JPH0399084A - Separating agent for organic compound - Google Patents
Separating agent for organic compoundInfo
- Publication number
- JPH0399084A JPH0399084A JP23485089A JP23485089A JPH0399084A JP H0399084 A JPH0399084 A JP H0399084A JP 23485089 A JP23485089 A JP 23485089A JP 23485089 A JP23485089 A JP 23485089A JP H0399084 A JPH0399084 A JP H0399084A
- Authority
- JP
- Japan
- Prior art keywords
- organic compound
- malonamide
- benzene
- complex
- metal complex
- 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
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 40
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 120
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 39
- WRIRWRKPLXCTFD-UHFFFAOYSA-N malonamide Chemical class NC(=O)CC(N)=O WRIRWRKPLXCTFD-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000203 mixture Substances 0.000 claims abstract description 37
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 22
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008096 xylene Substances 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 abstract description 18
- -1 Cu<2+> Chemical class 0.000 abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002904 solvent Substances 0.000 abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 238000001953 recrystallisation Methods 0.000 abstract description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 2
- 150000004820 halides Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract 4
- 238000000605 extraction Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 19
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 12
- 238000000113 differential scanning calorimetry Methods 0.000 description 9
- 238000002411 thermogravimetry Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- OBZHMICJQVRDOF-UHFFFAOYSA-N n,n'-di(quinolin-8-yl)propanediamide Chemical compound C1=CN=C2C(NC(CC(=O)NC=3C4=NC=CC=C4C=CC=3)=O)=CC=CC2=C1 OBZHMICJQVRDOF-UHFFFAOYSA-N 0.000 description 8
- 230000004580 weight loss Effects 0.000 description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- PYKSXWASTAWCSS-UHFFFAOYSA-N 2-(cyclohexylmethyl)propanedioic acid Chemical compound OC(=O)C(C(O)=O)CC1CCCCC1 PYKSXWASTAWCSS-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- WYEHGLSPWYCMOF-UHFFFAOYSA-N diethyl 2-(cyclohexylmethyl)propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)CC1CCCCC1 WYEHGLSPWYCMOF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 1
- 101100481028 Arabidopsis thaliana TGA2 gene Proteins 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000748023 Dimeresia howellii Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- UUWSLBWDFJMSFP-UHFFFAOYSA-N bromomethylcyclohexane Chemical compound BrCC1CCCCC1 UUWSLBWDFJMSFP-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 150000004699 copper complex Chemical class 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
[技術分野]
本発明は、ベンゼン、トルエン、キシレン等を有する有
機液体からこれらの有機化合物を選択的に分離する包接
化合物に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to clathrate compounds that selectively separate organic compounds from organic liquids containing benzene, toluene, xylene, etc.
[従来技術]
例えば、ベンゼンの沸点は80〜81℃で、シクロヘキ
サンとほぼ等しく、又エタノールの沸点とも近似してお
り、ベンゼンをこれらの混合物から蒸留によって分離す
ることは極めて困難である。また、o −, m −,
p−キシレンの構造異性体からの蒸留法による分離
も容易ではない。[Prior Art] For example, the boiling point of benzene is 80 to 81° C., which is approximately the same as that of cyclohexane and also close to the boiling point of ethanol, and it is extremely difficult to separate benzene from a mixture of these by distillation. Also, o −, m −,
Separation of p-xylene from structural isomers by distillation is also not easy.
以上の例のように、従来技術では、共沸混合物や近沸点
混合物、さらに構造異性体含有混合物からある特定の化
合物を選択的に分離するのに困難を伴ってきた。As shown in the above examples, in the prior art, it has been difficult to selectively separate a specific compound from an azeotropic mixture, a near-boiling point mixture, or a mixture containing structural isomers.
[目 的]
本発明はベンゼン、トルエン、キシレン等の単独又は混
合有機液体からこれらの有機化合物を選択的に分離する
ための新しい方法を提供することを目的とする。[Objective] The object of the present invention is to provide a new method for selectively separating benzene, toluene, xylene, and other organic compounds from single or mixed organic liquids.
[構 或]
本発明者らは、前記目的を達威すべく鋭意研究を重ねた
結果、マロンアミド誘導体の金属錯体がいくつかの有機
化合物と高選択的に反応して包接組成物を形成すること
を見出すとともに、この原理を用いることにより、有機
化合物そのものの分離精製を達戊し得るばかりでなく、
繰返し該マロンアミド誘導体の金属錯体を用いることが
できることを見出し、本発明を完或するに致った。[Structure] As a result of extensive research to achieve the above object, the present inventors have discovered that a metal complex of a malonamide derivative reacts with several organic compounds in a highly selective manner to form an inclusion composition. By discovering this and using this principle, it is not only possible to separate and purify organic compounds themselves, but also to
It was discovered that the metal complex of the malonamide derivative can be repeatedly used, and the present invention was completed.
