JPS58177927A - Preparation of alpha-aryl tertiary alcohol - Google Patents
Preparation of alpha-aryl tertiary alcoholInfo
- Publication number
- JPS58177927A JPS58177927A JP57059789A JP5978982A JPS58177927A JP S58177927 A JPS58177927 A JP S58177927A JP 57059789 A JP57059789 A JP 57059789A JP 5978982 A JP5978982 A JP 5978982A JP S58177927 A JPS58177927 A JP S58177927A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- tertiary alcohol
- mol
- reaction system
- boron compound
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 37
- 239000003518 caustics Substances 0.000 claims abstract description 12
- 150000001639 boron compounds Chemical class 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 229910021538 borax Inorganic materials 0.000 claims abstract description 6
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 6
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 6
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims abstract description 3
- VGTPKLINSHNZRD-UHFFFAOYSA-N oxoborinic acid Chemical compound OB=O VGTPKLINSHNZRD-UHFFFAOYSA-N 0.000 claims abstract 2
- 238000004519 manufacturing process Methods 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 3
- NVIFVTYDZMXWGX-UHFFFAOYSA-N sodium metaborate Chemical compound [Na+].[O-]B=O NVIFVTYDZMXWGX-UHFFFAOYSA-N 0.000 claims description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract description 18
- -1 methoxy, ethoxy Chemical group 0.000 abstract description 15
- 239000000047 product Substances 0.000 abstract description 12
- 239000007864 aqueous solution Substances 0.000 abstract description 9
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 125000000217 alkyl group Chemical group 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 3
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 150000002978 peroxides Chemical class 0.000 abstract description 2
- 238000007086 side reaction Methods 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229960001922 sodium perborate Drugs 0.000 abstract 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 abstract 1
- 238000000034 method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- BUZYGTVTZYSBCU-UHFFFAOYSA-N 1-(4-chlorophenyl)ethanone Chemical compound CC(=O)C1=CC=C(Cl)C=C1 BUZYGTVTZYSBCU-UHFFFAOYSA-N 0.000 description 4
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 150000003509 tertiary alcohols Chemical group 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- SBUIQTMDIOLKAL-UHFFFAOYSA-N (2-ethylphenyl)methanol Chemical compound CCC1=CC=CC=C1CO SBUIQTMDIOLKAL-UHFFFAOYSA-N 0.000 description 1
- FHBSIIZALGOVLM-UHFFFAOYSA-N 1-chloro-4-propan-2-ylbenzene Chemical compound CC(C)C1=CC=C(Cl)C=C1 FHBSIIZALGOVLM-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropanol Chemical compound CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-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
Abstract
Description
【発明の詳細な説明】
本発明はα−アリールＨＳ級アルコールの製造方法に関
し、詳しくはアリールジアルキルメタンを含む反応係に
、苛性アルカリ水溶液ならびに硼素化合物の存在下で酸
素含有ガスを供給することによって、アリールジアルキ
ルメタンから効率よくα−７リール第５級アルコールを
製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an α-aryl HS alcohol, and more specifically, the present invention relates to a method for producing an α-aryl HS alcohol, and more specifically, by supplying an oxygen-containing gas to a reaction system containing an aryl dialkylmethane in the presence of an aqueous caustic alkali solution and a boron compound. , relates to a method for efficiently producing α-7 aryl tertiary alcohol from aryldialkylmethane.
従来からα−アリール第５級アルコールは、アリールジ
アルキルメタンを酸化することによって製造できること
が広く知られている。たとえば＋１１燃料協会誌５５，
５１８〜５２４には、炭酸ナトリウムと遷移金属化合物
を触媒として用いる方法、（２）特公昭５９−１９！５
５５号公報には苛性アルカリとマンガン塩類を触媒とし
て用いる方法、（３）特公昭５９−２１２４２号公報に
は、非常に高濃度の苛性ソーダを用いる方法がそれぞれ
開示されておシ、これらの方法によって了り一ルジアル
キルメタンからα−アリール第３級アルコールが製造さ
れている。It has been widely known that α-aryl tertiary alcohols can be produced by oxidizing aryldialkylmethanes. For example, +11 Fuel Association Magazine 55,
518 to 524, a method using sodium carbonate and a transition metal compound as a catalyst, (2) Japanese Patent Publication No. 59-19!5
No. 55 discloses a method using caustic alkali and manganese salts as catalysts, and (3) Japanese Patent Publication No. 59-21242 discloses a method using extremely high concentration of caustic soda. Alpha-aryl tertiary alcohols have been produced from dialkylmethanes.
