JPH07316131A - Process for producing pyrrole derivative - Google Patents
Process for producing pyrrole derivativeInfo
- Publication number
- JPH07316131A JPH07316131A JP11496794A JP11496794A JPH07316131A JP H07316131 A JPH07316131 A JP H07316131A JP 11496794 A JP11496794 A JP 11496794A JP 11496794 A JP11496794 A JP 11496794A JP H07316131 A JPH07316131 A JP H07316131A
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- compound
- pyrrole derivative
- following general
- lithium
- 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
- 150000003233 pyrroles Chemical class 0.000 title claims abstract description 7
- 238000000034 method Methods 0.000 title description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 20
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 3
- 238000004519 manufacturing process Methods 0.000 claims abstract 2
- 239000012448 Lithium borohydride Substances 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- 239000003638 chemical reducing agent Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- -1 metal complex compound Chemical class 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- GGSGPPFRVNQBCV-UHFFFAOYSA-N 2,5-bis(1h-pyrrol-2-ylmethyl)-1h-pyrrole Chemical class C=1C=C(CC=2NC=CC=2)NC=1CC1=CC=CN1 GGSGPPFRVNQBCV-UHFFFAOYSA-N 0.000 description 1
- QOXOZONBQWIKDA-UHFFFAOYSA-N 3-hydroxypropyl Chemical compound [CH2]CCO QOXOZONBQWIKDA-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- JALCMIKHVMIZKG-UHFFFAOYSA-N benzyl 5-[[3,4-diethyl-5-[[3-(3-methoxy-3-oxopropyl)-4-methyl-5-phenylmethoxycarbonyl-1h-pyrrol-2-yl]methyl]-1h-pyrrol-2-yl]methyl]-4-(3-methoxy-3-oxopropyl)-3-methyl-1h-pyrrole-2-carboxylate Chemical compound N1C(CC2=C(C(C)=C(C(=O)OCC=3C=CC=CC=3)N2)CCC(=O)OC)=C(CC)C(CC)=C1CC(=C(C=1C)CCC(=O)OC)NC=1C(=O)OCC1=CC=CC=C1 JALCMIKHVMIZKG-UHFFFAOYSA-N 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940039227 diagnostic agent Drugs 0.000 description 1
- 239000000032 diagnostic agent Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- AARXZCZYLAFQQU-UHFFFAOYSA-N motexafin gadolinium Chemical compound [Gd].CC(O)=O.CC(O)=O.C1=C([N-]2)C(CC)=C(CC)C2=CC(C(=C2C)CCCO)=NC2=CN=C2C=C(OCCOCCOCCOC)C(OCCOCCOCCOC)=CC2=NC=C2C(C)=C(CCCO)C1=N2 AARXZCZYLAFQQU-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Natural products C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
Abstract
(57)【要約】
【目的】 医療分野で有用なテキサフィリン類の合成中
間体として有用なピロール誘導体を、容易かつ安価に、
高純度で得る製造方法の提供。
【構成】 下記一般式（Ｉ）
【化１】
（上記式中で、ＲはＣ1〜Ｃ4のアルキル基を表し、ｐｈ
はフェニル基を表す。）で表される化合物をＬｉＢＨ4
で還元させて、下記一般式（II）
【化２】
で表されるピロール誘導体を製造する。(57) [Summary] [Objective] A pyrrole derivative useful as a synthetic intermediate for texaphyrins useful in the medical field can be easily and inexpensively produced.
Providing a manufacturing method with high purity. [Structure] The following general formula (I): (In the above formula, R represents a C 1 -C 4 alkyl group, and ph
Represents a phenyl group. ) The compound represented by LiBH 4
With the following general formula (II): The pyrrole derivative represented by
Description
【０００１】[0001]
【産業上の利用分野】本発明は、医療分野において有用
な化合物であるテキサフィリン類の製造に有用な合成中
間体であるピロール誘導体の製造方法に関し、詳しくは
２，５−ビス［（ピロール−２−イル）メチル］ピロー
ル誘導体の製造方法に関する。TECHNICAL FIELD The present invention relates to a process for producing a pyrrole derivative which is a synthetic intermediate useful for producing texaphyrins which are compounds useful in the medical field, and more specifically to 2,5-bis [(pyrrole-2 -Yl) methyl] pyrrole derivatives.
