JP4515083B2 - Process for the preparation of pyran and hydroxypyran mixtures - Google Patents
Process for the preparation of pyran and hydroxypyran mixtures Download PDFInfo
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Description
本発明は、ピラン及びヒドロキシピラン混合物の効率的な製造法に関する。 The present invention relates to an efficient process for the preparation of pyran and hydroxypyran mixtures.
ピラン及びヒドロキシピラン混合物は、香料の重要な工業原料である。例えば、α−フェニル−ジヒドロピランは、ピラン環の還元的開環により、香料として特に重要な５−フェニル−３−メチルペンタノールへ転化できる。また、テトラヒドロ−４−ヒドロキシ−２−イソブチル−４−メチル−ピランは、それ自身香料として有用である。 Pyran and hydroxypyran mixtures are important industrial raw materials for fragrances. For example, α-phenyl-dihydropyran can be converted to 5-phenyl-3-methylpentanol, which is particularly important as a fragrance, by reductive opening of the pyran ring. Tetrahydro-4-hydroxy-2-isobutyl-4-methyl-pyran is also useful as a perfume itself.
特許文献１には、芳香族アルデヒドとイソプレノールとを酸性脱水剤を用いて反応させて、ピラン誘導体を製造する方法が開示されている。しかしこの方法では、ピラン及びヒドロキシピラン混合物の反応収率が低下する場合があり、また、トルエン等の溶媒を大量に使用すると、生産性が低下する問題がある。 Patent Document 1 discloses a method for producing a pyran derivative by reacting an aromatic aldehyde and isoprenol using an acidic dehydrating agent. However, in this method, the reaction yield of the pyran and hydroxypyran mixture may be reduced, and when a large amount of a solvent such as toluene is used, productivity is lowered.
特許文献２には、アルデヒドとイソプレン等のジエン化合物を、ルイス酸触媒の存在下で反応させて、ピラン誘導体を製造する方法が開示されている。しかし、この方法では、塩化アルミニウム等のハロゲン化ルイス酸触媒を使用しているために、反応中にハロゲン化水素ガスを発生する可能性があり、耐食性のある製造設備が必要となる。また、特許文献２に記載のイソプレン等のジエン化合物は、引火性や重合性が強く、低温で取り扱う設備が必要となる。
本発明の課題は、製造設備の負担を低減し、高生産性で、効率的なピラン及びヒドロキシピラン混合物の製造法を提供することにある。 An object of the present invention is to provide a method for producing a pyran and hydroxypyran mixture efficiently by reducing the burden on a production facility, and having high productivity.
本発明は、一般式（Ｉ）
R1−CHO （Ｉ）
（式中、R1は水素原子、炭素数１〜12のアルキル基又はアルケニル基、アルキル基で置換されていてもよい総炭素数３〜12のシクロアルキル基、あるいはアルキル基又はアルコキシ基で置換されていてもよい総炭素数６〜12のアリール基を示す。）
で表されるアルデヒド（以下アルデヒド（Ｉ）という）と、イソプレノールとを反応させ、一般式(II)
The present invention relates to general formula (I)
R 1 -CHO (I)
(In the formula, R 1 is substituted with a hydrogen atom, an alkyl or alkenyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may be substituted with an alkyl group, or an alkyl group or an alkoxy group. And represents an aryl group having 6 to 12 carbon atoms in total.
Is reacted with isoprenol to produce a compound represented by the general formula (II):
で表されるピラン及び一般式(III) And the general formula (III)
（式中、R1は前記の意味を示す。）
で表されるヒドロキシピランの混合物を製造する方法であって、アルデヒド（Ｉ）／イソプレノールのモル比が１より大きい系で反応を開始する、ピラン及びヒドロキシピラン混合物の製造法を提供する。
(In the formula, R 1 has the above-mentioned meaning.)
A process for producing a mixture of pyran and hydroxypyran, wherein the reaction is initiated in a system in which the molar ratio of aldehyde (I) / isoprenol is greater than 1, is provided.