即ち、本発明によれば、ベンゼン、トルエン、キシレン
等の単独又は混合有機液体を、一般式(式中、Rl,R
!は水素原子、アルキル基、アルアルキル基、又はアリ
ール基 y1 2+.はC u *+N i ”, C
o ”, Z n ”, P d ”,等はアル
キル基、の二価重金属イオンを示す)
で表されるマロンアミド誘導体の金属錯体と接触させ、
該有機化合物を、該マロンアミド誘導体の金属錯体に包
接させることを特徴とするベンゼン、トルエン、キシレ
ン等の分離方法が提供される。That is, according to the present invention, organic liquids such as benzene, toluene, xylene, etc. alone or in combination with the general formula (where Rl, R
! is a hydrogen atom, an alkyl group, an aralkyl group, or an aryl group y1 2+. is C u *+N i ”, C
o ”, Z n ”, P d ”, etc. are alkyl groups, and represent divalent heavy metal ions).
A method for separating benzene, toluene, xylene, etc. is provided, which is characterized by including the organic compound in the metal complex of the malonamide derivative.
前記マロンアミド誘導体の金属錯体ベンゼン、トルエン
、キシレン等の有機化合物が包接され、包接組底物を形
戒することは従来全く知られておらず、本発明は、この
現象を利用することにより、ベンゼン、トルエン、キシ
レン等の単独、又は混合液体から一旦これらの包接組成
物を単離し、分離しようとするものである。It has not been previously known that organic compounds such as benzene, toluene, and xylene are clathrated into metal complexes of the malonamide derivatives to form clathrate complexes, and the present invention utilizes this phenomenon. , benzene, toluene, xylene, etc. alone or in a mixed liquid to isolate and separate these clathrate compositions.
以下、本発明について詳述する。The present invention will be explained in detail below.
Rl,R2として種々の置換基をもつマロンアミドは既
に特許出願中(特願昭63− 25043)であるジプ
チル N,N’−ビス(8−キノリル)マロンアミド製
造方法に準じて製造した。Malonamides having various substituents as R1 and R2 were produced according to the method for producing diptyl N,N'-bis(8-quinolyl)malonamide, which is already patent pending (Japanese Patent Application No. 63-25043).
本発明のマロンアミド誘導体の金属錯体は前記一般式(
1)で表されるマロンアミド誘導体と二価重金属イオン
の1:1錯体であり、種々の製造法によって得ることが
できる。最も一般的にはマロンアミド誘導体と金属イオ
ンのハロゲン化物や酢酸塩とを反応させることにより容
易に高収率で得ることができる。The metal complex of the malonamide derivative of the present invention has the general formula (
It is a 1:1 complex of a malonamide derivative represented by 1) and a divalent heavy metal ion, and can be obtained by various production methods. Most commonly, it can be easily obtained in high yield by reacting a malonamide derivative with a halide or acetate of a metal ion.
この反応を行う場合、反応温度は0℃〜100℃、好ま
しくは20〜80℃であり、反応媒体としては上記マロ
ンアミド誘導体と金属塩をわずかでも溶解し、それらに
不活性な溶媒であれば、任意の溶媒が使用可能であり、
このようなものには例えば、エタノール、メタノール、
クロロホルム、ジオキサン、テトラヒド口フラン、ジメ
チルホルムアミドなどがあるが、特に、エタノール等の
アルコール類が好適である。得られた反応生底物は溶媒
留去後クロロホルムやベンゼンで抽出し再結晶法により
精製できる。When carrying out this reaction, the reaction temperature is 0°C to 100°C, preferably 20 to 80°C, and the reaction medium may be a solvent that dissolves even a small amount of the above malonamide derivative and metal salt and is inert to them. Any solvent can be used;
Examples of such substances include ethanol, methanol,
Examples include chloroform, dioxane, tetrahydrofuran, dimethylformamide, and alcohols such as ethanol are particularly preferred. The obtained reaction raw material can be purified by distilling off the solvent, extracting it with chloroform or benzene, and recrystallizing it.
本発明において、前記一般式(1)のマロンアミド誘導
体の金属錯体と有機化合物との包接組成物を得るには、
種々の方法が適用される。例えば有機化合物中に前記マ
ロンアミド誘導体の金属錯体を添加しても良いし、また
包接化を完全に行わしめるために上記のようにマロンア
ミド誘導体の金属錯体を添加して得られる混合物を加熱
し、完全に溶解した溶液とし、これを冷却して生じた結
晶を分離することによっても得られる。いずれの方法に
よっても容易にマロンアミド誘導体の金属錯体にベンゼ
ン等の有機化合物が包接した包接組成物を得ることがで
きる。被包接戊分/マロンアミド誘導体のモル比は金属
イオンや置換基の種類により整数比で変化する。In the present invention, to obtain an inclusion composition of a metal complex of a malonamide derivative of the general formula (1) and an organic compound,
Various methods are applied. For example, the metal complex of the malonamide derivative may be added to the organic compound, or the mixture obtained by adding the metal complex of the malonamide derivative as described above may be heated in order to complete the clathration. It can also be obtained by preparing a completely dissolved solution, cooling the solution, and separating the resulting crystals. By either method, an inclusion composition in which an organic compound such as benzene is included in a metal complex of a malonamide derivative can be easily obtained. The molar ratio of the clathrate/malonamide derivative changes in an integer ratio depending on the metal ion and the type of substituent.
