JPS62265250A - Novel calixarene derivative and production thereof - Google Patents
Novel calixarene derivative and production thereofInfo
- Publication number
- JPS62265250A JPS62265250A JP11013886A JP11013886A JPS62265250A JP S62265250 A JPS62265250 A JP S62265250A JP 11013886 A JP11013886 A JP 11013886A JP 11013886 A JP11013886 A JP 11013886A JP S62265250 A JPS62265250 A JP S62265250A
- Authority
- JP
- Japan
- Prior art keywords
- alkyl
- formula
- producing
- general formula
- formulas
- 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
- 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 27
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 23
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- -1 nitro, amino Chemical group 0.000 claims abstract description 13
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 10
- 239000002168 alkylating agent Substances 0.000 claims abstract description 6
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 6
- 125000005208 trialkylammonium group Chemical group 0.000 claims abstract description 6
- 150000001450 anions Chemical class 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 150000001350 alkyl halides Chemical group 0.000 claims description 11
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 5
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000003638 chemical reducing agent Substances 0.000 claims description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011630 iodine Substances 0.000 claims description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 10
- 125000005843 halogen group Chemical group 0.000 claims 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine group Chemical group NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 4
- 229910052801 chlorine Inorganic materials 0.000 claims 3
- 239000000460 chlorine Substances 0.000 claims 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 230000029936 alkylation Effects 0.000 claims 1
- 229940006460 bromide ion Drugs 0.000 claims 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims 1
- 229910052794 bromium Inorganic materials 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 150000003839 salts Chemical class 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 238000006911 enzymatic reaction Methods 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 238000002844 melting Methods 0.000 description 9
- 230000008018 melting Effects 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 5
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910017604 nitric acid Inorganic materials 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 4
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 4
- 125000000542 sulfonic acid group Chemical group 0.000 description 4
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001361 allenes Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- MAGFQRLKWCCTQJ-UHFFFAOYSA-N 4-ethenylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(C=C)C=C1 MAGFQRLKWCCTQJ-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 241001164374 Calyx Species 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 102000036858 Metal ion transporters Human genes 0.000 description 2
- 108091006974 Metal ion transporters Proteins 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229940102396 methyl bromide Drugs 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- 241000345998 Calamus manan Species 0.000 description 1
- 108010078791 Carrier Proteins Proteins 0.000 description 1
- 101100400378 Mus musculus Marveld2 gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 150000001348 alkyl chlorides Chemical class 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 150000001649 bromium compounds Chemical class 0.000 description 1
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 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
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 210000000080 chela (arthropods) Anatomy 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- 150000001923 cyclic compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- PVWOIHVRPOBWPI-UHFFFAOYSA-N n-propyl iodide Chemical compound CCCI PVWOIHVRPOBWPI-UHFFFAOYSA-N 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical class CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上の利用分野
本発明は、新規なカリツクスアレン誘導体及びその製造
方法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a novel calixarene derivative and a method for producing the same.
従来の技術
カリツクスアレン（ｃａｌｉｘａｒｅｎｅ）又はカリツ
クス（ｎ）アレンとは、一般式（■）
で表わされる環状化合物であって、ここに、ｎは例えば
４〜８の整数であり、カワックスアレンを形成する環数
を示す。このようなカリツクスアレンの名称は、ギリシ
ャ語の「杯Ｊ （ｃａｌｉｘ）に類似する芳香環（ａ
ｒｅｎｅ）からなる立体構造を有することに因んで、慣
用的に付された名称である。かかるカリツクス（ｎ）ア
レンの研究の歴史、合成、立体構造及び応用等について
は、例えば、ＧｕＬｓｃｈｅらによって詳細に報告され
ており（Ｊ、Ａｍ、 Ｃｈｅｍ。BACKGROUND OF THE INVENTION Calixarene or calixarene (n)arene is a cyclic compound represented by the general formula (■), where n is an integer of 4 to 8, for example. Indicates the number of rings formed. The name calixarene is derived from the aromatic ring (a), which is similar to the Greek word calix.
It is a name conventionally given because it has a three-dimensional structure consisting of (rene). The history, synthesis, three-dimensional structure, applications, etc. of the research on calyx(n)arenes have been reported in detail by, for example, GuLsche et al. (J. Am. Chem.
Ｓｏｃ、、 １０３．３７８２ （１９８１）； ＡＣ
Ｃ，Ｃｈｅｍ、 Ｒｅｓ、、 １６゜１６１ （１９８
３）） 、上記式で表わされるカリツクス（ｎ）アレン
は、代表的には、ｐ−ｔ−ブチルフェノールとホルムア
ルデヒドとを水酸化カリウムや水酸化ルビジウムのよう
な塩基の存在下に反応させることによってｐ−ｔ−プチ
ルカリツクスアレンを得、これを脱アルキルすることに
よって得ることができる。Soc, 103.3782 (1981); AC
C, Chem, Res,, 16°161 (198
3)) Calix (n) arene represented by the above formula is typically prepared by reacting p-t-butylphenol and formaldehyde in the presence of a base such as potassium hydroxide or rubidium hydroxide. -t-butyl calixarene is obtained and dealkylated.
又貝が解決しようとする問題卓
上記のようなカリツクスアレンは、分子の立体構造的に
は、分子中央にベンゼン環に囲まれた空孔を有する筒状
構造をもち、しかも、この空孔が水酸基に対してｐ−位
置の方向に閉じている。従って、かかるカリツクスアレ
ンは、例えば、酵素反応において安定なホスト・ゲスト
錯体を形成するための包接化合物として注目されている
。例えば、カリツクスアレンは、従来、固体状態におい
てクロロホルムやトルエンのような比較的小さい分子を
包接することが知られている。また、上記空孔を囲む水
酸基群の金属に対する選択的な配位子としての機能を利
用して、疎水性液膜による金属イオンの輸送体としても
注目されている。Problem table that Matagai tries to solveCalixarene, as shown above, has a cylindrical structure with a hole surrounded by benzene rings in the center of the molecule. is closed towards the p-position relative to the hydroxyl group. Therefore, such calixarene is attracting attention as an inclusion compound for forming a stable host-guest complex in, for example, an enzyme reaction. For example, calixarene is known to include relatively small molecules such as chloroform and toluene in the solid state. It is also attracting attention as a metal ion transporter using a hydrophobic liquid film, utilizing the function of the hydroxyl groups surrounding the pores as selective ligands for metals.
しかしながら、従来より知られているカリツクスアレン
は、一般に、非環状の類縁化合物に比較して高い融点を
有する以外に、多くの有磯溶剤に対して難溶性であって
、従来、水溶性であるカリックスアレンは知られていな
い。従って、当然に水溶液中でホスト・ゲスト錯体を形
成するカリツクスアレンは知られていない。しかし、酵
素反応や触媒反応、或いは金属の輸送体としての実用化
を図るには、水溶性のカリツクスアレンが要求され、ま
た、かかる水溶性のカリツクスアレンは、酵素反応や触
媒反応の理論的研究にも不可欠であろう。However, conventionally known calixarene generally has a higher melting point than its acyclic analogue compounds, and is poorly soluble in many organic solvents. One Calix Allen is unknown. Therefore, naturally, calixarene that forms a host-guest complex in an aqueous solution is not known. However, water-soluble calixarene is required for practical use in enzymatic reactions, catalytic reactions, or as a metal transporter. It will also be essential for research.
