JPS649302B2 - - Google Patents
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- Publication number
- JPS649302B2 JPS649302B2 JP57150026A JP15002682A JPS649302B2 JP S649302 B2 JPS649302 B2 JP S649302B2 JP 57150026 A JP57150026 A JP 57150026A JP 15002682 A JP15002682 A JP 15002682A JP S649302 B2 JPS649302 B2 JP S649302B2
- Authority
- JP
- Japan
- Prior art keywords
- naphthol
- tetrahydro
- catalyst
- reaction
- nickel
- 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
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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
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、５，６，７，８―テトラヒドロ―２
―ナフトールの製造法に関するものである。さら
に詳しくは、β―ナフトールをニツケル担持触媒
存在下水素と接触させることにより５，６，７，
８―テトラヒドロ―２―ナフトールを製造する方
法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides 5,6,7,8-tetrahydro-2
- Concerning the method for producing naphthol. More specifically, by contacting β-naphthol with hydrogen in the presence of a nickel-supported catalyst, 5,6,7,
The present invention relates to a method for producing 8-tetrahydro-2-naphthol.
５，６，７，８―テトラヒドロ―２―ナフトー
ルは医薬及び農薬の中間体として有用な化合物で
ある。 5,6,7,8-tetrahydro-2-naphthol is a compound useful as an intermediate for pharmaceuticals and agricultural chemicals.
例えば、ドイツ公開特許公報2313845号には、
本発明化合物を原料とする殺菌剤が、そしてブー
チン オブ ワールド ヘルス オルガニゼーシ
ヨン40巻369―75頁（1970年）には、本発明化合
物を原料とする殺虫剤がそれぞれ開示されてい
る。 For example, in German Published Patent Application No. 2313845,
A fungicide made from the compound of the present invention and an insecticide made from the compound of the present invention are disclosed in Book of World Health Organization, Vol. 40, pp. 369-75 (1970).
β―ナフトールを水素化触媒存在下水素と接触
させる５，６，７，８―テトラヒドロ―２―ナフ
トールの製造方法は公知である。 A method for producing 5,6,7,8-tetrahydro-2-naphthol in which β-naphthol is contacted with hydrogen in the presence of a hydrogenation catalyst is known.
日本化学会誌、51巻、208〜221頁、（1930年）
には、β―ナフトールを担体に担持させることな
く還元ニツケル触媒存在下水素と接触させる５，
６，７，８―テトラヒドロ―２―ナフトールの製
造が開示されている。それによると、硝酸ニツケ
ルを砂浴上にて350℃に加熱して酸化ニツケルと
し、次いで290〜320℃にて水素還元ニツケル触媒
とする。この還元ニツケル触媒を用いてβ―ナフ
トールを反応温度160℃、反応水素圧７Kg／cm2に
て水素化し５，６，７，８―テトラヒドロ―２―
ナフトールを51.6％の収率で得ている。 Journal of the Chemical Society of Japan, Vol. 51, pp. 208-221, (1930)
In this method, β-naphthol is brought into contact with hydrogen in the presence of a reduced nickel catalyst without being supported on a carrier5.
The production of 6,7,8-tetrahydro-2-naphthol is disclosed. According to the report, nickel nitrate is heated to 350°C on a sand bath to form nickel oxide, and then heated to 290-320°C to form a hydrogen-reduced nickel catalyst. Using this reduced nickel catalyst, β-naphthol was hydrogenated at a reaction temperature of 160°C and a reaction hydrogen pressure of 7 kg/cm 2 to 5,6,7,8-tetrahydro-2-
Naphthol is obtained with a yield of 51.6%.
しかし、その他に副生成物として１，２，３，
４―テトラヒドロ―２―ナフトールが47.2％生成
している。 However, other by-products include 1, 2, 3,
4-tetrahydro-2-naphthol was produced at 47.2%.
以上の如く、担体に担持させることなく、還元
ニツケル触媒を用いる公知の方法で、β―ナフト
ールを水素化すると目的の５，６，７，８―テト
ラヒドロ―２―ナフトールとほぼ等量の１，２，
３，４―テトラヒドロ―２―ナフトールが生成す
る重大な欠点を有している。 As described above, when β-naphthol is hydrogenated by a known method using a reduced nickel catalyst without being supported on a carrier, approximately the same amount of 1, 2,
It has the serious disadvantage of producing 3,4-tetrahydro-2-naphthol.
