JPS6183156A - Novel calixarene derivative and its preparation - Google Patents
Novel calixarene derivative and its preparationInfo
- Publication number
- JPS6183156A JPS6183156A JP20599084A JP20599084A JPS6183156A JP S6183156 A JPS6183156 A JP S6183156A JP 20599084 A JP20599084 A JP 20599084A JP 20599084 A JP20599084 A JP 20599084A JP S6183156 A JPS6183156 A JP S6183156A
- Authority
- JP
- Japan
- Prior art keywords
- water
- sulfonic acid
- salt
- calixalene
- calix
- 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 abstract description 5
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- -1 alkylammonium ion Chemical class 0.000 claims abstract description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 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
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 abstract description 2
- 230000007704 transition Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 239000000725 suspension Substances 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011734 sodium Substances 0.000 description 11
- 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
- 239000002904 solvent Substances 0.000 description 8
- 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 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 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
- 239000000243 solution Substances 0.000 description 4
- 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 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 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
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical group 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-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
- 241001164374 Calyx Species 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
- 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
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000706 filtrate Substances 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
- 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
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 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
- 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
- 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 class 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
- 239000007795 chemical reaction product Substances 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 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
- 238000007865 diluting Methods 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005185 salting out Methods 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
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000003021 water soluble solvent Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
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（
Ｉ）
（ここでｌ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）
で示すカリキサシン−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 −フルキル誘導体、及びその
製造法に係る。DETAILED DESCRIPTION OF THE INVENTION 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 (
I) Calixacin-p- (where l 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) Sulfonic acid, its ammonium or lower alkyl ammonium salts, and metal salts,
The present invention also relates to these O-n-furkyl derivatives and methods for producing the same.
°グツチェ（Ｑ ｕｔｓｃｈｅ）らは最近“カリキサレ
ン″（その形がコツプ（Ｃａｌｉｘ）に似ていることと
芳香族化合物（ａｒｅｎｅ）であることがらｃａｌｉｘ
ａｒｅｎｃ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、Ｃ００゜Ｇｕ
ｔｓｃｈｅ、 Ａｃｃ、Ｃｈｅｓ 、 Ｒｅｓ、、 １
６ 、 １６１（１９８３））。これらのカリキサシン
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。° Qutsche et al. recently discovered that ``calixalene'' (calix because its shape resembles calix and is an aromatic compound)
have reported on a series of cyclic host molecules (named C00°Gu
tsche, Acc, Ches, Res,, 1
6, 161 (1983)). These calixacins 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 a host in an aqueous solution.
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ざ、官能基の種類等
を自由に設計しうろことから、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ざるホスト化合
物になると考え、鋭意研究の結果、本発明をついに完成
するに至った。If the present inventors were to impart water solubility to the calixarene derivative, they would be able to freely design the size of the cavity as a host, the type of functional group, etc. As a result of intensive research, we finally completed the present invention.
即ち、本発明は
１）一般式（Ｉ）
で示されるカリキサレンー〇−スルホン酸、及びその塩
、並びに０−ｎ−アルキル力リキサレンーｐ〜スルホン
酸、及びその塩。That is, the present invention provides 1) calixalene--sulfonic acid represented by the general formula (I) and salts thereof, and 0-n-alkyl calixalene-p--sulfonic acid and salts thereof.
（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
キル基参示す。）
２）１１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９反応させることを特徴とする
カリキサシン−ｐ−スルホン酸、及びその塩の製造方法
。(Here, m is an integer of 1 to 5, M is hydrogen, ammonium, lower alkylammonium ion, metal ion, R is hydrogen, and n-alkyl group having 1 to 18 carbon atoms.) 2) 11 degrees or more 90% Preparation of calixacin-p-sulfonic acid and its salts, characterized in that calixalen 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 subjected to a reaction9. Method.
３）水、又は水溶性有ｍ溶剤と水との混合溶媒中、カリ
キサレンー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Ｑ−ｎ −アルキル力リキサレン
ーｐ−スルホン酸、及びその塩の製造方法。3) Q-n-alkyl lyxalene-p-sulfonic acid, which is characterized by reacting a calixalene-p-sulfonic acid salt with an alkylating agent in water or a mixed solvent of a water-soluble solvent and water; How to make that salt.
４）濃度９５％以上の濃硫酸中でカリキサレンを懸濁、
９０℃以上に加熱８反応させ、次いで冷却。4) Suspending calixalen in concentrated sulfuric acid with a concentration of 95% or more,
Heat to 90°C or higher for 8 reactions, then cool.
