JPH0475896B2 - - Google Patents
Info
- Publication number
- JPH0475896B2 JPH0475896B2 JP60151868A JP15186885A JPH0475896B2 JP H0475896 B2 JPH0475896 B2 JP H0475896B2 JP 60151868 A JP60151868 A JP 60151868A JP 15186885 A JP15186885 A JP 15186885A JP H0475896 B2 JPH0475896 B2 JP H0475896B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- propylene
- phenol
- isopropylphenol
- molar ratio
- 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
- 238000006243 chemical reaction Methods 0.000 claims description 67
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 22
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000002989 phenols Chemical class 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- CRBJBYGJVIBWIY-UHFFFAOYSA-N 2-isopropylphenol Chemical compound CC(C)C1=CC=CC=C1O CRBJBYGJVIBWIY-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 12
- 238000009835 boiling Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 8
- QWVGKYWNOKOFNN-UHFFFAOYSA-N o-cresol Chemical compound CC1=CC=CC=C1O QWVGKYWNOKOFNN-UHFFFAOYSA-N 0.000 description 8
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 8
- IXQGCWUGDFDQMF-UHFFFAOYSA-N o-Hydroxyethylbenzene Natural products CCC1=CC=CC=C1O IXQGCWUGDFDQMF-UHFFFAOYSA-N 0.000 description 7
- NKTOLZVEWDHZMU-UHFFFAOYSA-N 2,5-xylenol Chemical compound CC1=CC=C(C)C(O)=C1 NKTOLZVEWDHZMU-UHFFFAOYSA-N 0.000 description 6
- TUAMRELNJMMDMT-UHFFFAOYSA-N 3,5-xylenol Chemical compound CC1=CC(C)=CC(O)=C1 TUAMRELNJMMDMT-UHFFFAOYSA-N 0.000 description 6
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 6
- 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 4
- 239000000126 substance Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- RECUKUPTGUEGMW-UHFFFAOYSA-N carvacrol Chemical compound CC(C)C1=CC=C(C)C(O)=C1 RECUKUPTGUEGMW-UHFFFAOYSA-N 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 230000000694 effects Effects 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
- 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 2
- 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
- -1 2,5-dimethyl-6-isopropylphenol Chemical compound 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
- 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
- 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
- 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
- 238000007796 conventional method Methods 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
- 239000002994 raw material Substances 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
- 150000003739 xylenols Chemical class 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
- AZXBHGKSTNMAMK-UHFFFAOYSA-N 3-methyl-2-propan-2-ylphenol Chemical compound CC(C)C1=C(C)C=CC=C1O AZXBHGKSTNMAMK-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
- 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
- 239000003905 agrochemical Substances 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
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229930003836 cresol Natural products 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
- 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
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Description
【発明の詳細な説明】
技術分野
本発明はフエノール類のｏ−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
（R1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）
で表わされるフエ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
特徴とするフエノール類のｏ−イソプロピル化方
法に関するものである。[Detailed Description of the Invention] Technical Field The present invention relates to a method for o-isopropylating phenols, and more specifically relates to a method for o-isopropylating phenols. (R 1 and R 2 represent H or a C 1-2 alkyl group,
However, the phenols represented by (excluding 2,6-disubstituted products) and propylene are
The present invention relates to a method for o-isopropylating phenols, which is characterized by carrying out the reaction in a gaseous state in the presence of an alumina catalyst.
従来技術
従来、フエノールのｏ−イソプロピル化によ
り、ｏ−イソプロピルフエ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
ルミニウムフエ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・ヘミー」
（Angewandte Chemie）69、699頁（1957）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。Prior Art Conventionally, as a method for producing o-isopropylphenol by o-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. 1977-7535, Japanese Patent Publication No. 49-40456, and "Angevante Chemie" which carry out the reaction using aluminum phenolate as a catalyst.
(Angewandte Chemie) 69 , p. 699 (1957), etc., all require temperatures of 200-300°C and pressures of several tens of atmospheres, and furthermore, the post-treatment method for removing aluminum from the reaction system is extremely troublesome. It is something.
