JPH055825B2 - - Google Patents
Info
- Publication number
- JPH055825B2 JPH055825B2 JP20599084A JP20599084A JPH055825B2 JP H055825 B2 JPH055825 B2 JP H055825B2 JP 20599084 A JP20599084 A JP 20599084A JP 20599084 A JP20599084 A JP 20599084A JP H055825 B2 JPH055825 B2 JP H055825B2
- Authority
- JP
- Japan
- Prior art keywords
- water
- hydrogen
- sulfonic acid
- formula
- ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- -1 alkylammonium ion Chemical class 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- 229940100198 alkylating agent Drugs 0.000 claims description 8
- 239000002168 alkylating agent Substances 0.000 claims description 8
- 239000013078 crystal Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- VTJUKNSKBAOEHE-UHFFFAOYSA-N calixarene Chemical compound 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 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000011734 sodium Substances 0.000 description 10
- 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 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 229910052708 sodium Inorganic materials 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- LHGMHYDJNXEEFG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminocyclohexa-2,5-dien-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C=CC(=O)C=C1 LHGMHYDJNXEEFG-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 4
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 241001164374 Calyx Species 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- BXOUPTJVBGEDIR-UHFFFAOYSA-N 102088-39-1 Chemical compound OC1=C(CC=2C(=C(CC=3C(=C(CC=4C(=C(CC=5C(=C(C6)C=C(C=5)S(O)(=O)=O)O)C=C(C=4)S(O)(=O)=O)O)C=C(C=3)S(O)(=O)=O)O)C=C(C=2)S(O)(=O)=O)O)C=C(S(O)(=O)=O)C=C1CC1=C(O)C6=CC(S(O)(=O)=O)=C1 BXOUPTJVBGEDIR-UHFFFAOYSA-N 0.000 description 2
- TVZRAEYQIKYCPH-UHFFFAOYSA-N 3-(trimethylsilyl)propane-1-sulfonic acid Chemical compound C[Si](C)(C)CCCS(O)(=O)=O TVZRAEYQIKYCPH-UHFFFAOYSA-N 0.000 description 2
- 241001120493 Arene Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-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
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000004816 paper chromatography Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- ZXQHSPWBYMLHLB-BXTVWIJMSA-M 6-ethoxy-1-methyl-2-[(e)-2-(3-nitrophenyl)ethenyl]quinolin-1-ium;methyl sulfate Chemical compound COS([O-])(=O)=O.C1=CC2=CC(OCC)=CC=C2[N+](C)=C1\C=C\C1=CC=CC([N+]([O-])=O)=C1 ZXQHSPWBYMLHLB-BXTVWIJMSA-M 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000010934 O-alkylation reaction Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- CXLSVMAGOLTCSL-UHFFFAOYSA-J calcium;barium(2+);dicarbonate Chemical compound [Ca+2].[Ba+2].[O-]C([O-])=O.[O-]C([O-])=O CXLSVMAGOLTCSL-UHFFFAOYSA-J 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 125000004122 cyclic group Chemical class 0.000 description 1
- 230000006210 debutylation Effects 0.000 description 1
- 150000008050 dialkyl sulfates Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は新規なカリキサレン誘導体及びその製
造方法に関する。更に具体的に述べるならば、本
発明は一般式（）
（ここでｍは１〜５の整数、Ｍは水素、アンモニ
ウム、低級アルキルアンモニウムイオン、金属イ
オン、Ｒは水素、炭素数１〜18のｎ−アルキル基
を示す。）
で示すカリキサレン−ｐ−スルホン酸、及びその
アンモニウム又は低級アルキルアンモニウム塩、
及び金属塩、ならびにこれらのＯ−ｎ−アルキル
誘導体、及びその製造法に係る。
グツチエ（Gutsche）らは最近“カリキサレ
ン”（一般式（）において、Ｒが水素であり、−
SO3M基が水素で置換された化合物。その形がコ
ツプ（Calix）に似ていることと芳香族化合物
（arene）であることからcalixareneと名づけられ
た）と呼ばれる、一連の環状ホスト分子について
報告している（例えば、C.D.Gutsche、Acc.