濾別した結晶を水に溶解し、精製、乾燥したカリキサシ
ン−ｐ−スルホン酸塩を、水、又′は水溶性有ＦＥＷ剤
と水との混合溶媒中、Ｓ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○〜ｎ−アルキル力リキ
すレンーｐ−スルホン酸、及びその塩の製造方法
に関する。The filtered crystals are dissolved in water, and the purified and dried calixacin-p-sulfonate is alkylated in water or a mixed solvent of a water-soluble FEW agent and water in the presence of an S binder. The present invention relates to a method for producing -n-alkyl-p-sulfonic acid and a salt thereof, which is characterized by reacting it with an agent.
本発明の原料であるカリキサレン（以下刃リックス［ｎ
］アレンと称す。：ｎは骨格となる芳香族環数を示す
。ンは前述した文献に記載された既知の方法で、ｐ−ｔ
ｅｒｔ−ブチルフェ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−プチルカリックス［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って得た。これらのカリック
ス［ｎ ］アレンを更に精製し、本発明のために使用し
た。Calixarene (hereinafter referred to as blade lix [n
] His name is Allen. :n indicates the number of aromatic rings forming the skeleton. The p-t
p-tert-butyl calix [n] obtained from the condensate obtained by heating ert-butylphenol, formaldehyde, and sodium hydroxide under various conditions
The 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.
以下に本発明について更に具体的に述べる。The present invention will be described in more detail below.
精製したカリックス［ｎｌ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ｇｍを適宜調整することによ
り、反応物を冷却・濾過することによって遊離のスルホ
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、カリックス［ｎ ］］アレンーｐ−スルホ
ンのバリウム塩（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
ることによりカリックス［ｎ ］］アレンーｐ−スルホ
ン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。It has been found that purified calix [nl arene can be relatively easily sulfonated regardless of the number of ring members by heating with concentrated sulfuric acid until the reactant is completely dissolved in water. Furthermore, by appropriately adjusting the sulfur gm, free sulfonic acid can be obtained as crystals by cooling and filtering the reaction product. The barium salt (calcium salt) of calix[n]]arene-p-sulfone is obtained by diluting the sulfonated product with water, neutralizing it with barium carbonate (or calcium carbonate), and filtering the barium sulfate (or calcium sulfate). Obtain an aqueous solution of To this aqueous solution, an aqueous solution of ammonium carbonate, alkylamine carbonate, alkali metal carbonate, etc. is added until no precipitate of barium (calcium) carbonate is formed, and the precipitate is filtered to obtain calix[n]]arene-p-sulfone. An aqueous solution of each salt can be obtained. Aqueous solutions of these salts are evaporated to dryness to obtain crystals of each salt.
カリックス［ｎｌアレン−ｐ−スルホン酸塩の０−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。O-alkylation of calix [nl 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.
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。For lower alkyl groups (methyl to butyl) water can be used as a solvent, but for higher alkyl groups methanol is used to dissolve the alkylating agent.
エタノール、丁ＨＦ、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０−フルキルカリックス［
０コアレンーρ−スルホンＭ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。It is preferable to use a solvent that mixes with water, such as ethanol, HF, dioxane, DMSO, and 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 generated 0-furkyl calix [
The higher the alkyl group of the 0-corerene-ρ-sulfone M salt, 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.
以下に実施例により更に具体的に述べる。This will be described in more detail below with reference to Examples.
実施例 １
カリックス［６］アレン２ｇを、９８％硫酸２０ｍ１に
懸濁し９０〜１００℃で４時間加熱攪拌した。常温まで
冷却し、析出したカリックス［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ＤＨ９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
、蒸発乾固してカリックス［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。Example 1 2 g of calix[6]arene was suspended in 20 ml of 98% sulfuric acid and heated and stirred at 90 to 100°C for 4 hours. After cooling to room temperature, precipitated calix[6]arene-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 DH9, 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%.
得られたカリックス［６］アレ゛ンー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
の有機溶媒には難溶性であった。The obtained sodium calix[6]arene-p-sulfonate was well soluble in water, but poorly soluble in alcohol and other organic solvents.
ペーパークロマト（展開溶媒 イソプロピルアルコール
：水−２：１１発色剤 ごナクリブトールエロー）で単
一スポット、元素分析による炭素対硫黄の原子比は７：
１゜Ｄ２０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、ＩＯＰＰＭ
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（Ｉ）
でｍ：３゜Ｒ：Ｈ，Ｍ：Ｎａのカリックス［６］アレン
−ｐ−スルホン酸と同定された。The atomic ratio of carbon to sulfur was determined to be 7: by single spot and elemental analysis using paper chromatography (developing solvent: isopropyl alcohol: water - 2:11 coloring agent: Nacributol yellow).
