JP4316688B2 - Substituted binaphthyl compound and process for producing the same - Google Patents
Substituted binaphthyl compound and process for producing the same Download PDFInfo
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Description
【０００１】
【発明の属する技術分野】
本発明は、オレフィン化合物から光学活性なエポキシ化合物を得る不斉エポキシ化反応において、光学活性サレンマンガン錯体触媒の中間体であるサリチルアルデヒド化合物の前駆物質となる新規な置換ビナフチル化合物及びその製造法に関する。
【０００２】
【従来の技術】
光学活性なエポキシ化合物は、医・農薬の中間体として重要である。
プロキラルなオレフィン化合物から光学活性なエポキシ化合物を製造する方法としては、例えば、特開平7-285983号公報、USP 5,420,314、Tetrahedron, 50,11827 (1994) 等の香月等の方法があり、これらは光学活性なサレンマンガン錯体を使用して触媒的不斉エポキシ化反応を行なう優れた方法である。
【０００３】
光学活性なサレンマンガン錯体触媒は、ジアミン化合物、サリチルアルデヒド化合物及びマンガン塩から合成されている。
サリチルアルデヒド化合物は、ビナフトールをモノトリフレート体としてフェニルグリニャールでクロスカップリング反応を行い、遊離のヒドロキシ基をメトキシメチル基として保護後、ｔ−ブチルリチウムでα位をリチオ化してホルミル化、脱保護して合成されている。
【０００４】
又、ベンゼン環上のヒドロキシ基のα位に、選択的にホルミル基を導入する方法として、J. Chem. Soc. Perkin I, 1980, 1862 には、ホルムアルデヒド／ベース／ルイス酸を使用する遊離のヒドロキシ基のα位のホルミル化法、J. Org. Chem., 59, 1939 (1994) には、ヘキサメチレンテトラミンを使用するＤｕｆｆ反応が記載されている。
【０００５】
【発明が解決しようとする課題】
しかし、香月等の方法は、遊離のヒドロキシ基の保護に発癌性等の問題があるクロロメチルメチルエーテルを使用していること、ホルミル化反応に発火性等があり取扱いに問題があるｔ−ブチルリチウムを使用していること、反応温度が−７８℃と極低温であること等、効率的な製造法とは言えない。
【０００６】
又、本発明のメトキシ基を有するビナフチル化合物について、ホルムアルデヒド／ベース／ルイス酸を使用する方法、Ｄｕｆｆ反応等を検討したが、いずれも反応が進行しないか低収率で満足のいく結果は得られなかった。
【０００７】
【課題を解決するための手段】
本発明者等は、上記問題点を解決すべくサリチルアルデヒド化合物の前駆体の製造法について鋭意検討した結果、新規なメトキシ基を有するビナフチル化合物のホミルミル反応に、リチオ化剤として工業的に取扱いが容易なｎ−ブチルリチウムが使用可能なことを見出し、本発明を完成するに至った。
【０００８】
即ち、本発明は、式（１）
【０００９】
【化４】
〔式中、Ｒ1及びＲ2は、独立に水素原子、ハロゲン原子、Ｃ1〜Ｃ4アルキル基、Ｃ1〜Ｃ4アルコキシ基、ニトロ基又はシアノ基を意味し、
Ａ1、Ａ2、Ａ3、Ａ4及びＡ5は、独立に水素原子、Ｃ1〜Ｃ4アルキル基、Ｃ1〜Ｃ4アルコキシ基を意味し、
ビナフチル部分はラセミ体でも光学活性体でもよい。〕
で表わされる置換ビナフチル化合物及び
式（２）
【００１１】
【化５】
〔式中、ビナフチル部分はラセミ体でも光学活性体でもよく、Ｒ1、Ｒ2、Ａ1、Ａ2、Ａ3、Ａ4及びＡ5は、前記に同じ。〕
で表わされるビナフチル化合物を、
ｎ−ブチルリチウムでリチオ化後、ホルミル化剤と反応させることを特徴とする
式（１）
【００１３】
【化６】
〔式中、ビナフチル部分はラセミ体でも光学活性体でもよく、Ｒ1、Ｒ2、Ａ1、Ａ2、Ａ3、Ａ4及びＡ5は、前記に同じ。〕
で表わされる置換ビナフチル化合物の製造法に関するものである。
【００１５】
【発明の実施の形態】
以下、更に詳細に本発明を説明する。
先ず、置換基Ｒ1、Ｒ2、Ａ1、Ａ2、Ａ3、Ａ4及びＡ5について説明する。
