JPS63185959A - Production of indolines - Google Patents
Production of indolinesInfo
- Publication number
- JPS63185959A JPS63185959A JP62016467A JP1646787A JPS63185959A JP S63185959 A JPS63185959 A JP S63185959A JP 62016467 A JP62016467 A JP 62016467A JP 1646787 A JP1646787 A JP 1646787A JP S63185959 A JPS63185959 A JP S63185959A
- Authority
- JP
- Japan
- Prior art keywords
- raney
- indolines
- indoles
- catalyst
- hydrogen
- 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
- 150000002476 indolines Chemical class 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 24
- 239000010941 cobalt Substances 0.000 claims abstract description 24
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 24
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002475 indoles Chemical class 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 10
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 125000002768 hydroxyalkyl group Chemical group 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000002904 solvent Substances 0.000 abstract description 5
- BFQARNDIMKOOQQ-UHFFFAOYSA-N 3-methyl-2,3-dihydro-1h-indole Chemical compound C1=CC=C2C(C)CNC2=C1 BFQARNDIMKOOQQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 16
- ZFRKQXVRDFCRJG-UHFFFAOYSA-N skatole Chemical compound C1=CC=C2C(C)=CNC2=C1 ZFRKQXVRDFCRJG-UHFFFAOYSA-N 0.000 description 10
- 238000006722 reduction reaction Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- NVUGEQAEQJTCIX-UHFFFAOYSA-N N-acetyltryptamine Chemical compound C1=CC=C2C(CCNC(=O)C)=CNC2=C1 NVUGEQAEQJTCIX-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 2
- HZEWFHLRYVTOIW-UHFFFAOYSA-N [Ti].[Ni] Chemical compound [Ti].[Ni] HZEWFHLRYVTOIW-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- JGDFBJMWFLXCLJ-UHFFFAOYSA-N copper chromite Chemical compound [Cu]=O.[Cu]=O.O=[Cr]O[Cr]=O JGDFBJMWFLXCLJ-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 125000001041 indolyl group Chemical group 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910001000 nickel titanium Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LJVFBUDYUADYER-UHFFFAOYSA-N 2,3-dihydro-1h-indol-3-ylmethanol Chemical compound C1=CC=C2C(CO)CNC2=C1 LJVFBUDYUADYER-UHFFFAOYSA-N 0.000 description 1
- BHNHHSOHWZKFOX-UHFFFAOYSA-N 2-methyl-1H-indole Chemical compound C1=CC=C2NC(C)=CC2=C1 BHNHHSOHWZKFOX-UHFFFAOYSA-N 0.000 description 1
- AYIYBBZENMJOER-UHFFFAOYSA-N 3-ethyl-2,3-dihydro-1h-indole Chemical compound C1=CC=C2C(CC)CNC2=C1 AYIYBBZENMJOER-UHFFFAOYSA-N 0.000 description 1
- ZCJGZUQXRFHPQL-UHFFFAOYSA-N 3-methyl-2,3,3a,4,5,6,7,7a-octahydro-1h-indole Chemical compound C1CCCC2C(C)CNC21 ZCJGZUQXRFHPQL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000003815 Interleukin-11 Human genes 0.000 description 1
- 108090000177 Interleukin-11 Proteins 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 235000003434 Sesamum indicum Nutrition 0.000 description 1
- 244000000231 Sesamum indicum Species 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229940060942 methylin Drugs 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- LGWUGAXPKZWKCB-UHFFFAOYSA-N n-[2-(2,3-dihydro-1h-indol-3-yl)ethyl]acetamide Chemical compound C1=CC=C2C(CCNC(=O)C)CNC2=C1 LGWUGAXPKZWKCB-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Indole Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
■
本発明は、インドリン類の製造方法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION (1) The present invention relates to a method for producing indolines.
近年、インドリン類は医薬、農薬、感光材料などの合成
中間化合物として注目されてきている。In recent years, indolines have attracted attention as synthetic intermediate compounds for pharmaceuticals, agricultural chemicals, photosensitive materials, etc.
ＬＬへ１１
インドール類を接触還元してインドリン類を得るには、
次の方法が知られている。To LL11 To obtain indolines by catalytic reduction of indoles,
The following methods are known.
■ 銅クロマイト触媒を使用する方法。（Ｉｌ、Ａｄｋ
ｉｎｓ、ｅｔａｌ、 Ｊ、Ａｍ、Ｃｈｅｍ、Ｓｏｃ、、
＋ｉ３，１５６３．（１９４１））■ ラネーニッケル
触媒を使用する方法、 （Ｗ、Ｅ。■ Method using copper chromite catalyst. (Il, Adk
ins, etal, J, Am, Chem, Soc,,
+i3,1563. (1941)) ■ Method using Raney nickel catalyst, (W, E.
