JP2810667B2 - Aminobenzoic acid derivative - Google Patents
Aminobenzoic acid derivativeInfo
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- JP2810667B2 JP2810667B2 JP63053927A JP5392788A JP2810667B2 JP 2810667 B2 JP2810667 B2 JP 2810667B2 JP 63053927 A JP63053927 A JP 63053927A JP 5392788 A JP5392788 A JP 5392788A JP 2810667 B2 JP2810667 B2 JP 2810667B2
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Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は一般式（Ｉ） ［式中、R1は水素又はカルボキシル基を、R2はヒドロ
キシル基、アミノ基又は低級アルキルアミノ基を、ｎは
１〜４の整数を意味する。ただし、R1がカルボキシル基
であり、R2がヒドロキシル基であり、ｎが１である場合
を除く。］で表わされる化合物及びその塩に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a compound represented by the general formula (I): [Wherein, R 1 represents a hydrogen or carboxyl group, R 2 represents a hydroxyl group, an amino group or a lower alkylamino group, and n represents an integer of 1 to 4. However, this excludes the case where R 1 is a carboxyl group, R 2 is a hydroxyl group, and n is 1. And a salt thereof.
本発明化合物は、優れた抗潰瘍作用を有し、抗潰瘍薬
として極めて有用なものである。The compound of the present invention has an excellent anti-ulcer effect and is extremely useful as an anti-ulcer drug.
［従来の技術］ 抗潰瘍作用を示す種々の化合物が知られているが、本
発明化合物に関連した安息香酸誘導体に抗潰瘍作用があ
ることは知られていない。[Prior Art] Various compounds exhibiting an anti-ulcer effect are known, but it is not known that a benzoic acid derivative related to the compound of the present invention has an anti-ulcer effect.
［発明によって解決された問題点］ 本発明者等は抗潰瘍作用を示す化合物を鋭意研究した
結果、式（Ｉ）の化合物が、優れた抗潰瘍作用を示すこ
とを見出し、本発明を完成した。[Problems Solved by the Invention] The present inventors diligently studied compounds exhibiting an anti-ulcer effect, and as a result, found that the compound of the formula (I) exhibited an excellent anti-ulcer effect, and completed the present invention. .
［発明の構成］ 本発明は式（Ｉ）の化合物及びその塩に関する。[Constitution of the Invention] The present invention relates to a compound of the formula (I) and a salt thereof.
上記式中、低級アルキルアミノ基とは、モノ低級アル
キルアミノ基又はジ低級アルキルアミノ基を意味し、該
ジ低級アルキルアミノ基のアルキル基は同一または異な
っていてもよい。該低級アルキル基としては、メチル、
エチル、プロピル、イソプロピル、ブチル等があげられ
る。In the above formula, the lower alkylamino group means a mono-lower alkylamino group or a di-lower alkylamino group, and the alkyl groups of the di-lower alkylamino group may be the same or different. Examples of the lower alkyl group include methyl,
Ethyl, propyl, isopropyl, butyl and the like can be mentioned.
式（Ｉ）の化合物の塩としては、塩酸、硫酸等の無機
酸の酸付加塩及びカルボキシル基とナトリウム、カリウ
ム等のアルカリ金属との塩等をあげることができる。Examples of the salt of the compound of the formula (I) include an acid addition salt of an inorganic acid such as hydrochloric acid and sulfuric acid, and a salt of a carboxyl group with an alkali metal such as sodium and potassium.
式（Ｉ）の化合物は下記の方法により製造することが
出来る。The compound of the formula (I) can be produced by the following method.