Ｃ1〜Ｃ4アルキル基としては、メチル基、エチル基、ｎ−プロピル基，ｉ−プロピル基、ｎ−ブチル基、ｉ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基等が挙げられる。
【００１６】
Ｃ1〜Ｃ4アルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基，ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基等が挙げられる。
以下、更に詳細に本発明を説明する。
リチオ化試剤であるｎ−ブチルリチウムの使用量は、式（２）のビナフチル化合物に対して当量〜１０当量の範囲、好ましくは、当量〜３当量の範囲がよい。
【００１７】
又、配位子の存在下、リチオ化を行うとリチオ化の収率が向上する。
配位子としては、テトラメチルエチレンジアミン、テトラメチルプロピレンジアミン、ジイソプロピルアミン、テトラメチル尿素、ジメチルプロピレン尿素、ヘキサメチルホスホリックトリアミド（ＨＭＰＡ）等が挙げられ、好ましくは、テトラメチルエチレンジアミン、テトラメチルプロピレンジアミンが挙げられる。
【００１８】
配位子の使用量としては、式（２）のビナフチル化合物に対して０．１モル倍〜１０倍モルの範囲、好ましくは、１モル倍〜５モル倍の範囲がよい。
ホルミル化剤としては、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−メチルフェニルホルムアミド、ギ酸メチル、オルトギ酸メチル、亜リン酸トリメチル、Ｎ−ホルミルモルホリン、Ｎ−ホルミルピペリジン等が挙げられ、好ましくは、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−メチルフェニルホルムアミド、Ｎ−ホルミルモルホリンが挙げられる。
【００１９】
ホルミル化剤の使用量は、ｎ−ブチルリチウムに対して、等モル〜１０倍モルの範囲、好ましくは、等モル〜５倍モルの範囲がよい。
反応溶媒としては、反応に関与しないものであれば特に制限はなく、例えば、ベンゼン、トルエン、キシレン、メシチレン、クロルベンゼン、ｏ−ジクロルベンゼン等の芳香族炭化水素類、ｎ−ヘキサン、シクロヘキサン、ｎ−オクタン、ｎ−デカン等の脂肪族炭化水素類、ジクロロメタン、ジクロロエタン、クロロホルム、四塩化炭素等のハロゲン化炭化水素類、テトラヒドロフラン、テトラヒドロピラン、ジエチルエーテル、ｔ−ブチルメチルエーテル、ジメトキシエタン等のエーテル類等が挙げられ、好ましくは、ヘキサン、テトラヒドロフラン、テトラヒドロピラン、ジエチルエーテル等が挙げられ、特に、テトラヒドロピランがよい。
【００２０】
更に、これらの溶媒は、単独又は組合せて使用することもできる。
反応温度は、通常−１００℃から使用する溶媒の沸点まで可能であるが、好ましくは−５０℃から５０℃の範囲、更に−２０℃〜３０℃の範囲がよい。
反応時間は、通常０．１〜１０００時間である。
反応終了後は、水を加えて適当な溶媒により目的物を抽出し、溶媒を減圧濃縮して粗製物を得るか、又は適当な溶媒から目的物を固体として析出させて粗製物を得ることができる。
【００２１】
更に、再結晶又はシリカゲルカラムクロマトグラフィー等の常法による精製を行なうことにより、純粋な式（１）の置換ビナフチル化合物を得ることができる。
【００２２】
【実施例】
以下、実施例を挙げて更に詳しく説明するが、本発明はこれらに限定されるものではない。
実施例１
【００２３】
【化７】
アルゴン雰囲気下、テトラヒドロピラン１００ｇ中に、ビナフチル化合物（１）１０．０ｇ（２７．７ミリモル）を加えて溶解し、０℃に冷却した。
次に、テトラメチルエチレンジアミン１２．９ｇ（１１０．８ミリモル）を加えた後、ｎ−ブチルリチウムのｎ−ヘキサン溶液３３．１ｍｌ（１．６９Ｍ／ｎ−ヘキサン、５５．４ミリモル）を滴下し、０℃で５時間攪拌した。
【００２５】
この反応液に、０℃でＮ，Ｎ−ジメチルホルムアミド４．９ｇ（６７．０ミリモル）を滴下し、２５℃で２時間攪拌した。
反応液に、１規定塩酸４０ｇを加え、有機層を分液し、更に１規定塩酸４０ｇで有機層を洗浄後、有機層を減圧下濃縮して、粗製物１３ｇを得た。
