JP2988856B2 - Method for producing 1,2-indanediols - Google Patents
Method for producing 1,2-indanediolsInfo
- Publication number
- JP2988856B2 JP2988856B2 JP7179636A JP17963695A JP2988856B2 JP 2988856 B2 JP2988856 B2 JP 2988856B2 JP 7179636 A JP7179636 A JP 7179636A JP 17963695 A JP17963695 A JP 17963695A JP 2988856 B2 JP2988856 B2 JP 2988856B2
- Authority
- JP
- Japan
- Prior art keywords
- indene
- hydrogen peroxide
- formic acid
- reaction
- temperature
- 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 - Fee Related
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- YKXXBEOXRPZVCC-UHFFFAOYSA-N 2,3-dihydro-1h-indene-1,2-diol Chemical class C1=CC=C2C(O)C(O)CC2=C1 YKXXBEOXRPZVCC-UHFFFAOYSA-N 0.000 title claims description 5
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Chemical compound C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 claims description 89
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 79
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 76
- 238000000034 method Methods 0.000 claims description 44
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 235000019253 formic acid Nutrition 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 2
- QUUSLJRWTDZCBF-UHFFFAOYSA-N 2,3-dihydroindene-1,1-diol Chemical class C1=CC=C2C(O)(O)CCC2=C1 QUUSLJRWTDZCBF-UHFFFAOYSA-N 0.000 description 11
- 239000003960 organic solvent Substances 0.000 description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000003317 industrial substance Substances 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- UMJJFEIKYGFCAT-UHFFFAOYSA-N indan-2-one Chemical compound C1=CC=C2CC(=O)CC2=C1 UMJJFEIKYGFCAT-UHFFFAOYSA-N 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- AKRZIHYKFIVGER-UHFFFAOYSA-N C(=O)OC1(CCC2=CC=CC=C12)O Chemical compound C(=O)OC1(CCC2=CC=CC=C12)O AKRZIHYKFIVGER-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- NWJXSVNLQJZDLV-UHFFFAOYSA-N formic acid;hydrogen peroxide Chemical compound OO.OC=O NWJXSVNLQJZDLV-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION
【０００１】[0001]
【産業上の利用分野】本発明は、医薬品及び工業薬品中
間体として有用なインダンジオール類の製造方法に関す
る。本発明において、インダンジオール類とは、１，２
−インダンジオール及びそのギ酸エステル誘導体を言
う。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing indanediols useful as intermediates for pharmaceuticals and industrial chemicals. In the present invention, indanediols refer to 1,2
-Refers to indanediol and its formate derivative.
【０００２】[0002]
【従来の技術】インデンに、ギ酸と過酸化水素を作用さ
せることによって、インダンジオール類が得られる事は
既に知られている。例えば、Ｊ．Ｅ．Ｈｏｒａｎ ａｎ
ｄ Ｒ．Ｗ．Ｓｃｈｉｌｅｓｓｌｅｒ，Ｏｒｇａｎｉｃ
Ｓｙｎｔｈｅｓｅｓ，４１，５３（１９６１）（以
下、文献１と呼ぶ。）においては、インデン１．０モル
に対して、１．３７倍モルの過酸化水素、及び２０．９
９倍モルのギ酸を用意し、先ずギ酸と過酸化水素を混合
しておき、その中にインデンを３５〜４０℃に保ちなが
ら、２ｈｒかけて滴下し、室温にて７ｈｒ反応させ、そ
の後、ギ酸を留去して、インダンジオールギ酸エステル
を得ている。（収率についての記述は無い。）文献１の
方法は、引き続き、これに硫酸を添加した後、水蒸気蒸
留して２−インダノンを得ている。（２−インダノンの
収率：６９〜８１％） 尚、ギ酸−過酸化水素系反応の反応温度について、著者
らは、３５〜４０℃がベストであり、これ以上温度を上
げると、反応が極めて激しくなり、 本反応には向かない
と述べている。2. Description of the Related Art It has been known that indanediols can be obtained by reacting indene with formic acid and hydrogen peroxide. For example, J. E. FIG. Horan an
dR. W. Schillersler, Organic
In Synthesiss, 41 , 53 (1961) (hereinafter referred to as Reference 1), 1.37 moles of hydrogen peroxide and 20.9 moles per 1.0 mole of indene.
