JPH0461875B2 - - Google Patents
Info
- Publication number
- JPH0461875B2 JPH0461875B2 JP3567284A JP3567284A JPH0461875B2 JP H0461875 B2 JPH0461875 B2 JP H0461875B2 JP 3567284 A JP3567284 A JP 3567284A JP 3567284 A JP3567284 A JP 3567284A JP H0461875 B2 JPH0461875 B2 JP H0461875B2
- Authority
- JP
- Japan
- Prior art keywords
- crown ether
- optically active
- asymmetric
- formula
- biphenanthryl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000003983 crown ethers Chemical class 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 description 12
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 10
- VQECOUFHPVSSCD-UHFFFAOYSA-N 1-phenanthren-1-ylphenanthrene Chemical group C1=CC2=CC=CC=C2C2=C1C(C1=C3C=CC=4C(C3=CC=C1)=CC=CC=4)=CC=C2 VQECOUFHPVSSCD-UHFFFAOYSA-N 0.000 description 4
- 239000013543 active substance Substances 0.000 description 4
- 230000032258 transport Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LYXQKPRYDFQZPL-UHFFFAOYSA-N 1-(2-hydroxyphenanthren-1-yl)phenanthren-2-ol Chemical group C1=CC2=CC=CC=C2C2=C1C(C1=C3C(C4=CC=CC=C4C=C3)=CC=C1O)=C(O)C=C2 LYXQKPRYDFQZPL-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 238000011914 asymmetric synthesis Methods 0.000 description 2
- 238000002983 circular dichroism Methods 0.000 description 2
- 238000001142 circular dichroism spectrum Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BUHGDYPBQWWWQS-UHFFFAOYSA-N 2-[2-[2-[2-[2-(4-methylphenyl)sulfonyloxyethoxy]ethoxy]ethoxy]ethoxy]ethyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCCOCCOCCOCCOCCOS(=O)(=O)C1=CC=C(C)C=C1 BUHGDYPBQWWWQS-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000006957 Michael reaction Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003444 phase transfer catalyst Substances 0.000 description 1
- ULSIYEODSMZIPX-UHFFFAOYSA-N phenylethanolamine Chemical compound NCC(O)C1=CC=CC=C1 ULSIYEODSMZIPX-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明は新規なクラウンエーテルに関する。更
に詳しくは１，1′−ビフエナンスリル基を含む次
の一般式(1)で示されるクラウンエーテルに関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to novel crown ethers. More specifically, it relates to a crown ether represented by the following general formula (1) containing a 1,1'-biphenanthryl group.
式中ｎは３乃至７の整数であり、好ましくは４
乃至６の整数である。上記一般式で示されるクラ
ウンエーテルにはラセミ体及び２種類の光学異性
体が含まれている。 In the formula, n is an integer from 3 to 7, preferably 4
It is an integer from 6 to 6. The crown ether represented by the above general formula includes a racemate and two types of optical isomers.
（産業上の利用分野）
従来クラウンエーテルは相間移動触媒やアニオ
ンを活性化するためにある種の反応に不可欠な要
素として広く使われてきた。このうち光学活性な
クラウンエーテルはその高い不斉識別能により光
学分割に用いられることが知られている。特に
種々の光学異性体の一方を選択的に輸送する不斉
輸送を効率的に行なわせることができる。このほ
か不斉合成反応における重要な不斉源として触媒
的に使用することができる。(Industrial Application Field) Crown ethers have traditionally been widely used as phase transfer catalysts and as essential elements in certain reactions to activate anions. Among these, optically active crown ethers are known to be used for optical resolution due to their high asymmetric discrimination ability. In particular, asymmetric transport that selectively transports one of various optical isomers can be carried out efficiently. In addition, it can be used catalytically as an important chiral source in asymmetric synthesis reactions.
