JPH0212219B2 - - Google Patents
Info
- Publication number
- JPH0212219B2 JPH0212219B2 JP2853482A JP2853482A JPH0212219B2 JP H0212219 B2 JPH0212219 B2 JP H0212219B2 JP 2853482 A JP2853482 A JP 2853482A JP 2853482 A JP2853482 A JP 2853482A JP H0212219 B2 JPH0212219 B2 JP H0212219B2
- Authority
- JP
- Japan
- Prior art keywords
- alumina
- catalyst
- indoline
- reaction
- water
- 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
Links
- 238000000034 method Methods 0.000 claims description 26
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 150000001639 boron compounds Chemical class 0.000 claims description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 5
- -1 aminophenyl Chemical group 0.000 claims description 4
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 3
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 239000000741 silica gel Substances 0.000 description 11
- 229910002027 silica gel Inorganic materials 0.000 description 11
- 239000002245 particle Substances 0.000 description 7
- 150000003018 phosphorus compounds Chemical class 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 description 2
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は、気相によるインドリンの改良された
製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an improved process for the production of indoline in the gas phase.
インドリンは、インドールの中間体であり、医
薬品等の合成原料や農薬の中間体として有用な化
合物である。２−（σ−アミノフエニル）エタノ
ールを出発物質とするインドリンの製造方法とし
ては、従来下記のような方法が知られている。 Indoline is an intermediate of indole, and is a compound useful as a synthetic raw material for pharmaceuticals and as an intermediate for agricultural chemicals. The following method is conventionally known as a method for producing indoline using 2-(σ-aminophenyl)ethanol as a starting material.
(1) ｐ−トルエンスルホン酸クロリドとピリジン
を用いて環化する方法（G.B.Bennet etal.、J.
Chem.Soc.、287（1941））。(1) Cyclization method using p-toluenesulfonic acid chloride and pyridine (GBBennet et al., J.
Chem.Soc., 287 (1941)).
(2) 気相で処理する方法（ドイツ特許第606027号
明細書）。(2) A method of processing in a gas phase (German Patent No. 606027).
(3) 加熱脱水処理する方法（特開昭52−108969号
公報）。(3) A method of heating and dehydrating (Japanese Patent Application Laid-open No. 108969/1983).
(4) 塩酸塩で環化する方法（特開昭56−86155号
公報）。(4) Method of cyclization with hydrochloride (Japanese Unexamined Patent Publication No. 1986-86155).
しかしながら、これらの従来方法は、副原料費
がかかることや、触媒の量を多く使用しなければ
ならないこと、触媒の寿命が短かい、収率が低
い、得られたインドリンを水と分離しなくてはな
らないなど、インドリンの工業的製法としては好
ましいものではなかつた。 However, these conventional methods require high costs for auxiliary raw materials, the need to use a large amount of catalyst, short catalyst life, low yield, and the indoline obtained cannot be separated from water. This was not a desirable method for industrial production of indoline.
本発明者らは、工業的に有利なインドリンの製
造方法を確立すべく気相における反応を鋭意研究
したところ、ホウ素化合物とシリカゲルを組み合
わせた触媒が高活性で寿命も長いことを見いだ
し、本発明を完成するに至つた。 The present inventors conducted intensive research on reactions in the gas phase in order to establish an industrially advantageous method for producing indoline, and found that a catalyst combining a boron compound and silica gel has high activity and a long life. I was able to complete it.
すなわち本発明は、ホウ素化合物とリン化合物
から選ばれた少なくとも１種をアルミナまたはシ
リカゲルに担持もしくは混合した触媒の存在下、
気相で２−（σ−アミノフエニル）エタノールを
脱水環化することを特徴とするインドリンの製造
方法に関するものである。 That is, in the presence of a catalyst in which at least one selected from boron compounds and phosphorus compounds is supported or mixed on alumina or silica gel,
The present invention relates to a method for producing indoline, which comprises cyclodehydrating 2-(σ-aminophenyl)ethanol in a gas phase.
