JPH02225584A - Novel anionic cyclophane derivative - Google Patents
Novel anionic cyclophane derivativeInfo
- Publication number
- JPH02225584A JPH02225584A JP1045969A JP4596989A JPH02225584A JP H02225584 A JPH02225584 A JP H02225584A JP 1045969 A JP1045969 A JP 1045969A JP 4596989 A JP4596989 A JP 4596989A JP H02225584 A JPH02225584 A JP H02225584A
- Authority
- JP
- Japan
- Prior art keywords
- cyclophane
- anionic
- derivative
- synthesis
- added
- 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.)
- Granted
Links
- 125000000129 anionic group Chemical group 0.000 title claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 4
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000000126 substance Substances 0.000 claims description 3
- 150000001767 cationic compounds Chemical class 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 7
- 150000002576 ketones Chemical class 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 238000004587 chromatography analysis Methods 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 238000004811 liquid chromatography Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 125000006850 spacer group Chemical group 0.000 abstract description 2
- 239000007858 starting material Substances 0.000 abstract description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 abstract 1
- 150000001721 carbon Chemical group 0.000 abstract 1
- 238000012856 packing Methods 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- -1 -C112CH Chemical class 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- KDCIHNCMPUBDKT-UHFFFAOYSA-N hexane;propan-2-one Chemical compound CC(C)=O.CCCCCC KDCIHNCMPUBDKT-UHFFFAOYSA-N 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- NLMDJJTUQPXZFG-UHFFFAOYSA-N 1,4,10,13-tetraoxa-7,16-diazacyclooctadecane Chemical class C1COCCOCCNCCOCCOCCN1 NLMDJJTUQPXZFG-UHFFFAOYSA-N 0.000 description 1
- ULTHEAFYOOPTTB-UHFFFAOYSA-N 1,4-dibromobutane Chemical compound BrCCCCBr ULTHEAFYOOPTTB-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000012230 colorless oil Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000000950 dibromo group Chemical group Br* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- OAYLNYINCPYISS-UHFFFAOYSA-N ethyl acetate;hexane Chemical compound CCCCCC.CCOC(C)=O OAYLNYINCPYISS-UHFFFAOYSA-N 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、例えば陽イオン性化合物同志の分離を行う機
能材料として極めて有用である新規なシクロファン誘導
体に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel cyclophane derivative that is extremely useful as a functional material for separating cationic compounds, for example.
〔従来の技術及び発明が解決しようとする課題〕従来、
クラウンエーテル誘導体やクリプタンド誘導体などを用
いた分離剤が知られており、アミノ酸やアミン頚などの
アンモニウム塩が良く分割されている。しかしながら、
更に陽イオン化合物同志の分離剤として優れた機能を発
揮する分離剤が要望されている。[Problems to be solved by conventional techniques and inventions] Conventionally,
Separating agents using crown ether derivatives and cryptand derivatives are known, and ammonium salts such as amino acids and amine necks are well separated. however,
Furthermore, there is a need for a separating agent that exhibits an excellent function as a separating agent for cationic compounds.
本発明は、シクロファン骨格に陰イオン性邪分と中性部
分を積極的に組み込むことにより、有機陽イオン性化合
物に対する分離能力をさらに高めた新規な陰イオン性シ
クロファン誘導体を提供しようとするものである。The present invention aims to provide a novel anionic cyclophane derivative that has further improved separation ability for organic cationic compounds by actively incorporating an anionic component and a neutral component into the cyclophane skeleton. It is something.
即ち本発明は、下記一般式（Ｉ）
（式中、Ｘ、Ｙユニットを構成する炭素原子数は１〜１
０であり、炭素原子の種類はＳＰ＋ Ｓ ｐ ” 、
Ｓｐ ３混成軌道を持つ炭素の１種類のみ或いは王者の
中からの組み合わせで選択され、ユニット中にヘテロ原
子を含んでいてもかまわない）で示される新規な陰イオ
ン性シクロファン誘導体に関する。That is, the present invention is based on the following general formula (I) (wherein, the number of carbon atoms constituting the X and Y units is 1 to 1
0, and the type of carbon atom is SP+ Sp”,
The present invention relates to a novel anionic cyclophane derivative represented by one or a combination of carbons having an Sp 3 hybrid orbital, which may contain a heteroatom in the unit.
