JPH0322381B2 - - Google Patents
Info
- Publication number
- JPH0322381B2 JPH0322381B2 JP6984882A JP6984882A JPH0322381B2 JP H0322381 B2 JPH0322381 B2 JP H0322381B2 JP 6984882 A JP6984882 A JP 6984882A JP 6984882 A JP6984882 A JP 6984882A JP H0322381 B2 JPH0322381 B2 JP H0322381B2
- Authority
- JP
- Japan
- Prior art keywords
- hours
- ammonia
- general formula
- reaction
- yield
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910052801 chlorine Inorganic materials 0.000 claims description 5
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000010898 silica gel chromatography Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- NZYIPVQQHZWTRB-UHFFFAOYSA-N 2,2,4-trichloro-3-(2,3-dichlorophenyl)butanal Chemical compound O=CC(Cl)(Cl)C(CCl)C1=CC=CC(Cl)=C1Cl NZYIPVQQHZWTRB-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- FSPXZKAEHGXEHN-RJRFIUFISA-N (z)-2,4-dichlorobut-2-enal Chemical compound ClC\C=C(/Cl)C=O FSPXZKAEHGXEHN-RJRFIUFISA-N 0.000 description 1
- VNJOVWYGVMZBNB-UHFFFAOYSA-N 2,2,4-trichloro-3-(2-chlorophenyl)butanal Chemical compound O=CC(Cl)(Cl)C(CCl)C1=CC=CC=C1Cl VNJOVWYGVMZBNB-UHFFFAOYSA-N 0.000 description 1
- GABOSZQDASEIMX-UHFFFAOYSA-N 2,2,4-trichloro-3-(2-nitrophenyl)butanal Chemical compound [O-][N+](=O)C1=CC=CC=C1C(CCl)C(Cl)(Cl)C=O GABOSZQDASEIMX-UHFFFAOYSA-N 0.000 description 1
- UMKXGODCJYHDSF-UHFFFAOYSA-N 2,2,4-trichloro-3-phenylbutanal Chemical compound O=CC(Cl)(Cl)C(CCl)C1=CC=CC=C1 UMKXGODCJYHDSF-UHFFFAOYSA-N 0.000 description 1
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 1
- 150000005358 3-phenylpyrroles Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 244000309464 bull Species 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 150000001989 diazonium salts Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 150000008060 phenylpyrroles Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
Landscapes
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyrrole Compounds (AREA)
Description
【発明の詳細な説明】
本発明は３−フエニルピロール誘導体の新規な
製造方法に関し、詳しくは一般式
（式中、Ｘはハロゲン原子、ニトロ基又はハロ
アルキル基を、Ｙは水素原子又は塩素原子を、ｎ
は０、１又は２を示す。）で表わされる化合物と、
アンモニアもしくはアンモニア水とを有機溶媒中
で反応させることを特徴とする一般式
（式中、Ｘ及びｎは前記と同一の意味を示し、
Ｚは水素原子又は塩素原子を示す。）で表わされ
る化合物の製造方法である。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 3-phenylpyrrole derivatives. (In the formula, X is a halogen atom, a nitro group or a haloalkyl group, Y is a hydrogen atom or a chlorine atom, n
indicates 0, 1 or 2. ) and a compound represented by
General formula characterized by reacting ammonia or aqueous ammonia in an organic solvent (In the formula, X and n have the same meanings as above,
Z represents a hydrogen atom or a chlorine atom. ) is a method for producing a compound represented by
前記一般式（）で表わされる化合物は、殺菌
剤又はその中間体として有用な化合物である（特
開昭54−103865、、55−157565、56−18960、55−
160760）。その製造方法としては特に４位が塩素
置換されている場合下記に示す如くピロールの反
応性に鑑みて、ピロールの両α位を脱離し易い保
護基で保護した後、β位に塩素化を行う方法が知
られている。しかしながらこれらの公知方法は工
程数が多く操作が煩雑となり工業的に好ましい方
法と言えるものではない。 The compound represented by the general formula () is a compound useful as a fungicide or an intermediate thereof (Japanese Patent Application Laid-open No. 103865/1986, 55-157565, 56-18960, 55-
160760). In particular, when the 4-position is substituted with chlorine, the manufacturing method is to protect both α-positions of pyrrole with easily removable protecting groups, and then chlorinate the β-position, as shown below, in view of the reactivity of pyrrole. method is known. However, these known methods involve a large number of steps and are complicated to operate, so they cannot be said to be industrially preferred.
