JPS59222472A - Indole-2,7-dicarboxylic acid compound and its preparation - Google Patents
Indole-2,7-dicarboxylic acid compound and its preparationInfo
- Publication number
- JPS59222472A JPS59222472A JP9645183A JP9645183A JPS59222472A JP S59222472 A JPS59222472 A JP S59222472A JP 9645183 A JP9645183 A JP 9645183A JP 9645183 A JP9645183 A JP 9645183A JP S59222472 A JPS59222472 A JP S59222472A
- Authority
- JP
- Japan
- Prior art keywords
- indole
- dicarboxylic acid
- formula
- compound
- acid
- 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
Landscapes
- Indole Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は下記一般式
(式中1モ1およびR2はそれぞれ水素原子または低級
アルキル基を表わし、同一でも相異ってもよい)で示さ
れるインドール−2,7−ジカルボン酸化合物およびそ
の製造方法tで関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to indole-2,7- The present invention relates to a dicarboxylic acid compound and a method for producing the same.
インド−ル−2,7−ジカルボン酸化合物ハ文献未記載
の新規な化合物であり、感光材料合成用中間体、医薬合
成用中間体、農薬合成用中間体として多様な用途が期待
される有用な化合物である。Indole-2,7-dicarboxylic acid compound is a new compound that has not been described in any literature, and is a useful compound that is expected to have a variety of uses as an intermediate for the synthesis of photosensitive materials, an intermediate for pharmaceutical synthesis, and an intermediate for agricultural chemical synthesis. It is a compound.
例えばインドール−2,7−ジカルボン酸の2位のカル
ボン酸基を選択的に脱炭酸することにより、容易にイン
ドール−7−カルボン酸を製造し得る。For example, indole-7-carboxylic acid can be easily produced by selectively decarboxylating the carboxylic acid group at the 2-position of indole-2,7-dicarboxylic acid.
インドール−7−カルボン酸は例えばポラロイド写真用
の感光素材や医薬品の製造原料として知られている有用
な化合物であり、それ故インドールー2.7−ジカルボ
ン酸はかかるインドール−7−カルボン酸を合成するた
めの中間体として極めて制置が高い。Indole-7-carboxylic acid is a useful compound known, for example, as a raw material for producing light-sensitive materials for Polaroid photography and pharmaceuticals, and therefore indole-2,7-dicarboxylic acid is used to synthesize such indole-7-carboxylic acid. It is extremely important as an intermediate for
本発明に係るインドール−2,7−ジカルボン酸化合物
は例えば次のように合成される。The indole-2,7-dicarboxylic acid compound according to the present invention is synthesized, for example, as follows.
アントラニル酸またはそのエステルに濃塩酸あるいは濃
硫酸の存在下に亜硝酸ナトリウムを反応させてジアゾニ
ウム塩とする。ついで2−メチルアセト酢酸エステルの
アルコール溶液に50係水酸化カリウムを加え、水冷下
に上記アントラニル酸のジアゾニウム溶液を手早くそそ
いで反応させ、フェニルヒドラゾン誘導体とする。この
フェニルヒドラゾン誘導体を結晶として単離した後、加
熱したポリリン酸中に加えて環化反応させ、インドール
−2,7−ジカルボン酸エステルが製造されるさらにこ
れをアルカリ水溶液中で加水分解すればインドール−2
,7−ジカルボン酸を得ることができる。Anthranilic acid or its ester is reacted with sodium nitrite in the presence of concentrated hydrochloric acid or concentrated sulfuric acid to form a diazonium salt. Next, 50% potassium hydroxide is added to the alcoholic solution of 2-methylacetoacetic ester, and the above diazonium solution of anthranilic acid is quickly poured into the solution while cooling with water to react to obtain a phenylhydrazone derivative. After isolating this phenylhydrazone derivative as a crystal, it is added to heated polyphosphoric acid and subjected to a cyclization reaction to produce indole-2,7-dicarboxylic acid ester.Furthermore, if this is hydrolyzed in an alkaline aqueous solution, indole -2
, 7-dicarboxylic acid can be obtained.
以下実施例によシ本発明を更に詳細に説明する実施例1
. インドール−2,7−ジ“カルボン酸−2メチル−
7−エチルジエステルの合成
アントラニル酸エチル37 fPK水9odを入れ攪拌
しながらこれに濃塩酸80m7!を加え塩酸塩とする。Example 1 The present invention will be explained in more detail with reference to the following examples.
.. Indole-2,7-di'carboxylic acid-2methyl-
Synthesis of 7-ethyl diester Ethyl anthranilate 37 Add 9 od of fPK water and add 80 m7 of concentrated hydrochloric acid to this with stirring! Add to make hydrochloride.
