JPS6320574B2 - - Google Patents
Info
- Publication number
- JPS6320574B2 JPS6320574B2 JP54099118A JP9911879A JPS6320574B2 JP S6320574 B2 JPS6320574 B2 JP S6320574B2 JP 54099118 A JP54099118 A JP 54099118A JP 9911879 A JP9911879 A JP 9911879A JP S6320574 B2 JPS6320574 B2 JP S6320574B2
- Authority
- JP
- Japan
- Prior art keywords
- silica gel
- solvent
- column
- hexane
- washing
- 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
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 34
- 239000000741 silica gel Substances 0.000 claims description 34
- 229910002027 silica gel Inorganic materials 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 11
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- 150000002430 hydrocarbons Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 5
- 150000003505 terpenes Chemical class 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 51
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 26
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 230000018109 developmental process Effects 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 sterine Chemical class 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000001707 (E,7R,11R)-3,7,11,15-tetramethylhexadec-2-en-1-ol Substances 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- BLUHKGOSFDHHGX-UHFFFAOYSA-N Phytol Natural products CC(C)CCCC(C)CCCC(C)CCCC(C)C=CO BLUHKGOSFDHHGX-UHFFFAOYSA-N 0.000 description 4
- HNZBNQYXWOLKBA-UHFFFAOYSA-N Tetrahydrofarnesol Natural products CC(C)CCCC(C)CCCC(C)=CCO HNZBNQYXWOLKBA-UHFFFAOYSA-N 0.000 description 4
- BOTWFXYSPFMFNR-OALUTQOASA-N all-rac-phytol Natural products CC(C)CCC[C@H](C)CCC[C@H](C)CCCC(C)=CCO BOTWFXYSPFMFNR-OALUTQOASA-N 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 description 4
- BOTWFXYSPFMFNR-PYDDKJGSSA-N phytol Chemical compound CC(C)CCC[C@@H](C)CCC[C@@H](C)CCC\C(C)=C\CO BOTWFXYSPFMFNR-PYDDKJGSSA-N 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- GLZPCOQZEFWAFX-UHFFFAOYSA-N Geraniol Chemical compound CC(C)=CCCC(C)=CCO GLZPCOQZEFWAFX-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- ACTIUHUUMQJHFO-UPTCCGCDSA-N coenzyme Q10 Chemical compound COC1=C(OC)C(=O)C(C\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CC\C=C(/C)CCC=C(C)C)=C(C)C1=O ACTIUHUUMQJHFO-UPTCCGCDSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- OILXMJHPFNGGTO-UHFFFAOYSA-N (22E)-(24xi)-24-methylcholesta-5,22-dien-3beta-ol Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)C=CC(C)C(C)C)C1(C)CC2 OILXMJHPFNGGTO-UHFFFAOYSA-N 0.000 description 2
- 239000001490 (3R)-3,7-dimethylocta-1,6-dien-3-ol Substances 0.000 description 2
- CDOSHBSSFJOMGT-JTQLQIEISA-N (R)-linalool Natural products CC(C)=CCC[C@@](C)(O)C=C CDOSHBSSFJOMGT-JTQLQIEISA-N 0.000 description 2
- OQMZNAMGEHIHNN-UHFFFAOYSA-N 7-Dehydrostigmasterol Natural products C1C(O)CCC2(C)C(CCC3(C(C(C)C=CC(CC)C(C)C)CCC33)C)C3=CC=C21 OQMZNAMGEHIHNN-UHFFFAOYSA-N 0.000 description 2
- AFPLNGZPBSKHHQ-UHFFFAOYSA-N Betulaprenol 9 Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCO AFPLNGZPBSKHHQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- HZYXFRGVBOPPNZ-UHFFFAOYSA-N UNPD88870 Natural products C1C=C2CC(O)CCC2(C)C2C1C1CCC(C(C)=CCC(CC)C(C)C)C1(C)CC2 HZYXFRGVBOPPNZ-UHFFFAOYSA-N 0.000 description 2
