JPS608232A - Preparation of 7-substituted quadricyclene-cyclodextrin chlathrate compound - Google Patents
Preparation of 7-substituted quadricyclene-cyclodextrin chlathrate compoundInfo
- Publication number
- JPS608232A JPS608232A JP58116729A JP11672983A JPS608232A JP S608232 A JPS608232 A JP S608232A JP 58116729 A JP58116729 A JP 58116729A JP 11672983 A JP11672983 A JP 11672983A JP S608232 A JPS608232 A JP S608232A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- substituted
- cyclodextrin
- quadricyclene
- clathrate compound
- 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
- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 229920000858 Cyclodextrin Polymers 0.000 title claims description 20
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003504 photosensitizing agent Substances 0.000 claims abstract description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 6
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims abstract description 6
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000012965 benzophenone Substances 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- -1 norbornadiene compound Chemical class 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- XSAYZAUNJMRRIR-UHFFFAOYSA-N 2-acetylnaphthalene Chemical compound C1=CC=CC2=CC(C(=O)C)=CC=C21 XSAYZAUNJMRRIR-UHFFFAOYSA-N 0.000 claims 1
- SLGBZMMZGDRARJ-UHFFFAOYSA-N Triphenylene Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC=C3C2=C1 SLGBZMMZGDRARJ-UHFFFAOYSA-N 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 claims 1
- CXAYOCVHDCXPAI-UHFFFAOYSA-N naphthalen-1-yl(phenyl)methanone Chemical compound C=1C=CC2=CC=CC=C2C=1C(=O)C1=CC=CC=C1 CXAYOCVHDCXPAI-UHFFFAOYSA-N 0.000 claims 1
- 125000005580 triphenylene group Chemical group 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 5
- 125000002872 norbornadienyl group Chemical class C12=C(C=C(CC1)C2)* 0.000 abstract description 4
- 125000004423 acyloxy group Chemical group 0.000 abstract description 2
- 125000003545 alkoxy group Chemical group 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract description 2
- PJKVFARRVXDXAD-UHFFFAOYSA-N 2-naphthaldehyde Chemical compound C1=CC=CC2=CC(C=O)=CC=C21 PJKVFARRVXDXAD-UHFFFAOYSA-N 0.000 abstract 1
- 238000009825 accumulation Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 6
- 239000001116 FEMA 4028 Substances 0.000 description 4
- WHGYBXFWUBPSRW-FOUAGVGXSA-N beta-cyclodextrin Chemical compound OC[C@H]([C@H]([C@@H]([C@H]1O)O)O[C@H]2O[C@@H]([C@@H](O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O[C@H]3O[C@H](CO)[C@H]([C@@H]([C@H]3O)O)O3)[C@H](O)[C@H]2O)CO)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@@H]3O[C@@H]1CO WHGYBXFWUBPSRW-FOUAGVGXSA-N 0.000 description 4
- 235000011175 beta-cyclodextrine Nutrition 0.000 description 4
- 229960004853 betadex Drugs 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- DGZUEIPKRRSMGK-UHFFFAOYSA-N quadricyclane Chemical compound C1C2C3C2C2C3C12 DGZUEIPKRRSMGK-UHFFFAOYSA-N 0.000 description 4
- 229920006395 saturated elastomer Polymers 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 238000007699 photoisomerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- XZWYAMYRMMMHKM-UHFFFAOYSA-N 1-(2-phenylphenyl)ethanone Chemical group CC(=O)C1=CC=CC=C1C1=CC=CC=C1 XZWYAMYRMMMHKM-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical class CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 235000008708 Morus alba Nutrition 0.000 description 1