本発明の製造法によると、香料の重要な工業原料であるピラン及びヒドロキシピラン混合物を、製造設備の負担を低減し、収率良く、また経済的に製造することができる。 According to the production method of the present invention, a pyran and hydroxypyran mixture, which is an important industrial raw material for perfume, can be produced with good yield and economically with reduced burden on production equipment.
本発明に用いられるアルデヒド（Ｉ）において、R1は、水素原子、炭素数１〜12のアルキル基又はアルケニル基、アルキル基で置換されていてもよい総炭素数３〜12のシクロアルキル基、あるいはアルキル基又はアルコキシ基で置換されていてもよい総炭素数６〜12のアリール基を示すが、好ましくは炭素数１〜12のアルキル基、又はアルキル基で置換されていてもよい総炭素数６〜12のアリール基であり、特に炭素数３〜12のアルキル基、又はアルキル基で置換されていてもよい総炭素数６〜12のアリール基が好ましく、フェニル基、ｏ−，ｍ−，ｐ−トリル基、ｎ−ブチル基、イソブチル基が最も好ましい。 In the aldehyde (I) used in the present invention, R 1 is a hydrogen atom, an alkyl group or alkenyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms that may be substituted with an alkyl group, Alternatively, an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group or an alkoxy group is shown, but preferably an alkyl group having 1 to 12 carbon atoms or a total carbon number which may be substituted with an alkyl group An aryl group having 6 to 12 carbon atoms, particularly an alkyl group having 3 to 12 carbon atoms, or an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group, is preferably a phenyl group, o-, m-, A p-tolyl group, n-butyl group and isobutyl group are most preferred.
アルデヒド（Ｉ）の具体例としては、ベンズアルデヒド、ｏ−, ｍ−, ｐ−トルアルデヒド、ナフトアルデヒド、ブチルアルデヒド、バレルアルデヒド、カプロンアルデヒド、ヘプトアルデヒド、カプリルアルデヒド、カプリンアルデヒド、ラウリンアルデヒド等及びそれらの異性体が挙げられ、ベンズアルデヒド、ｏ−, ｍ−, ｐ−トルアルデヒド、バレルアルデヒド、イソバレルアルデヒドが好ましく、ベンズアルデヒドが特に好ましい。 Specific examples of the aldehyde (I) include benzaldehyde, o-, m-, p-tolualdehyde, naphthaldehyde, butyraldehyde, valeraldehyde, capronaldehyde, heptaldehyde, caprylaldehyde, caprinaldehyde, laurinaldehyde and the like. Benzaldehyde, o-, m-, p-tolualdehyde, valeraldehyde, and isovaleraldehyde are preferred, and benzaldehyde is particularly preferred.
本発明に用いられるイソプレノールは、式(IV) The isoprenol used in the present invention has the formula (IV)
で表される化合物であり、イソブチレンとホルムアルデヒドを反応させることにより容易に製造することができる。 It can be easily produced by reacting isobutylene with formaldehyde.
本発明の方法では、目的混合物の収率を向上させる観点から、アルデヒド（Ｉ）／イソプレノールのモル比が１より大きい系で反応を開始することが必要である。アルデヒド（Ｉ）／イソプレノールのモル比が１より大きい系で反応を開始するには、反応器にアルデヒド（Ｉ）の全量を仕込み、そこにイソプレノールを滴下して反応させる方法、アルデヒド（Ｉ）の一部を反応器に仕込み、残りのアルデヒド（Ｉ）とイソプレノールの混合液を滴下して反応させる方法、反応器中に、アルデヒド（Ｉ）／イソプレノールのモル比が１より大きいアルデヒド（Ｉ）とイソプレノールの混合液を滴下して反応させる方法、予め反応器に、アルデヒド（Ｉ）／イソプレノールのモル比が１より大きい混合比率で全量を仕込んだ後に、反応を開始する方法等が挙げられるが、反応器にアルデヒド（Ｉ）の全量を仕込み、そこにイソプレノールを滴下して反応させる方法が好ましい。滴下時間は、副反応物の生成を抑制する観点より、１時間以上が好ましい。一方、生産性を考慮すると１２時間以下が好ましい。従って、滴下時間は１〜１２時間が好ましく、１〜８時間が更に好ましい。 In the method of the present invention, it is necessary to start the reaction in a system in which the molar ratio of aldehyde (I) / isoprenol is greater than 1 from the viewpoint of improving the yield of the target mixture. In order to start the reaction in a system in which the molar ratio of aldehyde (I) / isoprenol is greater than 1, a method in which the whole amount of aldehyde (I) is charged into a reactor and isoprenol is dropped into the reactor and reacted, A method in which a part of the mixture is charged into the reactor and the remaining aldehyde (I) and isoprenol mixed solution is dropped to react, and in the reactor, the aldehyde (I) / isoprenol molar ratio is greater than 1. Examples include a method in which a mixed liquid of isoprenol is dropped and reacted, a method in which the reaction is started after the whole amount is charged in a reactor at a mixing ratio of aldehyde (I) / isoprenol in a molar ratio larger than 1, and the like. A method in which the whole amount of aldehyde (I) is charged in a reactor and isoprenol is added dropwise to react with the reactor is preferable. The dropping time is preferably 1 hour or longer from the viewpoint of suppressing the formation of by-products. On the other hand, in consideration of productivity, 12 hours or less is preferable. Accordingly, the dropping time is preferably 1 to 12 hours, and more preferably 1 to 8 hours.
