JPH0254814B2 - - Google Patents
Info
- Publication number
- JPH0254814B2 JPH0254814B2 JP59124562A JP12456284A JPH0254814B2 JP H0254814 B2 JPH0254814 B2 JP H0254814B2 JP 59124562 A JP59124562 A JP 59124562A JP 12456284 A JP12456284 A JP 12456284A JP H0254814 B2 JPH0254814 B2 JP H0254814B2
- Authority
- JP
- Japan
- Prior art keywords
- methyl group
- iron chloride
- reaction
- general formula
- chlordiketone
- 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.)
- Expired - Lifetime
Links
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 8
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- -1 cyclic olefin compound Chemical class 0.000 claims description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 6
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 239000005297 pyrex Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- FKHIFSZMMVMEQY-UHFFFAOYSA-N talc Chemical compound [Mg+2].[O-][Si]([O-])=O FKHIFSZMMVMEQY-UHFFFAOYSA-N 0.000 description 3
- YONXEBYXWVCXIV-HLTSFMKQSA-N (1r,5s,7r)-7-ethyl-5-methyl-6,8-dioxabicyclo[3.2.1]octane Chemical compound C1CC[C@@H]2[C@@H](CC)O[C@@]1(C)O2 YONXEBYXWVCXIV-HLTSFMKQSA-N 0.000 description 2
- SZQINPXTYBNYCZ-UHFFFAOYSA-N 1-ethyl-6-methylcyclohexene Chemical compound CCC1=CCCCC1C SZQINPXTYBNYCZ-UHFFFAOYSA-N 0.000 description 2
- CTMHWPIWNRWQEG-UHFFFAOYSA-N 1-methylcyclohexene Chemical compound CC1=CCCCC1 CTMHWPIWNRWQEG-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001882 dioxygen Inorganic materials 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
- 239000003016 pheromone Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MIBPMIMLABIQGY-UHFFFAOYSA-N 1-hydroxynonan-2-one Chemical compound CCCCCCCC(=O)CO MIBPMIMLABIQGY-UHFFFAOYSA-N 0.000 description 1
- ZTMRFIKDSHCFSW-UHFFFAOYSA-N 5-(3-ethyloxiran-2-yl)pentan-2-one Chemical compound CCC1OC1CCCC(C)=O ZTMRFIKDSHCFSW-UHFFFAOYSA-N 0.000 description 1
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007539 photo-oxidation reaction Methods 0.000 description 1
- 238000006552 photochemical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は新規な光反応によつて環状オレフイン
よりα−クロルジケトン化合物を製造する方法、
及び、この方法を利用して得られたα−クロルジ
ケトン化合物より昆虫フエロモンとして知られて
いるブレビコミンの合成法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a method for producing an α-chlorodiketone compound from a cyclic olefin by a novel photoreaction;
The present invention also relates to a method for synthesizing brevicomin, known as an insect pheromone, from an α-chlordiketone compound obtained using this method.
従来の、塩化鉄（）の存在下環状オレフイン
を光酸素酸化させることにより、該オレフインの
置換様式によつて、中間体としてβ−クロルヒド
ロペルオキシドを経由して下記の三つの反応生成
物が生ずることが知られている。（A.Kohda、et.
al.、JOO、1983（42）425参照）
また、上記の中間体であるβ−クロルヒドロペ
ルオキシドを一旦単離後、種々のＸの存在下鉄
（）イオン触媒下で分解させると、Ｘ置換を有
する生成物が得られることから次のような反応機
構が考えられた。 Conventional photooxygen oxidation of a cyclic olefin in the presence of iron chloride () produces the following three reaction products via β-chlorohydroperoxide as an intermediate, depending on the substitution mode of the olefin. It is known. (A.Kohda, et.
al., JOO, 1983 (42) 425) In addition, once the above intermediate β-chlorohydroperoxide is isolated, if it is decomposed under an iron () ion catalyst in the presence of various types of X, a product having an X substitution is obtained. A reaction mechanism was considered.
