JPS5950674B2 - Method for producing N'-substituted hydrazide derivative - Google Patents
Method for producing N'-substituted hydrazide derivativeInfo
- Publication number
- JPS5950674B2 JPS5950674B2 JP10631774A JP10631774A JPS5950674B2 JP S5950674 B2 JPS5950674 B2 JP S5950674B2 JP 10631774 A JP10631774 A JP 10631774A JP 10631774 A JP10631774 A JP 10631774A JP S5950674 B2 JPS5950674 B2 JP S5950674B2
- Authority
- JP
- Japan
- Prior art keywords
- room temperature
- mercury lamp
- pressure mercury
- producing
- distilled
- 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
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- Pyridine Compounds (AREA)
Description
【発明の詳細な説明】
この発明はＮ’一置換ヒドラジド誘導体の新規な製造法
に関するものであり、これを式で示すと次の通りである
。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing N' monosubstituted hydrazide derivatives, which is represented by the following formula.
ひＣ０ＮＨＮＨ２（Ｉ）
＞ＣＨ０−Ｒ３Ｑ］）
（紫外線照射下）
ａＣ０ＮＨＮ＝Ｃ＜：二 皿
（式中、Ｒ、はアルキル基またはアリール基、Ｒ、は水
素原子またはアルキル基、Ｒ、は水素原子またはアシル
基をそれぞれ意味する）この発明の方法は化合物（Ｉ）
に化合物（１１）を紫外線照射下に反応させることによ
り行なわれる。hC0NHNH2(I) >CH0-R3Q]) (under ultraviolet irradiation) aC0NHN=C<:2 plate (wherein, R is an alkyl group or an aryl group, R is a hydrogen atom or an alkyl group, R is a hydrogen atom or acyl group, respectively)) The method of the present invention applies to compound (I)
This is carried out by reacting compound (11) under ultraviolet irradiation.
この発明の方法で使用される化合物（Ｉ）としては、具
体的にピコリノヒドラジド、ニコチノヒドラジドが例示
される。Specific examples of compound (I) used in the method of this invention include picolinohydrazide and nicotinohydrazide.
また、化合物（１１）はメチル、エチル、プロピル、イ
ソプロピル、ブチル、イソブチル、ペンチル、ヘキシル
等のアルキル基またはフェニル、ナフチル、トリル、キ
シリル等のアリール基をＲ１として有し、水素原子また
は前記のようなアルキル基をＲ。Further, compound (11) has an alkyl group such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, etc. or an aryl group such as phenyl, naphthyl, tolyl, xylyl as R1, and a hydrogen atom or the above-mentioned R is an alkyl group.
として有し、水素原子またはホルミル、アセチル、プロ
ピオニル、ブチリル、ベンゾイル等のアシル基をＲ、と
して有する化合物を意味する。この反応は紫外線照射下
に行なわれ、紫外線照射は、通常、低圧水銀灯を使用し
て行なわれる。It means a compound having as R a hydrogen atom or an acyl group such as formyl, acetyl, propionyl, butyryl, benzoyl, etc. This reaction is carried out under ultraviolet irradiation, which is usually carried out using a low pressure mercury lamp.
この反応は通常、化合物（１１）を溶媒を兼ねて使用し
、室温で行なわれることが多い。この反応により生成す
るＮ’一置換ヒドラジド誘導体（１１１）は常法により
単離、採取される。次にこの発明の方法を実施例により
説明する。This reaction is usually carried out at room temperature using compound (11) which also serves as a solvent. The N' monosubstituted hydrazide derivative (111) produced by this reaction is isolated and collected by a conventional method. Next, the method of the present invention will be explained using examples.
実施例 １ニコチノヒドラジド１３５ｍｇを含むベンジ
ルアルコール溶液５０ｍ１を室温で低圧水銀灯を用い、
３９時間紫外線照射する。Example 1 50 ml of a benzyl alcohol solution containing 135 mg of nicotinohydrazide was heated at room temperature using a low-pressure mercury lamp.
Irradiate with ultraviolet light for 39 hours.