このほかに、γ−アルミナを触媒とする特公昭
39−5021号公報及び米国特許第3367981号等の方
法が公知となつているが、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、亜鉛、鉄、ニツ
ケル等の硫酸塩を加えた触媒を用い、プロピレン
圧10−40Kg／cm2、250℃という反応条件でｏ−イ
ソプロピルフエノールを合成している。即ち、γ
−アルミナを触媒としてフエノールのｏ−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つた。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2430190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
て漸くフエノールのエーテル化がおこる程度のも
のである。 In addition, special public
Methods such as No. 39-5021 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, and these methods are not particularly effective. In Publication No. 46-3053, γ-
Since the activity of alumina is low, o-isopropylphenol is synthesized using a catalyst containing sulfates of copper, zinc, iron, nickel, etc. under reaction conditions of propylene pressure of 10-40 kg/cm 2 and 250°C. That is, γ
- When performing the o-isopropylation of phenol using alumina as a catalyst, high temperature and high pressure are common sense, and if you try to lower the temperature and pressure lower than that, you must add a co-catalyst to increase the activity. This was common knowledge among those skilled in the art. Even if it is desired to carry out the reaction at such a low temperature, for example 200°C, at normal pressure, no reaction will occur in the liquid phase reaction using γ-alumina as a catalyst, as shown in US Pat. No. 2,430,190. However, the etherification of phenol only occurs when an alkyl halide such as isopropyl chloride is added in place of propylene.
クレゾール、エチルフエノール等のアルミナ触
媒によるｏ−イソプロピル化に関しては僅かに西
独特許第586150号に記載されているのみで、然も
その反応は250−350℃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、
ｏ−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。 The o-isopropylation of cresol, ethylphenol, etc. using an alumina catalyst is only described in West German Patent No. 586150, and the reaction is carried out at a high temperature of 250-350°C. However, according to additional tests conducted by the present inventors, diisopropylation becomes the main reaction in such a high temperature range.
It was acknowledged that this deviates from the gist of the present invention, which uses o-isopropylation as the main reaction.
目 的
本発明の目的は従来技術の欠点を克服したフエ
ノール類のｏ−イソプロピル化方法を提供するこ
とである。Object The object of the present invention is to provide a process for the o-isopropylation of phenols which overcomes the drawbacks of the prior art.
構 成
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。よつて本発明者等は、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
エノールのｏ−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エノールのｏ
−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つた。即ち反応温度150−250
℃、好ましくは170−240℃でγ−アルミナ上にフ
エ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ｏ−イソプロピルフエノールを収率よく取得出
来たのである。Structure 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 conducted extensive research in search of reaction conditions that would allow the o-isopropylation of phenol to occur at a temperature of at most 250 DEG C. or lower and at normal pressure using .gamma.-alumina. However, surprisingly, by selecting appropriate conditions such as temperature, phenol o
- It was discovered that isopropylation can occur, leading to the completion of the present invention. That is, reaction temperature 150−250
℃, preferably 170-240℃, a mixed gas of phenol and propylene is introduced onto γ-alumina at normal pressure, and the resulting reaction liquid is fractionated to produce high-purity o-isopropylphenol in good yield. I was able to obtain it.
すなわち、本発明者等は、
一般式
（R1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）
で表わされるフエ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
150−250℃、好ましくは170−240℃、プロピレ
ン：フエノール類＝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
エノール類のｏ−イソプロピル化方法を提供する
ことによつて前記目的が達成できることを見出し
た。 That is, the inventors have the general formula (R 1 and R 2 represent H or a C 1-2 alkyl group,
(excluding 2,6-disubstituted products) and propylene, γ
- In the presence of an alumina catalyst, in a gaseous state at normal pressure, at a reaction temperature of
150-250°C, preferably 170-240°C, propylene:phenols = 1:1-10, preferably 1:
It has been found that the above object can be achieved by providing a method for o-isopropylating phenols, which is characterized in that the reaction is carried out at a molar ratio of 1-3.
上記一般式(1)で示されるフエノール類としては
フエノール、クレゾール類（ｏ−、ｍ−、ｐ−）、
エチルフエノール類（ｏ−、ｍ−、ｐ−）、キシ
レノール及びジエチルフエノール類（２，３−、
２，４−、２，５−、３，４−、３，５−）等が
含まれるが、本発明の方法の一例としてフエノー
ルを取上げて、そのｏ−イソプロピル化方法につ
いて以下述べることとする。 The phenols represented by the above general formula (1) include phenols, cresols (o-, m-, p-),
Ethylphenols (o-, m-, p-), xylenol and diethylphenols (2,3-,
2,4-, 2,5-, 3,4-, 3,5-), etc., but the o-isopropylation method thereof will be described below, taking phenol as an example of the method of the present invention. .
ｏ−イソプロピルフエノールは最近、農薬原料
として漸く需要増加を示しているアルキルフエノ
ールであつて、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。 O-isopropylphenol is an alkylphenol whose demand has recently been increasing as a raw material for agricultural chemicals, and the method of the present invention, which enables it to be supplied to the market in large quantities at a low price, has extremely high industrial value. be.