前記一般式(1)のマロンアミド誘導体の金属錯体の使
用量は、有機液体中の被包接戊分1モル当り、10−4
〜100モル、好ましくは104〜lOモルの割合が有
利である。The amount of the metal complex of the malonamide derivative of the general formula (1) used is 10-4 per mole of encapsulated fraction in the organic liquid.
Advantageous proportions are from 10 to 100 mol, preferably from 10 to 10 mol.
前述のようにしてマロンアミド誘導体の金属錯体にベン
ゼン等の有機化合物を包接させる場合、一般に−50〜
120℃、好ましくは0〜80℃の範囲の温度で行われ
る。かくして形成された包接組成物を、それを含有する
混合物から分離するには、通常、固液分離(例えば濾過
、遠心分離、沈降等)によるか或いは溶液成分を蒸留に
より蒸発除去する方法が好ましく利用できる。いずれの
方法であってもその操作温度は−50〜120℃、好ま
しくは0〜80℃の範囲が望ましい。When an organic compound such as benzene is included in a metal complex of a malonamide derivative as described above, generally -50 to
It is carried out at a temperature of 120°C, preferably in the range from 0 to 80°C. In order to separate the clathrate composition thus formed from the mixture containing it, it is usually preferable to use solid-liquid separation (for example, filtration, centrifugation, sedimentation, etc.) or to remove solution components by evaporation by distillation. Available. In either method, the operating temperature is preferably in the range of -50 to 120°C, preferably 0 to 80°C.
本発明における被包接有機化合物としては、ベンゼン、
トルエン、キシレン等を含有しているものであればよく
、被包接有機化合物以外の戊分として包接化を阻害した
り、生成した包接組成物から被包接有機化合物を容易に
脱離したりしないものであればよく、特に、包接組或物
を容易に溶解したりしないものが好適である。被包接有
機化合物含有混合物として、n−ヘキサン、シクロヘキ
サン、メチルシクロヘキサン、クロロホルム等の包接さ
れない有機化合物から選択的に包接絹成物を分離するこ
とができる。Examples of the clathrate organic compound in the present invention include benzene,
It is sufficient that it contains toluene, xylene, etc., and can inhibit inclusion as a component other than the clathrated organic compound, or easily remove the clathrated organic compound from the generated clathrate composition. Any material may be used as long as it does not dissolve the clathrate, and in particular, one that does not easily dissolve the inclusion complex is preferred. As a mixture containing clathrated organic compounds, the clathrated silk composition can be selectively separated from non-clathrated organic compounds such as n-hexane, cyclohexane, methylcyclohexane, and chloroform.
また,0−+ m + p−キシレンを含む有機溶
媒から、m−キンレンを選択的に包接する等の構造異性
体の分離も行なうことができる。It is also possible to separate structural isomers by selectively including m-kylene from an organic solvent containing 0-+ m + p-xylene.
本発明におけるマロンアミド誘導体の金属錯体はその機
能もさることながら、まず安価に合成できること、経済
的なプロセスを自由に選択しうろことなどの有利な点を
有している。また、マロンアミド誘導体の金属錯体と有
機化合物との包接組成物は、種々の方法により容易に包
接された有機化合物を脱着させることができ、純粋な選
択的な有機化合物の分離を行うことができる。The metal complex of the malonamide derivative of the present invention has advantages such as not only its function but also the fact that it can be synthesized at a low cost and that an economical process can be freely selected. In addition, in the inclusion composition of a metal complex of a malonamide derivative and an organic compound, the clathrated organic compound can be easily desorbed by various methods, and pure and selective separation of the organic compound can be performed. can.
本発明においてマロンアミド誘導体の金属錯体と有機化
合物との包接組威物から有機化合物を分離する場合には
、柿々の方法が採用されるが、例えば、(a)包接組成
物を、常圧で80〜250℃、好ましくは120−15
0℃の範囲の温度に加熱するが減圧下、40〜250℃
、好ましくは60〜150℃の範囲の温度に加熱して被
包接有機化合物を分離する方法、(b)包接組戊物に例
えば、良溶媒であるクロロホルム、アセトン等の溶媒を
接触させて被包接有機化合物を分離する方法等が有利に
適用される。In the present invention, when an organic compound is separated from a clathrate composition of a metal complex of a malonamide derivative and an organic compound, the method of Kakinata is adopted. 80-250℃ at pressure, preferably 120-15
Heat to a temperature in the range of 0°C but under reduced pressure, 40-250°C
(b) A method of separating the clathrate organic compound by heating preferably to a temperature in the range of 60 to 150°C; (b) contacting the clathrate with a good solvent such as chloroform or acetone; A method of separating clathrated organic compounds is advantageously applied.
以下、本発明を実施例によりさらに詳細に説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
[実施例コ
(1)ベンジル、シクロヘキシルメチル、N,N’(8
−キノリル)マロンアミド(一般式(1)においてR1
=ベンジル、R2=シクロへキシルメチル、R8=8−
キノリル)の製造
既にマロンアミド誘導体の製造方法は 特願昭63−2
5043に示しているが、新規化合物の一例として上記
の化合物の製造方法を示す。[Example (1) Benzyl, cyclohexylmethyl, N,N'(8
-quinolyl) malonamide (R1 in general formula (1)
=benzyl, R2=cyclohexylmethyl, R8=8-
The method for producing malonamide derivatives (quinolyl) has already been disclosed in patent application 1986-2.