この粗製物を、液体クロマトグラフ（カラム：Ｉｎｅｒｔｓｉｌ ＯＤＳ−２４．６φ×２５０ｍｍ、カラム温度：４０℃、溶離液：アセトニトリル／水＝３／１（酢酸０．１％）、流量：１．０ｍｌ／ｍｉｎ．、検出：ＵＶ２５４ｎｍ）を使用して内標定量したところ、置換ビナフチル化合物（２）９．１ｇ（収率８５％）が含まれていた。
【００２６】
この粗製物に、トルエン３．３ｇを加え、加熱溶解後、ｎ−ヘプタン８．０ｇを加え室温まで冷却し、結晶を析出させた。
得られた結晶をろ別して、純粋な置換ビナフチル化合物（２）８．２ｇを得た。
アルゴン雰囲気下、テトラヒドロピラン１０ｍｌ中に、ビナフチル化合物（１）１．０ｇ（２．７ミリモル）を加えて溶解し、−１０℃に冷却した。
【００２７】
次に、テトラメチルエチレンジアミン０．８ｍｌ（５．３ミリモル）を加えて、ｎ−ブチルリチウムのｎ−ヘキサン溶液３．５ｍｌ（１．６９Ｍ／ｎ−ヘキサン、５．９ミリモル）を滴下し、−１０℃で６時間攪拌した。
この反応液に、−１０℃でＮ，Ｎ−ジメチルホルムアミド０．６５ｍｌ（８．４ミリモル）を滴下し、２５℃で２時間攪拌した。
【００２８】
反応液に、１規定塩酸を加え、有機層を分液後、有機層を実施例１と同様に内標定量したところ、置換ビナフチル化合物（２）０．６２ｇ（収率５８％）及びビナフチル化合物（１）０．３８ｇ（回収率３８％）が含まれていた。
実施例３
アルゴン雰囲気下、テトラヒドロピラン１０ｍｌ中に、ビナフチル化合物（１）１．０ｇ（２．７ミリモル）を加えて溶解し、−２０℃に冷却した。
【００２９】
次に、テトラメチルエチレンジアミン０．８ｍｌ（５．３ミリモル）を加えて、ｎ−ブチルリチウムのｎ−ヘキサン溶液３．５ｍｌ（１．６９Ｍ／ｎ−ヘキサン、５．９ミリモル）を滴下し、−２０℃で４時間攪拌した。
この反応液に、−１０℃でＮ，Ｎ−ジメチルホルムアミド０．６５ｍｌ（８．４ミリモル）を滴下し、２５℃で２時間攪拌した。
【００３０】
反応液に、１規定塩酸を加え、有機層を分液後、有機層を実施例１と同様に内標定量したところ、置換ビナフチル化合物（２）０．３７ｇ（収率３４％）及びビナフチル化合物（１）０．５６ｇ（回収率５６％）が含まれていた。
実施例４
アルゴン雰囲気下、テトラヒドロピラン１０ｍｌ中に、ビナフチル化合物（１）１．０ｇ（２．７ミリモル）を加えて溶解し、２５℃でテトラメチルエチレンジアミン０．８ｍｌ（５．３ミリモル）を加えて、ｎ−ブチルリチウムのｎ−ヘキサン溶液３．５ｍｌ（１．６９Ｍ／ｎ−ヘキサン、５．９ミリモル）を滴下し、２５℃で１５時間攪拌した。
【００３１】
この反応液に、Ｎ，Ｎ−ジメチルホルムアミド０．６５ｍｌ（８．４ミリモル）を滴下し、２５℃で２時間攪拌した。
反応液に、１規定塩酸を加え、有機層を分液後、有機層を実施例１と同様に内標定量したところ、置換ビナフチル化合物（２）０．８３ｇ（収率７７％）及びビナフチル化合物（１）０．１ｇ（回収率９％）が含まれていた。
実施例５
アルゴン雰囲気下、テトラヒドロピラン１０ｍｌ中に、ビナフチル化合物（１）１．０ｇ（２．７ミリモル）を加えて溶解し、０℃に冷却した。
【００３２】
次に、テトラメチルエチレンジアミン１．６ｍｌ（１０．６ミリモル）を加えて、ｎ−ブチルリチウムのｎ−ヘキサン溶液３．５ｍｌ（１．６９Ｍ／ｎ−ヘキサン、５．９ミリモル）を滴下し、０℃で３時間攪拌した。
この反応液に、０℃でＮ−ホルミルモルホリン０．８５ｍｌ（８．４ミリモル）を滴下して、２５℃で２時間攪拌した。
【００３３】
反応液に、１規定塩酸を加え、有機層を分液後、有機層を実施例１と同様に内標定量したところ、置換ビナフチル化合物（２）０．８２ｇ（収率７６％）及びビナフチル化合物（１）０．２２ｇ（回収率２２％）が含まれていた。
実施例６
アルゴン雰囲気下、テトラヒドロピラン１０ｍｌ中に、ビナフチル化合物（１）１．０ｇ（２．７ミリモル）を加えて溶解し、０℃に冷却した。
【００３４】
次に、テトラメチルエチレンジアミン１．６ｍｌ（１０．６ミリモル）を加えて、ｎ−ブチルリチウムのｎ−ヘキサン溶液３．５ｍｌ（１．６９Ｍ／ｎ−ヘキサン、５．９ミリモル）を滴下し、０℃で３時間攪拌した。
この反応液に、０℃でＮ−ホルミルピペリジン０．９３ｍｌ（８．４ミリモル）を滴下して、２５℃で２時間攪拌した。
【００３５】
反応液に、１規定塩酸を加え、有機層を分液後、有機層を実施例１と同様に内標定量したところ、置換ビナフチル化合物（２）０．７５ｇ（収率７０％）及びビナフチル化合物（１）０．１７ｇ（回収率１７％）が含まれていた。
