JPH0653702B2 - Vitamin K 2) Isolation and purification method of isomers - Google Patents
Vitamin K 2) Isolation and purification method of isomersInfo
- Publication number
- JPH0653702B2 JPH0653702B2 JP61133750A JP13375086A JPH0653702B2 JP H0653702 B2 JPH0653702 B2 JP H0653702B2 JP 61133750 A JP61133750 A JP 61133750A JP 13375086 A JP13375086 A JP 13375086A JP H0653702 B2 JPH0653702 B2 JP H0653702B2
- Authority
- JP
- Japan
- Prior art keywords
- vitamin
- supercritical fluid
- isomers
- fluid chromatography
- isomer
- 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 - Lifetime
Links
- PFRQBZFETXBLTP-RCIYGOBDSA-N 2-[(2e,6e,10e,14e,18e)-3,7,11,15,19,23-hexamethyltetracosa-2,6,10,14,18,22-hexaen-1-yl]-3-methyl-1,4-dihydronaphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C(C/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)C(=O)C2=C1 PFRQBZFETXBLTP-RCIYGOBDSA-N 0.000 title claims description 18
- 238000000034 method Methods 0.000 title claims description 12
- 238000000746 purification Methods 0.000 title claims description 6
- 238000002955 isolation Methods 0.000 title 1
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 title 1
- 229940010250 vitamin k 2 Drugs 0.000 title 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- 238000004808 supercritical fluid chromatography Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 229930003448 Vitamin K Natural products 0.000 claims 1
- 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 claims 1
- 235000019168 vitamin K Nutrition 0.000 claims 1
- 239000011712 vitamin K Substances 0.000 claims 1
- 150000003721 vitamin K derivatives Chemical class 0.000 claims 1
- 229940046010 vitamin k Drugs 0.000 claims 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 10
- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000000741 silica gel Substances 0.000 description 5
- 229910002027 silica gel Inorganic materials 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 methylene chloride Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-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
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 208000032843 Hemorrhage Diseases 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229940124597 therapeutic agent Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】 本発明は，ビタミンＫ２幾何異性体の分離精製法に関す
るものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for separating and purifying vitamin K 2 geometric isomers.
ビタミンＫ２にはシス体およびトランス体の両幾何異性
体が存在し，そのうちトランス体は低プロトロンビン
症，出血症の治療剤として知られている。このビタミン
Ｋ２トランス体の化学合成においては，副反応物として
シス体が生成するが，このトランス体とシス体の分離精
製法として，従来あまり適切な方法が見つかっていな
い。たとえば，低温による分離結晶化法，液体クロマト
グラフィー法等が知られているが，前者は両幾何異性体
の物性が近似しているために効率よく分離することがで
きなく，純度の高いトランス体を得ようとすれば，トラ
ンス体の回収率は低くなる。また，後者は効率よく分離
することができるが，分離の際に多量の有機溶媒を使用
するため，トランス体の取り出しの際に多量の液を濃縮
しなければならなく，実験室における微量の物質の分離
精製法としては優れていても，工業的な分離精製法とは
いえない。Vitamin K 2 has both cis and trans geometric isomers, and the trans isomer is known as a therapeutic agent for hypoprothrombinism and hemorrhage. In the chemical synthesis of this vitamin K 2 trans isomer, a cis isomer is produced as a by-product, but a suitable method has not been found so far as a method for separating and purifying the trans isomer and the cis isomer. For example, a low temperature separation crystallization method and a liquid chromatography method are known, but the former cannot be efficiently separated because the physical properties of both geometric isomers are close to each other. However, the recovery rate of the trans form will be low. Although the latter can be efficiently separated, a large amount of the organic solvent is used for the separation, and therefore a large amount of the liquid must be concentrated when the trans form is taken out. Although it is excellent as a method for separation and purification, it cannot be said to be an industrial separation and purification method.
そこで本発明者等は，超臨界流体クロマトグラフィーに
よるビタミンＫ２幾何異性体の分離精製を検討した。気
体と液体とが共存できる臨界温度，臨界圧力以上の状態
では，物質は気体とも液体ともいえない状態にあり，こ
れを超臨界流体と呼んでいる。この超臨界流体を移動相
として用い，シリカゲルなどの分離充填剤を通して物質
の分離精製を行なうのが，超臨界流体クロマトグラフィ
ーである。本発明者等は，当初，通常の超臨界流体クロ
マトグラフィーによるビタミンＫ２幾何異性体の分離を
試みたが，両幾何異性体は分離しなかった。そこで鋭意
研究のすえ，試料に特定の有機溶媒を添加すれば，両幾
何異性体を分離精製できることを見い出し，本発明を完
成した。Therefore, the present inventors examined the separation and purification of vitamin K 2 geometric isomers by supercritical fluid chromatography. At a temperature above the critical temperature and pressure at which gas and liquid can coexist, substances are neither gas nor liquid, and this is called supercritical fluid. Supercritical fluid chromatography uses this supercritical fluid as a mobile phase to separate and purify substances through a separation filler such as silica gel. The present inventors initially attempted to separate vitamin K 2 geometric isomers by ordinary supercritical fluid chromatography, but did not separate both geometric isomers. Then, after intensive research, they found that both geometric isomers could be separated and purified by adding a specific organic solvent to the sample, and completed the present invention.