アルデヒド（Ｉ）とイソプレノールの最終的な仕込みモル比は、アルデヒド（Ｉ）が過剰でも、あるいはイソプレノールが過剰でも良いが、収率を向上させる観点から、アルデヒド（Ｉ）が過剰であることが好ましく、アルデヒド（Ｉ）／イソプレノール（モル比）＝１〜１０が更に好ましく、１〜３．５が特に好ましい。 The final charge molar ratio of aldehyde (I) and isoprenol may be excess of aldehyde (I) or excess of isoprenol, but from the viewpoint of improving the yield, aldehyde (I) is preferably excessive. Aldehyde (I) / isoprenol (molar ratio) = 1 to 10 is more preferable, and 1 to 3.5 is particularly preferable.
また、アルデヒド（Ｉ）とイソプレノールの最終的な仕込みモル比によりピラン及びヒドロキシピランの生成割合を制御することもできる。アルデヒド（Ｉ）／イソプレノール（モル比）が大きくなる程、ヒドロキシピランの割合が高くなり、アルデヒド（Ｉ）／イソプレノール（モル比）が小さくなる程、ピランの割合が高くなる。 Moreover, the production | generation ratio of a pyran and a hydroxypyran can also be controlled with the final charging molar ratio of aldehyde (I) and isoprenol. As the aldehyde (I) / isoprenol (molar ratio) increases, the proportion of hydroxypyran increases. As the aldehyde (I) / isoprenol (molar ratio) decreases, the proportion of pyran increases.
また、ヒドロキシピランを選択的に高収率で得るには、アルデヒド（Ｉ）とイソプレノールの最終的な仕込みモル比が、３以上であることが好ましく、３〜６が更に好ましい。 In order to selectively obtain hydroxypyran in high yield, the final charge molar ratio of aldehyde (I) and isoprenol is preferably 3 or more, and more preferably 3-6.
本発明の反応に用いられる触媒としては、メタンスルホン酸、パラトルエンスルホン酸、硫酸、塩酸等が挙げられ、メタンスルホン酸、パラトルエンスルホン酸が好ましい。触媒の添加量は、アルデヒド（Ｉ）に対し、０．０５〜５モル％が好ましく、０．１〜１モル％が更に好ましい。 Examples of the catalyst used in the reaction of the present invention include methanesulfonic acid, paratoluenesulfonic acid, sulfuric acid, hydrochloric acid and the like, and methanesulfonic acid and paratoluenesulfonic acid are preferable. The addition amount of the catalyst is preferably 0.05 to 5 mol%, more preferably 0.1 to 1 mol%, relative to the aldehyde (I).
本発明の反応は、無溶媒でも、又はトルエン、シクロヘキサン、ジクロロメタン等の溶媒を用いても行うことができるが、生産性を向上させる観点から、無溶媒で行うのが好ましい。 The reaction of the present invention can be carried out without solvent or using a solvent such as toluene, cyclohexane, dichloromethane, etc., but it is preferably carried out without solvent from the viewpoint of improving productivity.
