JPH026339B2 - - Google Patents
Info
- Publication number
- JPH026339B2 JPH026339B2 JP56166355A JP16635581A JPH026339B2 JP H026339 B2 JPH026339 B2 JP H026339B2 JP 56166355 A JP56166355 A JP 56166355A JP 16635581 A JP16635581 A JP 16635581A JP H026339 B2 JPH026339 B2 JP H026339B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- hydroxybenzaldehyde
- catalyst
- hydroxybenzyl alcohol
- raney 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 - Lifetime
Links
- BVJSUAQZOZWCKN-UHFFFAOYSA-N p-hydroxybenzyl alcohol Chemical compound OCC1=CC=C(O)C=C1 BVJSUAQZOZWCKN-UHFFFAOYSA-N 0.000 claims description 25
- 229910000564 Raney nickel Inorganic materials 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- CQRYARSYNCAZFO-UHFFFAOYSA-N o-hydroxybenzyl alcohol Natural products OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 15
- 239000007868 Raney catalyst Substances 0.000 claims description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims description 13
- 239000001257 hydrogen Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 3
- -1 hydroxybenzyl alcohols Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 40
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000004458 analytical method Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 5
- 235000019345 sodium thiosulphate Nutrition 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 208000005374 Poisoning Diseases 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 2
- OKVJCVWFVRATSG-UHFFFAOYSA-N 3-hydroxybenzyl alcohol Chemical compound OCC1=CC=CC(O)=C1 OKVJCVWFVRATSG-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229930003836 cresol Natural products 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052979 sodium sulfide Inorganic materials 0.000 description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- DMNNZUXHUVUGOD-UHFFFAOYSA-N C(=S)=S.S1C=NC2=C1C=CC=C2 Chemical compound C(=S)=S.S1C=NC2=C1C=CC=C2 DMNNZUXHUVUGOD-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000001555 benzenes Chemical group 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-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
- 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】
本発明はヒドロキシベンズアルデヒド類を水素
還元してヒドロキシベンジルアルコール類を製造
する際、遊離硫黄もしくは硫酸含有化合物で被毒
処理したラネーニツケルを使用することを特徴と
するヒドロキシベンジルアルコール類の製造法に
関する。Detailed Description of the Invention The present invention is a hydroxybenzyl alcohol characterized by using Raney nickel poisoned with free sulfur or a sulfuric acid-containing compound when producing hydroxybenzyl alcohol by hydrogen reduction of hydroxybenzaldehyde. Concerning the manufacturing method of
ヒドロキシベンジルアルコールは工業薬品とし
て有用なものである。ヒドロキシベンズアルデヒ
ドを水素還元してヒドロキシベンジルアルコール
を得る方法はすでによく知られており、種々の触
媒が提案されている。しかしながら、ヒドロキシ
ベンズアルデヒドを水素還元する場合にいずれの
触媒を使用しても、一且生成したヒドロキシベン
ジルアルコールがクレゾールまで還元されやすい
ためヒドロキシベンジルアルコールを選択的に得
ることは困難であり、またたとえ得られたとして
も、工業的に有利な条件を設定するのが難しい。 Hydroxybenzyl alcohol is useful as an industrial chemical. A method for obtaining hydroxybenzyl alcohol by hydrogen reduction of hydroxybenzaldehyde is already well known, and various catalysts have been proposed. However, no matter which catalyst is used when hydroxybenzaldehyde is hydrogen-reduced, it is difficult to selectively obtain hydroxybenzyl alcohol because the produced hydroxybenzyl alcohol is easily reduced to cresol. Even if it were possible, it would be difficult to set industrially advantageous conditions.
たとえばパラジウムを触媒として用いるとＯ−
ヒドロキシベンズアルデヒドはＯ−クレゾールま
で還元される〔ベリヒテ・デル・ドイツチエン・
ヘミツシエン・ゲジエルシヤフト、56巻、846ペ
ージ（1923年）〕。また特開昭51−86432ではパラ
ジウム触媒とホウ酸亜鉛等を添加し、水素圧40
Kg／cm2ゲージ反応温度200℃でヒドロキシベンジ
ルアルコールを得ているが、高価な貴金属触媒を
使用する点、高温高圧反応などの点で工業的に不
利である。 For example, when palladium is used as a catalyst, O-
Hydroxybenzaldehyde is reduced to O-cresol [Berichte der Deutschen
Hemitsien Gesiershaft, volume 56, page 846 (1923)]. In addition, in JP-A-51-86432, a palladium catalyst and zinc borate were added, and hydrogen pressure of 40
Although hydroxybenzyl alcohol is obtained at a Kg/cm 2 gauge reaction temperature of 200°C, it is industrially disadvantageous in that it requires an expensive noble metal catalyst and requires a high-temperature, high-pressure reaction.