Chem.Res.、16、161（1983））。これらのカリキサ
レン類は固体状態においてクロロホルム、トルエ
ン等の比較的小さな分子を包接することが知られ
ているが、水溶液中でホストとして働くものは未
だ知られていない。
本発明者らは該カリキサレン誘導体に水溶性を
付与するならば、ホストとしての空洞の大きさ、
官能基の種類等を自由に設計しうることから、従
来の水溶性ホスト分子として知られるシクロデキ
ストリンにまさるホスト化合物になると考え、鋭
意研究の結果、本発明をついに完成するに至つ
た。
即ち、本発明は
(1) 一般式（）
で示されるカリキサレン−ｐ−スルホン酸、及
びその塩、並びにＯ−ｎ−アルキルカリキサレ
ン−ｐ−スルホン酸、及びその塩。
（ここでｍは１〜５の整数、Ｍは水素、アンモ
ニウム、低級アルキルアンモニウムイオン、金
属イオン、Ｒは水素、炭素数１〜18のｎ−アル
キル基を示す。）
(2) 濃度90％以上好ましくは95％以上の濃硫酸中
にカリキサレンを投入、懸濁、80℃以上、好ま
しくは90℃以上に加熱、溶解、反応させること
を特徴とする上記一般式（）（但し、Ｒは水
素を示す）で示されるカリキサレン−ｐ−スル
ホン酸、及びその塩の製造方法。
(3) 水、又は水溶性有機溶剤と水との混合溶媒
中、上記一般式（）（但し、Ｒは水素を示す）
で示されるカリキサレン−ｐ−スルホン酸塩と
アルキル化剤とを反応させることを特徴とする
上記一般式（）（但し、Ｒは炭素数１〜18の
ｎ−アルキル基を示す）で示されるＯ−ｎ−ア
ルキルカリキサレン−ｐ−スルホン酸、及びそ
の塩の製造方法。
(4) 濃度90％以上好ましくは95％以上の濃硫酸中
でカリキサレンを懸濁、80℃以上好ましくは90
℃以上に加熱、反応させ、次いで冷却、濾別し
た結晶を水に溶解し、塩を形成させて得たカリ
キサレン−ｐ−スルホン酸塩を、水、又は水溶
性有機溶剤と水との混合溶媒中、酸結合剤の存
在下、アルキル化剤と反応させることを特徴と
する上記一般式（）（但し、Ｒは炭素数１〜
18のｎ−アルキル基を示す）で示されるＯ−ｎ
−アルキルカリキサレン−ｐ−スルホン酸、及
びその塩の製造方法
に関する。
本発明の原料であるカリキサレン（以下カリツ
クス［ｎ］アレンと称す。：ｎは骨格となる芳香
族環数を示す。）は前述した文献に記載された既
知の方法で、ｐ−tert−ブチルフエノールとホル
ムアルデヒド、及び水酸化ナトリウムを種々の条
件で加熱し、得られた縮合物より得られるｐ−
tert−ブチルカリツクス［ｎ］アレンを、トルエ
ン中、無水塩化アルミニウムと加熱して脱ブチル
化することによつて得た。これらのカリツクス
［ｎ］アレンを更に精製し、本発明のために使用
した。以下に本発明について更に具体的に述べ
る。
精製したカリツクス［ｎ］アレンは、濃硫酸と
共に反応物が水に完全に溶解するまで加熱するこ
とにより、環員数に関係なく比較的容易にスルホ
ン化することができることを見い出した。又、硫
酸量を適宜調整することにより、反応物を冷却・
濾過することによつて遊離のスルホン酸を結晶と
して得ることができる。該スルホン化物を水で希
釈し、炭酸バリウム（又は炭酸カルシウム）で中
和し、硫酸バリウム（又は硫酸カルシウム）を濾
過することにより、カリツクス［ｎ］アレン−ｐ
−スルホン酸のバリウム塩（カルシウム塩）の水
溶液を得る。この水溶液に炭酸アンモニウム、ア
ルキルアミンの炭酸塩又はアルカリ金属の炭酸塩
等の水溶液を炭酸バリウム（カルシウム）の沈澱
が生じなくなる迄加え、沈澱を濾別することによ
りカリツクス［ｎ］アレン−ｐ−スルホン酸のそ
れぞれの塩の水溶液を得ることができる。これら
の塩の水溶液を蒸発乾固することにより、それぞ
れの塩の結晶を得る。
カリツクス［ｎ］アレン−ｐ−スルホン酸塩の
Ｏ−アルキル化はアルキル化剤のアルキル基の大
きさにより溶媒を適当に選択し、酸結合剤の存在
下加熱することにより容易に行なうことができ
る。低級アルキル基（メチル〜ブチル）では水を
溶媒として使用できるが、それより高級になるに
つれてアルキル化剤を溶解させるためにメタノー
ル、エタノール、THF、ジオキサン、DMSO、
テトラメチレンスルホン等の水と混合する溶剤を
水との混合溶媒として使用するのが好ましい。ア
ルキル化剤としてはハロゲン化アルキル、ｐ−ト
ルエンスルホン酸、アルキルエステル、ジアルキ
ル硫酸等、通常用いられるアルキル化剤が使用で
きる。生成したＯ−アルキルカリツクス［ｎ］ア
レン−ｐ−スルホン酸塩はアルキル基が高級にな
る程、水に対する溶解性が小さくなり、冷却する
ことにより反応液より析出する。又、低級のアル
キル化物は塩析により析出させることができる。
以下に実施例により更に具体的に述べる。
実施例 １
