JPH0334955A - Calix arene derivative - Google Patents
Calix arene derivativeInfo
- Publication number
- JPH0334955A JPH0334955A JP16882889A JP16882889A JPH0334955A JP H0334955 A JPH0334955 A JP H0334955A JP 16882889 A JP16882889 A JP 16882889A JP 16882889 A JP16882889 A JP 16882889A JP H0334955 A JPH0334955 A JP H0334955A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- general formula
- expressed
- calixarene
- 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.)
- Pending
Links
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical class COC(=O)COC1=C(CC=2C(=C(CC=3C(=C(C4)C=C(C=3)C(C)(C)C)OCC(=O)OC)C=C(C=2)C(C)(C)C)OCC(=O)OC)C=C(C(C)(C)C)C=C1CC1=C(OCC(=O)OC)C4=CC(C(C)(C)C)=C1 VTJUKNSKBAOEHE-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 abstract description 24
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 7
- 150000001266 acyl halides Chemical class 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000003960 organic solvent Substances 0.000 abstract description 5
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 abstract description 4
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 3
- 125000002252 acyl group Chemical group 0.000 abstract description 3
- 239000012312 sodium hydride Substances 0.000 abstract description 3
- 229910000104 sodium hydride Inorganic materials 0.000 abstract description 3
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 125000005843 halogen group Chemical group 0.000 abstract description 2
- 239000002585 base Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 230000002209 hydrophobic effect Effects 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- 238000006243 chemical reaction Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 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
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-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
- 230000015572 biosynthetic process Effects 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000007529 inorganic bases Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 150000007530 organic bases Chemical class 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- RQXXCWHCUOJQGR-UHFFFAOYSA-N 1,1-dichlorohexane Chemical compound CCCCCC(Cl)Cl RQXXCWHCUOJQGR-UHFFFAOYSA-N 0.000 description 1
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- UNSAJINGUOTTRA-UHFFFAOYSA-N 3-(3-bromophenyl)prop-2-yn-1-ol Chemical compound OCC#CC1=CC=CC(Br)=C1 UNSAJINGUOTTRA-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- MMYYTPYDNCIFJU-UHFFFAOYSA-N calix[6]arene Chemical compound C1C(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC(C=2)=CC=CC=2CC2=CC=CC1=C2 MMYYTPYDNCIFJU-UHFFFAOYSA-N 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- BIIPHRRRSVZMLK-UHFFFAOYSA-N decanoyl bromide Chemical compound CCCCCCCCCC(Br)=O BIIPHRRRSVZMLK-UHFFFAOYSA-N 0.000 description 1
- 125000001891 dimethoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QTHQYNCAWSGBCE-UHFFFAOYSA-N docosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCC(Cl)=O QTHQYNCAWSGBCE-UHFFFAOYSA-N 0.000 description 1
- NQGIJDNPUZEBRU-UHFFFAOYSA-N dodecanoyl chloride Chemical compound CCCCCCCCCCCC(Cl)=O NQGIJDNPUZEBRU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000002555 ionophore Substances 0.000 description 1
- 230000000236 ionophoric effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- BASNZTUXPUAQLZ-UHFFFAOYSA-N nonadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCC(Cl)=O BASNZTUXPUAQLZ-UHFFFAOYSA-N 0.000 description 1
- RTQIXXGJUAQHLB-UHFFFAOYSA-N nonanoyl bromide Chemical compound CCCCCCCCC(Br)=O RTQIXXGJUAQHLB-UHFFFAOYSA-N 0.000 description 1
- WTBAHSZERDXKKZ-UHFFFAOYSA-N octadecanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCC(Cl)=O WTBAHSZERDXKKZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- ODZPKZBBUMBTMG-UHFFFAOYSA-N sodium amide Chemical compound [NH2-].[Na+] ODZPKZBBUMBTMG-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229950011008 tetrachloroethylene Drugs 0.000 description 1
- SQQKMLPDURPFNG-UHFFFAOYSA-N tetracosanoyl chloride Chemical compound CCCCCCCCCCCCCCCCCCCCCCCC(Cl)=O SQQKMLPDURPFNG-UHFFFAOYSA-N 0.000 description 1
Landscapes
- 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〕
本発明は新規なカリッグスアレーン誘導体に関し、詳し
くは機能性累積膜用の両親媒性化合物としての有用性が
期待される新規カリツクスアレーン誘導体に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a novel calixarene derivative, and more specifically, a novel calixarene derivative that is expected to be useful as an amphipathic compound for functional cumulative membranes. Regarding.
