JP5178179B2 - 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-Hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol Method - Google Patents
4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-Hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol Method Download PDFInfo
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本発明は、４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールの製造方法に関するものである。 The present invention relates to 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl. ] It relates to a process for producing resorcinol.
４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールは、例えば、レゾルシンおよびシクロヘキサノンをメタノールあるいは酢酸エチル等の溶媒の存在下で反応させ製造されることは公知である（特許文献１〜３）。 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol is For example, it is known that resorcin and cyclohexanone are produced in the presence of a solvent such as methanol or ethyl acetate (Patent Documents 1 to 3).
反応後に、得られた４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールは、使用された溶媒、例えば、メタノールあるいは酢酸エチルとの付加物として分離する。この付加物からメタノールあるいは酢酸エチルといった付加物の成分類を分離する方法としては、通常、減圧下に、メタノールあるいは酢酸エチル等の成分類を分離し留去させる方法が用いられる。しかし、この方法では減圧下、長時間を要すること、メタノールあるいは酢酸エチル等の成分類の分離が不十分で包接率が３０％以上となる場合があり、目的物中の成分類を一定値以下に保てない等の欠点を有している。メタノールとの１：１付加物の場合、包接率が２４％以下であればメタノール含有量が２％以下となって、工業的な用途において求められているレベルに達することができるため、より工業的に有利に包接率が２４％以下の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールを得られる製造方法の開発が望まれていた。 After the reaction, the obtained 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a -Yl] resorcinol is separated as an adduct with the solvent used, for example methanol or ethyl acetate. As a method for separating components of the adduct such as methanol or ethyl acetate from this adduct, a method of separating and distilling off components such as methanol or ethyl acetate under reduced pressure is usually used. However, in this method, it takes a long time under reduced pressure, the separation of components such as methanol or ethyl acetate is insufficient, and the inclusion rate may be 30% or more. It has drawbacks such as the following cannot be maintained. In the case of a 1: 1 adduct with methanol, if the inclusion rate is 24% or less, the methanol content becomes 2% or less, and can reach the level required in industrial applications. An industrially advantageous 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9 ′) having an inclusion rate of 24% or less Development of a production method capable of obtaining -xanthene) -4'a-yl] resorcinol has been desired.
本発明の目的は、工業的に極めて有利に包接率が２４％以下の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールを得ることができる製造方法を提供することである。 The object of the present invention is to make 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro having an inclusion rate of 24% or less very advantageously industrially. It is to provide a production method capable of obtaining (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol.
本発明者等はこれらの欠点を解決するために鋭意検討した結果、レゾルシンおよびシクロヘキサノンから得られる４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールの製造方法において、４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールとメタノールとの付加物をメタノール溶媒中に溶解した溶液を水中に滴下する工程を含むことにより、メタノールの除去が容易になり工業的に有利に包接率が２４％以下の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールが得られることを見いだし、本発明を完成させた。 As a result of intensive studies to solve these drawbacks, the present inventors have found that 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6 obtained from resorcin and cyclohexanone. In the process for producing '-hydroxyspiro (cyclohexane-1,9'-xanthene) -4'a-yl] resorcinol, 4- [1', 2 ', 3', 4 ', 4'a, 9'a- By adding a solution of hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol and methanol dissolved in methanol solvent dropwise into water, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro having an inclusion rate of 24% or less, which facilitates removal of methanol and is industrially advantageous. (Sh Rohekisan 1,9'-xanthene) -4'A- yl] found that resorcinol is obtained, thereby completing the present invention.
本発明の製造方法により、包接率が２４％以下の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールを工業的に有利に得ることができる。 By the production method of the present invention, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1, 9′-xanthene) -4′a-yl] resorcinol can be advantageously obtained industrially.
以下、本発明について詳細に説明する。
本発明はレゾルシンおよびシクロヘキサノンから得られる４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールの製造方法に関するものであり、該方法は４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールとメタノールとの付加物をメタノール溶媒中に溶解した溶液を水中に滴下する工程を含むことを特徴としている。
Hereinafter, the present invention will be described in detail.
The present invention relates to 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene)-derived from resorcin and cyclohexanone 4'a-yl] resorcinol, which relates to 4- [1 ', 2', 3 ', 4', 4'a, 9'a-hexahydro-6'-hydroxyspiro (cyclohexane) -1,9'-xanthene) -4'a-yl] resorcinol and methanol dissolved in a methanol solvent, the method is characterized in that it comprises a step of dripping into water.