実施例７
【００３６】
【化８】
実施例１のビナフチル化合物（１）を、光学活性な（Ｒ）−ビナフチル化合物（３）に代えた他は、実施例１と同様に反応及び後処理を行ない、透明で黄色の光学活性な（Ｒ）−置換ビナフチル化合物（４）８．５ｇ（収率８０％）を得た。
【００３８】
【化９】
アルゴン雰囲気下、１，２−ジクロルエタン３０ｍｌ中に、無水塩化アルミニウム２．６９ｇ（２０．２ミリモル）を加え、更に置換ビナフチル化合物（２）５．１４ｇ（純度９０％、１１．９ミリモル）を１，２−ジクロルエタン２０ｍｌに溶解させた溶液を加え、２５℃で３時間攪拌した。
この反応液に、氷冷下１規定塩酸３０ｇを加えて有機層を分液し、水洗後、有機層を減圧濃縮し粗製物５．１２ｇを得た。
【００４０】
この粗製物を内標定量したところ、目的物のサリチルアルデヒド化合物（５）４．２２ｇ（収率９５％）が含まれていた。
【００４１】
【発明の効果】
本発明により、式（２）のビナフチル化合物から、光学活性サレンマンガン錯体触媒の中間体であるサリチルアルデヒド化合物の前駆物質として有用な新規な式（１）の置換ビナフチル化合物を容易に製造することができる。
尚、式（１）の置換ビナフチル化合物より、脱メチル化反応を経由してサリチル化合物を容易に製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel substituted binaphthyl compound that is a precursor of a salicylaldehyde compound that is an intermediate of an optically active salen manganese complex catalyst in an asymmetric epoxidation reaction for obtaining an optically active epoxy compound from an olefin compound, and a method for producing the same .
[0002]
[Prior art]
Optically active epoxy compounds are important as intermediates for medicine and agricultural chemicals.
Examples of a method for producing an optically active epoxy compound from a prochiral olefin compound include, for example, Katsuki et al., Such as JP-A-7-285983, USP 5,420,314, Tetrahedron, 50 , 11827 (1994), and the like. This is an excellent method for carrying out catalytic asymmetric epoxidation reaction using an optically active salen manganese complex.
[0003]
The optically active salen manganese complex catalyst is synthesized from a diamine compound, a salicylaldehyde compound and a manganese salt.
The salicylaldehyde compound is obtained by cross-coupling reaction with phenyl Grignard using binaphthol as a monotriflate, protecting the free hydroxy group as a methoxymethyl group, and then lithiating the α position with t-butyllithium to formylate and deprotect Are synthesized.