そこで本発明者らは、１，２，３，４―テトラ
ヒドロ―２―ナフトールの副生を抑制する方法に
ついて、種々の試験をし鋭意検討した。 Therefore, the present inventors conducted various tests and intensively studied methods for suppressing the by-product of 1,2,3,4-tetrahydro-2-naphthol.
その結果、ニツケル（ニツケルの外に他の金属
を含んでいてもよい）を適当な担体に担持させた
ニツケル担持触媒存在下β―ナフトールと水素を
接触させれば１，２，３，４―テトラヒドロ―２
―ナフトールの副生を低減でき、収率よく５，
６，７，８―テトラヒドロ―２―ナフトールを製
造できることを見い出し本発明を完成した。 As a result, if β-naphthol and hydrogen are brought into contact with hydrogen in the presence of a nickel-supported catalyst in which nickel (which may contain other metals in addition to nickel) is supported on a suitable carrier, 1,2,3,4- Tetrahydro-2
- Naphthol by-product can be reduced and the yield is good5.
The present invention was completed by discovering that 6,7,8-tetrahydro-2-naphthol can be produced.
本発明に用いるニツケル担持触媒とはケイソウ
土、アルミナ或いはアルカリ性担体に過半量のニ
ツケルと鉄、クロム、モリブデン、バナジウム、
マンガン、タングステン、鉛、コバルト、銅、
銀、錫その他の金属を担持した触媒であり、ニツ
ケルの担持量は10〜50重量％が適当である。 The nickel-supported catalyst used in the present invention is a diatomaceous earth, alumina, or alkaline carrier containing a majority of nickel and iron, chromium, molybdenum, vanadium,
Manganese, tungsten, lead, cobalt, copper,
It is a catalyst supporting silver, tin, and other metals, and the amount of nickel supported is suitably 10 to 50% by weight.
触媒として反応に用いる場合には、このニツケ
ル担持触媒をβ―ナフトールに対して重量で５％
以上用いればよい。 When used as a catalyst in a reaction, this nickel-supported catalyst is used at a concentration of 5% by weight based on β-naphthol.
The above may be used.
そして反応を円滑に進めるためには、メタノー
ル、エタノール等のアルコール、酢酸エチル等の
カルボン酸エステル、テトラヒドロフラン等のエ
ーテル等の水素化反応に耐えうる溶媒を用いる。 In order to proceed with the reaction smoothly, a solvent that can withstand the hydrogenation reaction is used, such as an alcohol such as methanol or ethanol, a carboxylic acid ester such as ethyl acetate, or an ether such as tetrahydrofuran.
反応温度及び反応水素圧力の上昇は反応速度を
高めるが、一方で副生成物の１，２，３，４―テ
トラヒドロ―２―ナフトールの生成量を増加させ
る、特に高温でかつ高圧下ではその生成は著し
い。そのため通常は反応温度は70〜200℃、好ま
しくは100〜150℃また反応水素圧力は20〜200
Kg／cm2、好ましくは30〜100Kg／cm2である。 Increasing the reaction temperature and reaction hydrogen pressure increases the reaction rate, but on the other hand increases the amount of by-product 1,2,3,4-tetrahydro-2-naphthol produced, especially at high temperatures and pressures. is remarkable. Therefore, the reaction temperature is usually 70 to 200℃, preferably 100 to 150℃, and the reaction hydrogen pressure is 20 to 200℃.
Kg/cm 2 , preferably 30 to 100 Kg/cm 2 .
反応は通常２〜20時間以内に完結させることが
できる。 The reaction can usually be completed within 2 to 20 hours.
この発明の方法によつて５，６，７，８―テト
ラヒドロ―２―ナフトールを収率良く製造するこ
とができる。 By the method of the present invention, 5,6,7,8-tetrahydro-2-naphthol can be produced in good yield.
しかも担持ニツケル触媒を用いることにより本
反応を固定床反応器により実施させることができ
触媒と生成物の分離を容易にし工業化に当つては
極めて好都合である。 Furthermore, by using a supported nickel catalyst, this reaction can be carried out in a fixed bed reactor, making it easy to separate the catalyst and product, which is extremely convenient for industrialization.
次に実施例により本発明を更に詳細に説明する
が、本発明はこれら実施例のみに限定されるもの
ではない。 EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited only to these Examples.