〔Chem Pharm Bull
17(3)582〜７（’69）
ibid17(3)588〜95（’69）〕
本発明者らは少い工程数で工業的に有利に３−
フエニルピロール類を製造する方法について研究
を重ね本発明を完成した。 [Chem Pharm Bull 17 (3) 582-7 ('69) ibid 17 (3) 588-95 ('69)] The present inventors have developed an industrially advantageous 3-
The present invention was completed after repeated research on methods for producing phenylpyrroles.
本発明の方法は、前記一般式（）で表わされ
る新規なブチルアルデヒドを原料として用いるこ
とにより、工程の大幅な短縮をはかつたものであ
る。 The method of the present invention significantly shortens the steps by using the novel butyraldehyde represented by the above general formula () as a raw material.
本発明の実施にあたつては、前記一般式（）
で表わされる化合物を無溶媒もしくは適当な有機
溶媒中、加熱してアンモニアもしくはアンモニア
水と反応させ、閉環反応と、脱ハロゲン化反応を
同時に行わせる。 In carrying out the present invention, the general formula ()
The compound represented by is heated without a solvent or in a suitable organic solvent to react with ammonia or aqueous ammonia to simultaneously carry out a ring-closing reaction and a dehalogenation reaction.
有機溶媒としてはエタノール、メタノール、ジ
オキサン、エチレングリコールジメチルエーテル
（グライム）、ジエチレングリコールジメチルエー
テル（ジグライム）等が用いられる。反応は30℃
〜溶媒の沸点で行われるが、３〜５時間加熱反応
させた後、室温迄冷却し、塩基を添加して更に数
時間〜10時間室温に放置することにより、収率の
向上を計ることもできる。 As the organic solvent, ethanol, methanol, dioxane, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), etc. are used. Reaction at 30℃
~The reaction is carried out at the boiling point of the solvent, but the yield can be improved by heating the reaction for 3 to 5 hours, cooling it to room temperature, adding a base, and leaving it at room temperature for an additional few to 10 hours. can.
塩基としては、トリエチルアミン、１，８−ジ
アザビシクロ〔５，４，０〕−７−ウンデセン等
一般の塩基が用いられる。 As the base, common bases such as triethylamine and 1,8-diazabicyclo[5,4,0]-7-undecene are used.
反応終了後は、アンモニアガスと反応させた場
合は生じる塩化アンモニウムを別し、液を濃
縮して粗生成物を得、アンモニア水と反応させた
場合は適当な有機溶媒で抽出した後溶媒を留去し
て粗生成物を得る。得られた粗生成物をカラムク
ロマトグラフイーで精製することにより目的物を
好収率で得ることができる。 After the reaction is complete, if the reaction is with ammonia gas, the ammonium chloride produced is separated and the liquid is concentrated to obtain a crude product; if the reaction is with aqueous ammonia, it is extracted with an appropriate organic solvent and the solvent is distilled off. to obtain the crude product. The target product can be obtained in good yield by purifying the obtained crude product by column chromatography.
前記一般式（）で表わされる原料化合物は文
献未記載の新規化合物であり、例えば相当するア
ニリンのジアゾニウム塩と２，４−ジクロロクロ
トンアルデヒドとを反応させることにより容易に
製造できる。 The raw material compound represented by the general formula () is a new compound that has not been described in any literature, and can be easily produced, for example, by reacting the corresponding diazonium salt of aniline with 2,4-dichlorocrotonaldehyde.
以下、実施例を挙げて本発明の方法について更
に詳しく説明する。 Hereinafter, the method of the present invention will be explained in more detail with reference to Examples.