上記式（Ｉ）中のＸ、Ｙユニットを具体的に例示するな
らば、−（Ｃ１１，）。−（ロー１−１０）。A specific example of the X and Y units in the above formula (I) is -(C11,). - (Rho 1-10).
ＣＨ。CH.
−ＣＨ２−［：ミＣ−ＣＨ２−、−ＣＩＩ２ＣＨ２−Ｎ
−Ｃ１１２ＣＨ，−などの炭化水素類やエーテル、アミ
ン類がある。また、ＸとＹは同一でも異なっていてもか
まわない。-CH2-[:MiC-CH2-, -CII2CH2-N
There are hydrocarbons such as -C112CH,-, ethers, and amines. Further, X and Y may be the same or different.
本発明に係る上記一般式（Ｉ）で示されるシクロファン
類は、液体クロマトグラフィーの移動相へ少量添加する
ことにより、或いは担体に保持させてクロマトグラフィ
ー充填材として用いることにより、有機陽イオン性化合
物同志の分離に対して優れた機能を発揮することが期待
される。The cyclophanes represented by the above general formula (I) according to the present invention can be used as organic cationic compounds by adding a small amount to the mobile phase of liquid chromatography, or by retaining them on a carrier and using them as chromatography fillers. It is expected to exhibit excellent functionality for separating compounds.
上記一般式（Ｉ，）で示される本発明のシクロファン誘
導体の合成は、例えば４．４′−ジメトキシ−３，５，
３’ 、 ５’−テトラメトキシカルボニルジフェニル
ケトンを出発原料として、ケトンの還元、メチルエーテ
ル結合の切断を行って３．５．３’ 。The synthesis of the cyclophane derivative of the present invention represented by the above general formula (I,) can be carried out, for example, by 4,4'-dimethoxy-3,5,
Using 3', 5'-tetramethoxycarbonyl diphenyl ketone as a starting material, reduction of the ketone and cleavage of the methyl ether bond were performed to obtain 3.5.3'.
５゛−テトラアルコキシカルボニル−４，４’−ジヒド
ロキジルジフェニルメタンとした後、Ｘ、Ｙに相当する
スペーサーを反応させてシクロファン骨格を形成し、エ
ステル結合を加水分解することにより得られる。It is obtained by preparing 5'-tetraalkoxycarbonyl-4,4'-dihydroxyldiphenylmethane, reacting spacers corresponding to X and Y to form a cyclophane skeleton, and hydrolyzing the ester bond.
以下、本発明を実施例によって詳述するが、本発明はこ
れらの実施例によって限定されるものではない。EXAMPLES Hereinafter, the present invention will be explained in detail with reference to Examples, but the present invention is not limited by these Examples.
合成例１
シクロファン（Ｉ）の合成
上記式（Ｉ）で示されるシクロファンを、下記の合成ス
キームに従って合成した。Synthesis Example 1 Synthesis of Cyclophane (I) Cyclophane represented by the above formula (I) was synthesized according to the following synthesis scheme.
Ｍｅｎ□Ｃ ■ （Ｉ） ・８に 以下、上記合成の各工程を詳述する。Men□C ■ (I) ・8 Each step of the above synthesis will be explained in detail below.
■ ４．４°−ジメトキシ−３，５，３°、５′ −
テトラメトキシカルボニルジフェニルケトン（２）の合
成
既知の方法〔文献；Ｆ、５ｅｅｂａｃｈ、 ８ｅｒ、、
７３゜１３３８ （Ｉ９４０） ）に従って合成した
。■ 4.4°-dimethoxy-3,5,3°,5'-
Known method for synthesis of tetramethoxycarbonyldiphenylketone (2) [Reference: F, 5eebach, 8er, .
73°1338 (I940)).