5043, a method for producing the above compound is shown as an example of a new compound.
80g (50ミリモル)のマロン酸ジエチルと1.2
g(50ミリモル)のNaHとをTHF中加熱還流1,
た後、8.9g (50ミリモル)のシクロヘキシルメ
チルブロミドを加え一昼夜還流する。その後、THFを
留去し、ベンゼンで抽出しベンゼン相を水洗した後無水
硫酸マグネシウムで乾燥する。ベンゼンを留去後残留物
を124℃/2mmHgで減圧蒸留することにより、8
6%のシクロヘキシルメチルマロン酸ジエチルを得た。80 g (50 mmol) diethyl malonate and 1.2
g (50 mmol) of NaH in THF at reflux 1,
After that, 8.9 g (50 mmol) of cyclohexylmethyl bromide was added and the mixture was refluxed overnight. Thereafter, THF is distilled off, extracted with benzene, the benzene phase is washed with water, and then dried over anhydrous magnesium sulfate. After distilling off benzene, the residue was distilled under reduced pressure at 124°C/2 mmHg to obtain 8
6% diethyl cyclohexylmethylmalonate was obtained.
シクロヘキシルメチルマロン酸ジエチル4g(25ミリ
モル)をTHFに溶解し0.6g (25ミリモル)の
NaHを加え2時間還流後4Jg(25ミリモル)のペ
ンジルブロミドを加え一昼夜還流する。4 g (25 mmol) of diethyl cyclohexylmethylmalonate was dissolved in THF, 0.6 g (25 mmol) of NaH was added, and the mixture was refluxed for 2 hours, and then 4 Jg (25 mmol) of pendyl bromide was added and refluxed overnight.
上記と同様の後処理をしたのち、161℃/ 0 .
2mmHgで減圧蒸留し、79%の収率でペンジルシク
口ヘキシルメチル、マロン酸ジエチルを得、た。After the same post-treatment as above, the temperature was 161℃/0.
Distillation was carried out under reduced pressure at 2 mmHg to obtain hexylmethyl penzylchloride and diethyl malonate in a yield of 79%.
ベンジル、シクロヘキシルメチルマロン酸ジエチル3.
5g (10ミリモル)をエタノールー水(3:1)の
混合溶媒中3等量の水酸化ナトリウムを加え一昼夜還流
する。溶媒留去後、水に溶解し、水冷下濃塩酸を滴下し
、白色沈澱物を得た。白色沈澱物を濾過後減圧乾燥し、
シクロヘキサンにより再結晶することにより25g (
86%)のベンジル、シクロヘキシルメチルマロン酸を
得た。Benzyl, diethyl cyclohexylmethylmalonate3.
5 g (10 mmol) was added to 3 equivalents of sodium hydroxide in a mixed solvent of ethanol and water (3:1), and the mixture was refluxed overnight. After evaporating the solvent, it was dissolved in water, and concentrated hydrochloric acid was added dropwise while cooling with water to obtain a white precipitate. The white precipitate was filtered and dried under reduced pressure.
By recrystallizing with cyclohexane, 25 g (
86%) of benzyl, cyclohexylmethylmalonic acid was obtained.
ベンジル、シクロヘキシルメチルマロン酸1.5g(5
ミリモル)に5ml塩化チオニルを加え3時間還流する
。過剰の塩化チオニル留去後、20mlベンゼン溶液と
し、1.5g (10ミリモル)の8−アミノキノリン
とIg(10ミリモル)のトリエチルアミンを加え5時
間還流する。反応後ベンゼン相を水でよく洗浄し、ベン
ゼン相を無水硫酸マグネシウムで乾燥する。ベンゼンを
減圧留去後、残留物をカラムクロマト(シリカゲル、ク
ロロホルム)により未反応物や副生戊物を除いた後、シ
クロヘキサン溶液から再結晶することによって1.7g
(63%)のベンジル、シクロヘキシルメチルN,N’
−ビス(8−キノリル)マロンアミドを得た。Benzyl, cyclohexylmethylmalonic acid 1.5g (5
5 ml of thionyl chloride was added to the mixture (mmol) and refluxed for 3 hours. After distilling off excess thionyl chloride, the mixture was made into a 20 ml benzene solution, 1.5 g (10 mmol) of 8-aminoquinoline and Ig (10 mmol) of triethylamine were added, and the mixture was refluxed for 5 hours. After the reaction, the benzene phase is thoroughly washed with water, and the benzene phase is dried over anhydrous magnesium sulfate. After distilling off benzene under reduced pressure, the residue was subjected to column chromatography (silica gel, chloroform) to remove unreacted substances and by-products, and then recrystallized from a cyclohexane solution to give 1.7 g.
(63%) of benzyl, cyclohexylmethyl N,N'
-bis(8-quinolyl)malonamide was obtained.