A 9-fold molar formic acid was prepared, and formic acid and hydrogen peroxide were first mixed, and indene was added dropwise over 2 hours while maintaining indene at 35 to 40 ° C., and allowed to react at room temperature for 7 hours. Is distilled off to obtain indanediol formate. (The yield is not described.) According to the method of Reference 1, sulfuric acid is added thereto, followed by steam distillation to obtain 2-indanone. (Yield of 2-indanone: 69-81%) Incidentally, regarding the reaction temperature of the formic acid-hydrogen peroxide-based reaction, the authors found that the best is 35-40 ° C., and if the temperature is further raised, the reaction becomes extremely He said he was not good at this reaction.
【０００３】また、Ｗｉｌｌｉａｍ Ｅ．Ｒｏｓｅｎ，
Ｌｏｕｉｓ Ｄｏｒｆｍａｎａｎｄ Ｍｙｒｏｎ Ｐ．
Ｌｉｎｆｉｅｌｄ，Ｊ．Ｏｒｇ．Ｃｈｅｍ．，２９，１
７２３（１９６４） （以下、文献２と呼ぶ。）におい
ては、インデン１．０モルに対して、１．３９８倍モル
の過酸化水素及び１７．５２倍モルのギ酸を用意し、先
ずギ酸と過酸化水素を混合しておき、温度３５〜４０℃
を保ちながら、インデンを２ｈｒかけて滴下し、１２ｈ
ｒ（全反応時間）反応を行っている。この時点でのイン
ダンジオール類の収率は報告されていないが、その後、
反応液を−１５℃に３日間冷却して結晶を析出させ、そ
れをろ別し、収率３５．０％でｃｉｓ−２−インダンジ
オールモノギ酸エステルを得ている。[0003] William E. et al. Rosen,
Louis Dorfmand Myron P.
Linfield, J .; Org. Chem. , 29 , 1
723 (1964) (hereinafter referred to as Reference 2), 1.398 moles of hydrogen peroxide and 17.52 moles of formic acid are prepared with respect to 1.0 mole of indene, and formic acid is first mixed with formic acid. Hydrogen oxide is mixed and the temperature is 35-40 ° C
While maintaining the above, indene was dripped over 2 hours, and 12 hours
r (total reaction time). No yields of indanediols at this point have been reported, but
The reaction solution was cooled to −15 ° C. for 3 days to precipitate crystals, which were separated by filtration to obtain cis-2-indanediol monoformate in a yield of 35.0%.
【０００４】これらの方法は、インデンに対して多量の
ギ酸を使用する方法であるため、原料コスト面での問
題、該廃液の処理に関する問題、および反応の体積効率
が極めて悪い問題等多くの問題を抱えている。さらに、
これらの方法は、一度に過酸化水素の全量を反応系内に
仕込む方法であるため、 工業的立場から見て極めて危険
であると考えねばならない。[0004] Since these methods use a large amount of formic acid with respect to indene, there are many problems such as a problem in raw material cost, a problem in treating the waste liquid, and a problem in that the volumetric efficiency of the reaction is extremely poor. I have further,
Since these methods involve charging the entire amount of hydrogen peroxide into the reaction system at one time, they must be considered extremely dangerous from an industrial standpoint.
【０００５】これらの問題を解決するために、特開昭６
２−１８５０３５号公報（以下、文献３と呼ぶ。）にお
いては、１，２−ジクロロエタン等の非水溶性有機溶剤
を使用する方法が提案されている。その実施例において
は、インデン１１６ｇ（１．０モル）を１，２−ジクロ
ロエタン３００ｇに溶解し、これに９０％ギ酸１５３ｇ
（対インデン３倍モル）と炭酸ナトリウム１５ｇ（対イ
ンデン０．１４モル）を添加し、これに３５％過酸化水
素１３０ｇ（対インデン１．３３８倍モル）を温度３０
〜４０℃で滴下し、滴下後、３５℃で６ｈｒ撹拌してい
る。この時点でのインダンジオールの収率は、報告され
ていないが、この後硫酸を作用させて２−インダノンを
得ており、その収率は、７２％である。In order to solve these problems, Japanese Patent Laid-Open Publication No.