しかしながら上記（１）〜（３）の方法は、選択率が低
く、ヘンシフエノンやクミルハイドロパーオキサイド等
の副生成物が多量に生成するか、あるいは原料化合物の
転化率が低いなどの欠点があり、実用上満足すべきもの
ではなかった。However, methods (1) to (3) above have drawbacks such as low selectivity, large amounts of by-products such as hensifhenone and cumyl hydroperoxide, or low conversion of raw material compounds. , which was not practically satisfactory.
さらに、反応系に硼素化合物を存在させると共に無水状
態にてアリールジアルキルメタンを醗化することも知ら
れている（特公昭５２−５９２０号公報）。しかし、こ
の場合の生成恢は主として過醗化物であ夛、アルコール
類を得ることはできないものであった。Furthermore, it is also known that a boron compound is present in the reaction system and aryldialkylmethane is dissolved in an anhydrous state (Japanese Patent Publication No. 52-5920). However, in this case, the product was mainly a superfluid, and alcohols could not be obtained.
そこで本発明者らは上記従来技術の欠点を克服して、転
化率が高くしかも副反応の少ないα−アリール第３級ア
ルコールの製造方法を開発すべく鋭意研究を重ねた。そ
の結果、反応系に苛性アルカリ水溶液と共に硼素化合物
を存在せしめることによって効率よく反応が進行するこ
とを見出し、本発明を完成するに至った。すなわち本発
明は、アリールジアルキルメタンを含む反応系に、苛性
アルカリ水溶液の存在下で重責を含む気体を供給してα
−アリール第３級アルコールを製造するにあたり、反応
系に硼素化合物を存在させることを特徴とするα−アリ
ール第５級アルコールの製造方法を提供するものである
。Therefore, the present inventors have conducted extensive research in order to overcome the drawbacks of the above-mentioned conventional techniques and to develop a method for producing α-aryl tertiary alcohols with a high conversion rate and with few side reactions. As a result, they discovered that the reaction can proceed efficiently by allowing the boron compound to exist together with the caustic aqueous solution in the reaction system, leading to the completion of the present invention. That is, the present invention provides a reaction system containing aryl dialkyl methane by supplying a gas containing heavy duty in the presence of an aqueous caustic solution.
- Provides a method for producing an α-aryl tertiary alcohol, which is characterized in that a boron compound is present in the reaction system in producing the aryl tertiary alcohol.
ルジアルキルメタンであり、この化合物はで表わされる
。ここで式中のＸは水素原子あるいは塩素原子、臭素原
子等のハロゲン原子またはメチル基、エチル基等のアル
キル基、メトキシル基、エトキシル基等のアルコキシル
基であり、ｎは１，２．Ｓのいずれかの整数である。is a radical alkylmethane, and this compound is represented by. Here, X in the formula is a hydrogen atom, a halogen atom such as a chlorine atom or a bromine atom, an alkyl group such as a methyl group or an ethyl group, or an alkoxyl group such as a methoxyl group or an ethoxyl group, and n is 1, 2, or 2. is any integer of S.
またＨｌ、Ｂ２はそれぞれメチル基、エチル基、ブ四ピ
ル基等の低級アルキル基である。具体的にはキュメン、
０−クロルキュメン、ｐ−クロルキュメン、１２１）ブ
チルベンゼン、０−クロル−第２級ブチルベンゼン、ｐ
−クロル−第２級ブチルベンゼン、ｐ−シメンなどをあ
げることができる。Further, Hl and B2 are each a lower alkyl group such as a methyl group, an ethyl group, or a butetyl group. Specifically, Cumen,
0-Chlorcumene, p-chlorcumene, 121) Butylbenzene, 0-chloro-sec-butylbenzene, p
Examples include -chloro-secondary butylbenzene, p-cymene, and the like.