一方ラネーニツケル触媒では多量の触媒を使用
して長時間室温で反応させヒドロキシベンジルア
ルコールを得ている例（Bull.Soc.Chim.
France1955、815−16.）もあるが工業的に有利で
あるとはいい難い。 On the other hand, with the Raney-nickel catalyst, hydroxybenzyl alcohol is obtained by using a large amount of catalyst and reacting at room temperature for a long time (Bull.Soc.Chim.
France 1955, 815-16.), but it is difficult to say that it is industrially advantageous.
本発明者等は上記のような欠点のないしかも簡
単な操作で効率よく比較的短い反応時間でヒドロ
キシベンジルアルコールを製造する方法について
種々検討した。その結果ヒドロキシベンズアルデ
ヒドの水素還元反応に際し、触媒として遊離硫黄
もしくは硫黄含有化合物により被毒処理したラネ
ーニツケルを用いて水素還元反応したところ、意
外にも、従来問題であつたヒドロキシベンズアル
デヒドがクレゾールにまで還元されるということ
による収率の低下がなく、高純度、高収率で目的
とするヒドロキシベンジルアルコールが得られる
ことを見出した。 The present inventors have studied various methods for producing hydroxybenzyl alcohol efficiently and in a relatively short reaction time with simple operations and without the above-mentioned drawbacks. As a result, when the hydrogen reduction reaction of hydroxybenzaldehyde was carried out using free sulfur or Raney nickel poisoned with sulfur-containing compounds as a catalyst, surprisingly, hydroxybenzaldehyde, which had been a problem in the past, was reduced to cresol. It has been found that the desired hydroxybenzyl alcohol can be obtained with high purity and high yield without any decrease in yield due to the process.
以下本発明をさらに詳細に説明する。 The present invention will be explained in more detail below.
本発明で使用するラネーニツケルは工業的に安
価にかつ簡便に入手し、利用することができる利
点を有している。 Raney nickel used in the present invention has the advantage that it can be obtained and used industrially at low cost and easily.
ラネーニツケルは一般にニツケル−アルミニウ
ム合金であり、他種金属、例えば鉄、クロム等数
％含むものもある。この合金を反応使用前にアル
カリで処理して展開し、下記の被毒処理を施す。
すなわち、先ず通常の方法で展開されたラネーニ
ツケルの水性ペーストを純水中に懸濁し、攪拌し
ながら遊離硫黄もしくは硫黄含有化合物を少量づ
つ加えて所定の温度で所定の時間処理する。処理
後上澄液を除き純水を加え攪拌し、洗浄する。こ
の洗浄操作を数回行ない、傾斜して上澄液を除
き、被毒されたラネーニツケル水性ペーストを得
る。 Raney nickel is generally a nickel-aluminum alloy, and may also contain several percent of other metals, such as iron and chromium. Before using this alloy for reaction, it is treated with alkali to develop it and subjected to the following poisoning treatment.
That is, first, an aqueous paste of Raney nickel developed in a conventional manner is suspended in pure water, free sulfur or a sulfur-containing compound is added little by little while stirring, and the paste is treated at a predetermined temperature for a predetermined period of time. After treatment, remove the supernatant liquid, add pure water, stir, and wash. This washing operation is repeated several times and the supernatant liquid is removed by decanting to obtain a poisoned Raney nickel aqueous paste.
使用される遊離硫黄もしくは硫黄含有化合物は
例えばチオ硫酸ソーダ、酸性亜硫酸ソーダ、硫化
ソーダ、チオ尿素、硫黄、ベンゾチアゾール二硫
化炭素、メルカプタン、チオシアン酸カリウム等
をあげることができる。 Free sulfur or sulfur-containing compounds used include, for example, sodium thiosulfate, acidic sodium sulfite, sodium sulfide, thiourea, sulfur, benzothiazole carbon disulfide, mercaptans, potassium thiocyanate, and the like.