（従来技術）
従来広く使われてきたクラウンエーテルとして
は環状ポリアルキレングリコールがあるが、大き
な芳香族基を有するクラウンエーテルは、疎水性
が大きく又立体的な規制性を持つなど、特異な用
途が開かれている。特に光学活性なクラウエーテ
ルとしてはD.J.クラムらによつて合成されたビナ
フチル基を有するものが知られており、多くの用
途例がある。(Prior art) Cyclic polyalkylene glycol is a crown ether that has been widely used in the past, but crown ethers with large aromatic groups have unique uses, such as being highly hydrophobic and having steric regulation. It's open. In particular, as an optically active clauether, one having a binaphthyl group synthesized by DJ Kram et al. is known, and there are many examples of its use.
〔D.J.Cram et al.J.Org.Chem.46，393（1981）、
D.J.Crem et al.J.Am.Chem.SOc.，101、4941
（1979）、D.J.Cram Chem・Commun.1981、625〕
しかしながらこれらは必ずしも満足すべき性能
を有しているとはいえず、より入手が容易で優れ
た能力を有する化合物が望まれていた。そこで本
発明者等は鋭意探索を行なつた結果本発明に到つ
たものである。[DJCram et al.J.Org.Chem. 46 , 393 (1981),
DJCrem et al.J.Am.Chem.SOc., 101 , 4941
(1979), DJCram Chem.Commun.1981, 625] However, these cannot necessarily be said to have satisfactory performance, and there has been a desire for a compound that is easier to obtain and has superior performance. Therefore, the inventors of the present invention conducted extensive research, and as a result, they arrived at the present invention.
本発明により提供されるクラウンエーテルの光
学活性体は、疎水性が向上し更に立体規制能力が
優れていることからより、高い選択性で不斉輸送
を行なわせることが可能となつた。 The optically active crown ether provided by the present invention has improved hydrophobicity and excellent stereoregulatory ability, making it possible to carry out asymmetric transport with high selectivity.
（発明の構成）
本発明は上記一般式(1)で表わされるクラウンエ
ーテルに関するものである。本発明によつて提供
されるクラウンエーテルは１，1′−ビフエナンス
リル基を有しており、２種類の光学異性体を含ん
でいる。それぞれの光学異性体は、いずれも容易
に得ることができる。得られた光学活性体はその
比旋光度の値が正又は負の符号を持ち、クロロホ
ルム中〔α〕24 D5.4°である。(Structure of the Invention) The present invention relates to a crown ether represented by the above general formula (1). The crown ether provided by the present invention has a 1,1'-biphenanthryl group and contains two types of optical isomers. Each optical isomer can be easily obtained. The obtained optically active substance has a specific optical rotation value having a positive or negative sign, and is [α] 24 D 5.4° in chloroform.
本発明に係る式(1)で表わされる化合物は例えば
２，2′−ジヒドロキシ−１，1′−ビフエナンスリ
ルをポリエチレングリコールジトシラート（ｎ＝
３〜７）と希釈条件下環化させることにより得ら
れる。 The compound represented by formula (1) according to the present invention is, for example, 2,2'-dihydroxy-1,1'-biphenanthryl combined with polyethylene glycol ditosylate (n=
3 to 7) under dilute conditions.
又式(1)で表わされるクラウンエーテルの光学活
性体は例えば光学活性な２，2′−ジヒドロキシ−
１，1′−ビフエナンスリルをポリエチレングリコ
ールジトシラートと希釈条件下環化させることに
より得ることができ、得られた光学活性体の光学
活性は出発物質である２，2′−ジヒドロキシ−
１，1′−ビフエナンスリルの光学活性に依存する
ため、そのいずれかを適宜選ぶことでいずれの光
学活性体をも得ることができる。 The optically active crown ether represented by formula (1) is, for example, optically active 2,2'-dihydroxy-
It can be obtained by cyclizing 1,1'-biphenanthryl with polyethylene glycol ditosylate under dilute conditions, and the optical activity of the obtained optically active substance is determined by the starting material 2,2'-dihydroxy-
Since it depends on the optical activity of 1,1'-biphenanthryl, any optically active substance can be obtained by appropriately selecting one of them.
勿論、ラセタ体のクラウンエーテルを光学分割
することによつても光学活性体を得ることが可能
である。 Of course, it is also possible to obtain an optically active substance by optically resolving a raceta crown ether.