■ ４，４°−ジメトキシ−３，５，３’ 、 ５’
−テトラメトキシカルボニルジフェニルメタン（３）
の合成
■で得たケトン（２＞ （４，７４ｇ、 １０ｍｍｏｌ
）のＴ ＨＦ （Ｉ５ｄ）溶液中にＥｔ、５ｉｔｌ（５
，Ｑｍｌ、 ３１ｍｍｏｌ）を加え、室温にて２０時間
攪拌する。反応液を冷水（２００ｍｆ）にあけ、析出す
る結晶を濾取し、乾燥後にアセトン−ヘキサンより再結
晶すると、無色針状晶の（，３＞ （４，５ｇ、 ９７
％）を得る。■ 4,4°-dimethoxy-3,5,3', 5'
-Tetramethoxycarbonyldiphenylmethane (3)
Synthesis of Ketone (2> (4.74g, 10mmol
) in T HF (I5d) solution of Et, 5 itl (5
, Qml, 31 mmol) and stirred at room temperature for 20 hours. The reaction solution was poured into cold water (200 mf), the precipitated crystals were collected by filtration, dried and recrystallized from acetone-hexane to give colorless needle-like crystals (,3> (4,5 g, 97
%).
その物性は次の通りであった。Its physical properties were as follows.
・融点；８４〜８５℃
−ＩＲスペクトル（ＣＨＣＩ、、 ｃｍ−’） ； １
７３０・’ Ｉｆ−ＮＭＲスペクトル（ＣＨＣＩ３．
６）；３．９２（Ｉ８Ｎ、ｓ）、 ４．０２（２ｆ（、
ｓ）、 ７．７２（４Ｎ、ｓ）・元素分析値（ＣｚＪｚ
４０ｒｏ＞ ：計算値；Ｃ５９，９９，Ｈ５，２５
実測値；ｃ ５９．８１． Ｈ５，２１■ ３．５
．３°、５゛−テトラカルボキシ−４，４°−ジヒドロ
キジルジフェニルメタン（４）の合成■で得たエステル
（３） （２ＪＯｇ、 ５ｍｍｏｌ）のＣＨ，Ｃ１２（
２０ｍｌ）溶液を一７８℃に冷却し、ＢＢｒ。・Melting point: 84-85°C -IR spectrum (CHCI, cm-'): 1
730·' If-NMR spectrum (CHCI3.
6); 3.92 (I8N, s), 4.02 (2f (,
s), 7.72 (4N, s)・Elemental analysis value (CzJz
40ro>: Calculated value; C59,99, H5,25 Actual value; c 59.81. H5, 21 ■ 3.5
．． Synthesis of 3°,5′-tetracarboxy-4,4°-dihydroxyldiphenylmethane (4) CH,C12(
20 ml) solution was cooled to -78°C and diluted with BBr.
（Ｉ，０ｍＡ！、 １１ｍ＋ｎｏｌ）のｃｏ、ｃ＋、（
６ｍｔ’）溶液を０．５時間かけて滴下する。−７８℃
にて２時間、室温にて２４時間攪拌して後、ＨＪ（５０
ｍｆ）を加える。沈澱物を濾取し、Ａｃ０ｔｉｔに溶解
し、５％炭酸ソーダ水溶液で抽出する。水層を合わせ、
ＩＯ％ＨＣＩ水溶液で酸性とし、析出する沈澱を濾取す
る。これを乾燥後、アセトン−ヘキサンより再結晶する
と、無色針状晶の（４）（Ｉ，６ｇ、８５％）を得る。(I, 0mA!, 11m+nol) co, c+, (
6mt') solution is added dropwise over 0.5 hours. -78℃
After stirring for 2 hours at room temperature and 24 hours at room temperature, HJ (50
mf). The precipitate is collected by filtration, dissolved in Ac0tit, and extracted with 5% aqueous sodium carbonate solution. Combine the water layers,
The mixture is acidified with an IO% HCI aqueous solution, and the precipitate is collected by filtration. After drying, this was recrystallized from acetone-hexane to obtain colorless needle crystals of (4) (I, 6 g, 85%).
その物性は次の通りである。Its physical properties are as follows.