被毒させる遊離硫黄もしくは硫黄含有化合物の
量はラネーニツケルのニツケル金属100部に対し
て例えば0.1〜50部の範囲でより好ましくは１〜
10部の範囲で選ぶことができる。 The amount of free sulfur or sulfur-containing compound to be poisoned is, for example, in the range of 0.1 to 50 parts, more preferably 1 to 50 parts, based on 100 parts of Raney nickel metal.
You can choose from a range of 10 copies.
展開したラネーニツケルの被毒処理の方法に関
しては、被毒の際に使用する水の量、添加方法、
処理温度、処理時間、処理後の洗浄回数等を一定
にすれば被毒効果に顕著な違いは生じないので被
毒効果の再現性は高い。 Regarding the method of poisoning the developed Raney nickel, the amount of water used during poisoning, the addition method,
If the treatment temperature, treatment time, number of times of washing after treatment, etc. are kept constant, there will be no noticeable difference in the poisoning effect, so the reproducibility of the poisoning effect is high.
遊離硫黄もしくは硫黄含有化合物の添加方法は
そのまま少量づつ又はその濃厚な水溶液を攪拌下
に触媒の水懸濁液に添加するが、それらに限定さ
れない。 The method of adding free sulfur or sulfur-containing compounds includes, but is not limited to, adding the free sulfur or the sulfur-containing compound in small portions or by adding its concentrated aqueous solution to the aqueous suspension of the catalyst under stirring.
工業的にはどの程度の条件で被毒処理したラネ
ーニツケル触媒を使用するのが適当であるかは、
水素還元反応をする時の反応条件（反応温度、反
応圧力、触媒滞留量等）によつて有利になるよう
な範囲で選択して決定することができる。 Under what conditions is it appropriate to use poisoned Raney nickel catalysts industrially?
It can be selected and determined within a range that is advantageous depending on the reaction conditions (reaction temperature, reaction pressure, catalyst retention amount, etc.) when carrying out the hydrogen reduction reaction.
使用される被毒したラネーニツケル触媒の使用
量は任意に選ぶことができるが、通常ヒドロキシ
ベンズアルデヒド100部に対してニツケル金属で
0.1〜50部、より好ましくは３〜20部で行なう。 The amount of poisoned Raney nickel catalyst used can be selected arbitrarily, but it is usually nickel metal per 100 parts of hydroxybenzaldehyde.
The amount is 0.1 to 50 parts, more preferably 3 to 20 parts.
水素還元の反応温度は室温から150℃の間の任
意の温度において行なわれるが、好ましくは40〜
80℃で行なう。反応圧力は0.1〜100Kg／cm2ゲージ
の間の任意の反応圧において行なわれるが、好ま
しくは１〜20Kg／cm2ゲージで行なう。 The hydrogen reduction reaction temperature is carried out at any temperature between room temperature and 150°C, but preferably between 40°C and 150°C.
Perform at 80℃. The reaction pressure may be any pressure between 0.1 and 100 kg/cm 2 gauge, preferably 1 and 20 kg/cm 2 gauge.
また本発明においては反応を行うに際し、必要
に応じ、触媒に対して不活性な溶媒を使用するこ
とができる。溶媒は例えば脂肪族アルコール、炭
化水素類及び水であり、さらに具体的にはメタノ
ール、エタノール、ヘキサン、トルエン等が使用
される。 Further, in the present invention, when carrying out the reaction, a solvent inert to the catalyst may be used if necessary. Examples of solvents include aliphatic alcohols, hydrocarbons, and water, and more specifically methanol, ethanol, hexane, toluene, and the like.
本発明においてはヒドロキシベンズアルデヒド
を一度に反応系に仕込むこともでき、逐次的に仕
込むこともできる。ここに逐次的とはヒドロキシ
ベンズアルデヒドをそのままもしくはアルコール
等に溶解して、反応進行中の反応系に連続的に又
は間欠的に仕込むことを意味する。 In the present invention, hydroxybenzaldehyde can be charged into the reaction system all at once or sequentially. The term "sequentially" as used herein means that hydroxybenzaldehyde is charged as it is or dissolved in alcohol or the like to the reaction system while the reaction is in progress, either continuously or intermittently.