そこで、本発明者らは、既に特願昭５９−２０５９９０
号公報に記載されているように、水溶性であるカリツク
スチレン−ｐ−スルホン酸及び〇−ｎ−アルキルカリツ
クスアレンーｐ−スルホン酸を得ることに成功し、更に
、従来、カリツクスアレンの直接ニトロ化によっては得
ることができなかったｐ−ニトロカリツクスアレンにつ
いても、上記カリツクスチレン−ｐ−スルホン酸を硝酸
又は硝酸塩にて処理して、スルホン酸基をニトロ基と置
換する方法によって得ることに成功している。Therefore, the inventors of the present invention have already applied for patent application No. 59-205990.
As described in the publication, we succeeded in obtaining water-soluble calix styrene p-sulfonic acid and 〇-n-alkyl calix arene p-sulfonic acid, and furthermore, we have succeeded in obtaining calix styrene p-sulfonic acid and Regarding p-nitrocalyxarene, which could not be obtained by direct nitration of , there is a method of treating the above calyxstyrene-p-sulfonic acid with nitric acid or a nitrate to replace the sulfonic acid group with a nitro group. I have been successful in obtaining this.
上記カリツクスチレン−ｐ−スルホン酸は、分子の筒状
構造の軸方向の両端にフェノール性水酸基と陰イオン性
基とを有するために、ホスト分子や酸触媒としても特異
な性質を有することが期待され、また、界面活性剤とし
ても興味深い。他方、ｐ−ニトロカリックスアレンは、
種々のカリックスアレンの合成原料として重要である。The above calixstyrene-p-sulfonic acid has a phenolic hydroxyl group and an anionic group at both ends of the axial direction of the cylindrical structure of the molecule, so it may have unique properties as a host molecule and an acid catalyst. It is expected to be useful and is also interesting as a surfactant. On the other hand, p-nitrocalyxarene is
It is important as a raw material for the synthesis of various calixarenes.
本発明者らは、カリックスアレンに関する研究を更に推
進した結果、ｐ−ニトロカリックスアレンから更に新規
なＳＡ１体を得ることができ、特に、前記カリツクスチ
レン−ｐ−スルボン酸と対照的に陽イオン性のｐ−）リ
アルキルアンモニオ−〇−アルキルカワックスアレンを
得ることができることを見出して、本発明に至ったもの
である。As a result of further research on calixarene, the present inventors were able to obtain a novel SA1 form from p-nitrocalixarene, and in particular, in contrast to the calixstyrene-p-sulfonic acid, the cation The inventors have discovered that it is possible to obtain p-)realkylammonio-〇-alkylkawaxarenes, and have thus arrived at the present invention.
従って、本発明は、新規なカリックスアレン誘導体及び
その製造方法を提供することを目的とする。Therefore, an object of the present invention is to provide a novel calixarene derivative and a method for producing the same.
問題点を解決するための手段
本発明による新規なカリックスアレンは、−８式（式中
、Ｒは炭素数１〜１８のアルキル基、Ｚはニトロ基、ア
ミノ基及びアルキル基の炭素数が１〜５であるトリアル
キルアンモニウムよりなる群から選ばれる置換基、ｎは
４〜８の整数を示し、Ｚがニトロ基又はアミノ基である
ときはｎｌ−０であり、Ｚがトリアルキルアンモニウム
であるときはＸトは対アニオンを示し、ａはこの対アニ
オンの価電数を示し、ｎ’＝ｎ／ａである。）で表わさ
れることを特徴とする。Means for Solving the Problems The novel calixarene according to the present invention has the following formula: -5, a substituent selected from the group consisting of trialkylammonium, n represents an integer of 4 to 8, when Z is a nitro group or an amino group, it is nl-0, and Z is trialkylammonium (where X represents a counter-anion, a represents a valence number of this counter-anion, and n'=n/a).
即ち、本発明によれば、新規なカリックスアレンとして
、第１に一般式（■）
で表わされるｐ−ニトロ−〇−アルキルカリツクスアレ
ンが、第２に一般式（ＩＩＩ）
で表わされるｐ−アミノ−０−アルキルカリツクスアレ
ンが、及び第３に一般式（ＩＶ）（式中、Ｒ”は炭素数
１〜５のアルキル基を示す。）で表わされるｐ−トリア
ルキルアンモニオ−０−アルキルカワックスアレンがそ
れぞれ提供される。That is, according to the present invention, as novel calixarenes, firstly, p-nitro-〇-alkyl calixarene represented by the general formula (■); secondly, p-nitro-〇-alkyl calixarene represented by the general formula (III); and thirdly, p-trialkylammonio-0- represented by the general formula (IV) (wherein R'' represents an alkyl group having 1 to 5 carbon atoms). Each alkyl wax arene is provided.
以下に本発明の詳細な説明する。The present invention will be explained in detail below.
前記一般式（ＩＩ）で表わされるｐ−ニトロ−〇−アル
キルカリツクスアレンは、対応するｐ−ニトロカワック
スアレンのアルカリ金属塩をアルキル化剤にてアルキル
化することによって得ることができる。ｐ−ニトロカリ
ツクスアレンは、カリツクスチレン−ｐ−スルホン酸の
スルホン酸基をニトロ基にて置換することによって得る
ことができる。このカリツクスチレン−ｐ−スルホン酸
は、前述したように、特願昭５９−２０５９９０号公報
に記載されており、例えば、カリツクスアレンを濃硫酸
に懸濁させ、８０℃以上、好ましくは９０°Ｃ以上の温
度に加熱溶解させることによって得ることができる。The p-nitro-0-alkyl calixarene represented by the general formula (II) can be obtained by alkylating the corresponding alkali metal salt of p-nitroca waxarene with an alkylating agent. p-Nitrocalyxarene can be obtained by substituting the sulfonic acid group of calyxstyrene-p-sulfonic acid with a nitro group. As mentioned above, this calixtyrene-p-sulfonic acid is described in Japanese Patent Application No. 59-205990. It can be obtained by heating and dissolving it at a temperature of °C or higher.
先ず、ｐ−ニトロカリツクスアレンの製造について説明
する。ｐ−ニトロカリツクスアレンを製造するには、カ
リツクスチレン−ｐ−スルホン酸を一旦製造し、分離し
た後、これをスルホン酸基−ニトロ基置換反応に付して
もよいが、カリツクスチレン−ｐ−スルホン酸を分離す
る必要がないときは、カリツクスアレンのスルホン化に
引き続いて、スルホン酸基−ニトロ基置換反応をさせれ
ばよい。First, the production of p-nitrocalyx arene will be explained. In order to produce p-nitrocalyxarene, calixstyrene-p-sulfonic acid may be once produced and separated, and then subjected to a sulfonic acid group-nitro group substitution reaction. When it is not necessary to separate -p-sulfonic acid, the sulfonic acid group-nitro group substitution reaction may be carried out subsequent to the sulfonation of calixarene.
