml of water, stirred at 60 ° C. for 1.5 hours, allowed to cool, and then the reaction solution was washed with 20 ml of toluene. After dilution, the solvent was removed under reduced pressure to obtain pure tetraol of formula (2).
[0037]
Example 3 (Method for producing compound of formula (5))
In a two-necked reaction bottle with a capacity of 200 ml containing a magnetic rotor, pentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14] tetradec-4,11-put diene (PCTD) 1.05 g (5.5mmol as PCTD), carbon tetrachloride 24 ml, acetonitrile 24 ml, was dissolved in a mixed solution of water 36 ml, periodic acid Sodium 11.7 g (55 mmol, 10 equivalents) and ruthenium trichloride trihydrate 63 mg (0.24 mmol, 4.4 mol%) were added, and the mixture was stirred at room temperature for 2 hours. After removing the oil layer, the aqueous layer was adjusted to pH 1 with concentrated hydrochloric acid, extracted three times with 50 ml of methylene chloride, and then dried by adding sodium sulfate. When the solvent was distilled off and washed with diethyl ether, the white solid of formula (5) 5,7-dioxa-4,8-dioxopentacyclo [7.6.0.0 ^2,6 . 0 ^3,14 . [ ⁰¹¹⁵ ] 211 mg (0.76 mmol, 14% yield) of pentadecane-13-carboxylic acid was obtained. A pure product was obtained by recrystallization from methanol.
[0038]
Example 4 (Production of compound of formula (5) from compound of formula (2))
2-neck reaction bottle volume 50ml containing the magnetic rotor, tetraol of formula (2) (4,5,11,12- tetrahydroxy penta cyclo [6.6.0.0 ^2,6 .0 ^{3 , 13.0 10, 14]} tetradecane) 505 mg (2.0 mmol), ruthenium trichloride trihydrate 20mg (0.076mmol, 3.8mol%), sodium periodate 2.0 g (9.4 mmol, 4. 7 equivalents), carbon tetrachloride 8.0 ml, acetonitrile 8.0 ml and water 12 ml were added and suspended, and the mixture was stirred at room temperature for 4 hours. After removing the oil layer, the aqueous layer was adjusted to pH 1 with concentrated hydrochloric acid, extracted three times with 15 ml of methylene chloride, and then dried by adding sodium sulfate. When the solvent was distilled off and washed with diethyl ether, the white solid of formula (5) 5,7-dioxa-4,8-dioxopentacyclo [7.6.0.0 ^2,6 . 0 ^3,14 . [ ⁰¹¹⁵ ] 173 mg (0.62 mmol, 31% yield) of pentadecane-13-carboxylic acid was obtained.
[0039]
Reference Example 1 (Production of compound of formula (7) or formula (8))
Into a 20 ml two-necked flask containing a magnetic rotator, pentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14] tetradec-4,11-put diene (PCTD) 370mg (1.93mmol as PCTD), was dissolved by adding nitromethane 2 ml, methyltrioxorhenium 5.9mg (1.2mol%), pyridine 0.039 ml (24 mol%) and 30% hydrogen peroxide solution 0.21 ml (2.1 mmol, 1.1 equivalents) were added, and the mixture was stirred at room temperature for 2 hours. From the gas chromatography analysis of the reaction solution, the yield of monoepoxide of formula (7) was 65% and the yield of diepoxide of formula (8) was 20%. After separating the oil layer, the aqueous layer was extracted 3 times with 5 ml of diethyl ether and added to the oil layer. After adding sodium sulfate and drying, the solvent is distilled off under reduced pressure, and after distillation with Kügelrohr (140 ° C./1.3 mmHg), separation is performed using preparative high performance liquid chromatography. 7) 4,5-epoxypentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14 ] tetradecene-4 was obtained.