但し、ＸはBr、Ｉ、SON、CN、N3を表わす。 However, X represents Br, I, SON, CN, N3 .
しかしながら、前記の中間体を単離することな
く、同じ条件下でさらに光酸素酸化を行つたとこ
ろα−クロルジケトンが収率よく生成することを
見出し、本発明を完成するに至つた。 However, when photooxidation with oxygen was further performed under the same conditions without isolating the intermediate, it was discovered that α-chlorodiketone was produced in good yield, and the present invention was completed.
すなわち、本発明は一般式
R1はメチル基、R2はメチル基、又はエチル基、
ｎは１又は３を表わす
で表わされる環状オレフイン化合物を塩化鉄で表
わされる環状オレフイン化合物を塩化鉄（）の
存在下、ピリジン中でガラス（登録商標パイレツ
クス）透過光を少なくしても４時間照射して一般
式
（R1、R2及びｎは前途のとおり）
で表わされるα−クロルジケトン化合物を得るこ
とを特徴とするα−クロルジケトン化合物の製造
方法である。 That is, the present invention is based on the general formula R 1 is a methyl group, R 2 is a methyl group or an ethyl group,
n represents 1 or 3 A cyclic olefin compound represented by iron chloride was irradiated with glass (registered trademark Pyrex) in pyridine in the presence of iron chloride for 4 hours even if the transmitted light was reduced. general formula (R 1 , R 2 and n are as described above) This is a method for producing an α-chlorodiketone compound, which is characterized by obtaining an α-chlordiketone compound represented by the following.
しかして、本発明においてはこのように置換基
を有する環状オレフイン化合物を塩化鉄（）の
存在下で長時間パイレツクス透過光を照射するこ
とによりα−クロルジケトンが得られるのである
が、この反応は原料オレフインの置換基及び環の
大きさを変えることにより広い範囲で標的化合物
の合成が可能なこと、その結果得られる生成物の
ケトン及びα−クロルケトン部分を選択的に変換
することにより有機合成反応として広く応用でき
る。 Therefore, in the present invention, α-chlordiketone is obtained by irradiating a cyclic olefin compound having a substituent with Pyrex transmitted light for a long time in the presence of iron chloride (), but this reaction It is possible to synthesize a wide range of target compounds by changing the substituents and ring size of the raw material olefin, and organic synthesis reactions can be achieved by selectively converting the ketone and α-chloroketone moieties of the resulting product. It can be widely applied as
この反応を利用した有機合成反応として昆虫フ
エロモンとして知られているブレビコミンの選択
的合成法があげられる。 An example of an organic synthesis reaction utilizing this reaction is a method for selectively synthesizing brevicomin, which is known as an insect pheromone.
すなわち、従来のブレビコミンの合成法として
はシスまたはトランスオレフインのエポキシ化
（例えばJ.Org.Chem.、42 2380（1977）参照）或
はC6、C7炭素の立体選択的Ｃ−Ｃ結合生成反応
（例えばChem.Lett.、1983 93参照）を利用する
方法等があるが後者は前者に比して特殊な試薬を
必要とするなどの欠点があり、他方、前者の方法
ではエナンチオ選択的な合成が極めて困難である
等の欠点があつた。 That is, conventional methods for synthesizing brevicomine include epoxidation of cis or trans olefin (see, for example, J.Org.Chem., 42 2380 (1977)) or stereoselective C-C bond formation at C6 and C7 carbons. Although there are methods that utilize reactions (see, for example, Chem. Lett., 1983 93), the latter method has disadvantages such as requiring special reagents compared to the former method. It had drawbacks such as extremely difficult synthesis.
ところが先に記載した新規な光化学反応を利用
することにより極めて容易に且つ選択的にexo−
ブレビコミンの合成が可能となつた。 However, by using the novel photochemical reaction described above, exo-
It became possible to synthesize brevicomine.