- 240000000249 Morus alba Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940097362 cyclodextrins Drugs 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- DCSRPHQBFSYJNN-UHFFFAOYSA-L disodium 4-[(2-arsonophenyl)diazenyl]-3-hydroxynaphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].Oc1c(N=Nc2ccccc2[As](O)(O)=O)c2ccc(cc2cc1S([O-])(=O)=O)S([O-])(=O)=O DCSRPHQBFSYJNN-UHFFFAOYSA-L 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Polysaccharides And Polysaccharide Derivatives (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、７−置換ノルボルナジェン
射による７−置換クワドリシクレン類への光異性換ノル
ボルナジェン類は、
一般式
Ｃト■ＩＣＨ
＼Ｃｌ−Ｉ ′（式中のＲは、水素原子、ヒドロキシル
基、アシルオキシ基及びアルキルオキシ基を示す）で表
わされるが、これらの化合物に適当な光化学増感剤を配
合して製したシフロブキストＩＪン包接化合物を光照射
すれば、さらに良ηｆな転化率で、４１４当する
一般式
キシ基を示す）で表わされる７−置換クワドリシクレン
類−シクロデキストリン包接化合物を得られることを見
い出した。DETAILED DESCRIPTION OF THE INVENTION The present invention provides that photoisomerized norbornadiens to 7-substituted quadricyclenes by 7-substituted norbornadiene injection have the general formula , a hydrogen atom, a hydroxyl group, an acyloxy group, and an alkyloxy group), but if a schiflobquist IJ clathrate compound prepared by blending these compounds with an appropriate photochemical sensitizer is irradiated with light, further It has been found that a 7-substituted quadricyclene-cyclodextrin clathrate compound represented by the general formula (representing an xy group corresponding to 414) can be obtained at a good conversion rate.
得られた７−置換クワドリシクレン類−シフロブキスト
リン包接化合物は、光エネルギーを熱エネルギーとして
貯えており、適当な触媒を用いて逆反応を行うと、たと
えば（１）式でＲ＝ ｉ（の場合２りＯｃａｔ ／ ！
／の熱量が得られる。このように、シクロデキストリン
包接化合物を用いて、光照射による蓄熱と逆反応による
放熱とを交互に行うことによって、有効に熱サイクルを
行うことができ、ソーラーシヌテムとして応用できるこ
とを見い出した。The obtained 7-substituted quadricyclenes-sifrobuxtrin clathrate stores light energy as thermal energy, and when a reverse reaction is performed using an appropriate catalyst, for example, R= If i(, then 2 Ocat /!
/ of heat can be obtained. In this way, we have found that by using a cyclodextrin clathrate compound and alternately storing heat through light irradiation and dissipating heat through a reverse reaction, it is possible to perform an effective thermal cycle, which can be applied as a solar synutem.
本発明に述べる、包接化合物を製造する際に光化学増感
剤を添加することは、７−置換ノルボルナジェン類−シ
フロブキストリン包接化合物の７−置換クワドリシクレ
ン類−シクロデキストリン包接化合物への転化率を向」
ニすることができ、さらに、高い熱効率がサイクル中で
期待できる。また、包接化合物を用いることによって、
原料化合物の臭気を大巾に減少させることができるとと
もに、粉体であるため、貯蔵、取り扱いが容易な利点が
ある。The addition of a photochemical sensitizer when producing the clathrate compound described in the present invention means that the 7-substituted quadricyclenes-cyclodextrin clathrate compound of the 7-substituted norbornadiene-sifrobuxtrin clathrate compound "Increase the conversion rate to"
Furthermore, high thermal efficiency can be expected during the cycle. In addition, by using clathrate compounds,
The odor of the raw material compound can be greatly reduced, and since it is a powder, it has the advantage of being easy to store and handle.
７−置換ノルボルナジェン類−シクロデキストリン包接
化合物のみを光照射した場合、転化率に上限があるが、
包接化合物を造る際に、光増感剤を添加することによっ
て転化率を冒めることかできることを見い出した。When only the 7-substituted norbornadiene-cyclodextrin clathrate is irradiated with light, there is an upper limit to the conversion rate;
It has been found that when preparing clathrate compounds, it is possible to influence the conversion rate by adding a photosensitizer.
本発明に用いられる７−置換ノルボルナジェン（１）式
で示すＲ中のアルキル基は、化合物が、固体を示さない
、炭素数／〜りが好捷しい。The alkyl group in R represented by the 7-substituted norbornadiene formula (1) used in the present invention preferably has a carbon number of 1 to 2 so that the compound does not exhibit a solid state.