実施例 １
200mlの電磁撹拌式オートクレーブにβ―ナフ
トール15gr.、エタノール100ml、耐硫黄性ニツケ
ル触媒注）
1gr.を取り反応温度150℃、反応圧力30
Kg／cm2で水素と２時間接触させた。Example 1 In a 200 ml electromagnetic stirring autoclave, 15 gr. of β-naphthol, 100 ml of ethanol, and 1 gr. of sulfur-resistant nickel catalyst (Note) were placed at a reaction temperature of 150°C and a reaction pressure of 30°C.
Contact with hydrogen at Kg/cm 2 for 2 hours.
反応終了後、内容物から触媒を分離し５，６，
７，８―テトラヒドロ―２―ナフトール11.9gr.，
１，２，３，４―テトラヒドロ―２―ナフトール
3.0gr.を得た。 After the reaction is completed, the catalyst is separated from the contents and 5,6,
7,8-tetrahydro-2-naphthol 11.9gr.,
1,2,3,4-tetrahydro-2-naphthol
Got 3.0gr.
５，６，７，８―テトラヒドロ―２―ナフトー
ルの収率はβ―ナフトール基準で77.2％であつ
た。 The yield of 5,6,7,8-tetrahydro-2-naphthol was 77.2% based on β-naphthol.
注 耐硫黄性ニツケル触媒（日揮化学株式会社
製）
化学的組成
Ni 45〜47％
Cr ２〜３％
Cu ２〜３％
ケイソウ土 27〜29％
黒鉛 ４〜５％
Niの形 Ni＋NiO
実施例 ２
実施例１と同一の反応装置にβ―ナフトール
20gr.酢酸エチル80ml、安定化ニツケル触媒注）
1.5gr.を取り反応温度100℃、反応圧力100Kg／cm2
で水素と４時間接触させた。Note Sulfur-resistant nickel catalyst (manufactured by JGC Chemical Co., Ltd.) Chemical composition Ni 45-47% Cr 2-3% Cu 2-3% Diatomaceous earth 27-29% Graphite 4-5% Ni form Ni+NiO Example 2 Implementation β-naphthol was added to the same reactor as in Example 1.
20gr. ethyl acetate 80ml, stabilized nickel catalyst Note)
Take 1.5gr., reaction temperature 100℃, reaction pressure 100Kg/cm 2
and was brought into contact with hydrogen for 4 hours.
反応終了後、内容物から触媒を分離し５，６，
７，８―テトラヒドロ―２―ナフトール15.4gr.，
１，２，３，４―テトラヒドロ―２―ナフトール
4.4gr.を得た。 After the reaction is completed, the catalyst is separated from the contents and 5,6,
7,8-tetrahydro-2-naphthol 15.4gr.,
1,2,3,4-tetrahydro-2-naphthol
Got 4.4gr.
５，６，７，８―テトラヒドロ―２―ナフトー
ルの収率はβ―ナフトール基準で74.9％であつ
た。 The yield of 5,6,7,8-tetrahydro-2-naphthol was 74.9% based on β-naphthol.
注 安定化ニツケル触媒（日揮化学株式会社製）
化学的組成
Ni 49〜52％
ケイソウ土 27〜29％
黒鉛 ４〜５％
実施例 ３
実施例１と同一の反応装置にβ―ナフトール
15gr.、メタノール100ml、耐硫黄性ニツケル触媒
注）
2gr.を取り、反応温度100℃、反応圧力30Kg／
cm2で水素と15時間接触させた。Note Stabilized nickel catalyst (manufactured by JGC Chemical Co., Ltd.) Chemical composition Ni 49-52% Diatomaceous earth 27-29% Graphite 4-5% Example 3 β-naphthol was added to the same reactor as Example 1.
15gr., methanol 100ml, sulfur-resistant nickel catalyst Note) 2gr., reaction temperature 100℃, reaction pressure 30Kg/
Contacted with hydrogen at cm 2 for 15 hours.
反応終了後、内容物から触媒を分離し５，６，
７，８―テトラヒドロ―２―ナフトール11.8gr.，
１，２，３，４―テトラヒドロ―２―ナフトール
3.2gr.を得た。 After the reaction is completed, the catalyst is separated from the contents and 5,6,
7,8-tetrahydro-2-naphthol 11.8gr.,
1,2,3,4-tetrahydro-2-naphthol
Got 3.2gr.
５，６，７，８―テトラヒドロ―２―ナフトー
ルの収率はβ―ナフトール基準で76.5％であつ
た。 The yield of 5,6,7,8-tetrahydro-2-naphthol was 76.5% based on β-naphthol.