【０００２】[0002]
【従来の技術および発明が解決しようとする課題】テキ
サフィリンの金属錯体、例えばガドリニウムテキサフィ
リンは体内診断薬として有用である（Ｓｅｓｓｌｅｒ，
ｅｔｃ．，Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１１５，１
０３６８（１９９３）、Ｓｅｓｓｌｅｒ．ｅｔｃ．，Ａ
ｃｃ．Ｃｈｅｍ．Ｒｅｓ．，２７，４３（１９９
４））。この化合物は、下記一般式（II）で表される化
合物を中間体とするルートで合成できることが知られて
おり（Ｓｅｓｓｌｅｒ，Ｉｎｏｒｇ．Ｃｈｅｍ．，３
２，３１７５（１９９３））、更に下記一般式（II）の
化合物は、下記一般式（Ｉ）の化合物より合成されてい
る。この時、下記一般式（Ｉ）の化合物の２種類のエス
テル基を選択的に還元する必要があり、還元剤としてジ
ボランを使用している。しかし、ジボランは極めて毒性
が高い還元剤であるため、エステル基を選択的に還元す
るジボラン以外の還元剤が強く求められていた。BACKGROUND OF THE INVENTION Metal complexes of texaphyrin, such as gadolinium texaphyrin, are useful as in-vivo diagnostic agents (Sessler,
etc. J. Am. Chem. Soc. , 115 , 1
0368 (1993), Sessler. etc. , A
cc. Chem. Res. , 27 , 43 (199
4)). It is known that this compound can be synthesized by a route using a compound represented by the following general formula (II) as an intermediate (Sessler, Inorg. Chem., 3
2 , 3175 (1993)), and the compound of the following general formula (II) is synthesized from the compound of the following general formula (I). At this time, it is necessary to selectively reduce two kinds of ester groups of the compound of the following general formula (I), and diborane is used as a reducing agent. However, since diborane is a highly toxic reducing agent, there has been a strong demand for reducing agents other than diborane that selectively reduce ester groups.
【０００３】[0003]
【問題を解決するための手段】本発明者らは、毒性の低
い還元剤の開発を目的として鋭意検討を重ねた結果、水
素化ホウ素リチウムを使用するとジボランと同等にエス
テル基を選択的に還元できることを見出し本発明に到達
した。即ち、本発明の要旨は、下記一般式（Ｉ）[Means for Solving the Problems] As a result of intensive studies aimed at developing a reducing agent having low toxicity, the present inventors have found that the use of lithium borohydride selectively reduces an ester group in the same manner as diborane. The inventors have found what can be done and have reached the present invention. That is, the gist of the present invention is the general formula (I)
【０００４】[0004]
【化３】 [Chemical 3]
【０００５】（上記式中で、ＲはＣ1〜Ｃ4のアルキル基
を表し、ｐｈはフェニル基を表す。）で表される化合物
を水素化ホウ素リチウムで還元させることを特徴とする
下記一般式（II）(In the above formula, R represents a C 1 -C 4 alkyl group and ph represents a phenyl group.) A compound represented by the following general formula characterized by reducing with lithium borohydride Formula (II)
【０００６】[0006]
【化４】 [Chemical 4]
【０００７】で表されるピロール誘導体の製造方法に存
する。以下、本発明につき詳細に説明する。上記一般式
（Ｉ）中のＲとしてはメチル基、エチル基、ｎ−プロピ
ル基、イソプロピル基、ｎ−ブチル基等のＣ1〜Ｃ4のア
ルキル基が挙げられる。本発明で用いられる水素化ホウ
素リチウムとしては市販品を用いることができるが、さ
らに経済的に反応を行うには、反応系中で水素化ホウ素
ナトリウムあるいは水素化ホウ素カリウムに塩化リチウ
ム、臭化リチウム、ヨウ化リチウム等のリチウム塩を作
用させ水素化ホウ素リチウムを調製することも可能であ
る。リチウム塩は水素化ホウ素ナトリウム等の金属水素
錯化合物に対して０．１〜１０モル当量、好ましくは
０．５〜２モル当量使用する。反応系中で、水素化ホウ
素リチウムを生成させる場合、水素化ホウ素リチウムを
あらかじめ生成させた後、上記一般式（Ｉ）の化合物を
反応させる方法、または、上記一般式（Ｉ）の化合物の
存在下、金属錯化合物にリチウム塩を作用させる方法の
どちらでもかまわない。水素化ホウ素リチウムの必要量
は、上記一般式（Ｉ）の化合物に対し０．１〜２０モル