したがって，本発明の目的は，ビタミンＫ２幾何異性体
の工業的分離精製法を提供することにある。Therefore, an object of the present invention is to provide an industrial method for separating and purifying geometrical isomers of vitamin K 2 .
本発明は，超臨界流体クロマトグラフィーによりビタミ
ンＫ２幾何異性体を分離精製するに際し，ビタミンＫ２
異性体可溶性有機溶媒を試料に添加することを特徴とす
る分離精製法である。Upon this invention, separating and purifying vitamin K 2 geometric isomers supercritical fluid chromatography, vitamin K 2
This is a separation and purification method characterized by adding an isomer-soluble organic solvent to a sample.
ビタミンＫ２幾何異性体可溶性有機溶媒としては，ビタ
ミンＫ２幾何異性体が可溶な有機溶媒，例えば，メタノ
ール，エタノール，イソプロパノール，ｎ−プロパノー
ルなどの低級アルコール，イソプロピルエーテル，エチ
ルエーテル，テトラヒドロフランなどのエーテル類，塩
化メチレンなどのハロゲン化低級炭化水素，ｎ−ヘキサ
ンなどの飽和炭化水素化合物などがあげられる。Examples of the vitamin K 2 geometric isomer-soluble organic solvent include organic solvents in which the vitamin K 2 geometric isomer is soluble, for example, lower alcohols such as methanol, ethanol, isopropanol, n-propanol, isopropyl ether, ethyl ether, and tetrahydrofuran. Examples include ethers, halogenated lower hydrocarbons such as methylene chloride, and saturated hydrocarbon compounds such as n-hexane.
また，超臨界流体としては，二酸化炭素，アンモニア，
二酸化イオウ，ハロゲン化水素，亜酸化窒素，硫化水
素，メタン，エタン，プロパン，ブタン，エチレン，プ
ロピレン，ハロゲン化炭化水素などが用いられる。可燃
性，爆発性，人体への有害性などを考慮すると，二酸化
炭素が最も望ましい。二酸化炭素の場合，臨界温度31.3
℃，臨界圧力72.9気圧であり，これ以上の温度，圧力下
で用いる。Also, as the supercritical fluid, carbon dioxide, ammonia,
Sulfur dioxide, hydrogen halide, nitrous oxide, hydrogen sulfide, methane, ethane, propane, butane, ethylene, propylene, halogenated hydrocarbon and the like are used. Considering flammability, explosiveness, and harmfulness to the human body, carbon dioxide is most preferable. For carbon dioxide, the critical temperature is 31.3
℃, critical pressure is 72.9 atm, use at higher temperature and pressure.
分離充填剤としては，シリカゲル，アルミナなどが用い
られる。シリカゲルの場合，その内部の細孔の口径が50
〜100Åのものが望ましい。As the separating filler, silica gel, alumina, etc. are used. In the case of silica gel, the pore size inside is 50
~ 100Å is preferable.
本発明方法によると，ビタミンＫ２トランス体とシス体
の各フラクションを分取後，常圧状態に戻してやれば，
超臨界流体は気体となって容量に除去できるので，目的
物を容易に得ることができる。According to the method of the present invention, if fractions of the vitamin K 2 trans form and the cis form are collected and then returned to normal pressure,
Since the supercritical fluid becomes a gas and can be removed to the volume, the target substance can be easily obtained.
次に実施例および実験例を示し，本発明をさらに詳しく
説明する。Next, the present invention will be described in more detail by showing Examples and Experimental Examples.
実施例１ ビタミンＫ２（トランス体とシス体の混合物）１mgをイ
ソプロパノール10μlに溶解し，超臨界流体クロマトグ
ラフィーを行なった。その条件は次のとうりである。Example 1 1 mg of vitamin K 2 (mixture of trans form and cis form) was dissolved in 10 μl of isopropanol and subjected to supercritical fluid chromatography. The conditions are as follows.
カラム：Nucleosil50-5μm（商品名，ナーゲル社製シリ
カゲル） 直径4.6mm，長さ250mm 移動相：二酸化炭素，圧力230kg／cm2，温度40℃，流量
2.0ml／分 この超臨界流体クロマトグラフィーのチャートを第１図
に示す。横軸は時間（一目盛４分），縦軸はUV270nmに
おける吸光度，Ｔはトランス体のピーク，Ｃはシス体の
ピーク，Ｓは試料注入時点を示す。Column: Nucleosil 50-5 μm (trade name, silica gel manufactured by Nagel) Diameter 4.6 mm, length 250 mm Mobile phase: carbon dioxide, pressure 230 kg / cm 2 , temperature 40 ° C., flow rate
2.0 ml / min This supercritical fluid chromatography chart is shown in FIG. The horizontal axis represents time (4 minutes per scale), the vertical axis represents absorbance at UV270 nm, T represents the peak of the trans form, C represents the peak of the cis form, and S represents the time of sample injection.