本発明の方法では、反応系に苛性アルカリ水溶液を存在
させ、原料化合物であるアリールジアルキルメタンと接
触させることが必要である。In the method of the present invention, it is necessary to make an aqueous caustic alkali solution exist in the reaction system and bring it into contact with the aryldialkylmethane, which is a raw material compound.
ここで上記アルカリ水溶液は苛性アルカリ、つまり水酸
化ナトリウムあるいは水酸化カリウムの水溶液が用いら
れる。さらにこの苛性アルカリ水溶液は、通常は濃度２
０〜６０％、好ましくは４０〜５０％のものが使用され
る。また、この苛性アルカリ水溶液の使用量は特に制限
はなく各種条件に応じて適宜定めればよいが、通常は原
料化合物であるアリールジアルキルメタン１００−に対
して５〜２００ ｆ、好ましくは５０〜１００デである
。Here, the aqueous alkali solution used is a caustic alkali, that is, an aqueous solution of sodium hydroxide or potassium hydroxide. Furthermore, this caustic alkaline aqueous solution usually has a concentration of 2
0-60%, preferably 40-50% is used. The amount of this caustic alkali aqueous solution to be used is not particularly limited and may be determined as appropriate depending on various conditions, but it is usually 5 to 200 f, preferably 50 to 100 It is de.
本発明の方法は、上述のアリールジアルキルメタンを含
む反応系に、苛性アルカリ水溶液と共に添加剤として硼
素化合物を存在させることが必要である。この添加剤と
して用いる硼素化合物は、転化率ならびにα−了り−ル
第５級アルコールの選択率の向上に大きく寄与するもの
であり、具体的には、硼砂、過硼醗ソータ゛、メタ硼酸
、メタ硼酸ソーダ、Ｓ＋ｓ力ＩＪウム、無水硼酸などを
あげることができ、これらを単独あるいは適宜混合して
用いればよい。またこの硼素化合物の使用量は、特に制
限はなく・各種条件に応じて定めればよいが、通常は原
料化合物に対してα５〜１０％、好ましくは１〜５％の
割合となるように定めればよい。The method of the present invention requires the presence of a boron compound as an additive together with an aqueous caustic alkali solution in the reaction system containing the above-mentioned aryldialkylmethane. The boron compound used as this additive greatly contributes to improving the conversion rate and the selectivity of α-tertiary tertiary alcohol. Examples include sodium metaborate, S + S, boric anhydride, etc., and these may be used alone or in an appropriate mixture. The amount of boron compound to be used is not particularly limited and may be determined according to various conditions, but it is usually determined to be α5 to 10%, preferably 1 to 5% of the raw material compound. That's fine.
本発明の方法では、上述の反応系に酸素を含む気体、た
とえば空気や酸素ガスを供給することによ松、アリール
ジアルキルメタンを重化して目的とするα−アリール第
３級アルコールを製造するのである。ここで酸素を含む
気体の供給速度は、反応温度、原料の種類等の各種条件
により異なり１一義的に定めることはできないが、通常
は原料化合物１００ｍ１あたり、酸素として１０〜１０
０１１／／分の割合で供給すればよい。In the method of the present invention, the target α-aryl tertiary alcohol is produced by polymerizing aryldialkylmethane by supplying an oxygen-containing gas, such as air or oxygen gas, to the above-mentioned reaction system. be. Here, the supply rate of the oxygen-containing gas varies depending on various conditions such as the reaction temperature and the type of raw material.1 Although it cannot be unambiguously determined, it is usually 10 to 10% as oxygen per 100 ml of raw material compound.
It may be supplied at a rate of 0.011//min.
また、この反応は一般に８０℃以上、好ましくは９０〜
１３０℃にて行なう。さらにこの反応は、常圧下で行な
ってもよく、必要に応じて加圧下で行なってもよい。Further, this reaction is generally carried out at 80°C or higher, preferably at 90°C or higher.
Perform at 130°C. Furthermore, this reaction may be carried out under normal pressure or, if necessary, under increased pressure.
