JP2002293781A - Method for producing dione monoacetals - Google Patents
Method for producing dione monoacetalsInfo
- Publication number
- JP2002293781A JP2002293781A JP2001098176A JP2001098176A JP2002293781A JP 2002293781 A JP2002293781 A JP 2002293781A JP 2001098176 A JP2001098176 A JP 2001098176A JP 2001098176 A JP2001098176 A JP 2001098176A JP 2002293781 A JP2002293781 A JP 2002293781A
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- general formula
- group
- formula
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- dione
- 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.)
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- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は液晶表示材料等の電
子材料や機能性材料または医農薬や香料、各種添加剤お
よびそれらの合成中間体として有用な、ジオンモノアセ
タール類の製造に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the production of dione monoacetals useful as electronic materials and functional materials such as liquid crystal display materials and the like, medicines, agrochemicals, fragrances, various additives and synthetic intermediates thereof.
【０００２】[0002]
【従来の技術】ジオンモノアセタール類は液晶表示材料
等の電子材料や機能性材料または医農薬や香料、各種添
加剤およびそれらの合成中間体として有用であり、製造
中間体として重要である。特にシクロヘキサン-1,4-ジ
オンやビシクロヘキサン-4,4'-ジオン等シクロヘキサノ
ン誘導体であるジオン類のモノアセタールは、液晶化合
物特にSTN液晶表示用等として用いられるアルケニル系
液晶化合物等の製造中間体として、非常に重要である。
このようなジオンモノアセタール類はこれまで、例えば
特開平1-156935号公報に示されるように対応するジケト
ン化合物のモノアセタール化により製造されてきた。し
かしながら、ジケトン化合物を選択的にモノアセタール
化することは決して容易ではなく、通常原料のジケトン
とジアセタール体及びモノアセタールの混合物から必要
なモノアセタールのみを分離する必要があり、コストの
上昇が避けられなかった。従って、ジオンモノアセター
ル類に対し、困難な分離工程が存在しないような、より
選択的で安価な製造方法が望まれていた。2. Description of the Related Art Dione monoacetals are useful as electronic materials and functional materials such as liquid crystal display materials, as well as pharmaceuticals, agricultural chemicals, fragrances, various additives, and synthetic intermediates thereof, and are important as production intermediates. In particular, monoacetals of diones, which are cyclohexanone derivatives such as cyclohexane-1,4-dione and bicyclohexane-4,4'-dione, are intermediates in the production of liquid crystal compounds, especially alkenyl liquid crystal compounds used for STN liquid crystal display and the like. As very important.
Such dione monoacetals have heretofore been produced, for example, by monoacetalization of the corresponding diketone compound as shown in JP-A-1-156935. However, it is not easy to selectively convert a diketone compound into a monoacetal, and it is necessary to separate only a necessary monoacetal from a mixture of a diketone, a diacetal compound, and a monoacetal, which are usually raw materials. Did not. Therefore, there has been a demand for a more selective and inexpensive production method that does not require a difficult separation step for dione monoacetals.
【０００３】[0003]
【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、ジオンモノアセタール類を得るために、困
難な分離工程が存在せず、より選択的で安価な製造方法
を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to provide a more selective and inexpensive process for obtaining dione monoacetals without a difficult separation step. is there.
【０００４】[0004]
【課題を解決するための手段】本発明は、上記課題を解
決するために鋭意検討した結果、ビスフェノール類の接
触還元等により容易に得られるヒドロキシケトン誘導体
を原料として、所望のジオンモノアセタール類が容易に
製造できることを見出し、本発明を完成するに至った。The present invention has been made as a result of intensive studies to solve the above-mentioned problems. As a result, a desired dione monoacetal is obtained by using a hydroxyketone derivative which can be easily obtained by catalytic reduction of bisphenol as a raw material. They have found that they can be easily manufactured, and have completed the present invention.