即ち、濃度９０％以上、好ましくは９５％以上の？滞硫
酸中にカワックスアレンを懸濁させ、８０°Ｃ以上、好
ましくは９０℃以上の温度に加熱して、カリツクスチレ
ン−ｐ−スルホン酸を生成させ、次いで、これを取り出
すことなく、反応混合物に硫酸濃度が３０〜７０％にな
るように水を加えて希釈し、次いで、冷却下、硝酸又は
硝酸ナトリウムや硝酸カリウム等のような硝酸塩を加え
て、スルホン酸基をニトロ基に置換させる。That is, the concentration is 90% or more, preferably 95% or more? Kawaxarene is suspended in retained sulfuric acid and heated to a temperature of 80°C or higher, preferably 90°C or higher to produce calaxstyrene-p-sulfonic acid, which is then reacted without removing it. The mixture is diluted with water to a sulfuric acid concentration of 30-70%, and then, under cooling, nitric acid or a nitrate such as sodium nitrate, potassium nitrate, etc. is added to replace the sulfonic acid groups with nitro groups.
この反応において、硝酸又は硝酸塩の使用量は、用いた
原料力リツクスアレンのフェノール単位当たりについて
１〜１．２モルが好適である。過多量の硝酸又は硝酸塩
を用いるときは、酸化反応等の副反応が増大し、収率の
低下をきたすので好ましくない。また、反応温度は、通
常、１０゛Ｃ以下であるが、特に５℃以下が好ましい。In this reaction, the amount of nitric acid or nitrate to be used is preferably 1 to 1.2 mol per phenol unit of the raw material Lixarene used. It is not preferable to use an excessive amount of nitric acid or nitrate because side reactions such as oxidation reactions increase and the yield decreases. Further, the reaction temperature is usually 10°C or lower, particularly preferably 5°C or lower.
反応時間は、通常、数時間乃至数十時間である。このニ
トロ化反応の後、反応混合物を水で希釈し、析出した結
晶を分離、水洗すれば、ｐ−ニトロカリックスアレンを
得ることができる。The reaction time is usually several hours to several tens of hours. After this nitration reaction, the reaction mixture is diluted with water, and the precipitated crystals are separated and washed with water to obtain p-nitrocalyxarene.
ｐ−ニトロカリツクスアレンのアルカリ金属塩、例えば
、ヘキサナトリウム塩は、上記ｐ−ニトロカリツクスア
レンを水酸化ナトリウム水溶液に溶解し、活性炭にて脱
色処理し、活性炭を濾別した後、濾液に約５重量％の水
酸化ナトリウムを加えて、ｐ−ニトロカリツクスアレン
を塩析し、濾別し、食塩水にて洗浄することによって得
ることができる。The alkali metal salt of p-nitrocalyxarene, for example, the hexasodium salt, can be obtained by dissolving the p-nitrocalyxarene in an aqueous sodium hydroxide solution, decolorizing it with activated carbon, filtering off the activated carbon, and adding it to the filtrate. It can be obtained by adding about 5% by weight of sodium hydroxide to salt out p-nitrocalyxarene, filtering it out, and washing it with brine.
尚、このｐ−ニトロカリツクスアレンのナトリウム塩を
水に溶解させ、この溶液を塩酸又は硫酸にて酸性にし、
析出した結晶を濾別し、水洗、乾燥することによって、
一層高純度のｐ−ニトロカリツクスアレンを得ることが
できる。In addition, this sodium salt of p-nitrocalyxarene is dissolved in water, and this solution is made acidic with hydrochloric acid or sulfuric acid.
By filtering the precipitated crystals, washing with water, and drying,
Even higher purity p-nitrocalyx arene can be obtained.
次に、このようにして得られるｐ−ニトロカリツクスア
レンのアルカリ金属塩を溶剤中にてアルキル化剤にてＯ
−アルキル化することによって、前記一般式（ｎ）で表
わされる本発明によるｐ−ニトロ−〇−アルキルカリツ
タスアレンを得ることができる。用いるアルキル化剤は
、目的とするｐ−ニトロ−Ｏ−アルキルカワックスアレ
ンに応じて適宜に選ばれる。例えば、ハロゲン化アルキ
ル、ジアルキル硫酸、ｐ−トルエンスルホン酸エステル
等を用いることができるが、特に、ハロゲン化アルキル
が好ましい。かかるハロゲン化アルキルとしては、例え
ば、炭素数１〜１８のアルキル基をもつ塩化、臭化又は
ヨウ化アルキルが好適であり、例えば、ヨウ化メチル、
塩化ｎ−ブチル、臭化ｎ−オクチル、臭化ｎ−ドデシル
等を挙げることができる。Next, the alkali metal salt of p-nitrocalyxarene obtained in this way was placed in a solvent and treated with an alkylating agent.
-Alkylation makes it possible to obtain the p-nitro-〇-alkylcaritutasarene according to the present invention represented by the general formula (n). The alkylating agent used is appropriately selected depending on the target p-nitro-O-alkylkawaxarene. For example, alkyl halides, dialkyl sulfates, p-toluenesulfonic acid esters, etc. can be used, and alkyl halides are particularly preferred. As such alkyl halide, for example, alkyl chloride, bromide or iodide having an alkyl group having 1 to 18 carbon atoms is suitable, such as methyl iodide,
Examples include n-butyl chloride, n-octyl bromide, and n-dodecyl bromide.
？容斉りとしては、テトラメチレンスルホン、ジメチル
スルホキシド、ジメチルホルムアミド等のような非プロ
トン性極性有機溶剤が好ましい。? As a solvent, aprotic polar organic solvents such as tetramethylene sulfone, dimethyl sulfoxide, dimethyl formamide, etc. are preferred.
このｐ−ニトロ−〇−アルキルカリックスアレンのニト
ロ基を還元剤にてアミノ基に還元すれば、前記一般式（
［）で表わされる本発明によるｐ−アミノ−０−アルキ
ルカリックスアレンを得ることができる。還元剤として
は、通常、芳香族ニトロ化合物のニトロ基をアミノ基に
還元する還元剤を任意に用いることができるが、例えば
、ヒドラジン永和物を触媒としての塩化鉄及び活性炭の
存左下に用いるのが好ましい。また、用いる溶剤として
は、例えば、メチルセロソルブが好ましい。If the nitro group of this p-nitro-〇-alkylcalixarene is reduced to an amino group using a reducing agent, the general formula (
A p-amino-0-alkyl calixarene according to the present invention represented by [) can be obtained. Any reducing agent that reduces the nitro group of an aromatic nitro compound to an amino group can be used as the reducing agent. is preferred. Furthermore, as the solvent to be used, for example, methyl cellosolve is preferable.