かくして得られるα−アリール第５級アルコールは、原
料化合物である前述の一般式（Ｉ）で表わされるアリ−
をジアルキルメタンの種類に応じて各種のものがあげら
れるが、基本的には、このアリールジアルキルメタンに
対応する第３級アルコールであシ、
〔式中のＸ、Ｒ１，Ｒ”およびｎは前記一般式（Ｉ）の
ものと同じ。〕
で表わされるものとなる。The α-aryl tertiary alcohol thus obtained is a raw material compound of the aryl tertiary alcohol represented by the above-mentioned general formula (I).
There are various kinds of dialkylmethane depending on the type of dialkylmethane, but basically it is a tertiary alcohol corresponding to this aryldialkylmethane, [in the formula, X, R1, R'' and n are The same as that of general formula (I)].
叙上の如き本発明の方法によれば、従来技術に比較して
、原料化合物であるアリールジアルキルメタンの転化率
および目的生成物であるα−アリール第５級アルコール
の選択率の両者を大幅に向上させることができる。また
生成物中に過酸化物等がほとんど存在しないため、安全
に後処理を行なうことができる。According to the method of the present invention as described above, both the conversion rate of aryldialkylmethane, which is a raw material compound, and the selectivity of α-aryl tertiary alcohol, which is a target product, are significantly increased compared to the conventional technology. can be improved. Furthermore, since there is almost no peroxide or the like in the product, post-treatment can be carried out safely.
従って、本発明の方法は、医薬や農薬の合成中間体等と
して有用なα−了り−ル第５級アルコールを効率よく製
造することができるものとして極めて利用価値の高いも
のである。Therefore, the method of the present invention has extremely high utility value as it can efficiently produce α-esteryl tertiary alcohol, which is useful as a synthetic intermediate for pharmaceuticals and agricultural chemicals.
次に本発明の実施例を示す。Next, examples of the present invention will be shown.
実施例１ モーターで駆動される攪拌機、気体導入管。Example 1 Stirrer driven by motor, gas introduction tube.
温度計および還流冷却器を取シっけた反応容器に、ｐ−
クロル−５ｅｃ−ブチルベンゼン２０ Ｆ。In a reaction vessel equipped with a thermometer and a reflux condenser,
Chlor-5ec-butylbenzene 20F.
濃度５０％苛性ソーダ水溶液９５？および硼砂α２ｔを
入れ、反応温度１２０℃にて攪拌しながら酸素ガスを気
体導入管より ４０ ｍｌ／分の割合で吹込んで５０時
間反応を行なった。反応後、冷却し、６規定塩酸で中和
して有機層１＆６？を得た。一方水層からは１．１５Ｐ
のｐ−クロル安息香酸が回収された。次いで得られた有
機層をガスクロマトグラフィーにより分析したところ、
未反応のｐ−クロル−５ｅｃ−ブチルベンゼンは＆５？
であった。このことからｐ−クロル−８ｅｅ −ブチル
ベンゼンの転化率１ｊ６１．７モル％であることがわか
った。また生成物の内訳けは、目的生成物であるｐ−ク
ロル−α−メチル−α−エチルベンジルアルコール６９
４モル％ （ＥＬｌ ）） テア！り、ｌｌ１４１Ｊと
してｐ−クロルアセトフェノン１α８モル襲（ｔｉｙ）
、 ｐ−クロル安息香−１１，７モル％（ｔｌｓＰ）
、その他＆１％ル％ （（１９ｆ）ｒあった。50% concentration caustic soda aqueous solution 95? and 2 tons of borax were added, and the reaction was carried out for 50 hours at a reaction temperature of 120°C by blowing oxygen gas at a rate of 40 ml/min from the gas introduction tube while stirring. After the reaction, it is cooled and neutralized with 6N hydrochloric acid to form organic layers 1 & 6? I got it. On the other hand, 1.15P from the water layer
of p-chlorobenzoic acid was recovered. Next, the obtained organic layer was analyzed by gas chromatography, and it was found that
Unreacted p-chloro-5ec-butylbenzene is &5?
Met. From this, it was found that the conversion rate of p-chloro-8ee-butylbenzene was 1j61.7 mol%. The product breakdown is as follows: p-chloro-α-methyl-α-ethylbenzyl alcohol, which is the target product, 69
4 mol% (ELl)) Thea! p-chloroacetophenone 1α8 mol as ll141J (tiy)
, p-chlorobenzoin-11,7 mol% (tlsP)
, Others &1% ((19f) r).
