JP2001253853A - New biadamantane derivative - Google Patents
New biadamantane derivativeInfo
- Publication number
- JP2001253853A JP2001253853A JP2000065930A JP2000065930A JP2001253853A JP 2001253853 A JP2001253853 A JP 2001253853A JP 2000065930 A JP2000065930 A JP 2000065930A JP 2000065930 A JP2000065930 A JP 2000065930A JP 2001253853 A JP2001253853 A JP 2001253853A
- Authority
- JP
- Japan
- Prior art keywords
- biadamantane
- group
- general formula
- derivative
- new
- 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.)
- Pending
Links
- MPXKIFWZOQVOLN-UHFFFAOYSA-N 1-(1-adamantyl)adamantane Chemical class C1C(C2)CC(C3)CC2CC13C(C1)(C2)CC3CC2CC1C3 MPXKIFWZOQVOLN-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- -1 n-octyl Chemical group 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000003136 n-heptyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 6
- XLLIQLLCWZCATF-UHFFFAOYSA-N 2-methoxyethyl acetate Chemical compound COCCOC(C)=O XLLIQLLCWZCATF-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- WZIXUNOHMHUVKU-UHFFFAOYSA-N methyl 3-(3-methoxycarbonyl-1-adamantyl)adamantane-1-carboxylate Chemical compound C1C(C2)CC(C3)CC2(C(=O)OC)CC13C(C1)(C2)CC3CC1CC2(C(=O)OC)C3 WZIXUNOHMHUVKU-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000013307 optical fiber Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- CBQQWGKYENSOHG-UHFFFAOYSA-N 3-(3-hydroxy-1-adamantyl)adamantan-1-ol Chemical compound C1C(C2)CC(C3)CC2(O)CC13C(C1)(C2)CC3CC1CC2(O)C3 CBQQWGKYENSOHG-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- LPEKGGXMPWTOCB-UHFFFAOYSA-N 8beta-(2,3-epoxy-2-methylbutyryloxy)-14-acetoxytithifolin Natural products COC(=O)C(C)O LPEKGGXMPWTOCB-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001793 charged compounds Chemical class 0.000 description 2
- ODQWQRRAPPTVAG-GZTJUZNOSA-N doxepin Chemical compound C1OC2=CC=CC=C2C(=C/CCN(C)C)/C2=CC=CC=C21 ODQWQRRAPPTVAG-GZTJUZNOSA-N 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- CATSNJVOTSVZJV-UHFFFAOYSA-N heptan-2-one Chemical compound CCCCCC(C)=O CATSNJVOTSVZJV-UHFFFAOYSA-N 0.000 description 2
- 238000004949 mass spectrometry Methods 0.000 description 2
- 229940057867 methyl lactate Drugs 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- ZYFDYGIJNFZXQV-UHFFFAOYSA-N propyl 3-(3-propoxycarbonyl-1-adamantyl)adamantane-1-carboxylate Chemical compound C1C(C2)CC(C3)CC2(C(=O)OCCC)CC13C(C1)(C2)CC3CC1CC2(C(=O)OCCC)C3 ZYFDYGIJNFZXQV-UHFFFAOYSA-N 0.000 description 2
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- CCHZMJCCPSQDSQ-UHFFFAOYSA-N 3-(3-carboxy-1-adamantyl)adamantane-1-carboxylic acid Chemical compound C1C(C2)CC(C3)CC2(C(O)=O)CC13C(C1)(C2)CC3CC1CC2(C(=O)O)C3 CCHZMJCCPSQDSQ-UHFFFAOYSA-N 0.000 description 1
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001028 reflection method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規なビアダマンタ
ン誘導体、具体的には３，３’−ジアルコキシカルボニ
ル−１，１’−ビアダマンタンに関し、さらに詳しく
は、ビアダマンタン類の特異的な機能を保持しつつ、各
種溶剤に対する溶解性に優れた新規なビアダマンタン誘
導体に関するものである。[0001] The present invention relates to a novel biadamantane derivative, specifically 3,3'-dialkoxycarbonyl-1,1'-biadamantane, and more specifically to a specific function of biadamantanes. And a novel biadamantane derivative having excellent solubility in various solvents.