製造法ａ ［式中、R4は低級アルキル基を、R3はヒドロキシ基、低
級アルコキシ基、アミノ基又は低級アルキルアミノ基を
意味し、R2,nは前記に同じ］ 即ち、式（II）で示される化合物を溶媒の存在下又は
非存在下、酸性又はアルカリ性条件で加水分解すること
により式（Ｉ）においてR1がカルボキシル基である化合
物を製造することができる。Manufacturing method a [In the formula, R 4 represents a lower alkyl group, R 3 represents a hydroxy group, a lower alkoxy group, an amino group or a lower alkylamino group, and R 2 and n are the same as above.] That is, represented by the formula (II) The compound of formula (I) wherein R 1 is a carboxyl group can be produced by hydrolyzing the compound to be obtained in the presence or absence of a solvent under acidic or alkaline conditions.
製造法ｂ ［式中、R5は炭素数１〜４の低級アルキル基を、R6は低
級アルコキシ基、アミノ基又は低級アルキルアミノ基を
意味し、R2は前記に同じ］ 即ち、式（III）で示される化合物を水酸化ナトリウ
ム、水酸化カリウム、アンモニア又は低級アルキルアミ
ンの水溶液と処理することにより、式（Ｉ）においてR1
が水素原子である化合物を製造することができる。反応
は室温で1/2〜30時間行われる。Manufacturing method b [Wherein, R 5 represents a lower alkyl group having 1 to 4 carbon atoms, R 6 represents a lower alkoxy group, an amino group or a lower alkylamino group, and R 2 is the same as described above] That is, in the formula (III), By treating the compound shown with an aqueous solution of sodium hydroxide, potassium hydroxide, ammonia or a lower alkylamine, R 1 in formula (I)
Is a hydrogen atom. The reaction is performed at room temperature for 1/2 to 30 hours.
上記原料化合物（II）及び（III）において、新規化
合物は下記方法により製造することが出来る。In the raw material compounds (II) and (III), a novel compound can be produced by the following method.
製造法１） ［式中Ｘはハロゲン原子又はパラトルエンスルフォニル
オキシ基を意味し、R3，R4,nは前記と同じ］ 即ち、式（IV）の化合物と式（Ｖ）の化合物を脱酸剤
の存在下ジメチルホルムアミド等の溶媒中反応させるこ
とにより式（II）の原料化合物を製造することができ
る。Manufacturing method 1) [In the formula, X represents a halogen atom or a paratoluenesulfonyloxy group, and R 3 , R 4 , and n are the same as described above.] That is, the compound of the formula (IV) and the compound of the formula (V) are mixed with a deoxidizing agent The starting compound of the formula (II) can be produced by reacting in a solvent such as dimethylformamide below.
製造法２） ［式中R5，R6,Xは前記と同じ］ 即ち、水素化ナトリウム等の存在下式（VI）の化合物
と式（VII）の化合物とを反応に関与しない溶媒中反応
させることにより式（III）の原料化合物を製造するこ
とができる。Manufacturing method 2) [Wherein R 5 , R 6 , and X are the same as described above] That is, the compound of the formula (VI) is reacted with the compound of the formula (VII) in a solvent that does not participate in the reaction in the presence of sodium hydride or the like. The starting compound (III) can be produced.
［発明の効果］ 本発明化合物の抗潰瘍作用は、高木、岡部等の水浸拘
束ストレス潰瘍法（ジャパニーズ・ジャーナル・オブ・
ファーマコロジー;18巻,9頁,1968年参照）に準じた抗潰
瘍試験により確認された。即ち、実験動物として１群７
匹のラット（体重300g前後）を選び、水温21℃で７時間
水浸拘束して実験潰瘍モデルを作成し、本発明化合物の
抑制効果を検討した。結果を表１に示した。[Effect of the Invention] The anti-ulcer effect of the compound of the present invention can be measured by the water immersion-restrained stress ulcer method of Takagi and Okabe (Japanese Journal of
Pharmacology; see volume 18, p. 9, 1968). That is, 7 animals per group as experimental animals
One rat (body weight: about 300 g) was selected and immersed in water at 21 ° C. for 7 hours to prepare an experimental ulcer model, and the inhibitory effect of the compound of the present invention was examined. The results are shown in Table 1.
