JP5118467B2 - 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からメタノールあるいは酢酸エチル等の溶媒の存在下で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 to be produced from resorcin and cyclohexanone 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、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. 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 provide an industrially advantageous 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro with an inclusion rate of 24% or less ( 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の付加物中の水分を１５〜２５重量％に調整した後、段階的に減圧乾燥処理を行うことにより、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- Hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol and methanol adduct was adjusted to 15 to 25% by weight and then stepwise dried under reduced pressure. By carrying out the process, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane) having an inclusion rate of 24% or less is industrially advantageous. -1,9 ' Found xanthene) -4'A- yl] that resorcinol is obtained, thereby completing the present invention.
本発明の製造方法により、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ることができる。 According to the production method of the present invention, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro having an inclusion rate of 24% or less is industrially advantageous. (Cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol can be obtained.
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の付加物中の水分を１５〜２５重量％に調整した後、段階的に減圧乾燥処理を行い、当該化合物を得る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 adduct was adjusted to 15-25 wt%, and then subjected to reduced-pressure drying treatment stepwise to obtain the compound. It is a feature.
本発明において、公知の方法で得た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］レゾルシノールとメタノールの付加物は、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１：１〜０．６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) obtained by a known method -4'a-yl] resorcinol and methanol 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: 1-0.6 adduct.
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の付加物は、通常の製造方法から得られるものが用いられるが、溶液中でプラスのゼータ電位を示す機械的ろ過と吸着ろ過とを組み合わせたろ材で処理した付加物を用いることが好ましい。この処理は、メタノール、酢酸エチル等に、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の付加物を溶解させ実施される。この処理により得られた付加物は処理をしない付加物に比し、金属含有量等の品質が優れる傾向がある。このため、この付加物を用い、段階的に減圧乾燥処理を行って得られる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］レゾルシノールは優れた品質のものが得られる傾向がある。 In the present invention, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl ] The adduct of resorcinol and methanol is obtained from a normal production method, but the adduct treated with a filter medium that combines mechanical filtration showing positive zeta potential and adsorption filtration in solution should be used. Is preferred. This treatment is carried out by adding 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) to methanol, ethyl acetate or the like. ) -4′a-yl] resorcinol and methanol adduct are dissolved. The adduct obtained by this treatment tends to be superior in quality such as metal content, compared to the adduct not treated. Therefore, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro obtained by using this adduct and subjecting it to reduced-pressure drying stepwise (Cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol tends to be of excellent quality.
本発明において、必要に応じて用いられる溶液中でプラスのゼータ電位を示す機械的ろ過と吸着ろ過とを組み合わせたろ材としては、ゼータプラスフィルター（登録商標）等が挙げられる。 In the present invention, a zeta plus filter (registered trademark) or the like may be mentioned as a filter medium that combines mechanical filtration exhibiting a positive zeta potential in a solution used as necessary and adsorption filtration.
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の付加物中の水分は１５〜２５重量％に調整される。好ましくは１８〜２２重量％の範囲であり、より好ましくは１９〜２１重量％の範囲である。水分が１５重量％未満の場合、乾燥後のメタノール包接率が高くなり好ましくない。水分が２５重量％を超えた場合、水分の乾燥に長時間必要になり好ましくない。 In the present invention, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl The water content in the adduct of resorcinol and methanol is adjusted to 15 to 25% by weight. Preferably it is the range of 18-22 weight%, More preferably, it is the range of 19-21 weight%. When the water content is less than 15% by weight, the methanol inclusion rate after drying is undesirably high. When the water content exceeds 25% by weight, it takes a long time to dry the water, which is not preferable.
本発明において、乾燥処理は減圧度を段階的に変化させることによって行われる。この方法によれば、急激な圧力変化を回避しながら、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からメタノールを効率的に除去することが可能となり包接率が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］レゾルシノールを得ることができる。さらには、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］レゾルシノールから水分を効率的に、ほぼ完全に除去することが可能となる。減圧度を段階的に変化させることなく乾燥を行った場合には、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ない。乾燥温度は７５℃前後まで徐々にあるいは段階的に昇温される。
段階的に変化させる減圧度の好ましい実施態様としては、下記の要件を満たす乾燥処理が挙げられる。
（１）減圧度５３〜２６ｋＰａで、主に目的化合物の付加物からメタノールを除去すること、
（２）減圧度２６〜１３ｋＰａに変化させ主に水を除去すること、
（３）減圧度１３〜２ｋＰａとし目的化合物から水分をほぼ完全に除去すること。
In the present invention, the drying process is performed by changing the degree of vacuum stepwise. According to this method, while avoiding a sudden pressure change, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1, 9′-xanthene) -4′a-yl] resorcinol and methanol can be efficiently removed and 4- [1 ′, 2 ′, 3 ′ having an inclusion rate of 24% or less. , 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol can be obtained. Furthermore, 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro-6′-hydroxyspiro (cyclohexane-1,9′-xanthene) -4′a-yl] It becomes possible to remove water from resorcinol efficiently and almost completely. When drying is performed without changing the degree of vacuum stepwise, the inclusion rate is 24% or less of 4- [1 ′, 2 ′, 3 ′, 4 ′, 4′a, 9′a-hexahydro -6'-hydroxyspiro (cyclohexane-1,9'-xanthene) -4'a-yl] resorcinol cannot be obtained. The drying temperature is raised gradually or stepwise to around 75 ° C.