次に、このようにして得られるｐ−アミノ−Ｏ−アルキ
ルカリツクスアレンを従来より知られている方法に従っ
て、ハロゲン下アルキルによって第４級塩化することに
よって、前記一般式（■）で表わされる本発明によるｐ
−トリアルキルアンモニオ−０−アルキルカリツクスア
レンを得ることができる。代表的な方法として例えば、
ジメチルホルムアミド等のような非プロトン性罹性溶剤
中にて炭酸カリウムのような酸捕捉剤としての塩基の存
在下に、ｐ−アミノ−Ｏ−アルキルカワックスアレンに
ハロゲン化アルキルを反応させればよい。ここに、ハロ
ゲンアルキルとしては、前述したと同様に種々のものを
用いることができるが、例えば、ヨウ化メチル、臭化メ
チル、塩化メチル、ヨウ化エチル、ヨウ化プロピル、ヨ
ウ化ブチル等を用いることができる。通常、炭素ＤＩ〜
５のアルキル基をもつハロゲン下アルキルが好適である
が、特に、ヨウ化メチルが好ましい。Next, the p-amino-O-alkylcalixarene thus obtained is subjected to quaternary salting with an alkyl halogen in accordance with a conventionally known method to obtain a compound represented by the general formula (■). p according to the invention
-trialkylammonio-0-alkylcalixarene can be obtained. For example, a typical method is
If p-amino-O-alkylkawaxarene is reacted with an alkyl halide in the presence of a base as an acid scavenger such as potassium carbonate in an aprotic susceptible solvent such as dimethylformamide etc. good. Here, various halogen alkyls can be used as mentioned above, but for example, methyl iodide, methyl bromide, methyl chloride, ethyl iodide, propyl iodide, butyl iodide, etc. are used. be able to. Usually carbon DI~
Subhalogenated alkyls having 5 alkyl groups are preferred, particularly methyl iodide.
しかしながら、ハロゲン化アルキルとしてヨウ化メチル
を用いる場合は、反応生成物が副生じたヨウ素によって
着色していることがある。このようなヨウ素による反応
生成物の着色は、例えば、反応生成物をエタノール水溶
液に溶解し、これに亜硫酸ガスを吹き込むことによって
除去することができる。However, when methyl iodide is used as the alkyl halide, the reaction product may be colored by iodine produced as a by-product. Such coloring of the reaction product due to iodine can be removed, for example, by dissolving the reaction product in an aqueous ethanol solution and blowing sulfur dioxide gas into the solution.
また、ハロゲン化アルキルとしてヨウ化メチルを用いて
得られるヨウ化ｐ−トリメチルアンモニオ−〇−アルキ
ルカリックスアレンは、−ａに、水に対する溶解度が小
さいが、これを塩素化物や臭素化物或いはその他の対ア
ニオンとアニオン交換することによって、一般に水への
溶解度の大きいｐ−）リメチルアンモニオー〇−アルキ
ルカワックスアレンを得ることができる。例えば、ヨウ
化ｐ−トリメチルアンモニオ−０−アルキルカリツクス
アレンをエタノール水溶液に溶解させ、塩素イオン型ア
ニオン交換樹脂にて処理して、ヨウ素イオンを塩素イオ
ンにてイオン交換すれば、塩化ｐ−）リメチルアンモニ
オー〇−アルキルカリツクスアレンを得ることができる
。In addition, p-trimethylammonio-〇-alkyl calixarene iodide obtained using methyl iodide as the alkyl halide has low solubility in water, but it can be treated with chlorides, bromides, or other By exchanging the anion with a counter anion, p-)limethylammonio-o-alkylkawaxarene, which generally has a high solubility in water, can be obtained. For example, if p-trimethylammonio-0-alkylcalixarene iodide is dissolved in an aqueous ethanol solution and treated with a chloride ion type anion exchange resin to exchange iodide ions with chloride ions, ) Limethylammonio-alkylcalixarene can be obtained.
発明の効果
以上のように、本発明によって新規なカリツクスアレン
誘導体が提供される。かかる化合物は、前述したように
、酵素反応、触媒反応や、金属イオン輸送体としての用
途が期待され、或いは更にその池のカリツクスチレンｍ
１体を製造するための原料として用いることができる。Effects of the Invention As described above, the present invention provides a novel calixarene derivative. As mentioned above, such compounds are expected to be used in enzymatic reactions, catalytic reactions, and as metal ion transporters, or they can also be used in calyx styrene m.
It can be used as a raw material for manufacturing one product.
大籐炭
以下に参考例と共に実施例を挙げて本発明を説明するが
、本発明はこれら実施例によって何ら限定されるもので
はない。Large rattan charcoal The present invention will be explained below with reference examples and examples, but the present invention is not limited to these examples in any way.
参考例１
カリツクス〔６〕７レン５．０ｇを濃硫酸５０ｍ１に加
え、８０°Ｃの温度にて４時間スルホン化反応を行なっ
た後、冷却し、これに冷水９０ｍ１を加えて希釈した。Reference Example 1 5.0 g of Calix[6]7lene was added to 50 ml of concentrated sulfuric acid, a sulfonation reaction was carried out at a temperature of 80° C. for 4 hours, and the mixture was cooled and diluted with 90 ml of cold water.
次いで、得られた反応混合物に６１％硝酸５．５ｇを加
え、温度を０〜５°Ｃに保ちつつ、スルホン酸基をニト
ロ基に置換する反応を１０時間行なった。この置換反応
の終了後、反応混合物を水で希釈し、生成した結晶を分
離し、水洗し、乾燥して、粗製ｐ−ニトロ力リすクス〔
６〕アレンを得た。Next, 5.5 g of 61% nitric acid was added to the obtained reaction mixture, and a reaction for substituting sulfonic acid groups with nitro groups was carried out for 10 hours while maintaining the temperature at 0 to 5°C. After completion of this substitution reaction, the reaction mixture is diluted with water, the formed crystals are separated, washed with water, and dried to obtain the crude p-nitroliquid
6] Obtained Allen.
収率は、カリックス〔６〕アレンに対して３５％であっ
た。The yield was 35% based on calix[6]arene.
次に、この粗製ｐ−ニトロ力リすクス〔６〕アレン５．
０ｇを水酸化ナトリウム１．５ｇを含む水３００ｍ１に
加熱溶解させ、これに活性炭２ｇを加えた後、活性炭を
濾別した。Next, this crude p-nitroliquid [6]alene 5.
0 g was heated and dissolved in 300 ml of water containing 1.5 g of sodium hydroxide, 2 g of activated carbon was added thereto, and the activated carbon was filtered off.
得られた°’ｆｉ、ｔ＆に水酸化ナトリウム１５ｇ （
溶液■の５重量％）を加え、ヘキサナトリウム塩を塩析
し、析出させた。これを濾過し、食塩水にて洗浄した後
、乾燥して、精’Ａ ｐ−ニトロ力リツクス〔６〕アレ
ンのヘキサナトリウム塩を得た。To the obtained °'fi, t&, add 15 g of sodium hydroxide (
5% by weight of solution (2) was added to salt out the hexasodium salt to precipitate it. This was filtered, washed with brine, and dried to obtain the hexasodium salt of purified Ap-nitrotrix[6]arene.
このヘキサナトリウム塩は、塩化ナトリウム及び水分を
含み、分析の結果、ｐ−ニトロ力リックス〔６〕アレン
のヘキサナトリウム塩としての純度は６３％であった。This hexasodium salt contains sodium chloride and water, and as a result of analysis, the purity of p-nitroforce[6]arene as hexasodium salt was 63%.
収率は、粗製ｐ−ニトロカリツクス〔６〕アレンに対し
て４５％であった。The yield was 45% based on crude p-nitrocalyx[6]arene.
