JPS61293936A - Liquid-phase dehydration of alcohol having aromatic side-chain at alpha-site - Google Patents
Liquid-phase dehydration of alcohol having aromatic side-chain at alpha-siteInfo
- Publication number
- JPS61293936A JPS61293936A JP60135790A JP13579085A JPS61293936A JP S61293936 A JPS61293936 A JP S61293936A JP 60135790 A JP60135790 A JP 60135790A JP 13579085 A JP13579085 A JP 13579085A JP S61293936 A JPS61293936 A JP S61293936A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- alcohol
- aromatic side
- catalyst
- solid acid
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
- C07C1/24—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by elimination of water
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/12—Silica and alumina
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
Abstract
Description
【発明の詳細な説明】
本発明は芳香族側鎖α−位アルコールの脱水法に関する
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for dehydrating aromatic side chain alpha-alcohols.
アルコールの脱水によるオレフィンの合成はよ（知られ
ておシ、硫酸、リン酸、塩化亜塩−塩酸等が液相での脱
水に、アルミナのような固体酸が気相での脱水に使用さ
れている。Synthesis of olefins by dehydration of alcohols is well known. Sulfuric acid, phosphoric acid, subchloride-hydrochloric acid, etc. are used for dehydration in the liquid phase, and solid acids such as alumina are used for dehydration in the gas phase. ing.
しかし、式（Ｉ）
Ｈｓ
ｌ
Ａｒ −Ｃ−ＯＨ（Ｉ）
（式中、Ａｒはフェニル基、１−す７チル基または２−
す７チル基、Ｒは水素またはメチル基を示す）
で表わされる芳香族側鎖α−位アルコールを、硫酸、リ
ン酸、塩化亜塩−塩酸の存在下液相で脱水（式中、Ａｒ
およびＲは前記と同義である）で表わされる芳香族ビニ
ル化合物へ変換しようとしても、弐個）
（式中、ＡｒおよびＲは前記と同義である）で表わされ
る環化二量体の副生が著しく、芳香族ビニル化合物■を
収率よく得ることはできない。However, the formula (I) Hs l Ar -C-OH(I) (wherein Ar is a phenyl group, a 1-s7tyl group or a 2-
An aromatic side chain alpha-alcohol represented by a 7-methyl group (R represents hydrogen or a methyl group) is dehydrated in a liquid phase in the presence of sulfuric acid, phosphoric acid, subchloride-hydrochloric acid (wherein, Ar
Even if an attempt is made to convert it into an aromatic vinyl compound represented by (Ar and R have the same meanings as above), a by-product of a cyclized dimer represented by 2) (wherein Ar and R have the same meanings as above) is so remarkable that aromatic vinyl compound (2) cannot be obtained in good yield.
芳香族ビニル化合物■は高分子モノマーとして有用であ
シ、これを芳香族側鎖α−位アルコール（Ｉ）から製造
することができれば工業的に有意義である。殊に高沸点
のビニル化合物、たとえば式α）ＯＨ３
で表わされる２−インプロペニルナフタレンは特開昭５
８−１０８２４４号公報に開示されているようにＡＢＳ
樹脂の耐熱性を向上させることができるので、これ等を
工業的に製造する目的には本発明の方法は特に有用であ
る。Aromatic vinyl compound (1) is useful as a polymeric monomer, and it would be industrially significant if it could be produced from the alpha-alcohol (I) in the aromatic side chain. In particular, high boiling point vinyl compounds, such as 2-impropenylnaphthalene represented by the formula α)OH3, are
ABS as disclosed in Publication No. 8-108244
Since the heat resistance of resins can be improved, the method of the present invention is particularly useful for industrially producing these resins.
なお芳香族側鎖α−位アル；−ルは、対応する炭化水素
をアルカリ水溶液共存下に酸素または空気で酸化するこ
とにより製造することができる。Incidentally, the aromatic side chain alpha-alcohol can be produced by oxidizing the corresponding hydrocarbon with oxygen or air in the coexistence of an aqueous alkali solution.
本発明者らは以上を考慮して、芳香族側鎖α−位アルコ
ール（Ｉ）を選択性よく脱水して芳香族ビニル化合物０
１）とする方法を開発すべ（鋭意研究に努めた結果、本
発明の方法に到達したものである。In consideration of the above, the present inventors dehydrated the alcohol (I) at the α-position of the aromatic side chain with good selectivity to form an aromatic vinyl compound with 0
1) As a result of intensive research, we have arrived at the method of the present invention.