The PMR spectrum (based on DSS) at 1°D20 has a singlet of aromatic hydrogen at 7.60 PPM and 4, IOPPM.
The methylene hydrogen singlet gave peaks with an area ratio of 1:1, respectively. From this, this product has the general formula (I)
It was identified as calix[6]arene-p-sulfonic acid with m:3°R:H, M:Na.
フェノールブルーは、その極大吸収波長く水中で６６８
ｎｍ ）が溶媒の極性によって、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。Phenol blue has a maximum absorption wave of 668 in water for a long time.
nm ) is known to vary 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.
カリックス［６コアレンーｐ−スルホン酸ナトリウムの
５ｍＭの水溶液中で、フェノールブルー（ＩＯＭ）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、フェノールブルーがカリ
ックス［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。このことよりカリックス［６］アレン−〇−ス
ルホン酸は原糸より分極した（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。In a 5 mM aqueous solution of sodium calix[6-core-p-sulfonate, the maximum absorption wavelength of a solution of phenol blue (IOM) was 685 nm, which was shifted to the longer wavelength side by a whopping 27 nm. This is extremely interesting as it indicates that the environment in which phenol blue is clathrated into calix[6]arene-p-sulfonic acid is more polar than water. From this, calix[6]arene-〇-sulfonic acid was more polarized than the filament (especially positively polarized).
This shows that it has the potential to be an excellent catalyst for reactions involving intermediates or transition states.
実施例 ２
実施例 １で得られたカリックス［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（Ｄ
ＭＳＯ）２０ｍｌ、水５ｍ１゜ｎ−臭化ヘキシル４ｇ、
Ｎａ ０８１ｇと共に、９０℃で２６時間加熱した。Example 2 1 g of sodium calix[6]arene-p-sulfonate obtained in Example 1 was dissolved in dimethyl sulfoxide (D
MSO) 20ml, water 5ml 1゜n-hexyl bromide 4g,
It was heated at 90° C. for 26 hours with 081 g of Na.
冷却後、析出した結晶を濾別、メタノールで洗浄、乾燥
してＱ−ｎ −ヘキシル力リックス［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。After cooling, the precipitated crystals were separated by filtration, washed with methanol, and dried to give Qn-hexyl ryx[6]arene-p-
Crystals of sodium sulfonate were obtained in a yield of 50%.
このもののＤ２０中（ＤＳＳ基Ｑ）の４０″ＣのＮＭＲ
は次のようであった。NMR of this product at 40″C in D20 (DSS group Q)
was as follows.
δ（ＰＰＭ） プロトン比 帰 属７．５４
（Ｓ） ２ Ａｒ Ｈ４，６６（Ｓ
） ２ −０−Ｃ１−１２−３，６２（Ｂ）
２ Ａｒ ＣＨ２Ａｒ元素分析よりの
Ｃｐｓの原子比は１３：１でペーパークロマトグラフィ
ーで単一スポットであった。これらのことより、このも
のは一般式（Ｉ＞１’ ｍ ： ３． Ｒ：Ｃｂ
Ｈ＋ｉ 、 Ｍ：Ｎａの０−ｎ−へキシル力リックス［
６］アレン−ｐ−スルホン酸ナトリウムと同定された。δ (PPM) Proton ratio Attribution 7.54
(S) 2 Ar H4,66(S
) 2-0-C1-12-3,62(B)
The atomic ratio of Cps from 2Ar CH2Ar elemental analysis was 13:1, and a single spot was found by paper chromatography. From these facts, this product has the general formula (I>1'm: 3.R:Cb
H+i, M: 0-n-hexyl force lix of Na [
6] It was identified as sodium allene-p-sulfonate.
Ｑ−ｎ−へキシル力リックス［６］アレン−ｐ−スルホ
ン酸ナトリウムの５．００ｍＭの水溶液中でフェノール
ブルーの（１０−’Ｍ）の極大吸収波長は６４３ｎｍを
示し、水中より１５ｎｍ青色移動した。このことはフェ
ノールブルーが０−ｎ−へキシル力リックス［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った。In a 5.00 mM aqueous solution of sodium Qn-hexyl [6]arene-p-sulfonate, the maximum absorption wavelength of phenol blue (10-'M) was 643 nm, which shifted 15 nm blue from water. . This means that the environment in which phenol blue is incorporated into 0-n-hexyl calyx [6] allene-p-sulfonic acid is a less polar environment than water, unlike calyx [6] allene-p-sulfonic acid. It turned out to be.