反応の進行状況は水素の吸収量によりチエツク
し、反応終点に到着させることができる。上記の
反応条件下では副反応による生成物は非常に少な
い。 The progress of the reaction can be checked by the amount of hydrogen absorbed, and the end point of the reaction can be reached. Under the above reaction conditions, there are very few products due to side reactions.
反応終了後は冷却後、触媒を沈降分離或は過
等により取り除いた後、必要に応じて溶媒を蒸留
等の操作により除去し、ヒドロキシベンジルアル
コールを得る。この触媒は繰返し反応に供するこ
とができる。 After the reaction is completed, after cooling, the catalyst is removed by sedimentation or filtration, and if necessary, the solvent is removed by distillation or the like to obtain hydroxybenzyl alcohol. This catalyst can be subjected to repeated reactions.
本発明の原料として用いられるヒドロキシベン
ジルアルデヒド類としてはＯ−ヒドロキシベンジ
ルアルデヒドｍ−ヒドロキシベンジルアルデヒ
ド、ｐ−ヒドロキシベンジルアルデヒドの他ベン
ゼン核が低級アルキル、低級アルコキシ又はハロ
ゲンで置換されたヒドロキシベンジルアルデヒド
が挙げられる。 Hydroxybenzylaldehydes used as raw materials in the present invention include O-hydroxybenzylaldehyde, m-hydroxybenzylaldehyde, p-hydroxybenzylaldehyde, and hydroxybenzylaldehydes in which the benzene nucleus is substituted with lower alkyl, lower alkoxy, or halogen. It will be done.
以下に実施例をあげて、本発明をさらに詳細に
説明するが、本発明はその要旨を越えない限りこ
れに限定されるものではない。 The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto unless it exceeds the gist thereof.
実施例 １
攪拌子を入れた1000c.c.ビーカーに展開したラネ
ーニツケル触媒（川研フアインケミカル株式会社
製）100ｇと水500c.c.を入れ攪拌しながら１ｇチオ
硫酸ソーダを５分を要して少量づつ投入し室温で
30分攪拌した。その後傾斜して上澄みの水を捨て
500c.c.の水で洗浄を行ない被毒ラネーニツケルを
得た。Example 1 100g of developed Raney nickel catalyst (manufactured by Kawaken Fine Chemical Co., Ltd.) and 500c.c. of water were placed in a 1000c.c. beaker containing a stirring bar, and 1g of sodium thiosulfate was added to the beaker while stirring for 5 minutes. Add a little at a time and let it cool at room temperature.
Stirred for 30 minutes. Then tilt it and discard the supernatant water.
Poisoned Raney nickel was obtained by washing with 500 c.c. of water.
攪拌機付の500c.c.オートクレーブに、この被毒
ラネーニツケル触媒8.0ｇとｐ−ヒドロキシベン
ズアルデヒド73.2ｇ、メタノール150c.c.を入れ、
水素置換後、攪拌しながら昇温、昇圧を行ない、
反応圧５Kg／cm2ゲージ、反応温度60℃で到達さ
せ、1000rpmにて水素還元反応を行なう。反応中
水素は連続的に供給を行なう。反応時間は120分。
水素吸収が完全に停止してから10分間同温度で攪
拌を続けた後、冷却静置を行ない、触媒を別し
て反応液を得た。この反応液の高圧液体クロマト
グラフイーによる分析ではｐ−ヒドロキシベンジ
ルアルコール97.22％、Ｐ−ヒドロキシベンズア
ルデヒド1.28％、Ｐ−クレゾール0.95％その他
0.55％であつた。この反応液からメタノールを留
去し、目的物を得た。得量73.6ｇ
実施例 ２
実施例１の方法で得た被毒ラネーニツケル触媒
8.0ｇとｐ−ヒドロキシベンズアルデヒド73.2ｇ、
メタノール150c.c.を実施例１で使用したオートク
レーブに仕込み、反応圧20Kg／cm2ゲージ、反応温
度40℃とし、135分反応した。この反応液の高圧
液体クロマトグラフイーによる分析ではｐ−ヒド
ロキシベンジルアルコール97.31％、ｐ−ヒドロ
キシベンズアルデヒド1.24％、ｐ−クレゾール
0.92％その他0.53％であつた。 Put 8.0 g of this poisoned Raney nickel catalyst, 73.2 g of p-hydroxybenzaldehyde, and 150 c.c. of methanol into a 500 c.c. autoclave equipped with a stirrer.