本発明の方法を実施するには、原料の芳香族側鎖α−位
アルコールを無溶媒または溶媒中で、固体酸を触媒とし
て反応させる。To carry out the method of the present invention, the aromatic side chain α-position alcohol as a raw material is reacted without a solvent or in a solvent using a solid acid as a catalyst.
本発明の方法を実施するにあたって溶媒の使用は必ずし
も必須ではないが、反応温度を制御するためには溶媒を
使用することが望ましい。溶媒とシテハ、ヘキサン、ヘ
プタン、ベンゼン、トルエン、キシレン、好まシフはト
ルエン、キシレンを使用する。Although the use of a solvent is not necessarily essential in carrying out the method of the present invention, it is desirable to use a solvent in order to control the reaction temperature. As a solvent, use hexane, heptane, benzene, toluene, xylene, preferably toluene and xylene.
また芳香族側鎖α−位アルコールの製造原料である芳香
族炭化水素を脱水反応の溶媒として使用することは何ら
支障ない。たとえば２−（２−ヒドロキシ−２−プロピ
ル）す７タレンの脱水反応の溶媒として２−イソプロピ
ルナフタレンを使用することができる。Further, there is no problem in using the aromatic hydrocarbon, which is the raw material for producing the alcohol at the α-position of the aromatic side chain, as a solvent for the dehydration reaction. For example, 2-isopropylnaphthalene can be used as a solvent for the dehydration reaction of 2-(2-hydroxy-2-propyl)s7talene.
本発明の方法を実施するにあたって、溶媒の使用量は原
料の０．５ないし２０倍（容量／重量）、好ましくは１
ないし１０倍である。In carrying out the method of the present invention, the amount of solvent used is 0.5 to 20 times (volume/weight) the amount of raw materials, preferably 1
or 10 times more.
本発明の方法を実施するにあたって、触媒としてケイ素
とアルミニウムの混合酸化物を主取分とする固体酸を使
用する。ケイ酸アルミニウム、ケインウ土、活性白土、
Ｈ−Ｗ合成ゼオライト等の固体酸触媒が本発明の方法に
適しているが、本発明者等の経験によれば、該固体酸触
媒表面のいわゆるブレンステッド酸の密度の高低が脱水
反応と三量化反応の進行する割合を決定する。すなわち
ブレンステッド酸密度の高い触媒を使用すると脱水反応
が主に進行し、密度の低い触媒を使用すると三量化反応
が主に進行する。ケイ酸アルミニウム、酸交換度の高い
Ｈ−型合成ゼオライドが本発明の方法に使用する触媒と
して特に適している。In carrying out the method of the invention, a solid acid containing a mixed oxide of silicon and aluminum as the main component is used as a catalyst. Aluminum silicate, cane earth, activated clay,
Solid acid catalysts such as H-W synthesized zeolite are suitable for the method of the present invention, but according to the experience of the present inventors, the density of so-called Brønsted acids on the surface of the solid acid catalyst is a factor in the dehydration reaction. Determine the rate at which the quantification reaction will proceed. That is, when a catalyst with a high Brønsted acid density is used, the dehydration reaction mainly proceeds, and when a catalyst with a low density is used, the trimerization reaction mainly proceeds. Aluminum silicates, H-type synthetic zeolides with a high degree of acid exchange, are particularly suitable as catalysts for use in the process of the invention.
本発明の方法を実施するにあたって、触媒の使用量は基
質に対して０．１ないし２０ｗｔ％、好ましくは０．５
ないし１０ｗｔ俤である。In carrying out the method of the present invention, the amount of catalyst used is 0.1 to 20 wt%, preferably 0.5 wt% based on the substrate.
It is about 10wt.
本発明の方法を実施するにあたって、芳香族側鎖α−位
アルコールと固体酸触媒と必要ならば溶媒を混合して５
０ないし３００℃、好ましくは１００ないし２００℃で
、１分間ないし２時間。In carrying out the method of the present invention, the alcohol at the α-position of the aromatic side chain, the solid acid catalyst and, if necessary, a solvent are mixed.
0 to 300°C, preferably 100 to 200°C, for 1 minute to 2 hours.
好ましくは２分間ないし１時間加熱攪拌する。Preferably, the mixture is heated and stirred for 2 minutes to 1 hour.