本発明において用いられるシクロデキストリンは、α−
１β−及びγ−タイプのいずれでも使用することができ
る。通常単独で用いられるが、２ｆΦ寸たは３種の混用
をしてもよい。好ましいのはβ−タイプのシクロデキス
トリンである。The cyclodextrin used in the present invention is α-
Both 1β- and γ-types can be used. Although it is usually used alone, it is also possible to use a 2fΦ size or a mixture of three types. Preferred are β-type cyclodextrins.
本発明に用いられる光増感剤は、アセトン、アセＩ・フ
ェノン、ベンゾフェノン、トルエン、−二ナフ１−アル
テ゛ヒト、Ｉ−リフェニレン、ベンジル、認、３−ペン
クシエン、フェナントレン、Ω−アセ１、ナフトン、ア
セチルビフェニル、ベンゼン、リーフチルフェニルケト
ン、アン１−ラキノン、ナフタレン、アントラセン及び
それらの化合物の誘導体あるいはＪｊ、、・１化銅（１
）等の金属塩の７種又は２種以」二を使用するもので、
７−置換ノルボルナジェン類を増感できる化合物であれ
ばいずれでもよく、単独または混合して用いられる。７
−置換ノルボルナジェン類に対する光増感剤の添加量は
、１０％までが適当であるが７００％まで添加できる。The photosensitizers used in the present invention include acetone, acetate-phenone, benzophenone, toluene, -dinaph-1-artethyl alcohol, I-rephenylene, benzyl, chloride, 3-penxyene, phenanthrene, Ω-acetate, naphthone. , acetylbiphenyl, benzene, leaf thylphenyl ketone, an-1-laquinone, naphthalene, anthracene and derivatives of these compounds or Jj, .Copper monide (1
) and other metal salts.
Any compound can be used as long as it can sensitize 7-substituted norbornadiens, and can be used alone or in combination. 7
The amount of photosensitizer added to the -substituted norbornadiens is suitably up to 10%, but up to 700% can be added.
本発明における包接化合物は、粉体であるため、不活性
ガス（たとえば窒素ガス）中で浮遊せしめるか、または
、広い面積に散布するがして光を照射するものである。Since the clathrate compound in the present invention is a powder, it is suspended in an inert gas (for example, nitrogen gas) or is dispersed over a wide area and irradiated with light.
この際に、包接化合物を均一に混合するとともに、均一
に光をあてる必要がある。At this time, it is necessary to mix the clathrate compounds uniformly and to apply light uniformly.
光源としては、太陽光、高圧水銀灯、低圧水銀灯及びキ
セノンランプなどが用いられる。As a light source, sunlight, a high pressure mercury lamp, a low pressure mercury lamp, a xenon lamp, etc. are used.
光異性化反応は、粉体の捷ま行うことができるが、また
、適当な溶媒、たとえば、水、ｎ−ヘキサン、ベンセン
、；・ルエン及ヒエチレンクリコー置換クワト′リシク
レン類−シクロデキヌトリン包接化合物は、たとえば、
次のような方法で包接化合物であることを確認できる。The photoisomerization reaction can be carried out by grinding the powder, but it can also be carried out using a suitable solvent, such as water, n-hexane, benzene, luene and hyethylene crico-substituted quat'lycyclenes - cyclodequine. Thorin clathrates are, for example,
You can confirm that it is an inclusion compound by the following method.
本発明の７−置換クワドリシクレン類−シクロデキスト
リン包接化合物に約７０倍容のベンゼンを加えて良くか
き混ぜる。シフロブキストリンよりベンセン層を分離し
たのち、ベンゼンを回収して残油を得る。この残油を蒸
留して７−置換クワ１−′リシクレン類が得られる、６
さらに、添加された光増感剤もガスクロマ１−グラフ法
により確認される。About 70 times the volume of benzene is added to the 7-substituted quadricyclenes-cyclodextrin clathrate compound of the present invention and stirred well. After separating the benzene layer from the siphlobuxtrin, the benzene is recovered to obtain a residual oil. This residual oil is distilled to obtain 7-substituted mulberry 1-'lycyclenes, 6
Furthermore, the added photosensitizer is also confirmed by gas chroma 1-graph method.