当量、好ましくは０．５〜５モル当量程度である。The method is for producing a pyrrole derivative represented by Hereinafter, the present invention will be described in detail. Examples of R in the general formula (I) include C 1 to C 4 alkyl groups such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group. As the lithium borohydride used in the present invention, commercially available products can be used, but in order to carry out the reaction more economically, sodium borohydride or potassium borohydride is added to lithium chloride or lithium bromide in the reaction system. It is also possible to prepare lithium borohydride by reacting a lithium salt such as lithium iodide. The lithium salt is used in an amount of 0.1 to 10 molar equivalents, preferably 0.5 to 2 molar equivalents, based on the metal hydrogen complex compound such as sodium borohydride. When lithium borohydride is produced in the reaction system, a method of reacting the compound of the above general formula (I) after previously producing lithium borohydride, or the presence of the compound of the above general formula (I) It does not matter whether the metal complex compound is reacted with a lithium salt. The required amount of lithium borohydride is 0.1 to 20 molar equivalents, preferably about 0.5 to 5 molar equivalents, with respect to the compound of the general formula (I).
【０００８】反応溶媒としては反応に悪い影響を与えな
ければ特に制限されないが、ジエチルエテ−ル、テトラ
ヒドロフラン、ｎ−ヘキサン、ベンゼン、トルエン、エ
タノール、イソプロパノール等が使用できる。反応温度
は−５０〜１５０℃の範囲、好ましくは−２０〜１００
℃の範囲である。こうして得られた粗組成物は再結晶、
カラムクロマトグラフィー等により精製できる。The reaction solvent is not particularly limited as long as it does not adversely affect the reaction, and diethyl ether, tetrahydrofuran, n-hexane, benzene, toluene, ethanol, isopropanol and the like can be used. The reaction temperature is in the range of -50 to 150 ° C, preferably -20 to 100.
It is in the range of ° C. The crude composition thus obtained is recrystallized,
It can be purified by column chromatography or the like.
【０００９】[0009]
【実施例】以下、本発明を実施例により更に詳細に説明
するが、本発明はその要旨を越えない限り以下の実施例
により限定されるものではない。 実施例１ 水素化ホウ素リチウム（２２．７ｍｇ、１．０ｍｍｏ
ｌ）のテトラヒドロフラン（ＴＨＦ）懸濁液（２ｍｌ）
に、２，５−ビス［（５−ベンジルオキシカルボニル−
３−メトキシカルボニルエチル−４−メチルピロール−
２−イル）メチル］−３，４−ジエチルピロール（一般
式（Ｉ）の化合物，Ｒ＝Ｍｅ）（１４１ｍｇ、０．１９
ｍｍｏｌ）を加え、４０℃で４時間加熱撹拌した。反応
液を冷却後、飽和食塩水を加え、酢酸エチルで抽出し
た。有機層を炭酸カリウムで乾燥後、濾過し溶媒を留去
することにより２，５−ビス［（５−ベンジルオキシカ
ルボニル−３−（３−ヒドロキシプロピル）−４−メチ
ルピロール−２−イル）メチル］−３，４−ジエチルピ
ロール（一般式（II）の化合物）（１１８ｍｇ、収率８
４％）を得た。The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. Example 1 Lithium borohydride (22.7 mg, 1.0 mmo
1) tetrahydrofuran (THF) suspension (2 ml)
2,5-bis [(5-benzyloxycarbonyl-
3-methoxycarbonylethyl-4-methylpyrrole-
2-yl) methyl] -3,4-diethylpyrrole (compound of general formula (I), R = Me) (141 mg, 0.19
mmol) was added and the mixture was heated with stirring at 40 ° C. for 4 hours. The reaction solution was cooled, saturated brine was added, and the mixture was extracted with ethyl acetate. The organic layer was dried over potassium carbonate, filtered, and the solvent was evaporated to remove 2,5-bis [(5-benzyloxycarbonyl-3- (3-hydroxypropyl) -4-methylpyrrol-2-yl) methyl. ] -3,4-diethylpyrrole (compound of general formula (II)) (118 mg, yield 8)
4%).