反応を終了した後で、反応混合物から触媒を取９除くに
は単に濾過するだけでよい。このように反応後の触媒の
除去が極めて容易なことは本発明の方法の大きな特長で
ある。After the reaction has ended, the reaction mixture can be simply filtered to remove the catalyst. A major feature of the method of the present invention is that the catalyst can be removed extremely easily after the reaction.
以下に非限定的実施例を挙げて本発明の方法を詳細に説
明する。The method of the invention will now be explained in detail by way of non-limiting examples.
実施例 １
クミルアルコール１．０７２ｇ（７，８７ｒｒｒｎｏｌ
）をキシレン１０．７＋ｄに溶解し、１４０℃に加熱攪
拌しながら、ケイ酸アルミニウム（渋川理化学■製。Example 1 1.072 g of cumyl alcohol (7,87 rrrnol
) in xylene 10.7+d and heated to 140°C while stirring, aluminum silicate (manufactured by Shibukawa Rikagaku ■) was heated to 140°C with stirring.
Ａｔ２０３・３ＳｉＯｓ）１０．７〜を加え、そのまま
２０分間反応させた。At203.3SiOs) 10.7~ was added and reacted as it was for 20 minutes.
薄層クロマトグラフ（メルクＨＰＴＬＣ５６２８，ヘキ
サン／酢酸エチル＝２００／１）によれば、原料クミル
アルコールは完全に消失し、環化二量体の生成はみとめ
られず、α−メチルスチレンのみが生成していた。According to thin layer chromatography (Merck HPTLC5628, hexane/ethyl acetate = 200/1), the raw material cumyl alcohol completely disappeared, no cyclized dimer was observed, and only α-methylstyrene was produced. Was.
２−アセトナフトンを内部標準としてガスクロマトグラ
フ（デキシル）によシ分析したところ、α−メチルスチ
レンの生成量は０．８７９．９（７，４４ｒｒｍｏ１．
収率９４．５ｍｏ１％）であった。When analyzed by gas chromatography (dexyl) using 2-acetonaphthone as an internal standard, the amount of α-methylstyrene produced was 0.879.9 (7,44 rrmo1.
The yield was 94.5 mo1%).
比較例 １
クミルアルコール１．０４１９ （７，６４ｒｒｍｏｌ
）をキシレン１０．４ｄに溶解し、１４０℃に加熱攪拌
しながら、濃硫酸０．１−を加え、そのまま１０分間反
応させた。Comparative example 1 cumyl alcohol 1.0419 (7,64rrmol
) was dissolved in 10.4 d of xylene, and while stirring and heating to 140° C., 0.1 − of concentrated sulfuric acid was added, and the mixture was allowed to react for 10 minutes.
薄層りｑマドグラフによれば、原料クミルアルコールは
完全に消失し、α−メチルスチレンはほとんど生成せず
、α−メチルスチレンよりもわずかに極性の高い化合物
が主に生成していた。According to the thin layer qmadgraph, the raw material cumyl alcohol completely disappeared, α-methylstyrene was hardly produced, and compounds slightly more polar than α-methylstyrene were mainly produced.
カラムクロマトグラフィーによりこの主生成物の一部を
単離し、ＮＭＲとＭＳの結果にょシ下の環化二量体と推
定した。A part of this main product was isolated by column chromatography, and as a result of NMR and MS, it was presumed to be a cyclized dimer.
ＮＭＲ（２５０ＭＨｚ 、 ＣＤＣ１５）δ−値：１．
３６ （３Ｈ，ｓ）
１．４０ （３Ｈ，ｓ）
２．０２ （３Ｈ，ｓ）
２．２４ （ＩＨ，ｄ）
２．３６ （ＬＨ，ｄ）
７．０ − ７．４ （９Ｈ，ｍ）
ＭＳ （Ｄ！、 ７０ｅＶ） ｒｎ／ｅ：２３６、
２２１
実施例 ２
２−（２−ヒドロキシ−２−プロピル）ナフタレン２５
３．４ ｆｎｆ （１，３６ｍｎｏｌ）をキシレン２．
５ ｒｎｌと混合して１４０℃に加熱攪拌し、一部未溶
解のままケイ酸アルミニウム（渋川理化学■製、 Ａｚ
ｚ Ｏｓ・３ＳｉＯｓ）２−５ｍ！７を加え、そのまま
１５分間反応させた。冷却後ケイ酸アルミニウムを戸別
し、溶媒を留去し、カラムクロマトグラフ（メルクＬｏ
ｂａｒ−Ｂ。NMR (250MHz, CDC15) δ-value: 1.