次に本発明の方法における原料について述べ
る。フエノールは一般市販の工業用合成フエノー
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 a commercially available industrially synthesized phenol, and the propylene may be one containing several percent of saturated hydrocarbons, although it is preferable that it be as pure as possible. 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（例えば日
揮化学製Ｎ−611N、Ｎ−612N等）でよく、普通
直径３mm×高さ３mm又は直径５mm×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 JGC Chemical Co., Ltd.), which is usually shaped into a column with a diameter of 3 mm and a height of 3 mm or a diameter of 5 mm and a height of 5 mm.
さて、本発明の方法をフエノールのｏ−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SUS304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。ついで空気をチツ素に置換して180℃
に冷却しプロピレン：フエノール＝１：１〜10、
好ましくは１：３〜５モル比の混合ガスをフエノ
ールLHSV＝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、ｏ
−イソプロピルフエノール35−50％、ｐ−イソプ
ロピルフエノール０−３％、ジイソプロピルフエ
ノール２−10％、未反応フエノール50−35％、高
沸点物数％であつてこれを分溜することにより99
％以上の高純度のｏ−イソプロピルフエノールを
得る。 Now, the method of the present invention for o-isopropylating phenol will be explained in detail. A typical 1-2 inch SUS304 reaction tube is filled with an appropriate amount of γ-alumina and activated by passing air through it at 450-550°C for several hours. Then replace the air with nitrogen and heat to 180℃
Cool to propylene:phenol=1:1~10,
A mixed gas preferably in a molar ratio of 1:3 to 5 is introduced at a phenol LHSV of 0.1-2, preferably 0.3-1 and a reaction temperature of 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 o
- 35-50% of isopropylphenol, 0-3% of p-isopropylphenol, 2-10% of diisopropylphenol, 50-35% of unreacted phenol, % of high boiling point substances, which can be fractionated to 99%
% or higher purity o-isopropylphenol is obtained.
以上、本発明の方法の一例としてフエノールの
ｏ−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、キシレノール、エチ
ルフエノール等についても全く同様にｏ−イソプ
ロピル化を行うことが出来る。 The o-isopropylation of phenol has been described above as an example of the method of the present invention.
Other cresols, xylenol, ethylphenol, etc. shown in can be o-isopropylated in exactly the same manner.
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つて限定される
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 １
SUS304製１インチ反応管に日揮化学製γ−ア
ルミナＮ−611Nを170c.c.充填し、空気を通しなが
ら500℃１時間処理し活性化を行つた。ついでチ
ツ素で空気を置換して180℃まで冷却し、これに
プロピレン：フエノール＝１：2.7モル比の混合
ガスをフエノールLHSV0.7で導入し、反応温度
を193−201℃に保つて10時間反応を行つた。得ら
れた反応液の組成は、ｏ−イソプロピルフエノー
ル36.93％、ｐ−イソプロピルフエノール0.2％、
２，６−ジイソプロピルフエノール2.41％、２，
４−ジイソプロピルフエノール0.57％、高沸点物
0.36％、未反応フエノール59.36％でフエノール
の転化率は30.82％、又ｏ−イソプロピルフエノ
ールの選択率は96.51％であつた。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
℃／40mmHgの溜分を集めて純度99.46％のｏ−イ
ソプロピルフエノールを得た。Example 1 A 1-inch reaction tube made of SUS304 was filled with 170 c.c. of γ-alumina N-611N manufactured by JGC Chemical Co., Ltd., and activated at 500° C. for 1 hour while passing air. 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 this with a phenol LHSV of 0.7, and the reaction temperature was maintained at 193-201°C for 10 hours. The reaction was carried out. The composition of the obtained reaction solution was 36.93% o-isopropylphenol, 0.2% p-isopropylphenol,
2,6-diisopropylphenol 2.41%, 2,
4-diisopropylphenol 0.57%, high boiling point
0.36%, unreacted phenol was 59.36%, the conversion rate of phenol was 30.82%, and the selectivity of o-isopropylphenol was 96.51%. This reaction solution was fractionated in a fractionation column with 20 theoretical plates, and the boiling point was 124.2-127.
C/40 mmHg fractions were collected to obtain o-isopropylphenol with a purity of 99.46%.