[0040]
Example 6 (Production of compound of formula (8))
In a two-necked reaction bottle with a capacity of 50 ml containing a magnetic rotator, pentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14] tetradec-4,11-put diene (PCTD) 1.69g (8.8mmol as PCTD), was dissolved by adding methylene chloride 10 ml, methyltrioxorhenium 23mg (1.0mol%), 0.20 ml (24 mol%) of pyridine and 3.1 ml (30 mmol, 3.4 equivalents) of 30% aqueous hydrogen peroxide were added, and the mixture was stirred at room temperature for 2 hours. After separating the oil layer, the aqueous layer was extracted 3 times with 5 ml of diethyl ether and added to the oil layer. After adding sodium sulfate and drying, the solvent was distilled off under reduced pressure and purified by Kügelrohr distillation (140 ° C./1.3 mmHg) to obtain colorless crystals of the formula (8) 4,5: 11,12- Diepoxypentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^{10, 14]} was obtained tetradecane 1.72g (7.95mmol, 90% yield).
Next, physical properties of each compound will be described.
[0041]
Compound of formula (1) 11,12-dihydroxypentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14 ] tetradecene-4
Colorless solid
MS (m / z): 218 (M ⁺ )
IR (KBr): 3412,3035,2936,2894,1364,1357,1262,1223,1095,1076,1057,1036,792 cm ⁻¹ .
¹ H NMR (400 MHz, CDCl ₃ ): δ 5.65 (dd, 1H, 11-H or 12-H, J = 5.4, 2.2 Hz), 5.52 (dd, 1H, 11-H or 12-H, J = 5.4, 2.2 Hz), 4.21 (br s, 1H, 4-H), 3.99 (br s, 1H, 5-H), 3.41 (m, 3H, 2-, 13- and 1 4-H), 3.18 ( br t, 1H, 6-H, J = 8.3 Hz), 2.89 (q, 1H, 1-H, J = 9.3 Hz), 2.72 (td, 1H, 3-H, J = 10.7,4.9 Hz), 2.44 (m, 1H, 8-H), 2.36 (ddd, 1H, 10-H, J = 10.8, 9.3, 8.3 Hz), 2.21 (d, 1H, OH, J = 3.5 Hz), 2.10 (d, 1H, OH, J = 6.4 Hz), 1.81 (ddd, 1H, 7-exo-H, J = 13.2,9.3,7.8 Hz), 1.72 (dt, 1H, 9-H, J = 12.7,8.3 Hz), 1.66 ( d, 1H, 7-endo-H, J = 13.2 Hz), 1.01 (dt, 1H, 9-H, J = 12.7, 11.2 Hz).
¹³ C NMR (100 MHz, CDCl ₃ ): δ 136.7 and 129.8 (C11 and C12), 80.3 (C5), 76.5 (C4), 58.1 (C2, C13 or C14), 57.1 (C3), 56.5 (C2, C13 or C14), 56.1 (C1), 53.3 (C2, C13 or C14), 52.6 (C6), 52.5 (C10), 47.8 (C8), 36.0 (C7), 35.4 (C9).
[0042]
Compound 4,5,11,12-tetrahydroxypentacyclo [6.6.0.0 ^2,6 . 0 ^{3 , 13} . 0 ^10,14 ] Tetradecane colorless solid
IR (KBr): 3468,3283,2943,2930,2859,1463,1349,1116,1100,1072,1059,1035,1018 cm ⁻¹ .
¹ HNMR (400 MHz, DMSO-d ₆ ): δ 4.29 (d, 2H, OH, J = 4.4 Hz), 4.18 (d, 2H, OH, J = 5.4 Hz), 3.99 (br d, 2H, 4 -and 12-H, J = 3.4 Hz), 3.87 (br d, 2H, 5- and 11-H, J = 3.9 Hz), 3.19 (q, 2H, 2- and 14-H, J = 9.8 Hz) , 2.80 (q, 1H, 1-H, J = 9.8 Hz), 2.53 (m, 3H, 3-, 8- and 13-H), 2.31 (m, 2H, 6- and 10-H), 1.86 ( dt, 2H, 7-exo- and 9-exo-H, J = 13.7,9.3 Hz), 1.32 (dt, 2H, 7-endo- and 9-endo-H, J = 13.7,5.9 Hz).
¹³ C NMR (75 MHz, DMSO-d ₆ ): δ80.2 and 75.2 (C4, C5, C11 and C12), 57.2 (C2 and C14 or C3 and C13), 56.2 (C1), 52.3 (C2 and C14 or C3 and C13), 52.3 (C6 and C10), 47.4 (C8), 36.6 (C7 and C9).
[0043]
Compound of formula (3) 14,14-dimethyl-13,15-dioxahexacyclo [9.6.0.0 ^2,9 . 0 ^3,7 . 0 ^4,17 . 0 ^12,16 ] heptadecene-5
Colorless solid, mp 57-58.5 ℃
MS (m / z): 258 (M ⁺ )
IR (KBr): 3034, 2979, 2949, 2923, 2905, 2851, 1375, 1370, 1264, 1259, 1224, 1160, 1053, 1045, 870, 733, 707cm- ¹ .