（発明の効果）
本発明により提供される新規なクラウンエーテ
ルは、従来の環状ポリアルキレングリコールに比
べ疎水性基を有することから、溶解度が異なり、
輸送能力が大きくなることが期待される。又、平
面性基を有し立体的規制性が大きいため、その光
学活性体の不斉識別能が増すものと期待される。
即ちこれらのクラウンエーテルは種々の不斉合成
反応の不斉源として用いることができる。例えば
不斉マイケル反応の触媒や不斉重合反応の開始剤
とすることができる。又種々の光学異性体を光学
分割する場合にも優れた不斉識別能を示し、アミ
ンの鉱酸塩の不斉輸送を行なわせることができる
ものと期待できる。(Effects of the Invention) The novel crown ether provided by the present invention has a hydrophobic group compared to conventional cyclic polyalkylene glycols, and therefore has a different solubility.
It is expected that the transportation capacity will increase. In addition, since it has a planar group and has great steric control, it is expected that the asymmetric discrimination ability of its optically active form will increase.
That is, these crown ethers can be used as chiral sources in various asymmetric synthesis reactions. For example, it can be used as a catalyst for an asymmetric Michael reaction or an initiator for an asymmetric polymerization reaction. It also exhibits excellent asymmetric discrimination ability when optically resolving various optical isomers, and is expected to be able to carry out asymmetric transport of mineral acid salts of amines.
次に本発明を実施例にもつて詳述する。 Next, the present invention will be explained in detail with reference to examples.
この中で記したNMR値、IR値、比旋光度値、
円偏光二色性スペクトル値は次の方法により測定
した。即ち、1HNMRスペクトルは日本電子製FX
−100型を用いてTMSを内部標準として用いて測
定した。又IR値は日立製260−１−０型を用いて
測定した。 The NMR values, IR values, specific rotation values,
Circular dichroism spectrum values were measured by the following method. That is, the 1 HNMR spectrum was obtained using JEOL FX.
-100 type and TMS was used as an internal standard. Further, the IR value was measured using Hitachi Model 260-1-0.
比旋光度値は日本分光工業製DIP−181を用い
クロロホルム溶液として測定した。円偏光二色性
スペクトル値はヘキサン溶液中、日本分光工業製
Ｊ−40を用いて測定した。 The specific optical rotation value was measured as a chloroform solution using DIP-181 manufactured by JASCO Corporation. The circular dichroism spectrum value was measured in a hexane solution using J-40 manufactured by JASCO Corporation.
実施例 １
２，2′−ジヒドロキシ−１，1′−ビフエナンス
リン0.5ｇ（1.29×10-3モル）を無水THF75mlに
溶かし、窒素気流下ｔ−BuOK0.35ｇ（3.12×
10-3モル）を加え、１時間撹拌環流した後、ペン
タエチレングリコールジトシラート0.65ｇ（1.34
×10-3モル）の無水THF75ml溶液を５時間かけ
て滴下して加える。滴下終了後３時間撹拌還流し
た後、氷冷下水100mlを加え、塩化メチレンにて
抽出する。2NHCl、2NNaHCO3、水で洗つた後
硫酸マグネシウムで乾燥させる。乾燥剤を除き溶
媒を留去した後、粗生成物を30ｇのシリカゲルを
用いてカラムクロマトを行ない精製する。展開剤
はベンゼン−エーテル（３：１）を用いる。得ら
れたものをベンゼン−メタノールから再結晶する
と、式(1)に於てｎ＝５のラセミクラウンエーテル
が得られる。このクラウンエーテルのラセミ体の
融点は211〜213℃であつた。1
HNMR；CDCl3（溶媒クロロホルム、TMS）3.1
〜4.2（ｍ）、7.1〜9.0（ｍ）
IR；KBr（cm-1）1595、1450、1305、1210、
1110、760、730
実施例 ２
実施例１と同様にして出発物質に（Ｓ）−（−）
−２，2′−ジヒドロキシ−１，1′−ビフエナンス
リルを用いると（−）体のクラウンエーテルが得
られる。式(1)に於てｎ＝５の（−）−クラウンエ
ーテルは収率40％で得られ融点は178〜180℃、比
旋光度は〔α〕24 D−5.4°（クロロホルム）であつた。
元素分析値は次のとおりであつた。Example 1 0.5 g (1.29×10 -3 mol) of 2,2'-dihydroxy-1,1'-biphenanthrin was dissolved in 75 ml of anhydrous THF, and 0.35 g (3.12×
After stirring and refluxing for 1 hour, 0.65 g of pentaethylene glycol ditosylate (1.34