[0004]
As a method for selectively introducing a formyl group into the α-position of the hydroxy group on the benzene ring, J. Chem. Soc. Perkin I, 1980 , 1862 includes a free formaldehyde / base / Lewis acid. A method for formylation of the α-position of a hydroxy group, J. Org. Chem., 59 , 1939 (1994), describes a Duff reaction using hexamethylenetetramine.
[0005]
[Problems to be solved by the invention]
However, the method of Katsuki et al. Uses chloromethyl methyl ether which has a problem such as carcinogenicity in protecting a free hydroxy group, and there is a problem in handling because the formylation reaction is ignitable. It cannot be said that it is an efficient manufacturing method, such as using butyl lithium and the reaction temperature being as low as -78 ° C.
[0006]
In addition, for the binaphthyl compound having a methoxy group of the present invention, a method using formaldehyde / base / Lewis acid, a Duff reaction, etc. were studied, but none of the reactions proceeded or satisfactory results were obtained with low yield. There wasn't.
[0007]
[Means for Solving the Problems]
As a result of intensive studies on a method for producing a precursor of a salicylaldehyde compound in order to solve the above-mentioned problems, the present inventors have industrially handled it as a lithiating agent for the homilmill reaction of a binaphthyl compound having a novel methoxy group. The inventors have found that easy n-butyllithium can be used, and have completed the present invention.
[0008]
That is, the present invention provides the formula (1)
[0009]
[Formula 4]
[Wherein, R 1 and R 2 independently represent a hydrogen atom, a halogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, a nitro group or a cyano group;
A 1 , A 2 , A 3 , A 4 and A 5 independently represent a hydrogen atom, a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group,
The binaphthyl moiety may be racemic or optically active. ]
A substituted binaphthyl compound represented by the formula (2)
[0011]
[Chemical formula 5]
[Wherein the binaphthyl moiety may be racemic or optically active, and R 1 , R 2 , A 1 , A 2 , A 3 , A 4 and A 5 are the same as above. ]
A binaphthyl compound represented by
Formula (1), characterized by reacting with a formylating agent after lithiation with n-butyllithium
[0013]
[Chemical 6]
[Wherein the binaphthyl moiety may be racemic or optically active, and R 1 , R 2 , A 1 , A 2 , A 3 , A 4 and A 5 are the same as above. ]
The present invention relates to a process for producing a substituted binaphthyl compound represented by the formula:
[0015]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
First, the substituents R 1 , R 2 , A 1 , A 2 , A 3 , A 4 and A 5 will be described.
The C 1 -C 4 alkyl group, a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl group, sec- butyl group, etc. tert- butyl group.
[0016]
The C 1 -C 4 alkoxy group, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, i- butoxy, sec- butoxy, tert- butoxy and the like.
Hereinafter, the present invention will be described in more detail.
The amount of n-butyllithium used as the lithiation reagent is in the range of 10 to 10 equivalents, preferably in the range of 3 to 3 equivalents, relative to the binaphthyl compound of formula (2).
[0017]
Further, when lithiation is performed in the presence of a ligand, the yield of lithiation is improved.
Examples of the ligand include tetramethylethylenediamine, tetramethylpropylenediamine, diisopropylamine, tetramethylurea, dimethylpropyleneurea, hexamethylphosphoric triamide (HMPA), and preferably tetramethylethylenediamine, tetramethylpropylene. Examples include diamines.
[0018]
As the usage-amount of a ligand, the range of 0.1 mol times-10 times mol with respect to the binaphthyl compound of Formula (2), Preferably the range of 1 mol times-5 mol times is good.
Examples of the formylating agent include N, N-dimethylformamide, N, N-methylphenylformamide, methyl formate, methyl orthoformate, trimethyl phosphite, N-formylmorpholine, N-formylpiperidine, and the like. N, N-dimethylformamide, N, N-methylphenylformamide, N-formylmorpholine can be mentioned.
[0019]
The amount of the formylating agent to be used is in the range of equimolar to 10-fold mol, preferably in the range of equimolar to 5-fold mol with respect to n-butyllithium.
The reaction solvent is not particularly limited as long as it does not participate in the reaction. For example, aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, chlorobenzene, o-dichlorobenzene, n-hexane, cyclohexane, Aliphatic hydrocarbons such as n-octane and n-decane, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, tetrahydrofuran, tetrahydropyran, diethyl ether, t-butyl methyl ether, dimethoxyethane, etc. Examples include ethers, preferably hexane, tetrahydrofuran, tetrahydropyran, diethyl ether and the like, and tetrahydropyran is particularly preferable.