【００１０】1Ｈ−ＮＭＲ １．１１（６Ｈ，ｔ，Ｊ＝７．５Ｈｚ，ＣＨ2ＣＨ3）
１．５７−１．６１（ｍ，４Ｈ，ＣＨ2ＣＨ2ＣＨ2Ｏ
Ｈ） ２．２４（６Ｈ，Ｓ，Ｐｙｒｒ−ＣＨ3） ２．４１−２．４８（８Ｈ，ｍ，ＣＨ2ＣＨ3 ａｎｄ
ＣＨ2ＣＨ2ＣＨ2ＯＨ） ３． ５１（４Ｈ，ｔ，Ｊ＝６．０Ｈｚ） ３．７５
（４Ｈ，Ｓ，Ｐｙｒｒ） 2−ＣＨ2） ４．９９（４Ｈ，
Ｓ，Ｃ6Ｈ5−ＣＨ2） ７．１７−７．４０（１０Ｈ，
ｍ） ８．５２（Ｓ，１Ｈ，ＮＨ） ９．４４（Ｓ，２
Ｈ，ＮＨ）[0010]1H-NMR 1.11 (6H, t, J = 7.5Hz, CH2CH3)
1.57-1.61 (m, 4H, CH2CH2CH2O
H) 2.24 (6H, S, Pyrr-CH3) 2.41-2.48 (8H, m, CH2CH3 and
CH2CH2CH2OH) 3. 51 (4H, t, J = 6.0 Hz) 3.75
(4H, S, Pyrr) 2-CH2) 4.99 (4H,
S, C6HFive-CH2) 7.17-7.40 (10H,
m) 8.52 (S, 1H, NH) 9.44 (S, 2)
H, NH)
【００１１】実施例２ 窒素雰囲気下、水素化ホウ素カリウム（５４．６ｍｇ，
１．０ｍｍｏｌ）と塩化リチウム（４３．４ｍｇ，１．
０ｍｍｏｌ）のＴＨＦ懸濁液（２ｍｌ）を室温で４時間
撹拌させ、反応液中に水素化ホウ素リチウムを生成させ
た後、一般式（Ｉ）の化合物（Ｒ＝Ｍｅ）（１４９．８
ｍｇ，０．２ｍｍｏｌ）を加え、１．５時間加熱還流し
た。実施例１の方法と同様に後処理をすることにより、
一般式（II）の化合物（１３７．５ｍｇ，収率９９％）
を得た。Example 2 Potassium borohydride (54.6 mg, under a nitrogen atmosphere)
1.0 mmol) and lithium chloride (43.4 mg, 1.
A THF suspension (2 ml) of 0 mmol) was stirred at room temperature for 4 hours to generate lithium borohydride in the reaction solution, and then the compound of general formula (I) (R = Me) (149.8).