【０００２】[0002]
【従来の技術】従来から、アダマンタン類は非常に安定
な炭素骨格を有すると共に、特異な機能を示すことか
ら、様々な用途に供せられ、特にその光学特性や耐熱性
から光ディスク基盤、光ファイバーあるいはレンズなど
に用いられている（特開平９−３０２０７７号公報およ
び特開平６−３０５０４４号公報など）。とりわけ、ア
ダマンタン骨格が二つ以上結合したビアダマンタン類
は、さらに高い耐熱性や特異な機能が期待されている。
しかしながら、従来から知られているビアダマンタン
類、特に３，３’−ジメトキシカルボニル−１，１’−
ビアダマンタン（米国特許第３３４２８８０号明細書）
は、溶解性に乏しく、種々の用途展開を行う上で大きな
制約となっていた。2. Description of the Related Art Conventionally, adamantanes have a very stable carbon skeleton and exhibit a unique function, so that they are used for various applications. In particular, due to their optical properties and heat resistance, optical disc substrates, optical fibers or optical fibers. It is used for lenses and the like (JP-A-9-302077 and JP-A-6-305044). In particular, biadamantanes having two or more adamantane skeletons are expected to have higher heat resistance and unique functions.
However, conventionally known biadamantanes, particularly 3,3′-dimethoxycarbonyl-1,1′-
Viadamantane (US Pat. No. 3,342,880)
Has poor solubility and has been a major limitation in developing various applications.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
状況下で、耐熱性、耐水性及び光学特性などに優れると
共に、各種溶剤に対する溶解性に優れた新規なビアダマ
ンタン類を提供することを目的とするものである。SUMMARY OF THE INVENTION The object of the present invention is to provide a novel biadamantane having excellent heat resistance, water resistance and optical properties, and excellent solubility in various solvents. It is intended for.
【０００４】[0004]
【課題を解決するための手段】本発明者は、前記目的を
達成するために鋭意研究を重ねた結果、炭素数３以上の
アルコキシカルボニル基（炭素数２以上のアルコキシ
基）を有する特定の構造のビアダマンタン類は文献未載
の新規な化合物であって、その目的に適合しうることを
見出した。本発明は、かかる知見に基づいて完成したも
のである。すなわち、本発明は、一般式（Ｉ）Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a specific structure having an alkoxycarbonyl group having 3 or more carbon atoms (an alkoxy group having 2 or more carbon atoms) has been obtained. It has been found that biadamantane is a novel compound which has not been described in the literature and can be adapted for the purpose. The present invention has been completed based on such findings. That is, the present invention provides a compound represented by the general formula (I):
【０００５】[0005]
【化２】 Embedded image
【０００６】（式中、Ｒは炭素数２〜８のアルキル基を
示す。）で表される新規なビアダマンタン誘導体を提供
するものである。(Wherein, R represents an alkyl group having 2 to 8 carbon atoms.) The present invention provides a novel biadamantane derivative represented by the formula:
【０００７】[0007]
【発明の実施の形態】本発明のビアダマンタン誘導体
は、上記一般式（Ｉ）で表される構造を有する文献未載
の新規な化合物である。上記一般式（Ｉ）において、Ｒ
は炭素数２〜８のアルキル基（直鎖あるいは分岐アルキ
ル基）、具体的には、エチル基，ｎ−プロピル基，イソ
プロピル基，ｎ−ブチル基，イソブチル基，ｓｅｃ−ブ
チル基，ｔｅｒｔ−ブチル基，ｎ−アミル基，イソアミ
ル基，ｎ−ヘキシル基，ｎ−ヘプチル基，ｎ−オクチル
基又はイソオクチル基などを示す。なお、一般式（Ｉ）
における２つのＲは、通常は同一のものであるが、場合
によっては異なっていてもよい。BEST MODE FOR CARRYING OUT THE INVENTION The biadamantane derivative of the present invention is a novel compound having a structure represented by the above general formula (I), which has not been published in any literature. In the above general formula (I), R
Represents an alkyl group having 2 to 8 carbon atoms (linear or branched alkyl group), specifically, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl And n-amyl, isoamyl, n-hexyl, n-heptyl, n-octyl and isooctyl. The general formula (I)
Are usually the same, but may be different in some cases.
