JPS6212733A - O-isopropylation of phenolic compound - Google Patents
O-isopropylation of phenolic compoundInfo
- Publication number
- JPS6212733A JPS6212733A JP60151868A JP15186885A JPS6212733A JP S6212733 A JPS6212733 A JP S6212733A JP 60151868 A JP60151868 A JP 60151868A JP 15186885 A JP15186885 A JP 15186885A JP S6212733 A JPS6212733 A JP S6212733A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- propylene
- isopropylphenol
- isopropylation
- phenol
- 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
- 150000002989 phenols Chemical class 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 69
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 125000000217 alkyl group Chemical group 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 abstract description 18
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 abstract description 7
- 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 abstract description 3
- 229930003836 cresol Natural products 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 150000003739 xylenols Chemical class 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 9
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 8
- 238000009835 boiling Methods 0.000 description 8
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 description 6
- DSTPUJAJSXTJHM-UHFFFAOYSA-N 4-methyl-2-propan-2-ylphenol Chemical compound CC(C)C1=CC(C)=CC=C1O DSTPUJAJSXTJHM-UHFFFAOYSA-N 0.000 description 6
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 5
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- QPVRKFOKCKORDP-UHFFFAOYSA-N 1,3-dimethylcyclohexa-2,4-dien-1-ol Chemical compound CC1=CC(C)(O)CC=C1 QPVRKFOKCKORDP-UHFFFAOYSA-N 0.000 description 3
- OLBCVFGFOZPWHH-UHFFFAOYSA-N propofol Chemical compound CC(C)C1=CC=CC(C(C)C)=C1O OLBCVFGFOZPWHH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KEUMBYCOWGLRBQ-UHFFFAOYSA-N 2,4-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC=C(O)C(C(C)C)=C1 KEUMBYCOWGLRBQ-UHFFFAOYSA-N 0.000 description 2
- KFETUQFRWIVAMU-UHFFFAOYSA-N 2-methyl-6-propan-2-ylphenol Chemical compound CC(C)C1=CC=CC(C)=C1O KFETUQFRWIVAMU-UHFFFAOYSA-N 0.000 description 2
- AXWIKVJVPDHROL-UHFFFAOYSA-N 3,5-dimethyl-2-propan-2-ylphenol Chemical compound CC(C)C1=C(C)C=C(C)C=C1O AXWIKVJVPDHROL-UHFFFAOYSA-N 0.000 description 2
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 2
- HFXZXGVECOWQGS-UHFFFAOYSA-N 4-ethyl-2-propan-2-ylphenol Chemical compound CCC1=CC=C(O)C(C(C)C)=C1 HFXZXGVECOWQGS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000005844 Thymol Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- -1 cooled to 180°C Chemical group 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000001896 cresols Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 229960000790 thymol Drugs 0.000 description 2
- RLEWTHFVGOXXTN-UHFFFAOYSA-N 2,3-diethylphenol Chemical class CCC1=CC=CC(O)=C1CC RLEWTHFVGOXXTN-UHFFFAOYSA-N 0.000 description 1
- NHBZPWOUQHAORZ-UHFFFAOYSA-N 2,5-dimethyl-4-propan-2-ylphenol Chemical compound CC(C)C1=CC(C)=C(O)C=C1C NHBZPWOUQHAORZ-UHFFFAOYSA-N 0.000 description 1
- PNTYWMCFKKJDAA-UHFFFAOYSA-N 4-methyl-2,6-di(propan-2-yl)phenol Chemical compound CC(C)C1=CC(C)=CC(C(C)C)=C1O PNTYWMCFKKJDAA-UHFFFAOYSA-N 0.000 description 1
- 229910015900 BF3 Inorganic materials 0.000 description 1
- 125000006538 C11 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000006266 etherification reaction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- OPSWAWSNPREEFQ-UHFFFAOYSA-K triphenoxyalumane Chemical compound [Al+3].[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1.[O-]C1=CC=CC=C1 OPSWAWSNPREEFQ-UHFFFAOYSA-K 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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)
Abstract
Description
【発明の詳細な説明】
五亙光互
本発明はフェノール類の０−イソプロピル化方法に関す
るものであり、さらに詳しくは一般式
（Ｒ工及びＲ２はＨまたはＣ１−２のアルキル基を示し
、但し２，６−ジ置換体を除く）
で表わされるフェノール類とプロピレンとをγ−アルミ
ナ触媒存在下にガス状で反応させることを特徴とするフ
ェノール類の０−イソプロピル化方法に関するものであ
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for 0-isopropylation of phenols, and more specifically, the present invention relates to a method for 0-isopropylation of phenols, and more specifically, the present invention relates to a method for 0-isopropylation of phenols, and more specifically, the present invention relates to a method for 0-isopropylation of phenols. The present invention relates to a method for 0-isopropylation of phenols, which is characterized by reacting phenols represented by the following (excluding 2,6-disubstituted products) with propylene in a gaseous state in the presence of a γ-alumina catalyst.