本発明における反応温度は、反応速度を高める観点から、４０℃以上が好ましい。一方、イソプレノールの分解、副反応物の生成を抑制する観点から、１２０℃以下が好ましい。従って、反応温度は４０〜１２０℃が好ましく、４０〜８０℃が更に好ましい。また、反応圧力は特に限定されないが、生成する水を系外に除去することでピランの収率を高めることが可能となる。そのためには、具体的には、１〜１０１．３ｋＰａが好ましく、１〜４０ｋＰａが更に好ましい。 The reaction temperature in the present invention is preferably 40 ° C. or higher from the viewpoint of increasing the reaction rate. On the other hand, 120 degreeC or less is preferable from a viewpoint of suppressing the decomposition | disassembly of isoprenol and the production | generation of a side reaction product. Therefore, the reaction temperature is preferably 40 to 120 ° C, more preferably 40 to 80 ° C. Further, the reaction pressure is not particularly limited, but it is possible to increase the yield of pyran by removing generated water out of the system. For that purpose, 1-101.3 kPa is specifically preferable, and 1-40 kPa is still more preferable.
本発明の反応には、反応原料等に含まれている水等を反応系内から取り除く為に、充填塔や脱水管等の装置を用いても構わない。また、イソプレノールや、アルデヒド（Ｉ）とイソプレノールの混合液の滴下終了後、転化率を更に高めるために必要に応じて熟成を行ってもよい。熟成時の温度や圧力は、原則、滴下時のままでよい。熟成時間は特に限定されないが、長くなると反応物の分解、重合等が進むため、１〜８時間程度が好ましい。 In the reaction of the present invention, an apparatus such as a packed tower or a dehydrating tube may be used in order to remove water contained in the reaction raw material from the reaction system. Moreover, after completion | finish of dripping of the mixed liquid of isoprenol or aldehyde (I), and isoprenol, you may age | cure | ripen as needed in order to further raise a conversion rate. In principle, the temperature and pressure at the time of ripening may be kept at the time of dropping. The aging time is not particularly limited, but is preferably about 1 to 8 hours because decomposition of the reaction product, polymerization, and the like proceed when the time is long.
実施例１
300mlの四つ口フラスコに、ベンズアルデヒド72.3ｇ（0.681mol）、メタンスルホン酸0.33ｇ（0.0034mol）を仕込み、室温にて混合を行った。この混合物を槽内圧力4.0kPaまで減圧し、その後、槽内温度が60℃となるまで昇温を行った。昇温後、攪拌を行いながらイソプレノール64.5ｇ(0.749mol)を３時間かけて滴下し、滴下終了後に４時間の熟成を行った。
Example 1
A 300 ml four-necked flask was charged with 72.3 g (0.681 mol) of benzaldehyde and 0.33 g (0.0034 mol) of methanesulfonic acid and mixed at room temperature. The mixture was depressurized to a tank internal pressure of 4.0 kPa, and then heated up until the tank internal temperature reached 60 ° C. After raising the temperature, 64.5 g (0.749 mol) of isoprenol was added dropwise over 3 hours with stirring, and aging was performed for 4 hours after the completion of the addition.
その結果、熟成終了時に下記式（Ｖ）で表されるジヒドロフェニルピラン44.4ｇ(0.255mol、収率37.4％ 対仕込みベンズアルデヒド)、下記式(VI)で表されるヒドロキシフェニルテトラヒドロピラン52.8ｇ(0.275mol、収率40.4％ 対仕込みベンズアルデヒド)を含む混合液が得られた。 As a result, 44.4 g (0.255 mol, yield 37.4% vs. charged benzaldehyde) of dihydrophenylpyran represented by the following formula (V) at the end of ripening, and 52.8 g (0.275 of hydroxyphenyltetrahydropyran represented by the following formula (VI) mol, yield 40.4% vs. charged benzaldehyde).
ジヒドロフェニルピランの収率とヒドロキシフェニルテトラヒドロピランの収率の合計は、77.8％であった。 The total yield of dihydrophenylpyran and hydroxyphenyltetrahydropyran was 77.8%.