反応液からベンジルアルコールを留去し、残留物を加温
下にエーテルで抽出する。抽出液を濃縮し、得られる残
渣をアルミナを用いたカラムクロマトグラフイ一に付し
て単離精製すると、Ｍｐｌ５２〜１５３℃のＮ’−ベン
ジリデンニコチノヒドラジドの無色結晶１７．７ｍｇを
得る。赤外線吸収スペクトルνＣＨＯ３（Ｃｍ−１）：
３２００、１６９５〜１６６５実施例 ２ニコチノヒド
ラジド２７０ｍｇを含むイソプロピルアルコール溶液１
００ｍ１を室温で低圧水銀灯を用い、１５時間紫外線照
射する。Benzyl alcohol was distilled off from the reaction solution, and the residue was extracted with ether while heating. The extract is concentrated, and the resulting residue is isolated and purified by column chromatography using alumina to obtain 17.7 mg of colorless crystals of N'-benzylidene nicotinohydrazide with an Mpl of 52 to 153°C. Infrared absorption spectrum νCHO3 (Cm-1):
3200, 1695-1665 Example 2 Isopropyl alcohol solution 1 containing 270 mg of nicotinohydrazide
00ml was irradiated with ultraviolet rays at room temperature for 15 hours using a low-pressure mercury lamp.
反応液からイソプロピルアルコールを留去し、残留物を
プレパラテイブ・クロマトグラフイ一に付して単離精製
すると、Ｍｐｌ４４．５〜１４５℃のＮ’−イソプロピ
リデンニコチノヒドラジドの無色結晶２０９ｍｇを得る
。赤外線吸収スペクトルνＣＨＣｌ３（Ｃｍ−１）：３
４５０、１６８５〜１６６５、１５９５実施例 ３ピコ
リノヒドラジド５５０ｍｇを含むエタノール溶液２００
ｍ１を室温で低圧水銀灯を用い３６時間紫外線照射を行
なう。Isopropyl alcohol is distilled off from the reaction solution, and the residue is isolated and purified by preparative chromatography to obtain 209 mg of colorless crystals of N'-isopropylidene nicotinohydrazide with an Mpl of 44.5 to 145°C. Infrared absorption spectrum νCHCl3 (Cm-1): 3
450, 1685-1665, 1595 Example 3 Ethanol solution containing 550 mg of picolinohydrazide 200
m1 was irradiated with ultraviolet light for 36 hours at room temperature using a low-pressure mercury lamp.
反応液からエタノールを留去し、残留物をプレパラテイ
ブ・クロマトグラフイ一に付して単離精製すると、Ｍｐ
９２〜９４℃のＮ’一エチリデンピコリノヒドラジドの
無色結晶３５３ｍｇを得る。赤外線吸収スペクトル
νＣＨＣｌ３（Ｃｍ−”）：３３５０、１６９５、１６
５０、１５１５実施例 ４ピコリノヒドラジド２７０ｍ
ｇを含むイソプロピルアルコール溶液１００ｍ１を室温
で低圧水銀灯を用い、１６時間紫外線照射する。Ethanol was distilled off from the reaction solution, and the residue was isolated and purified by preparative chromatography, resulting in Mp
353 mg of colorless crystals of N'-ethylidene picolinohydrazide are obtained at 92-94°C. Infrared absorption spectrum νCHCl3 (Cm-”): 3350, 1695, 16
50, 1515 Example 4 Picolinohydrazide 270m
100 ml of an isopropyl alcohol solution containing g is irradiated with ultraviolet rays at room temperature for 16 hours using a low-pressure mercury lamp.
反応液からイソプロピルアルコールを留去し、残留物を
プレパラテイブ・クロマトグラフイ一に付して単離精製
すると、Ｍｐ９８〜９９℃のＮ’−イソプロピリデンピ
コリノヒドラジドの無色結晶１８８ｍｇを得る。赤外線
吸収スペクトルνＣＨＣｌ３（Ｃｍ−１）：３４５０、
１６９５、１６４５、１５１０実施例 ５ピコリノヒド
ラジド１３５ｍｇを含むベンジルアルコール溶液５０ｍ
１を室温で低圧水銀灯を用い、３０時間紫外線照射する
。The isopropyl alcohol is distilled off from the reaction solution, and the residue is isolated and purified by preparative chromatography to obtain 188 mg of colorless crystals of N'-isopropylidene picolinohydrazide with an Mp of 98 to 99°C. Infrared absorption spectrum νCHCl3 (Cm-1): 3450,
1695, 1645, 1510 Example 5 50 ml of benzyl alcohol solution containing 135 mg of picolinohydrazide
1 was irradiated with ultraviolet rays at room temperature for 30 hours using a low-pressure mercury lamp.