In Japanese Patent Application Laid-Open No. 2-185035 (hereinafter referred to as Document 3), a method using a water-insoluble organic solvent such as 1,2-dichloroethane is proposed. In that example, 116 g (1.0 mol) of indene was dissolved in 300 g of 1,2-dichloroethane, and 153 g of 90% formic acid was added thereto.
(3 times the mole of indene) and 15 g of sodium carbonate (0.14 mole of the indene) were added, and 130 g of 35% hydrogen peroxide (1.338 mole of the indene) was added thereto at a temperature of 30.
The mixture was added dropwise at ４０40 ° C., and after the addition, the mixture was stirred at 35 ° C. for 6 hours. Although the yield of indanediol at this point is not reported, 2-indanone was obtained by subsequently reacting with sulfuric acid, and the yield was 72%.
【０００６】しかしながら、１，２−ジクロロエタン等
の塩素系有機溶剤は、それ自体毒性が強く、また火災発
生時には、ホスゲン等の猛毒性ガスの発生のおそれがあ
る。また、文献３の方法は、インデンに対して２．５９
重量倍も有機溶剤を使用する方法であるため、容積効率
は以前として悪いという問題も抱えている。尚、近年に
おいては地球環境問題から、このような有機塩素系溶剤
の使用は廃止、あるいは制限される趨勢にある。However, chlorinated organic solvents such as 1,2-dichloroethane are highly toxic in themselves, and may cause toxic gas such as phosgene when a fire occurs. In addition, the method of Reference 3 applies 2.59 to indene.
Since the method uses an organic solvent by weight, the volume efficiency is still poor. In recent years, due to global environmental problems, the use of such organic chlorinated solvents has been abolished or restricted.
【０００７】[0007]
【発明が解決しようとする課題】本発明が解決しようと
する課題は、１，２−ジクロロエタン等の有機溶剤を使
用せず、ギ酸の使用を極力減少させた方法で、しかも安
全にインデンを酸化し、収率良くインダンジオール類を
得る方法を見出す事にある。An object of the present invention is to provide a method for oxidizing indene safely without using an organic solvent such as 1,2-dichloroethane and by minimizing the use of formic acid. It is another object of the present invention to find a method for obtaining indanediols with a high yield.
【０００８】[0008]
【課題を解決するための手段】本発明者らは、インデン
に、過酸化水素とギ酸を作用させてインダンジオール類
を得る方法について鋭意研究した結果、インデンと過酸
化水素を同時に反応系内に供給する事が重要である事を
発見し、本発明を完成するに至った。Means for Solving the Problems The present inventors have conducted intensive studies on a method for obtaining indanediols by reacting hydrogen peroxide and formic acid on indene. As a result, the indene and hydrogen peroxide were simultaneously introduced into the reaction system. The discovery that supply was important led to the completion of the present invention.
【０００９】すなわち、本発明は、インデンに、ギ酸と
過酸化水素を作用させて、１，２−インダンジオール類
を製造する方法において、インデンと過酸化水素を同時
に反応系内に供給する事を特徴とする、１，２−インダ
ンジオール類の製造方法である。That is, the present invention provides a method for producing 1,2-indanediols by reacting indene with formic acid and hydrogen peroxide, wherein the indene and hydrogen peroxide are simultaneously supplied into the reaction system. A method for producing 1,2-indanediols, which is a feature.
【００１０】本発明の基本的手段は、反応器中に先ずギ
酸のみを仕込み、そこにインデンと過酸化水素とを同時
に添加する方法であるが、添加スタイル（連続的、間欠
的等）、添加時間、速度等には種々のバリエーションが
あり得る。The basic means of the present invention is a method in which only formic acid is first charged into a reactor, and indene and hydrogen peroxide are simultaneously added thereto, but the addition style (continuous, intermittent, etc.), There can be various variations in time, speed, and the like.