実施例 １
２，２，４−トリクロロ−３−（２，３−ジク
ロロフエニル）ブチルアルデヒド1.6ｇをジグラ
イム５mlに溶解し、、28％アンモニア水５mlを加
えて約100℃で３時間加熱攬拌した。28％アンモ
ニア水を２ml追加し、更に１時間加熱攬拌した
後、室温で１夜静置した。エチルエーテル20mlで
抽出し、硫酸マグネシウムで乾燥後、エチルエー
テルを留去して褐色油状物を得た。この油状物を
シリカゲルカラムクロマトにより精製して目的物
0.54ｇを得た。融点59〜60℃、収率43.8％
実施例 ２
２，２，４−トリクロロ−３−フエニル−ブチ
ルアルデヒド1.9ｇをジオキサン10mlに溶解し、
25％アンモニア水５mlを適加して90℃で３時間加
熱攬拌した。25％アンモニア水５mlを追加し、更
に３時間加熱攬拌した後、室温14時間静置した。
ジオキサンを留去した後、酢酸エチル20mlで抽出
し、飽和食塩水で水洗、硫酸マグネシウムで乾燥
後、溶媒を留去した。得られた粗生物をシリカゲ
ルカラムクロマトにより精製して目的物0.65ｇを
得た。n16.5 D1.6343 収率48.5％
実施例 ３
２，２，４−トリクロロ−３−（２−クロロフ
エニル）ブチルアルデヒド1.5ｇをジオキサン10
mlに溶解し、25％アンモニア水５mlを滴加して90
℃で３時間加熱攬拌した。25％アンモニア水５ml
を追加し、更に３時間加熱攬拌した後、室温で16
時間静置した。ジオキサンを留去した後、酢酸エ
チル20mlで抽出し、飽和食塩水で水洗、硫酸マグ
ネシウムで乾燥後溶媒を留去した。得られた粗成
物をシリカゲルカラムクロマトで精製して目的物
0.75ｇを得た。融点68〜70℃ 収率67.5％
実施例 ４
２，２，４−トリクロル−３−（２−ニトロフ
エニル）ブチルアルデヒド1.5ｇをジオキサン10
mlに溶かし、実施例３と同様にして目的物0.8ｇ
を得た。mp111〜113℃ 収率64％
実施例 ５
２，２，４−トリクロロ−３−（２，３−ジク
ロロフエニル）ブチルアルデヒド3.2ｇをグライ
ム40mlに溶解し、加熱還流下アンモニアガスを５
時間吹き込んだ。室温迄反応溶液を冷却した後、
生じた沈澱を別し、液に１，８−ジアザビシ
クロ〔５，４−０〕−７−ウンデセン0.8ｇを加え
て室温で一夜攬拌した。不溶物を別し、液を
減圧下濃縮した後、得られた残留物をシリカゲル
カラムクロマトで精製して目的物２ｇを得た。融
点59〜60℃ 収率81％
実施例 ６
２，２，４−トリクロロ−３−（２−トリクロ
ロメチル）ブチルアルデヒド3.1ｇをグライム40
mlに溶解し、室温でアンモニアガスを３時間吹き
込み更に40℃で３時間アンモニアガスを吹き込ん
だ。室温迄冷却後、実施例５と同様に処理して目
的物1.5ｇを得た。融点43〜52℃ 収率63％Example 1 1.6 g of 2,2,4-trichloro-3-(2,3-dichlorophenyl)butyraldehyde was dissolved in 5 ml of diglyme, 5 ml of 28% aqueous ammonia was added, and the mixture was heated and stirred at about 100 DEG C. for 3 hours. After adding 2 ml of 28% aqueous ammonia and heating and stirring for an additional hour, the mixture was allowed to stand overnight at room temperature. After extraction with 20 ml of ethyl ether and drying over magnesium sulfate, the ethyl ether was distilled off to obtain a brown oil. This oil is purified by silica gel column chromatography to obtain the desired product.