カリツクスアレーン（ｃａｌｉｘａｒｅｎｅ）又はカリ
ツクス［ｎ］アレーンは下記一般式（■１）で示される
環状オリゴマーである。Calixarene or calixarene or calix[n]arene is a cyclic oligomer represented by the following general formula (1).
（但し、」１式中ｎは４〜８の整数を表わす。）このカ
リックスアレーンの研究の歴史、合成法、構造的特徴、
応用などについては、例えばＣ，Ｄ、 ＧｕＬｓｃｈｅ
ｅｔ ａｌ、 （Ａｃｃ、Ｃｈｅｍ、Ｒｅｓ、、 １
６．１６１（１９８３）ＨＰｕｒｅ＆ Ａｐｐｌ、Ｃｈ
ｅｍ、、６０，４８３（１９８８）］あるいは新海ら〔
日化、、 １９＋７（１９８８）］によって、詳細に報
告されている。これまで、カリックスアレーン誘導体に
ついては、イオノホアとしての機能、包接化合物として
の機能などが報告されているが、クラウンエーテル誘導
体などに比較し、分子認識能はあまり高くなく、今後更
に種々の誘導体を合成し、検討する必要がある。(However, in formula 1, n represents an integer from 4 to 8.) History of research on this calixarene, synthesis method, structural characteristics,
For applications, see C, D, GuLsche.
et al, (Acc, Chem, Res,, 1
6.161 (1983) HPure & Appl, Ch.
Em., 60, 483 (1988)] or Shinkai et al.
Nikka, 19+7 (1988)] reported in detail. So far, calixarene derivatives have been reported to function as ionophores and clathrate compounds, but their molecular recognition ability is not very high compared to crown ether derivatives, etc., and we hope to develop more various derivatives in the future. It is necessary to synthesize and consider.
〔発明が解決しようとする課題］
例えば、新海らによって次のカリックスアレーン誘導体
が報告されている［Ｂｕｌｌ、Ｃｈｅｍ、Ｓｏｃ、Ｊｐ
ｎ、 。[Problems to be Solved by the Invention] For example, the following calixarene derivatives have been reported by Shinkai et al. [Bull, Chem, Soc, Jp.
n.
６１．３７３３（１９８８）］。61.3733 (1988)].
ただ、このようなカリックスアレーン誘導体において更
にアシル鎖の長い化合物が得られると、疎水性が高まっ
た、両親媒性化合物としてより適したものとなることが
考えられる。However, if a compound with a longer acyl chain is obtained among such calixarene derivatives, it is thought that it will become more suitable as an amphipathic compound with increased hydrophobicity.
従って、本発明の目的は、両親媒性化合物として適した
構造を有する、新規なカリックスアレーン誘導体を提供
することにある。Therefore, an object of the present invention is to provide a novel calixarene derivative having a structure suitable as an amphipathic compound.
本発明によれば、下記一般式（１）で示されるカリック
スアレーン誘導体が提供され、
（ＣＨ，）ｍ−ＣＨ。According to the present invention, a calixarene derivative represented by the following general formula (1) is provided, (CH,)m-CH.
（但し、上式中ｎは４〜８の整数を、またｍは６〜２２
の整数を、夫々表わす。）
また、下記一般式（ＩＩ）で示されるカリックスアレー
ン誘導体が提供される。(However, in the above formula, n is an integer of 4 to 8, and m is 6 to 22
represents an integer of . ) Also provided is a calixarene derivative represented by the following general formula (II).
Ｃ１］。C1].