この精製、−ニトロ力リックス〔６〕アレンのヘキサナ
トリウム塩４．０ｇを水１００ｍ１に加熱溶解させ、加
熱下にこれに濃塩酸１ｍｌを加え、析出した結晶を濾別
、水洗、乾燥して、高純度のｐ−ニトロ力リツクス〔６
〕アレンを２．１ｇ得た。収率は、ｐ−ニトロカリツク
ス〔６〕アレンのヘキサナトリウム塩に対して９６％で
あった。For this purification, 4.0 g of hexasodium salt of nitroforce[6]arene was dissolved in 100 ml of water by heating, 1 ml of concentrated hydrochloric acid was added thereto under heating, and the precipitated crystals were separated by filtration, washed with water, and dried. High purity p-nitrodynamics [6
] 2.1 g of arene was obtained. The yield was 96% based on the hexasodium salt of p-nitrocalyx[6]arene.
融占 ３００℃以上
元素分析亘（ＣＪｓＮ（ｈ）・４１１．ＯＣＨＮ
計算値 ５１．５３ ３．８９ ８．５９実験値
５１，９４ ３．３２ ８．５９・・外線吸収
スペクトル（ＫＢｒ法）
波数（ｃｍ−’） 帰属
３４５０ ν０１１ｔ３３０
ｖ ＮＯｘ１４８０
νＮＯ□焦玖久韮膿λづ至上上（ＣＤＣｌ２．参照Ｔ
ＭＳ）δ（ｐｐｍ） 帰属 積分強度比３
．９６ −Ｃ）１２− １２
Ｈ８、１０ＡｒＣＨｚＡｒ １２Ｈ尚、種
々の環数を有するｐ−ニトロ力リツクス（ｎ）アレンを
同様にして得ることができることは、特願昭６０−１３
２７２０号明細書に記載されている。Elemental analysis over 300℃ (CJsN(h)・411.OCHN Calculated value 51.53 3.89 8.59 Experimental value 51,94 3.32 8.59... External absorption spectrum (KBr method) Wave number ( cm-') Attribution 3450 ν011t330
vNOx1480
νNO
MS) δ (ppm) Attribution Integrated intensity ratio 3
．． 96-C)12-12
H8, 10ArCHzAr 12H Furthermore, it is known that p-nitroforce(n)arenes having various ring numbers can be obtained in the same manner, as disclosed in Japanese Patent Application No. 1986-13.
It is described in the specification of No. 2720.
実施例Ｉ
■二三上三二立二エニ土久±火互ユズ又入（６）アレン
の製造
ｐ−ニトロ力リツクス〔６〕アレンヘキサナトリウム塩
３．０ ｇ （４ｍｍｏｌ）をテトラメチレンスルホン
４０ｍ１に加熱溶解させ、これに臭化ｎ−オクチル５．
０ ｇ （３０ｍｍｏｌ）を加えて、１００−１２０℃
の温度で６〜８時間加熱下に攪拌した。冷却した後、水
にて希釈し、生じた沈殿を濾別し、ヘンゼンから再結晶
した。融点１９８℃、収量３．０ｇ（収率４８％）。Examples I ■ 23 above, 3rd two Eii, Tsuchiku ± Fires Matsuto (6) Allen's manufacturing P -Nitro Power Ritsukus [6] Allen Hexana Torium 3.0 g (4 mmol) Tetramethylance Sulfon 40m1 5.5% of n-octyl bromide was added to the solution by heating.
Add 0 g (30 mmol) and heat at 100-120℃
The mixture was stirred under heating for 6 to 8 hours at a temperature of . After cooling, it was diluted with water, and the resulting precipitate was filtered off and recrystallized from Hensen. Melting point: 198°C, yield: 3.0 g (yield: 48%).
云左分捉菫（Ｃ＋５ｌｌｚ＋Ｎ０ｚ）ａＣＨＮ
計算値 ６８．４４ ７．９８ ５．３２実験値
６８．４４ Ｂ、１１ ５．３１ハ外線吸収
スペクトル（ＫＢｒ法）
波数（ｃｍ−’） 帰属
２９２０、２８５０ シＣ０１６１０、
１５９０νＣ＝Ｃ（芳香族）１５２０
ν３ｓＮ（ｈ１４６０ シ５
−ＣＨｚ−（挟み）１３５０ ν５
ＮＯｚ１２２０ シＣ−０−Ｃ挨稚
久夫咀スご久上酉（ＣＤＣＩ＋、参照ＴＭＳ）δ（ｐｐ
ｍ） 帰属 積分強度比８．５０−６．４
０ ＡｒＨ２Ｈ
４，００ＡｒＣ）ＩｚＡｒ ４）ＩＡｒＯＣＩ
Ｉ２−
２．２０−１．００ −ＣＩ！２− １２０
０．８０ −ＣＨ３３ｔｌ
実施例２
実施例１において、臭化ｎ−オクチルに代えて臭化メチ
ル及び臭化ｎ−ドデシルを用いた以外は、実施例１と同
様にして、それぞれｐ−ニトロ−〇−メチル力すツクス
〔６〕アレン及びｐ−ニトロ−０−ｎ−ドデシル力リツ
クス〔６〕アレンを得た。Calculated value 68.44 7.98 5.32 Experimental value 68.44 B, 11 5.31 C External absorption spectrum (KBr method) Wavenumber (cm-') Attribution 2920, 2850 C01610,
1590νC=C (aromatic) 1520
ν3sN(h1460 si5
-CHz- (pincer) 1350 ν5
NOz1220 ShiC-0-C Hisao Tsui Gokukami Tori (CDCI+, reference TMS) δ (pp
m) Attribution Integrated intensity ratio 8.50-6.4
0 ArH2H 4,00ArC) IzAr 4) IArOCI
I2- 2.20-1.00 -CI! 2-120
0.80 -CH33tl Example 2 In the same manner as in Example 1, except that methyl bromide and n-dodecyl bromide were used in place of n-octyl bromide, p-nitro- -Methyl trix[6]arene and p-nitro-0-n-dodecyl trix[6]arene were obtained.
これらの融点及び元素分析値を示す。Their melting points and elemental analysis values are shown.
ｐ−ニトロ−Ｏ−メチル力リツクス〔６〕アレン融点
３００℃以上
天王分扼亘（ＣＩｌＩＩ？ＮＯ：ｌ） ｂＣＩＩ
Ｎ
計算値 ５８．１８ ４．２７ ８．４６実験値
５Ｂ、０１ ４．３０ ８．３０上二三上三二
旦二エニ上ヱ２酉左ユ又り久」立しヱＬ／７
融点 １５５〜１５６℃
天見分梶菫（Ｃ，Ｉｌｌ□９ＮＯ３）ｌ。p-nitro-O-methyl forces[6]arene melting point
300℃ or more Tennobu 扼优 (CIlII?NO:l) bCII
N Calculated value 58.18 4.27 8.46 Experimental value 5B. ~156℃ Amamibu Kajisumi (C, Ill□9NO3)l.