- 229930003448 Vitamin K Natural products 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- LGJMUZUPVCAVPU-UHFFFAOYSA-N beta-Sitostanol Natural products C1CC2CC(O)CCC2(C)C2C1C1CCC(C(C)CCC(CC)C(C)C)C1(C)CC2 LGJMUZUPVCAVPU-UHFFFAOYSA-N 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- CCCXGQLQJHWTLZ-UHFFFAOYSA-N geranyl linalool Natural products CC(=CCCC(=CCCCC(C)(O)CCC=C(C)C)C)C CCCXGQLQJHWTLZ-UHFFFAOYSA-N 0.000 description 2
- IQDXAJNQKSIPGB-HQSZAHFGSA-N geranyllinalool Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CCC(C)(O)C=C IQDXAJNQKSIPGB-HQSZAHFGSA-N 0.000 description 2
- 229930007744 linalool Natural products 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 150000003904 phospholipids Chemical class 0.000 description 2
- SHUZOJHMOBOZST-UHFFFAOYSA-N phylloquinone Natural products CC(C)CCCCC(C)CCC(C)CCCC(=CCC1=C(C)C(=O)c2ccccc2C1=O)C SHUZOJHMOBOZST-UHFFFAOYSA-N 0.000 description 2
- 239000011772 phylloquinone Substances 0.000 description 2
- MBWXNTAXLNYFJB-LKUDQCMESA-N phylloquinone Chemical compound C1=CC=C2C(=O)C(C/C=C(C)/CCCC(C)CCCC(C)CCCC(C)C)=C(C)C(=O)C2=C1 MBWXNTAXLNYFJB-LKUDQCMESA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- AFPLNGZPBSKHHQ-MEGGAXOGSA-N solanesol Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CO AFPLNGZPBSKHHQ-MEGGAXOGSA-N 0.000 description 2
- HCXVJBMSMIARIN-PHZDYDNGSA-N stigmasterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)/C=C/[C@@H](CC)C(C)C)[C@@]1(C)CC2 HCXVJBMSMIARIN-PHZDYDNGSA-N 0.000 description 2
- 229940032091 stigmasterol Drugs 0.000 description 2
- BFDNMXAIBMJLBB-UHFFFAOYSA-N stigmasterol Natural products CCC(C=CC(C)C1CCCC2C3CC=C4CC(O)CCC4(C)C3CCC12C)C(C)C BFDNMXAIBMJLBB-UHFFFAOYSA-N 0.000 description 2
- 235000016831 stigmasterol Nutrition 0.000 description 2
- 239000011712 vitamin K Substances 0.000 description 2
- 235000019168 vitamin K Nutrition 0.000 description 2
- 150000003721 vitamin K derivatives Chemical class 0.000 description 2
- 229940046010 vitamin k Drugs 0.000 description 2
- RORDEOUGMCQERP-UHFFFAOYSA-N (2Z,6Z,10Z,14Z,18Z,22Z,26E,30E,34E)-3,7,11,15,19,23,27,31,35,39-decamethyl-tetraconta-2,6,10,14,18,22,26,30,34,38-decaen-1-ol Natural products CC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCCC(C)=CCO RORDEOUGMCQERP-UHFFFAOYSA-N 0.000 description 1
- RORDEOUGMCQERP-CMVHWAPMSA-N (2e,6e,10e,14e,18e,22e,26e,30e,34e)-3,7,11,15,19,23,27,31,35,39-decamethyltetraconta-2,6,10,14,18,22,26,30,34,38-decaen-1-ol Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CO RORDEOUGMCQERP-CMVHWAPMSA-N 0.000 description 1
- TUTMVAYTCHJDDP-RYEKIIQNSA-N (6e,10e,14e,18e,22e,26e,30e,34e)-3,7,11,15,19,23,27,31,35,39-decamethyltetraconta-1,6,10,14,18,22,26,30,34,38-decaen-3-ol Chemical compound CC(C)=CCC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CC\C(C)=C\CCC(C)(O)C=C TUTMVAYTCHJDDP-RYEKIIQNSA-N 0.000 description 1
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005792 Geraniol Substances 0.000 description 1
- GLZPCOQZEFWAFX-YFHOEESVSA-N Geraniol Natural products CC(C)=CCC\C(C)=C/CO GLZPCOQZEFWAFX-YFHOEESVSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940113087 geraniol Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000787 lecithin Substances 0.000 description 1
- 229940067606 lecithin Drugs 0.000 description 1
- 235000010445 lecithin Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
本発明はカラムクロマトグラフにおいて吸着剤
として使用されたシリカゲルを簡単且つ確実に再
生する方法に関する。
物質の分離精製の手段としてシリカゲルを吸着
剤として使用するカラムクロマトグラフイーがあ
る。このカラムクロマトグラフで物質を展開分離
した後シリカゲルを再生する場合通常シリカゲル
を水またはアルコール等で洗滌した後に１回ごと
にそれを燬焼または加熱乾燥するのがもつとも一
般的である。この方法によればシリカゲルをカラ