【００１１】過酸化水素とインデンの添加方法におい
て、当該両化合物の添加時間帯は、少なくとも７０％以
上、好ましくは８０％以上重なり合うように添加する必
要がある。過酸化水素とインデンの供給時間をずらす場
合には、過酸化水素を先行させて供給する方が好まし
く、例えば、先ず過酸化水素の添加を開始し、その１５
分間後にインデンの供給を開始し、その後過酸化水素と
インデンを同時間内に添加するか、あるいは過酸化水素
の方を早く添加終了する等の方法が具体的な方法であ
る。In the method for adding hydrogen peroxide and indene, it is necessary to add the two compounds so that at least 70% or more, preferably 80% or more overlaps. When shifting the supply time of hydrogen peroxide and indene, it is preferable to supply hydrogen peroxide in advance. For example, first, the addition of hydrogen peroxide is started, and
A specific method is to start supplying the indene after a minute, and then add the hydrogen peroxide and the indene within the same time, or terminate the addition of the hydrogen peroxide earlier.
【００１２】本発明の対象となるインデンは、一般工業
薬品グレードで良く、純度８０〜１００％のものが一般
的な対象である。The indene which is the object of the present invention may be of general industrial chemical grade, and is generally 80 to 100% pure.
【００１３】本発明で用いる過酸化水素は、一般的な工
業薬品で良く、その濃度は、３０〜７０％の範囲のもの
を使用する事が出来るが、３５％品を使用するのが一般
的である。過酸化水素の使用量は、インデンに対して
１．０〜４．０倍モルの範囲で使用されるが、特には
１．１〜１．６倍モルの範囲で使用するのが好ましい。The hydrogen peroxide used in the present invention may be a general industrial chemical, and its concentration can be in the range of 30-70%, but generally 35% is used. It is. The amount of hydrogen peroxide to be used is in the range of 1.0 to 4.0 moles per mole of indene, but it is particularly preferable to use it in the range of 1.1 to 1.6 moles.
【００１４】本発明で用いるギ酸は、一般的な工業薬品
で良く、その濃度は、７０〜１００％の範囲のものを使
用する事が出来るが、通常８５〜９０％濃度のものを使
用する。ギ酸の使用量は、インデンに対して、１．１〜
５．０倍モルの範囲で使用されるが、特には、１．２〜
３．０倍モルの範囲で使用するのが好ましい。本発明の
最大の特徴は、このような少量のギ酸量においても収率
良く反応を行うことができることにあるが、そのため
に、反応器の容積効率は大幅に高まる。The formic acid used in the present invention may be a general industrial chemical, and its concentration may be in the range of 70 to 100%, but usually 85 to 90%. Formic acid is used in an amount of 1.1 to
It is used in a range of 5.0 moles, and in particular,
It is preferably used in a range of 3.0 moles. The greatest feature of the present invention is that the reaction can be carried out with a high yield even with such a small amount of formic acid, but the volumetric efficiency of the reactor is greatly increased.
【００１５】尚、ギ酸は、下記のいずれかの方法によっ
て添加する。 （ａ）予め全量を反応系内に添加しておく。 （ｂ）全量を過酸化水素、あるいはインデンと同時に反
応系内に添加する。 （ｃ）予め一部を反応系内に添加しておき、残部は、過
酸化水素あるいはインデンと同時に反応系内に添加す
る。The formic acid is added by any of the following methods. (A) The entire amount is previously added to the reaction system. (B) The whole amount is added to the reaction system simultaneously with hydrogen peroxide or indene. (C) A part is added to the reaction system in advance, and the remainder is added to the reaction system simultaneously with hydrogen peroxide or indene.