質量分析二計算値542.26789 (CsgHm4
N40J ,実測値542.2663 I R (KB
r) : 33g0, 3320. 3250(NH
) , 1680 (C=O)。Mass spectrometry calculation value 542.26789 (CsgHm4
N40J, actual value 542.2663 I R (KB
r): 33g0, 3320. 3250 (NH
), 1680 (C=O).
(B)N,N’−ビス(8−キノリル)マロンアミド誘
導体の金属錯体の製造
(1)ジベンジルN,N’−ビス(8−キノリル)マロ
ンアミドの銅(II)錯体
ジベンジルN,N’−ビス(8−キノリル)マロンアミ
ド0.54g (1.0ミリモル)を50mlのエタノ
ールに溶解し、0.6gのCu(OAC)1H20を加
え一昼夜加熱還流する。エタノール留去後クロロホルム
を加え不溶の銅塩を濾別し3回水洗した後無水硫酸マグ
ネシウムで乾燥する。クロロホルム留去後、得られた黄
複色の個体をベンゼンで再結晶し、100℃5時間真空
乾燥することにより051g(85%)の当該マロンア
ミドとCu (II)の1二1錯体を得た。I R :
1600cm−I(C=O)融点〉250℃。(B) Production of metal complex of N,N'-bis(8-quinolyl)malonamide derivative (1) Copper(II) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide dibenzyl N,N'-bis 0.54 g (1.0 mmol) of (8-quinolyl)malonamide was dissolved in 50 ml of ethanol, 0.6 g of Cu(OAC)1H20 was added, and the mixture was heated under reflux overnight. After distilling off the ethanol, chloroform is added and insoluble copper salts are filtered off, washed with water three times, and then dried over anhydrous magnesium sulfate. After chloroform was distilled off, the obtained yellow solid was recrystallized from benzene and vacuum-dried at 100°C for 5 hours to obtain 051 g (85%) of the 121 complex of the malonamide and Cu (II). . IR:
1600cm-I (C=O) Melting point>250°C.
(2)ジベンジルN,N’−ビス(8−キノリル)マロ
ンアミドのニッケル(n)錯体
前記(B) 一(1)と同様にして3当量過剰のNj
(OAc).−4H.0と反応させることにより83
%の当該マロンアミドとNi(II)の1:1錯体を得
た。I R : 1605cm−’ (C=O)融点〉
250℃、”H NMR (C D C I a,pp
m) : 3.50(4H, singlet,
CH.) , 6.5 〜7.6 (18H,mult
iplet,芳香環) 8.10 (2H, doub
let,芳香環) 8.90 (2H, double
t,芳香環)。(2) Nickel (n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide In the same manner as in the above (B) 1 (1), 3 equivalents of excess Nj
(OAc). -4H. 83 by reacting with 0
% of the malonamide and Ni(II) were obtained. IR: 1605cm-' (C=O) melting point>
250°C, "H NMR (CDCI a,pp
m): 3.50 (4H, singlet,
CH. ), 6.5 ~ 7.6 (18H, mult
iplet, aromatic ring) 8.10 (2H, doub
let, aromatic ring) 8.90 (2H, double
t, aromatic ring).
(3)ベンジル、シクロヘキシルメチルN,N’一ビス
(8−キノリル)マロンアミドのi (II)錯体(1
)と同様にして0.60g (1 ミリモル)の当該マ
ロンアミドと0.6gのCu (OAc) ・H.O
と反応させることにより、0.51g (80%)の
当該マロンアミドとCu(II)のl;1錯体を得た。(3) i (II) complex of benzyl, cyclohexylmethyl N,N'-bis(8-quinolyl)malonamide (1
), 0.60 g (1 mmol) of the malonamide and 0.6 g of Cu (OAc) .H. O
By reacting with Cu(II), 0.51 g (80%) of the 1;1 complex of the malonamide and Cu(II) was obtained.
IR : 1 6 1 0 cm” (C=0)
,融点230〜232℃
(4)ベンジル、シクロヘキシルメチル N, N’一
ビス(8−キノリル)マロンアミドのニッケル(ff)
錯体
(1)と同様にして0.60g (1 ミリモル)の当
該マロンアミドと0.8gのN i (OAc) 1
4H*Oと反応させることにより、0.45g (75
%)の当該マロンアミドとNt(II)の1:1錯体を
得た。IR: 1610 cm” (C=0)
, melting point 230-232℃ (4) Nickel (ff) of benzyl, cyclohexylmethyl N, N'-bis(8-quinolyl)malonamide
Similarly to complex (1), 0.60 g (1 mmol) of the malonamide and 0.8 g of N i (OAc) 1
By reacting with 4H*O, 0.45g (75
%) of the malonamide and Nt(II) were obtained.
IR: 1610cm−’ (C=O)融点
237 〜240℃。’HNMR (CDC ls,p
pm): 1.0 〜1.7 (IIH, m, cy
lnhexyl) 2.22 (2 H,d,cH2)
3.23 (2H,S,CH2),6.7〜7.7 (
13H,m,芳香環) 8.24 (2H, d,芳香
環) , 8.97 (2H,d1芳香環)。IR: 1610 cm-' (C=O) melting point 237-240°C. 'HNMR (CDC ls,p
pm): 1.0 to 1.7 (IIH, m, cy
lnhexyl) 2.22 (2 H, d, cH2) 3.23 (2H, S, CH2), 6.7~7.7 (
13H, m, aromatic ring) 8.24 (2H, d, aromatic ring), 8.97 (2H, d1 aromatic ring).