すなわち、exo−ブレビコミンの合成は、次の
とおりである。 That is, the synthesis of exo-brevicomine is as follows.
構造式
を有する１−エチル−６−メチル−１−シクロヘ
キセンを塩化鉄（）の存在下、光酸素酸化させ
ることにより、構造式
で表わされる６−クロロ−２、７−ノナジオンを
得しかる後該化合物を環元して６−クロル−７−
ヒドロキシ−２−ノナノンとし、これをエポキシ
化後酸処理することを特徴とするブレビコミンの
合成法である。 Structural formula By photooxidizing 1-ethyl-6-methyl-1-cyclohexene with the structural formula in the presence of iron chloride (), the structural formula 6-Chloro-2,7-nonadione represented by
This is a method for synthesizing brevicomine, which is characterized by epoxidizing hydroxy-2-nonanone and then treating it with an acid.
しかして、本発明は次のような反応経路によ
る。 Therefore, the present invention is based on the following reaction route.
以下、実施例をもつて本発明を説明する。 The present invention will be explained below with reference to Examples.
実施例 １
１，12−ジメチルシクロドデセン776mgおよび
塩化鉄（）1.08ｇを40mlのピリジンにとかし、
パイレツクス管中酸素ガスを通しながら450W高
圧水銀灯を４時間照射する。希塩酸で中和しクロ
ロホルムで抽出する。抽出液を短いフロリジルカ
ラムを通した後溶媒を除去することにより精製す
る。Example 1 776 mg of 1,12-dimethylcyclododecene and 1.08 g of iron chloride () were dissolved in 40 ml of pyridine,
Irradiate with a 450W high-pressure mercury lamp for 4 hours while passing oxygen gas through the Pyrex tube. Neutralize with dilute hydrochloric acid and extract with chloroform. The extract is purified by passing it through a short Florisil column and then removing the solvent.
収率64％
参考例 １
１−エチル−６−メチル−１−シクロヘキセン
496mg及び塩化鉄（）1.08ｇを40mlのピリジン
にとかし、パイレツクス管中酸素ガスを通しなが
ら、450W高圧水銀灯を４時間照射する。希塩酸
で中和しクロロホルムで抽出する。抽出液から少
量の鉄化合物を除くため、短いフロリジルカラム
を通した後溶媒を除くため、短いフロリジルカラ
ムを通した後溶媒を除去する。収率79％bp.95〜
98℃／1.2mmHg。得られたα−クロルジケトン
500mgをｎ−ブタノール15mlにとかし、−50℃で水
素化ホウ素ナトリウム100mgを加えて45分間かく
はんする。溶液を希塩酸で酸性にし、エーテル抽
出し食塩水で洗滌した後無水硫酸ナトリウムによ
り乾燥する。残渣をシリガルカラムにより精製
し、６−クロル−７−ヒドロキシ−２−ノナノン
380mgが得られた。収率76％。このもの142mgを
133mgのKOHを含む７mlのメタノールにとかし15
分間還流する。水を加えジクロルメタンで抽出
し、抽出液を無水硫酸ナトリウムで乾燥した後溶
媒を除去すると、６，７−エポキシ−２−ノナノ
ンが得られる。これを単離することなく、0.9ml
アセトン及び0.9ml水の混合溶媒にとかし、硫酸
245mgを氷冷下加え、室温で１時間攪拌する。反
応液を重曹水で中和しエーテル抽出する。エーテ
ル溶液を無水硫酸ナトリウムで乾燥した後エーテ
ルを除去するとブレビコミン99mgが得られた。こ
れはGC−MS、NMRによりエキソ：エンド＝
93：７であることがわかつた。１−エチル−６−
メチルシクロヘキセンよりの通算収率は51％であ
つた。 Yield 64% Reference example 1 1-ethyl-6-methyl-1-cyclohexene
Dissolve 496 mg and 1.08 g of iron chloride in 40 ml of pyridine, and irradiate with a 450 W high-pressure mercury lamp for 4 hours while passing oxygen gas through a Pyrex tube. Neutralize with dilute hydrochloric acid and extract with chloroform. To remove a small amount of iron compounds from the extract, the extract is passed through a short Florisil column and the solvent is removed after passing through a short Florisil column. Yield 79% bp.95~
98℃/1.2mmHg. Obtained α-chlordiketone
Dissolve 500 mg in 15 ml of n-butanol, add 100 mg of sodium borohydride at -50°C, and stir for 45 minutes. The solution is made acidic with dilute hydrochloric acid, extracted with ether, washed with brine, and dried over anhydrous sodium sulfate. The residue was purified using a siligal column to obtain 6-chloro-7-hydroxy-2-nonanone.