【００１６】本発明の方法における反応温度は、３０〜
８０℃の範囲が良いが、特には、４０〜７０℃、さらに
は、５０〜６０℃の範囲で行うのが良い。本発明が、従
来方法よりも高い温度（例えば、５０〜８０℃の温度）
で反応を行う事が出来るのは、以下の「作用」の項で詳
述するような理由によるものと推定されるが、このよう
な温度でも反応を行うことができるのは、本発明の特徴
のもう一つであり、工業的には次のような利点がある。The reaction temperature in the method of the present invention is from 30 to
The temperature is preferably in the range of 80 ° C, but particularly preferably in the range of 40 to 70 ° C, more preferably 50 to 60 ° C. The present invention has a higher temperature (for example, a temperature of 50 to 80 ° C.) than the conventional method.
It is presumed that the reaction can be carried out at a temperature as described in the section of "action" below, but it is a feature of the present invention that the reaction can be carried out even at such a temperature. In addition, there are the following industrial advantages.
【００１７】本反応は、反応熱の発生量が大きいため、
この反応を工業的スケールで行う場合には、冷却効率の
良し悪しが重要な問題となる。従来法においては、その
反応の最適温度は、３５〜４０℃であり、反応温度と冷
却水温度との温度差が小さく、冷却効率が悪いのに対し
て、本発明の方法では、従来法よりも高い温度で反応を
行うことが出来るため、冷却水と反応器との温度差を取
ることができ、冷却を効率よく行うことができる。This reaction generates a large amount of heat of reaction,
When this reaction is carried out on an industrial scale, the cooling efficiency is an important issue. In the conventional method, the optimum temperature of the reaction is 35 to 40 ° C., the temperature difference between the reaction temperature and the cooling water temperature is small, and the cooling efficiency is poor. Since the reaction can be performed at a high temperature, the temperature difference between the cooling water and the reactor can be taken, and the cooling can be performed efficiently.
【００１８】[0018]
【作用】本発明の方法に関する反応の機構については不
明な部分が多いが、インデン、過酸化水素、ギ酸の３成
分系の反応機構を次の三通りの手法について推定した。 ［１］インデンとギ酸を混合しておき、そこに過酸化水
素を添加する方法。 ［２］ギ酸と過酸化水素を混合しておき、そこにインデ
ンを添加して行く方法。（文献１及び文献２の方法） ［３］ギ酸のみを仕込んでおき、過酸化水素とインデン
を同時に添加して行く方法。（本発明の方法）The mechanism of the reaction according to the method of the present invention is largely unknown, but the reaction mechanism of the three-component system of indene, hydrogen peroxide and formic acid was estimated by the following three methods. [1] A method in which indene and formic acid are mixed, and hydrogen peroxide is added thereto. [2] A method in which formic acid and hydrogen peroxide are mixed, and indene is added thereto. (Methods of Documents 1 and 2) [3] A method in which only formic acid is charged, and hydrogen peroxide and indene are simultaneously added. (Method of the present invention)
【００１９】［１］の方法は、通常の有機反応のスタイ
ルとして、すぐに思いつく方法であるが、この場合に
は、インデンの重合反応が起こりやすく、収率低下を招
く。この故に、文献１及び文献２においても、この方法
を採用せず、［２］の手法を取っている。The method [1] is a method which can be immediately conceived as a normal organic reaction style. In this case, however, a polymerization reaction of indene is likely to occur, resulting in a decrease in yield. For this reason, also in Documents 1 and 2, this method is not adopted, and the method of [2] is employed.
【００２０】［２］の手法が従来法における方法である
が、この方法において、使用するギ酸量を少なくして行
くと、およそ８倍モル以下から急速に収率の低下が起こ
り、ギ酸量をインデンに対して２倍モルで反応させた場
合には、インダンジオール類の収率は、６０％程度まで
低下してしまう。これは、ギ酸に対して相対的に過酸化
水素濃度が高いと、やはり重合反応が起こりやすくなる
ために起こるものと思われる。The method [2] is a conventional method. In this method, when the amount of formic acid used is reduced, the yield rapidly decreases from about 8 times or less, and the amount of formic acid is reduced. When the reaction is carried out at twice the molar amount to indene, the yield of indanediols is reduced to about 60%. This is considered to occur because the polymerization reaction tends to occur when the concentration of hydrogen peroxide is relatively high with respect to formic acid.