カリツクス［６］アレン２ｇを、98％硫酸20ml
に懸濁し90〜100℃で４時間加熱撹拌した。常温
まで冷却し、析出したカリツクス［６］アレン−
ｐ−スルホン酸を濾別し、少量の98％硫酸で洗浄
する。遊離スルホン酸の結晶を水に溶解し炭酸バ
リウムで中和、析出した硫酸バリウムを濾過、水
洗し、濾液、洗液を合せ、炭酸ナトリウム水溶液
をPH９になるまで加え、析出した炭酸バリウムの
溶液を濾別、水洗し、濾液、洗液を合せ、蒸発乾
固してカリツクス［６］アレン−ｐ−スルホン酸
ナトリウムの結晶を収率75％で得た。
得られたカリツクス［６］アレン−ｐ−スルホ
ン酸ナトリウムは水には良く溶解するが、アルコ
ール、その他の有機溶媒には離溶性であつた。
ペーパークロマト（展開溶媒 イソプロピルア
ルコール：水＝２：１、発色剤 ピナクリプトー
ルエロー）で単一スポツト、元素分析による炭素
対硫黄の原子比は７：１、D2O中でのPMRスペ
クトル（DSS基準で）は7.60PPMに芳香族水素
の１重線と4.10PPMにメチレン水素の１重線が
それぞれ１：１の面積比のピークを与えた。この
ことより、このものは一般式（）でｍ：３、
Ｒ：Ｈ、Ｍ：Naのカリツクス［６］アレン−ｐ
−スルホン酸と同定された。
フエノールブルーは、その極大吸収波長（水中
で668nｍ）が溶媒の極性によつて、大きく変化
することが知られている。すなわち非極性溶媒で
あるシクロヘキサン中では552nｍと極大吸収が
短波長側に移動する。カリツクス［６］アレン−
ｐ−スルホン酸ナトリウムの５ｍＭの水溶液中
で、フエノールブルー（10-5M）の溶液の極大吸
収波長は685nｍと、何と27nｍも長波長側に移動
した。このことは、フエノールブルーがカリツク
ス［６］アレン−ｐ−スルホン酸に包接された環
境は、水よりもより極性な場にあることを示し、
極めて興味深い。このことによりカリツクス
［６］アレン−ｐ−スルホン酸は原系より分極し
た（特に正荷電化分極した）中間体、又は遷移状
態を含む反応のすぐれた触媒になりうる可能性を
示している。
実施例 ２
実施例１で得られたカリツクス［６］アレン−
ｐ−スルホン酸ナトリウム１ｇをジメチルスルホ
キサイド（DMSO）20ml、水５ml、ｎ−臭化ヘ
キシル４ｇ、NaOH1ｇと共に、90℃で26時間加
熱した。冷却後、析出した結晶を濾別、メタノー
ルで洗浄、乾燥してＯ−ｎ−ヘキシルカリツクス
［６］アレン−ｐ−スルホン酸ナトリウムの結晶
を収率50％で得た。
このもののD2O中（DSS基準）の40℃のNMR
は次のようであつた。
The present invention relates to a novel calixarene derivative and a method for producing the same. More specifically, the present invention is based on the general formula () (Here, m is an integer of 1 to 5, M is hydrogen, ammonium, lower alkylammonium ion, metal ion, and R is hydrogen or an n-alkyl group having 1 to 18 carbon atoms.) acids, and ammonium or lower alkyl ammonium salts thereof;
and metal salts, O-n-alkyl derivatives thereof, and methods for producing the same. Recently, Gutsche et al.
A compound in which the SO 3 M group is replaced with hydrogen. reported a series of cyclic host molecules called calixarene (named because its shape resembles a calix and is an aromatic compound (arene) (e.g., CDGutsche, Acc.
Chem. Res., 16 , 161 (1983)). These calixarenes are known to clathrate relatively small molecules such as chloroform and toluene in a solid state, but it is not yet known that they function as hosts in an aqueous solution. The present inventors believe that if water solubility is imparted to the calixarene derivative, the size of the cavity as a host,
