JPS6399031A - Calixaren derivative - Google Patents
Calixaren derivativeInfo
- Publication number
- JPS6399031A JPS6399031A JP24486986A JP24486986A JPS6399031A JP S6399031 A JPS6399031 A JP S6399031A JP 24486986 A JP24486986 A JP 24486986A JP 24486986 A JP24486986 A JP 24486986A JP S6399031 A JPS6399031 A JP S6399031A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- formula
- liquid
- hexylcalix
- derivative
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 5
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000012074 organic phase Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000007795 chemical reaction product Substances 0.000 abstract description 3
- 238000000622 liquid--liquid extraction Methods 0.000 abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 3
- 238000000638 solvent extraction Methods 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 2
- 229930040373 Paraformaldehyde Natural products 0.000 abstract description 2
- 229920002866 paraformaldehyde Polymers 0.000 abstract description 2
- 238000010992 reflux Methods 0.000 abstract description 2
- SZWBRVPZWJYIHI-UHFFFAOYSA-N 4-n-Hexylphenol Chemical compound CCCCCCC1=CC=C(O)C=C1 SZWBRVPZWJYIHI-UHFFFAOYSA-N 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- WYICGPHECJFCBA-UHFFFAOYSA-N dioxouranium(2+) Chemical compound O=[U+2]=O WYICGPHECJFCBA-UHFFFAOYSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 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 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- -1 uranyl ions Chemical class 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 1
- NJZWLEZSGOTSHR-UHFFFAOYSA-N 3-[(2-arsonophenyl)diazenyl]-4,5-dihydroxynaphthalene-2,7-disulfonic acid Chemical compound OC1=C2C(O)=CC(S(O)(=O)=O)=CC2=CC(S(O)(=O)=O)=C1N=NC1=CC=CC=C1[As](O)(O)=O NJZWLEZSGOTSHR-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 101150016772 acoA gene Proteins 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- BBGKDYHZQOSNMU-UHFFFAOYSA-N dicyclohexano-18-crown-6 Chemical compound O1CCOCCOC2CCCCC2OCCOCCOC2CCCCC21 BBGKDYHZQOSNMU-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 1
- 125000005289 uranyl group Chemical group 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、ｐ−ｎ−ヘキシルカリックス〔６〕アレンに
関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to p-n-hexylcalix[6]arene.
（従来の技術）
Ｚｉｎｋｅらの報告（Ｂｅｒ、 ｄｔｓｃｈ、 Ｃｈｅ
ｍ、 Ｇｅｓ、 。(Prior art) Report by Zinke et al. (Ber, dtsch, Che
m, Ges, .
７４ １７２９（１９４１））は各１フ工ノール籾４体
とホルムアルデヒドから環状反応生成物を得、続いて０
ｏｒｎｆｏｒｔｈら（Ｂｒ１ｔ 、 Ｊ、 Ｐｈａｒｍ
ａｃｏＡ！、 ＊１Ｇ ７Ｂ（１９５５）
） ｓ ＫＳｍｍｅｒｅｒ ら （Ｍａｋｒｏ
ｍｏＪ。74 1729 (1941)) obtained a cyclic reaction product from four 1-phenol rice grains and formaldehyde, and then
ornforth et al. (Brlt, J., Pharm.
acoA! , *1G 7B (1955)
) s KSmmerer et al.
moJ.
（３ｈｅｍ、、１６２ １７９ （１９７２））、Ｍ
ｕｎｃｈ（Ｍａｋｒｏｍｏｊ、Ｃｈｅｍ、、１７８．６
９ （１９７７））及びＧｕｔｓｃｈｅら（Ｊ、ム
ｍ、 Ｃｈｅｍ、 ８ｏｃ、 １０８８７８２ （１９
８１’）’）等により、各皿のカリキサレン誘導体の製
造法や構造・物性についての詳細な検討がなされてきた
。(3hem,, 162 179 (1972)), M
unch (Makromoj, Chem,, 178.6
9 (1977)) and Gutsche et al.
81')') and others have conducted detailed studies on the manufacturing method, structure, and physical properties of each calixarene derivative.