どれをOCまで冷却後、亜硝酸ナトリウム15、5 %
を水90 m、lに爵解しり液をo〜1ocに保ちなが
ら加え、アントラニル酸エチルのジアゾニウム塩とした
。次に21のフラスコに2−メチルアセト酢酸メチル3
0 y−、エタノール460ゴ、50%水酸化カリウム
水溶液100m/!および氷水460dを入れ、ocま
で冷却しておく。これに上記ジアゾニウム塩溶液を手早
く加えると、結晶が析出してくるが、10〜20分攪拌
後さらに水を加え結晶を児全に析出させる。これ金沢取
乾燥後メタノールで再結晶し、黄色針状結晶4〔)?を
得た。1几お゛よびNMRの分析にょシ、本結晶はビル
、ビン酸メチルの2−エトキシカルボニルフェニルヒド
ラゾンであることが確認された。After cooling to OC, sodium nitrite 15.5%
was added to 90 ml of water while maintaining the diazonium salt at 0 to 1 oc to obtain a diazonium salt of ethyl anthranilate. Next, methyl 2-methylacetoacetate 3 was added to flask 21.
0 y-, ethanol 460g, 50% potassium hydroxide aqueous solution 100m/! Add 460 d of ice water and cool to OC. If the diazonium salt solution is quickly added to this, crystals will precipitate out, but after stirring for 10 to 20 minutes, water is further added to cause the crystals to precipitate completely. After drying this in Kanazawa, it was recrystallized with methanol and yellow needle-like crystals were obtained (4)? I got it. After 1 liter and NMR analysis, it was confirmed that this crystal was 2-ethoxycarbonylphenylhydrazone of methyl bilate.
次に500 mlのフラスコに1231のボリシん酸を
入れ、反応温度を95〜ll0Uに保ちつつ攪拌しなが
ら上記フェニルヒドラゾンの結晶を少食づつ〃口える。Next, 1231 boricic acid was placed in a 500 ml flask, and the above phenylhydrazone crystals were sipped in small portions while stirring while maintaining the reaction temperature at 95-110 U.
反応後60rまで冷却し、400−の水を加えると茶色
オイル状物が分離するので、これをクロロホルムで抽出
後さらにアルコールで再結晶21製し、インドール−2
,7−ジカルボン酸−2−メチル−7−エチルジエステ
ルの黄色結晶19Li−を得た。After the reaction, cool to 60r and add 400ml of water to separate a brown oily substance.This was extracted with chloroform and further recrystallized with alcohol to produce indole-2.
, 7-dicarboxylic acid-2-methyl-7-ethyl diester 19Li- was obtained as yellow crystals.
融点 86.2〜86.5 C
I R(KBr、 ν) 3470Crn−”(N−
H) 。Melting point 86.2-86.5 C I R (KBr, ν) 3470Crn-”(N-
H).
1710(e=0) 1680(e=0)N M R
(C]、) C13,δ) 1.431)pm (3
H、t 、 J=7H2)3.90(311,s) 、
4.43(2H,q、J=7H2)7.20(21(、
m)、7JO(2H,m)。1710 (e=0) 1680 (e=0) N M R
(C], ) C13, δ) 1.431) pm (3
H, t, J=7H2) 3.90 (311,s),
4.43 (2H, q, J = 7H2) 7.20 (21 (,
m), 7JO (2H, m).
10.20 (14(、s )
実施例2 インドール−2,7−ジカルボン酸の合成
実施例1で得たインドール−2,7−ジカルボン酸−7
−エチル−2−メチルジエステル18ti−に5チ水酸
化ナトリウム水溶液174?を加え、加熱し還流下で1
.5時間加水分解反応を行う。冷却後希塩酸を加えて酸
性にすると結晶析出し、これを濾過乾燥してインドール
−2,7−ジカルボン酸14y−を得た。10.20 (14(,s) Example 2 Synthesis of indole-2,7-dicarboxylic acid Indole-2,7-dicarboxylic acid-7 obtained in Example 1
-Ethyl-2-methyl diester 18ti- to 5ti sodium hydroxide aqueous solution 174? and heated under reflux.
.. The hydrolysis reaction is carried out for 5 hours. After cooling, dilute hydrochloric acid was added to acidify the mixture to precipitate crystals, which were filtered and dried to obtain indole-2,7-dicarboxylic acid 14y-.
融点 300C以上
I 1% (KBy 、 v ) 34.70Cr
n−’ (N H)3200〜2400(eool(
)、1680(C=O)N M Hl(CC14+ d
6DMS O、δ)7−30 pI”” (2Ii +
rr+ ) + 7−96 (2H、m) 。Melting point 300C or higher I 1% (KBy, v) 34.70Cr
n-' (NH) 3200-2400 (eool(
), 1680(C=O)N M Hl(CC14+ d
6DMSO, δ) 7-30 pI”” (2Ii +
rr+ ) + 7-96 (2H, m).
10.33(IH,s)、12.56(2H,s)実、
tllJ3 インドール−2,7−ジカルボン酸−2
−メチルエステルの合成
実施例1においてアントラニル酸エチルに代、tてアン
トラニル酸を使用した以外は実施例1に準じた反応操作
によ、ってインドール−2,7−ジカルボン酸−2−メ
チルエステルの黄色結晶7.37を得た。10.33 (IH, s), 12.56 (2H, s) real,
tllJ3 Indole-2,7-dicarboxylic acid-2
- Synthesis of methyl ester Indole-2,7-dicarboxylic acid-2-methyl ester was prepared by the reaction procedure according to Example 1 except that anthranilic acid was used instead of ethyl anthranilate in Example 1. 7.37 of yellow crystals were obtained.