ＣＨＮ
計算値 ７１．１６ ９．０９ ４．３９実験値
７１．４７ ９．２１ ４．３４実施例３
ｐ−アミノ−０−ｎ−オクチル力リツクス（６〕アレン
の製造
ｐ−ニトロ−〇−ｎ−オクチル力リックす〔６〕アレン
１．５ ｇ （０，Ｓ ５ｍｍｏｌ）をメチルセロソル
ブ８０ｍ１に加え、これに活性炭０．３ｇと塩化第二鉄
六水和物０．０５ ｇを加えて、８０ ’Ｃの温度にて
３０分間加熱下に攪拌した。次いで、ヒドラジン−水和
物１０ｍ１を滴下し、更に、６時間加熱攪拌した後、熱
時濾過にて活性炭を濾別した。濾液を冷却し、析出した
結晶を濾別して、エタノールから再結晶した。融点２０
８〜２０９℃、収Ｎ １．２ ｇ（収率９０％）。CHN Calculated value 71.16 9.09 4.39 Experimental value 71.47 9.21 4.34 Example 3 Production of p-amino-0-n-octyl forces (6) allene p-nitro-〇-n - Add 1.5 g (0,S 5 mmol) of octyl liquefaction [6]alene to 80 ml of methyl cellosolve, add 0.3 g of activated carbon and 0.05 g of ferric chloride hexahydrate, and mix 80 The mixture was heated and stirred for 30 minutes at a temperature of 'C. Next, 10 ml of hydrazine hydrate was added dropwise, and the mixture was heated and stirred for an additional 6 hours. The activated carbon was removed by filtration while hot. The filtrate was cooled. The precipitated crystals were filtered and recrystallized from ethanol. Melting point: 20
8-209°C, yield N 1.2 g (yield 90%).
元素分析値（Ｃ，Ｊ□ＪＯ） ｂ・２．５１１□ＯＣ１
１Ｎ
計算値 ７４．８４ ９．９１ ５．８２実験値
７４．８９ １０．０１ ５．２２赤外線吸収ス
ペクトル（ＫＢｒ法）
波数（ｃｍ−’） 帰属
３４００ νＮＨ
２９００シＣ１１
１６１０νＣ＝Ｃ，δＮＨ
１４８０ｖ ５−Ｃ１１２−
１２２０シＣ−０−Ｃ
核磁気共１！ヘスベクトル（ＣＤＣｈ、参照ＴＭＳ）δ
（ｐｐｍ） 帰属 積分強度比６．００
Ａｒ１１ ２Ｈ３，７２ＡｒＣＩ
ＩｚＡｒ ４Ｈ八ｒＯＣＨ２−
２，６０−Ｎｌ２ ２＋＋
１．８０ −０ＣＩＩ□ＣＩ！２− ３Ｈ
１，２０−ＣＨ，−１０！１
０．８４ −Ｃ１１３３１１
実施例４
実施例３において、ｐ−ニトロ−〇−ｎ−オクチル力リ
ツクす〔６〕アレンに代えて、ｐ−ニトロ−〇−メチル
力すツクス〔６〕アレン及びｐ−ニトロ−０−、ｎ−ド
デシル力リツクス〔６〕アレンを用いた以外は、実施例
３と同様にして、それぞれｐ−アミノ−０−メチル力リ
ツクス〔６〕アレン及びｐ−アミノ−０−ｎ−ドデシル
力リツクス〔６〕アレンを得た。Elemental analysis value (C, J□JO) b・2.511□OC1
1N Calculated value 74.84 9.91 5.82 Experimental value 74.89 10.01 5.22 Infrared absorption spectrum (KBr method) Wave number (cm-') Attribution 3400 νNH 2900C11 1610νC=C, δNH 1480v 5- C112- 1220 C-0-C Nuclear magnetism 1! Hess vector (CDCh, reference TMS) δ
(ppm) Attribution Integrated intensity ratio 6.00
Ar11 2H3,72ArCI
IzAr 4H8rOCH2- 2,60-Nl2 2++ 1.80 -0CII□CI! 2-3H
1,20-CH, -10!1 0.84 -C113311 Example 4 In Example 3, p-nitro-〇-n-octyl [6]alene was replaced with p-nitro-〇-methyl. In the same manner as in Example 3, except that p-nitro-0-, n-dodecyl forces [6] arene and p-amino-0-methyl forces [6] allene were used, respectively. ]Alene and p-amino-0-n-dodecyl forces [6]arene were obtained.
これらの化合物の融点及び元素分析値を示す。The melting points and elemental analysis values of these compounds are shown.
１二１ユノニ」二ノ」ソリピし乙とと１６）７とヱ融点
２８０°Ｃ以上
兄素光扼碌（Ｃａ Ｈｑ Ｎ Ｏ３） ｂＣＩＩ
Ｎ
計算値 ７１．１８ ６．７２ １０．３８実験値
７１．００ ６．８５ １０．２５ｐ−アミノ−
０−ｎ−ドデシル力リツクス〔６］ア乞Ｚ
融点 １６４〜１６７°Ｃ
元素分析値（Ｃ，、＋１□ＪＯｉ）ｂ
Ｃ１１Ｎ
計算値 ７８．８９ １０．７３ ４．８４実験値
７８．４１ １０．９４ ４．３２実施例５
ｐ−アミノ−０−ｎ−オクチル力リツクス〔６〕アレン
１． Ｏｇ （０，７ｍｍｏｌ）をジメチルホルムアミ
ド３Ｑｍｌに）容′Ａ￥させ、炭酸カリウム１．０ｇ（
７３ｍｍｏ ｌ ）を加え、更に、これにヨウ化メチル
１０ｍ１（０，１７ｍｏｌ）を加えて、６０〜６５°Ｃ
の温度にて４８時間攪拌した。冷却した後、水にて希釈
し、析出した沈殿を濾別し、水洗した。121 ``Nino'' Soripi 16) 7 and ヱMelting point 280°C or higher Brother element optical power (Ca Hq N O3) bCII
N Calculated value 71.18 6.72 10.38 Experimental value 71.00 6.85 10.25p-amino-
0-n-dodecyl force [6] Aki Z Melting point 164-167°C Elemental analysis value (C,,+1□JOi)b C11N Calculated value 78.89 10.73 4.84 Experimental value 78.41 10. 94 4.32 Example 5 p-amino-0-n-octyl tric[6]alene 1. Og (0.7 mmol) was dissolved in dimethylformamide (3 Q ml) to a volume of 1.0 g (1.0 g).
73 mmol) was added thereto, and 10 ml (0.17 mol) of methyl iodide was added thereto, and the mixture was heated at 60-65°C.
The mixture was stirred at a temperature of 48 hours. After cooling, it was diluted with water, and the deposited precipitate was filtered off and washed with water.
このようにして得たヨウ化ｐ−）リメチルアンモニオー
〇−ｎ−オクチル力すツクス〔６〕アレンをエタノール
／水（２／１）に溶解させ、この溶液中に亜硫酸ガスを
吹き込んで、ヨウ素による着色を除いた後、塩素イオン
型アニオン交換樹脂にて処理し、蒸発乾固させて、塩化
ｐ−１−リメチルアンモニオ一〇−〇−オクチル力すツ
クス〔６〕アレンを得た。融点１８０〜１８２°Ｃ１収
量１．０ｇ（収率７６％）。The thus obtained p-)limethylammonio-n-octyl lactox[6]arene iodide was dissolved in ethanol/water (2/1), and sulfur dioxide gas was blown into this solution. After removing the coloring caused by iodine, it was treated with a chloride ion type anion exchange resin and evaporated to dryness to obtain p-1-limethylammonio-10-0-octyltristhux[6]arene chloride. . Melting point: 180-182° C. Yield: 1.0 g (76% yield).
元素分析イ直（Ｃ＋８１１ｓｏＮＯＣ１）６・９．８１
Ｈｚ。Elemental analysis I direct (C+811soNOC1) 6.9.81
Hz.