【００２１】［３］の手法においては、ギ酸に対する過
酸化水素の比率が適当な範囲に保たれるため、重合反応
があまり起こらずに、目的とする酸化反応が優先的に起
こるものと考えられる。さらに、反応系において生成す
る過ギ酸は、熱的に不安定であり、［２］の手法におい
て温度を５０℃以上に上げた場合には、反応系で生成し
た過ギ酸が短時間に分解し、反応温度をコントロールす
るのが困難であり危険である。また、収率も低下する。In the method [3], since the ratio of hydrogen peroxide to formic acid is kept in an appropriate range, it is considered that the desired oxidation reaction occurs preferentially without much polymerization reaction. . Furthermore, the formic acid generated in the reaction system is thermally unstable, and when the temperature is raised to 50 ° C. or more in the method of [2], the formic acid generated in the reaction system is decomposed in a short time. It is difficult and dangerous to control the reaction temperature. Also, the yield decreases.
【００２２】本発明の方法においては、系内に存在する
過ギ酸の濃度は必要最低限に保たれるので、温度を５０
℃以上に上げる事が出来、反応温度を上げられる結果、
少量の過ギ酸であっても、高収率でインダンジオール類
が得られるものと思われる。In the method of the present invention, since the concentration of formic acid present in the system is kept to the minimum necessary,
℃ or higher, the reaction temperature can be raised,
It seems that indanediols can be obtained in high yield even with a small amount of formic acid.
【００２３】[0023]
【発明の効果】本発明方法に従えば、従来法に比べて極
めて少量のギ酸量で収率良く反応を行うことができ、ま
た、反応温度も広い範囲で選択することができるため、
特に工業的スケールにおいては冷却効率等も効率良く管
理することができものである。以上のように、本発明が
もたらす工業的意義は大きなものがある。尚、本発明
は、基本的には非水溶性有機溶剤を使用しない方法に関
するものであるが、必要により、適宜、有機溶剤を用い
ても良い。According to the method of the present invention, the reaction can be carried out with a very small amount of formic acid in good yield as compared with the conventional method, and the reaction temperature can be selected in a wide range.
Particularly on an industrial scale, the cooling efficiency and the like can be efficiently managed. As described above, the present invention has great industrial significance. The present invention basically relates to a method not using a water-insoluble organic solvent, but may use an organic solvent as needed.
【００２４】[0024]
【実施例】以下、実施例により、本発明の方法を具体的
に説明する。 実施例１〜６ ５００ｍｌ容量のガラス製反応フラスコに、撹拌羽根、
温度計、コンデンサーを用意する。インデン（純度 ９
３．７％）１６１．２ｇ （１．３０モル）に対して、
所定倍モル数のギ酸 （８８％品、 実施例１の場合に
は、１３５．９ｇ、対インデン２．００倍モル）及び所
定倍モル量の過酸化水素（３５％品、 実施例１の場
合、１７６．８ｇ、１．４倍モル）を用意し、次に示す
いずれかの方法で反応させる。滴下終了後、所定した時
間まで、所定温度を保ちながら反応させ、反応終了後、
液の一部を取ってガスクロマトグラフィーで分析し、イ
ンダンジオール類の収率（インデンベース）を求めた。
得られた結果を、表１に示す。EXAMPLES The method of the present invention will be specifically described below with reference to examples. Examples 1 to 6 In a glass reaction flask having a capacity of 500 ml, stirring blades,
Prepare a thermometer and a condenser. Inden (purity 9
3.7%) for 161.2 g (1.30 mol)
Predetermined molar number of formic acid (88%, 135.9 g in Example 1, 2.00 times mol of indene) and hydrogen peroxide in predetermined molar amount (35%, Example 1) , 176.8 g, 1.4-fold mol) and reacted by any of the following methods. After the completion of the dropwise addition, the reaction is continued for a predetermined time while maintaining the predetermined temperature.
A portion of the liquid was taken and analyzed by gas chromatography to determine the yield of indanediols (based on indene).
Table 1 shows the obtained results.