・融点；２９８℃
−ＩＲスペクトル（ＫＢｒ、 ｃｍ−’） ；３０７
０． １７１７・’）Ｉ−ＮＭＲスペクトル（ＤＭＳＯ
−ｄ、、、 δ） ：３．９８（２Ｈ，ｓ）、 ７．
８９（４Ｈ，ｓ）、 １１．５７（６Ｈ，ｓ。・Melting point: 298°C -IR spectrum (KBr, cm-'): 307
0. 1717・') I-NMR spectrum (DMSO
-d,,, δ): 3.98 (2H, s), 7.
89 (4H, s), 11.57 (6H, s.
Ｄ、０で消失）
・元素分析値（Ｃ，ｖＬ２０＋−・１１．０） ；計算
値；ｃ ５１．８２． Ｈ３，５８実測値；ｃ
５１．６７、 Ｈ３，２６■ ３．５．３°、５”−
テトラエトキシカルボニル−４，４′−ジヒドロキシジ
フェニルメタン（５）の合成
■で得たカルボン酸（４） （５，０ｇ、 １３Ｊｍｍ
ｏｌ）、ｐ ＴｓＯ）１−８２０（４，０ｇ、 ２１ｍ
ｍ０１）の［ＥｔＯＨ（６０ｍｆ）−ベンゼン（４０−
）溶液を８時間還流下に加熱して後、溶媒を留去する。D, disappears at 0) Elemental analysis value (C, vL20+-・11.0); Calculated value; c 51.82. H3,58 actual measurement value; c
51.67, H3, 26■ 3.5.3°, 5”-
Synthesis of tetraethoxycarbonyl-4,4'-dihydroxydiphenylmethane (5) Carboxylic acid (4) obtained in ① (5.0 g, 13 Jmm
ol), p TsO) 1-820 (4.0g, 21m
m01) [EtOH (60mf)-benzene (40-
) After heating the solution under reflux for 8 hours, the solvent is distilled off.
残渣をＡｃ０Ｅｔ （２００−）に溶解し、８％ＮａＨ
ＣＯｓ水溶液、飽和食塩水で洗い、Ｍｇ５Ｏ，で乾燥す
る。ＡｃＯＥｔを留去し、残渣をカラムクロマトグラフ
ィー（シリカゲル、 Ａｃ０Ｅｉｔ）にかけ、粗（５）
（４，４０ｇ、 ６８％）を得る。＾ｃＯＥｔ−へキ
サンより再結晶すると、無色針状晶となる。その物性は
次の通りである。The residue was dissolved in Ac0Et (200-) and 8% NaH
Wash with COs aqueous solution and saturated saline, and dry with Mg5O. AcOEt was distilled off, the residue was subjected to column chromatography (silica gel, AcOEit), and the crude (5)
(4.40g, 68%) is obtained. When recrystallized from ^cOEt-hexane, it becomes colorless needle crystals. Its physical properties are as follows.
・融点；８４〜８５℃
−ＩＲスペクトル（ＣＨＣＩ、、 ｃｍす） ； １
７２０． １６７５・’Ｈ−ＮＭＲスペクトル（ＣＤＣ
１，、δ）；ＩＪ６（Ｉ２ｆｔ、ｔ、Ｊ＝７Ｈｚ）、
３．８５（２）１．ｓ）、 ４Ｊ２（８）１．ｑ、
Ｊ＝７Ｈｚ）、 ７．６８（４）１．ｓ）、 １１
．７８（２Ｈ，ｓ）・質量スペクト／ｌ／ Ｉｌｌ／Ｚ
； ４８ｇ（Ｍ”）・元素分析値（Ｃ２ｓＨｔｓＯ＋
ｏ） ；計算値；ｃ ６１．４７． Ｈ５，７８実
測値；ｃ ６１．２２． Ｈ５，６２■ ４．４”
−ジ（４−ブロモブトキシ）−３，５，３″。・Melting point: 84-85℃ -IR spectrum (CHCI, cm): 1
720. 1675·'H-NMR spectrum (CDC
1,, δ); IJ6 (I2ft, t, J=7Hz),
3.85(2)1. s), 4J2(8)1. q,
J=7Hz), 7.68(4)1. s), 11
．． 78(2H,s)・Mass spectrum/l/Ill/Z
; 48g (M”)・Elemental analysis value (C2sHtsO+
o); Calculated value; c 61.47. H5,78 actual value; c 61.22. H5,62■ 4.4”
-di(4-bromobutoxy)-3,5,3″.