【０００５】すなわち、本発明は一般式(I)That is, the present invention provides a compound represented by the general formula (I)
【化６】 (式中、Qは置換基を有していてもよい炭素原子数1〜4の
アルキレン基を表し、Yは一般式(IIa)、(IIb)または(II
c)Embedded image (In the formula, Q represents an alkylene group having 1 to 4 carbon atoms which may have a substituent, and Y represents a general formula (IIa), (IIb) or (II
c)
【化７】 (式(IIb)においてVは置換基を有していても良い炭素原
子数1〜4のアルキレン基を表す。)で表される基のいず
れかを表す。)で表されるジオンモノアセタール類の製
造方法であって、一般式(III)Embedded image (In the formula (IIb), V represents an alkylene group having 1 to 4 carbon atoms which may have a substituent.) A method for producing dione monoacetals represented by the general formula (III)
【化８】 (式中、Zは一般式(IVa)、(IVb)または(IVc)Embedded image (In the formula, Z is the general formula (IVa), (IVb) or (IVc)
【化９】 (式(IVb)においてVは一般式(IIb)と同じ意味を表す。)
で表される基のいずれかを表す。)で表されるヒドロキ
シケトン誘導体を原料とし、一般式(V)Embedded image (In the formula (IVb), V has the same meaning as in the general formula (IIb).)
Represents any of the groups represented by ) Represented by the general formula (V)
【化１０】 (式中、Zは一般式(III)、Qは一般式(I)で表されると同
じ意味を表す。)で表されるヒドロキシアセタール誘導
体を酸化する工程を含むことを特徴とする製造方法を提
供する。Embedded image (Wherein, Z represents the general formula (III), and Q represents the same meaning as represented by the general formula (I).) A process for oxidizing a hydroxyacetal derivative represented by the formula: I will provide a.
【０００６】[0006]
【発明の実施の形態】上述のごとく、本発明の製造方法
により得られるジオンモノアセタール類は一般式(I)As described above, dione monoacetals obtained by the production method of the present invention have the general formula (I)
【化１１】 で表すことができる。一般式(I)において、Qは置換基を
有していてもよい炭素原子数1〜4のアルキレン基を表
す。置換基としては製造上の反応工程で不活性な基であ
れば特に制限はないが、低級アルキル基またはアリール
基または無置換であることが好ましい。アルキレンの主
鎖としては炭素原子数が2または3が好ましく、Qとして-
CH2CH2CH 2-または-CH2CH2-が好ましい。Embedded imageCan be represented by In the general formula (I), Q represents a substituent
The alkylene group having 1 to 4 carbon atoms which may be
You. Substituents are groups that are inactive in the production reaction process.
Is not particularly limited as long as it is a lower alkyl group or an aryl.
It is preferably unsubstituted or substituted. Alkylene lord
The chain preferably has 2 or 3 carbon atoms, and Q is-
CHTwoCHTwoCH Two-Or-CHTwoCHTwo-Is preferred.
【０００７】Yは一般式(IIa)、(IIb)または(IIc)Y is a compound represented by the general formula (IIa), (IIb) or (IIc)
【化１２】 で表される基のいずれかを表す。式(IIb)においてVは置
換基を有していても良い炭素原子数1〜4のアルキレン基
を表すが、-CH2CH2-が好ましい。従って、一般式(I)の
化合物としては以下に例示する(Ia-1)〜(Ic-2)Embedded image Represents any of the groups represented by Although in the formula (IIb) V represents an alkylene group having from 1 to 4 carbon atoms which may have a substituent group, -CH 2 CH 2 - is preferred. Accordingly, the compounds of the general formula (I) are exemplified below (Ia-1) to (Ic-2)
【化１３】 が好ましく、(Ia-1)及び(Ic-1)が、汎用性が高く特に好
ましい。Embedded image And (Ia-1) and (Ic-1) are particularly preferred because of high versatility.
【０００８】本発明の製造方法において、一般式(I)の
化合物は一般式(V)In the production method of the present invention, the compound of the general formula (I) is
【化１４】 で表されるヒドロキシアセタールを酸化する工程を含む
ことを特徴として得ることができる。一般式(V)におい
て、Qは一般式(I)と同じ意味を有し、Zは一般式(IVa)、
(IVb)または(IVc)Embedded image And a step of oxidizing the hydroxyacetal represented by the formula: In the general formula (V), Q has the same meaning as in the general formula (I), Z is the general formula (IVa),
(IVb) or (IVc)
【化１５】 で表され、式(IVb)においてVは一般式(IIb)と同じ意味
を表す。これらのなかで、(IVa)、(IVc)及び(IVb)でVが
-CH2CH2-である化合物が好ましい。Embedded image In the formula (IVb), V has the same meaning as in the general formula (IIb). Among them, (IVa), (IVc) and (IVb) have V
Compounds that are -CH 2 CH 2- are preferred.
