JP2003306469A - New ester compound of adamantanecarboxylic acid - Google Patents
New ester compound of adamantanecarboxylic acidInfo
- Publication number
- JP2003306469A JP2003306469A JP2002115712A JP2002115712A JP2003306469A JP 2003306469 A JP2003306469 A JP 2003306469A JP 2002115712 A JP2002115712 A JP 2002115712A JP 2002115712 A JP2002115712 A JP 2002115712A JP 2003306469 A JP2003306469 A JP 2003306469A
- Authority
- JP
- Japan
- Prior art keywords
- group
- tricyclo
- compound
- bis
- decane
- 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.)
- Granted
Links
- -1 ester compound Chemical class 0.000 title claims abstract description 54
- JIMXXGFJRDUSRO-UHFFFAOYSA-N adamantane-1-carboxylic acid Chemical compound C1C(C2)CC3CC2CC1(C(=O)O)C3 JIMXXGFJRDUSRO-UHFFFAOYSA-N 0.000 title abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 11
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- PAVQGHWQOQZQEH-UHFFFAOYSA-N adamantane-1,3-dicarboxylic acid Chemical compound C1C(C2)CC3CC1(C(=O)O)CC2(C(O)=O)C3 PAVQGHWQOQZQEH-UHFFFAOYSA-N 0.000 claims description 4
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000654 additive Substances 0.000 abstract description 7
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 5
- 239000003905 agrochemical Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 2
- 150000001875 compounds Chemical class 0.000 description 25
- 238000005886 esterification reaction Methods 0.000 description 14
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 13
- 238000000034 method Methods 0.000 description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical group CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- AMYRYTZWSMZCSD-UHFFFAOYSA-N C1CC2C3CCC(C3)(C2(C1)COC(=O)C45CC6CC(C4)CC(C6)C5)COC(=O)C78CC9CC(C7)CC(C9)C8 Chemical compound C1CC2C3CCC(C3)(C2(C1)COC(=O)C45CC6CC(C4)CC(C6)C5)COC(=O)C78CC9CC(C7)CC(C9)C8 AMYRYTZWSMZCSD-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- MIBQYWIOHFTKHD-UHFFFAOYSA-N adamantane-1-carbonyl chloride Chemical compound C1C(C2)CC3CC2CC1(C(=O)Cl)C3 MIBQYWIOHFTKHD-UHFFFAOYSA-N 0.000 description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- DPSKBNVJTHNAQE-UHFFFAOYSA-N C12(CC3CC(CC(C1)C3)C2)C(=O)OCC23C1(CCC(C3CCC2)C1)CO Chemical compound C12(CC3CC(CC(C1)C3)C2)C(=O)OCC23C1(CCC(C3CCC2)C1)CO DPSKBNVJTHNAQE-UHFFFAOYSA-N 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 150000005690 diesters Chemical class 0.000 description 1
- 229940052761 dopaminergic adamantane derivative Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000006606 n-butoxy group Chemical group 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 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 description 1
- 125000001298 n-hexoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000005920 sec-butoxy group Chemical group 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 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】本発明は新規なアダマンタン
カルボン酸エステル化合物に関し、より詳しくはフォト
レジスト添加剤を始めとして、医薬・農薬中間体、樹脂
添加剤（特に耐熱向上剤）等として有用なアダマンタン
カルボン酸エステル化合物に関する。TECHNICAL FIELD The present invention relates to a novel adamantane carboxylic acid ester compound, and more specifically, to adamantane useful as photoresist additives, pharmaceutical / agrochemical intermediates, resin additives (especially heat resistance improver), etc. It relates to a carboxylic acid ester compound.
【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、光ファイバー又はレンズ等に用い
られている（特開平９−３０２０７７号公報、特開平６
−３０５０４４号公報等）。また、アダマンタンエステ
ル類は、その酸感応性と紫外線に対する透明性を利用し
て、フォトレジスト添加剤として利用されている。本発
明者らは、従来から、ジカルボン酸ジアダマンチル類化
合物（特開２００１−７２６４５公報）、（ビス）アダ
マンタン系化合物（特開２００１−２０６８５９公報）
及びビスアダマンタン誘導体（特開２００１−２５３８
５３公報）等のアダマンタン誘導体を研究してきた。こ
れらは、何れもアダマンタン骨格が直接或いは幾つかの
炭素結合又はエステル結合を介して、２個のアダマンタ
ン骨格が結合した化合物であるが、アダマンタン骨格と
脂環式化合物が一つ又は二つのエステル結合でつながっ
たアダマンタンカルボン酸エステル化合物は知られてい
ない。2. Description of the Related Art Conventionally, adamantanes have a very stable carbon skeleton and exhibit a unique function, so that they can be used for various purposes. Especially, due to their optical characteristics and heat resistance, optical disk substrates, optical fibers or Used in lenses and the like (Japanese Patent Laid-Open Nos. 9-302077 and 6)
-305044 gazette etc.). Further, adamantane esters are used as photoresist additives by utilizing their acid sensitivity and transparency to ultraviolet rays. The inventors of the present invention have heretofore used diadamantyl dicarboxylic acid compounds (JP 2001-72645 A) and (bis) adamantane compounds (JP 2001-206859 A).
And a bisadamantane derivative (JP 2001-2538A).
53) and other adamantane derivatives have been studied. These are compounds in which two adamantane skeletons are bonded to each other either directly or through some carbon bonds or ester bonds, but the adamantane skeleton and the alicyclic compound are one or two ester bonds. The adamantane carboxylic acid ester compound linked by is not known.
