JPH02108646A - Production of 2,6-dimethyl-4-phenylphenol - Google Patents
Production of 2,6-dimethyl-4-phenylphenolInfo
- Publication number
- JPH02108646A JPH02108646A JP63261331A JP26133188A JPH02108646A JP H02108646 A JPH02108646 A JP H02108646A JP 63261331 A JP63261331 A JP 63261331A JP 26133188 A JP26133188 A JP 26133188A JP H02108646 A JPH02108646 A JP H02108646A
- Authority
- JP
- Japan
- Prior art keywords
- catalyst
- phenylphenol
- oxide
- methanol
- metal oxides
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- SPDODUOTLRAEOR-UHFFFAOYSA-N 2,6-dimethyl-4-phenylphenol Chemical compound CC1=C(O)C(C)=CC(C=2C=CC=CC=2)=C1 SPDODUOTLRAEOR-UHFFFAOYSA-N 0.000 title 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- YXVFYQXJAXKLAK-UHFFFAOYSA-N biphenyl-4-ol Chemical compound C1=CC(O)=CC=C1C1=CC=CC=C1 YXVFYQXJAXKLAK-UHFFFAOYSA-N 0.000 claims abstract description 28
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 5
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910003437 indium oxide Inorganic materials 0.000 claims abstract description 4
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 229910001935 vanadium oxide Inorganic materials 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 238000000034 method Methods 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000001953 recrystallisation Methods 0.000 abstract description 2
- 239000012808 vapor phase Substances 0.000 abstract 2
- 150000002739 metals Chemical class 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- QNWUYYIJOWZXNB-UHFFFAOYSA-N [O-2].[In+3].[Fe+2] Chemical compound [O-2].[In+3].[Fe+2] QNWUYYIJOWZXNB-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- LLEMOWNGBBNAJR-UHFFFAOYSA-N biphenyl-2-ol Chemical class OC1=CC=CC=C1C1=CC=CC=C1 LLEMOWNGBBNAJR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 2
- WWDJZBIPKJNQBZ-UHFFFAOYSA-N 2-methyl-4-phenylphenol Chemical group C1=C(O)C(C)=CC(C=2C=CC=CC=2)=C1 WWDJZBIPKJNQBZ-UHFFFAOYSA-N 0.000 description 1
- HUPGZEYAAFYLSC-UHFFFAOYSA-N 4-methoxy-3,5-dimethylaniline Chemical compound COC1=C(C)C=C(N)C=C1C HUPGZEYAAFYLSC-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- DWWOZCUXMGDXEX-UHFFFAOYSA-N [Fe+2].[O-2].[V+5] Chemical compound [Fe+2].[O-2].[V+5] DWWOZCUXMGDXEX-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229940071870 hydroiodic acid Drugs 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004972 metal peroxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- FKWANUZUMUJWAL-UHFFFAOYSA-N oxotin vanadium Chemical compound [V].[Sn]=O FKWANUZUMUJWAL-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、４−フェニルフェノールとメタノールとを、
触媒の存在下気相で接触反応させて、２．６−’／メ？
ルー４−フェニルフェノールを製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention provides a method for combining 4-phenylphenol and methanol.
A catalytic reaction in the gas phase in the presence of a catalyst results in a reaction of 2.6-'/m?
The present invention relates to a method for producing 4-phenylphenol.
２．６−ジメチル−４−ツエニルフエノールハ医薬、農
薬等の原料、或いは近年特に有機高分子材料の原料とし
て注目を集めている化合物である。2,6-dimethyl-4-tzenylphenol is a compound that has recently attracted attention as a raw material for medicines, agricultural chemicals, etc., and especially as a raw material for organic polymer materials in recent years.
Ｋ来−２，６−ノメチルー４−フェニルフェノールの製
造方法としては５次のような方法が提案されている。The following five methods have been proposed for producing K-2,6-nomethyl-4-phenylphenol.