注 耐硫黄性ニツケル触媒
実施例１と同じ
実施例 ４
実施例１と同一の反応装置にβ―ナフトール
15gr.、エタノール100ml、ニツケル担持触媒注）
3.5gr.を取り反応温度90℃、反応圧力100Kg／cm2
で水素と４時間接触させた。Note Sulfur-resistant nickel catalyst Same example as Example 1 4 β-naphthol in the same reactor as Example 1
15gr., ethanol 100ml, nickel supported catalyst Note)
Take 3.5gr., reaction temperature 90℃, reaction pressure 100Kg/cm 2
and was brought into contact with hydrogen for 4 hours.
反応終了後、内容物から触媒を分離し５，６，
７，８―テトラヒドロ―２―ナフトール11.4gr.，
１，２，３，４―テトラヒドロ―２―ナフトール
3.5gr.を得た。 After the reaction is completed, the catalyst is separated from the contents and 5,6,
7,8-tetrahydro-2-naphthol 11.4gr.,
1,2,3,4-tetrahydro-2-naphthol
Got 3.5gr.
５，６，７，８―テトラヒドロ―２―ナフトー
ルの収率はβ―ナフトール基準で73.9％であつ
た。 The yield of 5,6,7,8-tetrahydro-2-naphthol was 73.9% based on β-naphthol.
注 ニツケル担持触媒（日産ガードラー触媒株式
会社製）
化学的組成
Ni 10〜12％
担体 活性アルミナ 88〜90％
比較例 １
実施例１と同一の反応装置にβ―ナフトール
15gr.，エタノール100ml、還元ニツケル触媒注）
（担体なし）0.5gr.を取り、反応温度150℃，反応
圧力30Kg／cm2で水素と２時間接触させた。Note Nickel supported catalyst (manufactured by Nissan Girdler Catalyst Co., Ltd.) Chemical composition Ni 10-12% Support Activated alumina 88-90% Comparative example 1 β-naphthol was added to the same reactor as in Example 1.
15gr., ethanol 100ml, reduced nickel catalyst Note)
(No carrier) was taken and brought into contact with hydrogen for 2 hours at a reaction temperature of 150° C. and a reaction pressure of 30 Kg/cm 2 .
反応終了後、内容物から触媒を分離し５，６，
７，８―テトラヒドロ―２―ナフトール8.1gr.，
１，２，３，４―テトラヒドロナフトール6.9gr.
を得た。 After the reaction is completed, the catalyst is separated from the contents and 5,6,
7,8-tetrahydro-2-naphthol 8.1gr.,
1,2,3,4-Tetrahydronaphthol 6.9gr.
I got it.
５，６，７，８―テトラヒドロ―２―ナフトー
ルの収率はβ―ナフトール基準で52.5％であつ
た。 The yield of 5,6,7,8-tetrahydro-2-naphthol was 52.5% based on β-naphthol.
注 還元ニツケル触媒（日興理化学株式会社製）。Note: Reduced nickel catalyst (manufactured by Nikko Rikagaku Co., Ltd.).
Claims (1)
液相状態で水素と接触させる５，６，７，８―テ
トラヒドロ―２―ナフトールの製造方法。1 β-naphthol in the presence of a nickel-supported catalyst,
A method for producing 5,6,7,8-tetrahydro-2-naphthol by contacting it with hydrogen in a liquid phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57150026A JPS5939841A (en) | 1982-08-31 | 1982-08-31 | Preparation of 5,6,7,8-tetrahydro-2-naphthol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57150026A JPS5939841A (en) | 1982-08-31 | 1982-08-31 | Preparation of 5,6,7,8-tetrahydro-2-naphthol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5939841A JPS5939841A (en) | 1984-03-05 |
| JPS649302B2 true JPS649302B2 (en) | 1989-02-16 |
Family
ID=15487868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57150026A Granted JPS5939841A (en) | 1982-08-31 | 1982-08-31 | Preparation of 5,6,7,8-tetrahydro-2-naphthol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5939841A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1097484C (en) * | 1999-05-27 | 2003-01-01 | 中国石油化工集团公司北京化工研究院 | Liquid phase hydrogenating catalyst, its preparation process and application |
| JP4626782B2 (en) * | 1999-07-27 | 2011-02-09 | Ｄｉｃ株式会社 | Hydrogenated naphthalene derivatives |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| HU177860B (en) * | 1979-05-22 | 1982-01-28 | Mta Koezponti Hivatala | Method for producing carrier metal catalyzers |
-
1982
- 1982-08-31 JP JP57150026A patent/JPS5939841A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5939841A (en) | 1984-03-05 |
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