５゛−テトラエトキシカルボニルジフェニルメタン（６
）の合成
１．４−ジブロモブタン（Ｉ，０，８ｇ、 ５０ａｌＩ
Ｔｌｏｌ）及びに２ｃＯｓ（６，９ｇ、 ５０ｍｍｏり
をＤＭ Ｆ （２５０社＞に加えて攪拌下に６０℃に保
ち、これに■で得たエステル（５） （２，４４ｇ、
５．０ｍｍｏｌ）のＤＭＦ（Ｉ００ｍｔ’）溶液を３時
間を要して滴下する。さらに６０℃にて１時間攪拌後−
夜室温にて放置する。反応液をセライト濾過し、濾液を
Ｅｔ、０（２００ｍｌりと飽和食塩水（Ｉ１）で分液す
る。5'-tetraethoxycarbonyldiphenylmethane (6
) Synthesis of 1,4-dibromobutane (I, 0.8 g, 50alI
Tlol) and 2cOs (6.9 g, 50 mmol) were added to DMF (250 companies) and kept at 60°C with stirring, and to this was added the ester (5) obtained in (2) (2.44 g,
5.0 mmol) of DMF (I00mt') solution was added dropwise over a period of 3 hours. After further stirring at 60°C for 1 hour -
Leave at room temperature overnight. The reaction solution was filtered through Celite, and the filtrate was separated between 200 ml of Et, 0 (200 ml) and saturated brine (I1).
Ｂｔ、０層を分取し、Ｍｇ５Ｏ，で乾燥後に濃縮し、得
られた残渣をカラムクロマトグラフィー（シリカゲル、
ａｔ、Ｏ−ヘキサン）で精製して、無色オイルの（６
） （２，８４ｇ、 ７５％）を得る。The Bt, 0 layer was separated, dried over Mg5O, and concentrated, and the resulting residue was subjected to column chromatography (silica gel,
at, O-hexane) to give a colorless oil (6
) (2.84 g, 75%) is obtained.
その物性は次の通りである。Its physical properties are as follows.
・ＩＲスペクトル（Ｆ＋Ｉｍ、 ｃｍ−’） ；１７
２０・’Ｈ−ＮＭＲスペクトル（ＣＤＣＩ３＋ δ）
：１、３９（Ｉ２Ｈ，ｔ、 Ｊ＝７．３Ｈｚ）、 １
．８〜２．３（８Ｈ，ｍ）。・IR spectrum (F+Im, cm-'); 17
20·'H-NMR spectrum (CDCI3+ δ)
:1, 39 (I2H, t, J=7.3Hz), 1
．． 8-2.3 (8H, m).
３、５２ （４）１． ｔ、 Ｊ・６．３Ｈｚ）、 ３
．９８（４，Ｈ，Ｌ、 Ｊ＝６．３１１ｚ）、 ４．１
０（２Ｈ，ｓ）、 ４．３７ （８Ｈ，ｑ、 Ｊ＝７．
３Ｈｚ＞７、６８ （４Ｎ、 ｓ）
・質量スペクトルｍ／ｚ ； ７５８（Ｍ”）・元素分
析値（Ｃｓ＊）Ｉ４２０＋ｏＢｒ２） ；計算値；ｃ
５２．２４． Ｈ５，５８実測値；ｃ ５１．
９８． １１ ５．４１■ シクロファンオクタエチル
エステル（７）の合成。3, 52 (4)1. t, J・6.3Hz), 3
．． 98 (4, H, L, J=6.311z), 4.1
0 (2H, s), 4.37 (8H, q, J=7.
3Hz>7,68 (4N, s) ・Mass spectrum m/z; 758 (M”) ・Elemental analysis value (Cs*) I420+oBr2); Calculated value; c
52.24. H5,58 actual value; c 51.
98. 11 5.41 ■ Synthesis of cyclophane octaethyl ester (7).