【０００９】この酸化工程において、酸化剤としては2
級アルコールをケトンに酸化しうるものであれば特に制
限はないが、ハロゲン系酸化剤またはクロム酸系酸化剤
が好ましく、特に塩素、臭素等のハロゲン、次亜塩素
酸、次亜臭素酸等の次亜ハロゲン酸、次亜塩素酸ナトリ
ウム、次亜臭素酸ナトリウム、さらし粉等の次亜ハロゲ
ン酸塩、N-クロロこはく酸イミド、N-ブロモこはく酸イ
ミド、N-ブロモアセトアミド、N-クロロイソシアヌル酸
等のN-ハロカルボン酸アミドが好ましく、次亜塩素酸ナ
トリウム、さらし粉等の次亜塩素酸塩が最も好ましい。In this oxidation step, the oxidizing agent is 2
There is no particular limitation as long as it can oxidize the secondary alcohol to ketone, but a halogen-based oxidizing agent or a chromic acid-based oxidizing agent is preferable, and in particular, halogen such as chlorine and bromine, hypochlorous acid, hypobromite and the like Hypohalous acid, sodium hypochlorite, sodium hypobromite, hypohalite such as bleached powder, N-chlorosuccinimide, N-bromosuccinimide, N-bromoacetamide, N-chloroisocyanuric acid And the like, and most preferred are hypochlorites such as sodium hypochlorite and bleached powder.
【００１０】(V)の酸化により得られた一般式(I)の化合
物はさらなる精製工程を経ることなく、所望の目的に供
することが可能な場合もあり、あるいは再結晶、蒸留、
カラムクロマトグラフィー等の通常の精製手段により精
製して用いる場合もある。The compound of general formula (I) obtained by the oxidation of (V) may be able to serve the desired purpose without going through a further purification step, or may be subjected to recrystallization, distillation,
In some cases, it is used after purification by ordinary purification means such as column chromatography.
【００１１】本発明においては原料として一般式(III)In the present invention, the raw material represented by the general formula (III)
【化１６】 で表されるヒドロキシケトン誘導体を用いることを特徴
とする。一般式(III)において、Zは一般式(V)のおける
と同じ意味を表す。ここで、(III)の化合物はハイドロ
キノン、4,4'-ビフェノールあるいは一般式(VI)Embedded image Characterized by using a hydroxyketone derivative represented by the formula: In the general formula (III), Z has the same meaning as in the general formula (V). Here, the compound of (III) is hydroquinone, 4,4′-biphenol or the general formula (VI)
【化１７】 で表されるビスフェノール誘導体を、例えば特開平12-1
59718号公報に記載された方法等により接触還元するこ
とで容易に得ることができる。ここで一般式(VI)におい
てV'は水素原子または炭素原子数1〜4のアルキレン基、
アルケニレン基またはアルキニレン基を表す。)Embedded image The bisphenol derivative represented by, for example, JP-A No. 12-1
It can be easily obtained by catalytic reduction according to the method described in 59718 or the like. Here, in the general formula (VI), V ′ is a hydrogen atom or an alkylene group having 1 to 4 carbon atoms,
Represents an alkenylene group or an alkynylene group. )
【００１２】一般式(V)のヒドロキシアセタールを一般
式(III)のヒドロキシケトン誘導体を原料として製造す
るルートはいくつか存在するが、以下に示すルートが好
ましい。There are several routes for producing the hydroxyacetal of the general formula (V) from the hydroxyketone derivative of the general formula (III), but the following route is preferred.