（ＣＢ、）ｍ
■
（但し、
上式中ｎは４〜８の整数、
またｍは６〜２２の整
数を、
夫々表わす。）
本光明における前記一般式（１）及び（１１）で示され
るカリックスアレーン誘導体は、何れも新規物質であっ
て、前者は後者を製造するための原料となるものである
。(CB,)m (However, in the above formula, n represents an integer of 4 to 8, and m represents an integer of 6 to 22, respectively.) Represented by the general formulas (1) and (11) in this light Both calixarene derivatives are new substances, and the former serves as a raw material for producing the latter.
前記一般式（１）で示されるカリックスアレーン誘導体
は、下記一般式（Ｉｎ）で示されるカリックスアレーン
誘導体を、
（似し、上式中ｎは４〜８の整数を表わす。）有機溶媒
中、塩基性物質の存在下、下記一般式（ＩＶ）で示され
るアシルハライドと反応させることによって得ることが
できる。The calixarene derivative represented by the general formula (1) above is a calixarene derivative represented by the following general formula (In) (similarly, n in the above formula represents an integer of 4 to 8) in an organic solvent, It can be obtained by reacting with an acyl halide represented by the following general formula (IV) in the presence of a basic substance.
ＣＨ３（ＣＩ−（、）ｍ−ＣＯＸ （
ＩＶ）（但し、上式中用は６〜２２の整数を、またＸは
ハロゲン原子を、夫々表わす。）
前記−・般式（…）で示されるカリックスアレーン誘導
体は、前記したＣ、 Ｄ、 Ｇｕ Ｌｓｃｈｅらの報文
に準じて得ることができる。また、前記一般式（ＩＶ）
で示されるアシルハライドとしては、例えばｎ−オクタ
ノイルクロライド、ｎ−ノナノイルブロマイド、ｎデカ
ノイルブロマイド、ｎ−ドデカノイルクロライド、ミリ
ストイルクロライド、バルミトイルクロライド、ステア
ロイルクロライド、ノナデカノイルクロライド、アラキ
トイルクロライド、ベヘノイルクロライド、ｎ−テトラ
コサノイルクロライドなどが挙げられる。CH3(CI-(,)m-COX (
IV) (However, in the above formula, each represents an integer of 6 to 22, and X represents a halogen atom.) The calixarene derivative represented by the above general formula (...) is the above-mentioned C, D, It can be obtained according to the report by Gu Lsche et al. Furthermore, the general formula (IV)
Examples of the acyl halide represented by include n-octanoyl chloride, n-nonanoyl bromide, n-decanoyl bromide, n-dodecanoyl chloride, myristoyl chloride, balmitoyl chloride, stearoyl chloride, nonadecanoyl chloride, arachitoyl. Examples include chloride, behenoyl chloride, n-tetracosanoyl chloride, and the like.
なお、上記反応で用いる有機溶媒としては、前記一般式
（Ｉｎ）で示されるカリックスアレーン誘導体と前記一
般式（ＴＶ）で示されるアシルハライドの両者を溶解す
るものが好ましく、例えばジオキサン、テトラヒドロフ
ラン、ジメトキシエタン、ジメチルスルホキシド、ジメ
チルホルムアミド、トルエン、ベンゼン、アセトニトリ
ルなどが挙げられる。これらは単独であるいは２種以上
の混合溶媒で使用される。The organic solvent used in the above reaction is preferably one that dissolves both the calixarene derivative represented by the general formula (In) and the acyl halide represented by the general formula (TV), such as dioxane, tetrahydrofuran, dimethoxy Examples include ethane, dimethyl sulfoxide, dimethyl formamide, toluene, benzene, acetonitrile, and the like. These solvents may be used alone or in a mixed solvent of two or more.