Ｎｏ１ａｎｄ、ｅｔａｌ、 Ｊ、Ｏｒｇ、Ｃｈａｍ、、
２５，１５２５．（１９６１１））■ ニッケルーチタ
ン触媒を使用し、銅、コバルト、カドミウム、鉄等の塩
を添加して行う方法。No1and, etal, J, Org, Cham,...
25,1525. (19611)) ■ A method using a nickel-titanium catalyst and adding salts such as copper, cobalt, cadmium, iron, etc.
（ＵＳＳＲ５７９，２７０）
■の方法の銅クロマイト触媒は、反応温度が１９０℃前
後と高温が必要な上、副反応が多く、収率は満足いくも
のではない。■の方法のラネーニッケル触媒で還元する
方法は、比較的低温で反応するが、選択性が悪く、イン
ドール環が完全１こ水添されたオクタヒドロインドール
類が大量に副生し、目的とするインドリン類の収率は低
いものしか得られていない。■のニッケルーチタン触媒
を使用する方法は、インドリン類の収率はほぼ満足でき
るものであるが触媒の入手が難しく、また第三物質を添
加する必要があるなど、工業的にインドリン類を製造す
るに際し、充分なものとはいえない。(USSR 579, 270) The copper chromite catalyst used in method (1) requires a high reaction temperature of around 190°C, and also has many side reactions, resulting in an unsatisfactory yield. Method (2), which involves reduction using a Raney nickel catalyst, reacts at a relatively low temperature, but the selectivity is poor and a large amount of octahydroindoles, in which the indole ring is completely monohydrogenated, is produced as a by-product. Only low yields have been obtained. The method using a nickel-titanium catalyst provides a nearly satisfactory yield of indolines, but it is difficult to obtain catalysts, and it is necessary to add a third substance to produce indolines industrially. However, it cannot be said to be sufficient.
Ｆｉ ｆ ゛ べ 。Fi f ゛ .
本発明は、インドール類を接触水素還元してインドリン
類を製造するに際して、肩記問題点を解決し工業的に容
易にインドリン類を製造する方法を提供するものである
。The present invention solves the above-mentioned problems when producing indolines by catalytic hydrogen reduction of indoles and provides a method for industrially and easily producing indolines.
ａ を ° 、。a ,.
すなわち、本発明は一般式（Ｉ）
（式中、Ｒはアルキル基、ヒドロキシアルキル基および
Ｎ−アシルアミノアルキル基から選ばれる一種の置換基
を表す）
で示されるインドリン類を製造するに際し、対応するイ
ンドール類をラネーコバルト触媒の存在下に水素還元す
ることを特徴とするインドリン類の製造方法である。That is, the present invention provides a method for producing indolines represented by the general formula (I) (wherein R represents a substituent selected from an alkyl group, a hydroxyalkyl group, and an N-acylaminoalkyl group). This is a method for producing indolines, which is characterized by reducing indoles with hydrogen in the presence of a Raney cobalt catalyst.
本発明で製造できるインドリン類を具体的に列挙すれば
、例えば、３−メチルインドリン、３−エチルインドリ
ン、３−ヒドロキシメチルインドリン゛、２．３−ジヒ
ドロトリプトホール、２，３−ジヒドロホモトリプトホ
ール、２，３−ジヒドロ−Ｎ−アセチルト、リプタミン
などである。Specific examples of indolines that can be produced in the present invention include 3-methylindoline, 3-ethylindoline, 3-hydroxymethylindoline, 2,3-dihydrotrypthol, 2,3-dihydrohomootryptophol. , 2,3-dihydro-N-acetylate, liptamine, and the like.
本発明で使用されるラネーコバルト触媒は、一般に市販
されているものでよい、ラネー合金はコバルト金属とア
ルミニウム金属をルツボで加熱溶融し、それを機械的に
粉砕したものが普通であるが、水流ジェ・ｌトないし高
圧ガスのエネルギーを利用して溶融合金を噴霧ないしＭ
１ヒさせ一挙に粉末状のラネー合金としたものでも同様
に使用できるう製法はともかくコバルトとアルミニウム
からなるラネー合金の微粉末をアルカリ水溶液中に投入
し、加熱してアルミニウムをアルカリ水溶液中に溶出し
、その後充分に水洗して得たものである。The Raney cobalt catalyst used in the present invention may be one that is generally commercially available.Raney alloys are usually made by heating and melting cobalt metal and aluminum metal in a crucible and then mechanically crushing it. Spraying or M of molten alloy using the energy of jet or high pressure gas
A Raney alloy that is made into a powdered Raney alloy by heating it for one time can be used in the same way.Aside from the production method, a fine powder of a Raney alloy consisting of cobalt and aluminum is put into an alkaline aqueous solution and heated to dissolve the aluminum into the alkaline aqueous solution. and then washed thoroughly with water.