（１） ２．６−シメチルー４−アミノアニソールの
ジアゾニウム塩をベンゼンと反応させ２，６−ノアミノ
−４−メトキシビフェニルとし、さらにヨウ化水素酸で
脱メチル化して得る方法。（Ｊｏｕｒｎａｌ ｏｆＯｒ
ｇａｎｌｃ Ｃｈ＠ｍ１ｓｔｒｙ、ｖｏｌ−２９（１
０）、３０１４〜２１（１９６４））（２） ３．５
−ジメチルベンゼン−１，４−ノアゾオ中シＰから３．
５−ジメチル−４−ヒドロキシベンゼンゾアゾニウムク
ロリドモノヒドラートを合成し、これにベンゼンを反応
させて得る方法。(1) A method in which a diazonium salt of 2,6-dimethyl-4-aminoanisole is reacted with benzene to obtain 2,6-noamino-4-methoxybiphenyl, which is further demethylated with hydroiodic acid. (Journal of Or
ganlc Ch@m1stry, vol-29(1
0), 3014-21 (1964)) (2) 3.5
-Dimethylbenzene-1,4-noazoo from P to 3.
A method of synthesizing 5-dimethyl-4-hydroxybenzenezazonium chloride monohydrate and reacting it with benzene.
（Ｊｏｕｒｎａｌ ｏｆ ｔｈｅ Ａｙｎｓｒｌｃａｎ
Ｃｈａｍｉｅａｌ ５ｏｅｉｅｔｙ、ｖｏｌ ８Ｌ７
６１〜４（１９６３）：１
然し々がらこれらの方法は工業的立場から見ると、原料
の特殊性や、中間体の不安定性、低い収率等多くの問題
がある。(Journal of the Aynsrlcan
Chamieal 5oeiety, vol 8L7
61-4 (1963): 1 However, from an industrial standpoint, these methods have many problems such as the special nature of the raw materials, the instability of intermediates, and low yields.
マ九上位概念的にフェニルフェノール類も含み得るフェ
ノール類とメタノールとを、金属化合物触媒の存在下気
相接触させてオルト−メチル化フェノール類を製造する
方法が開示されている。A method is disclosed for producing ortho-methylated phenols by bringing phenols, which may also include phenylphenols in a general concept, into contact with methanol in the gas phase in the presence of a metal compound catalyst.
〔特公昭５１−１０２２４．特開昭５５−７６８３０゜
同５６−４３２２９ 、同５６−６３９３２．同５６−
６８６２９゜同５６−１１０６３４．同５７−８５３３
４．同５８−４９３２６゜同５９−７３５３４号各公報
等〕
然しなから、これらは総て４−フェニルフェノールカラ
の２，６−ノメチルー４−フェニルフェノールの製造に
関しては全く具体的記載はなく、勿論実施例も開示され
ていない。[Special Publication No. 51-10224. JP-A No. 55-76830, No. 56-43229, No. 56-63932. 56-
68629゜56-110634. 57-8533
4. Publications No. 58-49326, No. 59-73534, etc.] However, none of these have any specific description of the production of 2,6-nomethyl-4-phenylphenol from 4-phenylphenol color, and of course they are not practical. No examples are disclosed.
そこで本発明者らは、かかる問題点を解決し工業的有利
に目的物を製造する方法について研究を重ね念結果、特
殊な装置や原料薬品類を必要とせず、作業環境、公害防
止等の点からも、又目的物の品質や収率の点からも満足
できる方法を見出し。Therefore, the inventors of the present invention have repeatedly researched a method to solve these problems and manufacture the desired product industrially, and have found that it does not require special equipment or raw chemicals, and has improved working environment, pollution prevention, etc. We found a method that was satisfactory in terms of the quality and yield of the target product.
４−フェニルフェノールカラの２．６− Ｘ）メチル−
４−フェニルフェノールの製造方法を完成した。2.6-X) methyl of 4-phenylphenol-
A method for producing 4-phenylphenol was completed.
すなわち本発明は、４−フェニルフェノールとメタノー
ルとを、不活性ガス雰囲気中で、酸化鉄、酸化バナジウ
ム、酸化インジウム及び酸化錫からなる群から選ばれる
少なくとも２種の金属酸化物を含有する触媒の存在下、
２５０〜５００℃の温度範囲で気相接触反応させること
を特徴とする。That is, the present invention combines 4-phenylphenol and methanol in an inert gas atmosphere with a catalyst containing at least two metal oxides selected from the group consisting of iron oxide, vanadium oxide, indium oxide, and tin oxide. In the presence of
It is characterized by carrying out a gas phase catalytic reaction in a temperature range of 250 to 500°C.