【００１３】即ち(V)のヒドロキシケトン誘導体の水酸
基を保護することにより一般式(VII)That is, by protecting the hydroxyl group of the hydroxyketone derivative (V), the compound represented by the general formula (VII)
【化１８】 で表される水酸基が保護されたヒドロキシケトン誘導体
類が得られる。ここで一般式(VII)において、Wは一般式
(VIIIa)、(VIIIb)または(VIIIc)Embedded image A hydroxyketone derivative having a hydroxyl group protected, represented by the following formula, is obtained. Here, in the general formula (VII), W is a general formula
(VIIIa), (VIIIb) or (VIIIc)
【化１９】 で表され、式(VIIIb)においてVは一般式(IIb)と同じ意
味を表す。Pは水酸基の保護基を表すが、メチル基、ベ
ンジル基、テトラヒドロピラニル基、テトラヒドロフリ
ル基、メトキシメチル基またはエトキシメチル基が好ま
しく、メチル基またはベンジル基が酸性条件や塩基性条
件に安定なため特に好ましい。これらの保護基は製造の
各工程において、脱保護される場合も存在するが、その
場合には必要に応じ再度保護すればよい。Embedded image In the formula (VIIIb), V has the same meaning as in the general formula (IIb). P represents a protecting group for a hydroxyl group, and is preferably a methyl group, a benzyl group, a tetrahydropyranyl group, a tetrahydrofuryl group, a methoxymethyl group or an ethoxymethyl group, and the methyl group or the benzyl group is stable under acidic or basic conditions. Therefore, it is particularly preferable. These protecting groups may be deprotected in each step of the production, but in such a case, they may be protected again if necessary.
【００１４】次いで、この(VII)の化合物のカルボニル
基をアセタール化することにより、一般式(V)のヒドロ
キシアセタールを得ることができる。アセタール化は(V
II)の化合物を、酸触媒存在下に対応する一般式(IX)Then, the carbonyl group of the compound (VII) is acetalized to obtain a hydroxyacetal of the general formula (V). Acetalization is (V
The compound of the formula (IX) in the presence of an acid catalyst
【化２０】 で表されるジオール(式中、Qは一般式(I)におけると同
じ意味を表す。)と反応させてもよく、あるいはアセタ
ール交換によっても良い。Embedded image (Wherein Q has the same meaning as in general formula (I)), or may be obtained by acetal exchange.
【００１５】以上のようにして、一般式(III)で表され
るヒドロキシケトン誘導体から、一般式(I)で表される
ジオンモノアセタール類を製造することができる。As described above, a dione monoacetal represented by the general formula (I) can be produced from the hydroxyketone derivative represented by the general formula (III).
【００１６】[0016]
【実施例】以下、実施例を挙げて本発明を更に詳述する
が、本発明はこれらの実施例に限定されるものではな
い。EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
【００１７】(実施例1) ビシクロヘキサン-4,4'-ジオ
ンモノエチレンアセタール(Ia-1)の製造 1-a) 4'-ヒドロキシビシクロヘキサン-4-オン(この化
合物はビフェノールから特開平12-159718号公報に準じ
た方法で製造でき、シス及びトランス体の混合物であ
る。)19.6gの50mLテトラヒドロフラン(THF)溶液をTHF20
0mL中に懸濁させた水素化ナトリウム(50％)5.0gに滴下
した。室温で1時間攪拌した後、塩化ベンジル15gのTHF3
0mL溶液を30分かけて滴下した。3時間攪拌した後、水を
加えて過剰の水素化ナトリウムを分解し、塩酸酸性とし
てトルエンで抽出した。水洗後、溶媒を溜去して4'-ベ
ンジルオキシビシクロヘキサン-4-オン24.5gを得た。 1-b) 得られた全量をトルエン200mLに溶解し、エチレ
ングリコール20mLを加え、共沸する水を除去しながら5
時間加熱還流させた。放冷後、炭酸水素ナトリウム水溶
液、水で洗浄し、溶媒を溜去して4'-ベンジルオキシビ
シクロヘキサン-4-オンエチレンアセタール25.2gを得
た。 1-c) この全量をエタノール100mLに溶解し、1.0gの5%
パラジウム/炭素とともにオートクレーブ中で、室温で4
時間接触還元(水素圧0.5MPa)した。触媒を濾別後、減圧
下に溶媒を溜去して4'-ヒドロキシビシクロヘキサン-4-
オンエチレンアセタールgを得た。 1-d) この全量をジクロロメタン50mLに溶解し、酢酸50
mLを加え、激しく攪拌しながら、これに8％次亜塩素酸
ナトリウム水溶液(アンチホルミン)100mLを滴下した。4
時間攪拌後、亜硫酸水素ナトリウム水溶液を加えて過剰
の酸化剤を分解し、水を加え、トルエンで抽出した。
水、飽和食塩水で洗浄後、溶媒を濃縮して得られた粗生
成物をヘキサン/酢酸エチル混合溶媒から再結晶させ
て、表記のビシクロヘキサン-4,4'-ジオンモノエチレン