ムから取出さねばならないという不利がある。
本発明者らは容易にシリカゲルクロマトグラフ
を再生する方法について検討を行つた結果、溶媒
を用いて展開を行つた場合、特定の混合割合のあ
る種の溶媒の組合せを用いて洗滌を行うことによ
り簡単でしかも充分にシリカゲルを再生すること
ができることを見出した。
本発明方法におけるシリカゲルカラムクロマト
グラフによる展開分離の対象となる物質としては
たとえばビタミンＫ、ソラネソール、CoQ10、イ
ソデカプレノールなどようなイソプレノイド系高
分子量含酸素炭化水素が挙げられる。
一般にこの種の物質の展開分離には溶媒は分離
の対象となる物質のシリカゲルに対する吸着能よ
り大きい溶出能をもつ溶媒（以下溶離性溶媒と云
う）単独かまたはそれと分離の対象となる物質の
シリカゲルに対する吸着能より小さい溶出能をも
つ溶媒（以下非溶離性溶媒と云う）の２種を用
い、その際混合溶媒の場合には展開分離を充分な
らしめるためには溶離性溶媒の方を混合溶媒系の
１〜30％とするのが通常である。
このようにして展開分離に使用したシリカゲル
には、イソプレノイド系高分子量含酸素炭化水素
類の製造に使用した原料化合物、途中段階生成
物、副生成物、少量の目的生成物等が付着してい
る。付着している化合物の種類は、用いた原料化
合物の種類、製造するイソプレノイド系高分子量
含酸素炭化水素類の種類、反応の形態等によつて
相違してくるが、通常、炭化水素類、高級アルコ
ール類、ステリン、リン脂質、重合物、イソプレ
ノイド系高分子量含酸素炭化水素等が付着してい
る。
そのような化合物を付着しているシリカゲルは
その後本発明方法に従つて洗滌されるがその際溶
媒を反復再使用するためには溶離性溶媒を溶媒全
体に対して50〜80容量％となるように調整するこ
とが肝要である。この場合もし溶離性溶媒の占め
る割合が前記範囲より大きいとその後の定着用溶
媒での置換操作が著しく困難となる。また前記範
囲より小さいと洗滌が充分行われず再生し得な
い。
洗滌時の条件は分離の対象となる物質の種類に
より適宜に選択されうる。
本発明方法による再生に当つての溶媒の組合せ
は分離の対象となる具体的物質のシリカゲルに対
する吸着能の大きさにより異なるが、一般に溶離
性溶媒は例えばイソプロピルエーテル、ジエチル
エーテル、酢酸エチル、アセトン、メタノール等
から選ばれ、そしてまた非溶離性溶媒としてはヘ
キサン、シクロヘキサン、ヘプタン、石油エーテ
ル、ベンゼン、ケロシン、石油ベンジン等が挙げ
られる。
次いで洗滌の終了したシリカゲルを次の展開分
離に用いることができるように置換を行う。置換
に用いる溶媒は前述の非溶離性溶媒ないしは展開
時に用いる溶媒がよく、この操作によりシリカゲ
ルは新たな操作に使用できる状態となつている。
シリカゲルの再生は本発明の方法によればシリ
カゲルを殊更取出して加熱等の処理をすることな
く10数回以上行うことができる。
本発明は以上述べたようにシリカゲルをカラム
に充填したまま少量の溶媒で容易に再生すること
ができ、またシリカゲルの洗滌が充分に行われる
ために10数回以上の使用が可能である。更にまた
再生に用いる溶媒の種類と同じものを展開に用い
ることにより、使用後の溶媒を調整して再使用す
ることができるので有利である。
以下の実施例により本発明を説明するが本発明
はこれらに限定されるものではない。尚実施例中
の溶媒の混合比はすべて容量比で表わす。
実施例 １
シリカゲル100ｇをベンゼンと共にカラムに充
填する。粗製ビタミンK1（純度85％）10.0ｇをベ
ンゼン10mlに溶解しこの溶液を前記カラムの頂部
から流下させて定着する。次いで酢酸エチル／ベ
ンゼン（５：95）の混合溶媒で展開分離を行つて
純度95％の精製ビタミンK1を得る（回収率90
％）。この時、カラム中のシリカゲルには、イソ
プレンなどの炭化水素、フイトールやゲラニオー
ル等の高級アルコール、フイトールやゲラニオー
ルのダイマーやトリアー等の重合物等が少量の粗
製ビタミンＫとともに付着している。次にこのカ
ラムを再生使用するためにカラム内の溶媒を切ら
すことなく酢酸エチル／ベンゼン（50：50）の混
合溶媒500mlで洗滌した後、ベンゼン500mlでカラ
ム内の溶媒の置換を行う。
次に前記と同様にして定着および展開分離を行
い20回繰り返し使用した場合の試験結果を示せば
第１表のとおりである。
The present invention relates to a method for simply and reliably regenerating silica gel used as an adsorbent in column chromatography. Column chromatography, which uses silica gel as an adsorbent, is a method for separating and purifying substances. When regenerating silica gel after developing and separating substances using this column chromatography, it is common to wash the silica gel with water or alcohol, and then sinter or heat dry it each time. This method has the disadvantage that the silica gel must be removed from the column. The present inventors investigated a method for easily regenerating a silica gel chromatograph, and found that when a solvent is used for development, washing is performed using a combination of certain solvents at a specific mixing ratio. It has been found that silica gel can be easily and sufficiently regenerated. Examples of substances to be subjected to development separation using silica gel column chromatography in the method of the present invention include isoprenoid-based high molecular weight oxygen-containing hydrocarbons such as vitamin K, solanesol, CoQ 10 and isodecaprenol. In general, in the development separation of this type of substance, the solvent is a solvent (hereinafter referred to as an eluent solvent) that has a greater elution capacity than the adsorption capacity of the substance to be separated on silica gel, or it is combined with the silica gel of the substance to be separated. Two types of solvents (hereinafter referred to