Since the type of functional group can be freely designed, the present invention was thought to be a better host compound than cyclodextrin, which is known as a conventional water-soluble host molecule, and as a result of intensive research, the present invention was finally completed. That is, the present invention provides (1) General formula () Calixalene-p-sulfonic acid and its salt, and O-n-alkylcalixalene-p-sulfonic acid and its salt. (Here, m is an integer of 1 to 5, M is hydrogen, ammonium, lower alkylammonium ion, metal ion, R is hydrogen or n-alkyl group having 1 to 18 carbon atoms.) (2) Concentration 90% or more The above general formula () is characterized in that calixalene is introduced into concentrated sulfuric acid of preferably 95% or more, suspended, heated to 80°C or higher, preferably 90°C or higher, dissolved, and reacted (where R represents hydrogen. A method for producing calixalene-p-sulfonic acid and its salts. (3) In water or a mixed solvent of a water-soluble organic solvent and water, the above general formula () (where R represents hydrogen)
O represented by the above general formula () (wherein R represents an n-alkyl group having 1 to 18 carbon atoms), characterized by reacting calixalene-p-sulfonate represented by the above with an alkylating agent. - A method for producing n-alkylcalixalene-p-sulfonic acid and a salt thereof. (4) Suspend calixsalen in concentrated sulfuric acid with a concentration of 90% or higher, preferably 95% or higher, at 80°C or higher, preferably at 90°C.
The calixalene-p-sulfonate obtained by heating to a temperature above ℃ to react, then cooling, and filtering the crystals is dissolved in water to form a salt, and then mixed with water or a mixed solvent of a water-soluble organic solvent and water. The above general formula () is characterized by reacting with an alkylating agent in the presence of an acid binder (wherein R is 1 to 1 carbon atoms).