また、塩基性物質としては、無機塩基と有機塩基の両方
が使用できる。この場合、無機塩基としては、例えばナ
トリウムアミド、ナトリウムハイドライド、金属ナトリ
ウム、ナトリウムアルコラード、水酸化ナトリウム、炭
酸ナトリウム、カリウムハイドライド、カリウムアルコ
ラード、水酸化カリウム、炭酸カリウムなどが、また有
機塩基としては、例えばトリエチルアミン、ピリジンな
どが挙げられる。これらの塩基性物質の使用量は、前記
一般式（ｍ）で示されるカリックスアレーン誘導体の水
酸基に対し、１〜数倍モルが適している。Further, as the basic substance, both inorganic bases and organic bases can be used. In this case, inorganic bases include, for example, sodium amide, sodium hydride, metallic sodium, sodium alcoholade, sodium hydroxide, sodium carbonate, potassium hydride, potassium alcoholade, potassium hydroxide, potassium carbonate, etc., and organic bases include , for example, triethylamine, pyridine, etc. The appropriate amount of these basic substances to be used is one to several times the molar amount of the hydroxyl group of the calixarene derivative represented by the general formula (m).
上記反応は通常、室温から１００℃の温度で、数時間行
なえばよいが、使用するアシルハライドあるいは塩基性
物質の種類により、反応条件は任意に設定することがで
きる。The above reaction is usually carried out at a temperature from room temperature to 100° C. for several hours, but the reaction conditions can be arbitrarily set depending on the type of acyl halide or basic substance used.
また、前記一般式（ＩＩ）で示されるカリックスアレー
ン誘導体は、前記一般式（＋）で示されるカリックスア
レーン誘導体を、有機溶媒中、無水塩化アルミニウムの
イｊ在下に反応させることによって得ることができる。Further, the calixarene derivative represented by the general formula (II) can be obtained by reacting the calixarene derivative represented by the general formula (+) in an organic solvent in the presence of anhydrous aluminum chloride. .
この場合に用いる有機溶媒としては、例えば、ニトロベ
ンゼン、クロルベンゼン、０−ジクロルベンゼン、テト
ラクロルエタン、テトラクロルエチレン、ジクロルエタ
ン、四塩化炭素、トルエン、二硫化炭素などが挙げられ
る。無水塩化アルミニウムの使用量は、前記一般式（Ｉ
）で示されるカリックスアレーン誘導体のエステル基に
対して、１〜５倍モルが適している。また、反応温度は
室温から約２００℃の温度が好ましく、特に３０〜７０
℃が好ましい。この温度で数時間から十数時間反応させ
ることにより、目的物を得ることができる。Examples of the organic solvent used in this case include nitrobenzene, chlorobenzene, 0-dichlorobenzene, tetrachloroethane, tetrachloroethylene, dichloroethane, carbon tetrachloride, toluene, and carbon disulfide. The amount of anhydrous aluminum chloride to be used is based on the general formula (I
) is suitable in a molar amount of 1 to 5 times the ester group of the calixarene derivative. Further, the reaction temperature is preferably from room temperature to about 200°C, particularly from 30 to 70°C.
°C is preferred. The desired product can be obtained by reacting at this temperature for several hours to more than ten hours.
〔発明の効果１
請求項（２）の前記一般式（ＩＩ）で示される新規なカ
リックスアレーン誘導体は、長鎖アシル基を有するため
に、従来公知のカリックスアレーン誘導体に比して、疎
水性が高まり、両親媒性化合物として適した構造を有し
ており、例えばラングミュア・プロジット法による機能
性累積膜等としての用途が期待されるものである。[Effect of the Invention 1] The novel calixarene derivative represented by the general formula (II) in claim (2) has a long-chain acyl group, and therefore has less hydrophobicity than conventionally known calixarene derivatives. It has a structure suitable as an amphipathic compound, and is expected to be used as a functional cumulative film using the Langmuir-Prodgit method, for example.
また、請求項（１）の前記一般式（１）で示されるカリ
ックスアレーン誘導体は、前記一般式（ＩＩ）で示され
るカリックスアレーン誘導体製造用の中間体として有用
なものである。Further, the calixarene derivative represented by the general formula (1) of claim (1) is useful as an intermediate for producing the calixarene derivative represented by the general formula (II).
［実施例］ 以下、本発明を実施例により詳細に説明する。[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.