２．６−シメチルー４−フェニルフェノールの製造方法
を提供するものである・
本発明について次に更に詳しく説明する。2. Provides a method for producing 6-dimethyl-4-phenylphenol. The present invention will be described in more detail below.
本発明に使用する触媒としては、酸化鉄、酸化バナジウ
ム、酸化インジウム及び酸化錫からなる群から選ばれる
少なくとも２種の金属酸化物を含有するものが使用され
る。The catalyst used in the present invention contains at least two metal oxides selected from the group consisting of iron oxide, vanadium oxide, indium oxide, and tin oxide.
これらの触媒は通常の方法で調製される。すなわち各金
属の水溶性化合物の所望量を含む水性溶液に、酸又はア
ルカリ、或いは還元剤等を添加して、金属化合物を共沈
させ、ｒ過、乾燥、破砕、粒度選別後空気中又は酸素含
有ガス気流中で４００〜８００℃で焼成し、金属酸化物
の均一な混合触媒が得られる。ｔた触媒は、適当な担体
、例えばアルミナ、シリカ−アルミナ、珪藻上等に担持
させ、加圧成形したものも使用できる。These catalysts are prepared by conventional methods. That is, an acid or alkali, or a reducing agent, etc. is added to an aqueous solution containing a desired amount of a water-soluble compound of each metal to co-precipitate the metal compound, and after filtration, drying, crushing, and particle size separation, it is released in air or oxygen. Calcination is performed at 400 to 800° C. in a gas stream containing the catalyst to obtain a uniform mixed catalyst of metal oxides. The catalyst may be supported on a suitable carrier such as alumina, silica-alumina, diatom, etc., and then pressure molded.
金属酸化物触媒中の各金属の原子比は、鉄−インジウム
酸化物系ではＦｅ ： Ｉｎが９８：２〜８０：２０、
鉄−バナジウム酸化物系ではＦｅ：Ｖが９０：１０〜１
０：９０、パテ・ゾウムー錫酸化物系ではＶ ：Ｓｎが
９９＝１〜５０ ： ５０が適当である。本混合金属殴
化物系触媒は各金属酸化物単独の触媒の場合に比べ、目
的反応の転化率、選択率及び触媒寿命が改良される。The atomic ratio of each metal in the metal oxide catalyst is 98:2 to 80:20 for Fe:In in the iron-indium oxide system;
In iron-vanadium oxide system, Fe:V is 90:10-1
0:90, and in the case of putty-zomu tin oxide systems, V:Sn is suitably 99=1 to 50:50. The present mixed metal peroxide catalyst has improved conversion rate, selectivity, and catalyst life for the target reaction, compared to catalysts containing each metal oxide alone.
本発明の方法を実施するに当っては、４−フェニルフェ
ノールとメタノールとの混合物を蒸発器を通して気化さ
せ、所定の温度に保持された触媒層を通過させ、反応混
合気体を冷却、凝縮して反応生成物を得る。反応原料の
触媒層への供給に際しては、窒素ガス、−酸化炭素、二
酸化炭素、水蒸気等を共存させても良く、特に水蒸気の
共存は触媒寿命向上の点からも好ましい。In carrying out the method of the present invention, a mixture of 4-phenylphenol and methanol is vaporized through an evaporator, passed through a catalyst bed maintained at a predetermined temperature, and the reaction mixture is cooled and condensed. Obtain the reaction product. When supplying the reaction raw material to the catalyst layer, nitrogen gas, carbon oxide, carbon dioxide, water vapor, etc. may be allowed to coexist, and the coexistence of water vapor is particularly preferred from the viewpoint of improving the catalyst life.
触媒層に供給する４−フェニルフェノールとメタノール
のモル比（４−フェニルフェノール／メタノール）は０
．０１〜１、好ましくＦｉｏ、０２〜０、１の範囲であ
る。水蒸気を共存させる場合は４−フェニルフェノール
１モル当り通常ｉ〜２０モル、好ましくは５〜１５モル
である。The molar ratio of 4-phenylphenol and methanol (4-phenylphenol/methanol) supplied to the catalyst layer is 0.
．． The range is 01-1, preferably Fio, 02-0.1. When water vapor is present, the amount is usually i to 20 mol, preferably 5 to 15 mol, per mol of 4-phenylphenol.
反応温度は通常２５０〜５００℃、好ましくは３００〜
４００℃である。The reaction temperature is usually 250-500°C, preferably 300-500°C.