380mg was obtained. Yield 76%. 142mg of this stuff
Dissolve in 7 ml methanol containing 133 mg KOH15
Reflux for minutes. Water is added and extracted with dichloromethane, the extract is dried over anhydrous sodium sulfate, and the solvent is removed to obtain 6,7-epoxy-2-nonanone. Without isolating this, 0.9ml
Dissolve in a mixed solvent of acetone and 0.9ml water, add sulfuric acid
Add 245 mg under ice cooling and stir at room temperature for 1 hour. The reaction solution was neutralized with aqueous sodium bicarbonate and extracted with ether. After drying the ether solution over anhydrous sodium sulfate and removing the ether, 99 mg of brevicomine was obtained. This was determined by GC-MS and NMR as exo:endo=
It turned out to be 93:7. 1-ethyl-6-
The total yield from methylcyclohexene was 51%.
Claims (1)
表し、ｎは１又は３である で表わされる環状オレフイン化合物を塩化鉄
（）の存在下、ピリジン中でガラス透過光を少
なくとも４時間照射して一般式 （R1、R2及びｎは前述のとおり） で表わされるα−クロルジケトン化合物を得るこ
とを特徴とするα−クロルジケトン化合物の製造
方法。[Claims] 1. General formula R 1 is a methyl group, R 2 is a methyl group or an ethyl group, and n is 1 or 3. A cyclic olefin compound represented by R 1 is a methyl group, R 2 is a methyl group or an ethyl group, and n is irradiated with glass transmitted light for at least 4 hours in pyridine in the presence of iron chloride (). general formula (R 1 , R 2 and n are as described above) A method for producing an α-chlorodiketone compound, which comprises obtaining an α-chlordiketone compound represented by the following.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59124562A JPS615039A (en) | 1984-06-19 | 1984-06-19 | Preparation of alpha-chlorodiketone compound by photochemical reaction and synthesis of brevicomin from obtained alpha-chlorodiketone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59124562A JPS615039A (en) | 1984-06-19 | 1984-06-19 | Preparation of alpha-chlorodiketone compound by photochemical reaction and synthesis of brevicomin from obtained alpha-chlorodiketone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS615039A JPS615039A (en) | 1986-01-10 |
| JPH0254814B2 true JPH0254814B2 (en) | 1990-11-22 |
Family
ID=14888548
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59124562A Granted JPS615039A (en) | 1984-06-19 | 1984-06-19 | Preparation of alpha-chlorodiketone compound by photochemical reaction and synthesis of brevicomin from obtained alpha-chlorodiketone |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS615039A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017104798A1 (en) * | 2015-12-18 | 2017-06-22 | 株式会社エースネット | Method for producing oxidation reaction product of hydrocarbon or derivative thereof, and method for producing oxidation reaction product of olefin |
| CN114652757B (en) * | 2020-12-23 | 2024-03-01 | 宣威市龙津生物科技有限责任公司 | Method for improving scutellarin content in erigeron breviscapus medicinal material |
-
1984
- 1984-06-19 JP JP59124562A patent/JPS615039A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS615039A (en) | 1986-01-10 |
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