18 n-alkyl group)
-A method for producing alkylcalixalene-p-sulfonic acid and a salt thereof. Calixsalene (hereinafter referred to as calix[n]arene; n indicates the number of aromatic rings serving as the skeleton), which is a raw material of the present invention, is prepared using p-tert-butylphenol by a known method described in the above-mentioned literature. p-
tert-Butylcalix[n]arene was obtained by heating debutylation with anhydrous aluminum chloride in toluene. These calix[n]arenes were further purified and used for the present invention. The present invention will be described in more detail below. It has been found that purified calix[n]arene can be sulfonated relatively easily regardless of the number of ring members by heating with concentrated sulfuric acid until the reactant is completely dissolved in water. In addition, by appropriately adjusting the amount of sulfuric acid, the reactants can be cooled and
Free sulfonic acid can be obtained as crystals by filtration. The sulfonated product is diluted with water, neutralized with barium carbonate (or calcium carbonate), and the barium sulfate (or calcium sulfate) is filtered to obtain calycus[n]alene-p.
- Obtaining an aqueous solution of barium salt (calcium salt) of sulfonic acid. To this aqueous solution, an aqueous solution of ammonium carbonate, alkylamine carbonate, alkali metal carbonate, etc. is added until no barium (calcium) carbonate precipitates are formed, and the precipitate is filtered to obtain calix[n]arene-p-sulfone. Aqueous solutions of the respective salts of the acids can be obtained. Aqueous solutions of these salts are evaporated to dryness to obtain crystals of each salt. O-alkylation of calix[n]arene-p-sulfonate can be easily carried out by appropriately selecting a solvent depending on the size of the alkyl group of the alkylating agent and heating in the presence of an acid binder. . Water can be used as a solvent for lower alkyl groups (methyl to butyl), but for higher alkyl groups, methanol, ethanol, THF, dioxane, DMSO, etc. can be used to dissolve the alkylating agent.
It is preferable to use a solvent that mixes with water, such as tetramethylene sulfone, as a mixed solvent with water. As the alkylating agent, commonly used alkylating agents such as alkyl halides, p-toluenesulfonic acid, alkyl esters, and dialkyl sulfates can be used. The higher the alkyl group of the produced O-alkylcalix[n]arene-p-sulfonate, the lower its solubility in water, and it precipitates from the reaction solution upon cooling. Further, lower alkylated products can be precipitated by salting out. This will be described in more detail below with reference to Examples. Example 1 2 g of calyx[6]alene was added to 20 ml of 98% sulfuric acid.
The suspension was heated and stirred at 90 to 100°C for 4 hours. Cooled to room temperature and precipitated calyx[6]alene.
The p-sulfonic acid is filtered off and washed with a small amount of 98% sulfuric acid. Dissolve the free sulfonic acid crystals in water, neutralize with barium carbonate, filter the precipitated barium sulfate, wash with water, combine the filtrate and washing liquid, add an aqueous sodium carbonate solution until the pH becomes 9, and remove the precipitated barium carbonate solution. The mixture was filtered, washed with water, and the filtrate and washing liquid were combined and evaporated to dryness to obtain crystals of sodium calix[6]arene-p-sulfonate in a yield of 75%. The obtained sodium calix[6]arene-p-sulfonate was well soluble in water, but was dissolvable in alcohol and other organic solvents. A single spot was obtained using paper chromatography (developing solvent: isopropyl alcohol: water = 2:1, coloring agent: pinacryptol yellow), the atomic ratio of carbon to sulfur was 7:1 by elemental analysis, and the PMR spectrum in D 2 O (DSS (based on the standard), a single line of aromatic hydrogen at 7.60 PPM and a single line of methylene hydrogen at 4.10 PPM gave peaks with an area ratio of 1:1, respectively. From this, this product has the general formula () where m:3,
R: H, M: Na calycus [6] allene-p
-Identified as sulfonic acid. It is known that the maximum absorption wavelength (668 nm in water) of phenol blue changes greatly depending on the polarity of the solvent. That is, in cyclohexane, which is a nonpolar solvent, the maximum absorption at 552 nm shifts to the shorter wavelength side. Calix [6] Allen-
In a 5mM aqueous solution of sodium p-sulfonate, the maximum absorption wavelength of a solution of phenol blue (10 -5 M) was 685nm, a shift of 27nm to the longer wavelength side. This indicates that the environment in which phenol blue is clathrated into calyx[6]arene-p-sulfonic acid is more polar than water.