After replacing with hydrogen, increase the temperature and pressure while stirring,
The reaction pressure is 5 Kg/cm 2 gauge, the reaction temperature is 60°C, and the hydrogen reduction reaction is carried out at 1000 rpm. Hydrogen is continuously supplied during the reaction. Reaction time is 120 minutes.
After hydrogen absorption had completely stopped, stirring was continued at the same temperature for 10 minutes, then the mixture was cooled and allowed to stand, and the catalyst was separated to obtain a reaction solution. Analysis of this reaction solution by high pressure liquid chromatography revealed that 97.22% p-hydroxybenzyl alcohol, 1.28% p-hydroxybenzaldehyde, 0.95% p-cresol, etc.
It was 0.55%. Methanol was distilled off from this reaction solution to obtain the desired product. Yield: 73.6g Example 2 Poisoned Raney nickel catalyst obtained by the method of Example 1
8.0g and p-hydroxybenzaldehyde 73.2g,
150 c.c. of methanol was charged into the autoclave used in Example 1, the reaction pressure was 20 Kg/cm 2 gauge, the reaction temperature was 40° C., and the reaction was carried out for 135 minutes. Analysis of this reaction solution by high pressure liquid chromatography revealed that p-hydroxybenzyl alcohol was 97.31%, p-hydroxybenzaldehyde was 1.24%, and p-cresol was 97.31%.
0.92%, other 0.53%.
ｐ−ヒドロキシベンズアルデヒドの代りにｍ−
ヒドロキシベンズアルデヒド73.2ｇを用いて上と
同様に反応を行ないｍ−ヒドロキシベンジルアル
コールを得た。 m- instead of p-hydroxybenzaldehyde
The reaction was carried out in the same manner as above using 73.2 g of hydroxybenzaldehyde to obtain m-hydroxybenzyl alcohol.
実施例 ３
チオ硫酸ソーダの代りに酸性亜硫酸ソーダ５ｇ
を用いたことを除き、実施例１の手順に従つて反
応させた。Example 3 5g of acidic sodium sulfite instead of sodium thiosulfate
The reaction was carried out according to the procedure of Example 1, except that
得られた反応液の高圧液体クロマトグラフイー
による分析ではｐ−ヒドロキシベンジルアルコー
ル97.33％ｐ−ヒドロキシベンズアルデヒド0.63
％、ｐ−クレゾール1.24％その他0.80％であつ
た。この反応液からメタノールを留去すると、ｐ
−ヒドロキシベンジルアルコールの白色結晶73.4
ｇ（98.6％）を得た。 Analysis of the resulting reaction solution by high pressure liquid chromatography revealed that p-hydroxybenzyl alcohol was 97.33% and p-hydroxybenzaldehyde was 0.63%.
%, p-cresol 1.24% and other 0.80%. When methanol is distilled off from this reaction solution, p
- White crystals of hydroxybenzyl alcohol 73.4
g (98.6%).
実施例 ４
実施例１のｐ−ヒドロキシベンズアルデヒドの
代りにＯ−ヒドロキシベンズアルデヒド73.2ｇを
用いて上記と同様にして反応させ、Ｏ−ヒドロキ
シベンジルアルコールを得た。Example 4 Using 73.2 g of O-hydroxybenzaldehyde instead of p-hydroxybenzaldehyde in Example 1, the reaction was carried out in the same manner as above to obtain O-hydroxybenzyl alcohol.
実施例 ５
チオ硫酸ソーダの代りに硫化ソーダ３ｇを用い
たことを除き、実施例１の手順に従つて反応させ
た。Example 5 The reaction was carried out according to the procedure of Example 1, except that 3 g of sodium sulfide was used instead of sodium thiosulfate.