これまでカリキサレン誘導体は、クラウンエーテルやシ
クロデキストリンと同じように、分子中に他のイオン、
化合物を捕捉するキャビティーを有したホスト化合物と
なる事がわかっている。これらのカリキサレン誘導体は
いずれも、水にはもちろん、有機溶剤にも難溶でかつ高
融点もしくは分解性のものであり、取り扱いが非常に困
難であった。Until now, calixsalene derivatives, like crown ethers and cyclodextrins, have been found to contain other ions,
It is known that it becomes a host compound with a cavity that traps the compound. All of these calixsalene derivatives are poorly soluble not only in water but also in organic solvents, have high melting points, or are decomposable, making them extremely difficult to handle.
特關昭５９−１２９１８号公報或いは０ａｒｌａムＪｆ
ｉｅｒｔらの論文（Ｊ、 （３ｈｅｍ、 ８ｏｃ、 （
３ｈｅｍ、Ｏｏｍｍｕｎ。Special Publication No. 59-12918 or Oarlam Jf
Iert et al.'s paper (J, (3hem, 8oc, (
3hem, Oommun.
１９８８．１０７５〜１０７７ ）には本発明のカリ
キサレン誌４体と類似のカリキサレン誘導体の提案があ
るが、金属吸着能等についでは全く判明されていす、仮
に性能の評価がなされていたとしても、十分な性能を有
するものではない頃がその１１造より予想される。1988.1075-1077) proposes calixalene derivatives similar to the four calixalene derivatives of the present invention, but their metal adsorption ability has not been fully clarified, and even if the performance had been evaluated, it would not be sufficient. Based on the 11th model, it is expected that it will not have such high performance.
（発明が解決しようとする問題点）
本発明者らは、カリキサレン誘導体がウラニルイオンに
対して良好なホストとなる小、有８Ａ溶剤溶解性を有す
る小、及び低融点である事を目標として、鋭意検討の結
果、本発明を完成するに至った。(Problems to be Solved by the Invention) The present inventors aim for the calixarene derivative to be a good host for uranyl ions, to have a small size that has solubility in 8A solvents, and a low melting point. As a result of intensive studies, we have completed the present invention.
本発明の目的はウラニルイオンに対してすぐれたホスト
・ゲスト錯体形成能を有しかつ、水不溶性かつ油溶性て
低融点の新規なカリキサレン誘導体を提案するにある。The object of the present invention is to propose a novel calixarene derivative which has an excellent ability to form a host-guest complex with uranyl ions, is water-insoluble and oil-soluble, and has a low melting point.
（ｒ：ｆｉ題点を解決する為の手段）
本発明は下記（１）式で示すｐ−ｎ−ヘキシルカリック
ス〔６〕アレンである。(Means for solving the r:fi problem) The present invention is pn-hexylcalix[6]arene represented by the following formula (1).
本発明のカリキサレン誘導体は白色結晶であり、窒素中
での融点は８０５〜８０６°Ｃである。又ＩＲスペクト
ル（ＫＢ、錠剤法）は８１５０ ｃｍ−”にムｒ −Ｏ
ＨのシＱ−Ｈ１２９２０ｃｍ−１に一０Ｈ２−のν。、
２８５０ ｃｍ に−（３Ｈｚ−のν＠ ｓ１４ＢＯ
ｃｍ−’にムｒの’０＝ｃｓ １２８０ ｃｍ にＡ
ｒ−ＯＨのν。−８の吸収を有する。The calixsalene derivative of the present invention is a white crystal and has a melting point in nitrogen of 805-806°C. Also, the IR spectrum (KB, tablet method) is at 8150 cm-''.
H's Q-H12920cm-1 and ν of -0H2-. ,
2850 cm -(3Hz-ν@s14BO
cm-' to '0=cs 1280 cm to A
ν of r-OH. It has an absorption of -8.
ＮＭＲ分析（ＣＤ（Ｉｓ溶剤、ＴＭ８内部標準）では但
し、ｓ：１本、ｍ：多数の***スペクトルを示す。However, in NMR analysis (CD (Is solvent, TM8 internal standard)), s: one line, m: many split spectra are shown.