従」Ｑ１髄
従来、フェノールの０−イソプロピル化により、０−イ
ソプロピルフェノールを製造する方法としては弗化ホウ
素、弗酸、無水リン酸等のルイス酸を触媒とする方法が
ある。これらはその反応温度が低いという特徴を有する
が、その反面副反応物が多く後処理の際、中和水洗した
後でないと分留出来ないという操作上の欠点がある。ま
たアルミニウムフェノラートを触媒として反応を行なう
特公昭３３−７５３５号公報、特公昭４９−４０４５６
号公報及び「アンゲヴアンテ・ヘミ−Ｊ （Ａｎｇｅｗ
ａｎｄｔｅ Ｃｈｅｍｉｅ） ６９，６９９頁（１９５
７）等に開示された方法は、何れも２００−３００℃の
温度と数十気圧の圧力を要し、更に反応系からアルミニ
ウムを除く後処理方法も甚だ厄介なものである。Conventionally, as a method for producing 0-isopropylphenol by 0-isopropylation of phenol, there is a method using a Lewis acid such as boron fluoride, hydrofluoric acid, or phosphoric anhydride as a catalyst. These are characterized by a low reaction temperature, but on the other hand, they have a disadvantage in operation that they produce a large number of by-reactants and can only be fractionated after washing with neutralizing water during post-treatment. In addition, Japanese Patent Publication No. 33-7535 and Japanese Patent Publication No. 49-40456 disclose reactions using aluminum phenolate as a catalyst.
Publication No. and “Angew Ante Hemi-J (Angew
andte Chemie) 69,699 pages (195
7) and others require a temperature of 200-300°C and a pressure of several tens of atmospheres, and furthermore, the post-treatment method for removing aluminum from the reaction system is extremely troublesome.
このほかに、γ−アルミナを特徴とする特公昭３９−５
０２１号公報及び米国特許第３，３６７．９８１号等の
方法が公知となっているが、 これらは３００℃の温度
と数十気圧以上の圧力をかけないと反応が起らないとさ
れており、特公昭４６−３０５３号公報ではγ−アルミ
ナの活性が低いために銅。In addition to this, we also have the Special Publication No. 39-5, which features γ-alumina.
Methods such as No. 021 and U.S. Patent No. 3,367.981 are known, but it is said that the reaction does not occur unless a temperature of 300°C and a pressure of several tens of atmospheres or more are applied. , Japanese Patent Publication No. 46-3053 uses copper because the activity of γ-alumina is low.
亜鉛、鉄、ニッケル等の硫酸塩を加えた触媒を用い、
プロピレン圧１０−４０ｋｇ／ｃｍ”、２５０”Ｃとい
う反応条件で０−イソプロピルフェノールを合成してい
る。即ち、γ−アルミナを触媒としてフェノールの０−
イソプロピル化を行う場合は高温高圧が常識であり、そ
れより温度を下げ圧力を低くしようとすると、助触媒を
添加して活性を強くしなければならないというのが当業
者の通念であった。そのように低い温度たとえば２００
℃で然も常圧で反応を行いたいとしても、米国特許第２
，４３０，１９０号に示されているようにγ−アルミナ
を触媒とする液相反応では何ら反応が起らず、プロピレ
ンのかわりにイソプロピルクロリドのようなハロゲン化
アルキルを加えて漸くフェノールのエーテル化がおこる
程度のものである。Using a catalyst containing sulfates of zinc, iron, nickel, etc.
0-isopropylphenol was synthesized under reaction conditions of propylene pressure of 10-40 kg/cm" and 250"C. That is, the 0-
When performing isopropylation, it is common knowledge that high temperature and high pressure are used, and those skilled in the art have believed that if the temperature and pressure are to be lowered further, a promoter must be added to increase the activity. such a low temperature e.g. 200
Even if you want to carry out the reaction at ℃ but at normal pressure, U.S. Patent No. 2
, 430, 190, no reaction occurred in the liquid phase reaction using γ-alumina as a catalyst, and etherification of phenol was finally achieved by adding an alkyl halide such as isopropyl chloride instead of propylene. This is the extent to which this occurs.