実施例２
500mlの四つ口フラスコに、ベンズアルデヒド260.1ｇ（2.451mol）、メタンスルホン酸1.18ｇ（0.012mol）を仕込み、室温にて混合を行った。この混合物を槽内圧力13.3kPaまで減圧し、その後、槽内温度が60℃となるまで昇温を行った。昇温後、攪拌を行いながらイソプレノール116.1ｇ(1.348mol)を４時間かけて滴下し、滴下終了後に３時間の熟成を行った。
Example 2
A 500 ml four-necked flask was charged with 260.1 g (2.451 mol) of benzaldehyde and 1.18 g (0.012 mol) of methanesulfonic acid and mixed at room temperature. The mixture was depressurized to a tank internal pressure of 13.3 kPa, and then heated up until the tank internal temperature reached 60 ° C. After the temperature was raised, 116.1 g (1.348 mol) of isoprenol was added dropwise over 4 hours while stirring, and aging was performed for 3 hours after completion of the addition.
その結果、熟成終了時にジヒドロフェニルピラン59.6ｇ(0.342mol、収率25.4％ 対仕込みイソプレノール)、ヒドロキシフェニルテトラヒドロピラン167.7ｇ(0.872mol、収率64.7％ 対仕込みイソプレノール)を含む混合液が得られた。ジヒドロフェニルピランの収率とヒドロキシフェニルテトラヒドロピランの収率の合計は、90.1％であった。 As a result, a mixed liquid containing 59.6 g of dihydrophenylpyran (0.342 mol, yield 25.4% to charged isoprenol) and 167.7 g of hydroxyphenyltetrahydropyran (0.872 mol, yield 64.7% to charged isoprenol) was obtained at the end of ripening. . The total yield of dihydrophenylpyran and hydroxyphenyltetrahydropyran was 90.1%.
実施例３
300mlの四つ口フラスコに、ベンズアルデヒド110.0ｇ（1.036mol）、メタンスルホン酸0.50ｇ（0.0052mol）を仕込み、室温にて混合を行った。この混合物を槽内圧力4.0kPaまで減圧し、その後、槽内温度が60℃となるまで昇温を行った。昇温後、攪拌を行いながらイソプレノール26.8ｇ(0.311mol)を３時間かけて滴下し、滴下終了後に４時間の熟成を行った。
Example 3
A 300 ml four-necked flask was charged with 110.0 g (1.036 mol) of benzaldehyde and 0.50 g (0.0052 mol) of methanesulfonic acid and mixed at room temperature. The mixture was depressurized to a tank internal pressure of 4.0 kPa, and then heated up until the tank internal temperature reached 60 ° C. After heating, 26.8 g (0.311 mol) of isoprenol was added dropwise over 3 hours while stirring, and aging was performed for 4 hours after the completion of the addition.
その結果、熟成終了時にジヒドロフェニルピラン8.69ｇ(0.050mol、収率16.1％ 対仕込みイソプレノール)、ヒドロキシフェニルテトラヒドロピラン46.7ｇ(0.243mol、収率78.1％ 対仕込みイソプレノール)を含む混合液が得られた。ジヒドロフェニルピランの収率とヒドロキシフェニルテトラヒドロピランの収率の合計は、94.2％であった。 As a result, a mixed liquid containing 8.69 g of dihydrophenylpyran (0.050 mol, yield 16.1% to charged isoprenol) and 46.7 g of hydroxyphenyltetrahydropyran (0.243 mol, yield 78.1% to charged isoprenol) was obtained at the end of ripening. . The total yield of dihydrophenylpyran and hydroxyphenyltetrahydropyran was 94.2%.
実施例４
300mlの四つ口フラスコに、ベンズアルデヒド95.2ｇ（0.897mol）、パラトルエンスルホン酸0.87ｇ（0.0046mol）を仕込み、室温にて混合を行った。この混合物を槽内圧力1.3kPaまで減圧し、その後、槽内温度が60℃となるまで昇温を行った。昇温後、攪拌を行いながらイソプレノール42.5ｇ(0.493mol)を４時間かけて滴下し、滴下終了後に３時間の熟成を行った。
Example 4
A 300 ml four-necked flask was charged with 95.2 g (0.897 mol) of benzaldehyde and 0.87 g (0.0046 mol) of paratoluenesulfonic acid and mixed at room temperature. The mixture was depressurized to a tank internal pressure of 1.3 kPa, and then heated up until the tank internal temperature reached 60 ° C. After heating, 42.5 g (0.493 mol) of isoprenol was added dropwise over 4 hours while stirring, and aging was performed for 3 hours after the completion of the addition.