Extremely interesting. This indicates that calix[6]arene-p-sulfonic acid has the potential to be a polarized (especially positively polarized) intermediate or an excellent catalyst for reactions involving a transition state. Example 2 Calix[6]arene obtained in Example 1
1 g of sodium p-sulfonate was heated at 90° C. for 26 hours with 20 ml of dimethyl sulfoxide (DMSO), 5 ml of water, 4 g of n-hexyl bromide, and 1 g of NaOH. After cooling, the precipitated crystals were separated by filtration, washed with methanol, and dried to obtain crystals of sodium O-n-hexylcalix[6]arene-p-sulfonate in a yield of 50%. NMR of this in D 2 O (DSS standard) at 40°C
was as follows.
【表】【table】
【表】
元素分析よりのＣ：Ｓの原子比は13：１でペー
パークロマトグラフイーで単一スポツトであつ
た。これらのことより、このものは一般式（）
でｍ：３、Ｒ：C6H13、Ｍ：NaのＯ−ｎ−ヘキ
シルカリツクス［６］アレン−ｐ−スルホン酸ナ
トリウムと同定された。
Ｏ−ｎ−ヘキシルカリツクス［６］アレン−ｐ
−スルホン酸ナトリウムの5.00ｍＭの水溶液中で
フエノールブルーの（10-5M）の極大吸収波長は
643nｍを示し、水中より15nｍ青色移動した。こ
のことはフエノールブルーがＯ−ｎ−ヘキシルカ
リツクス［６］アレン−ｐ−スルホン酸に取り込
まれた環境は、カリツクス［６］アレン−ｐ−ス
ルホン酸とは異なり水より非極性な環境であるこ
とがわかつた。
実施例 ３〜６
実施例１と同様にして各環数のカリツクス
［ｎ］アレンを用いてスルホン化を行なつた。
結果は以下の表に示す。[Table] The atomic ratio of C:S from elemental analysis was 13:1, and paper chromatography showed a single spot. From these things, this is the general formula ()
It was identified as sodium O-n-hexylcalix[6]arene-p-sulfonate with m: 3, R: C 6 H 13 , M: Na. O-n-hexyl calix [6] allene-p
-The maximum absorption wavelength of phenol blue (10 -5 M) in a 5.00 mM aqueous solution of sodium sulfonate is
It showed a wavelength of 643 nm and moved 15 nm bluer than water. This means that the environment in which phenol blue is incorporated into O-n-hexyl calix [6] allene-p-sulfonic acid is a more non-polar environment than water, unlike calix [6] allene-p-sulfonic acid. I found out. Examples 3 to 6 Sulfonation was carried out in the same manner as in Example 1 using calix[n]arenes of various ring numbers. The results are shown in the table below.
【表】
実施例 ７〜12
実施例２と同様の方法により実施例３〜６で得
たカリツクス［ｎ］アレン−ｐ−スルホン酸ナト
リウムを用いてアルキル化反応を行なつた。
用い溶媒は有機溶剤と水の混合比４：１の混合
溶媒を用いた。
結果を以下の表に示す。[Table] Examples 7 to 12 Alkylation reactions were carried out in the same manner as in Example 2 using sodium calix[n]arene-p-sulfonate obtained in Examples 3 to 6. The solvent used was a mixed solvent of an organic solvent and water at a mixing ratio of 4:1. The results are shown in the table below.