ＣＩｔ ｆｉｌ ｅｌ計算値
６３．３６ ９．７６ ４．１１ １０．４１実
験値 ６３．４７ ９．９０ ４．２０ ９．
６２赤外線吸収スペクトル（ＫＢｒ法）
波数（ｃｍ−’） 帰属
２９２０、２８４０ シＣ１＋１６００
νＣ−Ｃ１４６０
ｖ ５−Ｃｆ１２−１３７０
δ５Ｎ−Ｃ１１３１２１０シＣ−０−
Ｃ
隻■墓共瓜丞さＬ上止（ＣＤ３０Ｄ、参照ＴＭＳ）δ（
ｐｐｍ） 帰属 積分強度比８．００−６
．５０ ＡｒＨ２Ｈ
４，２０−３，００ＡｒＣｌ１ｚ八ｒ
ＩＩＨＡｒＯＣ１ｆｆ２−＋ −Ｎ”Ｃｆ１３１．８
０ −０ＣＨｚＣＩｌｚ−２１１１，３２−Ｃ
Ｈｚ−１２Ｉ
Ｏ，８５−ＣＩｌ：ｔ ３８実施例６
実施例５において、ｐ−アミノ−０−ｎ−オクチルカリ
ックス〔６〕アレンに代えて、ｐ−アミノ−○−ｎ−メ
チル力リツクす〔６〕アレンを用いた以外は、実施例５
と全（同様にして、塩化−ｐ−１リメチルアンモニオー
〇−メチル力リツクス〔６〕アレンを得た。CIt fil el calculated value
63.36 9.76 4.11 10.41 Experimental value 63.47 9.90 4.20 9.
62 Infrared absorption spectrum (KBr method) Wave number (cm-') Attribution 2920, 2840 C1+1600
νC-C1460
v 5-Cf12-1370
δ5N-C1131210shiC-0-
C ship ■ grave together with Urijosa L upper end (CD30D, reference TMS) δ (
ppm) Attribution Integrated intensity ratio 8.00-6
．． 50 ArH2H 4,20-3,00ArCl1z8r
IIHArOC1ff2-+ -N"Cf131.8
0 -0CHzCIlz-2111,32-C
Hz-12I O,85-CIl:t 38 Example 6 In Example 5, in place of p-amino-0-n-octylcalix[6]arene, p-amino-○-n-methyl calix[6] 6] Example 5 except that allene was used
and total (in the same manner, p-1trimethylammonio 0-methyl chloride [6]arene was obtained.
融点 ２８０℃以上
元免光捉皿（ＣＩｌｌｒｌｂＮＯＣＩ）６３Ｈ２０ＣＩ
Ｉ ＮMelting point: 280°C or higher Original luminescent capture dish (CIllrlbNOCI) 63H20CI
IN
Claims (17)
基、アミノ基及びアルキル基の炭素数が１〜５であるト
リアルキルアンモニウムよりなる群から選ばれる置換基
、ｎは４〜８の整数を示し、Ｚがニトロ基又はアミノ基
であるときはｎ’＝０であり、Ｚがトリアルキルアンモ
ニウムであるときはＸ＾ａ＾−は対アニオンを示し、ａ
はこの対アニオンの価電数を示し、ｎ’＝ｎ／ａである
。） で表わされることを特徴とするカリツクスアレン誘導体
。(1) General formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, R is an alkyl group with 1 to 18 carbon atoms, Z is a nitro group, an amino group, and an alkyl group with a carbon number of a substituent selected from the group consisting of trialkylammonium of 1 to 5, n represents an integer of 4 to 8, n'=0 when Z is a nitro group or an amino group, and Z is a trialkylammonium When , X^a^- indicates the counter anion, and a
represents the valence number of this counteranion, and n'=n/a. ) A calixarene derivative characterized by being represented by:
載のカリツクスアレン誘導体。(2) The calixarene derivative according to claim 1, characterized in that it is represented by the general formula (II) ▲A mathematical formula, a chemical formula, a table, etc.▼(II).
載のカリツクスアレン誘導体。(3) The calixarene derivative according to claim 1, characterized in that it is represented by the general formula (III) ▲A mathematical formula, a chemical formula, a table, etc.▼(III)
表わされることを特徴とする特許請求の範囲第１項記載
のカリツクスアレン誘導体。(4) General formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (IV) (In the formula, R' represents an alkyl group having 1 to 5 carbon atoms.) A patent claim characterized by being represented by the following: The calixarene derivative according to item 1.
ことを特徴とする特許請求の範囲第４項記載のカリツク
スアレン誘導体。(5) The calixarene derivative according to claim 4, wherein R' is a methyl group and X is a halogen atom.
特許請求の範囲第５項記載のカリツクスアレン誘導体。(6) The calixarene derivative according to claim 5, wherein the halogen atom is a chlorine atom.
ルキル化剤にてアルキル化することを特徴とする一般式
（II） ▲数式、化学式、表等があります▼（II） （式中、Ｒは炭素数１〜１８のアルキル基を示し、ｎは
前記と同じである。） で表わされるｐ−ニトロ−Ｏ−アルキルカリツクスアレ
ンの製造方法。(7) General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, M is an alkali metal, and n is an integer from 4 to 8.) p-Nitrocalyxarene represented by General formula (II) characterized by alkylation with an alkylating agent in a solvent ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (II) and n is the same as above).
特徴とする特許請求の範囲第７項記載のｐ−ニトロ−Ｏ
−アルキルカリツクスアレンの製造方法。(8) p-nitro-O according to claim 7, wherein the alkylating agent is an alkyl halide.
- A method for producing an alkyl calytux arene.
の整数を示す。） で表わされるｐ−ニトロ−Ｏ−アルキルカリツクスアレ
ンを還元剤にて還元することを特徴とする一般式（III
） ▲数式、化学式、表等があります▼（III） （式中、Ｒ及びｎは前記と同じでる。） で表わされるｐ−アミノ−Ｏ−アルキルカリツクスアレ
ンの製造方法。(9) General formula (II) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (II) (In the formula, R is an alkyl group having 1 to 18 carbon atoms, and n is 4 to 8
indicates an integer. ) The general formula (III
) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) (In the formula, R and n are the same as above.) A method for producing p-amino-O-alkyl calyxarene represented by the following.
許請求の範囲第９項記載のｐ−アミノ−Ｏ−アルキルカ
リツクスアレンの製造方法。(10) The method for producing p-amino-O-alkyl calyxarene according to claim 9, wherein the reducing agent is hydrazine.
還元することを特徴とする特許請求の範囲第９項項記載
のｐ−アミノ−Ｏ−アルキルカリツクスアレンの製造方
法。(11) A method for producing p-amino-O-alkyl calyxarene according to claim 9, characterized in that the reduction is carried out with hydrazine using iron chloride and activated carbon as catalysts.