【０００３】[0003]
【発明が解決しようとする課題】本発明は、このような
状況下でなされたもので、非常に安定な炭素骨格を有す
ると共に、その酸感応性と紫外線に対する透明性を利用
して、フォトレジスト添加剤を始めとして種々の用途が
期待される新規なアダマンタンカルボン酸エステル化合
物を提供することを目的とするものである。SUMMARY OF THE INVENTION The present invention has been made under such circumstances and has a very stable carbon skeleton, and by utilizing its acid sensitivity and transparency to ultraviolet rays, it can be used as a photoresist. It is an object of the present invention to provide a novel adamantanecarboxylic acid ester compound which is expected to have various uses including additives.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、前記目的
を達成するために鋭意研究を重ねた結果、アダマンタン
骨格とトリシクロ［５．２．１．０2,6］デカン骨格か
らなるアダマンタンカルボン酸エステル化合物は新規な
化合物であって、上記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。即ち、本発明の要旨は下記のとおりである。
１．下記一般式（１）Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that adamantane composed of an adamantane skeleton and a tricyclo [5.2.1.0 2,6 ] decane skeleton. It was found that the carboxylic acid ester compound is a novel compound and can meet the above purpose. The present invention has been completed based on such findings. That is, the gist of the present invention is as follows. 1. The following general formula (1)
【０００５】[0005]
【化４】 [Chemical 4]
【０００６】（式中、Ｘ1及びＸ2は、それぞれ水素原
子、ハロゲン原子、炭素数１〜８のアルキル基、水酸
基、炭素数１〜８のアルコキシ基、カルボキシル基又は
ＣＯＯＲ1（Ｒ1は、炭素数１〜８のアルキル基）を示
し、それらはたがいに同一でも異なっていてもよい。）
で表されるビス（１−アダマンチルカルボニロキシメチ
ル）トリシクロ［５．２．１．０2,6］デカン化合物。
２．Ｘ1及びＸ2が水素原子である前記１記載のビス（１
−アダマンチルカルボニロキシメチル）トリシクロ
［５．２．１．０2,6］デカン化合物。
３．下記一般式（２）又は（３）(Wherein X 1 and X 2 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group or COOR 1 (R 1 is , An alkyl group having 1 to 8 carbon atoms), which may be the same or different.
A bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound represented by: 2. Bis (1) according to 1 above, wherein X 1 and X 2 are hydrogen atoms.
An adamantyl carbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound. 3. The following general formula (2) or (3)
【０００７】[0007]
【化５】 [Chemical 5]
【０００８】（式中、Ｘ3は、水素原子、ハロゲン原
子、炭素数１〜８のアルキル基、水酸基、炭素数１〜８
のアルコキシ基、カルボキシル基又はＣＯＯＲ2（Ｒ
2は、炭素数１〜８のアルキル基）を示す。）で表され
る（１−アダマンチルカルボニロキシメチル）（ヒドロ
キシメチル）トリシクロ［５．２．１．０2,6］デカン
化合物。
４．Ｘ3が水素原子である前記３記載の（１−アダマン
チルカルボニロキシメチル）（ヒドロキシメチル）トリ
シクロ［５．２．１．０2,6］デカン化合物。
５．下記一般式（４），（５）又は（６）(In the formula, X 3 is a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, or 1 to 8 carbon atoms.
Alkoxy group, carboxyl group or COOR 2 (R
2 represents an alkyl group having 1 to 8 carbon atoms). (1-adamantyl carbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound represented by the formula: 4. The (1-adamantylcarbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound described in 3 above, wherein X 3 is a hydrogen atom. 5. The following general formula (4), (5) or (6)
【０００９】[0009]
【化６】 [Chemical 6]
【００１０】で表される１，３−アダマンタンジカルボ
ン酸ビス（ヒドロキシメチルトリシクロ［５．２．１．
０2,6］デシル化合物。1,3-adamantanedicarboxylic acid bis (hydroxymethyltricyclo [5.2.1.
0 2,6 ] decyl compound.
【００１１】[0011]
【発明の実施の形態】以下に、本発明について、詳細に
説明する。まず、前記一般式（１）で表される、本願第
一発明のビス（１−アダマンチルカルボニロキシメチ
ル）トリシクロ［５．２．１．０2,6］デカン化合物に
ついて説明する。前記一般式（１）において、Ｘ1及び
Ｘ2のハロゲン原子としては、具体的には、塩素原子、
臭素原子、ヨウ素原子を挙げることができる。Ｘ1及び
Ｘ2の炭素数１〜８のアルキル基（直鎖又は分岐アルキ
ル基）としては、具体的には、メチル基、エチル基、ｎ
−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｉ−ブ
チル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−
アミル基、ｉ−アミル基、ｎ−ヘキシル基、ｉ−ヘキシ
ル基、ｎ−ヘプチル基、ｉ−ヘプチル基、ｎ−オクチル
基、ｉ−オクチル基又は２−エチル−ヘキシル基等を挙
げることができるBEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. First, the bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound represented by the general formula (1) of the first invention of the present application will be described. In the general formula (1), the halogen atom of X 1 and X 2 is specifically a chlorine atom,
Examples thereof include a bromine atom and an iodine atom. Specific examples of the alkyl group having 1 to 8 carbon atoms (straight or branched alkyl group) for X 1 and X 2 include a methyl group, an ethyl group, and n.
-Propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-
Examples thereof include amyl group, i-amyl group, n-hexyl group, i-hexyl group, n-heptyl group, i-heptyl group, n-octyl group, i-octyl group and 2-ethyl-hexyl group.
【００１２】Ｘ1及びＸ2の炭素数１〜８のアルコキシ基
としては、具体的には、メトキシ基、エトキシ基、ｎ−
プロポキシ基、ｉ−プロポキシ基、ｎ−ブトキシ基、ｉ
−ブトキシブチル基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−
ブトキシ基、ｎ−ペントキシ基、ｉ−ペントキシ基、ｎ
−ヘキソキシ基、ｉ−ヘキソキシ基、ｎ−ヘプトキシ
基、ｉ−ヘプトキシ基、ｎ−オクトキシ基、ｉ−オクト
キシ基又は２−エチル−ヘキソキシ基等を挙げることが
できる。Ｘ1及びＸ2のＣＯＯＲ1［Ｒ1は、炭素数１〜８
のアルキル基（直鎖又は分岐アルキル基）］を示す。）
としては、具体的には、ＣＯＯＣＨ3 、ＣＯＯＣ
2Ｈ5、ＣＯＯｎ−Ｃ3Ｈ7 、ＣＯＯｉ−Ｃ3Ｈ7 、ＣＯ
Ｏｎ−Ｃ4Ｈ9 、ＣＯＯｉ−Ｃ4Ｈ9 、ＣＯＯｓｅｃ−
Ｃ4Ｈ9 、ＣＯＯｔｅｒｔ−Ｃ4Ｈ9 、ＣＯＯｎ−Ｃ5
Ｈ11 、ＣＯＯｉ−Ｃ5Ｈ11 、ＣＯＯｎ−Ｃ6Ｈ13 、
ＣＯＯｉ−Ｃ6Ｈ13、ＣＯＯｎ−Ｃ7Ｈ15、ＣＯＯｉ−Ｃ
7Ｈ15、ＣＯＯｎ−Ｃ8Ｈ17、及びＣＯＯｉ−Ｃ8Ｈ17等
を挙げることができる。Specific examples of the alkoxy group having 1 to 8 carbon atoms for X 1 and X 2 include methoxy group, ethoxy group and n-
Propoxy group, i-propoxy group, n-butoxy group, i
-Butoxybutyl group, sec-butoxy group, tert-
Butoxy group, n-pentoxy group, i-pentoxy group, n
-Hexoxy group, i-hexoxy group, n-heptoxy group, i-heptoxy group, n-octoxy group, i-octoxy group, 2-ethyl-hexoxy group and the like can be mentioned. COOR 1 of X 1 and X 2 [R 1 has 1 to 8 carbon atoms
Of alkyl group (straight chain or branched alkyl group)]. )
Specifically, COOCH 3 , COOC
2 H 5 , COOn-C 3 H 7 , COOi-C 3 H 7 , CO
On-C 4 H 9, COOi -C 4 H 9, COOsec-
C 4 H 9, COOtert-C 4 H 9, COOn-C 5
H 11, COOi-C 5 H 11, COOn-C 6 H 13,
COOi-C 6 H 13, COOn -C 7 H 15, COOi-C
It may be mentioned 7 H 15, COOn-C 8 H 17, and COOi-C 8 H 17 and the like.