0.54g was obtained. Melting point 59-60℃, yield 43.8% Example 2 Dissolve 1.9 g of 2,2,4-trichloro-3-phenyl-butyraldehyde in 10 ml of dioxane,
5 ml of 25% ammonia water was added, and the mixture was heated and stirred at 90°C for 3 hours. After adding 5 ml of 25% ammonia water and heating and stirring for an additional 3 hours, the mixture was allowed to stand at room temperature for 14 hours.
After distilling off dioxane, the mixture was extracted with 20 ml of ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to obtain 0.65 g of the target product. n 16.5 D 1.6343 Yield 48.5% Example 3 1.5 g of 2,2,4-trichloro-3-(2-chlorophenyl)butyraldehyde in dioxane 10
ml, add dropwise 5 ml of 25% ammonia water to 90%
The mixture was heated and stirred at ℃ for 3 hours. 5ml of 25% ammonia water
After heating and stirring for an additional 3 hours,
Let it stand for a while. After distilling off dioxane, the mixture was extracted with 20 ml of ethyl acetate, washed with saturated brine, dried over magnesium sulfate, and then the solvent was distilled off. The obtained crude product is purified by silica gel column chromatography to obtain the desired product.
0.75g was obtained. Melting point 68-70℃ Yield 67.5% Example 4 1.5 g of 2,2,4-trichloro-3-(2-nitrophenyl)butyraldehyde in dioxane 10
ml and proceed as in Example 3 to obtain 0.8g of the target substance.
I got it. mp111-113℃ Yield 64% Example 5 Dissolve 3.2 g of 2,2,4-trichloro-3-(2,3-dichlorophenyl)butyraldehyde in 40 ml of glyme, and add 5 ml of ammonia gas under heating under reflux.
I blew time. After cooling the reaction solution to room temperature,
The resulting precipitate was separated, and 0.8 g of 1,8-diazabicyclo[5,4-0]-7-undecene was added to the solution, followed by stirring at room temperature overnight. Insoluble matter was separated and the liquid was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography to obtain 2 g of the target product. Melting point 59-60℃ Yield 81% Example 6 3.1 g of 2,2,4-trichloro-3-(2-trichloromethyl)butyraldehyde in 40 grams of grime
ml, and ammonia gas was blown into the solution at room temperature for 3 hours, and then at 40°C for 3 hours. After cooling to room temperature, it was treated in the same manner as in Example 5 to obtain 1.5 g of the desired product. Melting point 43-52℃ Yield 63%
Claims (1)
アルキル基を、ｎは０、１又は２を、Ｙは水素原
子又は塩素原子を示す。）で表わされる化合物と、
アンモニア又はアンモニア水とを有機溶媒中で反
応させることを特徴とする一般式 （式中、Ｘ及びｎは前記と同一の意味を示し、
Ｚは水素原子又は塩素原子を示す。）で表わされ
る化合物の製造方法。[Claims] 1. General formula (In the formula, X represents a halogen atom, a nitro group, or a haloalkyl group, n represents 0, 1, or 2, and Y represents a hydrogen atom or a chlorine atom.)