その結果、熟成終了時にジヒドロフェニルピラン35.6ｇ(0.204mol、収率41.4％ 対仕込みイソプレノール)、ヒドロキシフェニルテトラヒドロピラン32.1ｇ(0.167mol、収率33.8％ 対仕込みイソプレノール)を含む混合液が得られた。ジヒドロフェニルピランの収率とヒドロキシフェニルテトラヒドロピランの収率の合計は、75.2％であった。 As a result, a liquid mixture containing 35.6 g of dihydrophenylpyran (0.204 mol, yield 41.4% to charged isoprenol) and 32.1 g of hydroxyphenyltetrahydropyran (0.167 mol, yield 33.8% to charged isoprenol) was obtained at the end of ripening. . The total yield of dihydrophenylpyran and hydroxyphenyltetrahydropyran was 75.2%.
実施例５
300mlの四つ口フラスコに、ベンズアルデヒド190.2ｇ（1.792mol）、メタンスルホン酸0.87ｇ（0.0091mol）を仕込み、室温にて混合を行った。この混合物を槽内圧力4.0kPaまで減圧し、その後、槽内温度が60℃となるまで昇温を行った。昇温後、攪拌を行いながらイソプレノール28.6ｇ（0.332mol）を3.6時間かけて滴下し、滴下終了後に3.5時間の熟成を行った。
Example 5
A 300 ml four-necked flask was charged with 190.2 g (1.792 mol) of benzaldehyde and 0.87 g (0.0091 mol) of methanesulfonic acid and mixed at room temperature. The mixture was depressurized to a tank internal pressure of 4.0 kPa, and then heated up until the tank internal temperature reached 60 ° C. After heating, 28.6 g (0.332 mol) of isoprenol was added dropwise over 3.6 hours with stirring, and aging was performed for 3.5 hours after the completion of the addition.
その結果、熟成終了時にジヒドロフェニルピラン7.3ｇ（0.042mol、収率12.7％ 対仕込みイソプレノール）、ヒドロキシフェニルテトラヒドロピラン47.9ｇ（0.249mol、収率75.0％対仕込みイソプレノール）を含む混合液が得られた。ジヒドロフェニルピランの収率とヒドロキシフェニルテトラヒドロピランの収率の合計は、87.7％であった。 As a result, a liquid mixture containing 7.3 g of dihydrophenylpyran (0.042 mol, yield 12.7% to charged isoprenol) and 47.9 g of hydroxyphenyltetrahydropyran (0.249 mol, yield 75.0% to charged isoprenol) was obtained at the end of ripening. . The total yield of dihydrophenylpyran and hydroxyphenyltetrahydropyran was 87.7%.
実施例６
200mlの四つ口フラスコに、イソバレルアルデヒド89.44ｇ（1.038mol）、メタンスルホン酸0.51ｇ（0.0053mol）を仕込み、室温にて混合を行った。この混合物を常圧で、槽内温度が60℃となるまで昇温を行った。昇温後、攪拌を行いながらイソプレノール26.81ｇ（0.311mol）を３時間かけて滴下し、滴下終了後に３時間の熟成を行った。
Example 6
A 200 ml four-necked flask was charged with 89.44 g (1.038 mol) of isovaleraldehyde and 0.51 g (0.0053 mol) of methanesulfonic acid and mixed at room temperature. The mixture was heated at normal pressure until the temperature in the tank reached 60 ° C. After heating, 26.81 g (0.311 mol) of isoprenol was added dropwise over 3 hours while stirring, and aging was performed for 3 hours after the completion of the addition.