本発明方法の触媒は、ホウ素化合物とリン化合
物から選ばれる少なくとも１種をアルミナまたは
シリカゲルに担持もしくは混合したものである。
ホウ素化合物としては、ホウ酸および無水ホウ酸
などがあげられ、リン化合物としてはリン酸およ
びメタリン酸などがあげられる。アルミナとシリ
カゲルはとくに限定されないが、アルミナはγ−
アルミナが好ましい。 The catalyst used in the method of the present invention is one in which at least one selected from boron compounds and phosphorus compounds is supported or mixed on alumina or silica gel.
Examples of boron compounds include boric acid and boric anhydride, and examples of phosphorus compounds include phosphoric acid and metaphosphoric acid. Alumina and silica gel are not particularly limited, but alumina is γ-
Alumina is preferred.
本発明方法の触媒は、次のような方法で調製さ
れる。 The catalyst for the method of the present invention is prepared by the following method.
(1) ホウ素化合物とリン化合物から選ばれる少な
くとも１種を水に溶解し、アルミナもしくはシ
リカゲルを懸濁させた水を除去後200〜600℃で
加熱乾燥し、担持させる方法。(1) A method in which at least one selected from a boron compound and a phosphorus compound is dissolved in water, and after removing the water in which alumina or silica gel is suspended, the method is heated and dried at 200 to 600°C to support it.
(2) ホウ素化合物とリン化合物から選ばれる少な
くとも１種をアルミナまたはシリカゲルと混合
する方法。(2) A method of mixing at least one selected from boron compounds and phosphorus compounds with alumina or silica gel.
ホウ素化合物とリン化合物から選ばれる少なく
とも１種を、アルミナ、シリカゲルへ担持あるい
は混合する割合は、アルミナまたはシリカゲルに
対して５ないし40wt％、好ましくは10ないし
30wt％である。本発明方法の反応は、使用する
アルミナおよびシリカゲルの粒度や結晶状態に関
係なく進行するが、これらの粒径の小さい方が反
応速度が早く好ましい。また、本発明方法の反応
は常圧、減圧のいずれの状態でも実施できる。 The proportion of at least one selected from boron compounds and phosphorus compounds supported or mixed on alumina or silica gel is 5 to 40 wt%, preferably 10 to 40 wt%, relative to alumina or silica gel.
It is 30wt%. The reaction in the method of the present invention proceeds regardless of the particle size and crystalline state of the alumina and silica gel used, but smaller particle sizes are preferred because the reaction rate is faster. Further, the reaction in the method of the present invention can be carried out under either normal pressure or reduced pressure.
本発明方法の反応温度は、用いる触媒の種類に
より異なるが、180ないし300℃、好ましくは220
ないし250℃の範囲で適宜選択される。180℃以下
では、反応速度が低いため、反応収率が悪く、
300℃よりも高いときは、副生成物としてのイン
ドールの生成が多くなる。 The reaction temperature in the method of the present invention varies depending on the type of catalyst used, but is preferably 180 to 300°C, preferably 220°C.
to 250°C. Below 180°C, the reaction rate is low and the reaction yield is poor.
When the temperature is higher than 300°C, more indole is produced as a by-product.
本発明方法の一実施態様として、触媒を反応塔
中に充填し、反応塔を180〜300℃に加熱し、予め
触媒の温度と同一もしくはそれに近い温度に予熱
した２−（σ−アミノフエニル）エタノールを気
相で上記反応塔中を流通させ、２−（σ−アミノ
フエニル）エタノールを環化させてインドリンを
得る方法をあげることができる。 In one embodiment of the method of the present invention, a catalyst is packed into a reaction tower, the reaction tower is heated to 180 to 300°C, and 2-(σ-aminophenyl)ethanol is preheated to a temperature that is the same as or close to the temperature of the catalyst. An example of this method is to flow 2-(σ-aminophenyl)ethanol in a gas phase through the reaction tower to cyclize 2-(σ-aminophenyl)ethanol to obtain indoline.