¹ H NMR (400 MHz, CDCl ₃ ): δ 5.69 (dd, 1H, 11-H or 12-H, J = 5.4, 2.0 Hz), 5.49 (dd, 1H, 11-H or 12-H, J = 5.4, 2.0 Hz), 4.67 (d, 1H, 4-H, J = 4.9 Hz), 4.34 (d, 1H, 5-H, J = 4.9 Hz), 3.42 (q, 1H, 2-H, J = 9.3 Hz), 3.41 (tt, 1H, 13-H, J = 9.3, 2.0 Hz), 3.31 (dt, 1H, 14-H, J = 10.3, 8.8 Hz), 3.18 (tt, 1H, 10-H, J = 8.1, 2.0 Hz), 3.02 (t, 1H, 3-H, J = 9.3 Hz), 2.92 (dt, 1H, 1-H, J = 10.3, 9.3 Hz), 2.55 (dt, 1H, 6- H, J = 11.2,9.3 Hz), 2.45 (m, 1H, 8-H), 1.77 (dt, 1H, 7-H, J = 13.7, 9.3 Hz), 1.74 (m, 2H, 9-H), 1.31 (dt, 1H, 7-H, J = 13.7, 11.2 Hz), 1.44 (s, 3H, Me), 1.26 (s, 3H, Me).
¹³ C NMR (100 MHz, CDCl ₃ ): δ 138.4 and 129.4 (C11 and C12), 108.9 (CMe ₂ ), 88.8 (C5), 85.3 (C4), 59.4 (C3), 57.0 (C14), 56.9 (C1 ), 56.6 (C2), 53.7 (C13), 52.9 (C6), 52.3 (C10), 47.9 (C8), 36.4 (C7), 35.8 (C9), 27.3 (Me), 24.8 (Me).
[0044]
Compound 6,6,16,16-tetramethyl-5,7,15,17-tetraoxaheptacyclo [9.9.0.0 ^2,9 . 0 ^3,19 . 0 ^4,8 . 0 ^13,20 . 0 ^14,18] icosane colorless solid, mp 106 to 108 ° C.
MS (m / z): 317 (M ⁺ -15)
Elemental analysis value: molecular formula C ₂₀ H ₂₈ O ₄ : calculated value: C, 72.26; H, 8.49 .; measured value: C, 72.16; H, 8.29.
IR (KBr): 2979,2952,2933,2901,2883,2855,1381,1371,1263,1255,1215,1210,1161,1056,1041,873cm ⁻¹ .
¹ H NMR (400 MHz, CDCl ₃ ): δ4.61 (d, 2H, 4- and 12-H or 5- and 11-H, J = 5.2 Hz), 4.50 (d, 2H, 4- and 12- H or 5- and 11-H, J = 5.2 Hz), 3.33 (q, 2H, 2- and 14-H, J = 9.3 Hz), 2.86 (br d, 2H, 3- and 13-H, J = 9.3 Hz), 2.83 (q, 1H, 1-H, J = 9.3 Hz), 2.69 (td, 2H, 6, and10-H, J = 9.3, 6.8 Hz), 2.40 (qt, 1H, 8-H, J = 9.3, 6.8 Hz), 1.96 (dt, 2H, J = 14.2, 9.3 Hz), 1.23 (dt, 2H, J = 14.2, 6.8 Hz), 1.41 (s, 6H, Me), 1.24 (s, 6H , Me).
¹³ C NMR (100 MHz, CDCl ₃ ): δ 109.3, 90.6 and 85.7 (C4, C5, C11 and C12), 57.8 (C1, C2 and C14), 56.7 (C3 and C13), 52.2 (C6 and C10), 47.5 (C8), 36.9 (C7 and C9), 27.2 (Me), 24.4 (Me).
[0045]
Compound 5,7-dioxa-4,8-dioxopentacyclo [7.6.0.0 ^2,6 . 0 ^3,14 . 0 ^11,15 ] pentadecane-13-carboxylic acid colorless solid elemental analysis value: molecular formula C ₁₄ H ₁₄ O ₆ : calculated value: C, 60.43; H, 5.07 .; measured value: C, 60.10; H, 5.15.
IR (KBr): 3433,2963,1783,1752,1707,1701,1691,1261,1124,1000,803 cm ⁻¹ .
¹ H NMR (400 MHz, DMSO-d ₆ ): δ 11.7 (br, 1H, CO ₂ H), 6.32 (d, 1H, 4-H, J = 6.6 Hz), 3.56 (dd, 1H, 13- H, J = 10.3,8.8 Hz), 3.35 (td, 1H, 3-H, J = 10.3,6.6 Hz), 3.27 (td, 1H, 10-H, J = 10.3,7.3 Hz), 3.20 (dt, 1H, 1-H, J = 11.0,8.8 Hz), 3.07 (dt, 1H, 6-H, J = 13.2,8.8 Hz), 3.00 (td, 1H, 14-H, J = 8.8,7.3 Hz), 2.91 (dt, 1H, 2-H, J = 10.3, 8.8 Hz), 2.66 (m, 1H, 8-H), 2.29 (dt, 1H, 7-H, J = 13.9, 8.8 Hz), 2.12 (dt , 1H, 9-H, J = 13.2,10.3 Hz), 1.56 (ddd, 1H, 9-H, J = 13.2,10.3,5.5 Hz), 1.30 (dt, 1H, 7-H, J = 13.9,13.2 Hz).
¹³ C NMR (100 MHz, DMSO-d ₆ ): δ 174.4 (CO), 174.0 (CO), 170.3 (CO), 99.8 (C4, J _CH = 186 Hz), 59.1 (C1), 48.8 (C13), 48.0 ( C14), 47.8 (C10), 45.0 (C6), 42.5 (C2), 41.4 (C3), 40.7 (C8), 38.3 (C7), 33.2 (C9).
Numbering is based on PCTD.
[0046]
【The invention's effect】
The present invention relates to a pentacyclotetradecane derivative having a functional group rich in reactivity and a method for producing the same, and is a useful compound as a functional polymer material or a physiologically active compound material.