クレゾール、エチルフェノール等のアルミナ触媒による
０−イソプロピル化に関しては僅かに西独特許第５８６
，１５０号に記載されているのみで、然もその反応は２
５０−３５０℃と高温で行われている。然しながら本発
明者等の追試によると、このような高温範囲ではジイソ
プロピル化が主反応となり、０−イソプロピル化を主反
応とする本発明の主旨から逸脱するものであることを認
めた。Regarding the 0-isopropylation of cresol, ethylphenol, etc. using an alumina catalyst, West German Patent No. 586
, No. 150, and the reaction is 2
It is carried out at high temperatures of 50-350°C. However, according to additional tests conducted by the present inventors, it was found that in such a high temperature range, diisopropylation becomes the main reaction, which deviates from the gist of the present invention, which has 0-isopropylation as the main reaction.
旦−一孜
本発明の目的は従来技術の欠点を克服したフェノール類
の。−イソプロピル化方法を提供することである。OBJECT OF THE INVENTION The object of the present invention is to develop phenols which overcome the drawbacks of the prior art. - To provide an isopropylation method.
碧−−−成。Ao---Nari.
従来技術のうちでγ−アルミナを触媒とする方法の利点
とする所は、反応液の中和洗浄等の処理を行わず直接そ
のまま蒸留にかけられるという点である。よって本発明
者等は、γ−アルミナを用いて高くとも２５０℃以下の
温度で、然も常圧でフェノールの。−イソプロピル化が
起る反応条件を求めて鋭意研究をすすめた。所が驚くべ
きことに、温度等の適当な条件を選ぶことによりγ−ア
ルミナを触媒として常圧ガス状でフェノールの０−イソ
プロピル化が起こり得ることを発見し、本発明を完成す
るに至った。Among the conventional techniques, the advantage of the method using γ-alumina as a catalyst is that the reaction solution can be directly subjected to distillation without undergoing any treatment such as neutralization and washing. Therefore, the present inventors used γ-alumina to react with phenol at a temperature of at most 250° C. or less and at normal pressure. -We conducted extensive research to find the reaction conditions that would cause isopropylation. However, surprisingly, the inventors discovered that by selecting appropriate conditions such as temperature, 0-isopropylation of phenol can occur in a gaseous state at normal pressure using γ-alumina as a catalyst, leading to the completion of the present invention. .
即ち反応温度１５０−２５０℃、好ましくは１７０−２
４０℃でγ−アルミナ上にフェノールとプロピレンとの
混合ガスを常圧で導入し、得られた反応液を分留するこ
とにより高純度の０−イソプロピルフェノールを収率よ
く取得出来たのである。That is, the reaction temperature is 150-250°C, preferably 170-2
By introducing a mixed gas of phenol and propylene at normal pressure onto γ-alumina at 40°C and fractionating the resulting reaction solution, it was possible to obtain highly pure 0-isopropylphenol in good yield.
すなわち１本発明者等は。In other words, the present inventors et al.
（Ｒ１及びＲ２はＨまたはＣ１１のアルキル基を示し、
但し２，６−ジ置換体を除く）
で表わされるフェノール類とプロピレンとを、γ−アル
ミナ触媒存在下に常圧ガス状で、反応温度１５０−２５
０℃、好ましくは１７０−２４０’Ｃ、プロピレン：フ
ェノール類＝１：１−１０、好ましくは１：１−３のモ
ル比で反応を行うことを特徴とするフェノール類の０−
イソプロピル化方法を提供することによって前記目的が
達成できることを見出した。(R1 and R2 represent H or a C11 alkyl group,
However, the phenols represented by
The reaction is carried out at 0°C, preferably 170-240'C, and at a molar ratio of propylene:phenols = 1:1-10, preferably 1:1-3.
It has been found that the above objects can be achieved by providing an isopropylation process.
上記一般式（１）で示されるフェノール類としてはフェ
ノール、クレゾール類（ｏ＋、ｍ＋。The phenols represented by the above general formula (1) include phenol and cresols (o+, m+).
