JPH0344337A - Production of indane derivative - Google Patents
Production of indane derivativeInfo
- Publication number
- JPH0344337A JPH0344337A JP17884089A JP17884089A JPH0344337A JP H0344337 A JPH0344337 A JP H0344337A JP 17884089 A JP17884089 A JP 17884089A JP 17884089 A JP17884089 A JP 17884089A JP H0344337 A JPH0344337 A JP H0344337A
- Authority
- JP
- Japan
- Prior art keywords
- alkene
- acid
- formula
- methylstyrene
- dimer
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 125000003392 indanyl group Chemical class C1(CCC2=CC=CC=C12)* 0.000 title claims 3
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003377 acid catalyst Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 3
- 239000000126 substance Substances 0.000 claims 4
- YZCKVEUIGOORGS-UHFFFAOYSA-N Hydrogen atom Chemical compound [H] YZCKVEUIGOORGS-UHFFFAOYSA-N 0.000 claims 1
- 239000000539 dimer Substances 0.000 abstract description 15
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 abstract description 11
- 239000006227 byproduct Substances 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract description 5
- 241000402754 Erythranthe moschata Species 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000000034 method Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000002304 perfume Substances 0.000 abstract description 2
- ZDGGJQMSELMHLK-UHFFFAOYSA-N m-Trifluoromethylhippuric acid Chemical compound OC(=O)CNC(=O)C1=CC=CC(C(F)(F)F)=C1 ZDGGJQMSELMHLK-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 150000002468 indanes Chemical class 0.000 description 9
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N indane Chemical compound C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- BKOOMYPCSUNDGP-UHFFFAOYSA-N 2-methylbut-2-ene Chemical compound CC=C(C)C BKOOMYPCSUNDGP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- MHNNAWXXUZQSNM-UHFFFAOYSA-N 2-methylbut-1-ene Chemical compound CCC(C)=C MHNNAWXXUZQSNM-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- YHQXBTXEYZIYOV-UHFFFAOYSA-N 3-methylbut-1-ene Chemical compound CC(C)C=C YHQXBTXEYZIYOV-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、インダン誘導体の製造方法に関する。[Detailed description of the invention] [Industrial application field] The present invention relates to a method for producing an indane derivative.
特に本発明は、調合香料組成物等に使用される化合物の
合成中間体として有用なポリアルキルインダンの製造方
法に関する。In particular, the present invention relates to a method for producing polyalkylindanes useful as intermediates for the synthesis of compounds used in blended fragrance compositions and the like.
［従来の技術］
米国特許第３３６０５３０号に、一般式（式中、Ｒ５〜
Ｒ”は水素原子または炭素数ｌ〜３のアルキル基を表す
。）
で表されるポリアルキルインダンをムスク系香料の合成
用中間体として使用することが記載されている。[Prior Art] U.S. Pat. No. 3,360,530 describes the general formula (where R5 to
R" represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.) It is described that polyalkylindanes represented by the following formula are used as intermediates for the synthesis of musk fragrances.
従来これらのインダンの製造法としては、特開昭５７−
１５９７２２号公報およびスイス国特許第３５３００３
号明細書に記載されているような酸触媒の存在下スチレ
ンとアルケン単量体を反応させる方法が一般に知られて
いる。Conventionally, the manufacturing method for these indans was disclosed in Japanese Patent Application Laid-open No. 1983-
Publication No. 159722 and Swiss Patent No. 353003
A method of reacting styrene and an alkene monomer in the presence of an acid catalyst is generally known, as described in the above specification.
しかし前述の何れの反応に於いても、所望のインダンの
他にアルケン２重体など副生物も多量に生成し、インダ
ンの収率を低下させるという問題を有する。However, in any of the above-mentioned reactions, there is a problem in that in addition to the desired indane, a large amount of by-products such as alkene dimers are produced, reducing the yield of indane.
［発明が解決しようとする課題］
本発明は、従来に於いて副生物であったアルケン２風体
を有効利用したインダンの製造方法を提供することを目
的とする。[Problems to be Solved by the Invention] An object of the present invention is to provide a method for producing indane that effectively utilizes an alkene 2 gas, which has been a by-product in the past.