本発明方法は、気相で反応させるため、生成す
るインドリン中に水が含まれないという利点を有
している。本発明方法の触媒は調製が容易であ
り、シリカゲル単独の触媒よりも触媒活性が高
く、寿命も長い。さらに、ホウ酸またはリン酸を
約10wt％担持した触媒は、PHが中性付近であり、
反応容器の保守が容易である。したがつて、本発
明方法は、インドリンの工業的製造方法として有
利である。 The method of the present invention has the advantage that the produced indoline does not contain water because the reaction is carried out in the gas phase. The catalyst of the present method is easy to prepare, has higher catalytic activity, and has a longer life than a silica gel alone catalyst. Furthermore, the catalyst supporting about 10 wt% of boric acid or phosphoric acid has a pH near neutrality,
Maintenance of the reaction vessel is easy. Therefore, the method of the present invention is advantageous as an industrial method for producing indoline.
以下、実施例により本発明方法をより詳しく説
明する。 Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例 １
リン酸3.2ｇを水50mlに溶解し、γ−アルミナ
（商品名「住友ガンマーアルミナ」、住友化学(株)
製、粒径；３mm）16.8ｇを加え、水を除去後、
300℃で２時間乾燥した。この触媒を水に分散し
たときのPHは6.8であつた。得られた触媒約16ml
を直径15mmの耐熱性ガラス管に充填し、220〜230
℃に加熱し、減圧（１〜15mmHg）下で２−（σ−
アミノフエニル）エタノール100ｇを気相で33〜
120ｇ／hrの割合で触媒塔へ送入した。減圧下で
反応させるため副生する水はドライアイストラツ
プにたまり、留出物は無色透明の均一な液体85ｇ
が得られた。標品のインドリン（アルドリツチ社
製）とこの液体を、Nmr、Ir、およびGLCで比
較したところ一致した。収率は98％であり、純度
（GLC）は98％であつた。Example 1 3.2 g of phosphoric acid was dissolved in 50 ml of water, and γ-alumina (trade name "Sumitomo Gamma Alumina", Sumitomo Chemical Co., Ltd.) was dissolved.
After removing water,
It was dried at 300°C for 2 hours. When this catalyst was dispersed in water, the pH was 6.8. Approximately 16ml of the resulting catalyst
Filled in a heat-resistant glass tube with a diameter of 15 mm, 220 to 230
2-(σ-) under reduced pressure (1-15 mmHg).
Aminophenyl) 100g of ethanol in the gas phase from 33~
It was fed into the catalyst column at a rate of 120 g/hr. Because the reaction is carried out under reduced pressure, the by-product water is collected in a dry ice trap, and the distillate is 85g of a colorless and transparent homogeneous liquid.
was gotten. When this liquid was compared with the standard indoline (manufactured by Aldritch) by Nmr, Ir, and GLC, they matched. The yield was 98% and the purity (GLC) was 98%.
実施例 ２
γ−アルミナ（粒径；３mm）を40〜100μの粒
径のアルミナに代え、得られた触媒の使用量を約
５mlとした他は実施例１と同様に操作したとこ
ろ、インドリンが、収率98％、純度98％で得られ
た。Example 2 The same procedure as in Example 1 was carried out except that γ-alumina (particle size: 3 mm) was replaced with alumina with a particle size of 40 to 100 μ and the amount of the obtained catalyst used was about 5 ml. , obtained in 98% yield and 98% purity.
実施例 ３
ホウ酸3.2ｇを水200mlに溶解し、γ−アルミナ
（商品名「住友ガンマーアルミナ」、住友化学(株)、
粒径；３mm）を加え、水を除去後300℃で２時間
乾燥した。この触媒を水に分散したときのPHは
7.4であつた。この触媒約20mlを用いて、塔温を
245〜255℃にして実施例１と同様に反応させたと
ころ、インドリン85ｇ（収率98％、純度98％）が
得られた。Example 3 3.2 g of boric acid was dissolved in 200 ml of water, and γ-alumina (trade name "Sumitomo Gamma Alumina", manufactured by Sumitomo Chemical Co., Ltd.,
After removing water, the mixture was dried at 300°C for 2 hours. When this catalyst is dispersed in water, the pH is
It was 7.4. Using about 20ml of this catalyst, reduce the tower temperature.
When the reaction was carried out in the same manner as in Example 1 at 245 to 255°C, 85 g of indoline (yield 98%, purity 98%) was obtained.