ｐ −）、 エチルフェノール類（ｏ−、ｍ＋、ｐ−）
、 キシレノール及びジエチルフェノール類（２，３−
１２，４−１２，５−，３，４−１３，５−）等が含ま
れるが、本発明の方法の一例としてフェノールを取上げ
て、その０−イソプロピル化方法について以下述べるこ
ととする。p-), ethylphenols (o-, m+, p-)
, xylenol and diethylphenols (2,3-
12,4-12,5-, 3,4-13,5-), etc. However, taking phenol as an example of the method of the present invention, the 0-isopropylation method thereof will be described below.
０−イソプロピルフェノールは最近、農薬原料として漸
く需要増加を示しているアルキルフェノールであって、
廉価且つ大量に市場に供給し得ることを可能にする本発
明の方法は工業的価値の極めて高いものである。0-isopropylphenol is an alkylphenol whose demand has recently been increasing as a raw material for agricultural chemicals.
The method of the present invention, which allows it to be supplied to the market in large quantities at low cost, is of extremely high industrial value.
次に本発明の方法における原料について述べる。フェノ
ールは一般市販の工業用合成フェノールでよく、又プロ
ピレンはなるべく高純度のものが好ましいけれども数％
の飽和炭化水素を含むものでも差支えない。但し、不純
物の多いプロピレンを用いると抜取る廃ガスが多くなり
、プロピレンの損失のおこることは免れない。Next, the raw materials used in the method of the present invention will be described. The phenol may be commercially available industrial synthetic phenol, and the propylene should preferably be as pure as possible, but only a few percent
There is no problem even if it contains saturated hydrocarbons. However, if propylene containing many impurities is used, a large amount of waste gas will be extracted, and loss of propylene will inevitably occur.
触媒は一般市販のγ−アルミナ触媒（例えば８揮化学製
Ｎ−６１１Ｎ、Ｎ−６１２Ｎ等）でよく、普通直径３
ｍ＋ｍ Ｘ高さ３＋ｏ＋ｏ又は直径５ｍｍＸ高さ５ｍｍ
の柱状に成型されたものである。The catalyst may be a commercially available γ-alumina catalyst (for example, N-611N, N-612N, manufactured by 8 Volatile Chemical Co., Ltd.), and is usually 3 in diameter.
m+m x height 3+o+o or diameter 5mm x height 5mm
It is molded into a columnar shape.
さて、本発明の方法をフェノールの０−イソプロピル化
方法について詳述する。通常の１〜２インチのＳ Ｕ
Ｓ ３０４製反応管に、適当量のγ−アルミナを充填し
４５０−５５０℃で数時間空気を通して活性化を行う、
ついで空気をチッ素に置換して１８０℃に冷却しプロピ
レン：フェノール＝１：１〜１０、好ましくは１：３〜
５モル比の混合ガスを７ ｘ ／ −／Ｌ／ Ｌ ＨＳ
Ｖ ＝０．１−２ 、好ましくは、０．３−１、反応
温度１５０−２５０℃、好ましくは１７０−２４０℃で
導入する。このとき、反応熱のため触媒層の温度が上昇
するので外部冷却により所定の温度に冷却する。反応ガ
スを冷却して得られた反応液の組成は、０−イソプロピ
ルフェノール３５−５０％、ｐ−イソプロピルフェノー
ルＯ−３％、ジイソプロピルフェノール２−１０％、未
反応フェノール５０−３５％、高沸点物数％であってこ
れを分溜することにより９９％以上の高純度の０−イソ
プロピルフェノールを得る。Now, the method of the present invention will be described in detail regarding the 0-isopropylation method of phenol. Normal 1-2 inch S U
Fill a suitable amount of γ-alumina into a reaction tube made of S 304, and activate it by passing air through it at 450-550°C for several hours.
Then, the air is replaced with nitrogen, cooled to 180°C, and propylene:phenol=1:1 to 10, preferably 1:3 to
Mixed gas with a molar ratio of 7 x / - / L / L HS
V = 0.1-2, preferably 0.3-1, and the reaction temperature is introduced at 150-250°C, preferably 170-240°C. At this time, the temperature of the catalyst layer increases due to the heat of reaction, so it is cooled to a predetermined temperature by external cooling. The composition of the reaction liquid obtained by cooling the reaction gas is 35-50% O-isopropylphenol, 3% p-isopropylphenol, 2-10% diisopropylphenol, 50-35% unreacted phenol, and high boiling point. By fractionating this, 0-isopropylphenol with a purity of 99% or more can be obtained.