【００１３】なお、前記一般式（１）において、Ｘ1及
びＸ2のアダマンタン骨格への結合位置は、１位（橋頭
部，３級炭素）あるいは２位（橋かけ部，２級炭素）の
いずれでもよい。前記一般式（１）のビス（１−アダマ
ンチルカルボニロキシメチル）トリシクロ［５．２．
１．０2,6］デカン化合物のなかで、Ｘ1及びＸ2が共に
水素原子であるビス（１−アダマンチルカルボニロキシ
メチル）トリシクロ［５．２．１．０2,6］デカンが化
合物の性質及び化合物の製造し易さの点で好ましい。In the general formula (1), the bonding position of X 1 and X 2 to the adamantane skeleton is at the 1-position (bridge head, tertiary carbon) or 2-position (bridge portion, secondary carbon). Either is fine. Bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.
Among the [1.0 2,6 ] decane compounds, bis (1-adamantyl carbonoxymethyl) tricyclo [5.2.1.0 2,6 ] decane in which both X 1 and X 2 are hydrogen atoms is a compound. And the ease of producing the compound are preferred.
【００１４】本願第一発明のビス（１−アダマンチルカ
ルボニロキシメチル）トリシクロ［５．２．１．
０2,6］デカン化合物の製造方法としては特に制限はな
いが、以下に示す方法に従えば、効率よく製造すること
ができる。その方法として、例えば、下記の二つの方法
が採用できる。
ビス（ヒドロキシメチル）トリシクロ［５．２．１．
０2,6］デカン（以下、トリシクロデカン化合物と略
す。）のリチオ化物とＸ1置換１−アダマンタンカルボ
ン酸ハライドとのエステル化反応
塩基存在下におけるトリシクロデカン化合物とＸ1置
換１−アダマンタンカルボン酸ハライドとのエステル化
反応Bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.
The method for producing the 0 2,6 ] decane compound is not particularly limited, but can be efficiently produced according to the following method. As the method, for example, the following two methods can be adopted. Bis (hydroxymethyl) tricyclo [5.2.1.
0 2,6] decane (hereinafter, referred to as tricyclodecane compound.) Tricyclodecane compound in the esterification reaction the presence of a base with lithio compound and the X 1 substituent adamantane carboxylic acid halide and X 1 substituted 1-adamantane Esterification reaction with carboxylic acid halide
【００１５】の方法については、まずトリシクロデカ
ン化合物（異性体混合物）をリチウム金属、ｎ−ブチル
リチウム、ｓｅｃ−ブチルリチウム、ｔｅｒｔ−ブチル
リチウム等のリチオ化剤でリチオ化する。生成したリチ
オ化物に対するＸ1置換１−アダマンタンカルボン酸ハ
ライドのモル比を２〜１０に調整してエステル化を行
う。そのエステル化反応の条件については、反応温度は
通常−７８〜１００℃、好ましくは−７８〜室温、反応
圧力は通常０．１〜１０ＭＰａ（Ｇ）、反応時間は通常
１〜２４時間、好ましくは３〜６時間である。溶媒は特
に必要ではないが、使用した方が好ましい。その場合の
溶媒としては、ヘキサン、ヘプタン、オクタン等の脂肪
族炭化水素、ベンゼン、トルエン、キシレン等の芳香族
炭化水素、ジエチルエーテル、テトラヒドロフラン、ジ
オキサン等のエーテル系化合物を挙げることができる。
溶媒を使用する場合の原料濃度は、特に制限はなく、飽
和溶解度までを採用できるが、好ましくは０．５〜１．
０モル／リットルである。In the method (1), a tricyclodecane compound (isomer mixture) is first lithiated with a lithiating agent such as lithium metal, n-butyllithium, sec-butyllithium or tert-butyllithium. The esterification is carried out by adjusting the molar ratio of the X 1 -substituted 1-adamantanecarboxylic acid halide to the produced lithiated product to 2 to 10. Regarding the conditions of the esterification reaction, the reaction temperature is usually −78 to 100 ° C., preferably −78 to room temperature, the reaction pressure is usually 0.1 to 10 MPa (G), the reaction time is usually 1 to 24 hours, preferably 3 to 6 hours. A solvent is not particularly required, but it is preferable to use it. Examples of the solvent in that case include aliphatic hydrocarbons such as hexane, heptane, and octane, aromatic hydrocarbons such as benzene, toluene, and xylene, and ether compounds such as diethyl ether, tetrahydrofuran, and dioxane.
The concentration of the raw material when a solvent is used is not particularly limited and may be up to the saturated solubility, but preferably 0.5 to 1.
It is 0 mol / liter.