【０００８】本発明のビアダマンタン誘導体は、一般式
（Ｉ）で表される３，３’−ジアルコキシカルボニル−
１，１’−ビアダマンタンであるが、具体的には、３，
３’−ジエトキシカルボニル−１，１’−ビアダマンタ
ン、３，３’−ジｎ−プロポキシカルボニル−１，１’
−ビアダマンタン、３，３’−ジイソプロポキシカルボ
ニル−１，１’−ビアダマンタン、３，３’−ジｎ−ブ
トキシカルボニル−１，１’−ビアダマンタン、３，
３’−ジイソブトキシカルボニル−１，１’−ビアダマ
ンタン、３，３’−ジｔ−ブトキシカルボニル−１，
１’−ビアダマンタン、３，３’−ジアミロキシカルボ
ニル−１，１’−ビアダマンタンなどを挙げることがで
きる。[0008] The biadamantane derivative of the present invention has a 3,3'-dialkoxycarbonyl-formula represented by the general formula (I).
1,1′-biadamantane, specifically, 3,
3′-diethoxycarbonyl-1,1′-biadamantane, 3,3′-di-n-propoxycarbonyl-1,1 ′
-Biadamantane, 3,3'-diisopropoxycarbonyl-1,1'-biadamantane, 3,3'-di-n-butoxycarbonyl-1,1'-biadamantane, 3,
3′-diisobutoxycarbonyl-1,1′-biadamantane, 3,3′-di-tert-butoxycarbonyl-1,
Examples thereof include 1′-biadamantane and 3,3′-diamyroxycarbonyl-1,1′-biadamantane.
【０００９】本発明のビアダマンタン誘導体の製造方法
としては特に制限はないが、例えば式（II）The method for producing the biadamantane derivative of the present invention is not particularly limited.
【００１０】[0010]
【化３】 Embedded image
【００１１】で表される３，３’−ジカルボキシ−１，
１’−ビアダマンタンと一般式ＲＯＨ（式中、Ｒは前記
と同じ。）で表されるアルコールとを酸触媒の存在下で
エステル化反応させる方法、又は上記式（II）の３，
３’−ジカルボキシ−１，１’−ビアダマンタンの代わ
りに、そのカルボキシル基を酸ハライドに変えた式（II
I)3,3'-dicarboxy-1,
A method of subjecting 1′-biadamantane and an alcohol represented by the general formula ROH (where R is the same as described above) to an esterification reaction in the presence of an acid catalyst, or 3 of the above formula (II)
In place of 3′-dicarboxy-1,1′-biadamantane, the formula (II) in which the carboxyl group is changed to an acid halide.
I)
【００１２】[0012]
【化４】 Embedded image
【００１３】（式中、Ｘはハロゲン原子を示す。）で表
される３，３’−ジハロゲノカルボニル−１，１’−ビ
アダマンタンと上記一般式ＲＯＨで表されるアルコール
とを反応させる方法などがある。ここで酸触媒として
は、例えば硫酸や塩酸等の鉱酸、ｐ−トルエンスルホン
酸等の有機酸、さらにはフッ化ホウ素エーテラート等の
ルイス酸などを挙げることができ、また上述のカルボキ
シル基（ＣＯＯＨ）を酸ハライド（ＣＯＸ）に変換する
試薬としては、塩化ホスホリル，塩化チオニル，五塩化
リン，三塩化リンなどを挙げることができる。(Wherein X represents a halogen atom) A method of reacting 3,3'-dihalogenocarbonyl-1,1'-biadamantane represented by the general formula ROH with an alcohol represented by the general formula ROH: and so on. Examples of the acid catalyst include mineral acids such as sulfuric acid and hydrochloric acid, organic acids such as p-toluenesulfonic acid, and Lewis acids such as boron fluoride etherate. ) Can be converted to an acid halide (COX), for example, phosphoryl chloride, thionyl chloride, phosphorus pentachloride, phosphorus trichloride and the like.