以上、本発明の方法の一例としてフェノールの０−イソ
プロピル化について述べたが、一般式（１）で示される
他のクレゾール、キシレノ−ル、エチルフェノール等に
ついても全く同様に０−イソプロピル化を行うことが出
来る。Although 0-isopropylation of phenol has been described above as an example of the method of the present invention, 0-isopropylation of other cresols represented by general formula (1), xylenol, ethylphenol, etc. can be carried out in exactly the same manner. I can do it.
次に本発明の方法について実施°例を示すが、本発明の
主旨はこれらの実施例によって限定されるものではない
ことを付記する。Next, examples of the method of the present invention will be shown, but it should be noted that the gist of the present invention is not limited by these examples.
実施例Ｉ
Ｓ Ｕ Ｓ ３０４製１インチ反応管に日揮化学製γ−
アルミナＮ−６１１Ｎを１７０ｃｃ充填し、空気を通し
ながら５００℃１時間処理し活性化を行った。Example I A 1-inch reaction tube made of SUS 304 was filled with γ-
170 cc of alumina N-611N was filled and activated at 500° C. for 1 hour while passing air.
ついでチッ素で空気を置換して１８０℃まで冷却し、こ
れにプロピレン：フェノール＝ １ ： ２．７モル比
の混合ガスをフェノールＬ ＨＳ Ｖｏ、７で導入し、
反応温度を１９３−２０１℃に保って１０時間反応を行
った。得られた反応液の組成は、０−イソプロピルフェ
ノール３６．９３％、 ｐ−イソプロピルフェノール０
．２％、２，６−ジイソプロピルフェノール２．４１％
、２，４−ジイソプロピルフェノール０．５７％、高沸
点物０．３６％、未反応フェノール５９．３６％でフェ
ノールの転化率は３０．８２％、又Ｏ−イソプロピルフ
ェノールの選択率は９６．５１％であった。この反応液
を理論段数２０段の分溜塔で分溜し、沸点１２４．２−
１２７℃／４０＋ｏｍＨｇの溜升を集めて純度９９．４
６％の０−イソプロピルフェノールを得た。Next, the air was replaced with nitrogen and cooled to 180°C, and a mixed gas of propylene:phenol = 1:2.7 molar ratio was introduced into it using phenol L HS Vo, 7.
The reaction was carried out for 10 hours while maintaining the reaction temperature at 193-201°C. The composition of the obtained reaction solution was 36.93% 0-isopropylphenol, 0% p-isopropylphenol.
．． 2%, 2,6-diisopropylphenol 2.41%
, 0.57% of 2,4-diisopropylphenol, 0.36% of high boilers, and 59.36% of unreacted phenol, the conversion rate of phenol was 30.82%, and the selectivity of O-isopropylphenol was 96.51. %Met. This reaction solution was fractionated in a fractionation column with 20 theoretical plates, and the boiling point was 124.2-
Collect the distillate at 127℃/40+omHg to obtain a purity of 99.4.
6% of 0-isopropylphenol was obtained.
実施例２
プロピレン：フェノール＝ １ ： １．６モル比１反
応温度を２１２−２２７℃である以外は実施例１と全く
同様に６反応を行って得られた反応液の組成は０−イソ
プロピルフェノール４９．３８％、 ｐ−イソプロピル
フェノール０．９９％、２，６−ジイソプロピルフェノ
ール７．１４％、２，４−ジイソプロピルフェノール２
．０２％、高沸点物１．２％、未反応フェノール３８．
９５％でフェノールの転化率は５０．１７％、又０−イ
ソプロピルヅエノールの選択率は８７．０２％であった
。この反応液を実施例１と同様に分溜して、沸点１３３
−１３６℃１５０ｍ＋ｓＨｇの溜置を集めて純度９９．
３９％の０−イソプロピルフェノールを得た。Example 2 Propylene:phenol = 1:1.6 molar ratio 1 Six reactions were carried out in exactly the same manner as in Example 1 except that the reaction temperature was 212-227°C. The composition of the reaction solution obtained was 0-isopropylphenol. 49.38%, p-isopropylphenol 0.99%, 2,6-diisopropylphenol 7.14%, 2,4-diisopropylphenol 2
．． 02%, high boilers 1.2%, unreacted phenol 38.
At 95%, the conversion rate of phenol was 50.17%, and the selectivity of 0-isopropyldienol was 87.02%. This reaction solution was fractionated in the same manner as in Example 1, and the boiling point was 133.