【００１６】の方法については、トリシクロデカン化
合物（異性体混合物）に対するＸ1置換１−アダマンタ
ンカルボン酸ハライドのモル比を２〜１０に調整して塩
基存在下エステル化を行う。塩基として、トリメチルア
ミン、トリエチルアミン、ピリジン、Ｎ，Ｎ−ジメチル
アニリンを挙げることができる。エステル化反応の条件
については、反応温度は通常−７８〜１００℃、好まし
くは−７８〜室温、反応圧力は通常０．１〜１０ＭＰａ
（Ｇ）、反応時間は通常１〜２４時間、好ましくは３〜
６時間である。溶媒は特に必要ではないが、使用した方
が好ましい。その場合の溶媒としては、ヘキサン、ヘプ
タン、オクタン等の脂肪族炭化水素、ベンゼン、トルエ
ン、キシレン等の芳香族炭化水素、ジクロロメタン、ク
ロロホルム、四塩化炭素、１，２−ジクロロエタン等の
ハロゲン系化合物、ジエチルエーテル、テトラヒドロフ
ラン、ジオキサン等のエーテル系化合物を挙げることが
できる。溶媒を使用する場合の原料濃度は、特に制限は
なく、飽和溶解度までを採用できるが、好ましくは０．
５〜１．０モル／リットルである。なお、前記一般式
（１）で表されるビス（１−アダマンチルカルボニロキ
シメチル）トリシクロ［５．２．１．０2,6］デカン化
合物の混合ジエステルを製造する場合には置換１−アダ
マンタンカルボン酸ハライドを二種類使用すればよい。In the method ( 1 ), the esterification is carried out in the presence of a base by adjusting the molar ratio of the X 1 -substituted 1-adamantanecarboxylic acid halide to the tricyclodecane compound (isomer mixture) to 2 to 10. Examples of the base include trimethylamine, triethylamine, pyridine and N, N-dimethylaniline. Regarding the conditions of the esterification reaction, the reaction temperature is usually −78 to 100 ° C., preferably −78 to room temperature, and the reaction pressure is usually 0.1 to 10 MPa.
(G), the reaction time is usually 1 to 24 hours, preferably 3 to
6 hours. A solvent is not particularly required, but it is preferable to use it. As the solvent in that case, hexane, heptane, aliphatic hydrocarbons such as octane, benzene, toluene, aromatic hydrocarbons such as xylene, dichloromethane, chloroform, carbon tetrachloride, halogen compounds such as 1,2-dichloroethane, Examples thereof include ether compounds such as diethyl ether, tetrahydrofuran and dioxane. The concentration of the raw material when a solvent is used is not particularly limited and may be up to the saturated solubility, but is preferably 0.
5 to 1.0 mol / liter. In the case of producing a mixed diester of bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound represented by the general formula (1), substituted 1-adamantane is used. Two kinds of carboxylic acid halides may be used.
【００１７】次いで、前記一般式（２）又は（３）で表
される、本願第二発明の（１−アダマンチルカルボニロ
キシメチル）（ヒドロキシメチル）トリシクロ［５．
２．１．０2,6］デカン化合物について説明する。前記
一般式（２）又は（３）において、Ｘ3は前記Ｘ1とＸ2
の説明と同様である。また、Ｒ2もＲ1の説明と同様であ
る。なお、前記一般式（２）又は（３）において、Ｘ3
のアダマンタン骨格への結合位置は、１位（橋頭部，３
級炭素）あるいは２位（橋かけ部，２級炭素）のいずれ
でもよい。前記一般式（２）又は（３）の（１−アダマ
ンチルカルボニロキシメチル）（ヒドロキシメチル）ト
リシクロ［５．２．１．０2,6］デカン化合物のなか
で、Ｘ3が水素原子である（１−アダマンチルカルボニ
ロキシメチル）（ヒドロキシメチル）トリシクロ［５．
２．１．０2,6］デカンが化合物の性質及び化合物の製
造し易さの点で好ましい。Then, the (1-adamantyl carbonyloxymethyl) (hydroxymethyl) tricyclo [5.
2.1.0 2,6 ] decane compound will be described. In the general formula (2) or (3), X 3 is the same as X 1 and X 2.
Is the same as the description above. Further, R 2 is the same as the description of R 1 . In the general formula (2) or (3), X 3
The position of the bond to the adamantane skeleton is 1 (bridge head, 3
Primary carbon) or the second rank (bridge, secondary carbon). In the (1-adamantylcarbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound of the general formula (2) or (3), X 3 is a hydrogen atom. (1-adamantyl carbonyloxymethyl) (hydroxymethyl) tricyclo [5.
2.1.0 2,6 ] decane is preferable in terms of the properties of the compound and the ease of producing the compound.
【００１８】本願第二発明の（１−アダマンチルカルボ
ニロキシメチル）（ヒドロキシメチル）トリシクロ
［５．２．１．０2,6］デカン化合物の製造方法として
は特に制限はないが、以下に示す方法に従えば、効率よ
く製造することができる。その方法として、例えば、下
記の二つの方法が採用できる。
ビス（ヒドロキシメチル）トリシクロ［５．２．１．
０2,6］デカン（以下、トリシクロデカン化合物と略
す。）のリチオ化物とＸ3置換１−アダマンタンカルボ
ン酸ハライドとのエステル化反応
塩基存在下におけるトリシクロデカン化合物とＸ3置
換１−アダマンタンカルボン酸ハライドとのエステル化
反応
上記の方法において、トリシクロデカン化合物（異性
体混合物）のリチオ化物とＸ3置換１−アダマンタンカ
ルボン酸ハライドとのモル比を約１に調整し、上記の
方法において、トリシクロデカン化合物（異性体混合
物）とＸ3置換１−アダマンタンカルボン酸ハライドと
のモル比を約１に調整してエステル化反応を行えばよ
い。それ以外のエステル化反応の反応条件は、は前記
と同様であり、は前記と同様である。The method for producing the (1-adamantylcarbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound of the second invention of the present application is not particularly limited, but is shown below. According to the method, it can be manufactured efficiently. As the method, for example, the following two methods can be adopted. Bis (hydroxymethyl) tricyclo [5.2.1.
0 2,6] decane (hereinafter, referred to as tricyclodecane compound.) Tricyclodecane compound in the esterification reaction the presence of a base with lithio compound and the X 3 substituent adamantane carboxylic acid halide and X 3 substituted 1-adamantane Esterification reaction with carboxylic acid halide In the above method, the molar ratio of the lithiated product of the tricyclodecane compound (isomer mixture) to the X 3 -substituted 1-adamantane carboxylic acid halide is adjusted to about 1, and The esterification reaction may be carried out by adjusting the molar ratio of the tricyclodecane compound (isomer mixture) to the X 3 -substituted 1-adamantanecarboxylic acid halide to about 1. Other reaction conditions of the esterification reaction are the same as those described above, and are the same as those described above.