36 (3H, s) 1.40 (3H, s) 2.02 (3H, s) 2.24 (IH, d) 2.36 (LH, d) 7.0 - 7.4 (9H, m) MS (D!, 70eV) rn/e:236,
221 Example 2 2-(2-hydroxy-2-propyl)naphthalene 25
3.4 fnf (1,36 mnol) in xylene 2.
5 rnl, heated to 140℃ and stirred, leaving some undissolved aluminum silicate (manufactured by Shibukawa Rikagaku ■, Az
zOs・3SiOs)2-5m! 7 was added, and the reaction was continued for 15 minutes. After cooling, the aluminum silicate was separated from each other, the solvent was distilled off, and the column chromatograph (Merck Lo
bar-B.
ヘキサン／酢酸エチル＝２００７１）により精製し、２
−インプロペニルナフタレンの純品２１３．６ｍｒ（１
，２７ｒｒｍｏｌ ＋収率９３．３％）を得た。Purified by hexane/ethyl acetate=20071),
- Pure impropenylnaphthalene 213.6 mr (1
, 27rrmol + yield 93.3%).
比較例 ２
２−（２−ヒドロキシ−２−プロピル）す７タレン１１
３．４ Ｑ （０，６０９ｒｒｒｎｏｌ）をキシレン１
ａと混合し、１４０℃に加熱攪拌しながら、濃硫酸０．
０２１１１ｊを加え、そのまま１０分間反応させた。Comparative example 2 2-(2-hydroxy-2-propyl)su7talene 11
3.4 Q (0,609rrrnol) in xylene 1
a, and while stirring and heating to 140°C, add 0.0% of concentrated sulfuric acid.
02111j was added and allowed to react for 10 minutes.
薄層クロマトグラフによれば、原料２−（２−ヒドロキ
シ−２−プロピル）ナフタレンは完全に消失したが、２
−インプロペニルナフタレンはほとんどみとめられず、
環化二量体が主生成物であった。According to thin layer chromatography, the raw material 2-(2-hydroxy-2-propyl)naphthalene completely disappeared, but 2
−Impropenylnaphthalene is rarely found;
Cyclized dimer was the main product.
カラムクロマトグラフ（メルクＬｏｂａｒ −Ｂ 、ヘ
キサン／酢酸エチル＝２００／１）によシ環化二量体９
３．５ｆｎｇ（０，２７８ｒｍ＋ｏｌ、収率９１．３ｑ
ｂ）を得た。Cycyclized dimer 9 by column chromatography (Merck Lobar-B, hexane/ethyl acetate = 200/1)
3.5fng (0,278rm+ol, yield 91.3q
b) was obtained.
ＮＭＲ（２５０ＭＨｚ 、 ＣＤＣＬｓ ）δ−値：１
．３８ （３Ｈ，ｓ）
１．４２ （３Ｈ，ｓ）
２．０５ （３Ｈ，ｓ ）
２．３２ （ＩＨ，ｄ）
２．４４ （ＩＨ，ｄ）
７．０ −７．９ （１３Ｈ，ｍ）
ＭＳ （ＤＩ 、 ７０ｅＶ） ｍ／ｅ ：３３６．
３２１
実施例３
２−（２−ヒドロキシ−２−プロピル）ナフタレン１１
２．７ ｍｆ （０，６０５ｒｒｒｎｏｌ）とトルエン
ＩＷＬｔを混合して１１０℃に加熱攪拌し、Ｈ−製ゼオ
ライド（東洋曹達■製、ＴＳＺ−３３０Ｈ８Ａ）１１．
２ｆｎｇを加え、そのまま１０分間反応させた。NMR (250MHz, CDCLs) δ-value: 1
．． 38 (3H, s) 1.42 (3H, s) 2.05 (3H, s) 2.32 (IH, d) 2.44 (IH, d) 7.0 -7.9 (13H, m) MS (DI, 70eV) m/e: 336.
321 Example 3 2-(2-hydroxy-2-propyl)naphthalene 11
2.7 mf (0,605 rrrnol) and toluene IWLt were mixed, heated to 110°C and stirred, and H-zeolide (manufactured by Toyo Soda ■, TSZ-330H8A) 11.
2fng was added and the reaction was continued for 10 minutes.