(C)N,N’−ビス(8−キノリル)マロンアミド誘
導体の金属錯体の有機化合物包接組成物の製造
(1) ジベンジルN,N’−ビス(8−キノリル)マ
ロンアミドの銅(n)錯体のベンゼンを包接組成物
当該アミドの1:1銅錯体0.1gをベンゼン中で加熱
溶解し、室温放置で再結晶した。黒色の結晶が定量的に
得られた。この桔晶が錯体1モルに対してベンゼン1.
0モルを含むことを熱重量測定(TGA),示差走査熱
量測定(DSC)により確認した。TGA:124〜1
45℃の範囲で11%の重量減少.これは錯体とベンゼ
ンの比1:1に相当。(C) Production of organic compound inclusion composition of metal complex of N,N'-bis(8-quinolyl)malonamide derivative (1) Copper(n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide 0.1 g of a 1:1 copper complex of the amide was dissolved in benzene by heating and recrystallized by standing at room temperature. Black crystals were quantitatively obtained. The amount of benzene per 1 mol of this quartz crystal is 1.
It was confirmed by thermogravimetry (TGA) and differential scanning calorimetry (DSC) that it contained 0 mol. TGA: 124-1
11% weight loss in the 45°C range. This corresponds to a 1:1 ratio of complex to benzene.
DSC :上記温度領域で吸熱ピークが観察された。DSC: An endothermic peak was observed in the above temperature range.
重量減少範囲がベンゼンの沸点80℃より40℃以上高
いことから包接化合物であることがわかる。The weight loss range is 40°C or more higher than the boiling point of benzene, 80°C, indicating that it is an clathrate compound.
(2)ジベンジルN,N’−ビス(8−キノリル)マロ
ンアミドのニッケル(n)錯体のベンゼン包接組戊物
前記(C)− (1)と同様にしてベンゼンを含むNi
(n)錯体(1 : 1)が定量的に得られた。(2) Benzene inclusion complex of nickel (n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide Ni containing benzene in the same manner as (C)-(1) above
(n) Complex (1:1) was obtained quantitatively.
確認は前記のTGA,DSCの他にNMRにより行った
。Confirmation was performed by NMR in addition to the above-mentioned TGA and DSC.
TGA:99〜119℃で11%の重量減少、これより
錯体とベンゼンのモル比は1:1。TGA: 11% weight loss at 99-119°C, hence the molar ratio of complex to benzene is 1:1.
DSC :この温度領域において吸熱ピーク。DSC: Endothermic peak in this temperature range.
NMR : 7J6ppmにベンゼンに基づくピーク。NMR: Benzene-based peak at 7J6ppm.
面積比より錯体ベンゼン=1=1であることを確認。It was confirmed from the area ratio that the complex benzene = 1 = 1.
(3)ジベンジルN,N’−ビス(8−キノリル)マロ
ンアミドの銅(n)錯体のピリジン包接組或物
(1)と同様にしてピリジンより再結晶するとピリジン
を含むCu (II)錯体(1 : 1)が得られた。(3) Pyridine clathrate complex of copper(n) complex of dibenzyl N,N'-bis(8-quinolyl)malonamide When recrystallized from pyridine in the same manner as in (1), a Cu(II) complex containing pyridine ( 1:1) was obtained.
TGA,DSCにより確認された。Confirmed by TGA and DSC.
T G A : 149 〜168℃delo%の重量
減少、これより錯体とピリジンのモル比は1:1。TGA: 149-168°C delo% weight loss, from which the molar ratio of complex and pyridine is 1:1.
DSC:この温度領域において吸熱ピーク。DSC: Endothermic peak in this temperature range.
(4)ベンジル、シクロ^、キシルメチルN, N’一
ビス(8−キノリル)マロンアミドの銅(U)錯体のベ
ンゼン包接組或物
(1)と同様にしてベンゼンで再結晶することにより包
接化合物を得た。(4) Benzene inclusion complex of copper (U) complex of benzyl, cyclo^, xylmethyl N, N'-bis(8-quinolyl)malonamide; or, inclusion by recrystallization with benzene in the same manner as in (1) The compound was obtained.
TGA:123〜130℃で15%の重量減少、これよ
り錯体とベンゼンの比は2:3。TGA: 15% weight loss at 123-130°C, hence the complex to benzene ratio is 2:3.
DSC :この温度領域において吸熱ピーク。DSC: Endothermic peak in this temperature range.
(5)ベンジル、シクロヘキシルメチルN,N’一ビス
(8−キノリル)マロンアミドの銅(n)錯体のトルエ
ン包接組成物
(1)と同様にしてベンゼンで再結晶することにより、
錯体とトルエンの2=1包接化合物を得た。(5) Toluene inclusion composition of copper (n) complex of benzyl, cyclohexylmethyl N,N'-bis(8-quinolyl)malonamide By recrystallizing with benzene in the same manner as in (1),
A 2=1 clathrate of the complex and toluene was obtained.