【００１９】最後に前記一般式（４），（５）又は
（６）で表される本願第三発明の１，３−アダマンタン
ジカルボン酸ビス（ヒドロキシメチルトリシクロ［５．
２．１．０2,6］デシル化合物について説明する。本願
第三発明の１，３−アダマンタンジカルボン酸ビス（ヒ
ドロキシメチルトリシクロ［５．２．１．０2,6］デシ
ル化合物の製造方法としては特に制限はないが、以下に
示す方法に従えば、効率よく製造することができる。そ
の方法として、例えば、下記の二つの方法が採用でき
る。
ビス（ヒドロキシメチル）トリシクロ［５．２．１．
０2,6］デカン（以下、トリシクロデカン化合物と略
す。）のリチオ化物と１，３−アダマンタンカルボン酸
ジハライドとのエステル化反応
塩基存在下におけるトリシクロデカン化合物と１，３
−アダマンタンカルボン酸ジハライドとのエステル化反
応
上記の方法において、１，３−アダマンタンカルボン
酸ジハライドに対するトリシクロデカン化合物（異性体
混合物）のリチオ化物とのモル比を２〜１０に調整し
て、上記の方法において、１，３−アダマンタンカル
ボン酸ジハライドに対するトリシクロデカン化合物（異
性体混合物）とのモル比を２〜１０に調整してエステル
化反応を行えばよい。それ以外のエステル化反応の反応
条件は、は前記と同様であり、は前記と同様で
ある。Lastly, 1,3-adamantanedicarboxylic acid bis (hydroxymethyltricyclo [5.0.5] of the third invention of the present application represented by the general formula (4), (5) or (6).
2.1.0 2,6 ] decyl compound will be described. The method for producing the 1,3-adamantanedicarboxylic acid bis (hydroxymethyltricyclo [5.2.1.0 2,6 ] decyl compound of the third invention of the present application is not particularly limited, but according to the method shown below, For example, the following two methods can be adopted: bis (hydroxymethyl) tricyclo [5.2.1.
0 2,6] decane (hereinafter, referred to as tricyclodecane compound.) Tricyclodecane compound in the esterification reaction the presence of a base with lithio compound with 1,3-adamantane carboxylic acid dihalides and 1,3
-Esterification reaction with adamantanecarboxylic acid dihalide In the above method, the molar ratio of the tricyclodecane compound (isomer mixture) to the lithiation product of 1,3-adamantanecarboxylic acid dihalide is adjusted to 2 to 10, In the above method, the esterification reaction may be performed by adjusting the molar ratio of the tricyclodecane compound (isomer mixture) to 1,3-adamantanecarboxylic acid dihalide to 2 to 10. Other reaction conditions of the esterification reaction are the same as those described above, and are the same as those described above.
【００２０】[0020]
【実施例】次に、本発明を実施例により、更に詳しく説
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］：ビス（１−アダマンチルカルボニロキシ
メチル）トリシクロ［５．２．１．０2,6］デカンの合
成
３００ミリリットルのナス型フラスコに、ビス（ヒドロ
キシメチル）トリシクロ［５．２．１．０2.6］デカン
［分子量：１９６．２９、２０．１ｇ（１０２ミリモ
ル）］を入れ、テトラヒドロフラン１００ミリリットル
で溶解させた。次に、フラスコを氷浴につけ、摘下ロー
トより１−アダマンタンカルボン酸クロライド［分子
量：１９８．６９、４１．２ｇ（２０７ミリモル）］を
滴下し、続いて、トリエチルアミン［分子量：１０１．
１９、密度：０．７２７、３４．５ミリリットル（２４
８ミリモル）］を数分間かけてゆっくり添加した。添加
後、１０分後に氷浴を外して室温で更に一晩反応させ
た。その後、反応混合物をグラスフィルターでろ過した
後、５０ミリリットルの水で４回洗浄し、無水硫酸ナト
リウムで乾燥させた。乾燥後の溶液をエバポレーターで
の濃縮後、ガラスチューブオーブンでの精製により目的
物のビス（１−アダマンチルカルボニロキシメチル）ト
リシクロ［５．２．１．０2,6］デカンを得た。
収量：４１．２ｇ(分子量：５２０．７５、７９．１ミ
リモル)、収率：７７．２％、純度（ＧＣ）：９５．０
％EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 Synthesis of bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane In a 300 ml eggplant-shaped flask, bis (hydroxymethyl) tricyclo [5.2]. .1.0 2.6 ] decane [molecular weight: 196.29, 20.1 g (102 mmol)] was added and dissolved in 100 ml of tetrahydrofuran. Next, the flask was placed in an ice bath, 1-adamantanecarboxylic acid chloride [molecular weight: 198.69, 41.2 g (207 mmol)] was added dropwise from the dropping funnel, and then triethylamine [molecular weight: 101.
19, density: 0.727, 34.5 ml (24
8 mmol)] was added slowly over a few minutes. After 10 minutes from the addition, the ice bath was removed and the reaction was continued at room temperature overnight. Then, the reaction mixture was filtered through a glass filter, washed with 50 ml of water four times, and dried over anhydrous sodium sulfate. The dried solution was concentrated with an evaporator and then purified with a glass tube oven to obtain bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane as a target substance. Yield: 41.2 g (molecular weight: 520.75, 79.1 mmol), yield: 77.2%, purity (GC): 95.0.
%
【００２１】（測定データ）
・核磁気共鳴スペクトル（ＮＭＲ）＝CDCl3 1
HNMR(270MHz):0.86〜0.99(m,1H),1.18〜1.32(m,1H),1.
36〜1.57(m,4H),1.71(br s,16H),1.89(br s,14H),2.01
(br s,6H),2.28〜2.48(m,2H),3.77〜3.94(m,4H)13
C-NMR(68MHz):24,58(CH2),25.44(CH2),27.50(CH2),2
7.72(CH2),27.78(CH2),28.02(CH),28.28(CH2),29.17(CH
2),30.42(CH2),30.79(CH2),32.41(CH2),32.72(CH2),32.
86(CH),33.43(CH),34.28(CH),34.41(CH),36.56(CH2),3
8.54(CH),38.91(CH2),38.98(CH2),39.30(CH),39.39(C
H2),40.30(CH2),40.39(CH),40.52(CH2),40.74(C),40.79
(C),40.83(C),40.99(CH),41.37(CH),41.50(CH),41.65(C
H2),41.84(CH),43.00(CH),43.11(CH),43.94(CH),44.46
(CH),44.59(CH),44.89(CH),45.00(CH),45.70(CH),45.83
(CH),49.10(CH),49.38(CH),67.00(CH2),67.20(CH2),67.