実施例 ３〜６
実施例１と同様にして各環数のカソックス［ｎ］アレン
を用いてスルホン化を行なった。Examples 3 to 6 Sulfonation was performed in the same manner as in Example 1 using cassox[n]arenes of various ring numbers.
結果は以下の表に示す。The results are shown in the table below.
実施例 ｎ数 硫Ｉ！Ｉ濃度 温 度 収率（％）
（’Ｃ） （％）３ ４ ９２
９０〜１００ ８３４ ５ ＊１
８５〜９５８０５ ７ ９８ ９０〜１
００ ７５６ ８ ＊２ ８５〜９５７０
＊１ クロロスルホン酸
＊２２８％発煙硫酸
実施例 ７〜１２
実施例２と同様の力泳により実施例３〜６で得たカリッ
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った。Example n number Sulfur I! I concentration Temperature Yield (%)
('C) (%) 3 4 92
90-100 834 5 *1
85~95805 7 98 90~1
00 756 8 *2 85-9570 *1 Chlorosulfonic acid *228% fuming sulfuric acid Examples 7-12 Sodium calix[n]arene-p-sulfonate obtained in Examples 3-6 by the same force swimming as in Example 2 The alkylation reaction was carried out using
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。The solvent used was a mixed solvent of an organic solvent and water at a mixing ratio of 4:1.
結果を以下の表に示す。The results are shown in the table below.
実施例 有Ｉａ溶剤 アルキル化剤 ｎ数 収 率（％
）
７ ジオキサン Ｃ＋２ＨｚｓＢｒ ８ ５３８
エタノール Ｃ４ＨＱ Ｃ１８５１９ＴＨＦ
Ｃ１ｔＨ２３Ｂｒ ６ ５８１０ メタノール
ＣｓＨ，、Ｓｒ ６ ５０１１ メタノール Ｃ
４ＨｑＣＩ ５ ４Ｂ１２ ＊１ ジメチ
ル硫酸 ４３３＊１ 水単独溶媒Example Ia solvent Alkylating agent Number of n Yield (%
) 7 Dioxane C+2HzsBr 8 538
Ethanol C4HQ C18519THF
C1tH23Br 6 5810 Methanol
CsH,, Sr 6 5011 Methanol C
4HqCI 5 4B12 *1 Dimethyl sulfate 433*1 Water sole solvent
Claims (1)
、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９
０℃以上に加熱、溶解、反応させることを特徴とするカ
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、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９５％以上の濃硫酸中でカリキサレンを懸濁、
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、精製し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 (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (I) Calixsalene-p-sulfonic acid and its salts, and O-n-alkylcalixsalene-p -Sulfonic acid and its salts. (Here, m is an integer from 1 to 5, M is hydrogen, ammonium,
lower alkylammonium ion, metal ion; R represents hydrogen or an n-alkyl group having 1 to 18 carbon atoms; ) 2) Add and suspend calixalen in concentrated sulfuric acid with a concentration of 90% or higher, preferably 95% or higher, and heat at 80°C or higher, preferably 90°C or higher.
A method for producing calixalene-p-sulfonic acid and a salt thereof, which comprises heating to 0° C. or higher, dissolving, and reacting. 3) O-n-alkyl calixalene, which is characterized by reacting calixalene p-sulfonate and an alkylating agent in water or a mixed solvent of a water-soluble organic solvent and water.
Method for producing p-sulfonic acid and its salt. 4) Suspending calixalen in concentrated sulfuric acid with a concentration of 95% or more,
The calixalene-p-sulfonate obtained by heating and reacting at 90° C. or higher, then cooling and filtering the crystals is dissolved in water, and purified in water or a mixed solvent of a water-soluble organic solvent and water. , an alkylcalixalene-p-sulfonic acid, characterized in that it is reacted with an alkylating agent in the presence of an acid binder,
and a method for producing 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 true JPS6183156A (en) | 1986-04-26 |
| JPH055825B2 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) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0215040A (en) * | 1988-07-01 | 1990-01-18 | Yutaka Morita | Novel calixarene derivative |
| 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
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0215040A (en) * | 1988-07-01 | 1990-01-18 | Yutaka Morita | Novel calixarene derivative |
| US5312837A (en) * | 1991-01-29 | 1994-05-17 | Genelabs Technologies, Inc. | Method of treating viral infections with aryl macrocyclic compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH055825B2 (en) | 1993-01-25 |
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