アセタール(Ia-1)の白色結晶13.5gを得た。(Example 1) Preparation of bicyclohexane-4,4'-dione monoethylene acetal (Ia-1) 1-a) 4'-Hydroxybicyclohexane-4-one (this compound was obtained from A mixture of cis and trans isomers can be produced by a method according to JP-159718A.) A solution of 19.6 g of 50 mL of tetrahydrofuran (THF) in THF 20
It was added dropwise to 5.0 g of sodium hydride (50%) suspended in 0 mL. After stirring at room temperature for 1 hour, 15 g of benzyl chloride in THF
The 0 mL solution was added dropwise over 30 minutes. After stirring for 3 hours, excess sodium hydride was decomposed by adding water, and the mixture was acidified with hydrochloric acid and extracted with toluene. After washing with water, the solvent was distilled off to obtain 24.5 g of 4'-benzyloxybicyclohexan-4-one. 1-b) Dissolve the entire amount obtained in 200 mL of toluene, add 20 mL of ethylene glycol, and remove 5
Heated to reflux for hours. After cooling, the mixture was washed with an aqueous sodium hydrogen carbonate solution and water, and the solvent was distilled off to obtain 25.2 g of 4'-benzyloxybicyclohexane-4-one ethylene acetal. 1-c) Dissolve the whole amount in 100 mL of ethanol, and add 1.0 g of 5%
4 at room temperature in autoclave with palladium / carbon
Catalytic reduction (hydrogen pressure 0.5 MPa) was carried out for an hour. After filtering off the catalyst, the solvent was distilled off under reduced pressure to give 4'-hydroxybicyclohexane-4-.
On-ethylene acetal g was obtained. 1-d) Dissolve the whole amount in 50 mL of dichloromethane and add 50 mL of acetic acid.
Then, 100 mL of an 8% aqueous sodium hypochlorite solution (antiformin) was added dropwise thereto with vigorous stirring. Four
After stirring for an hour, an aqueous sodium hydrogen sulfite solution was added to decompose excess oxidant, water was added, and the mixture was extracted with toluene.
After washing with water and saturated saline, the crude product obtained by concentrating the solvent was recrystallized from a mixed solvent of hexane / ethyl acetate to give the indicated bicyclohexane-4,4'-dione monoethylene acetal (Ia- 13.5 g of white crystals of 1) were obtained.
【００１８】(比較例1) ビシクロヘキサン-4,4'-ジオ
ンを原料とするビシクロヘキサン-4,4'-ジオンモノエチ
レンアセタールの製造 68gのビシクロヘキサン-4,4'-ジオンをトルエン340mLに
溶解し、エチレングリコール30g及び硫酸水素カリウム
0.5gを加え、生成共沸する水を系外に除去しながら、4
時間加熱還流させた。放冷後得られた混合物の溶液(ビ
シクロヘキサン-4,4'-ジオン/ビシクロヘキサン-4,4'-
ジオンモノエチレンアセタール/ビシクロヘキサン-4,4'
-ジオンジエチレンアセタール＝13/51/16)に4.7％亜硫
酸水素ナトリウム水溶液300mLを加え、1時間攪拌した。
析出した結晶を濾別後、濾液の有機層を減圧下に濃縮
し、残渣を酢酸エチル400mLに溶解した。32％亜硫酸水
素ナトリウム水溶液250mLを加え、1時間攪拌して析出結
晶を濾取した。結晶を酢酸エチルで洗浄した後、10％ア
ンモニア水を加え、1時間攪拌した。トルエンで抽出
し、洗浄、乾燥後、溶媒を溜去して得られた残渣を、ヘ
キサンと酢酸エチルの混合溶媒から再結晶させて表記の
ビシクロヘキサン-4,4'-ジオンモノエチレンアセタール
(Ia-1)の白色結晶28.4gを得た。Comparative Example 1 Production of Bicyclohexane-4,4'-dione Monoethylene Acetal from Bicyclohexane-4,4'-dione 68 g of bicyclohexane-4,4'-dione was added to 340 mL of toluene. Dissolve, 30 g ethylene glycol and potassium hydrogen sulfate
Add 0.5 g and remove the azeotropically generated water out of the system.