［課題を解決するための手段］
上記目的を達成する為に、アルケン２量体を反応系中に
於いてアルケンに分解して反応させれば優れた功を奏す
ることを見出し、本発明を成すに至った。[Means for Solving the Problems] In order to achieve the above object, it has been discovered that an excellent effect can be achieved by decomposing an alkene dimer into an alkene in a reaction system and reacting it, and the present invention has been accomplished. reached.
即ち本発明は、
ｌ９式
で表わされるアルケン２量体またはそれらの混合物とα
−メチルスチレンを酸触媒の存在下反応さ仕ることより
なる、式
（式中、Ｒ１とＲ４は水素原子又はメチル基、Ｒ３とＲ
４は同−又は異なっても良いメチル基若しくはエチル基
を表す。）
で表わされるインダン誘導体の製造方法を提供する。That is, the present invention provides an alkene dimer represented by the formula 19 or a mixture thereof and α
- methylstyrene is reacted in the presence of an acid catalyst with the formula (wherein R1 and R4 are hydrogen atoms or methyl groups, R3 and R
4 represents a methyl group or an ethyl group which may be the same or different. ) provides a method for producing an indane derivative represented by:
本発明で使用するアルケン２重体は、上記式［ｒ］〜［
ＩＩＩ］で表わされる化合物またはそれらの混合物であ
る。これらの化合物は、例えば２−メチルブテン−１，
２−メチルブテン−２及び３−メチルブテン−１等のア
ルケンの２量化によって得られるものでよく、従来のイ
ンダン誘導体の製造に於いて生成する副生物を使用する
ことが出来る。The alkene doublet used in the present invention has the above formulas [r] to [
III] or a mixture thereof. These compounds include, for example, 2-methylbutene-1,
It may be obtained by dimerization of alkenes such as 2-methylbutene-2 and 3-methylbutene-1, and by-products produced in the conventional production of indane derivatives can be used.
上記アルケン２日体は、本発明の反応系中に於いてアル
ケンに分解され、これがα−メチルスチレンと反応して
式［ＩＶ］で表わさｔ。るインダン誘導体を与える。The alkene 2-day compound is decomposed into an alkene in the reaction system of the present invention, and this reacts with α-methylstyrene to form the alkene represented by the formula [IV]. gives an indane derivative.
本発明で使用するα−メチルスチレンは、市販品又は通
常の方法で合成した合成品であってもよい。The α-methylstyrene used in the present invention may be a commercially available product or a synthetic product synthesized by a conventional method.
本発明で使用する酸触媒は、上記アルケン２量体の分解
とα−メチルスチレンとの反応を促進するものである。The acid catalyst used in the present invention promotes the decomposition of the alkene dimer and the reaction with α-methylstyrene.
そのようなものとしては特に硫酸と酢酸の混合酸等が好
ましく、混合酸の混合（重量）比率は、硫酸ｌに対し酢
酸０．°１〜２，０、好ましくは０．５〜１．５、更に
好ましくは０．８〜１．２である。父上記の混合酸触媒
の使用量は広範囲にわたって変えることができるが、α
−メチルスチレン１．０モルあたり混合酸触媒中の硫酸
分が０．２〜５．０モル、好ましくは０．５〜２．０モ
ルとなるように使用する。As such, a mixed acid of sulfuric acid and acetic acid is particularly preferable, and the mixing (weight) ratio of the mixed acid is 1 liter of sulfuric acid to 0.0 liter of acetic acid. °1 to 2.0, preferably 0.5 to 1.5, more preferably 0.8 to 1.2. Although the amount of mixed acid catalyst used above can vary over a wide range, α
- Use so that the sulfuric acid content in the mixed acid catalyst is 0.2 to 5.0 mol, preferably 0.5 to 2.0 mol, per 1.0 mol of methylstyrene.
本発明の反応の化学量論に於いてｌヨ、実質上等モル量
のα−メチルスチレンとアルケン２量体とを反応させる
ことによって行うことが出来るが、α−メチルスチレン
１．０モルあたり例えば５．０モルまでの過剰量でのア
ルケン２量体を使用してもよい。Regarding the stoichiometry of the reaction of the present invention, it can be carried out by reacting substantially equimolar amounts of α-methylstyrene and an alkene dimer, but per 1.0 mole of α-methylstyrene, For example, an excess of up to 5.0 molar alkene dimer may be used.