The temperature is 400°C.
触媒層への原料の供給はＬＨ８Ｖ （ｍｌ／ ｃａｔ−
ｍｌ −Ｈｒ ）で０．０５〜１０、好ましくは０．１
〜２．０である。The raw material is supplied to the catalyst layer at LH8V (ml/cat-
ml-Hr) from 0.05 to 10, preferably 0.1
~2.0.
ＬＨ８Ｖが０．０５より小さい場合はガス状生成物が多
く、１０より大きい場合は反応の進行が不十分である。When LH8V is smaller than 0.05, there are many gaseous products, and when it is larger than 10, the reaction progresses insufficiently.
長時間の反応使用により活性が劣化した触媒は空気中又
は酸素ガス気流中で４００〜８００℃で焼成すれば再生
することができる。A catalyst whose activity has deteriorated due to long-term reaction use can be regenerated by firing at 400 to 800° C. in air or in an oxygen gas stream.
次に本発明の実施例について説明する。 Next, examples of the present invention will be described.
実施例１
硝酸第二鉄（Ｆｅ（ＮＯｘ）ｓ’９Ｈ２０） ５００９
と塩化インジウム（ＩｎＣ／、、−４Ｈ２０〕２５ ＃
を水１０２に溶解し。Example 1 Ferric nitrate (Fe(NOx)s'9H20) 5009
and indium chloride (InC/, -4H20) 25 #
Dissolved in water 102.
攪拌下１２．５％（重量、以下同じ）アンモニア水でｐ
Ｈ７，５に中和した。さらに室温で１時間攪拌し死後、
沈殿を濾過、水洗して１８０℃で８時間乾燥し、破砕し
て篩分性１６〜３２メツシュ粒度の鉄−インジウム酸化
物触媒を得た。この触媒１６０づを内径４５＋＋＋ｓ＋
の反応管に充填し、空気を通しながら４５０〜４８０℃
で５時間焼成し九。P with 12.5% (weight, same below) ammonia water under stirring.
Neutralized to H7.5. After further stirring for 1 hour at room temperature, the
The precipitate was filtered, washed with water, dried at 180° C. for 8 hours, and crushed to obtain an iron-indium oxide catalyst having a sieveability of 16 to 32 mesh particles. This catalyst 160 has an inner diameter of 45+++s+
Fill a reaction tube and heat to 450-480℃ while passing air.
Bake for 5 hours.
この触媒層を３５０℃に保持し、窒素ガス５−／ ｍ
ｉ ｎを通しながら、（４−フェニルフェノールとメタ
ノールと水）とをモル比でＩ ：３５：１０の割合で混
合した溶液２４Ｊ、／’ｈｒ （ＬＨ８Ｖ＝０．１５
）を供給し反応させた。反応生成気体は冷却トラップで
凝縮書せ反応生成物を取り出した。反応生成物の組成分
析（ガスクロマトグラフィーによる）の結果を表−１に
示す。（但しメタノール、水は除く）
表 １
注１）２−メチル体＝２−メチルー４−フェニルフェノ
ール２）２．６−ジメチル体：２．６−シメチルー４−
フェニルフェノール３）その他：２，６−ノメチルー４
−（４’−メチルフェニル）フェノール、その細工確認
化合物の合計
この実験で得られ九反応生成物（乾燥品、２．６−ノメ
チルー４−フェニルフェノール含有率８９．９％）５０
Ｉｌをシクロへ牛サン３００Ｍで再結晶精製し、精製品
３８．０１／Ｃ純度換算収率８３．９係。純度９９．３
係。融点９６〜９７℃（文献値９６．５〜９７．０℃）
〕を得九０実施例２
硝酸第二鉄（Ｆ＠（ＮＯ５） ３・９Ｈ２０） ３００
１！、メタバナジン酸アンモニウム（ＮＩ（４ＶＯ，）
８７ ＃ 及びシュウ酸６０ｇを水３ｐに溶解したも
のに１２．５％アンモニア水１４．６ ｍｌを添加して
生成し九沈殿を濾過、水洗、乾燥後実施例１と同様にし
て得られ九鉄−パナジウム酸化物触媒３２０プを反応管
に充填し、４５０℃で５時間焼成した。この反応管を３
５０℃に保持し、窒素ガス５０ｖ／／ｈｒを通しながら
、４−フェニルフェノール：メタノール：水の重量混合
比１０：６５：１０の混合溶液を５４Ｊ ／ ｈｒ（Ｌ
Ｈ８Ｖ０．１７）で供給した。反応ラップサンプルの分
析値は表２に示すとおシであった。This catalyst layer was maintained at 350°C and nitrogen gas 5-/m