実施例 ２
プロピレン：フエノール＝１：1.6モル比、反
応温度を212−227℃である以外は実施例１と全く
同様に反応を行つて得られた反応液の組成はｏ−
イソプロピルフエノール49.38％、ｐ−イソプロ
ピルフエノール0.99％、２，６−ジイソプロピル
フエノール7.14％、２，４−ジイソプロピルフエ
ノール2.02％、高沸点物1.2％、未反応フエノー
ル38.95％でフエノールの転化率は50.17％、又ｏ
−イソプロピルフエノールの選択率は87.02％で
あつた。この反応液を実施例１と同様に分溜し
て、沸点133−136℃／50mmHgの溜分を集めて純
度99.39％のｏ−イソプロピルフエノールを得た。Example 2 The reaction was carried out in exactly the same manner as in Example 1 except that the molar ratio of propylene:phenol was 1:1.6 and the reaction temperature was 212-227°C. The composition of the reaction solution obtained was o-
Isopropylphenol 49.38%, p-isopropylphenol 0.99%, 2,6-diisopropylphenol 7.14%, 2,4-diisopropylphenol 2.02%, high boilers 1.2%, unreacted phenol 38.95%, phenol conversion rate is 50.17%, Also o
- The selectivity of isopropyl phenol was 87.02%. This reaction solution was fractionated in the same manner as in Example 1, and fractions with a boiling point of 133-136°C/50 mmHg were collected to obtain o-isopropylphenol with a purity of 99.39%.
実施例 ３
実施例１の反応管を用いプロピレン：ｏ−クレ
ゾール＝１：2.3モル比の混合ガスをｏ−クレゾ
ールLHSV0.7、反応温度210℃で10時間反応を行
つた。得られた反応液の組成は２−メチル−６−
イソプロピルフエノール48.34％、未反応ｏ−ク
レゾール46.67％、高沸点物3.57％、で、ｏクレ
ゾールの転化率は45.42％、２−メチル−６−イ
ソプロピルフエノールの選択率は89.57％であつ
た。この反応液を実施例１と同様に分溜し、沸点
114−116℃／20mmHgの溜分を集め純度99.30％の
２−メチル−６−イソプロピルフエノールを得
た。Example 3 Using the reaction tube of Example 1, a mixed gas of propylene:o-cresol=1:2.3 molar ratio was reacted for 10 hours at an o-cresol LHSV of 0.7 and a reaction temperature of 210°C. The composition of the obtained reaction solution was 2-methyl-6-
48.34% of isopropylphenol, 46.67% of unreacted o-cresol, and 3.57% of high boilers, the conversion of o-cresol was 45.42% and the selectivity of 2-methyl-6-isopropylphenol was 89.57%. This reaction solution was fractionated in the same manner as in Example 1, and the boiling point
Fractions at 114-116°C/20 mmHg were collected to obtain 2-methyl-6-isopropylphenol with a purity of 99.30%.
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−クレゾール
LHSV0.7、反応温度204−210℃で通し10時間反
応を行つた。得られた反応液の組成は２−イソプ
ロピル−４−メチルフエノール42.55％、未反応
ｐ−クレゾール54.09％、２，６ジイソプロピル
−４−メチルフエノール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−メチルフエノールの選択率
は94.50％であつた。この反応液を実施例１と同
様に分溜し、沸点123−124℃／25mmHgの溜分を
集めて、純度99.40％の２−イソプロピル−４−
メチルフエノールを得た。Example 4 A mixed gas of propylene: p-cresol = 1:2.3 molar ratio was added to p-cresol in the reaction tube of Example 1.
The reaction was carried out for 10 hours at LHSV 0.7 and reaction temperature 204-210°C. The composition of the resulting reaction solution was 42.55% 2-isopropyl-4-methylphenol, 54.09% unreacted p-cresol, 2.81% 2,6 diisopropyl-4-methylphenol, and other high-boiling substances.
At 0.29%, the conversion rate of p-cresol was 36.76%, 2
-Isopropyl-4-methylphenol selectivity was 94.50%. This reaction solution was fractionated in the same manner as in Example 1, and the fraction with a boiling point of 123-124°C/25 mmHg was collected.
Methylphenol was obtained.
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
LHSV0.7、反応温度228−232℃で導入し10時間
反応を行つた。得られた反応液の組成はｏ−チモ
ール46.22％、未反応ｍ−クレゾール47.98％、２
イソプロピル−３−メチルフエノール2.2％、高
沸点物3.6％であつてｍ−クレゾール転化率は
42.69％、ｏ−チモール選択率は91.4％であつた。
この反応液を分溜し、沸点123−125℃／20mmHg
溜分を集めて純度97.7％のｏ−チモールを得た。Example 5 A mixed gas of propylene: m-cresol = 1:2 molar ratio was added to m-cresol in the reaction tube of Example 1.