（このようなラネー合金あ活性化の手段を「展開」と呼
ぶ） また、コバルトを主成分とするラネー触媒であれ
ば他種金属を少量含むものであっても良い。他種金属と
しては、マンガン、モリブデン、鉄および鉛などが挙げ
られる。たとえば、コバルト３０％、マンガン３．５％
、アルミニウム６６．５％からなるラネー合金が市販さ
れている。(Such a means of activating a Raney alloy is called "expansion") Furthermore, as long as the Raney catalyst is mainly composed of cobalt, it may contain a small amount of other metals. Examples of other metals include manganese, molybdenum, iron, and lead. For example, 30% cobalt, 3.5% manganese
, a Raney alloy consisting of 66.5% aluminum is commercially available.
これをアルカリ水溶液中で展開して得たラネーコバルト
触媒はインドリン類の製造において、コバルトのみのラ
ネー触媒よりもむしろ良い結果を与えることが見いださ
れた。It has been found that a Raney cobalt catalyst obtained by developing this in an alkaline aqueous solution gives better results in the production of indolines than a Raney catalyst containing only cobalt.
本発明の方法は無溶媒でも溶媒中でも行われるが、使用
される溶媒としては、アルコール顛、エステル類、エー
テル類、炭化水素類などの内からう、オ・−触媒で水素
添加を受けない溶媒であれば、何れでも使用可能である
。特にメタノール、エタノール、イソプロパツール等の
低級アルコールが ′本発明の方法には好適である。The method of the present invention can be carried out without a solvent or in a solvent, but the solvents used include alcohols, esters, ethers, hydrocarbons, etc., and solvents that do not undergo hydrogenation with an O-catalyst. Any of them can be used. In particular, lower alcohols such as methanol, ethanol, and isopropanol are suitable for the method of the present invention.
次に、本発明を実施する際の水素還元条件について説明
する。まずラネーコバルト触媒の使用量は、原料のイン
ドール類に対し３〜５０重量％の範囲で使用すれば良く
、好ましくは１０〜３０重ｆｆｉ ？０の使用が望まし
い０反応水素圧力は比較的高圧のほうが好ましく、２０
〜１５０にζ／ｃｍ’での反応がインドリン類の選択生
成率に良い結果を与える。したがって本発明の方法はオ
ートクレーブ中で実施する必要がある。反応温度は５０
〜２５０℃で行われるが、特に７０ないし１５０°Ｃの
範囲の温度で実施することが好ましい。反応温度が低ず
ぎる場合には反応完結の所要時間がいたずらに長くかか
り、また反応温度が高すぎる場合には副反応が生起しや
すく、インドリン類の収率は低下する。Next, hydrogen reduction conditions when carrying out the present invention will be explained. First, the Raney cobalt catalyst may be used in an amount of 3 to 50% by weight based on the raw material indoles, preferably 10 to 30% by weight. It is preferable to use 0 reaction hydrogen pressure, which is preferably relatively high pressure, 20
The reaction at ~150 ζ/cm' gives good results for the selective production of indolines. Therefore, the method of the invention must be carried out in an autoclave. The reaction temperature is 50
It is carried out at a temperature of -250°C, but it is particularly preferred to carry out at a temperature in the range of 70 to 150°C. If the reaction temperature is too low, the time required to complete the reaction is unnecessarily long, and if the reaction temperature is too high, side reactions are likely to occur and the yield of indolines is reduced.
本発明の方法によってインドール類の水素添加反応を行
った場合、反応所要時間は工ないし６時間を要する。そ
してインドール類の転化率が８０％程度の場合、インド
リン類の実収率は約７５％。When the hydrogenation reaction of indoles is carried out by the method of the present invention, the reaction time is 1 to 6 hours. When the conversion rate of indoles is about 80%, the actual yield of indolines is about 75%.
転（ヒしたインドール類に対する選択生成率は約９５％
以上らの高率でインドリン類を得ることが出来る。副生
成物としてはインドール環が完全に水添されたオクタヒ
ドロインドール類が生成してくるが、インドール類の転
ｆヒ率を８０％以上に上げた場合には、当然その生成量
が多くなり、インドリン類の選択生成率は減少する。未
反応のインドール類の分離回収は蒸留法や塩基性の差を
利用する方法で容易に行われるので、未反応のインドー
ル類は回収して次回の原料として利用していくのが有利
な方法である。The selective production rate for converted indoles is approximately 95%.