本発明の反応は、上記酸触媒にα−メチルスチレン反応
剤とアルケン反応剤の混合物を除々に添加撹拌すること
によって行う。反応温度は特に限定されないが、４０〜
１２０℃好ましくは６０〜１００℃である。反応温度が
低い場合、アルケン２量体のアルケンへの分解が起こり
にくく、本発明のインダン誘導体の収率は低下する。叉
、反応温度が高過ぎると所望の化合物［ＩＶｌの収率低
下をきたし好ましくない。又反応時間も特に限定されな
いが１〜５時間、好ましくは１〜２時間である。The reaction of the present invention is carried out by gradually adding and stirring a mixture of an α-methylstyrene reactant and an alkene reactant to the acid catalyst. The reaction temperature is not particularly limited, but 40~
The temperature is 120°C, preferably 60 to 100°C. When the reaction temperature is low, decomposition of the alkene dimer into alkenes is difficult to occur, and the yield of the indane derivative of the present invention decreases. On the other hand, if the reaction temperature is too high, the yield of the desired compound [IVl] will decrease, which is not preferable. The reaction time is also not particularly limited, but is 1 to 5 hours, preferably 1 to 2 hours.
更に上記反応は溶媒、例えば沸点が反応温度より高い炭
化水素又はハロゲン化炭化水素等の存在下行なってもよ
い。Furthermore, the above reaction may be carried out in the presence of a solvent, such as a hydrocarbon or halogenated hydrocarbon having a boiling point higher than the reaction temperature.
上記反応終了後の反応混合物は速やかに酸触媒層および
有機層に分離するので、酸触媒層は容易に分離回収でき
て再使用することができる。有機層は、通常方法で処理
してよい。即ち、希アルカリ、例えば希苛性ソーダ水溶
液等で洗浄した後減圧蒸留等によって、アルケン２量体
を回収し、式［■］で表わされるインダン誘導体を得る
。Since the reaction mixture after the above reaction is quickly separated into an acid catalyst layer and an organic layer, the acid catalyst layer can be easily separated and recovered and reused. The organic layer may be processed in the usual manner. That is, after washing with a dilute alkali, such as a dilute aqueous caustic soda solution, the alkene dimer is recovered by vacuum distillation or the like to obtain an indane derivative represented by the formula [■].
本発明のインダン誘導体、米国特許第３３６０５３０号
に記載のような調合香料組成物として使用されるインク
ロマン化合物の合戊申間体等に有用である。The indane derivatives of the present invention are useful in the synthesis of inchroman compounds used as perfume compositions such as those described in US Pat. No. 3,360,530.
［発明の効果］
本発明により、従来副生物として廃棄されていたアルケ
ン２量体を有効利用することが出来、インダン誘導体を
経済的に製造することが出来る。[Effects of the Invention] According to the present invention, alkene dimers, which were conventionally discarded as by-products, can be effectively utilized, and indane derivatives can be economically produced.
し実施例］
以下本発明を実施例で更に詳細に説明するが、本発明は
これにより限定されるものではない。EXAMPLES] The present invention will be described in more detail below with reference to Examples, but the present invention is not limited thereto.
参考例１
α−メチルスチレン１１２．３９（０，９５ｎｏｌ）と
２−メチルブテン−２７１，１９（０，９５ｎｏｌ）を
、硫酸９３．２９、酢酸９３．２ｇの混酸に、撹拌下２
０〜３０℃にて約３時間を要して添加し、添加終了後も
２０〜３０℃にてさらに１時間撹拌を続けた。その後反
応液は静置することにより速やかに酸触媒層と有機層の
２層に分層した。有機層を５％水酸化ナトリウム水溶演
２００９で洗浄し、次いで減圧下に蒸留して２−メチル
ブテン−２の二量体混合物２７．６９（ｂ、ｐ、４０〜
８５℃／２０ｕＨｇ）、次いでインダン誘導体２０５
、９９（ｂ、ｐ。Reference Example 1 112.39 (0.95 nol) of α-methylstyrene and 271,19 (0.95 nol) of 2-methylbutene-2 were added to a mixed acid of 93.29 g of sulfuric acid and 93.2 g of acetic acid with stirring for 2 hours.