as non-eluting solvents) having an elution capacity smaller than the adsorption capacity for It is usually 1 to 30% of the system. In this way, the silica gel used for development separation is contaminated with raw materials, intermediate products, by-products, small amounts of target products, etc. used in the production of isoprenoid-based high molecular weight oxygenated hydrocarbons. . The types of attached compounds vary depending on the type of raw material compound used, the type of isoprenoid-based high molecular weight oxygenated hydrocarbons to be produced, the form of the reaction, etc., but usually hydrocarbons, high-grade Alcohols, sterine, phospholipids, polymers, isoprenoid-based high molecular weight oxygenated hydrocarbons, etc. are attached. The silica gel with such compounds attached thereto is then washed according to the method of the present invention, with the eluent being added at 50-80% by volume based on the total solvent in order to reuse the solvent repeatedly. It is important to adjust the In this case, if the proportion occupied by the eluent solvent is larger than the above range, the subsequent replacement operation with the fixing solvent becomes extremely difficult. Moreover, if it is smaller than the above range, washing will not be carried out sufficiently and regeneration will not be possible. Conditions for washing can be appropriately selected depending on the type of substance to be separated. The combination of solvents used for regeneration according to the method of the present invention varies depending on the adsorption capacity of the specific substance to be separated on silica gel, but in general, eluent solvents include isopropyl ether, diethyl ether, ethyl acetate, acetone, Methanol and the like are selected, and non-eluting solvents also include hexane, cyclohexane, heptane, petroleum ether, benzene, kerosene, petroleum benzene and the like. Next, replacement is performed so that the washed silica gel can be used for the next development and separation. The solvent used for substitution is preferably the above-mentioned non-eluting solvent or the solvent used during development, and by this operation the silica gel is ready for use in a new operation. According to the method of the present invention, silica gel can be regenerated more than ten times without taking out the silica gel and performing any treatment such as heating. As described above, in the present invention, silica gel packed in a column can be easily regenerated with a small amount of solvent, and since the silica gel is sufficiently washed, it can be used more than 10 times. Furthermore, by using the same type of solvent for development as that used for regeneration, it is advantageous because the used solvent can be adjusted and reused. The present invention will be explained by the following examples, but the present invention is not limited thereto. In addition, all the mixing ratios of solvents in the examples are expressed in volume ratios. Example 1 100 g of silica gel is packed into a column along with benzene. 10.0 g of crude vitamin K 1 (purity 85%) is dissolved in 10 ml of benzene and this solution is allowed to flow down from the top of the column and is fixed. Next, purified vitamin K 1 with a purity of 95% is obtained by developing and separating with a mixed solvent of ethyl acetate/benzene (5:95) (recovery rate of 90%).