The mixture was introduced at a LHSV of 0.7 and a reaction temperature of 228-232°C, and the reaction was carried out for 10 hours. The composition of the obtained reaction solution was 46.22% o-thymol, 47.98% unreacted m-cresol, 2
Isopropyl-3-methylphenol 2.2%, high boiling point substances 3.6%, m-cresol conversion rate
The o-thymol selectivity was 91.4%.
This reaction liquid was fractionally distilled and the boiling point was 123-125℃/20mmHg.
The fractions were collected to obtain o-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−
エチルフエノール＝１：2.3モル比の混合ガスを
ｐ−エチルフエノールLHSV0.7、反応温度215−
220℃で導入し10時間反応を行つた。得られた反
応液の組成は４−エチル−６イソプロピルフエノ
ール38.45％、未反応ｐ−エチルフエノール55.68
％、高沸点物5.87％、ｐ−エチルフエノールの転
化率は36.00％、４−エチル−６イソプロピルフ
エノールの選択率は89.11％であつた。Example 6 Using the reaction tube of Example 1, propylene: p-
Mixed gas of ethylphenol = 1:2.3 molar ratio was mixed with p-ethylphenol LHSV 0.7, reaction temperature 215-
The mixture was introduced at 220°C and the reaction was carried out for 10 hours. The composition of the resulting reaction solution was 38.45% 4-ethyl-6 isopropylphenol and 55.68% unreacted p-ethylphenol.
%, high boilers 5.87%, p-ethylphenol conversion rate was 36.00%, and 4-ethyl-6 isopropylphenol selectivity 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−キシレノールLHSV0.7、反応温度234−
239℃で導入し10時間反応を行つた。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％であつて、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
つた。Example 7 Using the reaction tube of Example 1, propylene: 3,
Mixed gas with a molar ratio of 5-xylenol = 1:4.5 was mixed with 3,5-xylenol LHSV 0.7, reaction temperature 234-
The mixture was introduced at 239°C and the reaction was carried out for 10 hours. The composition of the resulting reaction solution was 22.9% 2-isopropyl 3,5-xylenol and 75.56% unreacted 3,5-xylenol.
% and other high-boiling substances 1.54%, the conversion rate of 3,5-xylenol was 18.44%, and the selectivity of 2-isopropyl 3,5-xylenol 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−キシレノールLHSV0.7、反応温度200−
210℃で10時間反応を行つて得られた反応液の組
成は２，５−ジメチル−６−イソプロピルフエノ
ール21.12％、未反応２，５−キシレノール76.74
％、２，５−ジメチル−４−イソプロピルフエノ
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
フエノールの選択率は93.69％であつた。Example 8 Using the reaction tube of Example 1, propylene: 2,
Mixed gas with 5-xylenol = 1:4.5 molar ratio, 2,5-xylenol LHSV 0.7, reaction temperature 200-
The composition of the reaction solution obtained by carrying out the reaction at 210°C for 10 hours was 21.12% of 2,5-dimethyl-6-isopropylphenol and 76.74% of unreacted 2,5-xylenol.
%, 2,5-dimethyl-4-isopropylphenol 1.67%, conversion rate of 2,5-xylenol
The selectivity for 2,5-dimethyl-6-isopropylphenol was 93.69%.
効 果
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エノールのｏ−
イソプロピル化を行うことができ、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つ
た利点をもたらす。Effects As described above, according to the method of the present invention, by selecting appropriate conditions, the o-
It is possible to carry out isopropylation, and 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)
但し２，６−ジ置換体を除く） で表わされるフエ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
150〜250℃、プロピレン：フエノール類＝１：１
〜10のモル比で反応を行うことを特徴とする、フ
エノール類の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：フエノール類モル比が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：フエノール類モル比が１：１〜３である特許
請求の範囲第１項記載の方法。[Claims] 1. General formula (R 1 and R 2 represent H or a C 1-2 alkyl group,
(excluding 2,6-disubstituted products) and propylene, γ
- In the presence of an alumina catalyst, in a gaseous state at normal pressure, at a reaction temperature of
150-250℃, propylene:phenols=1:1
A method for o-isopropylating phenols, characterized by carrying out the reaction at a molar ratio of ~10. 2. The method according to claim 1, wherein the reaction temperature is 170 to 240°C. 3 The propylene:phenol 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 JPS6212733A (en) | 1987-01-21 |
| JPH0475896B2 true 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) |
Families Citing this family (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 |
| FI912102A (en) * | 1991-04-30 | 1992-10-31 | Leiras Oy | FOERFARANDE FOER RENING AV 2,6-DIISOPROPYLFENOL |
| 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 |
| 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 |
-
1985
- 1985-07-10 JP JP60151868A patent/JPS6212733A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6212733A (en) | 1987-01-21 |
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