２．６−ジインプロピルナフタレンを内を標準としてガ
スクロマトグラフによシ分析したところ、２−インプロ
ペニルナフタレン９２．３１Ｆ（０，５４９ｍｎｏｌ、
収率９０．７％）が生成していた。なお薄層クロマドグ
、７７およびガスクロマトグラフにより分析したところ
、原料は完全に消失していた。Gas chromatography analysis using 2.6-diimpropylnaphthalene as a standard revealed that 2-impropenylnaphthalene 92.31F (0,549 mnol,
90.7% yield) was produced. Analysis using a thin-layer chromadog, 77, and a gas chromatograph revealed that the raw material had completely disappeared.
比較例 ３
２−（２−ヒドロヤシ−２−プロピル）ナフタレｙ ９
９．０ ■（０，５３２ｒｒｔｎｏｌ）とトルエン１嵯
を混合して１１０℃に加熱攪拌し、Ｈ−型ゼオライド（
東洋曹達■製、ＴＳＺ−３３０ＨＵ人）ｓ、ｏｑを加え
、そのまま１０分間反応させた。Comparative example 3 2-(2-hydroyac-2-propyl)naphthalene 9
9.0 (0,532 rrtnol) and 1 ton of toluene were mixed and heated to 110°C with stirring to form H-type zeolide (
TSZ-330HU (manufactured by Toyo Soda), oq was added, and the mixture was allowed to react for 10 minutes.
２．６−ジインプロピルナフタレンを内部標準としてガ
スクロマトグラフによシ分析したところ、２−インプロ
ペニルナフタレン４３．２哩（０，２５７ｒｒｔｎｏｌ
、収率４５．１チ）が生成していた。原料は完全に消失
（薄層クロマトグラフ、ガスクロマトグラフ）し、環化
二量体がもうひとつの生成物であった（薄層クロマトグ
ラフ）。なお実施例３のＴＳＺ−３３０Ｈ３Ａ と比較
例３のＴＳＺ−３３０ＨＵＡの相違はイオン交換量の大
小であり、比表面積はほぼ等しいもノテある。ＴＳＺ−
３３０）ＩＳＡはＴＳＺ−３３０ＨＵＡの２倍程度の数
の酸点をもつことが知られている。Gas chromatography analysis using 2.6-diimpropylnaphthalene as an internal standard revealed that 2-impropenylnaphthalene was 43.2 m (0,257 rrtnol).
, yield 45.1 h) was produced. The raw material disappeared completely (thin layer chromatography, gas chromatography) and the cyclized dimer was another product (thin layer chromatography). Note that the difference between TSZ-330H3A of Example 3 and TSZ-330HUA of Comparative Example 3 is the amount of ion exchange, and that the specific surface areas are almost the same. TSZ-
330) ISA is known to have about twice the number of acid sites as TSZ-330HUA.
実施例 ４
ケイ酸アルミニウム（部用理化学■ＩＩ ＊ Ａｔｘｏ
ｓ・３５ｉｎｓ） ２７．６ ’ｆとキシレン２．８−
を１４０℃に加熱攪拌し、メチルフェニルカルビノール
２７６．３１１１９ （２，２６ｍｎｏｌ）を滴下し、
そのまま３０分間反応させた。Example 4 Aluminum silicate (Departmental Physics and Chemistry ■II * Atxo
s・35ins) 27.6'f and xylene 2.8-
was heated to 140°C and stirred, and methylphenyl carbinol 276.31119 (2.26 mnol) was added dropwise.
The reaction was continued for 30 minutes.
ガスクロマトグラフ（内部標準はα−メチルスチレン）
と薄層クロマドグ２７により分析したところ、原料は完
全に消失し、スチレン２１７ ＃（２，０８ｒｒｍｏｌ
ｅ収率９２．１９＆ ）が生成していた。Gas chromatograph (internal standard is α-methylstyrene)
When analyzed using thin-layer chromadog 27, the raw material completely disappeared and styrene 217# (2.08rrmol
A yield of 92.19 & ) was produced.
環化二量体はみとめられなかった。No cyclized dimer was observed.