%). At this time, hydrocarbons such as isoprene, higher alcohols such as phytol and geraniol, and polymers such as phytol and geraniol dimers and triers are attached to the silica gel in the column, along with a small amount of crude vitamin K. Next, in order to reuse this column, without running out of the solvent in the column, it is washed with 500 ml of a mixed solvent of ethyl acetate/benzene (50:50), and then the solvent in the column is replaced with 500 ml of benzene. Next, the test results were shown in Table 1 when fixing, development and separation were carried out in the same manner as described above, and the test results were used repeatedly 20 times.
【表】
さらに、洗滌時の混合溶媒の混合割合を変えて
上記と同様の操作を行つた結果、シリカゲルの再
生状況は、下記の第２表に示したとおりである。[Table] Further, the same operation as above was carried out by changing the mixing ratio of the mixed solvent during washing, and the results of the regeneration of the silica gel were as shown in Table 2 below.
【表】
さらに比較のために上記と同じシリカゲルの再
生を従来法と同様にして行つた場合洗滌および置
換に要する溶媒の量を比較した。従来法(1)は前記
シリカゲルを展開溶媒をそのまま用いて洗滌した
場合であり、また従来法(2)は前記シリカゲルをメ
タノールで洗滌した後、まずベンゼンそして次い
で展開溶媒で置換を行つた場合を示す。なお用い
た溶媒量は本発明で洗滌に用いた溶媒（酢酸エチ
ルとベンゼンの混合割合＝50：50）および置換に
用いた溶媒（ベンゼン）の合計を１としたときの
量比で表わす。次にその結果を示せば第３表のと
おりである。[Table] Furthermore, for comparison, the amount of solvent required for washing and substitution was compared when the same silica gel as above was regenerated in the same manner as in the conventional method. Conventional method (1) is the case where the silica gel is washed using the developing solvent as it is, and conventional method (2) is the case where the silica gel is washed with methanol and then replaced with benzene and then with the developing solvent. show. The amount of solvent used in the present invention is expressed as a quantitative ratio when the sum of the solvent used for washing (mixing ratio of ethyl acetate and benzene = 50:50) and the solvent used for substitution (benzene) is 1. Next, the results are shown in Table 3.
【表】
実施例 ２
シリカゲル150ｇをヘキサンと共にカラムに充
填する。粗製フイトール25ｇをヘキサン25mlに溶
解しこのものを前記カラムに仕込み定着する。次
にジエチルエーテル／ヘキサン（５：95）の混合
溶媒で展開分離を行う。この時、カラム中のシリ
カゲルには少量の粗製フイトールの他に、スチグ
マステロール等のステリン、レシチン等のリン脂
質、リナロール等の高級アルコール等が付着して
いる。次いでエーテル／ヘキサン（80：20）の混
合溶媒600mlを用いて洗滌を行つた後、エーテ
ル／ヘキサン（５：95）の混合溶媒900mlを用い
てカラム内の溶媒の置換を行う。
更に上記と同様にして定着、展開分離および洗
滌を行い15回繰り返して使用した場合の試験結果
を示すと、次の第４表のとおりである。[Table] Example 2 150 g of silica gel is packed into a column together with hexane. 25 g of crude phytol was dissolved in 25 ml of hexane, and this was charged into the column and fixed. Next, separation is carried out using a mixed solvent of diethyl ether/hexane (5:95). At this time, in addition to a small amount of crude phytol, sterine such as stigmasterol, phospholipid such as lecithin, and higher alcohol such as linalool are attached to the silica gel in the column. Next, washing is performed using 600 ml of a mixed solvent of ether/hexane (80:20), and then the solvent in the column is replaced using 900 ml of a mixed solvent of ether/hexane (5:95). Further, the test results were shown in Table 4 when fixing, developing, separating and washing were repeated 15 times in the same manner as above.
【表】
実施例 ３
シリカゲル50ｇをヘキサンと共にカラムに充填
する。ゲラニルリナロール10ｇをヘキサン10mlに
溶解し、このものを前記カラムに仕込み定着す
る。定着後ジエチルエーテル／ヘキサン（７：
93）の混合溶媒で展開分離を行う。この時、カラ
ム中のシリカゲルには、少量の粗製ゲラニルリナ
ロールの他にスチグマステロール等のステリン、
リナロール等の高級アルコール等が付着してい
る。次いでジエチルエーテル／ヘキサン（80：
20）の混合溶媒200mlで洗滌を行つた後ヘキサン
200mlで置換を行う。
更に、上記と同様にして定着、展開分離および
洗滌を行い10回繰り返して使用した場合の結果を
示すと次の第５表のとおりである。[Table] Example 3 Fill a column with 50 g of silica gel together with hexane. 10 g of geranyl linalool was dissolved in 10 ml of hexane, and this was charged into the column and fixed. After fixing diethyl ether/hexane (7:
93) and conduct development separation using a mixed solvent. At this time, in addition to a small amount of crude geranyl linalool, the silica gel in the column contains sterine such as stigmasterol.