37(CH2),67.42(CH2),67.78(CH2),68.02(CH2),68.30(C
H2),177.43(C=O),177.47(C=O),177.53(C=O)
・赤外吸収スペクトル（ＩＲ）：ＫＢｒ
１７２７．３ｃｍ-1（Ｃ＝Ｏ）
・融点（ｍｐ）：ＤＳＣ
８４．７〜９９．９℃(Measurement Data) Nuclear Magnetic Resonance Spectrum (NMR) = CDCl 3 1 H NMR (270 MHz): 0.86 to 0.99 (m, 1H), 1.18 to 1.32 (m, 1H), 1.
36〜1.57 (m, 4H), 1.71 (br s, 16H), 1.89 (br s, 14H), 2.01
(br s, 6H), 2.28 to 2.48 (m, 2H), 3.77 to 3.94 (m, 4H) 13 C-NMR (68MHz): 24,58 (CH 2 ), 25.44 (CH 2 ), 27.50 (CH 2 ), 2
7.72 (CH 2 ), 27.78 (CH 2 ), 28.02 (CH), 28.28 (CH 2 ), 29.17 (CH
2), 30.42 (CH 2) , 30.79 (CH 2), 32.41 (CH 2), 32.72 (CH 2), 32.
86 (CH), 33.43 (CH), 34.28 (CH), 34.41 (CH), 36.56 (CH 2 ), 3
8.54 (CH), 38.91 (CH 2 ), 38.98 (CH 2 ), 39.30 (CH), 39.39 (C
H 2 ), 40.30 (CH 2 ), 40.39 (CH), 40.52 (CH 2 ), 40.74 (C), 40.79
(C), 40.83 (C), 40.99 (CH), 41.37 (CH), 41.50 (CH), 41.65 (C
H 2 ), 41.84 (CH), 43.00 (CH), 43.11 (CH), 43.94 (CH), 44.46
(CH), 44.59 (CH), 44.89 (CH), 45.00 (CH), 45.70 (CH), 45.83
(CH), 49.10 (CH), 49.38 (CH), 67.00 (CH 2 ), 67.20 (CH 2 ), 67.
37 (CH 2 ), 67.42 (CH 2 ), 67.78 (CH 2 ), 68.02 (CH 2 ), 68.30 (C
H 2 ), 177.43 (C = O), 177.47 (C = O), 177.53 (C = O) -infrared absorption spectrum (IR): KBr 1727.3 cm -1 (C = O) -melting point (mp): DSC 84.7-99.9 ° C
【００２２】［実施例２］：（１−アダマンチルカルボ
ニロキシメチル）（ヒドロキシメチル）トリシクロ
［５．２．１．０2,6］デカンの合成
３００ミリリットルのナス型フラスコに、ビス（ヒドロ
キシメチル）トリシクロ［５．２．１．０2.6］デカン
［分子量：１９６．２９、１９．４ｇ（９８．８ミリモ
ル）］を入れ、テトラヒドロフラン１００ミリリットル
で溶解させた。次に、フラスコを氷浴につけ、摘下ロー
トより１−アダマンタンカルボン酸クロライド［分子
量：１９８．６９、１９．７ｇ（９９．１ミリモル）］
を滴下し、続いて、トリエチルアミン［分子量：１０
１．１９、密度：０．７２７、１６．５ミリリットル
（１１９ミリモル）］を数分間かけてゆっくり添加し
た。添加後、１０分後に氷浴を外して室温で更に一晩反
応させた。その後、反応混合物をグラスフィルターでろ
過した後、５０ミリリットルの水で４回洗浄し、無水硫
酸ナトリウムで乾燥させた。乾燥後の溶液をエバポレー
ターでの濃縮後、ガラスチューブオーブンでの精製によ
り目的物の（１−アダマンチルカルボニロキシメチル）
（ヒドロキシメチル）トリシクロ［５．２．１．
０2,6］デカンを得た。
収量：１１．０ｇ(分子量：３５８．５２、３０．７ミ
リモル)、収率：３１．０％、純度（ＧＣ）：９９．２
％Example 2 Synthesis of (1-adamantylcarbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane In a 300 ml eggplant-shaped flask, bis (hydroxymethyl) was added. ) tricyclo [5.2.1.0 2.6] decane: put the molecular weight 196.29,19.4g (98.8 mmol)] was dissolved in tetrahydrofuran 100 ml. Next, the flask was placed in an ice bath, and 1-adamantanecarboxylic acid chloride [molecular weight: 198.69, 19.7 g (99.1 mmol)] was added from the dropping funnel.
Was added dropwise, followed by triethylamine [molecular weight: 10
1.19, density: 0.727, 16.5 ml (119 mmol)] was added slowly over a few minutes. After 10 minutes from the addition, the ice bath was removed and the reaction was continued at room temperature overnight. Then, the reaction mixture was filtered through a glass filter, washed with 50 ml of water four times, and dried over anhydrous sodium sulfate. The solution after drying was concentrated in an evaporator and then purified in a glass tube oven to give the desired product (1-adamantyl carbonyloxymethyl).
(Hydroxymethyl) tricyclo [5.2.1.
0 2,6 ] decane was obtained. Yield: 11.0 g (molecular weight: 358.52, 30.7 mmol), yield: 31.0%, purity (GC): 99.2
%
【００２３】（測定データ）
・核磁気共鳴スペクトル（ＮＭＲ）＝CDCl3 1
HNMR(270MHz):0.92〜0.93(m,1H),1.21〜1.25(m,1H),1.
35〜1.67(m,4H),1.71(br s,8H),1.89(br s,4H),2.01(br
s,6H),2.06〜2.18(m,1H),2.30〜2.50(m,2H),3.40〜3.5
2(m,2H),3.79〜3.91(m,2H)13
C-NMR(68MHz):24,61(CH2),24.67(CH2),25.32(CH2),2
5.38(CH2),27.41(CH2),27.45(CH2),27.49(CH2),27.80(C
H2),27.91(CH2),28.05(CH),28.32(CH2),28.37(CH2),29.