（実施例） 以下に実施例を示して、本発明を更に詳細に説明する。(Example) The present invention will be explained in more detail by showing examples below.
実施例−１
ｐ −Ｈ−ヘキシルフェノール４４．７５ｇと８０％パ
ラホルムアルデヒド１８．８０ｇをｐ−キシレン８５０
ｍＪに５Ｎ−ＫＯＨ２０ｍ ｌと共に溶解し、窒素気流
中１６時間加熱還流させた。反応後、反応液を減圧濃縮
し、１１縮物を塩化メチレンに溶解し、希塩酸を加えて
液々抽出により有機相へ反応生成物を抽出した。Example-1 44.75 g of p-H-hexylphenol and 18.80 g of 80% paraformaldehyde were mixed with 850 g of p-xylene.
mJ with 20 ml of 5N-KOH and heated under reflux for 16 hours in a nitrogen stream. After the reaction, the reaction solution was concentrated under reduced pressure, the 11-condensate was dissolved in methylene chloride, diluted hydrochloric acid was added, and the reaction product was extracted into the organic phase by liquid-liquid extraction.
有機相は、純水で洗浄後、脱水乾燥させ、減圧ａ縮した
。石油エーテルに沈澱した結晶を、塩化メチレン−石油
エーテルにより再結晶・精製し１８．０７ｇの白色結晶
を得た。The organic phase was washed with pure water, dehydrated and dried, and compressed under reduced pressure. The crystals precipitated in petroleum ether were recrystallized and purified using methylene chloride-petroleum ether to obtain 18.07 g of white crystals.
得られた結晶を第１表〜第４表に示すエル分析、ＮＭＲ
分析、元素分析の結果、前述した中成で示されるｐ−ｎ
−ヘキシルカリックス〔６〕アレンである拳がわかった
。The obtained crystals were subjected to El analysis and NMR as shown in Tables 1 to 4.
As a result of the analysis and elemental analysis, the p-n indicated by the above-mentioned intermediate
-Hexylcalix [6] I found the fist that was Allen.
第１表 エル分析績果 但しムｒは芳香環を示す。Table 1 El analysis results However, MU r indicates an aromatic ring.
第２表
第８表
元 素 分 析 結 果
但し計算値はｐ−ｎ−ヘキシルカリックス（６Ｊアレン
とした場合。Table 2 Table 8 Element Analysis Results However, the calculated values are p-n-hexyl calix (6J allene).
本発明のカリキサレン誘導体は、特異なウラン吸着性を
有する。ホウ酸にてｐ Ｈ８，１又は１０．０に調整し
た水中にＵＯ２（ＯＨ８０００） ２を１０ｐ’ｐｍ溶
解した水溶液を上記本発明のカリキサレンを２．Ｉ Ｘ
１０−８Ｍの濃度で溶解した０−ジクロルベンゼン溶
液と８０℃、２４時間接触させ、液々抽出した。The calixarene derivative of the present invention has unique uranium adsorption properties. An aqueous solution containing 10 p'pm of UO2(OH8000)2 dissolved in water adjusted to pH 8.1 or 10.0 with boric acid was mixed with the above calixarene of the present invention. IX
It was brought into contact with a solution of 0-dichlorobenzene dissolved at a concentration of 10 −8 M at 80° C. for 24 hours, and liquid-liquid extraction was performed.
対照としてジシクロヘキシル１８−クラウン−６を用い
て同様の抽出テストを行った。A similar extraction test was performed using dicyclohexyl 18-crown-6 as a control.
水相中のＴＪＯ２２＋イオンをアルセナゾＩで常法によ
り分析する事により、ＵＯ２２＋イオンの有機相への抽
出率を決定した、結果を第４表に示すが％ ｐＨ８，１
では全く抽出されず、ｐＨ１０，０では対照として用い
たクラウンエーテルよりも１０倍以上大きい抽出率を示
した。The extraction rate of UO22+ ions into the organic phase was determined by analyzing TJO22+ ions in the aqueous phase using Arsenazo I using a conventional method.The results are shown in Table 4.% pH8.1
At pH 10.0, the extraction rate was more than 10 times higher than that of crown ether used as a control.