Higher alcohols such as linalool are attached. Then diethyl ether/hexane (80:
After washing with 200ml of the mixed solvent of 20), hexane
Perform replacement with 200ml. Furthermore, the following Table 5 shows the results when fixing, developing, separating and washing were repeated 10 times in the same manner as above.
【表】
実施例 ４
シリカゲル50ｇをジエチルエーテル／ヘキサン
（３：97）と共にカラムに充填する。合成した粗
CoQ105ｇをジエチルエーテル／ヘキサン（３：
97）10mlに溶解し、このものを前記カラムに仕込
んで定着させる。定着後、ジエチルエーテル／ヘ
キサン（３：97）で展開分離を行う。この時、カ
ラム中のシリカゲルには、少量の粗製CoQ10の他
に、イソプレン等の炭化水素、デカプレノールや
ソラネソール等の高級アルコール、高級アルコー
ルのダイマー等の重合物等が付着している。次い
で、ジエチルエーテル／ヘキサン（70：30）の混
合溶媒180mlで洗滌しそしてジエチルエーテル／
ヘキサン（３：97）の混合溶媒で置換する。
更に、上記と同様にして定着、展開分離および
洗滌を行い10回繰り返して使用した場合の試験結
果を示すと次の第６表のとおりである。Table Example 4 50 g of silica gel is packed into a column with diethyl ether/hexane (3:97). Synthesized crude
CoQ 10 5g in diethyl ether/hexane (3:
97) Dissolve in 10 ml and charge this into the column for fixation. After fixing, develop and separate with diethyl ether/hexane (3:97). At this time, in addition to a small amount of crude CoQ 10 , hydrocarbons such as isoprene, higher alcohols such as decaprenol and solanesol, and polymers such as higher alcohol dimers are attached to the silica gel in the column. Then, it was washed with 180 ml of a mixed solvent of diethyl ether/hexane (70:30) and then washed with diethyl ether/hexane (70:30).
Replace with a mixed solvent of hexane (3:97). Furthermore, the following Table 6 shows the test results when fixing, developing, separating, and washing were repeated 10 times in the same manner as above.
Claims (1)
イド系高分子量含酸素炭化水素の展開分離に使用
したシリカゲルを、そのシリカゲルから前記含酸
素炭化水素を溶出せしめる能力の大きい含酸素有
機溶媒と、前記シリカゲルから前記含酸素炭化水
素を溶出せしめる能力の小さい炭化水素溶媒とを
50：50〜80：20の容量比で含有する混合溶媒系で
洗滌して再生することを特徴とする、シリカゲル
の再生方法。1. The silica gel used for the development separation of isoprenoid-based high molecular weight oxygenated hydrocarbons by column chromatography is treated with an oxygenated organic solvent having a large ability to elute the oxygenated hydrocarbons from the silica gel, and the oxygenated carbonized silica gel. Hydrocarbon solvents with low ability to elute hydrogen
A method for regenerating silica gel, comprising washing and regenerating with a mixed solvent system containing a volume ratio of 50:50 to 80:20.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9911879A JPS5624044A (en) | 1979-08-04 | 1979-08-04 | Regeneration of adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9911879A JPS5624044A (en) | 1979-08-04 | 1979-08-04 | Regeneration of adsorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5624044A JPS5624044A (en) | 1981-03-07 |
| JPS6320574B2 true JPS6320574B2 (en) | 1988-04-28 |
Family
ID=14238867
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9911879A Granted JPS5624044A (en) | 1979-08-04 | 1979-08-04 | Regeneration of adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5624044A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105424839A (en) * | 2015-12-15 | 2016-03-23 | 袁泳 | Regeneration method of reversed-phase packing column of HPLC (high performance liquid chromatograph) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5293724A (en) * | 1976-02-02 | 1977-08-06 | Asahi Chem Ind Co Ltd | Improved separation of cresols |
-
1979
- 1979-08-04 JP JP9911879A patent/JPS5624044A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5293724A (en) * | 1976-02-02 | 1977-08-06 | Asahi Chem Ind Co Ltd | Improved separation of cresols |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5624044A (en) | 1981-03-07 |
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