24 J of a solution of (4-phenylphenol, methanol, and water) mixed at a molar ratio of I:35:10 while passing in.
) was supplied and reacted. The reaction product gas was condensed in a cooling trap and the reaction product was taken out. Table 1 shows the results of compositional analysis (by gas chromatography) of the reaction product. (However, methanol and water are excluded) Table 1 Note 1) 2-methyl form = 2-methyl-4-phenylphenol 2) 2.6-dimethyl form: 2.6-dimethyl-4-
Phenylphenol 3) Others: 2,6-nomethyl-4
-(4'-Methylphenyl)phenol, its workmanship The total number of confirmed compounds obtained in this experiment is 9 reaction products (dry product, 2.6-nomethyl-4-phenylphenol content 89.9%) 50
Il was recrystallized and purified using cyclohexane 300M, yield of purified product 38.01/C purity equivalent 83.9. Purity 99.3
Person in charge. Melting point 96-97°C (literature value 96.5-97.0°C)
] Obtained 90 Example 2 Ferric nitrate (F@(NO5) 3.9H20) 300
1! , ammonium metavanadate (NI(4VO,)
87# and 60 g of oxalic acid dissolved in 3 parts of water were added with 14.6 ml of 12.5% ammonia water, and the nine precipitate was filtered, washed with water, dried, and obtained in the same manner as in Example 1. - A reaction tube was filled with 320 grams of a panadium oxide catalyst and calcined at 450°C for 5 hours. This reaction tube
While maintaining the temperature at 50°C and passing nitrogen gas at 50v//hr, a mixed solution with a weight mixing ratio of 4-phenylphenol:methanol:water of 10:65:10 was added at 54J/hr (L).
H8V0.17). The analytical values of the reaction wrap samples were as shown in Table 2.
ｉ！！２
実施例３
メタバナジン酸アンモニウム（ＮＨ４ｖｏ、） １１７
１とシュウ酸８１１を水ＩＪ３に溶解し、この溶液に、
硫酸第一錫（ＳｎＳＯ４） ２１．５ ｆ！を２Ｎ硝酸
水溶液２５０ゴに溶解し九溶液を１２．５％アンモニア
水で中和し次後、添加した。かくして得られた混合物を
蒸発乾固し、破砕、篩分けして得られ次１６〜３２メツ
シュのバナジウム−錫酸化物触媒６０づを反応管に充填
し、４００℃で３時間焼成し次のち、反応管を３５０℃
に保持し、窒素ガス５０ｍ１／ｈｒを通しながら、４−
フェニルフェノール：メタノール：水の重量混合比１０
：２００：１０の混合溶液を１５ａｆｆ／ ｈｒ （Ｌ
Ｈ８Ｖ Ｏ，２５）で供給し九。反応１０時間めの反応
生成物の分析値は表３の通りであった。i! ! 2 Example 3 Ammonium metavanadate (NH4vo,) 117
1 and oxalic acid 811 were dissolved in water IJ3, and in this solution,
Stannous sulfate (SnSO4) 21.5 f! was dissolved in 250 g of a 2N aqueous nitric acid solution, the solution was neutralized with 12.5% ammonia water, and then added. The mixture thus obtained was evaporated to dryness, crushed and sieved, and then 60 pieces of vanadium-tin oxide catalyst of 16 to 32 meshes were filled into a reaction tube and calcined at 400° C. for 3 hours. Heat the reaction tube to 350℃
while passing nitrogen gas at 50ml/hr.
Phenylphenol:methanol:water weight mixing ratio: 10
:200:10 mixed solution at 15af/hr (L
H8V O, 25). The analytical values of the reaction product at the 10th hour of the reaction were as shown in Table 3.