上記■で得たジブロモ体（６） （７５８ｍｇ、 １ｍ
ｍｏｌ）とテトラエステル体（５）（４８８ｍｇ、
１．ｍｍ０１）のＤＭＦ （４０ｍｊｌり溶液を６０℃
に保ったＬＣＬ（６９０ｍｇ、 ５ｍｍｏｌ）のＤＭＦ
（６０ｍｆ） 部局液中に攪拌しなから１，５時間を
要して滴下する。さらに６０℃にて９時間攪拌後−夜室
温にて放置する。反応液をセライト濾過し、濾液にＡｃ
ＯＥｔ（２００ｍｆｆ）を加え、これを飽和食塩水（Ｉ
１） で洗う。有機層を分取し、Ｍｇ５Ｏ，で乾燥後減
圧にて濃縮し、残渣をカラムクロマトグラフィー（シリ
カゲル、 ＡｃＯＥｔ−ヘキサン）で精製すると、無色
固体の（７） （２４０ｍｇ、 ２２％）を得る。＾ｃ
０８ｔ−ヘキサンで再結晶すると、無色針状晶となる。Dibromo derivative (6) obtained in the above (■) (758 mg, 1 m
mol) and tetraester body (5) (488 mg,
1. mm01) in DMF (40 mjl) at 60°C.
LCL (690 mg, 5 mmol) kept in DMF
(60 mf) Drop into the local solution over 1.5 hours without stirring. After further stirring at 60° C. for 9 hours, the mixture was left at room temperature overnight. The reaction solution was filtered through Celite, and the filtrate was added with Ac
OEt (200mff) was added and this was dissolved in saturated saline (I
1) Wash with. The organic layer was separated, dried over Mg5O, and concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel, AcOEt-hexane) to obtain colorless solid (7) (240 mg, 22%). ^c
Recrystallization from 08t-hexane gives colorless needle-like crystals.
その物性は次の通りである。Its physical properties are as follows.
・融点；１５６〜１５７℃
−ＩＲスペクトル（Ｎｕｊｏｌ、 ｃｍ−’） ；１７
２５・’）Ｉ−ＮＭＲスペクトル（ＣＤＣＩ、、 δ
） ；１．３５（２４Ｈ，ｔ、Ｊ＝７Ｈｚ）、 〜１．
９（８Ｈ，ｍ）、 ３．８７（４Ｈ，ｓ）、 〜３．
９（ＩＩＩＨ，ｍ）、 ４．３１（Ｉ６Ｈ，ｑ、Ｊ＝７
Ｈｚ）、 ７．６６ （８Ｎ、ｓ）
・質量スペクトルｍ／ｚ ； １１０８５（”）・元素
分析値（Ｃ，、＋１゜、、０２゜・Ｉ２０） ；計算値
；ｃ ６３．１５． Ｈ６，４０実測値；ｃ ６
３．２４． Ｈ６，２１■ シクロファンオクタカル
ボン酸（８）の合上記■で得たオクタエチルエステル（
７）（７ｈｇ、 ０．０６５ｍｍｏｌ） に５Ｎ ＫＯ
Ｈメタノール溶液（２，０ｍ１）及びＨ２Ｏ（Ｉ，０ｍ
ｇ＞を加え、これを還流下に２時間加熱する。放冷後ｌ
Ｏ％ＨＣＩ水を加えてｐＨを約１とし、析出する結晶を
濾取し乾燥すると、無色針状晶の（８） （２５，４ｍ
ｇ、 ４６％）を得る。その物性は次の通りである。・Melting point: 156-157°C -IR spectrum (Nujol, cm-'): 17
25・') I-NMR spectrum (CDCI, δ
); 1.35 (24H, t, J=7Hz), ~1.
9 (8H, m), 3.87 (4H, s), ~3.
9 (IIIH, m), 4.31 (I6H, q, J=7
Hz), 7.66 (8N, s) ・Mass spectrum m/z; 11085 ('') ・Elemental analysis value (C,, +1°, 02°・I20); Calculated value; c 63.15. H6, 40 Actual value; c 6
3.24. H6,21 ■ Synthesis of cyclophane octacarboxylic acid (8) The octaethyl ester obtained in the above (■)
7) (7hg, 0.065mmol) to 5N KO
H methanol solution (2,0 ml) and H2O (I, 0 m
g> and heat it under reflux for 2 hours. After cooling
O% HCI water was added to adjust the pH to approximately 1, and the precipitated crystals were collected by filtration and dried to give colorless needle-like crystals (8) (25.4 m
g, 46%). Its physical properties are as follows.