実施例 ５
２−インプロピルナフタレン１０．０！１（５８，７ｍ
ｍｏｌ）と３，０チ水酸化ナトリウム水溶液１００ｇを
、攪拌器、ガス吹き込み管、還流冷却器をつけた３００
ｄ３つロフラスコ中へ仕込み、内温８５℃に加熱し、毎
時４．０１Ｊツトルの酸素を吹き込みながら毎分５０６
回転で激しく攪拌した。８時間後に反応を停止し、冷却
後フラスコ内容物を取ｐ出し、酢酸エチル１００ｒＩＬ
ｔで３回抽出した。酢酸エチル屑を集め、５−塩酸水、
飽和食塩水で洗浄した後で無水硫酸ナトリウムにより乾
煉し、酢酸エチルを留去して淡黄色のオイル１０．５．
９を得た。Example 5 2-inpropylnaphthalene 10.0!1 (58.7 m
mol) and 100 g of an aqueous solution of sodium 3,0 hydroxide in a 300 m
d into a flask, heated to an internal temperature of 85°C, and heated at 506 m/min while blowing 4.01 J/h of oxygen.
The mixture was vigorously stirred by rotation. After 8 hours, the reaction was stopped, the contents of the flask were taken out after cooling, and 100 rIL of ethyl acetate was added.
Extracted three times at t. Collect ethyl acetate scraps, add 5-hydrochloric acid solution,
After washing with saturated brine, it was dried with anhydrous sodium sulfate and ethyl acetate was distilled off to give a pale yellow oil 10.5.
I got a 9.
ガスクロマトグラフを使用してこのオイルの組成を分析
した（内部標準へキサメチルベンゼン）ところ、２−イ
ンプロピルナフタレン５．２ Ｉｉ（３０，５ｒｒｔｎ
ｏ１．反応率４８．０％）、２−（２−ヒドロキシ−２
−プロピル）ナフタレン４．５１ （２４，２ｎＴ！Ｉ
ｔｐｌ。The composition of this oil was analyzed using a gas chromatograph (internal standard hexamethylbenzene) and found to be 2-inpropylnaphthalene 5.2Ii (30,5rrtn).
o1. reaction rate 48.0%), 2-(2-hydroxy-2
-propyl) naphthalene4.51 (24,2nT!I
tpl.
収″＄４１．１チ１選択率８５．６％）、２−アセトナ
フトン０．３３ Ｊｉ’ （１，９４ｎｔｎｏｌ、収率
３．３％、選択率６．９チ）を含んでいた。It contained 0.33 Ji' (1,94 ntnol, yield 3.3%, selectivity 6.9 Ti).
このオイルの全量を１４０℃に加熱し、ケイ酸アルミニ
ウム（温州理化学■Ｉｔ）３００４を１００■ずつ三回
に分けて注意深く加えた。その後３０分間加熱攪拌を続
けてから、冷却後触媒を戸別し、ガスクロマトグラフで
分析したところ、２−（２−ヒドロキシ−２−プロピル
）す７タレンハ完全に消失し、２−インプロペニルナフ
タレン３．７１１（２２，１ｍｍｏｌ ）を生成してい
た。 なお別の検討によれば、２−インプロピルナフタ
レンと２−インゾロベニルナフタレンの混合物から、ヘ
キサン。The entire amount of this oil was heated to 140°C, and aluminum silicate (Unshu Rikagaku ■It) 3004 was carefully added in three 100cm portions. After that, heating and stirring was continued for 30 minutes, and after cooling, the catalyst was separated from each other and analyzed by gas chromatography. As a result, 2-(2-hydroxy-2-propyl)7talene completely disappeared, and 2-impropenylnaphthalene3. 711 (22.1 mmol) was produced. According to yet another study, hexane was obtained from a mixture of 2-inpropylnaphthalene and 2-inzorobenylnaphthalene.
メタノール等で再結晶することによυ容易に２−インプ
ロペニルナフタレンの結晶を取シ出すことができる。ま
た実測によれば、２−インプロピルナフタレンの５．１
０．２０ｆｌＨ，Ｓ’での沸点はそれぞれ１１８，１２
９，１４３℃であシ、２−インプロペニルナフタレンの
５ 、１０ 、２０ｆｉＨｊ！での沸点はそれぞれ１２
９，１３８，１５４℃であった。したがって２−インプ
ロピルナフタレンと２−インプロペニルナフタレンの分
離は減圧蒸留によっても容易に実施できる。Crystals of 2-impropenylnaphthalene can be easily extracted by recrystallizing with methanol or the like. Also, according to actual measurements, 5.1 of 2-inpropylnaphthalene
The boiling points at 0.20flH and S' are 118 and 12, respectively.