上記反応におけるｐ−クロル−α−メチル−α−エチル
ベンジルアルコールの生成の経時変化は第１図に示すと
おシである。The time course of the production of p-chloro-α-methyl-α-ethylbenzyl alcohol in the above reaction is shown in FIG.
比較例１
実施例１において、硼砂を加えなかったこと以外は、実
施例１と同様の操作を行なった。その結果ｐ−クロル−
８＠ｃ−ブチルベンゼン（７）転化率は２９．４モル％
であった。また生成物の内訳けけ目的生成物であるｐ−
クロル−α−メチル−α−エチルベンジルアルコール６
１．２モル％であわ、副生物としてｐ−クロルアセトフ
ェノン＆０モル％、ｐ−クロル安息香酸１９．６モル％
、その他１＆２モル％であった。Comparative Example 1 The same operation as in Example 1 was performed except that borax was not added. As a result, p-chlor-
8@c-butylbenzene (7) conversion rate is 29.4 mol%
Met. In addition, the product breakdown is the target product p-
Chlor-α-methyl-α-ethylbenzyl alcohol 6
1.2 mol%, p-chloroacetophenone &0 mol% as by-products, p-chlorobenzoic acid 19.6 mol%
, and others were 1 & 2 mol%.
なお、上記反応におけるｐ−クロル−α−メチル−α−
エチルベンジルアルコールの生成の経時変化は第１図に
示すように、約１０時間紅過時がピークであった。In addition, p-chloro-α-methyl-α- in the above reaction
As shown in FIG. 1, the time course of the production of ethylbenzyl alcohol peaked at about 10 hours.
比較例２
比較例１において、苛性ソーダ水溶液を濃度４０％のも
の１ｔ９？とし、また反応温度１２０’Ｃを１００℃と
したこと以外は比較例１と同様の操作を行なった。その
結果、転化率は４＆５モル凱ｐ−クロルーα−メチル−
α−エチルベンジルアルコールの選択率は４４．５モル
％であった。Comparative Example 2 In Comparative Example 1, the caustic soda aqueous solution with a concentration of 40% was 1t9? The same operation as in Comparative Example 1 was performed except that the reaction temperature was changed from 120'C to 100°C. As a result, the conversion rate was 4 & 5 moles p-chloro-α-methyl-
The selectivity of α-ethylbenzyl alcohol was 44.5 mol%.
比較例３
比較例１において、苛性ソーダ水溶液を濃度６０弾のも
の７．９１とし、また反応温度１２０″Ｃを１５５°Ｃ
としたこと以外は比較例１と同様の操作を行なった。そ
の結果、転化率は２７．５モル％。Comparative Example 3 In Comparative Example 1, the concentration of the caustic soda aqueous solution was 7.91 with a concentration of 60, and the reaction temperature was changed from 120"C to 155°C.
The same operation as in Comparative Example 1 was performed except for the following. As a result, the conversion rate was 27.5 mol%.
ｐ−クロル−α−メチル−α−エチルベンジルアルコー
ルの選択率１−ｉ６３モル％であった。The selectivity of p-chloro-α-methyl-α-ethylbenzyl alcohol was 1-i63 mol%.
実施例２
実施例１において硼砂の代わりに硼酸カリウムα２ｆを
用い、反応時間を３２．５時間としたこと以外は実施例
１と同様の操作を行なった。その結果、ｐ−クロル−５
ｅｃ −ブチルベンゼンの転化率は４＆５モル％（９，
３８Ｆ）であった。また生成物の内訳けは目的生成物で
あるｐ−クロル−α−メチル−α−エチルベンジルアル
コール７４．８モル％（７，２８Ｆ）であり、副生物と
してｐ−クロルアセトフェノン１α８モル％（α５ｓｆ
ｆ）、ｐ−クロル安息香酸１Ｎ５モル％（ｔｌｆ）、そ
の他ｔｏ８モル％（α１１ｉ）であった。なお回収した
有機層は１Ｚ６５グであった。Example 2 The same operation as in Example 1 was performed except that potassium borate α2f was used instead of borax and the reaction time was 32.5 hours. As a result, p-chlor-5
The conversion rate of ec-butylbenzene was 4 & 5 mol% (9,
38F). The breakdown of the product is 74.8 mol% (7,28F) of p-chloro-α-methyl-α-ethylbenzyl alcohol, which is the target product, and 1α8 mol% of p-chloroacetophenone (α5sf) as a by-product.
f), p-chlorobenzoic acid 1N 5 mol% (tlf), and others to 8 mol% (α11i). The organic layer recovered had a weight of 1Z65g.