Claims (1)
その塩、並びにＯ−ｎ−アルキルカリキサレン−
ｐ−スルホン酸、及びその塩。 （上記式中、ｍは１〜５の整数、Ｍは水素、アン
モニウム、低級アルキルアンモニウムイオン又は
金属イオン、Ｒは水素又は炭素数１〜18のｎ−ア
ルキル基を示す。） ２ 濃度90％以上の濃硫酸中にカリキサレンを投
入し、懸濁させ、80℃以上に加熱して溶解し、反
応させることを特徴とする下記一般式（−ａ） （式中、ｍは１〜５の整数、Ｍは水素、アンモニ
ウム、低級アルキルアンモニウムイオン又は金属
イオン、Ｒは水素を示す。） で示されるカリキサレン−ｐ−スルホン酸、及び
その塩の製造方法。 ３ 水、又は水溶性有機溶剤と水との混合溶媒
中、下記一般式（−ｂ） （式中、ｍは１〜５の整数、Ｍはアンモニウム、
低級アルキルアンモニウムイオン又は金属イオ
ン、Ｒは水素を示す。） で示されるカリキサレン−ｐ−スルホン酸塩とア
ルキル化剤とを反応させることを特徴とする下記
一般式（−ｃ） （式中、ｍは１〜５の整数、Ｍは水素、アンモニ
ウム、低級アルキルアンモニウムイオン又は金属
イオン、Ｒは炭素数１〜18のｎ−アルキル基を示
す。） で示されるＯ−ｎ−アルキルカリキサレン−ｐ−
スルホン酸、及びその塩の製造方法。 ４ 濃度90％以上の濃硫酸中でカリキサレンを懸
濁させ、80℃以上に加熱して反応させ、次いで、
冷却、濾別した結晶を水に溶解し、塩を形成させ
て得たカリキサレン―ｐ−スルホン酸塩を、水、
又は水溶性有機溶剤と水との混合溶媒中、酸結合
剤の存在下、アルキル化剤と反応させることを特
徴とする下記一般式（−ｃ） （式中、ｍは１〜５の整数、Ｍは水素、アンモニ
ウム、低級アルキルアンモニウムイオン又は金属
イオン、Ｒは炭素数１〜18のｎ−アルキル基を示
す。） で示されるＯ−ｎ−アルキルカリキサレン−ｐ−
スルホン酸、及びその塩の製造方法。[Claims] 1 General formula () calixalene-p-sulfonic acid and its salts, and O-n-alkyl calixalene-
p-sulfonic acid and its salts. (In the above formula, m is an integer of 1 to 5, M is hydrogen, ammonium, lower alkylammonium ion or metal ion, and R is hydrogen or an n-alkyl group having 1 to 18 carbon atoms.) 2 Concentration 90% or more The following general formula (-a) is characterized in that calixarene is added to concentrated sulfuric acid, suspended, heated to 80°C or higher to dissolve, and react. (In the formula, m is an integer of 1 to 5, M is hydrogen, ammonium, a lower alkylammonium ion, or a metal ion, and R is hydrogen.) A method for producing calixalene-p-sulfonic acid and a salt thereof. 3 In water or a mixed solvent of a water-soluble organic solvent and water, the following general formula (-b) (In the formula, m is an integer of 1 to 5, M is ammonium,
Lower alkylammonium ion or metal ion, R represents hydrogen. ) The following general formula (-c) is characterized by reacting calixalene-p-sulfonate represented by the formula with an alkylating agent. (In the formula, m is an integer of 1 to 5, M is hydrogen, ammonium, lower alkylammonium ion or metal ion, and R is an n-alkyl group having 1 to 18 carbon atoms.) calixsalen-p-
A method for producing sulfonic acid and its salt. 4. Suspend calixalen in concentrated sulfuric acid with a concentration of 90% or higher, heat it to 80°C or higher to react, and then
The cooled and filtered crystals were dissolved in water to form a salt.