本発明化合物−1:3−カルボキシメチルアミノ−Ｎ−メ
チルベンズアミド塩酸塩 本発明化合物−2:3−メチルアミノ安息香酸 表１に示される通り、本発明化合物は優れたストレス潰
瘍抑制効果を示した。従って、本発明化合物は抗潰瘍剤
として優れたものである。 Compound of the present invention-1: 3-carboxymethylamino-N-methylbenzamide hydrochloride Compound of the present invention-2: 3-methylaminobenzoic acid As shown in Table 1, the compound of the present invention showed an excellent inhibitory effect on stress ulcer. . Therefore, the compound of the present invention is excellent as an anti-ulcer agent.
以下参考例及び実施例を挙げて本発明を説明する。 Hereinafter, the present invention will be described with reference to Reference Examples and Examples.
参考例１ ３−（エトキシカルボニルメチルアミノ）−Ｎ−メチル
ベンズアミド Ｎ−メチル−３−アミノベンズアミド4.51g、クロロ
酢酸エチル3.68g、無水炭酸カルシウム6.00gをジメチル
ホルムアミド15mlに加え４時間加熱還流した。冷却後不
溶物を濾去し、不溶物をジメチルホルムアミドで洗い、
洗液を濾液と合わせ溶媒を減圧留去した。残留物は放置
すると固化した。これを水洗後エタノールより再結晶し
黄色針状晶として標記化合物5.0gを得た。Reference Example 1 3- (Ethoxycarbonylmethylamino) -N-methylbenzamide 4.51 g of N-methyl-3-aminobenzamide, 3.68 g of ethyl chloroacetate and 6.00 g of anhydrous calcium carbonate were added to 15 ml of dimethylformamide, and the mixture was heated under reflux for 4 hours. After cooling, the insoluble material was removed by filtration, and the insoluble material was washed with dimethylformamide.
The washing solution was combined with the filtrate, and the solvent was distilled off under reduced pressure. The residue solidified on standing. This was washed with water and recrystallized from ethanol to obtain 5.0 g of the title compound as yellow needles.
融点110〜113℃ 元素分析値C12H16N203として 計算値:C,61.00;H,6.83;N,11.86 実測値:C,61.04;H,6.83;N,11.94 NMRスペクトル（CDCl3）δ： 1.27（3H,t,J＝6Hz）,2.93（3H,d,J＝5Hz）,3.87（2H,
s）,4.19（2H,q,J＝6Hz）,6.37（1H,m）,6.6−6.7（1H,
m）,6.9−7.2（3H,m）。Mp 110-113 ° C. Elemental analysis C 12 H 16 N 2 0 3 Calculated: C, 61.00; H, 6.83 ; N, 11.86 Found: C, 61.04; H, 6.83 ; N, 11.94 NMR spectrum (CDCl 3 ) Δ: 1.27 (3H, t, J = 6Hz), 2.93 (3H, d, J = 5Hz), 3.87 (2H,
s), 4.19 (2H, q, J = 6 Hz), 6.37 (1H, m), 6.6-6.7 (1H,
m), 6.9-7.2 (3H, m).
参考例２ ３−（Ｎ−トリフルオロアセチル−Ｎ−メチルアミノ）
安息香酸メチルエステル ｉ）３−トリフルオロアセタミノ安息香酸メチルエステ
ル ３−アミノ安息香酸メチルエステル6.1gをジクロロメ
タン100mlに溶解し、室温でトリフルオロ酢酸無水物10.
2gを滴下し２時間攪拌した。反応液を濃縮し、残留物に
クロロホルムを加えてさらに濃縮した。石油エーテル−
イソプロピルエーテル（1:1）を加えて結晶を濾取し、
無色結晶として標記化合物9.7gを得た。Reference Example 2 3- (N-trifluoroacetyl-N-methylamino)
Benzoic acid methyl ester i) 3-trifluoroacetaminobenzoic acid methyl ester 6.1 g of 3-aminobenzoic acid methyl ester is dissolved in 100 ml of dichloromethane, and trifluoroacetic anhydride is added at room temperature.