【００１４】なお、ここで原料として用いる式（II）で
表される３，３’−ジカルボキシ−１，１’−ビアダマ
ンタンは、ビアダマンタン、１，１’−ジブロモ−３，
３’−ビアダマンタンあるいは３，３’−ジヒドロキシ
−１，１’−ビアダマンタンを出発原料として、これを
発煙硫酸、濃硫酸、濃硝酸等の強酸の存在下でギ酸を添
加して反応させることにより、あるいは一酸化炭素雰囲
気下で合成される。The 3,3′-dicarboxy-1,1′-biadamantane represented by the formula (II) used as a raw material here is biadamantane, 1,1′-dibromo-3,
Using 3'-biadamantane or 3,3'-dihydroxy-1,1'-biadamantane as a starting material and reacting it with formic acid in the presence of a strong acid such as fuming sulfuric acid, concentrated sulfuric acid or concentrated nitric acid Or under a carbon monoxide atmosphere.
【００１５】[0015]
【実施例】次に、本発明を実施例により、さらに詳しく
説明するが、本発明は、これらの例によってなんら限定
されるものではない。 実施例 （１）３，３’−ジｎ−プロポキシカルボニル−１，
１’−ビアダマンタンの合成 ３，３’−ジヒドロキシ−１，１’−ビアダマンタン
０．５ｇ（１．６５ミリモル）を濃硫酸５ミリリットル
に溶解させ、２０℃でギ酸１ミリリットルをゆっくり滴
下した。その後、さらに２時間攪拌した。反応液を氷に
注ぎ、析出物をろ取し、それを水酸化ナトリウム水溶液
に溶解させた後、ろ過して不溶分を除いた。再度、ろ液
を塩酸で強酸性としてカルボン酸を析出させ、それをろ
取し、洗液が中性になるまで水洗、その後メタノール洗
浄を行い、さらに真空乾燥した。上記で得られた３，
３’−ジカルボキシ−１，１’−ビアダマンタンに塩化
チオニル１０ミリリットルを添加し、３時間還流して均
一溶液とした後、過剰の塩化チオニルを減圧下で留去
し、そこへ脱水処理したｎ−プロパノール１０ミリリッ
トルを添加し、１時間還流した。その後、反応液にメタ
ノールを加えてろ過し、ろ液を濃縮し、さらにヘキサン
を加えて不溶分をろ過した後、濃縮し、さらにアセトン
を加えて不溶分をろ過した後、濃縮した。得られた生成
物の収量は０．６ｇであり、ガスクロマトグラフィーに
よる純度は９９．７％であった。また、この生成物につ
いて、下記の如く分析を行った。その結果は、次の通り
である。 ガスクロマトグラフィーによる質量分析（ＣＩ法） 分子イオン（Ｍ−１）：４４３ ガスクロマトグラフィーによる質量分析（ＥＩ法） ｍ／ｅ（スペクトル強度（％））：４４２（１０．２
１），３５５（１８．４０），２２１（１００），１７
９（４８．３１），１３３（４１．５３） プロトン核磁気共鳴分析(1Ｈ−ＮＭＲ）（溶媒：重ク
ロロホルム） δ(1Ｈ／ｐｐｍ）：０．８６９（ｔ，６Ｈ），１．４〜
１．９０（ｍ，２８Ｈ），２．０２５（ｍ，４Ｈ），
３．９４３（ｔ，４Ｈ） 同位体炭素核磁気共鳴分析（13Ｃ−ＮＭＲ）（溶媒：
重クロロホルム） δ13Ｃ／ｐｐｍ）：１０．３４１， ２２．０３８，
２８．６０７， ３４．３８５， ３６．９０７， ３
６．９４９， ３８．６７１， ４１．７１３， ６
５．６２５， １７８．２１０ フーリエ変換赤外線吸収分析（ＦＴ−ＩＲ，拡散反射
法） 吸収（ｃｍ-1）：１７２６．６カルボニル化合物（エス
テル） 上記分析の結果、得られた生成物は下式（IV）で表され
る３，３’−ジｎ−プロポキシカルボニル−１，１’−
ビアダマンタンであることが同定された。Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples (1) 3,3′-di-n-propoxycarbonyl-1,
Synthesis of 1′-biadamantane 0.5 g (1.65 mmol) of 3,3′-dihydroxy-1,1′-biadamantane was dissolved in 5 ml of concentrated sulfuric acid, and 1 ml of formic acid was slowly added dropwise at 20 ° C. Thereafter, the mixture was further stirred for 2 hours. The reaction solution was poured into ice, and the precipitate was collected by filtration, dissolved in an aqueous sodium hydroxide solution, and filtered to remove insoluble components. The filtrate was again made strongly acidic with hydrochloric acid to precipitate a carboxylic acid, which was collected by filtration, washed with water until the washing became neutral, then washed with methanol, and further dried under vacuum. 3, obtained above