A preferred embodiment of the degree of reduced pressure that is changed stepwise includes a drying treatment that satisfies the following requirements.
(1) removing methanol mainly from the adduct of the target compound at a reduced pressure of 53 to 26 kPa,
(2) Change the degree of vacuum to 26-13 kPa to mainly remove water;
(3) The degree of vacuum is 13 to 2 kPa, and moisture is almost completely removed from the target compound.
本発明において、通常、目的物を乾燥するために使用される乾燥機としては、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, a general dryer such as a plate dryer, a stirrer dryer, a paddle dryer or the like is usually used as a dryer used for drying the object.
本発明によれば、乾燥時間が短縮され、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′-hydroxyspiro has a drying time shortened and an inclusion rate of 24% or less. (Cyclohexane-1,9′-xanthene) -4′a-yl] resorcinol is easily obtained, which is an industrially very 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。前記の溶解液に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重量％に調整した。７５℃で４０ｋＰａに減圧して、１０時間乾燥後、２０ｋＰａに減圧して１時間乾燥、さらに、２ｋＰａに減圧して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、この時の包接率は３．５％であり、各種金属（Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｆｅ，Ｃｕ，Ｍｎ，Ａｌ，Ｚｎ，Ｎｉ，Ｃｒ，Ｐｂ）濃度は、合計で１２０ｐｐｂ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. 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 charged into 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. and dried for 10 hours, then the pressure was reduced to 20 kPa and dried for 1 hour, and the pressure was further reduced to 2 kPa and dried 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 Resorcinol) has a water content of 0.3% by weight, and the inclusion rate at this time is 3.5%. Various metals (Na, K, Mg, Ca, Fe, Cu, Mn, Al, Zn, Ni, The total concentration of Cr, Pb) was 120 ppb.
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。前記の溶解液をゼータプラスフィルター（登録商標）で処理して得られた溶液に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重量％に調整した。７５℃で４０ｋＰａに減圧して、１０時間乾燥後、２０ｋＰａに減圧して１時間乾燥、さらに、２ｋＰａに減圧して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、この時の包接率は３．５％であり、各種金属（Ｎａ，Ｋ，Ｍｇ，Ｃａ，Ｆｅ，Ｃｕ，Ｍｎ，Ａｌ，Ｚｎ，Ｎｉ，Ｃｒ，Ｐｂ）濃度は，合計で１５ｐｐｂ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. 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 a solution obtained by treating the solution with a Zeta Plus filter (registered trademark), and 45.0 g of crystals were obtained after crystallization and filtration. The water content of the obtained crystal was 11.6% by weight, and the inclusion rate was 90%.
The crystals were charged into 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. and dried for 10 hours, then the pressure was reduced to 20 kPa and dried for 1 hour, and the pressure was further reduced to 2 kPa and dried 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 Resorcinol) has a water content of 0.3% by weight, and the inclusion rate at this time is 3.5%. Various metals (Na, K, Mg, Ca, Fe, Cu, Mn, Al, Zn, Ni, The total concentration of Cr, Pb) was 15 ppb.
（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。前記の溶解液に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、７５℃で４０ｋＰａに減圧して、４時間乾燥後、２０ｋＰａに減圧して１時間乾燥、さらに、２ｋＰａに減圧して４時間乾燥した。乾燥後の得量は３８．７ｇ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、この時の包接率は５０％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 charged in a 0.5 liter flask, dried at 40 ° C. at 75 ° C., dried for 4 hours, dried at 20 kPa for 1 hour, further dried at 2 kPa and dried for 4 hours. The amount obtained after drying was 38.7 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 rate at this time was 50%.
（比較例２）
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重量％に調整し、７５℃で２ｋＰａに減圧して、８時間乾燥した。乾燥後の得量は３９．１ｇ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、この時の包接率は４０％であった。
(Comparative Example 2)
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 (water content: 10% by weight, clathrate compound: 90% by weight) is charged into a 0.5 liter four-necked round bottom flask equipped with a thermometer, stirrer, condenser, and dropping funnel. Then, 123.0 g of methanol was added and heated 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 charged into a 0.5 liter flask, 4.7 g of ion exchange water was added, the water content was adjusted to 20% by weight, the pressure was reduced to 2 kPa at 75 ° C., and the mixture was dried for 8 hours. The yield after drying was 39.1 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 rate at this time was 40%.
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