表
成 分 組成（係）
４−フェニルクエノｉル ２．０２
−メチル体 ４．７
２．６−ジメチル体 ７７．３そ の
他 １６．０〔発明の効果〕
本発明の方法によれば４−フェニルフェノールとメタノ
ールとから２．６−シメチルー４−フェニルフェノール
が連続的に高転化率、高選択率で製造され、高純度品が
要求される場合も簡単な再結晶で容ＡＫ精製され、かつ
触媒の寿命も長く、工業的に極めて有利である。Surface component Composition (Part) 4-phenylquenoyl 2.02
-Methyl compound 4.7 2.6-dimethyl compound 77.3 Others 16.0 [Effects of the invention] According to the method of the present invention, 2.6-dimethyl-4-phenylphenol is produced from 4-phenylphenol and methanol. is produced continuously at a high conversion rate and high selectivity, and even when a high purity product is required, it can be purified by simple recrystallization, and the catalyst has a long life, making it extremely advantageous industrially.
Claims (1)
雰囲気中で、酸化鉄、酸化バナシウム、酸化インジウム
及び酸化錫からなる群から選ばれる少なくとも２種の金
属酸化物を含有する触媒の存在下、２５０〜５００℃の
温度範囲で気相接触反応させることを特徴とする、２，
６−ジメチル−４−フェニルフェノールの製造方法。4-phenylphenol and methanol are heated in an inert gas atmosphere in the presence of a catalyst containing at least two metal oxides selected from the group consisting of iron oxide, vanadium oxide, indium oxide, and tin oxide at 250 to 2, characterized by carrying out a gas phase catalytic reaction in a temperature range of 500°C;
A method for producing 6-dimethyl-4-phenylphenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261331A JPH02108646A (en) | 1988-10-19 | 1988-10-19 | Production of 2,6-dimethyl-4-phenylphenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63261331A JPH02108646A (en) | 1988-10-19 | 1988-10-19 | Production of 2,6-dimethyl-4-phenylphenol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02108646A true JPH02108646A (en) | 1990-04-20 |
Family
ID=17360330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63261331A Pending JPH02108646A (en) | 1988-10-19 | 1988-10-19 | Production of 2,6-dimethyl-4-phenylphenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02108646A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7642392B2 (en) | 2003-09-03 | 2010-01-05 | Bp Oil International Limited | Process for preparing branched chain hydrocarbons |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5645428A (en) * | 1979-09-21 | 1981-04-25 | Mitsui Toatsu Chem Inc | Preparation of o-alkylated phenol |
| JPS5663932A (en) * | 1979-10-29 | 1981-05-30 | Mitsui Toatsu Chem Inc | Preparation of selectively ortho-alkylated phenol compound |
| JPS5785334A (en) * | 1980-11-17 | 1982-05-28 | Mitsui Toatsu Chem Inc | Ortho-alkylation process |
| JPS5791936A (en) * | 1980-11-26 | 1982-06-08 | Asahi Chem Ind Co Ltd | Preparation of ortho-methylated phenolic compound |
| JPS57112343A (en) * | 1980-12-01 | 1982-07-13 | Asahi Chem Ind Co Ltd | Ortho-methylation of phenolic compound |
| JPS5973534A (en) * | 1982-10-20 | 1984-04-25 | Mitsui Toatsu Chem Inc | Alkylation of phenolic compound |
-
1988
- 1988-10-19 JP JP63261331A patent/JPH02108646A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5645428A (en) * | 1979-09-21 | 1981-04-25 | Mitsui Toatsu Chem Inc | Preparation of o-alkylated phenol |
| JPS5663932A (en) * | 1979-10-29 | 1981-05-30 | Mitsui Toatsu Chem Inc | Preparation of selectively ortho-alkylated phenol compound |
| JPS5785334A (en) * | 1980-11-17 | 1982-05-28 | Mitsui Toatsu Chem Inc | Ortho-alkylation process |
| JPS5791936A (en) * | 1980-11-26 | 1982-06-08 | Asahi Chem Ind Co Ltd | Preparation of ortho-methylated phenolic compound |
| JPS57112343A (en) * | 1980-12-01 | 1982-07-13 | Asahi Chem Ind Co Ltd | Ortho-methylation of phenolic compound |
| JPS5973534A (en) * | 1982-10-20 | 1984-04-25 | Mitsui Toatsu Chem Inc | Alkylation of phenolic compound |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7642392B2 (en) | 2003-09-03 | 2010-01-05 | Bp Oil International Limited | Process for preparing branched chain hydrocarbons |
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