14(CH2),29.24(CH2),30.44(CH2),30.51(CH2),30.68(C
H2),30.89(CH2),32.14(CH2),32.17(CH2),32.70(CH2),3
2.79(CH2),32.87(CH),33.54(CH),34.27(CH),34.43(CH),
36.36(CH2),36.50(CH2),36.59(CH2),37.02(CH),37.89(C
H),38.03(CH),38.36(CH),38.94(CH2),38.96(CH2),39.00
(CH2),39.02(CH2),39.23(C),39.30(C),39.38(CH2),39.4
5(CH2),40.30(CH),40.36(CH2),40.41(CH2),40.44(CH2),
40.60(CH2),40.65(CH),40.69(CH),40.78(C),40.82(C),4
0.86(CH),41.34(CH),41.52(CH),41.60(CH2),41.70(CH),
41.80(CH),42.10(CH),42.58(CH),42.70(CH),42.81(CH),
43.00(CH),43.29(CH),43.64(CH),43.99(CH),44.48(CH),
44.70(CH),44.74(CH),44.80(CH),44.99(CH),45.06(CH),
45.33(CH),45.57(CH),45.78(CH),45.93(CH),48.07(CH),
48.69(CH),49.29(CH),49.33(CH),49.78(CH),66.89(C
H2),66.95(CH2),67.04(CH2),67.30(CH2),67.38(CH2),6
7.45(CH2),67.51(CH2),68.09(CH2),68.15(CH2),68.57(C
H2),177.56(C=O),177.59(C=O),177.62(C=O),177.64(C=
O),177.67(C=O)
・赤外吸収スペクトル（ＩＲ）：ＫＢｒ
１７２７．０ｃｍ-1（Ｃ＝Ｏ），３４４５．７ｃｍ
-1（ＯＨ）
・沸点（ｂｐ）
１５０．０〜１５２．５℃／１ｋＰａ(Measurement data) Nuclear magnetic resonance spectrum (NMR) = CDCl 3 1 H NMR (270 MHz): 0.92 to 0.93 (m, 1H), 1.21 to 1.25 (m, 1H), 1.
35〜1.67 (m, 4H), 1.71 (br s, 8H), 1.89 (br s, 4H), 2.01 (br
s, 6H), 2.06 to 2.18 (m, 1H), 2.30 to 2.50 (m, 2H), 3.40 to 3.5
2 (m, 2H), 3.79~3.91 (m, 2H) 13 C-NMR (68MHz): 24,61 (CH 2), 24.67 (CH 2), 25.32 (CH 2), 2
5.38 (CH 2 ), 27.41 (CH 2 ), 27.45 (CH 2 ), 27.49 (CH 2 ), 27.80 (C
H 2 ), 27.91 (CH 2 ), 28.05 (CH), 28.32 (CH 2 ), 28.37 (CH 2 ), 29.
14 (CH 2 ), 29.24 (CH 2 ), 30.44 (CH 2 ), 30.51 (CH 2 ), 30.68 (C
H 2 ), 30.89 (CH 2 ), 32.14 (CH 2 ), 32.17 (CH 2 ), 32.70 (CH 2 ), 3
2.79 (CH 2 ), 32.87 (CH), 33.54 (CH), 34.27 (CH), 34.43 (CH),
36.36 (CH 2 ), 36.50 (CH 2 ), 36.59 (CH 2 ), 37.02 (CH), 37.89 (C
H), 38.03 (CH), 38.36 (CH), 38.94 (CH 2 ), 38.96 (CH 2 ), 39.00
(CH 2 ), 39.02 (CH 2 ), 39.23 (C), 39.30 (C), 39.38 (CH 2 ), 39.4
5 (CH 2 ), 40.30 (CH), 40.36 (CH 2 ), 40.41 (CH 2 ), 40.44 (CH 2 ),
40.60 (CH 2 ), 40.65 (CH), 40.69 (CH), 40.78 (C), 40.82 (C), 4
0.86 (CH), 41.34 (CH), 41.52 (CH), 41.60 (CH 2 ), 41.70 (CH),
41.80 (CH), 42.10 (CH), 42.58 (CH), 42.70 (CH), 42.81 (CH),
43.00 (CH), 43.29 (CH), 43.64 (CH), 43.99 (CH), 44.48 (CH),
44.70 (CH), 44.74 (CH), 44.80 (CH), 44.99 (CH), 45.06 (CH),
45.33 (CH), 45.57 (CH), 45.78 (CH), 45.93 (CH), 48.07 (CH),
48.69 (CH), 49.29 (CH), 49.33 (CH), 49.78 (CH), 66.89 (C
H 2 ), 66.95 (CH 2 ), 67.04 (CH 2 ), 67.30 (CH 2 ), 67.38 (CH 2 ), 6
7.45 (CH 2), 67.51 ( CH 2), 68.09 (CH 2), 68.15 (CH 2), 68.57 (C
H 2 ), 177.56 (C = O), 177.59 (C = O), 177.62 (C = O), 177.64 (C =
O), 177.67 (C = O) -infrared absorption spectrum (IR): KBr 1727.0 cm -1 (C = O), 3445.7 cm
-1 (OH) -Boiling point (bp) 150.0-152.5 ° C / 1 kPa
【００２４】[0024]
【発明の効果】本発明の新規なアダマンタンカルボン酸
エステル化合物、非常に安定な炭素骨格を有すると共
に、その酸感応性と紫外線に対する透明性を利用して、
フォトレジスト添加剤を始めとして種々の用途が期待さ
れる。また、本化合物は分子内にトリシクロ［５．２．
１．０2,6］デカン骨格を有しているため、分子自体の
対称性が低く、各種溶媒や多くの化合物との親和性が高
い。The novel adamantanecarboxylic acid ester compound of the present invention, which has a very stable carbon skeleton, and utilizes its acid sensitivity and transparency to ultraviolet rays,
Various applications are expected, including photoresist additives. In addition, the present compound has tricyclo [5.2.
Since it has a [1.0 2,6 ] decane skeleton, the molecule itself has low symmetry and high affinity with various solvents and many compounds.
Claims (5)
子、炭素数１〜８のアルキル基、水酸基、炭素数１〜８
のアルコキシ基、カルボキシル基又はＣＯＯＲ1（Ｒ
1は、炭素数１〜８のアルキル基）を示し、それらはた
がいに同一でも異なっていてもよい。）で表されるビス
（１−アダマンチルカルボニロキシメチル）トリシクロ
［５．２．１．０2,6］デカン化合物。1. The following general formula (1): (In the formula, X 1 and X 2 are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a hydroxyl group, and 1 to 8 carbon atoms.
