JPH0368892B2

JPH0368892B2 -

Info

Publication number: JPH0368892B2
Application number: JP58137084A
Authority: JP
Inventors: Masaki Hasegawa; Kazuhiko Saigo; Nobuyuki Yonezawa; Toshio Shikae
Original assignee: Individual
Current assignee: Individual
Priority date: 1983-07-27
Filing date: 1983-07-27
Publication date: 1991-10-30
Also published as: JPS6028430A

Description

[Detailed description of the invention]

本発明は光学活性アンチ頭−頭クマリン二量体
の誘導体に相当する新規な光学活性ポリアミドに
関する。クマリンを光二量化することによりアンチ頭−
頭クマリン二量体が得られる。この物質は下記二種の光学異性体の混合物であ
り光学的に不活性である。このラセミ体は本発明者らの発明した方法によ
り光学活性アミンとの反応で得られるジアステレ
オジアミドの溶解性の差を利用して分割される。本発明者等は、このようにして得られた光学活
性体〔（＋）及び（−）二量体〕をジアミノ化合
物と反応させることにより新規な光学活性ポリマ
ーが得られることを発見し、本発明に到つた。本発明のポリアミドは、相当するラセミ体ポリ
アミドとは光学的性質の外、溶解性、熱的性質等
も異る。本発明のポリアミドは分子内に反応性の高いフ
エノール基を有し、又光学活性がシクロブタン環
に由来する特徴を有するため、その自体又はフエ
ノールの誘導体又は部分的にシクロブタン環を開
裂させた形で不斉合成、光学分割分析等に有用な
物質である。本発明の光学活性ポリアミドは一般式（）又
は（）で表わされ、還元粘度（ジメチルアセト
アミド中、0.3ｇ／dl、30℃）が0.1〜1.0のポリマ
ーである。ここでＡは第１又は第２ジアミンの２個のアミ
ノ基から１個づつの活性水素を除いた残基であ
る。かかるジアミンは飽和であつてもよく又不飽
和であつてもよい。又二種以上のジアミンの混合
物であつてもよく、必要に応じ３価以上のアミン
で変性してもよい。下記にＡで示される基の一例を示す。 −NH（CH₂）₂−NH−，−HN−（CH₂）₆−NH
−， The present invention relates to novel optically active polyamides corresponding to derivatives of optically active anti-head-to-head coumarin dimers. By photodimerizing coumarin, anti-head
A head coumarin dimer is obtained. This substance is a mixture of the following two optical isomers and is optically inactive. This racemate is resolved by the method invented by the present inventors by utilizing the difference in solubility of diastereodiamide obtained by reaction with an optically active amine. The present inventors discovered that a novel optically active polymer could be obtained by reacting the optically active substance [(+) and (-) dimer] thus obtained with a diamino compound, and the present invention I came up with an invention. The polyamide of the present invention differs from the corresponding racemic polyamide not only in optical properties but also in solubility, thermal properties, and the like. The polyamide of the present invention has a highly reactive phenol group in its molecule, and its optical activity is derived from the cyclobutane ring. It is a useful substance for asymmetric synthesis, optical resolution analysis, etc. The optically active polyamide of the present invention is a polymer represented by the general formula () or () and has a reduced viscosity (0.3 g/dl in dimethylacetamide, 30°C) of 0.1 to 1.0. Here, A is a residue obtained by removing one active hydrogen from each of the two amino groups of the first or second diamine. Such diamines may be saturated or unsaturated. It may also be a mixture of two or more types of diamines, and may be modified with a trivalent or higher valent amine if necessary. An example of the group represented by A is shown below. −NH(CH ₂ ) ₂ −NH−, −HN−(CH ₂ ) ₆ −NH
−、