9,143℃, 5, 10, 20fiHj of 2-impropenylnaphthalene! The boiling point at each is 12
The temperature was 9,138,154°C. Therefore, 2-impropylnaphthalene and 2-impropenylnaphthalene can be easily separated by distillation under reduced pressure.
手続補正書
昭和６０年１２月ｑ日
１、事件の表示 昭和６０年特許願第１３５７９０
号２、発明の名称 芳香族側鎖α−位アルコールの
液相脱水法３、補正をする者
事件との関係 特許出願人
名 称 （ｉｉｏ）呉羽化学工業株式会社４、代
理 人 東京都新宿区新宿１丁目１番１４号 山
田ビル５、補正命令の日付 自 発
６、補正により増加する発明の数
８、補正の内容
（１） 明ｍ書中、第６頁第１行目の「できる。」と
あるを、
［できる。Procedural amendment dated December q, 1985 1, case description 1985 patent application No. 135790
No. 2, Title of the invention Liquid-phase dehydration method for alcohols at the α-position of aromatic side chains 3. Relationship to the case of the person making the amendment Patent applicant name (iio) Kureha Chemical Industry Co., Ltd. 4, Agent Shinjuku-ku, Tokyo Yamada Building 5, 1-1-14 Shinjuku, Date of amendment order Voluntary 6, Number of inventions increased by amendment 8, Contents of amendment (1) Memorandum, page 6, line 1: “Can be done.” "It is possible."
さらにまた、溶媒選定時に脱水反応生成物よりも高沸点
の溶媒を選べば、反応生成物を蒸溜によって分離するこ
とができて好適である。たとえばα−メチルスチレンを
製造するときには２−イソプロピルナフタレン、２−イ
ソプロペニルナフタレンを製造するときには２．６−ジ
イツブロビル少フタレン、２，７−ジイツブロビルナフ
タレンあるいは２．６−／２．７−ジイツブロビルナフ
タレン混合物が反応召媒として好適である。」
と補正する。Furthermore, when selecting a solvent, it is preferable to select a solvent with a boiling point higher than that of the dehydration reaction product, since the reaction product can be separated by distillation. For example, when producing α-methylstyrene, 2-isopropylnaphthalene; when producing 2-isopropenylnaphthalene, 2,6-diitubrobyl oligophthalene, 2,7-diitubrobylnaphthalene, or 2.6-/2.7- Diitubrobylnaphthalene mixtures are suitable as reaction media. ” he corrected.
Claims (3)
ナフチル基、Ｒは水素またはメ チル基を示す） で表わされる芳香族側鎖α−位アルコールを固体酸触媒
の存在下で加熱して、式（II） ▲数式、化学式、表等があります▼（II） （式中、ＡｒおよびＲは前記と同義である）で表わされ
る芳香族ビニル化合物へ変換させることを特徴とする芳
香族側鎖α−位アルコールの液相脱水法。(1) Formula (I) ▲Mathematical formulas, chemical formulas, tables, etc.▼(I) (In the formula, Ar is a phenyl group, 1-naphthyl group, or 2-
(Naphthyl group, R represents hydrogen or methyl group) is heated in the presence of a solid acid catalyst to form formula (II) ▲Mathematical formula, chemical formula, table, etc.▼( II) A liquid phase dehydration method for an alcohol at the α-position of an aromatic side chain, characterized by converting it into an aromatic vinyl compound represented by the formula (wherein Ar and R have the same meanings as above).
ことを特徴とする特許請求の範囲第１項に記載の方法。(2) The method according to claim 1, characterized in that aluminum silicate is used as the solid acid catalyst.