実施例１
［一般式（＋）において、ｎ＝６、ｍ＝６で示される化
合物の合成］
カリックス〔６〕アレーン［一般式（ＩＩｌ）において
、ｎ＝６で示される化合物］１．９１ｇｒを、モレキュ
ラー・シーブスで脱水処理したテトラヒドロフラン（３
５ｍＱ）／Ｎ、Ｎ−ジメチルホルムアミド（８ｍＱ）混
合溶媒に溶解した。この溶液へ、１０〜２０℃でナトリ
ウムハイドライド（油性、含有率約６０％）２．８８ｇ
ｒを加えた。Example 1 [Synthesis of a compound represented by n = 6 and m = 6 in the general formula (+)] Calix [6] arene [a compound represented by n = 6 in the general formula (IIl)] 1.91 gr. , tetrahydrofuran dehydrated with molecular sieves (3
It was dissolved in a mixed solvent of 5mQ)/N,N-dimethylformamide (8mQ). Add 2.88 g of sodium hydride (oil-based, content approximately 60%) to this solution at 10-20°C.
Added r.
１０〜２０℃で更に１時間撹拌した後、オクタノイルク
ロライド２０．４９ｇｒとテトラヒドロフラン１ｏｒｒ
ｌｆ！、からなる溶液を、７〜１１℃の温度で、１．５
時間を要して滴下した。室温で１．５時間反応させた後
、徐々に昇温し、６６〜６９℃で５時間反応させた。After stirring for an additional hour at 10-20°C, 20.49 gr of octanoyl chloride and 1 orr of tetrahydrofuran were added.
lf! 1.5 at a temperature of 7 to 11°C.
It took some time to drip. After reacting at room temperature for 1.5 hours, the temperature was gradually raised and the reaction was carried out at 66-69°C for 5 hours.
放冷後、約２００−の氷水へ反応液を投じ、これにトル
エン５０ｍＱを加え、抽出操作を行なった。トルエン相
を水洗後、無水硫酸マグネシウムで脱水後、トルエンを
留去し、得られた淡黄色液体をカラムクロマトグラフィ
ー（シリカゲル、溶媒ニジクロヘキサン）で処理し、得
られた結晶をエタノールで再結晶を行ない、無色板状結
晶２．７９ｇｒ（収率６６．７χ）を得た。After cooling, the reaction solution was poured into approximately 200 ml of ice water, and 50 mQ of toluene was added thereto for extraction. After washing the toluene phase with water and dehydrating it with anhydrous magnesium sulfate, the toluene was distilled off. The pale yellow liquid obtained was treated with column chromatography (silica gel, solvent dichlorohexane), and the obtained crystals were recrystallized with ethanol. 2.79g of colorless plate-like crystals (yield 66.7χ) were obtained.
得られた化合物の融点は１３４．０〜１３５．５℃であ
り、またその元素分析値は次の通りであった。なお、計
算値は一般式（Ｔ）において、ｎ・６、ｍ・６としたも
のである。The melting point of the obtained compound was 134.0 to 135.5°C, and the elemental analysis values were as follows. In addition, the calculated values are set to n·6 and m·6 in general formula (T).
この化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を第
１図に示す。第１図から判るように、２９６０．２９３
０．２８６０ｃｍ−にアルキル基に１帰属される、また
１７６０ｃｍ−にエステル基に帰属される吸収が認めら
れた。The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG. As can be seen from Figure 1, 2960.293
An absorption attributable to an alkyl group at 0.2860 cm- and an absorption attributable to an ester group at 1760 cm- was observed.
また、ｌ−１ｌ−１−Ｎ溶媒ＣＤＣｆｌ 、 、内部標
準テトラメチルシラン）による測定結果は次の通りであ
った。In addition, the measurement results using l-1l-1-N solvent CDCfl, internal standard tetramethylsilane) were as follows.
以」二の結果より、目的物を得たことか確認された。From the above two results, it was confirmed that the target object was obtained.
実施例２〜４
実施例１で用いたオクタノイルクロライドの代わりに表
−１に示したアシルハライドを用いた以外は、実施例Ｉ
と同様に操作して、種々の一般式（１）で示される化合
物を得た。それらの結果を表−１に示す。Examples 2 to 4 Example I except that the acyl halide shown in Table 1 was used instead of the octanoyl chloride used in Example 1.