の整数を示す。） で表わされるｐ−アミノ−Ｏ−アルキルカリツクスアレ
ンを溶剤中において塩基の存在下にハロゲン化アルキル
と反応させることを特徴とする一般式（VI） ▲数式、化学式、表等があります▼（VI） （但し、Ｘはハロゲン原子を示し、Ｒ及びｎは前記と同
じである。） で表わされるｐ−トリアルキルアンモニオ−Ｏ−アルキ
ルカリツクスアレンの製造方法。(12) General formula (III) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (III) (In the formula, R is an alkyl group having 1 to 18 carbon atoms, and n is 4 to 8
indicates an integer. General formula (VI) characterized by reacting p-amino-O-alkylcalixarene represented by ) with an alkyl halide in the presence of a base in a solvent ▲There are mathematical formulas, chemical formulas, tables, etc.▼ ( VI) (However, X represents a halogen atom, and R and n are the same as above.) A method for producing p-trialkylammonio-O-alkyl calixarene represented by:
ることを特徴とする特許請求の範囲第１２項記載のｐ−
トリアルキルアンモニオ−Ｏ−アルキルカレツクスアレ
ンの製造方法。(13) p- according to claim 12, wherein R' is a methyl group and X is a halogen atom.
A method for producing trialkylammonio-O-alkylcalexarene.
とを特徴とする特許請求の範囲第１３項記載のｐ−トリ
アルキルアンモニオ−Ｏ−アルキルカリツクスアレンの
製造方法。(14) The method for producing p-trialkylammonio-O-alkyl calixarene according to claim 13, wherein the halogen atom is chlorine, bromine or iodine.
ることを特徴とする特許請求の範囲第１２項記載のハロ
ゲン化ｐ−トリアルキルアンモニオ−Ｏ−アルキルカリ
ツクスアレンの製造方法。(15) The method for producing a halogenated p-trialkylammonio-O-alkyl calyxarene according to claim 12, characterized in that methyl iodide is used as the alkyl halide.
てヨウ化ｐ−トリメチルアンモニオ−Ｏ−アルキルカリ
ツクスアレンを得、これを塩素イオンとアニオン交換し
て、塩化ｐ−トリメチルアンモニオ−Ｏ−アルキルカリ
ツクスアレンを得ることを特徴とする特許請求の範囲第
１２項記載のハロゲン化ｐ−トリアルキルアンモニオ−
Ｏ−アルキルカリツクスアレンの製造方法。(16) Using methyl iodide as the alkyl halide, p-trimethylammonio-O-alkylcalixarene iodide is obtained, and this is anion-exchanged with chlorine ions to produce p-trimethylammonio-O-alkyl chloride. The halogenated p-trialkylammonio-
A method for producing O-alkyl calyxarene.
てヨウ化ｐ−トリメチルアンモニオ−Ｏ−アルキルカリ
ツクスアレンを得、これを臭素イオンとアニオン交換し
て臭化ｐ−トリメチルアンモニオ−Ｏ−アルキルカリツ
クスアレンを得ることを特徴とする特許請求の範囲第１
２項記載のハロゲン化ｐ−トリアルキルアンモニオ−Ｏ
−アルキルカリツクスアレンの製造方法。(17) Using methyl iodide as the alkyl halide, p-trimethylammonio-O-alkylcalixarene iodide is obtained, which is anion-exchanged with bromide ion to p-trimethylammonio-O-alkyl bromide. Claim 1 characterized in that calixarene is obtained.
Halogenated p-trialkylammonio-O according to item 2
- A method for producing an alkyl calytux arene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11013886A JPH0729993B2 (en) | 1986-05-13 | 1986-05-13 | Novel Calix allene derivative and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11013886A JPH0729993B2 (en) | 1986-05-13 | 1986-05-13 | Novel Calix allene derivative and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62265250A true JPS62265250A (en) | 1987-11-18 |
| JPH0729993B2 JPH0729993B2 (en) | 1995-04-05 |
Family
ID=14527991
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11013886A Expired - Lifetime JPH0729993B2 (en) | 1986-05-13 | 1986-05-13 | Novel Calix allene derivative and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0729993B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0237265A2 (en) * | 1986-03-07 | 1987-09-16 | LOCTITE (IRELAND) Ltd. | Calixarene derivatives and use of such compounds for sequestration of metals |
| JPH0215040A (en) * | 1988-07-01 | 1990-01-18 | Yutaka Morita | Novel calixarene derivative |
| US5043415A (en) * | 1987-09-24 | 1991-08-27 | Loctite (Ireland) Ltd. | Nitrogen-containing oxacalixarene and calixarene derivatives, polymers including groups related to such derivatives, and use of such compounds |
| US5049467A (en) * | 1989-01-30 | 1991-09-17 | Orient Chemical Industries, Ltd. | Toner for use in the development of electrostatic latent images |
| US5210216A (en) * | 1985-03-28 | 1993-05-11 | Loctite (Ireland) Limited | Calixarene and oxacalixarene derivatives and use thereof of sequestration metals |
| US5434208A (en) * | 1992-07-10 | 1995-07-18 | Akzo Nobel N.V. | Optically non-linear active waveguiding material comprising a dopant having multiple donor-n-acceptor systems |
| WO1996014878A3 (en) * | 1994-11-15 | 1996-07-11 | Molecular Biosystems Inc | Calixarene conjugates useful as MRI and CT diagnostic imaging agents |
| JP2007056055A (en) * | 2005-08-22 | 2007-03-08 | Wakayama Prefecture | Porous thin film, its production method, gas sensor, and quartz oscillator microbalance |
| KR100698763B1 (en) * | 2000-10-23 | 2007-03-26 | (주)바이오메트릭스 테크놀로지 | Novel aminocalixarene derivatives, method of preparation thereof, self-assembledmonolayer prepared by using them and fixing method of oligo-dna by using the same and dna chip prepared by the method |
-
1986
- 1986-05-13 JP JP11013886A patent/JPH0729993B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5210216A (en) * | 1985-03-28 | 1993-05-11 | Loctite (Ireland) Limited | Calixarene and oxacalixarene derivatives and use thereof of sequestration metals |
| EP0237265A2 (en) * | 1986-03-07 | 1987-09-16 | LOCTITE (IRELAND) Ltd. | Calixarene derivatives and use of such compounds for sequestration of metals |
| US5043415A (en) * | 1987-09-24 | 1991-08-27 | Loctite (Ireland) Ltd. | Nitrogen-containing oxacalixarene and calixarene derivatives, polymers including groups related to such derivatives, and use of such compounds |
| JPH0215040A (en) * | 1988-07-01 | 1990-01-18 | Yutaka Morita | Novel calixarene derivative |
| US5049467A (en) * | 1989-01-30 | 1991-09-17 | Orient Chemical Industries, Ltd. | Toner for use in the development of electrostatic latent images |
| US5434208A (en) * | 1992-07-10 | 1995-07-18 | Akzo Nobel N.V. | Optically non-linear active waveguiding material comprising a dopant having multiple donor-n-acceptor systems |
| WO1996014878A3 (en) * | 1994-11-15 | 1996-07-11 | Molecular Biosystems Inc | Calixarene conjugates useful as MRI and CT diagnostic imaging agents |
| KR100698763B1 (en) * | 2000-10-23 | 2007-03-26 | (주)바이오메트릭스 테크놀로지 | Novel aminocalixarene derivatives, method of preparation thereof, self-assembledmonolayer prepared by using them and fixing method of oligo-dna by using the same and dna chip prepared by the method |
| JP2007056055A (en) * | 2005-08-22 | 2007-03-08 | Wakayama Prefecture | Porous thin film, its production method, gas sensor, and quartz oscillator microbalance |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0729993B2 (en) | 1995-04-05 |
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