[0020]
Furthermore, these solvents can be used alone or in combination.
The reaction temperature is usually from −100 ° C. to the boiling point of the solvent to be used.
The reaction time is usually 0.1 to 1000 hours.
After completion of the reaction, water is added and the target product is extracted with an appropriate solvent, and the solvent is concentrated under reduced pressure to obtain a crude product, or the target product is precipitated as a solid from an appropriate solvent to obtain a crude product. it can.
[0021]
Furthermore, a pure substituted binaphthyl compound of the formula (1) can be obtained by purification by a conventional method such as recrystallization or silica gel column chromatography.
[0022]
【Example】
EXAMPLES Hereinafter, although an Example is given and it demonstrates in detail, this invention is not limited to these.
Example 1
[0023]
[Chemical 7]
Under an argon atmosphere, 10.0 g (27.7 mmol) of the binaphthyl compound (1) was added and dissolved in 100 g of tetrahydropyran and cooled to 0 ° C.
Next, after adding 12.9 g (110.8 mmol) of tetramethylethylenediamine, 33.1 ml (1.69 M / n-hexane, 55.4 mmol) of n-hexane solution of n-butyllithium was added dropwise, Stir at 0 ° C. for 5 hours.
[0025]
To this reaction solution, 4.9 g (67.0 mmol) of N, N-dimethylformamide was added dropwise at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours.
To the reaction mixture was added 40 g of 1N hydrochloric acid, and the organic layer was separated. The organic layer was washed with 40 g of 1N hydrochloric acid, and then concentrated under reduced pressure to obtain 13 g of a crude product.
This crude product was subjected to liquid chromatography (column: Inertsil ODS-24.6φ × 250 mm, column temperature: 40 ° C., eluent: acetonitrile / water = 3/1 (acetic acid 0.1%), flow rate: 1.0 ml / min., detection: UV254 nm), and 9.1 g (yield 85%) of the substituted binaphthyl compound (2) was contained.
[0026]
To this crude product was added 3.3 g of toluene, and after dissolution by heating, 8.0 g of n-heptane was added and cooled to room temperature to precipitate crystals.
The obtained crystal was separated by filtration to obtain 8.2 g of a pure substituted binaphthyl compound (2).
Under an argon atmosphere, 1.0 g (2.7 mmol) of the binaphthyl compound (1) was added and dissolved in 10 ml of tetrahydropyran and cooled to −10 ° C.
[0027]
Next, 0.8 ml (5.3 mmol) of tetramethylethylenediamine was added, and 3.5 ml of an n-hexane solution of n-butyllithium (1.69 M / n-hexane, 5.9 mmol) was added dropwise. Stir at 10 ° C. for 6 hours.
To this reaction solution, 0.65 ml (8.4 mmol) of N, N-dimethylformamide was added dropwise at −10 ° C., and the mixture was stirred at 25 ° C. for 2 hours.
[0028]
1N Hydrochloric acid was added to the reaction mixture, and the organic layer was separated, and the organic layer was quantified in the same manner as in Example 1. As a result, 0.62 g (yield 58%) of the substituted binaphthyl compound (2) and the binaphthyl compound were obtained. (1) 0.38 g (recovery rate 38%) was contained.
Example 3
Under an argon atmosphere, 1.0 g (2.7 mmol) of the binaphthyl compound (1) was added and dissolved in 10 ml of tetrahydropyran and cooled to -20 ° C.
[0029]
Next, 0.8 ml (5.3 mmol) of tetramethylethylenediamine was added, and 3.5 ml of an n-hexane solution of n-butyllithium (1.69 M / n-hexane, 5.9 mmol) was added dropwise. Stir at 20 ° C. for 4 hours.
To this reaction solution, 0.65 ml (8.4 mmol) of N, N-dimethylformamide was added dropwise at −10 ° C., and the mixture was stirred at 25 ° C. for 2 hours.
[0030]
1N Hydrochloric acid was added to the reaction mixture, and the organic layer was separated. The organic layer was quantified in the same manner as in Example 1. As a result, 0.37 g (yield 34%) of the substituted binaphthyl compound (2) and the binaphthyl compound were obtained. (1) 0.56 g (recovery rate 56%) was contained.
Example 4
Under an argon atmosphere, 1.0 g (2.7 mmol) of the binaphthyl compound (1) is added and dissolved in 10 ml of tetrahydropyran, and 0.8 ml (5.3 mmol) of tetramethylethylenediamine is added at 25 ° C. -3.5 ml (1.69 M / n-hexane, 5.9 mmol) of n-hexane solution of butyllithium was added dropwise, and the mixture was stirred at 25 ° C for 15 hours.