10 ml of thionyl chloride was added to 3'-dicarboxy-1,1'-biadamantane, and the mixture was refluxed for 3 hours to form a homogeneous solution. Then, excess thionyl chloride was distilled off under reduced pressure, and the residue was dehydrated. 10 ml of n-propanol was added and refluxed for 1 hour. Thereafter, methanol was added to the reaction solution, followed by filtration, and the filtrate was concentrated. Further, hexane was added to filter the insoluble matter, and the mixture was concentrated. Acetone was added, the insoluble matter was filtered, and the mixture was concentrated. The yield of the obtained product was 0.6 g, and the purity by gas chromatography was 99.7%. The product was analyzed as follows. The results are as follows. Mass spectrometry by gas chromatography (CI method) Molecular ion (M-1): 443 Mass spectrometry by gas chromatography (EI method) m / e (spectral intensity (%)): 442 (10.2)
1), 355 (18.40), 221 (100), 17
9 (48.31), 133 (41.53) Proton nuclear magnetic resonance analysis ( 1 H-NMR) (solvent: deuterated chloroform) δ ( 1 H / ppm): 0.869 (t, 6H), 1.4 ~
1.90 (m, 28H), 2.025 (m, 4H),
3.943 (t, 4H) isotope carbon nuclear magnetic resonance analysis (< 13 > C-NMR) (solvent:
Deuterated chloroform) δ 13 C / ppm): 10.341, 22.038,
28.607, 34.385, 36.907, 3
6.949, 38.671, 41.713, 6
5.625, 178.210 Fourier transform infrared absorption analysis (FT-IR, diffuse reflection method) Absorption (cm -1 ): 1726.6 carbonyl compound (ester) As a result of the above analysis, the obtained product is represented by the following formula ( IV) 3,3'-di-n-propoxycarbonyl-1,1'-
It was identified as Biadamantane.
【００１６】[0016]
【化５】 Embedded image
【００１７】（２）３，３’−ジｎ−プロポキシカルボ
ニル−１，１’−ビアダマンタンの溶解性 上記（１）で得られた３，３’−ジｎ−プロポキシカル
ボニル−１，１’−ビアダマンタン０．５ｇを、２−ヘ
プタノン１ミリリットル、２−ヘキサノン１ミリリット
ル、乳酸メチル１ミリリットル、乳酸エチル１ミリリッ
トル、エチレングリコールメチルエーテルアセテート１
ミリリットル、又はプロピレングリコールメチルエーテ
ルアセテート１ミリリットルに添加したところ、いずれ
も容易に溶解した。(2) Solubility of 3,3'-di-n-propoxycarbonyl-1,1'-biadamantane 3,3'-Di-n-propoxycarbonyl-1,1 'obtained in the above (1) 0.5 g of Viadamantane was added to 1 ml of 2-heptanone, 1 ml of 2-hexanone, 1 ml of methyl lactate, 1 ml of ethyl lactate, and 1 ml of ethylene glycol methyl ether acetate.
Both were readily dissolved when added to milliliters or 1 milliliter of propylene glycol methyl ether acetate.