Indolines can be obtained at a high rate from the above methods. Octahydroindoles, in which the indole ring is completely hydrogenated, are produced as by-products, but when the conversion rate of indoles is increased to 80% or more, the amount produced naturally increases. , the selective production rate of indolines decreases. Separation and recovery of unreacted indoles can be easily carried out by distillation or a method that utilizes the difference in basicity, so it is an advantageous method to collect unreacted indoles and use them as raw materials for the next time. be.
以下、実施例により本発明を更に詳しく説明する。Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例 １
上下攪拌式２００１オートクレーブに３−メチルインド
ール２０ｇ、メタノール１００１、ラネ。Example 1 20 g of 3-methylindole, 1001 methanol, and Rane were placed in a 2001 autoclave with vertical stirring.
−コバルト触媒４．０ｇ（川研ファインケミカル株式会
社製０ＤＨＴ−６０；コバルトとアルミニウムの比が１
：１であるラネー合金を６０゛Ｃ″′Ｃ′展開した触媒
）を入れ、密閉して水素室ｔＡ後、水素初′圧１００
ｋｇ／ｃｍ”を充填し、１００ ’Ｃに加熱しながら５
．５時間攪拌した。反応終了後冷却してから触媒を濾過
し、反応液をガスクロマトグラフィーで分析した。その
結果は、３−メチルインドール２ ａ １ ？６．３−
メチルインドリン６９．０％、３−メチルオクタヒＹロ
インドール１．７ ｒ＝であり、これより計算すると３
−メチルインドールの転１ヒ率７１．９％を基準とする
３−メチルイン・ドリノの選択生成率は９５．８％であ
った。- 4.0 g of cobalt catalyst (0DHT-60 manufactured by Kawaken Fine Chemical Co., Ltd.; ratio of cobalt to aluminum is 1)
: 60゛C'''C' developed catalyst) is placed in the hydrogen chamber, and after tA, the hydrogen initial pressure is 100.
kg/cm” and heated to 100’C for 5 minutes.
．． Stirred for 5 hours. After the reaction was completed and cooled, the catalyst was filtered, and the reaction solution was analyzed by gas chromatography. The result is 3-methylindole 2 a 1 ? 6.3-
Methyl indoline 69.0%, 3-methyloctahyY loindole 1.7 r = calculated from this, 3
- The selective production rate of 3-methylin dolino was 95.8% based on the conversion rate of methylindole of 71.9%.
実施例 ２
トリプトホール２０ｇをマンガン・入すラネーコバルト
触媒４．０ｇ（川研ファインゲミカル株式会社製０ＦＴ
−５５；コバルト３０％、マンガン′３．５％、アルミ
ニウム６ ｂ、 ５ ｃ′６のラネー合金を５５°Ｃで
展開して得た触媒）を使用し、池の反応条件は実施例１
とまったく同様に還元反応を行った。Example 2 4.0 g of Raney cobalt catalyst containing 20 g of tryptopole and manganese (0FT manufactured by Kawaken Fine Gemical Co., Ltd.)
-55; a catalyst obtained by developing a Raney alloy of 30% cobalt, 3.5% manganese, and aluminum 6b, 5c'6 at 55°C), and the reaction conditions of the pond were as in Example 1.
The reduction reaction was carried out in exactly the same way.
反応終了液の分析結果は、トリプトホール２３．０？６
．２，３−ジヒドロトリプトホール７７．０％であり、
オクタヒドロトリプトホールは検出されなかった。The analysis result of the reaction completed liquid is tryptopole 23.0?6
．． 2,3-dihydrotryptophol 77.0%,
Octahydrotrypthol was not detected.
実施例 ３
ω−Ｎ−アセチルトリプタミン２０ｇをマンガン入すラ
ネーコバルト触媒４．０ｇ（川研ファインクミカル株式
会社製０ＦＴ−５５；コバ！レト３０９６、マンガン３
．５ ％６、アルミニウム６６．５％のラネー合金を５
５℃で展開して得た触媒）を使用し。Example 3 4.0 g of Raney cobalt catalyst containing 20 g of ω-N-acetyltryptamine and manganese (0FT-55 manufactured by Kawaken Fine Chemical Co., Ltd.; Koba! Reto 3096, Manganese 3)
．． Raney alloy of 5% 6 and aluminum 66.5%
A catalyst obtained by developing at 5°C was used.