・融点；３００℃
−ＩＲスペクトル（ＫＢｒ、 ｃｍ−’） ；１７１８
・’ ）Ｉ−ＮＭＲスペクトル（ＤＡＩＳＯ−ｄ、＋Ｄ
、ロ、δ） ；１．８５（８Ｈ，ｍ）、 ３．９９（Ｉ
２１，ｍ）、 ７．７０（８Ｈ，ｓ）・元素分析値（Ｃ
，２Ｈ，。０２゜・２Ｈ２０） ：計算値、Ｃ５６，
２５，Ｈ４，５０
実測値；ｃ ５６．２０． Ｈ４，７９■ シクロ
ファンオクタカリウム塩（Ｉ）の合成
ａ〉に０Ｈ（Ｉ，０ｇ、 １７．９ｍｍｏｌ）のＭｅＯ
Ｈ（４０−）溶液中に上記■で得たオクタカルボン酸（
８）（Ｉ８５ｍｇ、 ０．２１ｍｍｏｌ）を加え、還流
下に２時間加熱する。ＭｅＯ）１ （約３０ＷＬＩりを
留去後放冷し、析出する沈澱を濾取し、ＭｅＯＨ，Ｅｔ
２０で洗うと、無色粉末の（Ｉ） （Ｉ５４ｍｇ、 ６
３％）を得る。その物性は次の通りである。・Melting point: 300°C -IR spectrum (KBr, cm-'): 1718
・') I-NMR spectrum (DAISO-d, +D
, b, δ); 1.85 (8H, m), 3.99 (I
21, m), 7.70 (8H, s), elemental analysis value (C
,2H,. 02°・2H20): Calculated value, C56,
25, H4, 50 Actual value; c 56.20. H4,79 ■ Synthesis of cyclophane octapotassium salt (I) a> 0H (I, 0 g, 17.9 mmol) of MeO
The octacarboxylic acid (obtained in ① above) was added to the H(40-) solution.
8) (I85 mg, 0.21 mmol) is added and heated under reflux for 2 hours. MeO)1 (approximately 30 WLI) was distilled off, allowed to cool, the precipitate was collected by filtration, and MeOH, Et
When washed with 20 ml, colorless powder (I) (I54 mg,
3%). Its physical properties are as follows.
・融 点：３００℃以上
・’ｌｌ−ＮＭＩ？スペクトル（０２０，δ） ：１．
５５（８）１．ｍ）、 ３．８０（Ｉ２Ｈ，ｍ）、 ？
、２４（８）１．５）ｂ） ５Ｎ ＫＯＨのメタノー
ル溶液（Ｉ，０ｍ１）及びＭｅＯＨ（２，０ｍｆ）の混
合液に上記■で得たオクタエチルエステル（８） （２
７３ｍｇ、 ０．２５ｍｍｏｌ）を加え、これを還流下
に４時間加熱する。・Melting point: 300℃ or higher ・'ll-NMI? Spectrum (020, δ): 1.
55(8)1. m), 3.80 (I2H, m), ?
, 24(8)1.5)b) Add the octaethyl ester (8) obtained in the above (■) to a mixture of 5N KOH in methanol (I, 0ml) and MeOH (2,0mf).
73 mg, 0.25 mmol) and heat it under reflux for 4 hours.
放冷後析出する沈澱を濾取し、冷Ｍ ｅ ＯＨ及びＥｔ
２０で洗うと、無色粉末の（Ｉ） （２４６ｍｇ。After cooling, the precipitate precipitated was collected by filtration, and cooled with M e OH and Et.
(I) (246 mg) as a colorless powder.
９２％）を得る。本島は上記ａ）で得たものと同一であ
る。92%). The main island is the same as that obtained in a) above.