融点 220.0〜220.5C
I R(KBr 、 I/) 3230crn−’
(N−H)t72o(e=0)、1.690(c二〇)
N M R(CCJ14 + d’ DMS O、δ
)3.93ppm(3H,s)、7.25(2H,m)
。Melting point 220.0-220.5C IR (KBr, I/) 3230crn-'
(NH) t72o (e=0), 1.690 (c20)
N M R (CCJ14 + d' DMSO, δ
) 3.93ppm (3H, s), 7.25 (2H, m)
.
7−90 (2H、+r+ ) 、10−30 (I
Hs s )実施例4 インドール−2,7−ジカルボ
ン酸ジメチルエステルの合成
実施例1においてアントラニル酸エチルに代えてアント
ラニル酸メチルを使用した以外は実施例1に準じた反応
操作によってインド°−ルー2,7−ジカルボン酸ジメ
チルエステルの結晶11.0P’を得た。7-90 (2H, +r+), 10-30 (I
Hs s) Example 4 Synthesis of indole-2,7-dicarboxylic acid dimethyl ester Indole-2,7-dicarboxylic acid dimethyl ester , 7-dicarboxylic acid dimethyl ester crystal 11.0P' was obtained.
融点 93.8〜95.0 C IR(KBr、ν) 347oz−”(N−H)。Melting point: 93.8-95.0C IR (KBr, ν) 347oz-” (NH).
1700(e、、=()ン
N M R(CDC1h 、δ)3.97ppm(2H
,s)4.00(3H,s)、7.20(2H,m)。1700(e,,=()nNMR(CDC1h,δ)3.97ppm(2H
, s) 4.00 (3H, s), 7.20 (2H, m).
Claims (1)
キル基を表わし、同一でも相異ってもよい。) で表わされるインドール−2,7−ジカルボン酸化合物
。 2、式〔1〕の化合物がインドール−2,7−ジカルボ
ン酸である特許請求の範囲第1項記載の化合物。 3、式〔1〕の化合物がインドール−2,7−ジカルボ
ン酸−2−メチルエステルである特許請求の範囲第1項
記載の化合物。 4、式〔1〕の化合物がインドール−2,7−ジカルボ
ン酸ジメチルエステルである特許請求の範囲第1項記載
の化合物。 5、 式〔1〕の化合物がインドール−2,7−ジカル
ボン酸−2−メチル−7−メチルジエステルである特許
請求の範囲第1項記載の化合物。 6、 アントラニル酸またはそのエステルのジアゾニウ
ム塩と、2−メチルアセト酢酸またはそのエステルを反
応させ、フェニルヒドラゾン誘導体とし、それを環化す
ることからなる式〔1〕で表ワサれるインドール−2,
7−ジカルボン酸化合物の製造方法。[Scope of Claims] 1. An indole-2,7-dicarboxylic acid compound represented by the formula (in the formula, & and R2 each represent a hydrogen atom or a lower alkyl group, and may be the same or different). 2. The compound according to claim 1, wherein the compound of formula [1] is indole-2,7-dicarboxylic acid. 3. The compound according to claim 1, wherein the compound of formula [1] is indole-2,7-dicarboxylic acid-2-methyl ester. 4. The compound according to claim 1, wherein the compound of formula [1] is indole-2,7-dicarboxylic acid dimethyl ester. 5. The compound according to claim 1, wherein the compound of formula [1] is indole-2,7-dicarboxylic acid-2-methyl-7-methyl diester. 6. Indole-2 represented by formula [1], which is obtained by reacting a diazonium salt of anthranilic acid or its ester with 2-methylacetoacetic acid or its ester to form a phenylhydrazone derivative, which is then cyclized.
7-Dicarboxylic acid compound manufacturing method.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9645183A JPS59222472A (en) | 1983-05-31 | 1983-05-31 | Indole-2,7-dicarboxylic acid compound and its preparation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9645183A JPS59222472A (en) | 1983-05-31 | 1983-05-31 | Indole-2,7-dicarboxylic acid compound and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS59222472A true JPS59222472A (en) | 1984-12-14 |
JPH038342B2 JPH038342B2 (en) | 1991-02-05 |
Family
ID=14165378
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9645183A Granted JPS59222472A (en) | 1983-05-31 | 1983-05-31 | Indole-2,7-dicarboxylic acid compound and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS59222472A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109160895A (en) * | 2018-10-24 | 2019-01-08 | 河南师范大学 | A kind of preparation method of 4,6- dichloro-indole |
-
1983
- 1983-05-31 JP JP9645183A patent/JPS59222472A/en active Granted
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109160895A (en) * | 2018-10-24 | 2019-01-08 | 河南师范大学 | A kind of preparation method of 4,6- dichloro-indole |
Also Published As
Publication number | Publication date |
---|---|
JPH038342B2 (en) | 1991-02-05 |
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