本発明において４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールとメタノールとの付加物をメタノール溶媒中に溶解した溶液を水中に滴下、晶析し、ろ過することにより結晶を得る。得られた結晶物はメタノールの付加物であり、４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール１モル当たり０.７〜２.１５モルのメタノールを含有している。付加物は好適には４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールとメタノールが約１：１付加物の形状である。 In the present invention, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] A solution in which an adduct of resorcinol and methanol is dissolved in a methanol solvent is dropped into water, crystallized, and filtered to obtain crystals. The obtained crystalline substance is an adduct of methanol, and 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9 ′ -Xanthene) -4'a-yl] resorcinol contains 0.7-2.15 mol of methanol. The adduct is preferably 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a -Yl] resorcinol and methanol are in the form of about 1: 1 adduct.
ろ過により取り出した付加物は、通常、２０〜１００μｍの結晶形をしている。これに対し、当該付加物をメタノールに溶解した溶液に水を滴下し、晶析することにより得られる結晶物の結晶形は、通常、２００〜３００μｍの結晶形をしている。しかし、これらの結晶の乾燥に要する時間は、本発明の製造法により得た当該化合物の乾燥時間の方が大幅に短く、メタノール溶媒中に水を滴下し、晶析し、取り出した当該化合物のおよそ３分の１時間と短時間で乾燥する事が出来る。 The adduct taken out by filtration usually has a crystal form of 20 to 100 μm. On the other hand, the crystal form of the crystal obtained by dropping water into a solution obtained by dissolving the adduct in methanol and crystallizing is usually a crystal form of 200 to 300 μm. However, the time required for drying these crystals is much shorter than the drying time of the compound obtained by the production method of the present invention. Water was dropped into a methanol solvent, crystallized, and the extracted compound was removed. It can be dried in as short as 1/3 hour.
本発明において、付加物の成分類の分離は、通常、付加物を取り出した後、減圧下、４０〜１００℃で加熱し、乾燥することによりメタノールが水とともに除去される。付加物の乾燥時の加熱温度は通常４０〜１００℃、好適には５０〜９０℃、さらに好適には、６０〜９０℃である。加熱温度が４０℃未満であれば、乾燥に要する時間が長くなる傾向がある。１００℃より高い温度で行った場合は熱劣化により不純物が増加するので好ましくない。 In the present invention, the components of the adduct are usually separated by removing the adduct, heating at 40 to 100 ° C. under reduced pressure, and drying to remove methanol together with water. The heating temperature during drying of the adduct is usually 40 to 100 ° C, preferably 50 to 90 ° C, more preferably 60 to 90 ° C. If heating temperature is less than 40 degreeC, there exists a tendency for the time required for drying to become long. When the temperature is higher than 100 ° C., impurities increase due to thermal deterioration, which is not preferable.
本発明の晶析工程で用いられる水の量は、好適には４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール１モルに対し、１５〜６００モルで実施され、より好適には３０〜１００モル、さらに好適には４０〜７０モルである。この範囲であれば、乾燥効率が特段に向上する。水が１５モル未満の場合収率が著しく低下する傾向がある。６００モルを超えると容積効率が悪くなり工業的に不利になる。 The amount of water used in the crystallization step of the present invention is preferably 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane- 1,9′-xanthene) -4′a-yl] resorcinol is carried out at 15 to 600 mol, more preferably 30 to 100 mol, and even more preferably 40 to 70 mol. If it is this range, drying efficiency will improve especially. When the amount of water is less than 15 moles, the yield tends to decrease remarkably. If it exceeds 600 moles, the volumetric efficiency becomes worse and industrially disadvantageous.
本発明において、乾燥は好ましくは水の存在下に減圧下で実施される。目的物を乾燥するために使用される乾燥機としては、通常、一般的な乾燥器、例えば、板乾燥器、撹拌乾燥器、パドル乾燥器などが使用される。 In the present invention, drying is preferably performed under reduced pressure in the presence of water. As the dryer used for drying the target product, a general dryer such as a plate dryer, a stirring dryer, a paddle dryer, or the like is usually used.
本発明によれば、乾燥時間が大幅に短縮され、包接率が２４％以下の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノールが容易に得られ、工業的に極めて有利な方法となる。 According to the present invention, 4- [1 ', 2', 3 ', 4', 4'a, 9'a-hexahydro-6'- having a drying time significantly reduced and an inclusion rate of 24% or less Hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol can be easily obtained, which is an industrially extremely advantageous method.
（実施例）
以下、実施例を挙げさらに本発明を説明するが、本発明はこれらに限定されるものではない。
なお、本明細書中、包接率は、以下の式で求められる。
包接率（％）＝メタノールのモル量÷（４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール）のモル量×１００
(Example)
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further, this invention is not limited to these.
In addition, in this specification, the inclusion rate is calculated | required with the following formula | equation.