2 g was added dropwise and stirred for 2 hours. The reaction solution was concentrated, chloroform was added to the residue, and the mixture was further concentrated. Petroleum ether
Isopropyl ether (1: 1) was added and the crystals were collected by filtration.
9.7 g of the title compound were obtained as colorless crystals.
融点108〜110℃ 元素分析値C10H8F3N03として 計算値:C,48.59;H,3.26;N,5.67 実測値:C,48.70;H,3.27;N,5.61 NMRスペクトル（CDCl3）δ： 3.93（3H,s）,7.40−8.28（4H,m）。Mp 108-110 ° C. Elemental analysis C 10 H 8 F 3 N0 3 Calculated: C, 48.59; H, 3.26 ; N, 5.67 Found: C, 48.70; H, 3.27 ; N, 5.61 NMR spectrum (CDCl 3 ) Δ: 3.93 (3H, s), 7.40-8.28 (4H, m).
ii）３−（Ｎ−トリフルオロアセチル−Ｎ−メチルアミ
ノ）安息香酸メチルエステル 60％水素化ナトリウム1.9gをテトラヒドロフランで洗
浄後、テトラヒドロフラン200mlに懸濁する。氷冷下、
これに３−トリフルオロアセチルアミノ安息香酸メチル
エステル9.3gをテトラヒドロフラン50mlに溶かして加
え、40分間攪拌した。次いでヨードメチル16.0gをテト
ラヒドロフラン30mlに溶かして加え、室温で一夜攪拌し
た。反応液に酢酸0.72gを加え30℃で濃縮し、油状物と
して標記化合物9.4gを得た。ii) 3- (N-trifluoroacetyl-N-methylamino) benzoic acid methyl ester 1.9 g of 60% sodium hydride is washed with tetrahydrofuran and suspended in 200 ml of tetrahydrofuran. below freezing,
9.3 g of 3-trifluoroacetylaminobenzoic acid methyl ester dissolved in 50 ml of tetrahydrofuran was added thereto, and the mixture was stirred for 40 minutes. Next, 16.0 g of iodomethyl was dissolved in 30 ml of tetrahydrofuran and added, followed by stirring at room temperature overnight. 0.72 g of acetic acid was added to the reaction solution, and the mixture was concentrated at 30 ° C. to obtain 9.4 g of the title compound as an oil.
NMRスペクトル（CDCl3）δ： 3.39（3H,bs）,3.95（3H,s）,7.43−8.23（4H,m）。NMR spectrum (CDCl 3) δ: 3.39 ( 3H, bs), 3.95 (3H, s), 7.43-8.23 (4H, m).
実施例１ ３−カルボキシメチルアミノ−Ｎ−メチルベンズアミド
塩酸塩 ３−（エトキシカルボニルメチルアミノ）−Ｎ−メチ
ルベンズアミド5.0gを1N水酸化ナトリウム25mlに加え室
温で12時間攪拌した。一部の不溶物を濾別し、濾液に1N
酢酸30mlを加えた。イオン交換樹脂IR−120B（H+）100m
lのカラムにかけ、水洗後3Nアンモニア水で溶出した。
溶出液を減圧濃縮すると、残留物は吸湿性のシロップと
なった。これをイオン交換樹脂IRA−400（OH-）50mlの
カラムにかけ、水洗後1N塩酸で溶出した。溶出液を減圧
下濃縮乾固し、残留物を水−アルコールより再結晶し、
白色粉末として標記化合物3.27gを得た。Example 1 3-Carboxymethylamino-N-methylbenzamide hydrochloride 5.0 g of 3- (ethoxycarbonylmethylamino) -N-methylbenzamide was added to 25 ml of 1N sodium hydroxide and stirred at room temperature for 12 hours. Some insolubles are separated by filtration, and 1N is added to the filtrate.