【００１８】比較例 （１）３，３’−ジメトキシカルボニル−１，１’−ビ
アダマンタンの合成 上記実施例において、ｎ−プロパノールの代わりにメタ
ノールを使用し、反応液にメタノールを加えてろ過し、
ろ液を濃縮してメタノールにより再結晶した以外は、実
施例と同様の操作を行って、収量０．３５ｇ、純度９
８．５％の３，３’−ジメトキシカルボニル−１，１’
−ビアダマンタンを得た。 （２）３，３’−ジメトキシカルボニル−１，１’−ビ
アダマンタンの溶解性 上記（１）で得られた３，３’−ジメトキシカルボニル
−１，１’−ビアダマンタン０．１ｇを、２−ヘキサノ
ン１ミリリットル、乳酸メチル１ミリリットル、乳酸エ
チル１ミリリットル、エチレングリコールメチルエーテ
ルアセテート１ミリリットル、又はプロピレングリコー
ルメチルエーテルアセテート１ミリリットルに添加した
ところ、いずれも殆ど溶解しなかった。Comparative Example (1) Synthesis of 3,3'-dimethoxycarbonyl-1,1'-biadamantane In the above example, methanol was used in place of n-propanol, and methanol was added to the reaction solution, followed by filtration. ,
The same operation as in the example was carried out except that the filtrate was concentrated and recrystallized from methanol, yield 0.35 g, purity 9
8.5% of 3,3′-dimethoxycarbonyl-1,1 ′
-Viadamantane was obtained. (2) Solubility of 3,3′-dimethoxycarbonyl-1,1′-biadamantane 0.1 g of 3,3′-dimethoxycarbonyl-1,1′-biadamantane obtained in the above (1) was mixed with 0.1 g of 2 When added to 1 ml of hexanone, 1 ml of methyl lactate, 1 ml of ethyl lactate, 1 ml of ethylene glycol methyl ether acetate or 1 ml of propylene glycol methyl ether acetate, none of them was dissolved.
【００１９】[0019]
【発明の効果】本発明の新規なビアダマンタン誘導体で
ある３，３’−ジアルコキシカルボニル−１，１’−ビ
アダマンタンは、耐熱性、耐水性及び光学特性などに優
れる共に、各種溶剤に対する溶解性に優れたものであ
る。そのため、多様な用途展開が可能であり、例えば光
ディスク基盤、光ファイバー、レンズ等の光学材料、さ
らには有機薬品の中間体などとしても広く利用すること
ができる。The novel biadamantane derivative of the present invention, 3,3'-dialkoxycarbonyl-1,1'-biadamantane, is excellent in heat resistance, water resistance, optical properties and the like, and is soluble in various solvents. It has excellent properties. Therefore, it can be used in a variety of applications, and can be widely used as optical materials such as optical disk substrates, optical fibers, and lenses, and as intermediates for organic chemicals.
Claims (2)
される新規なビアダマンタン誘導体。1. A compound of the general formula (I) (Wherein, R represents an alkyl group having 2 to 8 carbon atoms.) A novel biadamantane derivative represented by the formula:
ｎ−プロピル基，イソプロピル基，ｎ−ブチル基，イソ
ブチル基，ｓｅｃ−ブチル基，ｔｅｒｔ−ブチル基，ｎ
−アミル基，イソアミル基，ｎ−ヘキシル基，ｎ−ヘプ
チル基，ｎ−オクチル基又はイソオクチル基である請求
項１記載のビアダマンタン誘導体。2. R in the general formula (I) is an ethyl group,
n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n
2. The biadamantane derivative according to claim 1, which is -amyl, isoamyl, n-hexyl, n-heptyl, n-octyl or isooctyl.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000065930A JP2001253853A (en) | 2000-03-10 | 2000-03-10 | New biadamantane derivative |
| PCT/JP2001/000355 WO2001055063A1 (en) | 2000-01-25 | 2001-01-19 | Novel bisadamantane compounds, process for preparing the same, and novel biadamantane derivatives |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000065930A JP2001253853A (en) | 2000-03-10 | 2000-03-10 | New biadamantane derivative |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001253853A true JP2001253853A (en) | 2001-09-18 |
Family
ID=18585375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000065930A Pending JP2001253853A (en) | 2000-01-25 | 2000-03-10 | New biadamantane derivative |
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| Country | Link |
|---|---|
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007269727A (en) * | 2006-03-31 | 2007-10-18 | Sumitomo Bakelite Co Ltd | Biadamantane compound |
| JP2014009171A (en) * | 2012-06-28 | 2014-01-20 | Mitsubishi Gas Chemical Co Inc | Process for producing hydroxy adamantane carboxylic acid compound |
-
2000
- 2000-03-10 JP JP2000065930A patent/JP2001253853A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007269727A (en) * | 2006-03-31 | 2007-10-18 | Sumitomo Bakelite Co Ltd | Biadamantane compound |
| JP2014009171A (en) * | 2012-06-28 | 2014-01-20 | Mitsubishi Gas Chemical Co Inc | Process for producing hydroxy adamantane carboxylic acid compound |
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