x 10 -3 mol) in 75 ml of anhydrous THF is added dropwise over a period of 5 hours. After the dropwise addition was completed, the mixture was stirred and refluxed for 3 hours, and then 100 ml of ice-cooled water was added, followed by extraction with methylene chloride. Wash with 2NHCl, 2NNaHCO 3 and water, then dry with magnesium sulfate. After removing the desiccant and evaporating the solvent, the crude product is purified by column chromatography using 30 g of silica gel. Benzene-ether (3:1) is used as a developing agent. When the obtained product is recrystallized from benzene-methanol, a racemic crown ether of formula (1) where n=5 is obtained. The melting point of this racemic crown ether was 211-213°C. 1 HNMR; CDCl 3 (solvent chloroform, TMS) 3.1
~4.2 (m), 7.1 ~ 9.0 (m) IR; KBr (cm -1 ) 1595, 1450, 1305, 1210,
1110, 760, 730 Example 2 Using (S)-(-) as the starting material in the same manner as in Example 1
When -2,2'-dihydroxy-1,1'-biphenanthryl is used, a (-) crown ether is obtained. In formula (1), the (-)-crown ether with n = 5 was obtained in a yield of 40%, with a melting point of 178-180°C and a specific optical rotation of [α] 24 D -5.4° (chloroform). .
The elemental analysis values were as follows.
C38H36O6
理論値 C77.53％、H6.16％
分析値 C77.41％、H6.11％
円偏光二色性（CD）；（ｎｍ） （ ）内は〔θ〕
値を示す。シクロヘキサン中）276（−4.12×
102）、279（−1.18×102）、292（−4.82×103）、
312（＋2.47×103）
実施例 ３
実施例２と全く同様にして出発物質に（Ｒ）−
（＋）−２，2′−ジヒドロキシ−１，1′−ビフエナ
ンスリルを用いると（＋）体のクラウンエーテル
が得られる。式(1)に於いてｎ＝５の（＋）−クラ
ウンエーテルの融点は178〜180℃、比旋光度は
〔α〕24 D＋5.4°（クロロホルム）であつた。 C 38 H 36 O 6 Theoretical value C77.53%, H6.16% Analytical value C77.41%, H6.11% Circular dichroism (CD); (nm) ( ) [θ]
Show value. in cyclohexane) 276 (−4.12×
10 2 ), 279 (−1.18×10 2 ), 292 (−4.82×10 3 ),
312 (+2.47×10 3 ) Example 3 In exactly the same manner as in Example 2, (R)-
When (+)-2,2'-dihydroxy-1,1'-biphenanthryl is used, a crown ether in the (+) form is obtained. In formula (1), the (+)-crown ether with n=5 had a melting point of 178 to 180°C and a specific optical rotation of [α] 24 D +5.4° (chloroform).
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3567284A JPS60181084A (en) | 1984-02-27 | 1984-02-27 | Novel crown ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3567284A JPS60181084A (en) | 1984-02-27 | 1984-02-27 | Novel crown ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60181084A JPS60181084A (en) | 1985-09-14 |
| JPH0461875B2 true JPH0461875B2 (en) | 1992-10-02 |
Family
ID=12448365
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3567284A Granted JPS60181084A (en) | 1984-02-27 | 1984-02-27 | Novel crown ether |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60181084A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0728786B2 (en) * | 1992-09-07 | 1995-04-05 | 森崎工芸株式会社 | Bedding rug |
-
1984
- 1984-02-27 JP JP3567284A patent/JPS60181084A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60181084A (en) | 1985-09-14 |
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