Alkoxy group, carboxyl group or COOR 1 (R
1 represents an alkyl group having 1 to 8 carbon atoms, which may be the same or different. ) (Bis- (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound represented by
載のビス（１−アダマンチルカルボニロキシメチル）ト
リシクロ［５．２．１．０2,6］デカン化合物。2. The bis (1-adamantylcarbonyloxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound according to claim 1, wherein X 1 and X 2 are hydrogen atoms.
８のアルキル基、水酸基、炭素数１〜８のアルコキシ
基、カルボキシル基又はＣＯＯＲ2（Ｒ2は、炭素数１〜
８のアルキル基）を示す。）で表される（１−アダマン
チルカルボニロキシメチル）（ヒドロキシメチル）トリ
シクロ［５．２．１．０2,6］デカン化合物。3. The following general formula (2) or (3): (In the formula, X 3 represents a hydrogen atom, a halogen atom, or a carbon number of 1 to 1.
8 alkyl group, hydroxyl group, alkoxy group having 1 to 8 carbon atoms, carboxyl group or COOR 2 (R 2 represents 1 to 8 carbon atoms)
8 alkyl group). (1-adamantyl carbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound represented by the formula:
（１−アダマンチルカルボニロキシメチル）（ヒドロキ
シメチル）トリシクロ［５．２．１．０2,6］デカン化
合物。4. The (1-adamantylcarbonyloxymethyl) (hydroxymethyl) tricyclo [5.2.1.0 2,6 ] decane compound according to claim 3 , wherein X 3 is a hydrogen atom.
ドロキシメチルトリシクロ［５．２．１．０2,6］デシ
ル化合物。5. The following general formula (4), (5) or (6): 1,3-Adamantanedicarboxylic acid bis (hydroxymethyltricyclo [5.2.1.0 2,6 ] decyl compound represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002115712A JP3999027B2 (en) | 2002-04-18 | 2002-04-18 | Novel adamantane carboxylic acid ester compounds |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002115712A JP3999027B2 (en) | 2002-04-18 | 2002-04-18 | Novel adamantane carboxylic acid ester compounds |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2003306469A true JP2003306469A (en) | 2003-10-28 |
| JP3999027B2 JP3999027B2 (en) | 2007-10-31 |
Family
ID=29396886
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002115712A Expired - Fee Related JP3999027B2 (en) | 2002-04-18 | 2002-04-18 | Novel adamantane carboxylic acid ester compounds |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3999027B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20140001897A (en) | 2010-12-09 | 2014-01-07 | 후지 덴키 가부시키가이샤 | Electrophotographic photoconductor and method for producing same |
| US8765336B2 (en) | 2010-03-01 | 2014-07-01 | Fuji Electric Co., Ltd. | Electrophotographic photoreceptor and manufacturing method therefor |
-
2002
- 2002-04-18 JP JP2002115712A patent/JP3999027B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8765336B2 (en) | 2010-03-01 | 2014-07-01 | Fuji Electric Co., Ltd. | Electrophotographic photoreceptor and manufacturing method therefor |
| KR20140001897A (en) | 2010-12-09 | 2014-01-07 | 후지 덴키 가부시키가이샤 | Electrophotographic photoconductor and method for producing same |
| US8748069B2 (en) | 2010-12-09 | 2014-06-10 | Fuji Electric Co., Ltd. | Electrophotographic photoconductor and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3999027B2 (en) | 2007-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4866237B2 (en) | Adamantane derivative, method for producing the same, and photosensitive material for photoresist | |
| TW200301760A (en) | Perfluoroadamantyl acrylate compound and intermediate thereof | |
| JP2003306469A (en) | New ester compound of adamantanecarboxylic acid | |
| JP2019172650A (en) | (meth)acrylic acid ester and manufacturing method therefor | |
| JP4271461B2 (en) | Halogenoacetoxyadamantane derivative and process for producing the same | |
| JP2003073339A (en) | New adamantane derivative | |
| US5151535A (en) | Fluorine-containing α,β-bifunctional compounds and process for their production | |
| CN112409176A (en) | Synthesis method of p-acetoxystyrene | |
| JP2002241342A (en) | Method for producing 2-hydrocarbyl-2-adamantyl acrylates | |
| JP4112912B2 (en) | Novel adamantanecarboxylic acid ester and process for producing the same | |
| AU665701B2 (en) | New (cyclohexyl)alkene compounds, processes for preparing them and pharmaceutical compositions containing them | |
| KR100908962B1 (en) | Novel Adamantane Derivatives | |
| WO2005100304A1 (en) | Adamantane derivative and process for producing the same | |
| KR20060043217A (en) | (Meth) acrylate and preparation method thereof | |
| KR101031383B1 (en) | Halogenoacetoxyadamantane derivatives and preparation methods thereof | |
| JP4015097B2 (en) | Polycyclic compound | |
| JP2018154592A (en) | Method for producing α-haloacrylic acid ester | |
| JP2001039926A (en) | Alicyclic di(meth)acrylate and its production | |
| JP4204397B2 (en) | Adamantane derivatives | |
| Csöregh et al. | Crystalline host-guest complexes involving carboxylic acid hosts and a dimethyl sulphoxide guest. X-ray crystal structures of two inclusion species | |
| JPH04321662A (en) | New thioacetal compound and production thereof | |
| JP2001072645A (en) | Diadamantyl dicarboxylate compound | |
| JP2003040842A (en) | beta-ALKYLCARBOXYLATES AND METHOD FOR PRODUCING THE SAME | |
| JPS5848544B2 (en) | N- | |
| JPS61134340A (en) | 2-oxo-cycloalkenylmethyl derivative |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A711 | Notification of change in applicant |
Effective date: 20041203 Free format text: JAPANESE INTERMEDIATE CODE: A712 |
|
| A621 | Written request for application examination |
Effective date: 20050127 Free format text: JAPANESE INTERMEDIATE CODE: A621 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20070724 |
|
| A61 | First payment of annual fees (during grant procedure) |
Effective date: 20070808 Free format text: JAPANESE INTERMEDIATE CODE: A61 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 3 Free format text: PAYMENT UNTIL: 20100817 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100817 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Year of fee payment: 6 Free format text: PAYMENT UNTIL: 20130817 |
|
| LAPS | Cancellation because of no payment of annual fees |