-136℃150m+sHg reservoir was collected and the purity was 99.
39% of 0-isopropylphenol was obtained.
実施例３
実施例１の反応管を用いプロピレン：０−クレゾール＝
１ ： ２．３モル比の混合ガスを０−フレジー／Ｌ
／ Ｌ ＨＳ Ｖｏ、７、反応温度２１０℃テ１０時間
反応を行った。得られた反応液の組成は２−メチル−６
−イソプロピルフェノール４８．３４％、未反応０−ク
レゾール４６．６７％、高沸点物３．５７％、で、０−
クレゾールの転化率は４５．４２％、 ２−メチル−６
−イソプロピルフェノールの選択率は８９．５７％であ
った。この反応液を実施例１と同様に分溜し、沸点１１
４−１１６℃／ ２０ｍｍＨｇの溜置を集め純度９９．
３０％の２−メチル−６−イソプロピルフェノールを得
た。Example 3 Using the reaction tube of Example 1, propylene:0-cresol=
1: Mixed gas with a molar ratio of 2.3 to 0-Fregie/L
/L HS Vo, 7, reaction temperature was 210° C. and the reaction was carried out for 10 hours. The composition of the obtained reaction solution was 2-methyl-6
-isopropylphenol 48.34%, unreacted 0-cresol 46.67%, high boilers 3.57%, and 0-
The conversion rate of cresol was 45.42%, 2-methyl-6
- The selectivity of isopropylphenol was 89.57%. This reaction solution was fractionated in the same manner as in Example 1, and the boiling point was 11.
The reservoir was collected at 4-116℃/20mmHg and the purity was 99.
30% of 2-methyl-6-isopropylphenol was obtained.
実施例４
実施例１の反応管にプロピレン：ｐ−クレゾール＝１：
２．３モル比の混合ガスをｐ−フレジー／Ｉ／ Ｌ Ｈ
Ｓ Ｖｏ、７、反応温度２０４−２１０℃で通し１０時
間反応を行った。得られた反応液の組成は２−イソプロ
ピル−４−メチルフェノール４２．５５％、未反応ｐ−
クレゾール５４．０９％、２，６ジイソプロピルー４−
メチルフェノール２．８１％、その他高沸点物０．２９
％でｐ−クレゾールの転化率は３６．７６％、 ２−イ
ソプロピル−４−メチルフェノールの選択率は９４．５
０％であった。この反応液を実施例１と同様に分溜し、
沸点１２３−１２４℃／２５＋＋ｎｏ）１ｇの溜置を集
めて、純度９９．４０％の２−イソプロピル−４−メチ
ルフェノールを得た。Example 4 In the reaction tube of Example 1, propylene: p-cresol = 1:
Mixed gas with a molar ratio of 2.3 is p-Frezy/I/LH
The reaction was carried out for 10 hours at a reaction temperature of 204-210°C. The composition of the resulting reaction solution was 42.55% 2-isopropyl-4-methylphenol, unreacted p-
Cresol 54.09%, 2,6 diisopropyl-4-
Methylphenol 2.81%, other high boiling point substances 0.29
%, the conversion rate of p-cresol is 36.76%, and the selectivity of 2-isopropyl-4-methylphenol is 94.5.
It was 0%. This reaction solution was fractionated in the same manner as in Example 1,
1 g of distillate (boiling point 123-124° C./25++ no.) was collected to obtain 2-isopropyl-4-methylphenol with a purity of 99.40%.
実施例５
実施例、１の反応管にプロピレン：ｍ−クレゾール＝１
＝２モル比の混合ガスをｍ−クレゾールＬ ＨＳ Ｖｏ
、７、反応温度２２８−２３２℃で導入し１０時間反応
を行った。得られた反応液の組成は〇−チモール４６．
２２％、未反応ｍ−クレゾール４７．９８％、 ２１′
ソプロピル−３−メチルフェノール２．２％、高沸点物
３．６％であってｍ−クレゾール転化率は４２．６９％
、 ０−チモール選択率は９１．４％であった。この反
応液を分溜し、沸点１２３−１２５℃／２０ｍｍＨｇの
溜置を集めて純度９７．７％の０−チモールを得た。Example 5 Propylene: m-cresol = 1 in the reaction tube of Example 1
= 2 molar ratio of mixed gas m-cresol L HS Vo
, 7. The mixture was introduced at a reaction temperature of 228-232°C and the reaction was carried out for 10 hours. The composition of the obtained reaction solution was 〇-thymol46.