池の反応条件は実施例１とまったく同様に還元反応を行
った。還元終了まで７時間を要した０反応終了液の分析
結果は、Ｎ−アセチルトリプタミン２３．０％、２，３
−ジヒドロ−Ｎ−アセチルトリプタミン７７．０％、オ
クタヒドロ−Ｎ−アセチルトリプタミン１．９％、であ
りこれより計算すると２３−ジヒドロ−Ｎ−アセチルト
リプタミンの選択率は９６，８％であった。The reduction reaction was carried out under the same conditions as in Example 1. The analysis results of the 0 reaction completed solution, which took 7 hours to complete the reduction, were 23.0% N-acetyltryptamine, 2,3
-dihydro-N-acetyltryptamine was 77.0% and octahydro-N-acetyltryptamine was 1.9%, and when calculated from these, the selectivity for 23-dihydro-N-acetyltryptamine was 96.8%.
比較例
ト下攪拌ｆ２００ｍｌオートクレーブに３−メチルイン
ドール２０ｇ、メタノール１００ｍ１、ラネーニラゲル
触媒４．０ｇ（川研ファインケミカル株式会社製ＮＤＴ
−９０；ニラゲルとアルミニウムの比が４：６であるラ
ネー合金を９０℃で展開した触媒）を入れ、密閉して水
素置換後、水素初圧１００ ｋｇ／Ｃｍ″を充填し、１
００℃に加熱しながら５．５時間攪拌した。反応終了後
冷却してから触媒を濾過し、反応液をガスクワマドグラ
フィーで分析した。その結果は、３−メチルインドール
１２．７％、３−メチルインドリンフ０．８％、３−メ
チルオクタヒドロインドール１３．７％であり、これよ
り計算すると３−メチルインドールの転ｆヒ率８７．３
％を基準とする３−メチルインドリンの選択生成率は８
１．１％であった。Comparative Example 20g of 3-methylindole, 100ml of methanol, 4.0g of Raney Nylagel catalyst (NDT manufactured by Kawaken Fine Chemical Co., Ltd.) were placed in a 200ml autoclave with stirring.
-90: A catalyst prepared by developing a Raney alloy with a ratio of 4:6 of Niragel and aluminum at 90°C) was placed in the container, the container was sealed, and after replacing with hydrogen, the initial pressure of hydrogen was 100 kg/Cm''.
The mixture was stirred for 5.5 hours while heating to 00°C. After the reaction was completed, the mixture was cooled, the catalyst was filtered, and the reaction solution was analyzed by gas quamography. The results were 12.7% of 3-methylindole, 0.8% of 3-methylindolph, and 13.7% of 3-methyloctahydroindole. Based on these calculations, the conversion rate of 3-methylindole was 87. .3
The selective production rate of 3-methylindoline based on % is 8
It was 1.1%.
ＩＬへ１１
本発明の方法により、インドリン類を工業的に容易に、
収率よく製造することが可能になった。To IL11 By the method of the present invention, indolines can be easily produced industrially.
It became possible to produce with good yield.
Claims (3)
Ｎ−アシルアミノアルキル基から選ばれる一種の置換基
を表す） で示されるインドリン類を製造するに際し、対応するイ
ンドール類をラネーコバルト触媒の存在下に水素還元す
ることを特徴とするインドリン類の製造方法。(1) General formula (I) ▲Mathematical formula, chemical formula, table, etc.▼(I) (In the formula, R represents a type of substituent selected from an alkyl group, a hydroxyalkyl group, and an N-acylaminoalkyl group) A method for producing indolines, which comprises reducing the corresponding indoles with hydrogen in the presence of a Raney cobalt catalyst.
から成るラネー合金から得られたものである特許請求の
範囲第一項記載の製造方法。(2) The manufacturing method according to claim 1, wherein the Raney cobalt catalyst is obtained from a Raney alloy consisting of cobalt and aluminum.
ルミニウムから成るラネー合金から得られたものである
特許請求の範囲第一項記載の製造方法。(3) The manufacturing method according to claim 1, wherein the Raney cobalt catalyst is obtained from a Raney alloy consisting of cobalt, manganese, and aluminum.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62016467A JPH0798801B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing indolines |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62016467A JPH0798801B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing indolines |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63185959A true JPS63185959A (en) | 1988-08-01 |
| JPH0798801B2 JPH0798801B2 (en) | 1995-10-25 |
Family
ID=11917061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62016467A Expired - Fee Related JPH0798801B2 (en) | 1987-01-27 | 1987-01-27 | Method for producing indolines |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0798801B2 (en) |
-
1987
- 1987-01-27 JP JP62016467A patent/JPH0798801B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0798801B2 (en) | 1995-10-25 |
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