Inclusion rate (%) = molar amount of methanol / (4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9 ′ -Xanthene) -4'a-yl] resorcinol) molar quantity x 100
メタノール包接率１００％の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール（水分：１０重量％、包接化合物：９０重量％）４５．８ｇを、温度計、攪拌装置、冷却管、滴下漏斗を付けた０．５リットル４つ口丸底フラスコに仕込み、メタノール１２３．０ｇを加えて６０℃に昇温し溶解した。溶解液を８０ｇのイオン交換水中に滴下して晶析、濾過後、結晶４５．０ｇを得た。得られた結晶の水分は、１１．６重量％で、包接率は９０％であった。
この結晶を０．５リットルフラスコに仕込み、イオン交換水４．７ｇを加え、水分２０重量％に調整。７５℃で４０ｋＰａに減圧して、４時間乾燥し、さらに、２ｋＰａに減圧し、同温度で４時間乾燥した。乾燥後の得量は３７．２ｇであった。この乾燥ケーキ（４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール）の水分は０．３重量％で、この時のメタノールの包接率は３．５％であった。
4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4 ′ having a methanol inclusion rate of 100% a-yl] resorcinol (moisture: 10% by weight, clathrate compound: 90% by weight) was placed in a 0.5 liter four-necked round bottom flask equipped with a thermometer, stirrer, condenser, and dropping funnel. First, 123.0 g of methanol was added, and the mixture was heated to 60 ° C. and dissolved. The solution was dropped into 80 g of ion-exchanged water to crystallize and filter to obtain 45.0 g of crystals. The water content of the obtained crystal was 11.6% by weight, and the inclusion rate was 90%.
The crystals were placed in a 0.5 liter flask, and 4.7 g of ion exchange water was added to adjust the water content to 20% by weight. The pressure was reduced to 40 kPa at 75 ° C., followed by drying for 4 hours. Further, the pressure was reduced to 2 kPa and drying was performed at the same temperature for 4 hours. The amount obtained after drying was 37.2 g. This dried cake (4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl The water content of resorcinol) was 0.3% by weight, and the inclusion ratio of methanol at this time was 3.5%.
（比較例１）
メタノール包接率１００％の４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール（水分：１０重量％、包接化合物：９０重量％）４５．８ｇを、温度計、攪拌装置、冷却管、滴下漏斗を付けた０．５リットル４つ口丸底フラスコに仕込み、メタノール１２３．０ｇを加えて６０℃に昇温し、溶解した。溶解液に８０ｇのイオン交換水を滴下して晶析、濾過後、結晶４５．０ｇを得た。得られた結晶の水分は１１．６重量％で、包接率は９０％であった。
この結晶を０．５ リットルフラスコに仕込み、イオン交換水４．７gを加え、水分２０％に調整。７５℃で４０ｋＰａに減圧して、４時間乾燥し、さらに、２ｋＰａに減圧し、同温度で４時間乾燥した。乾燥後の得量は３８．３ｇであった。この乾燥ケーキ（４−［１’，２’，３’，４’，４’ａ，９’ａ−ヘキサヒドロ−６’−ヒドロキシスピロ（シクロヘキサン−１，９’−キサンテン）−４’ａ−イル］レゾルシノール）の水分は０．３％で、この時のメタノールの包接率は４０％であった。
(Comparative Example 1)
4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4 ′ having a methanol inclusion rate of 100% a-yl] resorcinol (moisture: 10% by weight, clathrate compound: 90% by weight) was placed in a 0.5 liter four-necked round bottom flask equipped with a thermometer, stirrer, condenser, and dropping funnel. Charge, 123.0 g of methanol was added, and the temperature was raised to 60 ° C. to dissolve. 80 g of ion-exchanged water was added dropwise to the solution to crystallize and filter to obtain 45.0 g of crystals. The water content of the obtained crystal was 11.6% by weight, and the inclusion rate was 90%.
The crystals were placed in a 0.5 liter flask, and 4.7 g of ion exchange water was added to adjust the moisture to 20%. The pressure was reduced to 40 kPa at 75 ° C., followed by drying for 4 hours. Further, the pressure was reduced to 2 kPa and drying was performed at the same temperature for 4 hours. The yield after drying was 38.3 g. This dried cake (4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl The water content of resorcinol was 0.3%, and the methanol inclusion rate at this time was 40%.
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| EP1028119B1 (en) * | 1992-06-23 | 2004-05-26 | The Dow Chemical Company | Process for producing tetrakisfluorophenylborate |
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| JPH08169937A (en) * | 1994-12-19 | 1996-07-02 | Sumitomo Chem Co Ltd | Epoxy resin composition and copper-clad laminate |
| WO2002032891A1 (en) * | 2000-10-18 | 2002-04-25 | Ribotargets Limited | Flavan compounds, their preparation and their use in therapy |
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| JP2004300133A (en) * | 2002-11-19 | 2004-10-28 | Takeda Chem Ind Ltd | Amine derivative |
| MX2008008119A (en) * | 2005-12-21 | 2008-09-24 | Tapestry Pharmaceuticals Inc | Processes for taxane derivatives and intermediates useful therein. |
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