（１）式中のＲ−Ｈの場合のクワドリシクレンを例にと
ると、留分のＮ Ｍ Ｒスペク） ／Ｉ／は、／り／訃
にシクロピロピルプロトンの吸収を、７９９ Ｆに７−
位のメチレンのプロトンの吸収を示し、との留分がクワ
ドリシクレンであることが確認される。Taking the quadricyclene in the case of RH in formula (1) as an example, the NMR spectrum of the fraction /I/ is the absorption of the cyclopropyl proton at /ri/, and the absorption of the cyclopropyl proton at 799F. 7-
It shows the absorption of protons of methylene at position, confirming that the fraction is quadricyclene.
本発明の光増感剤を添加したシクロデキストリン包接化
合物を用いる光異性化反応の原理は、７−置換ノルボル
ナジェン
７−置換グツトリシクレン類の生成と、とのものの触媒
による逆反応で、もとの７−置換７ルボルナシエン
ギーを目的とした、ソーラーシステムに応用ができる。The principle of the photoisomerization reaction using the cyclodextrin clathrate compound to which the photosensitizer of the present invention has been added is the production of 7-substituted norbornadiene and 7-substituted guttlicyclenes, and the catalytic reverse reaction between the two and the original It can be applied to solar systems aimed at 7-substitution 7 rubornaciency.
しかも、その際に、副反応がなく、サイクルを長期間に
わたって行うことが可能な有用なものである。Furthermore, it is a useful product that does not cause side reactions and can be cycled for a long period of time.
次に、実施例により、本発明をさらに詳細に説明する。Next, the present invention will be explained in more detail with reference to Examples.
実施例／
β−シクロデキストリンの飽和水溶ｔｆｉ３ 、！；
０ｗｌ中に、ノルボルナジェン０． ３ 、２ Ｐ ト
アセ１ーフェノンｏ． ｏ ｓ ｙの混合液を投入して
かき混ぜ、生成した沈殿を乾燥して／ＳＳフグ収率，！
２％）のシクロデキストリン包接化合物を得た。この粉
末ＯＳ０７を外径乙Ｏπｍの硬質ガラス製シャーレに均
一に拡げ、同質のふたをしたのち、外気温で７時間太陽
光を照射した。照射後、内容物はＯＳ／７となる。生成
したクワドリシクレンは、次のようにして、ガスクロマ
トグラフ法で分析し、原料に苅する転化率をめた。照射
した包接化合物０１０ｙを正１１″（ｆにとり、ベンセ
ン０ ３ ０ ｍｌを加えてよくかき混ぜて抽出すると
、生成したクワドリシクレンがベンセン層に移行する。Example/Saturated aqueous tfi3 of β-cyclodextrin,! ;
Norbornagen 0.0 in 0 wl. 3,2P toace-1-phenone o. Pour in the mixed solution of o sy and stir, dry the formed precipitate, /SS puffer fish yield,!
2%) of cyclodextrin inclusion compound was obtained. This powder OS07 was uniformly spread in a hard glass Petri dish with an outer diameter of Oπm, covered with a homogeneous lid, and then exposed to sunlight for 7 hours at outside temperature. After irradiation, the contents become OS/7. The produced quadricyclene was analyzed by gas chromatography as follows, and the conversion rate for raw material was determined. When the irradiated clathrate compound 010y is taken to 11'' (f), 30 ml of benzene is added and extracted by stirring well, the generated quadricyclene is transferred to the benzene layer.
一定量のベンゼン溶液をとり、ガスクロマトグラフ法に
より面積をめる。次に、同様の方法で未照射の試料の分
析を行って、ベンセンを基準とした両者の面積比から転
化率をめたところ、７３７％を得た。Take a certain amount of benzene solution and measure the area using gas chromatography. Next, an unirradiated sample was analyzed in the same manner, and the conversion rate was calculated from the area ratio of both with benzene as the standard, and it was found to be 737%.