その結果、熟成終了時に、下記式(VII)で表されるジヒドロイソブチルピラン15.30ｇ（0.099mol、収率31.9％ 対仕込みイソプレノール）、下記式(VIII)で表されるヒドロキシイソブチルテトラヒドロピラン30.81ｇ（0.179mol、収率57.5％対仕込みイソプレノール）を含む混合液が得られた。ジヒドロイソブチルピランの収率とヒドロキシイソブチルテトラヒドロピランの収率の合計は、89.4％であった。 As a result, at the end of the ripening, 15.30 g of dihydroisobutylpyran represented by the following formula (VII) (0.099 mol, yield 31.9% vs. charged isoprenol), 30.81 g of hydroxyisobutyltetrahydropyran represented by the following formula (VIII) ( A mixed solution containing 0.179 mol, yield 57.5% vs. charged isoprenol was obtained. The total yield of dihydroisobutylpyran and hydroxyisobutyltetrahydropyran was 89.4%.
比較例１
300mlの四つ口フラスコにイソプレノール64.5ｇ（0.749mol）を仕込み、槽内圧力9.3kPaまで減圧し、槽内温度が60℃となるまで昇温、混合を行った。昇温後に、攪拌を行いながら予め混合しておいたベンズアルデヒド72.3ｇ（0.681mol）とメタンスルホン酸0.32ｇ（0.0033mol）から成る混合物を３時間かけて滴下し、滴下終了後に４時間の熟成を行った。
Comparative Example 1
In a 300 ml four-necked flask, 64.5 g (0.749 mol) of isoprenol was charged, the pressure in the tank was reduced to 9.3 kPa, and the temperature in the tank was raised to 60 ° C. and mixed. After raising the temperature, a mixture of 72.3 g (0.681 mol) of benzaldehyde and 0.32 g (0.0033 mol) of benzsulfonic acid mixed in advance with stirring was added dropwise over 3 hours. After completion of the addition, the mixture was aged for 4 hours. went.
その結果、熟成終了時にジヒドロフェニルピラン34.3ｇ(0.197mol、収率28.9％ 対仕込みベンズアルデヒド)、ヒドロキシフェニルテトラヒドロピラン20.6ｇ(0.107mol、収率15.7％ 対仕込みベンズアルデヒド)を含む混合液が得られた。ジヒドロフェニルピランの収率とヒドロキシフェニルテトラヒドロピランの収率の合計は、44.6％であった。 As a result, a liquid mixture containing 34.3 g of dihydrophenylpyran (0.197 mol, yield 28.9% with respect to benzaldehyde) and 20.6 g of hydroxyphenyltetrahydropyran (0.107 mol, yield 15.7% with respect to benzaldehyde) was obtained at the end of ripening. . The total yield of dihydrophenylpyran and hydroxyphenyltetrahydropyran was 44.6%.
Claims (3)
R1−CHO （Ｉ）
（式中、R1はアルキル基で置換されていてもよい総炭素数６〜12のアリール基を示す。）
で表されるアルデヒド（以下アルデヒド（Ｉ）という）と、イソプレノールとを反応させ、一般式(II)
で表されるヒドロキシピランの混合物を製造する方法であって、メタンスルホン酸及びパラトルエンスルホン酸から選ばれる少なくとも１種の触媒の存在下、アルデヒド（Ｉ）／イソプレノールのモル比が１より大きい系で反応を開始し、アルデヒド（Ｉ）とイソプレノールの最終的な仕込みモル比が、アルデヒド（Ｉ）／イソプレノール＝３〜３．５であり、反応圧力が４．０〜１３．３ｋＰａである、ピラン及びヒドロキシピラン混合物の製造法。 Formula (I)
R 1 -CHO (I)
(In the formula, R 1 represents an aryl group having 6 to 12 carbon atoms which may be substituted with an alkyl group.)
Is reacted with isoprenol to produce a compound represented by the general formula (II):
In which a molar ratio of aldehyde (I) / isoprenol is greater than 1 in the presence of at least one catalyst selected from methanesulfonic acid and paratoluenesulfonic acid. The final charge molar ratio of aldehyde (I) and isoprenol is aldehyde (I) / isoprenol = 3 to 3.5, and the reaction pressure is 4.0 to 13.3 kPa. And a process for producing a hydroxypyran mixture.
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