22%, unreacted m-cresol 47.98%, 21'
Sopropyl-3-methylphenol 2.2%, high boilers 3.6%, m-cresol conversion rate 42.69%
The 0-thymol selectivity was 91.4%. This reaction solution was fractionally distilled, and the fractions with a boiling point of 123-125°C/20 mmHg were collected to obtain 0-thymol with a purity of 97.7%.
実施例６
実施例１の反応管を用いて、プロピレン：ｐ−エチルフ
ェノール−＝ １ ： ２．３モル比の混合ガスをｐ−
エチルフェノールＬ ＨＳ Ｖｏ、７、反応温度２１５
−２２０℃で導入し１０時間反応を行った。得られた反
応液の組成は４−エチル−６イソプロビルフエノール３
８．４５％、未反応ｐ−エチルフェノール５５．６８％
、高沸点物５．８７％で、ｐ−エチルフェノールの転化
率は３６．００％、 ４−エチル−６イソプロビルフエ
ノールの選択率は８９．１１％であった。Example 6 Using the reaction tube of Example 1, a mixed gas of propylene:p-ethylphenol=1:2.3 molar ratio was p-
Ethylphenol L HS Vo, 7, reaction temperature 215
The mixture was introduced at -220°C and the reaction was carried out for 10 hours. The composition of the obtained reaction solution was 4-ethyl-6 isopropyl phenol 3
8.45%, unreacted p-ethylphenol 55.68%
, high boilers were 5.87%, the conversion rate of p-ethylphenol was 36.00%, and the selectivity of 4-ethyl-6 isopropylphenol was 89.11%.
実施例７
実施例１の反応管を用いて、プロピレン＝３゜５−キシ
レノール＝ １ ： ４．５モル比の混合ガスを３．５
１シレ／−／Ｌ／ＬＨ８Ｖ０．７、反応温度２３４−２
３９℃で導入し１０時間反応を行った。得られた反応液
の組成は２−イソプロピル３，５−キシレノール２２．
９％、未反応３，５−キシレノール７５．５６％、その
他高沸点物１．５４％であって、３．５−キシレノール
の転化率は１８．４４％、２−イソプロピル３，５−キ
シレノールの選択率は９４．１５％であった。Example 7 Using the reaction tube of Example 1, a mixed gas of propylene=3°5-xylenol=1:4.5 in a molar ratio of 3.5
1 shot/-/L/LH8V0.7, reaction temperature 234-2
The mixture was introduced at 39°C and the reaction was carried out for 10 hours. The composition of the obtained reaction solution was 2-isopropyl 3,5-xylenol 22.
9%, unreacted 3,5-xylenol 75.56%, and other high-boiling substances 1.54%, the conversion rate of 3.5-xylenol was 18.44%, and the conversion rate of 2-isopropyl 3,5-xylenol was 18.44%. The selectivity was 94.15%.
実施例８
実施例１の反応管を用いて、プロピレン：２゜５−キシ
レノール＝ １ ： ４．５モル比の混合ガスを２．５
−キシ１７ ／−ルＬ ＨＳ Ｖｏ、７．反応温度２０
０−２１０℃で１０時間反応を行って得られた反応液の
組成は２，５−ジメチル−６−イソプロピル
Ｉフェノール２１．１２％、未反応２，５−キシレ
ノ−（ルア６．７４％、２，５−ジメチル−４−イソプ
ロピルフェノール１．６７％で、２，５−キシレノール
の転化率１７．３９％、２，５−ジメチル−６−イソプ
ロピルフェノールの選択率は９３．６９％であった。Example 8 Using the reaction tube of Example 1, a mixed gas with a molar ratio of propylene:2°5-xylenol=1:4.5 was prepared at 2.5 molar ratio.
-Ki 17 /-ru L HS Vo, 7. Reaction temperature 20
The composition of the reaction solution obtained by conducting the reaction at 0-210°C for 10 hours was 2,5-dimethyl-6-isopropyl.
I phenol 21.12%, unreacted 2,5-xylenol (Lua 6.74%, 2,5-dimethyl-4-isopropylphenol 1.67%, conversion of 2,5-xylenol 17.39%) , 2,5-dimethyl-6-isopropylphenol selectivity was 93.69%.