実施例５
実施例１において硼砂の代わりにメタ硼酸ソーダα２Ｌ
ｔを用い、反応時間を３０時間としたこと以外は実施例
１と同様の操作を行なった。Example 5 Sodium metaborate α2L was used instead of borax in Example 1.
The same operation as in Example 1 was performed except that t was used and the reaction time was 30 hours.
その結果、ｐ−クロル−５ｅａ−ブチルベンゼンの転化
率は４２．９モル％（９，４Ｆ）であった。また生成物
の内訳けは目的生成物であるｐ−クロル−α−メチル−
α−エチルベンジルアルコール７５．５モル％（５，８
Ｆ）であシ、副生物としてｐ−クロルアセトフェノン＆
８モル％（（１５Ｆ）、 ｐ −クロル安息香酸１Ｓ、
９モル％（１，０５ＳＬ）？その他０モル％（０５’）
であった。なお回収した有機層は１５．７）であった。As a result, the conversion rate of p-chloro-5ea-butylbenzene was 42.9 mol% (9,4F). The product breakdown is the target product p-chloro-α-methyl-
α-Ethylbenzyl alcohol 75.5 mol% (5,8
F) Ash, p-chloroacetophenone & as a by-product
8 mol% ((15F), p-chlorobenzoic acid 1S,
9 mol% (1,05SL)? Others 0 mol% (05')
Met. The organic layer recovered was 15.7).
第１図は実施例１および比較例１におけるｐ−クロル−
α−メチル−α−エチルベンジルアルコールの生成の経
時変化を示すグラフである。Figure 1 shows p-chloro-
1 is a graph showing changes over time in the production of α-methyl-α-ethylbenzyl alcohol.
特許出願人 出光興産株式会社Patent applicant: Idemitsu Kosan Co., Ltd.
Claims (1)
アルカリ水溶液の存在下で酸素を含む気体を供給して、
α−アリール第５級アルコールをｇ造するにあたり、反
応系に硼素化合物を存在させることを特徴とするα−ア
リール第３級アルコールの製造方法。 （２）硼素化合物が、硼砂、過硼醗ソーダ、メタ硼酸、
メタ硼酸ソーダ、硼酸カリウムあるいは無水硼酸である
特許請求の範囲第１項記載の製造方法。[Claims] (Supplying a gas containing oxygen to a reaction system containing 11-aryldialkylmethane in the presence of an aqueous caustic alkali solution,
1. A method for producing an α-aryl tertiary alcohol, which comprises making a boron compound exist in the reaction system in producing the α-aryl tertiary alcohol. (2) The boron compound is borax, perborous soda, metaboric acid,
The manufacturing method according to claim 1, wherein sodium metaborate, potassium borate, or boric anhydride is used.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57059789A JPS58177927A (en) | 1982-04-12 | 1982-04-12 | Preparation of alpha-aryl tertiary alcohol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57059789A JPS58177927A (en) | 1982-04-12 | 1982-04-12 | Preparation of alpha-aryl tertiary alcohol |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS58177927A true JPS58177927A (en) | 1983-10-18 |
Family
ID=13123395
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57059789A Pending JPS58177927A (en) | 1982-04-12 | 1982-04-12 | Preparation of alpha-aryl tertiary alcohol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58177927A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012082142A (en) * | 2010-10-07 | 2012-04-26 | Mitsui Fine Chemicals Inc | Method for preparing benzene carbinol derivative |
-
1982
- 1982-04-12 JP JP57059789A patent/JPS58177927A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012082142A (en) * | 2010-10-07 | 2012-04-26 | Mitsui Fine Chemicals Inc | Method for preparing benzene carbinol derivative |
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