反応液からベンジルアルコールを留去し、残留物を熱時
エーテル抽出する。抽出液を濃縮し、得られる残渣をア
ルミナを用いたカラムクロマトグラフイ一に付して単離
精製すると、Ｍｐｌ９７．５〜１９９℃のＮ’−ベンジ
リデンピコリノヒドラジドの無色結晶４５ｍｇを得る。
赤外線吸収スペクトル
νＣＨＣｌ３（Ｃｍ−１）：３４００、１７００、１５
２０実施例 ６イソニコチノヒドラジド２７０ｍｇを含
むエタノール溶液１００ｍ１を室温で低圧水銀灯を用い
、１９時間紫外線照射する。Benzyl alcohol was distilled off from the reaction solution, and the residue was extracted with ether while hot. The extract is concentrated, and the resulting residue is isolated and purified by column chromatography using alumina to obtain 45 mg of colorless crystals of N'-benzylidene picolinohydrazide with an Mpl of 97.5 to 199°C.
Infrared absorption spectrum νCHCl3 (Cm-1): 3400, 1700, 15
20 Example 6 100 ml of an ethanol solution containing 270 mg of isonicotinohydrazide is irradiated with ultraviolet rays at room temperature for 19 hours using a low-pressure mercury lamp.
反応液からエタノールを留去し、得られる残渣をメタノ
ールで結晶化し、工ーテル・メタノール混液から再結晶
すると、Ｍｐｌ７４．５〜１７５．５℃のＮ’一エチリ
デンイソニコチノヒドラジドの無色結晶１８９ｍｇを得
る。Ethanol was distilled off from the reaction solution, and the resulting residue was crystallized with methanol and recrystallized from a mixture of ether and methanol to give 189 mg of colorless crystals of N'-ethylidene isonicotinohydrazide with an Mpl of 74.5 to 175.5°C. obtain.
赤外線吸収スペクトルνＣＨＣ”３（Ｃｍ−１）：３４
５０、１６９０〜１６７５、１６００核磁気共鳴吸収ス
ペクトルδＣＤＯ゜（Ｐｐｎ）：１．９７（３Ｈ、ｄ、
Ｊ＝５仕）７．９５（２Ｈ，．ｍ）約８．１０（ＩＷｑ
、Ｊ ＝ ５Ｉｋ）
８．９０（２ＨＮｍ）
１１．５８（ＩＷｂｒＯａｄｓ）
質量分析
Ｍ＋゜１６３
実施例 フ
イソニコチノヒドラジド１３５ｍｇを含むベンジルアル
コール溶液５０ｍ１を室温で低圧水銀灯を用い、１０時
間紫外線照射する。Infrared absorption spectrum νCHC”3 (Cm-1): 34
50, 1690-1675, 1600 Nuclear magnetic resonance absorption spectrum δCDO° (Ppn): 1.97 (3H, d,
J=5 types) 7.95 (2H,.m) approx. 8.10 (IWq
, J = 5Ik) 8.90 (2HNm) 11.58 (IWbrOads) Mass spectrometry M+゜163 Example 50ml of a benzyl alcohol solution containing 135mg of fisonicotinohydrazide was irradiated with ultraviolet rays at room temperature using a low-pressure mercury lamp for 10 hours.
反応液からベンジルアルコールを留去し、得られる残渣
を熱時エーテルで数回抽出する。抽出液を濃縮し、得ら
れる残渣をアルミナを用いたカラムクロマトダラフイ一
に付して単離精製し、クロロホルムから再結晶すると、
Ｍｐｌ９９〜１９９．５℃のＮ’−ベンジリデンイソニ
コチノヒドラジドの無色結晶３８ｍｇを得る。赤外線吸
収スペクトルνＣＨＯ゜（Ｃｍ−１）：３４５０、１６
９０〜１６７５、１５５５Ｊ実施例 ８イソニコチノヒ
ドラジド２７０ｍｇを含むイソプロピルアルコール溶液
１００ｍ１を室温で低圧水銀灯を用い、１５時間紫外線
照射する。Benzyl alcohol is distilled off from the reaction solution, and the resulting residue is extracted several times with hot ether. The extract is concentrated, the resulting residue is isolated and purified by column chromatography using alumina, and recrystallized from chloroform.