By operating in the same manner as above, various compounds represented by general formula (1) were obtained. The results are shown in Table-1.
２
実施例５
〔一般式（１１）において、ｎ・６、ｍ＝６で示される
化合物の合成］
実施例１で得られたカリックスアレーン誘導体［一般式
（１）においてｎ・６、■・６で示される化合物］１
、３９ｇｒを、１，１，２，２．−テトラクロルエタン
１５＋ｕＱに溶解した。この溶液に無水塩化アルミニウ
ム１．６０ｇｒを室温で加え、１時間撹拌後、約５０°
Ｃで１０時間反応させた。2 Example 5 [Synthesis of compound represented by n·6, m=6 in general formula (11)] Calixarene derivative obtained in Example 1 [n·6, m=6 in general formula (1)] Compound represented by ]1
, 39gr, 1,1,2,2. -Dissolved in 15+uQ of tetrachloroethane. 1.60g of anhydrous aluminum chloride was added to this solution at room temperature, and after stirring for 1 hour,
The reaction was carried out at C for 10 hours.
放冷後、約ＩＮ塩酸（１００＋ｎＱ）へ反応液を投じ、
クロロホルム約２００ｍｆ２で抽出を行なった。クロロ
ホルム相を水洗後、無水硫酸マグネシウムで脱水した後
、溶媒を留去し、赤褐色樹脂状物を得た。これにメタノ
ール約＋５０ｍＱを加え、褐黄色沈澱を得た。これをク
ロロホルム／メタノール及びトルエン／ｎ−ヘキサンで
再沈澱精製を行ない、淡黄色粉末Ｑ、４３ｇｒ（収率３
１％）を得た。After cooling, the reaction solution was poured into about IN hydrochloric acid (100+nQ),
Extraction was performed with approximately 200 mf2 of chloroform. After washing the chloroform phase with water and dehydrating it with anhydrous magnesium sulfate, the solvent was distilled off to obtain a reddish brown resinous material. Approximately +50 mQ of methanol was added to this to obtain a brownish yellow precipitate. This was purified by reprecipitation with chloroform/methanol and toluene/n-hexane to produce pale yellow powder Q, 43g (yield 3).
1%).
得られた化合物の融点は３００℃以」二であり、またそ
の元素分析値は次の通りであった。なお、計算植は一般
式（ＩＩ）において、ｒｌ−６、■・６としたものであ
る。The melting point of the obtained compound was 300° C. or higher, and its elemental analysis values were as follows. Note that the calculation is based on general formula (II) with rl-6 and ■.6.
この化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を第
２図に示す。第２図から判るように、３４２０．３２５
０−′に水酸基に帰属される、また１６７５ｃｍ−’に
カルボニル基に帰属される吸収が認められた。なお、１
７６０ｃｍ−’のエステル基による吸収は消失した。The infrared absorption spectrum (KBr tablet method) of this compound is shown in FIG. As can be seen from Figure 2, 3420.325
An absorption attributable to a hydroxyl group at 0-' and an absorption attributable to a carbonyl group at 1675 cm-' were observed. In addition, 1
The absorption due to the ester group at 760 cm-' disappeared.
また、＋（−ＮＭＲ（溶媒１重水素化Ｎ、Ｎ−ジメチル
ホルムアミド：内部標準：テトラメチルシラン）による
測定結果は次の通りであった。Further, the measurement results by +(-NMR (solvent 1 deuterated N, N-dimethylformamide: internal standard: tetramethylsilane) were as follows.
（フェノール性プロトンは、明確なピークを示さなかっ
た。）
以上の結果より、
目的物を得たことが確認され
た。(The phenolic proton did not show a clear peak.) The above results confirmed that the target product was obtained.
実施例６〜８
実施例１で得られたカリックスアレーン誘導体の代わり
に、夫々実施例２〜４で得られたカリックスアレーン誘
導体を出発原料として用いた以外は、実施例５と同様に
操作して、対応する一般式（ｒＪ）で示される化合物を
得た。それらの結果を表−２に示す。Examples 6 to 8 The procedure was repeated in the same manner as in Example 5, except that the calixarene derivatives obtained in Examples 2 to 4 were used as starting materials instead of the calixarene derivatives obtained in Example 1. , a compound represented by the corresponding general formula (rJ) was obtained. The results are shown in Table-2.