応 用 例（分離剤）
本発明による陰イオン性シクロファンのＤ２０中での有
機陽イオン性化合物に対する取り込み能の違いを’ Ｈ
−ＮＭＲの化学シフトの変化から錯体の安定度定数Ｋｓ
を算出することにより調べた〔文献：古賀憲司、ファル
マシア、２２．’２１（Ｉ９８６） ；平岡道夫、柳
田博明、小原正明、古賀憲司編著、ホスト・ゲスト・ケ
ミストリー講談社すイエンティフィク、 １９８４年
〕。Application example (separation agent) The difference in the ability of the anionic cyclophane according to the present invention to take up organic cationic compounds in D20 was
- From the change in NMR chemical shift, the stability constant Ks of the complex
[Reference: Kenji Koga, Pharmacia, 22. '21 (I986); Michio Hiraoka, Hiroaki Yanagita, Masaaki Ohara, Kenji Koga (eds.), Host Guest Chemistry Kodansha Scientific, 1984].
次に各種陽イオン性化合物に対する錯体安定度定数（に
Ｓ）の違いを下記に示す。Next, the differences in complex stability constants (S) for various cationic compounds are shown below.
−１，，９３゜
〆
１．０９”
〆
■
（Ｋｓ＝１．９ Ｘ １０３）
／゛
一〇９７゜
（Ｋｓ＝３ Ｘ １０”）
−０，６８゜
（にｓ＝１．２ Ｘ １０３）
本マイナスは取り込まれて、化学シフトが高磁場ヘシフ
トすることを示す。-1,,93゜〆1.09"〆■ (Ks=1.9 x 103) /゛1097゜(Ks=3 x 10") -0,68゜(s=1.2 x 103 ) This minus sign is incorporated to indicate that the chemical shift shifts to higher magnetic fields.
本発明の新規な陰イオン性シクロファン誘導体は、有機
化合物を特定の形で取り込む分子包接機能を有する。特
に芳香環を有する４級アンモニウム塩やスルホニウム塩
等のカチオン性有機化合物を水溶液中で包接し、それら
の分離剤として有用である。The novel anionic cyclophane derivatives of the present invention have a molecular inclusion function that incorporates organic compounds in a specific form. In particular, it is useful as a separating agent for cationic organic compounds having aromatic rings, such as quaternary ammonium salts and sulfonium salts, by including them in an aqueous solution.
出顆人代理人 古 谷 馨representative agent old valley Kaoru
Claims (1)
０であり、炭素原子の種類はｓｐ、ｓｐ＾２、ｓｐ＾３
混成軌道を持つ炭素の１種類のみ或いは三者の中からの
組み合わせで選択され、ユニット中にヘテロ原子を含ん
でいてもかまわない） で示される新規な陰イオン性シクロファン誘導体。[Claims] The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, the number of carbon atoms constituting the X and Y units is 1 to 1
0, and the types of carbon atoms are sp, sp^2, sp^3
A novel anionic cyclophane derivative selected from only one type of carbon having a hybrid orbital or a combination of the three, and which may contain a heteroatom in the unit.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1045969A JP2659237B2 (en) | 1989-02-27 | 1989-02-27 | New anionic cyclophane derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1045969A JP2659237B2 (en) | 1989-02-27 | 1989-02-27 | New anionic cyclophane derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02225584A true JPH02225584A (en) | 1990-09-07 |
| JP2659237B2 JP2659237B2 (en) | 1997-09-30 |
Family
ID=12734058
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1045969A Expired - Lifetime JP2659237B2 (en) | 1989-02-27 | 1989-02-27 | New anionic cyclophane derivatives |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2659237B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014100691A1 (en) * | 2012-12-21 | 2014-06-26 | Northwestern University | Tetracationic cyclophanes and their use in the sequestration of polyaromatic hydrocarbons by way of complexation |
-
1989
- 1989-02-27 JP JP1045969A patent/JP2659237B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014100691A1 (en) * | 2012-12-21 | 2014-06-26 | Northwestern University | Tetracationic cyclophanes and their use in the sequestration of polyaromatic hydrocarbons by way of complexation |
| US9290495B2 (en) | 2012-12-21 | 2016-03-22 | Northwestern University | Tetracationic cyclophanes and their use in the sequestration of polyaromatic hydrocarbons by way of complexation |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2659237B2 (en) | 1997-09-30 |
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