Claims (9)

Formula (1)

11,12-dihydroxypentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14 ] tetradecene-4. Formula (2)

4,5,11,12-tetrahydroxypentacyclo [6.6.0.0 ^2,6 . 0 ^3,13 . 0 ^10,14 ] Tetradecane. Formula (3)

14,14-dimethyl-13,15-dioxahexacyclo [9.6.0.0 ^2,9 . 0 ^3,7 . 0 ^4,17 . 0 ^12,16 ] Heptadecene-5. Formula (4)

And 6,6,16,16-tetramethyl-5,7,15,17-tetraoxaheptacyclo [9.9.0.0 ^2,9 . 0 ^3,19 . 0 ^4,8 . 0 ^13,20 . 0 ^14,18 ] Ikosan. Formula (5)

5,7-dioxa-4,8-dioxopentacyclo [7.6.0.0 ^2,6 . 0 ^{3 , 14} . 0 ^11,15 ] Pentadecane-13-carboxylic acid. Formula (6)

A process for producing a pentacyclotetradecane derivative comprising reacting potassium osmate as an oxidizing agent with pentacyclotetradecadiene represented by formula (1) or (2) to produce a compound represented by formula (1): Producing a compound represented by formula (5) by reacting pentacyclotetradecadiene represented by formula (6) with ruthenium trichloride as an oxidizing agent in the presence of sodium periodate as a co-oxidant. A process for producing a pentacyclotetradecane derivative characterized by the above.   The compound represented by formula (1) or formula (2) is reacted with acetone or acetone dimethyl ketal in the presence of an acid catalyst to produce a compound represented by formula (3) or formula (4). A method for producing a pentacyclotetradecane derivative. A compound represented by the formula (5) is produced by reacting a compound represented by the formula (2) with ruthenium trichloride as an oxidizing agent in the presence of sodium periodate as a co-oxidant. A method for producing a pentacyclotetradecane derivative.