を特徴とする特許請求の範囲第１項に記載の方法。(3) The method according to claim 1, characterized in that a synthetic zeolite is used as the solid acid catalyst.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60135790A JPS61293936A (en) | 1985-06-21 | 1985-06-21 | Liquid-phase dehydration of alcohol having aromatic side-chain at alpha-site |
| GB08614739A GB2176801A (en) | 1985-06-21 | 1986-06-17 | Liquid-phase dehydration of aromatic alcohols |
| DE19863620512 DE3620512A1 (en) | 1985-06-21 | 1986-06-19 | METHOD FOR LIQUID PHASE DEHYDRATION OF AN AROMATIC ALCOHOL |
| FR8608962A FR2585016A1 (en) | 1985-06-21 | 1986-06-20 | LIQUID PHASE DEHYDRATION PROCESS OF AROMATIC ALCOHOL |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60135790A JPS61293936A (en) | 1985-06-21 | 1985-06-21 | Liquid-phase dehydration of alcohol having aromatic side-chain at alpha-site |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61293936A true JPS61293936A (en) | 1986-12-24 |
Family
ID=15159894
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60135790A Pending JPS61293936A (en) | 1985-06-21 | 1985-06-21 | Liquid-phase dehydration of alcohol having aromatic side-chain at alpha-site |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JPS61293936A (en) |
| DE (1) | DE3620512A1 (en) |
| FR (1) | FR2585016A1 (en) |
| GB (1) | GB2176801A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011074069A (en) * | 2009-09-02 | 2011-04-14 | Tosoh Finechem Corp | Diethylzinc composition, method for heat-stabilizing diethylzinc, compound to improve heat-stability of diethylzinc |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2178401T3 (en) | 1998-02-18 | 2002-12-16 | Shell Int Research | PROCESS FOR THE PREPARATION OF NARROWS. |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5387320A (en) * | 1977-01-07 | 1978-08-01 | Mitsui Toatsu Chem Inc | Method of recovering useful substances from distillation residue of phenolprepared by cumene process |
| JPS55102521A (en) * | 1979-01-31 | 1980-08-05 | Sumitomo Chem Co Ltd | Improved method for preparation of styrene |
| JPS5655318A (en) * | 1968-08-05 | 1981-05-15 | Halcon International Inc | Manufacture of aralkene |
| JPS5942327A (en) * | 1982-09-03 | 1984-03-08 | Toshiba Corp | Preparation of trifluoromethylstyrene derivative |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB626313A (en) * | 1945-07-13 | 1949-07-13 | Koppers Co Inc | Improvements relating to the manufacture of derivatives of ethyl naphthalene |
| GB668763A (en) * | 1950-01-04 | 1952-03-19 | Dow Chemical Co | Improvements in or relating to the production of nuclear substituted alkenyl aromatic compounds and boric acid esters thereof |
| BE657838A (en) * | 1964-01-07 | 1965-06-30 | ||
| US3403193A (en) * | 1965-06-28 | 1968-09-24 | Halcon International Inc | Process for the co-production of a styrene and a di-olefin |
| GB1583091A (en) * | 1976-05-10 | 1981-01-21 | Exxon Research Engineering Co | Process for the manufacture of styrene |
| DE2736948C3 (en) * | 1977-08-17 | 1981-12-03 | The Dow Chemical Co., 48640 Midland, Mich. | Process for the preparation of a monovinylidene aromatic monomer by dehydration |
| US4255599A (en) * | 1980-03-12 | 1981-03-10 | Gulf Research & Development Company | Preparation of styrene from ethylbenzene |
| JPS6172727A (en) * | 1984-09-17 | 1986-04-14 | Nippon Sheet Glass Co Ltd | Production of styrene |
-
1985
- 1985-06-21 JP JP60135790A patent/JPS61293936A/en active Pending
-
1986
- 1986-06-17 GB GB08614739A patent/GB2176801A/en not_active Withdrawn
- 1986-06-19 DE DE19863620512 patent/DE3620512A1/en not_active Ceased
- 1986-06-20 FR FR8608962A patent/FR2585016A1/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5655318A (en) * | 1968-08-05 | 1981-05-15 | Halcon International Inc | Manufacture of aralkene |
| JPS5387320A (en) * | 1977-01-07 | 1978-08-01 | Mitsui Toatsu Chem Inc | Method of recovering useful substances from distillation residue of phenolprepared by cumene process |
| JPS55102521A (en) * | 1979-01-31 | 1980-08-05 | Sumitomo Chem Co Ltd | Improved method for preparation of styrene |
| JPS5942327A (en) * | 1982-09-03 | 1984-03-08 | Toshiba Corp | Preparation of trifluoromethylstyrene derivative |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011074069A (en) * | 2009-09-02 | 2011-04-14 | Tosoh Finechem Corp | Diethylzinc composition, method for heat-stabilizing diethylzinc, compound to improve heat-stability of diethylzinc |
Also Published As
| Publication number | Publication date |
|---|---|
| FR2585016A1 (en) | 1987-01-23 |
| GB8614739D0 (en) | 1986-07-23 |
| DE3620512A1 (en) | 1987-01-02 |
| GB2176801A (en) | 1987-01-07 |
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