(mg, 0.2 mmol) was added and the mixture was heated under reflux for 1.5 hours. By performing the post-treatment in the same manner as in the method of Example 1,
Compound of general formula (II) (137.5 mg, yield 99%)
Got
【００１２】実施例３ 窒素雰囲気下、水素化ホウ素カリウム（５２．１ｍｇ，
１．０ｍｍｏｌ）、塩化リチウム（４２．５ｍｇ，１．
０ｍｍｏｌ）のＴＨＦ懸濁液（２ｍｌ）、および一般式
（Ｉ）の化合物（Ｒ＝Ｍｅ）（１４０．７ｍｇ，０．１
９ｍｍｏｌ）を混合し、４０℃で６時間加熱撹拌した。
実施例１の方法と同様に後処理をすることにより、一般
式（II）の化合物（１２２．２ｍｇ，収率９３％）を得
た。Example 3 Potassium borohydride (52.1 mg,
1.0 mmol), lithium chloride (42.5 mg, 1.
0 mmol) in THF (2 ml), and a compound of general formula (I) (R = Me) (140.7 mg, 0.1
(9 mmol) was mixed, and the mixture was heated with stirring at 40 ° C. for 6 hours.
Post-treatment was carried out in the same manner as in the method of Example 1 to obtain a compound of the general formula (II) (122.2 mg, yield 93%).
【００１３】[0013]
【発明の効果】本発明の方法によれば、医療分野等で有
用な化合物であるテキサフィリン類の合成中間体として
有用なピロール誘導体を、毒性が高いジボランを使用す
ることなく、容易かつ安価な製造方法にて高純度に製造
できる。Industrial Applicability According to the method of the present invention, a pyrrole derivative useful as a synthetic intermediate for texaphyrins, which is a compound useful in the medical field and the like, can be easily and inexpensively produced without using highly toxic diborane. It can be produced in high purity by the method.
Claims (1)
はフェニル基を表す。）で表される化合物を水素化ホウ
素リチウムで還元させることを特徴とする下記一般式
（II） 【化２】 で表されるピロール誘導体の製造方法。1. The following general formula (I): (In the above formula, R represents a C 1 -C 4 alkyl group, and ph
Represents a phenyl group. ) A compound represented by the following general formula (II), which is characterized by reducing with lithium borohydride. The manufacturing method of the pyrrole derivative represented by.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11496794A JPH07316131A (en) | 1994-05-27 | 1994-05-27 | Process for producing pyrrole derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11496794A JPH07316131A (en) | 1994-05-27 | 1994-05-27 | Process for producing pyrrole derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07316131A true JPH07316131A (en) | 1995-12-05 |
Family
ID=14651069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11496794A Pending JPH07316131A (en) | 1994-05-27 | 1994-05-27 | Process for producing pyrrole derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07316131A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159669A1 (en) * | 2016-03-15 | 2017-09-21 | 塩野義製薬株式会社 | Method for producing phenoxyethanol derivative |
-
1994
- 1994-05-27 JP JP11496794A patent/JPH07316131A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017159669A1 (en) * | 2016-03-15 | 2017-09-21 | 塩野義製薬株式会社 | Method for producing phenoxyethanol derivative |
| CN108137457A (en) * | 2016-03-15 | 2018-06-08 | 盐野义制药株式会社 | The manufacturing method of Phenoxyethanol derivative |
| KR20180122330A (en) * | 2016-03-15 | 2018-11-12 | 시오노기 앤드 컴파니, 리미티드 | Process for producing phenoxyethanol derivative |
| US20190084910A1 (en) * | 2016-03-15 | 2019-03-21 | Shionogi & Co., Ltd.[ | Method for Producing Phenoxyethanol Derivative |
| US10472312B2 (en) | 2016-03-15 | 2019-11-12 | Shionogi & Co., Ltd. | Method for producing phenoxyethanol derivative |
| EA039048B1 (en) * | 2016-03-15 | 2021-11-26 | Сионоги Энд Ко., Лтд. | Method for producing phenoxyethanol derivatives |
| CN108137457B (en) * | 2016-03-15 | 2022-09-06 | 盐野义制药株式会社 | Method for producing phenoxyethanol derivative |
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