得られた反応液の高圧液体クロマトグラフイー
による分析ではｐ−ヒドロキシベンジルアルコー
ル97.05％ｐ−ヒドロキシベンズアルデヒド0.86
％、ｐ−クレゾール1.31％その他0.78％であつ
た。この反応液からメタノールを留去し、目的物
を得た。得量73.1ｇ
実施例 ６
チオ硫酸ソーダの代りに粉砕した硫黄１ｇを用
いたことを除き、実施例１の手順に従つて反応さ
せた。 Analysis of the resulting reaction solution by high pressure liquid chromatography revealed that p-hydroxybenzyl alcohol 97.05% p-hydroxybenzaldehyde 0.86
%, p-cresol 1.31% and other 0.78%. Methanol was distilled off from this reaction solution to obtain the desired product. Yield 73.1 g Example 6 The procedure of Example 1 was followed except that 1 g of ground sulfur was used instead of sodium thiosulfate.
得られた反応液の高圧液体クロマトグラフイー
による分析ではｐ−ヒドロキシベンジルアルコー
ル97.13％、ｐ−ヒドロキシベンズアルデヒド
0.82％、ｐ−クレゾール1.39％その他0.66％であ
つた。この反応液からメタノールを留去し、目的
物を得た。得量72.9ｇ
比較例 １
実施例１で使用した被毒ラネーニツケル触媒の
代りにラネーニツケル、触媒水性ペースト8.0ｇ
を用いて実施例１と同じ反応条件で反応を行なつ
た。反応終了後反応液の高圧液体クロマトグラフ
イーによる分析では、目的物であるｐ−ヒドロキ
シベンジルアルコールは88.24％であり、ｐ−ヒ
ドロキシベンズアルデヒド2.31％、ｐ−クレゾー
ル4.98％その他4.47％であつた。 Analysis of the resulting reaction solution by high pressure liquid chromatography revealed that p-hydroxybenzyl alcohol was 97.13% and p-hydroxybenzaldehyde was 97.13%.
0.82%, p-cresol 1.39%, and other 0.66%. Methanol was distilled off from this reaction solution to obtain the desired product. Yield 72.9g Comparative Example 1 Raney nickel and catalyst aqueous paste 8.0g instead of the poisoned Raney nickel catalyst used in Example 1
The reaction was carried out under the same reaction conditions as in Example 1. After completion of the reaction, analysis of the reaction solution by high pressure liquid chromatography revealed that the target product, p-hydroxybenzyl alcohol, was 88.24%, p-hydroxybenzaldehyde was 2.31%, p-cresol was 4.98%, and others were 4.47%.
Claims (1)
てヒドロキシベンジルアルコールを製造する際、
遊離硫黄もしくは硫黄含有化合物で被毒処理した
ラネーニツケルを使用することを特徴とするヒド
ロキシベンジルアルコール類の製造法。1. When producing hydroxybenzyl alcohol by hydrogen reduction of hydroxybenzaldehydes,
A method for producing hydroxybenzyl alcohols, characterized by using Raney nickel poisoned with free sulfur or a sulfur-containing compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56166355A JPS5867637A (en) | 1981-10-20 | 1981-10-20 | Preparation of hydroxybenzyl alcohol compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP56166355A JPS5867637A (en) | 1981-10-20 | 1981-10-20 | Preparation of hydroxybenzyl alcohol compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5867637A JPS5867637A (en) | 1983-04-22 |
| JPH026339B2 true JPH026339B2 (en) | 1990-02-08 |
Family
ID=15829842
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP56166355A Granted JPS5867637A (en) | 1981-10-20 | 1981-10-20 | Preparation of hydroxybenzyl alcohol compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5867637A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5535723B2 (en) * | 2010-03-31 | 2014-07-02 | 株式会社クラレ | Method for producing isoamyl alcohol |
| CN103030528B (en) * | 2011-09-29 | 2015-08-12 | 中国石油化工股份有限公司 | Preparation of benzyl alcohol by liquid-phase hydrogenation of benzaldehyde |
| JP7353295B2 (en) * | 2018-04-10 | 2023-09-29 | バイエル・アクチエンゲゼルシヤフト | Method for producing 2,6-dialkylphenylacetic acid |
-
1981
- 1981-10-20 JP JP56166355A patent/JPS5867637A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5867637A (en) | 1983-04-22 |
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