【００２５】（方法Ａ）：ギ酸のみを先ず仕込んでお
き、インデンと過酸化水素を同時に供給する。 （方法Ｂ）：ギ酸のみを先ず仕込んでおき、過酸化水素
を供給開始し、その１５分後、インデンの供給を開始す
る。供給に要する時間は両者とも同時間内である。（つ
まり、過酸化水素の供給が１５分間先に終了する。） （方法Ｃ）：ギ酸、インデン、過酸化水素の３者を同時
に供給する。ただし、ギ酸の供給は３０ｍｉｎで行い、
インデンと過酸化水素は、５ｈｒで供給する。(Method A): Only formic acid is first charged, and indene and hydrogen peroxide are supplied simultaneously. (Method B): First, only formic acid is charged, and the supply of hydrogen peroxide is started. After 15 minutes, the supply of indene is started. The time required for the supply is within the same time. (That is, the supply of hydrogen peroxide ends 15 minutes earlier.) (Method C): Formic acid, indene, and hydrogen peroxide are simultaneously supplied. However, supply of formic acid is performed in 30 minutes,
Indene and hydrogen peroxide are supplied for 5 hours.
【００２６】比較例１〜４ 実施例と同様な反応装置および薬剤を使用して、次のい
ずれかの方法で行った。供給終了後は、実施例と全く同
様に処理した。得られた結果を、実施例と並列して表１
に示した。 （方法Ｄ）：ギ酸と過酸化水素を混合しておき、そこに
インデンを供給する。 （方法Ｅ）：インデンとギ酸を混合しておき、そこに過
酸化水素を供給する。Comparative Examples 1 to 4 Using the same reaction apparatus and chemicals as in the examples, the reaction was carried out by any of the following methods. After the completion of the supply, the treatment was performed in exactly the same manner as in the example. Table 1 shows the obtained results in parallel with the examples.
It was shown to. (Method D): Formic acid and hydrogen peroxide are mixed, and indene is supplied thereto. (Method E): Indene and formic acid are mixed, and hydrogen peroxide is supplied thereto.
【００２７】[0027]
【表１】 [Table 1]
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 35/32 C07C 29/48 C07C 35/23 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) C07C 35/32 C07C 29/48 C07C 35/23
Claims (4)
させて、１，２−インダンジオール類を製造する方法に
おいて、インデンと過酸化水素を同時に反応系内に供給
する事を特徴とする、１，２−インダンジオール類の製
造方法。1. A method for producing 1,2-indanediols by reacting indene with formic acid and hydrogen peroxide, wherein indene and hydrogen peroxide are simultaneously supplied into a reaction system. , 1,2-Indandiol production method.
る方法において、当該両化合物の添加時間帯の少なくと
も７０％以上が重なり合っている請求項１の製造方法。2. The method according to claim 1, wherein in the method of simultaneously supplying indene and hydrogen peroxide, at least 70% or more of the addition time periods of the two compounds overlap.
１．１〜５．０倍モル、過酸化水素を１．０〜４．０倍
モル使用する請求項１の製造方法。3. The method according to claim 1, wherein formic acid is used in an amount of 1.1 to 5.0 times mol and hydrogen peroxide is used in an amount of 1.0 to 4.0 times mol with respect to 1.0 mol of indene.
求項１の製造方法。4. The method according to claim 1, wherein the reaction according to claim 1 is performed at 30 to 80 ° C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7179636A JP2988856B2 (en) | 1995-06-23 | 1995-06-23 | Method for producing 1,2-indanediols |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7179636A JP2988856B2 (en) | 1995-06-23 | 1995-06-23 | Method for producing 1,2-indanediols |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0912494A JPH0912494A (en) | 1997-01-14 |
| JP2988856B2 true JP2988856B2 (en) | 1999-12-13 |
Family
ID=16069237
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7179636A Expired - Fee Related JP2988856B2 (en) | 1995-06-23 | 1995-06-23 | Method for producing 1,2-indanediols |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2988856B2 (en) |
-
1995
- 1995-06-23 JP JP7179636A patent/JP2988856B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0912494A (en) | 1997-01-14 |
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