TGA二83〜98℃で7.0%の重量減少、これより
錯体とトルエンのモル比は2:1。TGA2 weight loss of 7.0% at 83-98°C, hence the molar ratio of complex to toluene is 2:1.
DSC :この温度領域において吸熱ピーク。DSC: Endothermic peak in this temperature range.
(6)ベンジル、シクロヘキシメチルN,N’ビス)8
−キノリル)マロンアミドのニッケル(n)錯体のキシ
レン包接組成物
(1)と同様にしてo +, m +, p−キシレ
ン(1 : 1 : 1)により再結晶することにより
キシレン包接化合物を得た。(6) Benzyl, cyclohexymethyl N, N'bis)8
The xylene clathrate compound of the nickel(n) complex of (quinolyl) malonamide was recrystallized from o +, m +, p-xylene (1:1:1) in the same manner as in xylene clathrate composition (1). Obtained.
TGA:99〜109℃で14%の重量減少。これより
錯体とキシレンのモル比は1:1。TGA: 14% weight loss at 99-109°C. From this, the molar ratio of the complex and xylene is 1:1.
DSC:この温度領域で吸熱ピーク。DSC: Endothermic peak in this temperature range.
NMR :キシレンのメチル基のピークの面積比よりo
−:m−:p一が約1:2:1の割合で含まれることを
確認した。NMR: O from the area ratio of the peak of the methyl group of xylene
It was confirmed that -:m-:p1 was contained in a ratio of about 1:2:1.
(7)ベンゼン及びシクロヘキサン混合溶媒中からのベ
ンジル、シクロヘキシルメチルN,N’ビス(8−キノ
リル)マロンアミドのニッケル(II)錯体の包接組或
物
(1)と同様にしてベンゼンとシクロヘキサンのモル比
1:1の混合溶媒より再結晶を行うとベンゼンのみを含
む包接化合物を得た。(7) Inclusion complex of nickel (II) complex of benzyl and cyclohexylmethyl N,N'bis(8-quinolyl)malonamide in a mixed solvent of benzene and cyclohexane. Similarly to (1), the moles of benzene and cyclohexane are determined. Recrystallization from a mixed solvent in a ratio of 1:1 yielded a clathrate compound containing only benzene.
TG.A:102〜115℃で15%の重量減少。T.G. A: 15% weight loss at 102-115°C.
(4)の場合と比べて温度領域が低くなっているが、N
MRよりシクロヘキサンはトレース量しか含まれておら
ず、ベンゼンのみが包接されていることがわかった。Although the temperature range is lower than in case (4), N
MR revealed that only a trace amount of cyclohexane was contained and only benzene was included.
(D)有機化合物包接組成物からの有機化合物の分離
前記(B)− (1)〜(7)で得られた包接絹成物を
真空ポンプにより100℃加熱下減圧(<1mmHg)
にして3時間処理することにより各々の被包接有機化合
物を液体窒素トラップ中に捕収することができた。各々
の被包接有機化合物が完全に脱離したマロンアミド誘導
体の銅(TI)又はニッケル(U)錯体は定量的に回収
でき、これは各々の被包接有機化合物にさらすことによ
り再度包接組戊物を形戊し、繰返し使用することができ
た。(D) Separation of organic compounds from organic compound inclusion composition The inclusion silk composition obtained in (B)-(1) to (7) above was heated at 100°C under reduced pressure (<1 mmHg) using a vacuum pump.
By treating the mixture in a liquid nitrogen trap for 3 hours, each clathrate organic compound could be captured in a liquid nitrogen trap. Copper (TI) or nickel (U) complexes of malonamide derivatives from which each clathrate organic compound has been completely eliminated can be recovered quantitatively, and this complex can be re-incorporated by exposing it to each clathrate organic compound. It was possible to shape the objects and use them repeatedly.
[効 果]
以上のように、本発明では、ベンゼン、ビリジン、トル
エン、キシレン等の有機化合物をいったんマロンアミド
誘導体の金属錯体との組戒物として分離することができ
、その後有機化合物を回収することができる。[Effect] As described above, in the present invention, organic compounds such as benzene, pyridine, toluene, xylene, etc. can be separated once as a combination of malonamide derivatives and metal complexes, and then the organic compounds can be recovered. I can do it.
Claims (5)
合物を、一般式 ▲数式、化学式、表等があります▼ (式中、R^1、R^2は水素原子、アルキル基、アル
アルキル基、又はアリール基M^2^+はCu^2^+
、Ni^2^+、Co^2^+、Zn^2^+、Pd^
2^+等の二価重金属イオンを示す。) で表されるマロンアミド誘導体の金属錯体と接触させ、
該単独又は混合物中の有機化合物を、該マロンアミド誘
導体の金属錯体に包接させることを特徴とする有機化合
物の包接組成物製造方法。(1) Benzene, toluene, xylene, etc., singly or as a mixture, can be expressed by the general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R^1, R^2 are hydrogen atoms, alkyl groups, aralkyl groups, Or the aryl group M^2^+ is Cu^2^+
, Ni^2^+, Co^2^+, Zn^2^+, Pd^
Indicates divalent heavy metal ions such as 2^+. ) in contact with a metal complex of a malonamide derivative represented by
A method for producing an inclusion composition of an organic compound, which comprises including the organic compound alone or in a mixture in the metal complex of the malonamide derivative.