General formula characterized by reacting ammonia or aqueous ammonia in an organic solvent (In the formula, X and n have the same meanings as above,
Z represents a hydrogen atom or a chlorine atom. ) A method for producing a compound represented by
Priority Applications (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57069848A JPS58185559A (en) | 1982-04-26 | 1982-04-26 | Production of 3-phenylpyrole derivative |
| US06/485,910 US4471126A (en) | 1982-04-26 | 1983-04-18 | Method for the production of 3-phenylpyrrole |
| KR1019830001722A KR860001335B1 (en) | 1982-04-26 | 1983-04-23 | Process for preparation of 3-phenyl pyroles |
| ES521830A ES8406066A1 (en) | 1982-04-26 | 1983-04-25 | Method for the production of 3-phenylpyrrole derivatives. |
| EP83200592A EP0092890A1 (en) | 1982-04-26 | 1983-04-25 | Method for the production of 3-phenylpyrrole derivatives |
| HU831433A HU190087B (en) | 1982-04-26 | 1983-04-26 | Process for preparing 3-phenyl-pyrrole derivatives |
| HU854800A HU193454B (en) | 1982-04-26 | 1983-04-26 | Process for producing 3-phenyl-butyraldehyde derivatives |
| IL68519A IL68519A (en) | 1982-04-26 | 1983-04-28 | Production of 3-phenylpyrrole derivatives,and novel 2,4-dichloro-3-phenylbutyraldehyde intermediates therefor |
| SU833657406A SU1225479A3 (en) | 1982-04-26 | 1983-10-31 | Method of producing aldehydes |
| ES528633A ES528633A0 (en) | 1982-04-26 | 1984-01-02 | A METHOD FOR THE PREPARATION OF NEW PHENYLBUTYLALDEHYDE DERIVATIVES |
| US06/615,328 US4532363A (en) | 1982-04-26 | 1984-05-30 | Phenylbutyraldehydes |
| KR8606472A KR860001388B1 (en) | 1982-04-26 | 1986-08-05 | Process for the preparation of intermedium for the 3-phenyl pyrrole |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57069848A JPS58185559A (en) | 1982-04-26 | 1982-04-26 | Production of 3-phenylpyrole derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58185559A JPS58185559A (en) | 1983-10-29 |
| JPH0322381B2 true JPH0322381B2 (en) | 1991-03-26 |
Family
ID=13414633
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57069848A Granted JPS58185559A (en) | 1982-04-26 | 1982-04-26 | Production of 3-phenylpyrole derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58185559A (en) |
-
1982
- 1982-04-26 JP JP57069848A patent/JPS58185559A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58185559A (en) | 1983-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPH0322381B2 (en) | ||
| JP2001521498A (en) | Method for producing O- (3-amino-2-hydroxy-propyl) -hydroxymic acid halide | |
| JP3101721B2 (en) | Method for producing aromatic fluorine compound | |
| JPH061776A (en) | Production of substituted pyrazinecarbonitrile | |
| KR860001335B1 (en) | Process for preparation of 3-phenyl pyroles | |
| JPS5923314B2 (en) | New pyrrole derivative | |
| JP5079809B2 (en) | Methods for the synthesis and synthesis of (3-alkyl-5-piperidin-1-yl-3,3a-dihydro-pyrazolo [1,5-a] pyrimidin-7-yl) -amino derivatives and intermediates Intermediate | |
| JPH0558985A (en) | Production of cyanoguanidine derivative | |
| JPH09132554A (en) | Production of 4-alkoxy-1,1,1-trifluoro-3-buten-2-one | |
| KR960010351B1 (en) | Method for preparing benzoxazine derivatives | |
| JPS59167591A (en) | Preparation of 8-(hydroxycarbonylmethyl)pyrrolizidine | |
| JP3328694B2 (en) | Method for producing nitrogen-containing heterocyclic compound | |
| KR20260062870A (en) | Method for preparing fmoc-lys(ivdde)-oh | |
| JP3023773B2 (en) | Nitrogen-containing heterocyclic compounds | |
| JP3961049B2 (en) | 3-Amino-4- (1-hydroxyalkyl) pyrazoline compound, method for producing the same and method for producing the same | |
| JPH10251259A (en) | 1,4,6,9-tetraza-5,10-dehydrophenazine derivative and its production | |
| KR0129007B1 (en) | 4-Chloro-2-fluoro-5- (pentyloxycarbonylmethyloxy) nitrobenzene and preparation method thereof | |
| JPH0285237A (en) | Production of methyl 3- aminocrotanate | |
| JP3148556B2 (en) | Method for producing 2-bisarylamino-9,9-dialkylfluorene | |
| JPS6317869A (en) | Production of 2-lower alkyl-4-amino-5-formylpyrimidine | |
| JPS5935392B2 (en) | Method for producing benzonitriles | |
| JPS5852995B2 (en) | Method for producing furfural derivatives | |
| JPS607624B2 (en) | 1-(N-aralkylcarbamoyl)-5-fluorouracils and their production method | |
| JPS6360023B2 (en) | ||
| JPS6223757B2 (en) |