Heated to reflux for hours. A solution of the mixture obtained after cooling (bicyclohexane-4,4'-dione / bicyclohexane-4,4'-
Dione monoethylene acetal / bicyclohexane-4,4 '
-Dionediethylene acetal (13/51/16) was added with 300 mL of a 4.7% aqueous sodium bisulfite solution, and stirred for 1 hour.
After the precipitated crystals were separated by filtration, the organic layer of the filtrate was concentrated under reduced pressure, and the residue was dissolved in 400 mL of ethyl acetate. 250 mL of a 32% aqueous sodium bisulfite solution was added, and the mixture was stirred for 1 hour, and the precipitated crystals were collected by filtration. After washing the crystals with ethyl acetate, 10% aqueous ammonia was added and the mixture was stirred for 1 hour. Extracted with toluene, washed and dried, the solvent was distilled off, and the obtained residue was recrystallized from a mixed solvent of hexane and ethyl acetate to give the indicated bicyclohexane-4,4'-dione monoethylene acetal.
28.4 g of white crystals of (Ia-1) were obtained.
【００１９】従って原料としてビシクロヘキサン-4,4'-
ジオンを用いた場合でも実施例1と同様に目的のビシク
ロヘキサン-4,4'-ジオンモノエチレンアセタールを得る
ことができるが、この場合、所望のモノアセタールを選
択的に合成することが困難であり、原料のジオンや副生
するジアセタール分離しなければならないため、実施例
1の4'-ヒドロキシビシクロヘキサン-4-オンを用いた場
合と比較して、収率が低くなっていることがわかり、実
施例1がコスト的に優れていることは明らかである。Accordingly, bicyclohexane-4,4'-
Even when dione is used, the target bicyclohexane-4,4'-dione monoethylene acetal can be obtained as in Example 1, but in this case, it is difficult to selectively synthesize the desired monoacetal. Example, since dione as a raw material and diacetal by-product must be separated
It was found that the yield was lower than in the case where 4′-hydroxybicyclohexane-4-one of 1 was used, and it is clear that Example 1 is superior in cost.
【００２０】[0020]
【発明の効果】本発明はジオンモノアセタール類の製造
において、原料としてジケトン化合物に換えて、ヒドロ
キシケトン誘導体を原料とする方法を提供し、これによ
り所望のジオン類のモノアセタールのより安価な製造を
可能とした。得られたジオン類のモノアセタールは、液
晶表示材料等の電子材料や機能性材料または医農薬や香
料、各種添加剤およびそれらの合成中間体として極めて
有用である。The present invention provides a method for producing dione monoacetals in which a hydroxyketone derivative is used as a raw material instead of a diketone compound as a raw material, whereby the desired dione monoacetal can be produced at lower cost. Was made possible. The obtained dione monoacetal is extremely useful as an electronic material such as a liquid crystal display material, a functional material, a medical and agricultural chemical, a fragrance, various additives, and a synthetic intermediate thereof.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4C022 FA02 HA04 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4C022 FA02 HA04
Claims (6)
アルキレン基を表し、Yは一般式(IIa)、(IIb)または(II
c) 【化２】 (式(IIb)においてVは置換基を有していても良い炭素原
子数1〜4のアルキレン基を表す。)で表される基のいず
れかを表す。)で表されるジオンモノアセタール類の製
造方法であって、一般式(III) 【化３】 (式中、Zは一般式(IVa)、(IVb)または(IVc) 【化４】 (式(IVb)においてVは一般式(IIb)と同じ意味を表す。)
で表される基のいずれかを表す。)で表されるヒドロキ
シケトン誘導体を原料とし、一般式(V) 【化５】 (式中、Zは一般式(III)、Qは一般式(I)で表されると同
じ意味を表す。)で表されるヒドロキシアセタール誘導
体を酸化する工程を含むことを特徴とする製造方法。1. A compound of the general formula (I) (In the formula, Q represents an alkylene group having 1 to 4 carbon atoms which may have a substituent, and Y represents a general formula (IIa), (IIb) or (II
c) (In the formula (IIb), V represents an alkylene group having 1 to 4 carbon atoms which may have a substituent.) A method for producing dione monoacetals represented by the general formula (III): (Wherein Z is a group represented by the general formula (IVa), (IVb) or (IVc)) (In the formula (IVb), V has the same meaning as in the general formula (IIb).)