Or, the following general formula (-c) is reacted with an alkylating agent in a mixed solvent of a water-soluble organic solvent and water in the presence of an acid binder. (In the formula, m is an integer of 1 to 5, M is hydrogen, ammonium, lower alkylammonium ion or metal ion, and R is an n-alkyl group having 1 to 18 carbon atoms.) calixsalen-p-
A method for producing sulfonic acid and its salt.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20599084A JPS6183156A (en) | 1984-09-29 | 1984-09-29 | Novel calixarene derivative and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20599084A JPS6183156A (en) | 1984-09-29 | 1984-09-29 | Novel calixarene derivative and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6183156A JPS6183156A (en) | 1986-04-26 |
| JPH055825B2 true JPH055825B2 (en) | 1993-01-25 |
Family
ID=16516073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20599084A Granted JPS6183156A (en) | 1984-09-29 | 1984-09-29 | Novel calixarene derivative and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6183156A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0822827B2 (en) * | 1988-07-01 | 1996-03-06 | 豊 森田 | Calix allene derivative and method for producing the same |
| US5312837A (en) * | 1991-01-29 | 1994-05-17 | Genelabs Technologies, Inc. | Method of treating viral infections with aryl macrocyclic compounds |
-
1984
- 1984-09-29 JP JP20599084A patent/JPS6183156A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6183156A (en) | 1986-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6393735A (en) | Manufacture of (2,2)-paracyclophane and derivatives of same | |
| CA2070663C (en) | Sulfonating agent and process | |
| US2325038A (en) | Nuclear substituted triarylmethane derivatives and process of making them | |
| CN101466664B (en) | Method for preparing metallic dixhydroxybenzenedisulfonates | |
| Maas et al. | Dication disulfides by reaction of thioureas and related compounds with trifluoromethanesulfonic anhydride. The role of triflic anhydride as an oxidizing agent | |
| JPH055825B2 (en) | ||
| JPH0729993B2 (en) | Novel Calix allene derivative and method for producing the same | |
| JP2006518754A (en) | Improved process for the preparation of benzhydrylthioacetamide. | |
| JP7085654B2 (en) | N-alkylation of acridans | |
| AU2021253118A1 (en) | Process for synthesizing sulfonated triaryl methane compounds | |
| EP1282590A2 (en) | A process for the preparation of anthracycline derivatives | |
| HU182010B (en) | Novel 2,2-dimethyl-1,2-dihydro-quinoline derivatives having anti-oxidant activity | |
| JPS6372669A (en) | Novel calix arene derivative and production thereof | |
| WO1998047878A1 (en) | A process for the preparation of highly pure 6,7-dichloro-5- nitro-2,3-dihydroquinoxaline-2,3-dione | |
| RU2680090C1 (en) | 2-(4,4-diftor-1,3,5,7-tetramethyl-2,6-disulfo-4-boro-3a,4a-diaza-s-indacen-8-yl)-benzoic acid and its derivatives, method of their production and their application for fluorescent blinding of protein molecules | |
| RU2181736C2 (en) | Method of production of sulfo-substituted phthalocyanines | |
| JPH0132825B2 (en) | ||
| CN110615858B (en) | Preparation method of sodium sugammadex intermediate | |
| JPS6140661B2 (en) | ||
| KR0148718B1 (en) | Process for the preparation of stilbazium | |
| JP3924027B2 (en) | Sodium orthohydroxymandelate / phenol / water complex, process for its preparation and use for the separation of sodium orthohydroxymandelate | |
| JP2891165B2 (en) | Method for producing metabenzenedisulfonic acid | |
| JPS61210061A (en) | Manufacture of 1,4-diaminoanthraquinone-2-sulfonic acid | |
| CN115485264A (en) | Method for synthesizing triarylmethane sulfone compound | |
| JPH08208594A (en) | Production of methylsulfonylaromatic compound by methylatingarylsulfinic acid with methyl chloride |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |