JPH0446274B2 - - Google Patents
Info
- Publication number
- JPH0446274B2 JPH0446274B2 JP14843683A JP14843683A JPH0446274B2 JP H0446274 B2 JPH0446274 B2 JP H0446274B2 JP 14843683 A JP14843683 A JP 14843683A JP 14843683 A JP14843683 A JP 14843683A JP H0446274 B2 JPH0446274 B2 JP H0446274B2
- Authority
- JP
- Japan
- Prior art keywords
- ethylenedioxy
- nitrophenol
- nitrophenoxy
- ethanol
- dihalo
- 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
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 5
- -1 5-ethylenedioxy-2-nitrophenol Chemical compound 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 8
- LRHFGBDYKMSVMK-UHFFFAOYSA-N 7-nitro-2,3-dihydro-1,4-benzodioxin-6-ol Chemical compound O1CCOC2=C1C=C(O)C([N+]([O-])=O)=C2 LRHFGBDYKMSVMK-UHFFFAOYSA-N 0.000 description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 241000196324 Embryophyta Species 0.000 description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 3
- 241000219095 Vitis Species 0.000 description 3
- 235000009754 Vitis X bourquina Nutrition 0.000 description 3
- 235000012333 Vitis X labruscana Nutrition 0.000 description 3
- 235000014787 Vitis vinifera Nutrition 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 3
- 229940045803 cuprous chloride Drugs 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- 241000233679 Peronosporaceae Species 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000004480 active ingredient Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 230000003902 lesion Effects 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- QNULZVZLSYAFSP-UHFFFAOYSA-N 2-(2,4-dichloro-5-nitrophenoxy)ethanol Chemical compound OCCOC1=CC([N+]([O-])=O)=C(Cl)C=C1Cl QNULZVZLSYAFSP-UHFFFAOYSA-N 0.000 description 1
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 1
- 239000005747 Chlorothalonil Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241000219094 Vitaceae Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- CRQQGFGUEAVUIL-UHFFFAOYSA-N chlorothalonil Chemical compound ClC1=C(Cl)C(C#N)=C(Cl)C(C#N)=C1Cl CRQQGFGUEAVUIL-UHFFFAOYSA-N 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- NFZJYJJVHFGPSI-UHFFFAOYSA-H dialuminum;ethyl-dioxido-oxo-$l^{5}-phosphane Chemical compound [Al+3].[Al+3].CCP([O-])([O-])=O.CCP([O-])([O-])=O.CCP([O-])([O-])=O NFZJYJJVHFGPSI-UHFFFAOYSA-H 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 238000011081 inoculation Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- LRDFRRGEGBBSRN-UHFFFAOYSA-N isobutyronitrile Chemical compound CC(C)C#N LRDFRRGEGBBSRN-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 150000003839 salts Chemical class 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
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
Landscapes
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Description
【発明の詳細な説明】
本発明は、一般式〔〕
〔式中、ＸおよびＹは同一または相異なり、ハ
ロゲン原子を表わす。〕
で示されるβ−（２，４−ジハロ−５−ニトロフ
エノキシ）エタノールを溶媒中、アルカリ金属水
酸化物の存在下、加熱することによる４，５−エ
チレンジオキシ−２−ニトロフエノールの製造法
に関する。
４，５−エチレンジオキシ−２−ニトロフエノ
ールは植物病害防除剤の有効成分の中間体であ
る。すなわち、４，５−エチレンジオキシ−２−
ニトロフエノールを例えば、Ｏ−エチル Ｎ−
sec−ブチル チオノリン酸アミドクロリドと反
応させることによつて製造することができるＯ−
エチル Ｏ−４，５−エチレンジオキシ−２−ニ
トロフエニル Ｎ−sec−ブチル ホスホロアミ
ドチオエートは、植物病害防除剤の有効成分であ
り、べと病や疫病等の植物病害に対して防除効力
を有する。
本発明者らは、４，５−エチレンジオキシ−２
−ニトロフエノールの製造法について検討した結
果、上記一般式〔〕で示されるβ−（２，４−
ジハロ−５−ニトロフエノキシ）エタノールを、
溶媒中、触媒の存在下または非存在下にβ−（２，
４−ジハロ−５−ニトロフエノキシ）エタノール
１モルに対して２モル以上のアルカリ金属水酸化
物の存在下で、通常、１時間から244時間、70℃
から200℃に加熱することによつて４，５−エチ
レンジオキシ−２−ニトロフエノールを製造する
ことができることを見出した。
溶媒としては、例えばジオキサン、テトラヒド
ロフラン、エチレングリコールジメチルエーテル
等のエーテル、アセトニトリル、イソブチロニト
リル等のニトリル、Ｎ，Ｎ−ジメチルホルムアミ
ド、Ｎ，Ｎ−ジメチルアセトアミド等の酸アミ
ド、ジメチルスルホキシド、スルホラン等の硫黄
化合物等が挙げられる。
アルカリ金属水酸化物としては、例えば水酸化
ナトリウム、水酸化カリウム等が挙げられる。
触媒としては、例えば銅粉、塩化第一銅等が挙
げられる。
反応終了後は、通常の後処理を行ない、必要な
らば、クロマトグラフイー、再結晶等によつて精
製する。
原料化合物である一般式〔〕で示されるβ−
（２，４−ジハロ−５−ニトロフエノキシ）エタ
ノールは、例えば一般式〔〕
〔式中、ＸおよびＹは前記と同一の意味を表わ
す。〕
で示される２，４−ジハロ−５−ニトロフエノー
ルと１〜５当量のエチレンハロヒドリンとをアセ
トニトリル、Ｎ，Ｎ−ジメチルホルムアミド、ジ
メチルスルホキシド等の溶媒中、１〜５当量の水
酸化ナトリウム、炭酸カリウム等の無機塩基の存
在下、60〜150℃で、１〜24時間反応させること
によつて製造することができる。
次に実施例を示す。
実施例 １
β−（２，４−ジクロロ−５−ニトロフエノキ
シ）エタノール2.0ｇをジメチルスルホキシド10
mlに溶かし、塩化第一銅0.1ｇを加えて100℃に加
熱し、さらに水酸化ナトリウム粉末1.5ｇを加え
130〜150℃に１時間保つた。冷却後、氷水100ml
中に注ぎ、酢酸エチル100mlを用いて２度抽出し、
抽出液を水洗後硫酸マグネシウムで乾燥した。酢
酸エチルを減圧留去してから、シリカゲルカラム
クロマトグラフイーで精製して４，５−エチレン
ジオキシ−２−ニトロフエノール0.67ｇを得た。
m.p. 170〜173℃
実施例 ２
β−（２−クロロ−４−フルオロ−５−ニトロ
フエノキシ）エタノール2.0ｇをジメチルスルホ
キシド10mlに溶かし、水酸化カリウム粉末1.40ｇ
を加えて加熱し、120〜130℃に３時間保つた。冷
却後、氷水100ml中に注ぎ、酢酸エチル100を用い
て２度抽出し、抽出液を水洗後、硫酸マグネシウ
ムで乾燥した。酢酸エチルを減圧留去してから、
シリカゲルカラムクロマトグラフイーで精製して
４，５−エチレンジオキシ−２−ニトロフエノー
ル0.72ｇを得た。
m.p. 170〜173℃
次に参考製造例および参考試験例を示す。
参考製造例
４，５−エチレンジオキシ−２−ニトロフエノ
ール（1.97ｇ、10mmol）をアセトニトリル100ml
に溶かし、無水炭酸カリウム末（1.40ｇ）と塩化
第一銅（10mg）とを加えて、40〜50℃に保つて30
分撹拌した。これにＯ−エチル Ｎ−sec−ブチ
ルチオノリン酸アミドクロリド（2.2ｇ、
10mmol）を40分で滴下し、さらに３時間撹拌還
流した。放冷後、無機塩を別して、アセトニト
リルを留去し、残分をトルエンに溶かし、希塩
酸、水、希アルカリ水溶液、次いで水で洗浄し、
無水硫酸マグネシウムで乾燥した。トルエンを留
去し、さらにシリカゲルカラムクロマトグラフイ
ーで精製してＯ−エチル Ｏ−４，５−エチレン
ジオキシ−２−ニトロフエニル Ｎ−sec−ブチ
ル ホスホロアミドチオエート2.33ｇを得た。
m.p. 59〜61℃ 収率62.0％
参考試験例
ブドウべと病防除試験（治療効果）
プラスチツクポツトに砂壌土を詰め、ブドウ
（ネオマスカツトの種）を播種し、温室内で50日
間育成した。第４〜５本葉が展開したブドウの幼
苗にブドウべと病菌の胞子懸濁液を噴霧接種し
た。接種後25℃、多湿下で１日間育成し、乳剤に
した供試化合物を水で希釈して所定濃度にし、そ
れを葉面に充分付着するように茎葉散布した。散
布後23℃温室内で10日間育成し、防除効力を調査
した。なお、防除効力は、調査時の供試植物の発
病状態すなわち葉、茎等の菌叢、病斑の程度を肉
眼観察し、菌叢、病斑が全く認められなければ
「５」、10％程度認られれば「４」、30％程度認め
られれば「３」、50％程度認められれば「２」、70
％程度認められれば「１」、それ以上で化合物を
供試していない場合の発病状態と差が認められな
ければ「０」として、０〜５の６段階に評価し、
０、１、２、３、４、５で表示した。
また、比較対照にクロロタロニールおよびトリ
（エチルホスホン酸）アルミニウムを用いた。そ
の結果を第１表に示す。
【表】[Detailed Description of the Invention] The present invention relates to the general formula [] [In the formula, X and Y are the same or different and represent a halogen atom. ] A method for producing 4,5-ethylenedioxy-2-nitrophenol by heating β-(2,4-dihalo-5-nitrophenoxy)ethanol shown in a solvent in the presence of an alkali metal hydroxide. Regarding. 4,5-ethylenedioxy-2-nitrophenol is an intermediate of the active ingredient of a plant disease control agent. That is, 4,5-ethylenedioxy-2-
Nitrophenol, for example, O-ethyl N-
O- which can be produced by reacting with sec-butyl thionolamide chloride
Ethyl O-4,5-ethylenedioxy-2-nitrophenyl N-sec-butyl phosphoroamide thioate is an active ingredient of a plant disease control agent, and is effective in controlling plant diseases such as downy mildew and late blight. has. The inventors have discovered that 4,5-ethylenedioxy-2
- As a result of studying the manufacturing method of nitrophenol, we found that β-(2,4-
dihalo-5-nitrophenoxy)ethanol,
β-(2,
(4-dihalo-5-nitrophenoxy)ethanol in the presence of 2 mol or more of alkali metal hydroxide per 1 mol of ethanol, usually at 70°C for 1 to 244 hours.
It has been found that 4,5-ethylenedioxy-2-nitrophenol can be produced by heating from to 200°C. Examples of solvents include ethers such as dioxane, tetrahydrofuran, and ethylene glycol dimethyl ether, nitriles such as acetonitrile and isobutyronitrile, acid amides such as N,N-dimethylformamide and N,N-dimethylacetamide, dimethylsulfoxide, and sulfolane. Examples include sulfur compounds. Examples of the alkali metal hydroxide include sodium hydroxide and potassium hydroxide. Examples of the catalyst include copper powder and cuprous chloride. After the reaction is completed, usual post-treatments are carried out, and if necessary, purification is carried out by chromatography, recrystallization, etc. β- represented by the general formula [] which is a raw material compound
(2,4-dihalo-5-nitrophenoxy)ethanol has the general formula [] [In the formula, X and Y represent the same meanings as above. ] 2,4-dihalo-5-nitrophenol represented by and 1 to 5 equivalents of ethylene halohydrin in a solvent such as acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, and 1 to 5 equivalents of sodium hydroxide. It can be produced by reacting at 60 to 150°C for 1 to 24 hours in the presence of an inorganic base such as potassium carbonate. Next, examples will be shown. Example 1 2.0 g of β-(2,4-dichloro-5-nitrophenoxy)ethanol was mixed with 10 g of dimethyl sulfoxide.
ml, add 0.1g of cuprous chloride, heat to 100℃, and add 1.5g of sodium hydroxide powder.
It was kept at 130-150°C for 1 hour. After cooling, add 100ml of ice water
Pour into the solution and extract twice with 100ml of ethyl acetate.
The extract was washed with water and dried over magnesium sulfate. After ethyl acetate was distilled off under reduced pressure, the residue was purified by silica gel column chromatography to obtain 0.67 g of 4,5-ethylenedioxy-2-nitrophenol. mp 170-173℃ Example 2 Dissolve 2.0g of β-(2-chloro-4-fluoro-5-nitrophenoxy)ethanol in 10ml of dimethyl sulfoxide, and dissolve 1.40g of potassium hydroxide powder.
was added and heated, and kept at 120-130°C for 3 hours. After cooling, the mixture was poured into 100 ml of ice water, extracted twice with 100 ml of ethyl acetate, and the extract was washed with water and dried over magnesium sulfate. After removing ethyl acetate under reduced pressure,
It was purified by silica gel column chromatography to obtain 0.72 g of 4,5-ethylenedioxy-2-nitrophenol. mp 170-173°C Next, reference production examples and reference test examples are shown. Reference production example 4,5-ethylenedioxy-2-nitrophenol (1.97g, 10mmol) in 100ml of acetonitrile
Add anhydrous potassium carbonate powder (1.40g) and cuprous chloride (10mg), and keep at 40-50℃ for 30 minutes.
Stir for 1 minute. To this was added O-ethyl N-sec-butylthionolamide chloride (2.2 g,
10 mmol) was added dropwise over 40 minutes, and the mixture was further stirred and refluxed for 3 hours. After cooling, inorganic salts were separated, acetonitrile was distilled off, the residue was dissolved in toluene, and washed with dilute hydrochloric acid, water, dilute aqueous alkali solution, and then water.
It was dried with anhydrous magnesium sulfate. Toluene was distilled off, and the residue was further purified by silica gel column chromatography to obtain 2.33 g of O-ethyl O-4,5-ethylenedioxy-2-nitrophenyl N-sec-butyl phosphoroamide thioate. mp 59-61℃ Yield 62.0% Reference test example Grape mildew control test (therapeutic effect) Plastic pots were filled with sandy loam, grapes (neomuscatus seeds) were sown, and grown in a greenhouse for 50 days. A spore suspension of grape downy mildew was spray inoculated to grape seedlings in which the 4th to 5th true leaves had developed. After inoculation, the plants were grown for 1 day at 25° C. under humid conditions, and an emulsion of the test compound was diluted with water to a predetermined concentration and sprayed on the foliage to ensure sufficient adhesion to the leaf surface. After spraying, they were grown in a greenhouse at 23°C for 10 days, and their control efficacy was investigated. The control efficacy is determined by visually observing the disease state of the test plants at the time of the survey, that is, the degree of bacterial flora and lesions on leaves, stems, etc., and if no bacterial flora or lesions are observed, it is rated "5", 10%. ``4'' if the degree is recognized, ``3'' if the degree is recognized by 30%, ``2'' if the degree is recognized by 50%, 70
If it is found to be about 1%, it is scored as "1", and if it is higher than that and there is no difference from the disease state when no compound is tested, it is given as "0".
Displayed as 0, 1, 2, 3, 4, 5. In addition, chlorothalonil and aluminum tri(ethylphosphonate) were used for comparison. The results are shown in Table 1. 【table】
Claims (1)
ロゲン原子を表わす。〕 で示されるβ−（２，４−ジハロ−５−ニトロフ
エノキシ）エタノールを溶媒中、アルカリ金属水
酸化物の存在下、加熱することを特徴とする４，
５−エチレンジオキシ−２−ニトロフエノールの
製造法。[Claims] 1. General formula [In the formula, X and Y are the same or different and represent a halogen atom. ] 4, characterized in that β-(2,4-dihalo-5-nitrophenoxy)ethanol represented by is heated in a solvent in the presence of an alkali metal hydroxide.
Method for producing 5-ethylenedioxy-2-nitrophenol.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14843683A JPS6041672A (en) | 1983-08-12 | 1983-08-12 | Production of 4,5-ethylenedioxy-2-nitrophenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14843683A JPS6041672A (en) | 1983-08-12 | 1983-08-12 | Production of 4,5-ethylenedioxy-2-nitrophenol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6041672A JPS6041672A (en) | 1985-03-05 |
| JPH0446274B2 true JPH0446274B2 (en) | 1992-07-29 |
Family
ID=15452746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14843683A Granted JPS6041672A (en) | 1983-08-12 | 1983-08-12 | Production of 4,5-ethylenedioxy-2-nitrophenol |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6041672A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6048983A (en) * | 1983-08-25 | 1985-03-16 | Sumitomo Chem Co Ltd | 2-halo-4,5-ethylenedioxynitrobenzene and its production |
-
1983
- 1983-08-12 JP JP14843683A patent/JPS6041672A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6041672A (en) | 1985-03-05 |
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