５ １６5 16
第１図は実施例１で得られた一般式（１）（ＩＩ・６、
ｍ＝６）で示されるカリックスアレーン誘導体の赤外線
吸収スペクトル図（ＫＢｒＢｒ法）であり、また第２図
は実施例５で得られた一般式（Ｕ）（ＩＩ・６、ｍ・６
）で示されるカリックスアレーン誘導体の赤外吸収スペ
クトル図（ＫＢｒ錠剤法）である。Figure 1 shows the general formula (1) (II・6,
FIG. 2 is an infrared absorption spectrum diagram (KBrBr method) of a calixarene derivative represented by m=6), and FIG.
) is an infrared absorption spectrum diagram (KBr tablet method) of the calixarene derivative shown in FIG.
Claims (2)
ン誘導体。 ▲数式、化学式、表等があります▼（ I ） （但し、上式中ｎは４〜８の整数を、またｍは６〜２２
の整数を、夫々表わす。）(1) A calixarene derivative represented by the following general formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) (However, in the above formula, n is an integer from 4 to 8, and m is an integer from 6 to 22.
represents an integer of . )
誘導体。 ▲数式、化学式、表等があります▼（II） （但し、上式中ｎは４〜８の整数、またｍは６〜２２の
整数を、夫々表わす。）(2) A calixarene derivative represented by the following general formula (II). ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (II) (However, in the above formula, n represents an integer from 4 to 8, and m represents an integer from 6 to 22, respectively.)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16882889A JPH0334955A (en) | 1989-06-30 | 1989-06-30 | Calix arene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16882889A JPH0334955A (en) | 1989-06-30 | 1989-06-30 | Calix arene derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0334955A true JPH0334955A (en) | 1991-02-14 |
Family
ID=15875273
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16882889A Pending JPH0334955A (en) | 1989-06-30 | 1989-06-30 | Calix arene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0334955A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997039077A1 (en) * | 1996-04-16 | 1997-10-23 | The University Of Sheffield | Improvements in or relating to calixarenes |
| US6184783B1 (en) | 1997-10-14 | 2001-02-06 | Harness System Technologies Research, Ltd. | Electronic control unit for car |
| KR100506357B1 (en) * | 2002-08-16 | 2005-08-05 | 현대모비스 주식회사 | Vehicle Controller Apparatus and Controlling Method for the Same |
| US8592113B2 (en) | 2009-10-08 | 2013-11-26 | Ricoh Company, Limited | Toner, method of manufacturing toner, developer, and image forming method |
| CN112029016A (en) * | 2020-09-03 | 2020-12-04 | 北京化工大学 | Application of liposoluble column (calixarene) as photoinitiator |
-
1989
- 1989-06-30 JP JP16882889A patent/JPH0334955A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997039077A1 (en) * | 1996-04-16 | 1997-10-23 | The University Of Sheffield | Improvements in or relating to calixarenes |
| US6358431B1 (en) | 1996-04-16 | 2002-03-19 | The University Of Sheffield | Calixarenes |
| US6184783B1 (en) | 1997-10-14 | 2001-02-06 | Harness System Technologies Research, Ltd. | Electronic control unit for car |
| KR100506357B1 (en) * | 2002-08-16 | 2005-08-05 | 현대모비스 주식회사 | Vehicle Controller Apparatus and Controlling Method for the Same |
| US8592113B2 (en) | 2009-10-08 | 2013-11-26 | Ricoh Company, Limited | Toner, method of manufacturing toner, developer, and image forming method |
| CN112029016A (en) * | 2020-09-03 | 2020-12-04 | 北京化工大学 | Application of liposoluble column (calixarene) as photoinitiator |
| CN112029016B (en) * | 2020-09-03 | 2022-09-13 | 北京化工大学 | Application of liposoluble column (calixarene) as photoinitiator |
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