Represents any of the groups represented by Using a hydroxyketone derivative represented by the formula (I) as a raw material, (Wherein, Z represents the general formula (III), and Q represents the same meaning as represented by the general formula (I).) A process for oxidizing a hydroxyacetal derivative represented by the formula: .
ン誘導体の水酸基を保護した後にカルボニル基をアセタ
ール化し、得られた化合物の水酸基の保護基をはずした
後、水酸基を酸化することを特徴とする請求項1記載の
製造方法。2. A hydroxyketone derivative represented by the general formula (III), wherein the hydroxy group is protected, the carbonyl group is acetalized, the hydroxy group of the obtained compound is removed, and then the hydroxy group is oxidized. 2. The production method according to claim 1, wherein
は-CH2CH2-を表すところの請求項1または2記載の製造方
法。3. The method according to claim 1, wherein Q in the general formula (I) represents —CH 2 CH 2 CH 2 — or —CH 2 CH 2 —.
されるところの請求項1〜3の何れかに記載の製造方法。4. The method according to claim 1, wherein Y in the general formula (I) is represented by the general formula (IIa).
基、テトラヒドロピラニル基、テトラヒドロフリル基、
メトキシメチル基またはエトキシメチル基から選ばれる
ことを特徴とする請求項2〜4の何れかに記載の製造方
法。5. The protecting group for a hydroxyl group is a methyl group, a benzyl group, a tetrahydropyranyl group, a tetrahydrofuryl group,
5. The method according to claim 2, wherein the method is selected from a methoxymethyl group and an ethoxymethyl group.
酸、次亜ハロゲン酸塩、N-ハロカルボン酸アミドを用い
ることを特徴とする請求項2〜5の何れかに記載の製造方
法。6. The method according to claim 2, wherein a halogen, hypohalous acid, hypohalite, or N-halocarboxylic amide is used as the oxidizing agent.
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Citations (6)
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|---|---|---|---|---|
| US4065573A (en) * | 1976-06-03 | 1977-12-27 | The Upjohn Company | 4-Amino-4-phenylcyclohexanone ketal compositions and process of use |
| US4587351A (en) * | 1984-04-18 | 1986-05-06 | Eli Lilly And Company | Synthesis of ketones with calcium hypochlorite |
| JPH01156935A (en) * | 1987-09-29 | 1989-06-20 | Dainippon Ink & Chem Inc | Cyclohexylcyclohexene ring-containing fluorine liquid crystal compound, synthetic intermediate thereof and production of said compound |
| JPH0232033A (en) * | 1988-07-19 | 1990-02-01 | Dainippon Ink & Chem Inc | Tricyclic cyclohexenylcyclohexane derivative |
| JPH09194473A (en) * | 1996-01-12 | 1997-07-29 | Wako Pure Chem Ind Ltd | New method for producing 4,4'-bicyclohexanedione monoketal compound |
| JP2000239214A (en) * | 1998-12-25 | 2000-09-05 | Dainippon Ink & Chem Inc | Decahydronaphthalene derivative and its production |
-
2001
- 2001-03-30 JP JP2001098176A patent/JP4735915B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4065573A (en) * | 1976-06-03 | 1977-12-27 | The Upjohn Company | 4-Amino-4-phenylcyclohexanone ketal compositions and process of use |
| US4587351A (en) * | 1984-04-18 | 1986-05-06 | Eli Lilly And Company | Synthesis of ketones with calcium hypochlorite |
| JPH01156935A (en) * | 1987-09-29 | 1989-06-20 | Dainippon Ink & Chem Inc | Cyclohexylcyclohexene ring-containing fluorine liquid crystal compound, synthetic intermediate thereof and production of said compound |
| JPH0232033A (en) * | 1988-07-19 | 1990-02-01 | Dainippon Ink & Chem Inc | Tricyclic cyclohexenylcyclohexane derivative |
| JPH09194473A (en) * | 1996-01-12 | 1997-07-29 | Wako Pure Chem Ind Ltd | New method for producing 4,4'-bicyclohexanedione monoketal compound |
| JP2000239214A (en) * | 1998-12-25 | 2000-09-05 | Dainippon Ink & Chem Inc | Decahydronaphthalene derivative and its production |
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