38 mg of colorless crystals of N'-benzylidene isonicotinohydrazide with a Mpl of 99 to 199.5°C are obtained. Infrared absorption spectrum νCHO゜(Cm-1): 3450, 16
90-1675, 1555J Example 8 100 ml of an isopropyl alcohol solution containing 270 mg of isonicotinohydrazide is irradiated with ultraviolet rays at room temperature for 15 hours using a low-pressure mercury lamp.
反応液からイソプロピルアルコールを留去し、得られる
残渣をプレパラテープクロマトグラフィーに付して単離
精製すると、Ｍｐｌ６Ｏ〜１６１℃のＮ″−イソプロピ
リデンイソニコチノヒドラジドの無色結晶２０３ｍｇを
得る。赤外線吸収スペクトル
ν０Ｈ０１３（Ｃｍ−１）：３４５０、１６９５〜１６
８０、１６０３実施例 ９イソニコチノヒドラジド５５
０ｍｇの酢酸エチル溶液２００ｍ１を室温で低圧水銀灯
を用い、２７時間紫外線照射する。Isopropyl alcohol is distilled off from the reaction solution, and the resulting residue is isolated and purified by preparatape chromatography to obtain 203 mg of colorless crystals of N''-isopropylidene isonicotino hydrazide with a temperature of Mpl6O to 161°C. Infrared absorption. Spectrum ν0H013 (Cm-1): 3450, 1695-16
80, 1603 Example 9 Isonicotinohydrazide 55
200 ml of a 0 mg ethyl acetate solution is irradiated with ultraviolet rays at room temperature for 27 hours using a low-pressure mercury lamp.
反応液から酢酸エチルを留去し、得られる残渣をプレパ
ラテイブクロマトグラフイ一に付して単離精製すると、
Ｍｐｌ７４〜１７５℃のＮ″エチリデンイソニコチノヒ
ドラジドの無色結晶１８３ｍｇを得る。赤外線吸収スペ
クトルEthyl acetate is distilled off from the reaction solution, and the resulting residue is isolated and purified by preparative chromatography.
Obtain 183 mg of colorless crystals of N″ ethylidene isonicotinohydrazide with Mpl 74-175°C. Infrared absorption spectrum
Claims (1)
は水素原子またはアルキル基、Ｒ＿３は水素原子または
アシル基をそれぞれ意味する）で示される化合物を紫外
線照射下に反応させて一般式▲数式、化学式、表等があ
ります▼ （式中、Ｒ＿１およびＲ＿２は前と同じ意味）で示され
るＮ′−置換ヒドラジド誘導体を得ることを特徴とする
Ｎ′−置換ヒドラジド誘導体の製造法。[Claims] 1 The compound represented by the general formula ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 is an alkyl group or an aryl group, R_2
is a hydrogen atom or an alkyl group, and R_3 is a hydrogen atom or an acyl group, respectively. is the same meaning as above).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10631774A JPS5950674B2 (en) | 1974-09-13 | 1974-09-13 | Method for producing N'-substituted hydrazide derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP10631774A JPS5950674B2 (en) | 1974-09-13 | 1974-09-13 | Method for producing N'-substituted hydrazide derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5132563A JPS5132563A (en) | 1976-03-19 |
| JPS5950674B2 true JPS5950674B2 (en) | 1984-12-10 |
Family
ID=14430577
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10631774A Expired JPS5950674B2 (en) | 1974-09-13 | 1974-09-13 | Method for producing N'-substituted hydrazide derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5950674B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10338673A (en) * | 1997-06-04 | 1998-12-22 | Nippon Bayeragrochem Kk | Isonicotinic acid hydrazide derivative and pest controlling agent |
-
1974
- 1974-09-13 JP JP10631774A patent/JPS5950674B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5132563A (en) | 1976-03-19 |
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