拗−−ユ敦
以上述べたように本発明の方法によれば、適当な条件を
選ぶことにより、γ−アルミナを触媒として２５０℃以
下の温度で常圧でフェノールの０−イソプロピル化を行
うことができ１反応液の中和洗浄等の処理を行わず、直
接そのまま蒸留にかけることが可能で、従来の方法では
達成できなかった利点をもたらす。As described above, according to the method of the present invention, by selecting appropriate conditions, 0-isopropylation of phenol can be carried out using γ-alumina as a catalyst at a temperature of 250°C or less and normal pressure. 1. The reaction solution can be directly subjected to distillation without undergoing treatments such as neutralization and washing, which brings advantages that could not be achieved with conventional methods.
Claims (1)
ル基を示し、但し２，６−ジ置換体を除く） で表わされるフェノール類とプロピレンとを、γ−アル
ミナ触媒存在下に常圧ガス状で、反応温度１５０〜２５
０℃、プロピレン：フェノール類＝１：１〜１０のモル
比で反応を行うことを特徴とする、フェノール類のｏ−
イソプロピル化方法。 ２、前記反応温度が１７０〜２４０℃である特許請求の
範囲第１項記載の方法。 ３、前記プロピレン：フェノール類モル比が１：１〜３
である特許請求の範囲第１項記載の方法。 ４、前記反応温度が１７０〜２４０℃で、前記プロピレ
ン：フェノール類モル比が１：１〜３である特許請求の
範囲第１項記載の方法。[Claims] 1. Represented by the general formula ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (R_1 and R_2 represent H or C_1_-_2 alkyl groups, excluding 2,6-disubstituted products) Phenols and propylene are reacted in a gaseous state at normal pressure in the presence of a γ-alumina catalyst at a reaction temperature of 150 to 25
The o-
Isopropylation method. 2. The method according to claim 1, wherein the reaction temperature is 170 to 240°C. 3. The propylene:phenols molar ratio is 1:1 to 3
The method according to claim 1. 4. The method according to claim 1, wherein the reaction temperature is 170 to 240°C and the propylene:phenol molar ratio is 1:1 to 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60151868A JPS6212733A (en) | 1985-07-10 | 1985-07-10 | O-isopropylation of phenolic compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60151868A JPS6212733A (en) | 1985-07-10 | 1985-07-10 | O-isopropylation of phenolic compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6212733A true JPS6212733A (en) | 1987-01-21 |
| JPH0475896B2 JPH0475896B2 (en) | 1992-12-02 |
Family
ID=15527974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60151868A Granted JPS6212733A (en) | 1985-07-10 | 1985-07-10 | O-isopropylation of phenolic compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6212733A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5133326A (en) * | 1989-07-05 | 1992-07-28 | Mazda Motor Corporation | Clutch control apparatus for a mechanical supercharger |
| US5175376A (en) * | 1991-04-30 | 1992-12-29 | Leiras Oy | Process for the purification of 2,6-diisopropyl phenol |
| KR970042454A (en) * | 1995-12-29 | 1997-07-24 | 황선두 | Method for producing high purity ortho isopropyl phenol |
| CN1064343C (en) * | 1998-05-09 | 2001-04-11 | 临湘市氨基化学品厂 | Preparation of o-isopropyl phenol |
| CN103086846A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Apparatus and method for continuously separating isopropylphenol |
-
1985
- 1985-07-10 JP JP60151868A patent/JPS6212733A/en active Granted
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5133326A (en) * | 1989-07-05 | 1992-07-28 | Mazda Motor Corporation | Clutch control apparatus for a mechanical supercharger |
| US5175376A (en) * | 1991-04-30 | 1992-12-29 | Leiras Oy | Process for the purification of 2,6-diisopropyl phenol |
| KR970042454A (en) * | 1995-12-29 | 1997-07-24 | 황선두 | Method for producing high purity ortho isopropyl phenol |
| CN1064343C (en) * | 1998-05-09 | 2001-04-11 | 临湘市氨基化学品厂 | Preparation of o-isopropyl phenol |
| CN103086846A (en) * | 2011-10-28 | 2013-05-08 | 中国石油化工股份有限公司 | Apparatus and method for continuously separating isopropylphenol |
| CN103086846B (en) * | 2011-10-28 | 2015-08-19 | 中国石油化工股份有限公司 | A kind of device and method being continuously separated isopropyl-phenol |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0475896B2 (en) | 1992-12-02 |
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