第 ４ 表Table 4
Claims (1)
ス〔６〕アレン。 ▲数式、化学式、表等があります▼・・・・・・（ I
）(1) p-n-hexylcalix[6]arene represented by the following formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・・・・( I
)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24486986A JPS6399031A (en) | 1986-10-14 | 1986-10-14 | Calixaren derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24486986A JPS6399031A (en) | 1986-10-14 | 1986-10-14 | Calixaren derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6399031A true JPS6399031A (en) | 1988-04-30 |
Family
ID=17125205
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24486986A Pending JPS6399031A (en) | 1986-10-14 | 1986-10-14 | Calixaren derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6399031A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049467A (en) * | 1989-01-30 | 1991-09-17 | Orient Chemical Industries, Ltd. | Toner for use in the development of electrostatic latent images |
| US5318883A (en) * | 1991-05-23 | 1994-06-07 | Orient Chemical Industries, Ltd. | Charge control agent and tower for developing electrostatic images |
-
1986
- 1986-10-14 JP JP24486986A patent/JPS6399031A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5049467A (en) * | 1989-01-30 | 1991-09-17 | Orient Chemical Industries, Ltd. | Toner for use in the development of electrostatic latent images |
| US5318883A (en) * | 1991-05-23 | 1994-06-07 | Orient Chemical Industries, Ltd. | Charge control agent and tower for developing electrostatic images |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Brown et al. | 2, 6-Di-Butylpyridine—An Unusual Pyridine Base | |
| Chen et al. | The synthesis of new binucleating polyaza macrocyclic and macrobicyclic ligands: dioxygen affinities of the cobalt complexes | |
| Campbell et al. | The structure of gossypol. I | |
| Buckingham et al. | Labile (sulfonato) pentaamminecobalt (III) complexes: synthesis and kinetics and mechanism of acid and base hydrolysis | |
| Reepmeyer et al. | Isolation of salicylsalicylic acid, acetylsalicylsalicylic acid, and acetylsalicylic anhydride from aspirin tablets by extraction and high‐pressure liquid chromatography | |
| DE3781574T2 (en) | CALIXAREN DERIVATIVES AND THE USE OF THESE COMPOUNDS FOR SEQUESTING METALS. | |
| WO1994017018A1 (en) | Thermally stable fullerene derivates and process for producing the same | |
| CN111518229A (en) | Method for removing element impurities and pigments in refined sugammadex sodium product | |
| JPS6399031A (en) | Calixaren derivative | |
| Baker et al. | ACHROMYCIN. 1 SYNTHETIC STUDIES. III. SYNTHESIS OF 3-AMINO-D-RIBOSE, A HYDROLYTIC PRODUCT | |
| Malek et al. | Potentially Heptadentate Ligands Derived from Tris (2-aminoethyl) amine (tren) | |
| Greenhill | Aromatic enaminones. Part 1. Ultraviolet absorption of N-aryl enaminones derived from dimedone | |
| CN112010825A (en) | Pamifixib impurity reference substance and preparation method thereof | |
| CN114349672A (en) | Sulfydryl chlorothalonil and synthesis method, purification method and application thereof | |
| CH678054A5 (en) | METHOD FOR PRODUCING tertiary amine SULPHUR trioxide COMPLEX. | |
| Cohen et al. | The Role of the Solvent in Radical Decomposition Reactions: p-Nitrophenylazotris-(p-anisyl)-methane | |
| JPH078818B2 (en) | Calixarene derivative | |
| JPS63197544A (en) | Adsorbent of uranium | |
| DE806457C (en) | Process for the preparation of pteroic acid or pteroic acid derivatives, in particular pteroylglutamic acid (folic acid) | |
| CN113135949B (en) | Tetraphenylethylene borate derivative hypochlorite fluorescent probe | |
| CN109503426B (en) | Method for purifying alpha- (o-chloroanilino) methine-beta-formamido propionitrile | |
| SU334806A1 (en) | The method of obtaining 3-hydroxymethyl | |
| JPH02124863A (en) | P-arylazocalix(n)arene, production thereof and method for extracting silver ion | |
| JPS6128646B2 (en) | ||
| SU1691292A1 (en) | Method for obtaining hydrochloric acid |