[0031]
To this reaction solution, 0.65 ml (8.4 mmol) of N, N-dimethylformamide was added dropwise and stirred at 25 ° C. for 2 hours.
1N Hydrochloric acid was added to the reaction mixture, and the organic layer was separated, and the organic layer was quantified in the same manner as in Example 1. As a result, 0.83 g (yield 77%) of the substituted binaphthyl compound (2) and the binaphthyl compound were obtained. (1) 0.1 g (recovery rate 9%) was contained.
Example 5
Under an argon atmosphere, 1.0 g (2.7 mmol) of the binaphthyl compound (1) was added and dissolved in 10 ml of tetrahydropyran and cooled to 0 ° C.
[0032]
Next, 1.6 ml (10.6 mmol) of tetramethylethylenediamine was added, and 3.5 ml (1.69 M / n-hexane, 5.9 mmol) of n-hexane solution of n-butyllithium was added dropwise. Stir at 0 ° C. for 3 hours.
To this reaction solution, 0.85 ml (8.4 mmol) of N-formylmorpholine was added dropwise at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours.
[0033]
1N hydrochloric acid was added to the reaction solution, the organic layer was separated, and the organic layer was internally standardized in the same manner as in Example 1. As a result, 0.82 g (yield 76%) of the substituted binaphthyl compound (2) and the binaphthyl compound were obtained. (1) 0.22 g (22% recovery rate) was included.
Example 6
Under an argon atmosphere, 1.0 g (2.7 mmol) of the binaphthyl compound (1) was added and dissolved in 10 ml of tetrahydropyran and cooled to 0 ° C.
[0034]
Next, 1.6 ml (10.6 mmol) of tetramethylethylenediamine was added, and 3.5 ml (1.69 M / n-hexane, 5.9 mmol) of n-hexane solution of n-butyllithium was added dropwise. Stir at 0 ° C. for 3 hours.
To this reaction solution, 0.93 ml (8.4 mmol) of N-formylpiperidine was added dropwise at 0 ° C., and the mixture was stirred at 25 ° C. for 2 hours.
[0035]
1N Hydrochloric acid was added to the reaction mixture, and the organic layer was separated, and the organic layer was quantified in the same manner as in Example 1. As a result, 0.75 g (yield 70%) of the substituted binaphthyl compound (2) and the binaphthyl compound were obtained. (1) 0.17 g (17% recovery rate) was included.
Example 7
[0036]
[Chemical 8]
The reaction and post-treatment were performed in the same manner as in Example 1 except that the binaphthyl compound (1) in Example 1 was replaced with the optically active (R) -binaphthyl compound (3), and a transparent yellow optically active ( 8.5 g (yield 80%) of R) -substituted binaphthyl compound (4) were obtained.
[Chemical 9]
Under an argon atmosphere, 2.69 g (20.2 mmol) of anhydrous aluminum chloride was added to 30 ml of 1,2-dichloroethane, and 5.14 g (purity 90%, 11.9 mmol) of a substituted binaphthyl compound (2) was added. Then, a solution dissolved in 20 ml of 2-dichloroethane was added and stirred at 25 ° C. for 3 hours.
To this reaction solution, 30 g of 1N hydrochloric acid was added under ice-cooling to separate the organic layer. After washing with water, the organic layer was concentrated under reduced pressure to obtain 5.12 g of a crude product.
[0040]
When this crude product was quantified internally, 4.22 g (yield 95%) of the target salicylaldehyde compound (5) was contained.
[0041]
【The invention's effect】
According to the present invention, a novel substituted binaphthyl compound of the formula (1) that is useful as a precursor of a salicylaldehyde compound that is an intermediate of an optically active salen manganese complex catalyst can be easily produced from a binaphthyl compound of the formula (2). it can.
In addition, a salicyl compound can be easily produced from a substituted binaphthyl compound of the formula (1) via a demethylation reaction.
Claims (5)
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| JP18461996A JP4316688B2 (en) | 1996-07-15 | 1996-07-15 | Substituted binaphthyl compound and process for producing the same |
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| JP18461996A JP4316688B2 (en) | 1996-07-15 | 1996-07-15 | Substituted binaphthyl compound and process for producing the same |
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