実施例２
β−シクロデキストリンの飽和水溶液３ ３ ０ ｔｎ
ｌ中Ｋ 、７ − ｔ，−ブ１ーキシノルボルナジェン
０９３７とアセトフェノンＱＯ！；９−の混合液全投入
してかき混ぜ、生成した沈ＥＶｉを乾燥して３７６ｇ（
収４４ 、５′０％）のシクロデキストリン包接化合物
を得た。この粉末Ｏ夕０７を外径乙Ｑ ｍｌＷの硬質ガ
ラス製シャーレに均一に拡げ、同質のふたをしたのち、
外気温で乙時間太陽光を照射した。照射後、内容物はＯ
Ｓ／２となった。実施例／と同様な方法で、／１成しｒ
ｖ ７ ７ ｔ−ブトキシクワドリシクレンをガスクロ
マ１−グラフ法で分析し、転化率り，０％を得介．１。Example 2 Saturated aqueous solution of β-cyclodextrin 3 30 tn
K in l, 7-t,-butycinorbornadiene 0937 and acetophenone QO! ;Pour in the entire mixture of step 9-, stir, and dry the resulting precipitate EVi to give 376g (
A cyclodextrin clathrate compound with a yield of 44% and 5'0% was obtained. After spreading this powder evenly in a hard glass petri dish with an outer diameter of QmlW and covering it with a homogeneous lid,
It was exposed to sunlight for an hour at the outside temperature. After irradiation, the contents are O
It became S/2. In the same manner as Example /, /1 is made r
v 7 7 T-Butoxyquadricyclene was analyzed by gas chroma 1-graph method, and the conversion rate was found to be 0%. 1.
実施例３
βーシクロデキストリン飽和水溶Ｗ３３Ｏｍｌ中に、７
−アセトキシノルボルナジェン
アセＩ・フェノンｏｏｓｙの混合ｉｔ投入してかき混ぜ
、生成した沈殿を乾燥して／３／ｙ−（収率／ｇ％）の
シクロデキストリン包接化合物を得た。Example 3 In 330 ml of β-cyclodextrin saturated aqueous solution, 7
A mixture of -acetoxynorbornagenease I and phenone oosy was added and stirred, and the resulting precipitate was dried to obtain a cyclodextrin clathrate compound with a yield of /3/y- (yield/g%).
？Ｃ （Ｄ粉末．０． ３ ０ ｆｊを外径乙Ｑ ｍｍ
の硬質ガラス製シャーレに均一に拡げ、同質のふたをし
たのち、外気温で乙時間太陽光を照射した。照射後、内
容物はＯＳ／２となる。実施例／と同様な方法で、イ１
ヒ成した７−アセトキシクワドリシクレンをガスクロマ
１゛グラフ法で分析し、転化率／Ｚ．２％を得た。? C (D powder.0.30 fj to outer diameter Q mm
After spreading it evenly in a hard glass petri dish and covering it with a homogeneous lid, it was exposed to sunlight for an hour at outside temperature. After irradiation, the contents become OS/2. In the same manner as in Example/, I1
The annealed 7-acetoxyquadricyclene was analyzed by gas chromagraph method and the conversion rate/Z. Obtained 2%.
実施例グ
β−シクロデキストリン飽和水溶液３ ３− Ｏ ｍｌ
＋１１に、７−ノルポルナジエノール
フェノン００５２の混合液を投入してかき混ぜ、生成し
た沈殿を乾燥して／／乙２（収率／乙り％）のシクロデ
キストリン包接化合物を得た。この粉末ａｓｏｙを外径
６０闘の硬質ガラス製シャーレに均一に拡げ、同質のふ
たをしたのち、外気温で６時間太陽光を照射した。照射
後、内容物はＯ５／２となる。実施例／と同様な方法で
、生成した７−クワドリンクレツールをガスクロマ１−
グラフ法で分析し、転化率、２２．３％を得た。Example G β-cyclodextrin saturated aqueous solution 3 3-O ml
At +11, a mixed solution of 7-norpornadienolphenone 0052 was added and stirred, and the resulting precipitate was dried to obtain a cyclodextrin clathrate compound with a yield of 2 (yield/%). This powdered asoy was uniformly spread in a hard glass petri dish with an outer diameter of 60 mm, covered with a homogeneous lid, and then exposed to sunlight for 6 hours at outside temperature. After irradiation, the contents become O5/2. In the same manner as in Example/, the generated 7-quadrinkle tool was subjected to gas chroma 1-
A conversion rate of 22.3% was obtained by graphical analysis.