合物包接化合物から有機化合物を分離する請求項1の方
法。(2) The method according to claim 1, wherein the organic compound is separated from the organic compound inclusion compound for the metal complex of the malonamide derivative.
アルキル基、又はアリール基、M^2^+、はCu^2
^+、Ni^2^+、Co^2^+、Zn^2^+、P
d^2^+、等はアルキル基、の二価重金属イオンを示
す。) で表されるマロンアミド誘導体の金属錯体に有機化合物
を包接させてなる包接組成物。(3) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and M^2^+ is Cu^ 2
^+, Ni^2^+, Co^2^+, Zn^2^+, P
d^2^+, etc. represent a divalent heavy metal ion of an alkyl group. ) An inclusion composition comprising an organic compound included in a metal complex of a malonamide derivative represented by:
アルキル基、又はアリール基、M^2^+、はCu^2
^+、Ni^2^+、Co^2^+、Zn^2^+、P
d^2^+、等はアルキル基、の二価重金属イオンを示
す。) で表されるマロンアミド誘導体の金属錯体の製造方法。(4) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and M^2^+ is Cu^ 2
^+, Ni^2^+, Co^2^+, Zn^2^+, P
d^2^+, etc. represent a divalent heavy metal ion of an alkyl group. ) A method for producing a metal complex of a malonamide derivative represented by
アルキル基、又はアリール基、M^2^+、はCu^2
^+、Ni^2^+、Co^2^+、Zn^2^+、P
d^2^+、等はアルキル基、の二価重金属イオンを示
す。) で表されるマロンアミド誘導体の金属錯体。(5) General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R^1 and R^2 are hydrogen atoms, alkyl groups, aralkyl groups, or aryl groups, and M^2^+ is Cu^ 2
^+, Ni^2^+, Co^2^+, Zn^2^+, P
d^2^+, etc. represent a divalent heavy metal ion of an alkyl group. ) is a metal complex of malonamide derivative.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23485089A JPH0399084A (en) | 1989-09-08 | 1989-09-08 | Separating agent for organic compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP23485089A JPH0399084A (en) | 1989-09-08 | 1989-09-08 | Separating agent for organic compound |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH0399084A true JPH0399084A (en) | 1991-04-24 |
JPH0543709B2 JPH0543709B2 (en) | 1993-07-02 |
Family
ID=16977336
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP23485089A Granted JPH0399084A (en) | 1989-09-08 | 1989-09-08 | Separating agent for organic compound |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH0399084A (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100914024B1 (en) * | 2008-06-12 | 2009-08-28 | 경희대학교 산학협력단 | Method for separation of p-xylene from xylene mixture by guanidinium 4-chlorophenethyl monosulfonate host |
KR100916287B1 (en) * | 2007-12-26 | 2009-09-10 | 경희대학교 산학협력단 | Separation of xylene isomer from xylene mixture by selective inclusion using guanidinium ortho¡ªterphenyl 4,4¡¯¡ªdisulfonate host compound |
KR100916286B1 (en) * | 2007-12-26 | 2009-09-10 | 경희대학교 산학협력단 | Selective separatin of xylene isomer from xylene mixture by inclusion using guanidinium biphenyl¡ª2,2¡¯¡ªdiyldimethanesulfonate host compound |
KR100984798B1 (en) * | 2008-06-12 | 2010-10-04 | 경희대학교 산학협력단 | Method for separation of p-xylene from xylene mixture by guanidinium 2-chlorophenethyl monosulfonate host |
-
1989
- 1989-09-08 JP JP23485089A patent/JPH0399084A/en active Granted
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100916287B1 (en) * | 2007-12-26 | 2009-09-10 | 경희대학교 산학협력단 | Separation of xylene isomer from xylene mixture by selective inclusion using guanidinium ortho¡ªterphenyl 4,4¡¯¡ªdisulfonate host compound |
KR100916286B1 (en) * | 2007-12-26 | 2009-09-10 | 경희대학교 산학협력단 | Selective separatin of xylene isomer from xylene mixture by inclusion using guanidinium biphenyl¡ª2,2¡¯¡ªdiyldimethanesulfonate host compound |
KR100914024B1 (en) * | 2008-06-12 | 2009-08-28 | 경희대학교 산학협력단 | Method for separation of p-xylene from xylene mixture by guanidinium 4-chlorophenethyl monosulfonate host |
KR100984798B1 (en) * | 2008-06-12 | 2010-10-04 | 경희대학교 산학협력단 | Method for separation of p-xylene from xylene mixture by guanidinium 2-chlorophenethyl monosulfonate host |
Also Published As
Publication number | Publication date |
---|---|
JPH0543709B2 (en) | 1993-07-02 |
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