【formula】

【式】【formula】

【formula】

本発明の光学活性ポリアミドは（＋）又は
（−）アンチ頭−頭クマリン二量体と相当するジ
アミンとの反応により容易に得られる。通常特別
な触媒を必要としない。両者の等モル量を非プロ
トン性極性溶媒中で反応させる方法は好ましい方
法である。非プロトン性極性溶媒としてはジメチ
ルアストアミド、ジオキサン、メチルピロリド
ン、ジメチルスルホキシド、ヘキサメチルホスホ
リツクトリアミド等は好ましい例である。以下実施例にて本発明を説明する。実施例１（−）アンチ頭−頭クマリン二量体0.2552ｇ
（0.9ｍmol）と当モル量のｐ−フエニレンジアミ
ンとをジメチルアセトアミド1.7ml中に溶解し、
80℃に24時間放置した。反応終了後生成物をメタノール中に滴下するこ
とによりポリマーを得た（収率87％）。得られたポリマーの還元粘度（ジメチルアセト
アミド中0.3ｇ／dl、30℃）は0.36であり、〔α〕_D
＝−89.4゜，〔α〕₄₃₅＝−260.0゜（ジメチルアセトア
ミド中0.5ｇ／100ml）であつた。実施例２ジアミンとしてヘキサメチレンジアミンを用
い、0.8ｍmolを1.6mlのジメチルアセトアミド中
で実施例１と同様に反応させた。収率及び性質を表−１に示す。実施例３ｍ−キシリレンジアミン2.1ｍmolを用い、4.3
mlのジメチルアセトアミド中で同様に反応させ
た。収率及び性質を表−１に示す。実施例４４，4′−ジアミノジフエニルエーテル１ｍmol
を用い、2.0mlのジメチルアセトアミド中同様に
反応させた。収率及び性質を表−１に示す。実施例５ピペラジン１ｍmolを用い、2.1mlのジメチル
アセトアミド中同様に反応させた。収率及び性質を表−１に示す。 The optically active polyamide of the present invention can be easily obtained by reacting a (+) or (-) anti-head-to-head coumarin dimer with the corresponding diamine. Usually no special catalyst is required. A preferred method is to react equimolar amounts of both in an aprotic polar solvent. Preferred examples of the aprotic polar solvent include dimethyl astamide, dioxane, methylpyrrolidone, dimethyl sulfoxide, and hexamethylphosphoric triamide. The present invention will be explained below with reference to Examples. Example 1 (-) Anti head-head coumarin dimer 0.2552 g
(0.9 mmol) and an equimolar amount of p-phenylenediamine were dissolved in 1.7 ml of dimethylacetamide,
It was left at 80°C for 24 hours. After the reaction was completed, the product was dropped into methanol to obtain a polymer (yield: 87%). The reduced viscosity of the obtained polymer (0.3 g/dl in dimethylacetamide, 30°C) was 0.36, and [α] _D
= -89.4°, [α] ₄₃₅ = -260.0° (0.5 g/100 ml in dimethylacetamide). Example 2 Using hexamethylene diamine as the diamine, 0.8 mmol was reacted in 1.6 ml of dimethylacetamide in the same manner as in Example 1. The yield and properties are shown in Table-1. Example 3 Using 2.1 mmol of m-xylylenediamine, 4.3
ml of dimethylacetamide. The yield and properties are shown in Table-1. Example 4 4,4'-diaminodiphenyl ether 1 mmol
The reaction was carried out in the same manner in 2.0 ml of dimethylacetamide. The yield and properties are shown in Table-1. Example 5 A similar reaction was carried out using 1 mmol of piperazine in 2.1 ml of dimethylacetamide. The yield and properties are shown in Table-1.

【表】比較例１ラセミ体のクマリン二量体を用いた他は実施例
２と同様に反応させてポリマーを得た（収率96
％）。得られたポリマーの還元粘度（ジメチルア
セトアミド中0.3ｇ／dl、30℃）は0.46であり、
〔α〕_D及び〔α〕₄₃₅な何れも０であつた。[Table] Comparative Example 1 A polymer was obtained by reacting in the same manner as in Example 2 except that racemic coumarin dimer was used (yield: 96
%). The reduced viscosity of the obtained polymer (0.3 g/dl in dimethylacetamide, 30°C) was 0.46,
[α] _D and [α] ₄₃₅ were both 0.

Claims

[Claims] 1 Represented by the general formula () or (), reduced viscosity (0.3 g/dl in dimethylacetamide, 30°C)
An optically active polyamide with a value of 0.1 to 1.0. (However, A is a residue obtained by removing one active hydrogen from each of the two amino groups of the first or second diamine.) 2 Optically active anti-head-to-head coumarin dimer and the first or second diamine 1. A method for producing an optically active polyamide represented by the general formula () or (), which comprises reacting. (However, A is a residue obtained by removing one active hydrogen from each of the two amino groups of the primary or secondary diamine)