実施例 ４
γ−アルミナ（粒径；３mm）を40〜100μの粒
径のアルミナに代え、得られた触媒の使用量を約
５mlとした他は実施例３と同様に操作したとこ
ろ、インドリン85ｇ（収率98％、純度98％）が得
られた。Example 4 The same procedure as in Example 3 was carried out except that γ-alumina (particle size: 3 mm) was replaced with alumina with a particle size of 40 to 100 μ and the amount of the obtained catalyst used was about 5 ml. As a result, 85 g of indoline was produced. (yield 98%, purity 98%) was obtained.
実施例 ５
無水ホウ酸２ｇを40〜100μの粒径のγ−アル
ミナ８ｇと充分に混合し、塔に充填し実施例１に
準じて反応させたところ、インドリン84ｇ（収率
97％、純度96％）が得られた。Example 5 2 g of boric anhydride was thoroughly mixed with 8 g of γ-alumina having a particle size of 40 to 100μ, and the mixture was packed into a column and reacted in accordance with Example 1. As a result, 84 g of indoline (yield
97%, purity 96%) was obtained.
実施例 ６
リン酸3.2ｇを水50mlに溶解し、シリカゲル
（メツシユ100〜200）16.8ｇを加え、水を除去後、
300℃で２時間乾燥した。この触媒を用い、塔温
を220〜300℃にして、実施例１と同様に反応した
ところ、インドリン84ｇ（収率97％、純度98％）
が得られた。Example 6 3.2 g of phosphoric acid was dissolved in 50 ml of water, 16.8 g of silica gel (mesh 100-200) was added, and after removing the water,
It was dried at 300°C for 2 hours. Using this catalyst, the reaction was carried out in the same manner as in Example 1 at a tower temperature of 220 to 300°C, resulting in 84 g of indoline (yield 97%, purity 98%).
was gotten.
実施例 ７
リン酸をホウ酸に代えた他は実施例４に準じて
反応を行つたところ、インドリン84ｇ（収率97
％、純度98％）が得られた。Example 7 The reaction was carried out according to Example 4 except that phosphoric acid was replaced with boric acid, and 84 g of indoline (yield 97
%, purity 98%) was obtained.
Claims (1)
くとも１種をアルミナまたはシリカゲルに担持も
しくは混合した触媒の存在下、気相で２−（σ−
アミノフエニル）エタノールを脱水環化すること
を特徴とするインドリンの製造方法。 ２ ホウ素化合物がホウ酸または無水ホウ酸であ
る特許請求の範囲第１項記載の方法。 ３ リン化合物がリン酸またはメタリン酸である
特許請求の範囲第１項記載の方法。[Scope of Claims] 1. 2-(σ-
A method for producing indoline, which comprises cyclodehydrating ethanol (aminophenyl). 2. The method according to claim 1, wherein the boron compound is boric acid or boric anhydride. 3. The method according to claim 1, wherein the phosphorus compound is phosphoric acid or metaphosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2853482A JPS58146562A (en) | 1982-02-24 | 1982-02-24 | Preparation of indoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2853482A JPS58146562A (en) | 1982-02-24 | 1982-02-24 | Preparation of indoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58146562A JPS58146562A (en) | 1983-09-01 |
| JPH0212219B2 true JPH0212219B2 (en) | 1990-03-19 |
Family
ID=12251328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2853482A Granted JPS58146562A (en) | 1982-02-24 | 1982-02-24 | Preparation of indoline |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58146562A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021145443A1 (en) | 2020-01-16 | 2021-07-22 | 旭化成株式会社 | Polycarbonate resin, polycarbonate resin composition, optical molded body containing these, and cyclic carbonate |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4833255A (en) * | 1984-05-16 | 1989-05-23 | Ciba-Geigy Corporation | Process for the preparation of indoline |
| US4886887A (en) * | 1985-11-08 | 1989-12-12 | Ciba-Geigy Corporation | Process for the preparation of indolines |
| JPS63211264A (en) * | 1987-02-27 | 1988-09-02 | Nippon Kayaku Co Ltd | Production of indolines |
-
1982
- 1982-02-24 JP JP2853482A patent/JPS58146562A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021145443A1 (en) | 2020-01-16 | 2021-07-22 | 旭化成株式会社 | Polycarbonate resin, polycarbonate resin composition, optical molded body containing these, and cyclic carbonate |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58146562A (en) | 1983-09-01 |
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