第１頁の続き ０発 明 者 用瀬薫 名古屋市千種区猫洞通り５丁目 ３１番地 ０発 明 者 山北尋巳 尾張旭市平子町西２６１番地 ０発 明 者 峠田博史 名古屋市北区金城二丁目５番６ 号Continuation of page 1 0 shots clear person Kaoru Yose 5-chome Nekodo-dori, Chikusa-ku, Nagoya City No. 31 0 shots Akira Hiromi Yamakita 261 Hirakocho Nishi, Owariasahi City 0 shots clear person Hiroshi Togeda 2-5-6 Kinjo, Kita-ku, Nagoya City issue
Claims (1)
類と光増感剤とよりなるシクロデキストリン包接化合物
の光照射による、 一般式 ギンノ、（を示す）で表わされる７−置換クワドリシク
レン類−シクロデキストリン包接化合物の製造方法。 λ 光増１６ Ｍ’ｌ トしてアセトン、アセトフェノ
ン、ベンゾフェノン、トルエン、−一ナントアルデヒド
、トリフェニレン、ベンジル１．２．３−ペンタジェン
、フェナントレン、２−アセトナフトン、アセチフレビ
フェニル、ベンゼン、ナフチルフェニルケトン、アンＩ
・ラギノン、ナフタレン、アントラセン及びそれらの化
合物の誘導体あるいは金属塩の７種又は２種以上を使用
する特許請求の範囲第１項記載の７−置換クワドリシク
レン類−シクロデキストリン包接化合物の製造方法。[Claims] / By irradiating a cyclodextrin clathrate compound consisting of a 7-substituted norbornadiene compound represented by the general formula Ginno, (representing the general formula Ginno group) and a photosensitizer, A method for producing a 7-substituted quadricyclene-cyclodextrin clathrate compound. λ Photointensification 16 M'l Acetone, acetophenone, benzophenone, toluene, -1-nanthaldehyde, triphenylene, benzyl 1.2.3-pentadiene, phenanthrene, 2-acetonaphthone, acetyflebiphenyl, benzene, naphthylphenyl ketone, Ann I
- A method for producing a 7-substituted quadricyclene-cyclodextrin clathrate compound according to claim 1, which uses seven or more types of raginone, naphthalene, anthracene, and derivatives or metal salts of these compounds. .
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58116729A JPS6049608B2 (en) | 1983-06-27 | 1983-06-27 | Method for producing 7-substituted quadricyclenes-cyclodextrin clathrate compound |
| US06/584,739 US4502930A (en) | 1983-06-27 | 1984-02-29 | Method for manufacture of 7-substituted quadricyclene-cyclodextrin inclusion compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58116729A JPS6049608B2 (en) | 1983-06-27 | 1983-06-27 | Method for producing 7-substituted quadricyclenes-cyclodextrin clathrate compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS608232A true JPS608232A (en) | 1985-01-17 |
| JPS6049608B2 JPS6049608B2 (en) | 1985-11-02 |
Family
ID=14694347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58116729A Expired JPS6049608B2 (en) | 1983-06-27 | 1983-06-27 | Method for producing 7-substituted quadricyclenes-cyclodextrin clathrate compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6049608B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6434927A (en) * | 1987-04-03 | 1989-02-06 | Daicel Chem | Method for asymmetric photochemical reaction |
| JPH01122438A (en) * | 1987-11-06 | 1989-05-15 | B J Trading Kk | Cylinder washing apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0176016U (en) * | 1987-11-10 | 1989-05-23 |
-
1983
- 1983-06-27 JP JP58116729A patent/JPS6049608B2/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6434927A (en) * | 1987-04-03 | 1989-02-06 | Daicel Chem | Method for asymmetric photochemical reaction |
| JPH01122438A (en) * | 1987-11-06 | 1989-05-15 | B J Trading Kk | Cylinder washing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6049608B2 (en) | 1985-11-02 |
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