The addition took about 3 hours at 0 to 30°C, and stirring was continued for an additional hour at 20 to 30°C after the addition was completed. Thereafter, the reaction solution was allowed to stand still and was immediately separated into two layers: an acid catalyst layer and an organic layer. The organic layer was washed with 5% aqueous sodium hydroxide solution 2009 and then distilled under reduced pressure to give a dimer mixture of 2-methylbutene-2 27.69 (b, p, 40~
85°C/20uHg), then indane derivative 205
, 99 (b, p.
１００〜ｂ
実施例１
α−メチルスチレン４４．９９（０，３８ｎｏｌ）と参
考例１で得た２−メチルブテン−２の二量体混合物５３
．：ｌ（０，３８ｎｏｌ）を、硫酸３７．３９、酢酸３
７．３９の混酸に、撹拌下６０〜９０℃にて約１時間を
要して添加し、添加終了後も６０〜９０°Ｃにてさらに
２時間撹拌を続けた。その後反応液は静置することによ
り速やかに酸触媒層と有機層の２層に分層した。有機層
を５％水酸化ナトリウム水溶液１００９で洗浄し、次い
で減圧下に蒸留して所望ツインダン誘導体４２．９９（
ｂ、ｐ、 １００〜１３５℃／２０鼎Ｈｇ）を得た。100-b Example 1 Dimer mixture of α-methylstyrene 44.99 (0.38nol) and 2-methylbutene-2 obtained in Reference Example 1 53
．． : l (0.38nol), sulfuric acid 37.39, acetic acid 3
It was added to the mixed acid of 7.39 at 60-90°C while stirring for about 1 hour, and stirring was continued at 60-90°C for an additional 2 hours after the addition was completed. Thereafter, the reaction solution was allowed to stand still and was immediately separated into two layers: an acid catalyst layer and an organic layer. The organic layer was washed with 5% aqueous sodium hydroxide solution 1009 and then distilled under reduced pressure to give the desired Thindan derivative 42.99
b, p, 100-135°C/20 Hg) were obtained.
Claims (1)
化学式、表等があります▼［II］、または▲数式、化学
式、表等があります▼［III］で表わされるアルケン２
量体またはそれらの混合物とα−メチルスチレンを酸触
媒の存在下反応させることよりなる、式 ▲数式、化学式、表等があります▼［IV］ （式中、Ｒ＾１とＲ＾２は水素原子又はメチル基、Ｒ＾
３とＲ＾４は同一又は異なっても良いメチル基若しくは
エチル基を表わす。） で表わされるインダン誘導体の製造方法。 ２、酸触媒として硫酸と酢酸との混合物を用いることを
特徴とする請求項１記載のインダン誘導体の製造方法。[Claims] 1. Formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [I], ▲ Mathematical formula,
There are chemical formulas, tables, etc. ▼ [II], or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [III] Alkene 2
There are formulas ▲ mathematical formulas, chemical formulas, tables, etc. ▼ [IV] (where R^1 and R^2 are hydrogen Atom or methyl group, R^
3 and R^4 represent a methyl group or an ethyl group which may be the same or different. ) A method for producing an indane derivative represented by: 2. The method for producing an indane derivative according to claim 1, characterized in that a mixture of sulfuric acid and acetic acid is used as the acid catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17884089A JPH0344337A (en) | 1989-07-11 | 1989-07-11 | Production of indane derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17884089A JPH0344337A (en) | 1989-07-11 | 1989-07-11 | Production of indane derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0344337A true JPH0344337A (en) | 1991-02-26 |
Family
ID=16055585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17884089A Pending JPH0344337A (en) | 1989-07-11 | 1989-07-11 | Production of indane derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0344337A (en) |
-
1989
- 1989-07-11 JP JP17884089A patent/JPH0344337A/en active Pending
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