チャートより明らかなように，本クロマトグラフィーに
より，トランス体とシス体はよく分離している。As is clear from the chart, the trans form and the cis form are well separated by this chromatography.
実施例２ ビタミンＫ２（トランス体とシス体の混合物）0.5mgを
エタノール10μlに溶解し，超臨界流体クロマトグラフ
ィーを行なった。条件は次のとうりである。Example 2 0.5 mg of vitamin K 2 (mixture of trans form and cis form) was dissolved in 10 μl of ethanol and subjected to supercritical fluid chromatography. The conditions are as follows.
カラム：Nucleosil 50−５μm（商品名，ナーゲル社製
シリカゲル） 直径4.6mm，長さ250mm 移動相：二酸化炭素，圧力220kg／cm2，温度40℃， 流量1.5ml／分 この超臨界流体クロマトグラフィーのチャートを第２図
に示す。横軸は時間（一目盛４分），縦軸はUV270nmに
おける吸光度，Ｔはトランス体のピーク，Ｃはシス体の
ピーク，Ｓは試料注入時点を示す。Column: Nucleosil 50-5 μm (trade name, silica gel manufactured by Nagel) Diameter 4.6 mm, length 250 mm Mobile phase: carbon dioxide, pressure 220 kg / cm 2 , temperature 40 ° C., flow rate 1.5 ml / min. The chart is shown in FIG. The horizontal axis represents time (4 minutes per scale), the vertical axis represents the absorbance at UV270 nm, T is the peak of the trans form, C is the peak of the cis form, and S is the time of sample injection.
チャートより明らかなとうり，トランス体とシス体はよ
く分離している。As is clear from the chart, the trans form and the cis form are well separated.
実施例１ ビタミンＫ２（トランス体とシス体の混合物）１mgを有
機溶媒に溶解しないで原液のまま用いる点を除き，実施
例１と同じ条件で超臨界流体クロマトグラフィーを行な
った。そのチャートを第３図に示す。横軸，縦軸，Ｓは
第１図と同じである。チャートより明らかなように，ピ
ークは１つしかなく，トランス体とシス体が全く分離し
ていないことを示している。Example 1 Supercritical fluid chromatography was performed under the same conditions as in Example 1 except that 1 mg of vitamin K 2 (mixture of trans isomer and cis isomer) was used as an undiluted solution without being dissolved in an organic solvent. The chart is shown in FIG. The horizontal axis, vertical axis and S are the same as in FIG. As is clear from the chart, there is only one peak, indicating that the trans form and the cis form are not separated at all.
第１図〜第３図は，ビタミンＫ２（トランス体とシス体
の混合物）の超臨界流体クロマトグラフィーのチャート
を示す。1 to 3 show charts of supercritical fluid chromatography of vitamin K 2 (mixture of trans isomer and cis isomer).
Claims (3)
ミンＫ２幾何異性体を分離精製するに際し、ビタミンＫ
２幾何異性体可溶性有機溶媒を試料に添加することを特
徴とする分離精製法。1. When separating and purifying vitamin K 2 geometric isomers by supercritical fluid chromatography, vitamin K is used.
A method for separation and purification, which comprises adding a 2 geometric isomer-soluble organic solvent to a sample.
低級アルコールである特許請求の範囲第１項記載の方
法。2. The method according to claim 1, wherein the vitamin K 2 geometric isomer-soluble organic solvent is a lower alcohol.
スの超臨界流体を用いた超臨界流体クロマトグラフィー
である特許請求の範囲第１項または第２項記載の方法。3. The method according to claim 1 or 2, wherein the supercritical fluid chromatography is supercritical fluid chromatography using a supercritical fluid of carbon dioxide gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61133750A JPH0653702B2 (en) | 1986-06-11 | 1986-06-11 | Vitamin K 2) Isolation and purification method of isomers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61133750A JPH0653702B2 (en) | 1986-06-11 | 1986-06-11 | Vitamin K 2) Isolation and purification method of isomers |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62292744A JPS62292744A (en) | 1987-12-19 |
| JPH0653702B2 true JPH0653702B2 (en) | 1994-07-20 |
Family
ID=15112060
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61133750A Expired - Lifetime JPH0653702B2 (en) | 1986-06-11 | 1986-06-11 | Vitamin K 2) Isolation and purification method of isomers |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0653702B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE59610489D1 (en) * | 1995-08-17 | 2003-07-10 | Hoffmann La Roche | Chromatography methods |
-
1986
- 1986-06-11 JP JP61133750A patent/JPH0653702B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62292744A (en) | 1987-12-19 |
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