30 ml of acetic acid were added. Ion exchange resin IR-120B (H + ) 100m
The column was washed with water and eluted with 3N aqueous ammonia.
When the eluate was concentrated under reduced pressure, the residue became a hygroscopic syrup. Ion exchange this resin IRA-400 (OH -) subjected to a column of 50 ml, and eluted in the washing after 1N hydrochloric acid. The eluate was concentrated to dryness under reduced pressure, and the residue was recrystallized from water-alcohol.
3.27 g of the title compound were obtained as a white powder.
融点143〜149℃ 元素分析値C10H13ClN2O3として 計算値:C,49.09;H,5.35;N,11.45 実測値:C,48.83;H,5.34;N,11.29 NMRスペクトル（D2O）δ： 2.92（3H,s）,4.24（2H,s）,7.4−7.6（4H,m）。Melting point: 143-149 ° C Elemental analysis: as C 10 H 13 ClN 2 O 3 Calculated: C, 49.09; H, 5.35; N, 11.45 Found: C, 48.83; H, 5.34; N, 11.29 NMR spectrum (D 2 O) δ: 2.92 (3H, s), 4.24 (2H, s), 7.4-7.6 (4H, m).
実施例２ ３−メチルアミノ安息香酸 ３−（Ｎ−トリフルオロアセチル−Ｎ−メチルアミ
ノ）安息香酸メチルエステル5.2gに1N水酸化ナトリウム
60mlを加え室温で一夜攪拌した。濃塩酸でpH3.0とし減
圧濃縮した。析出結晶を濾取し、水より再結晶し淡黄色
結晶として標記化合物1.8gを得た。Example 2 3-methylaminobenzoic acid 3- (N-trifluoroacetyl-N-methylamino) benzoic acid methyl ester in 5.2 g of 1N sodium hydroxide
60 ml was added and the mixture was stirred at room temperature overnight. The mixture was adjusted to pH 3.0 with concentrated hydrochloric acid and concentrated under reduced pressure. The precipitated crystals were collected by filtration and recrystallized from water to obtain 1.8 g of the title compound as pale yellow crystals.
融点227〜228℃ 元素分析値C8H9NO2として 計算値:C,63.57;H,6.00;N,9.27 実測値:C,63.25;H,6.27;N,9.24 NMRスペクトル（DMSO-d6）δ： 2.69（3H,s）,5.55−6.38（1H,bs）,6.64−7.30（4H,
m）。Melting point: 227-228 ° C Elemental analysis: C 8 H 9 NO 2 Calculated: C, 63.57; H, 6.00; N, 9.27 Found: C, 63.25; H, 6.27; N, 9.24 NMR spectrum (DMSO-d 6 ) Δ: 2.69 (3H, s), 5.55-6.38 (1H, bs), 6.64-7.30 (4H,
m).
実施例３ ３−メチルアミノ−Ｎ−メチルベンズアミド ３−（Ｎ−トリフルオロアセチル−Ｎ−メチルアミ
ノ）安息香酸メチルエステル4.7gに40％メチルアミン水
溶液12mlを加え、室温で一夜攪拌した。少量のトルエン
を加え攪拌後水層を分取した。水層を減圧濃縮し、残留
物をクロロホルムで抽出した。抽出液を乾燥後溶媒を留
去した。残留物にエーテルを加えて結晶化させ、ジクロ
ロメタン−エーテルより再結晶し、無色結晶として標記
化合物1.2gを得た。Example 3 3-Methylamino-N-methylbenzamide To 4.7 g of 3- (N-trifluoroacetyl-N-methylamino) benzoic acid methyl ester, 12 ml of a 40% aqueous solution of methylamine was added, and the mixture was stirred at room temperature overnight. After adding a small amount of toluene and stirring, the aqueous layer was separated. The aqueous layer was concentrated under reduced pressure, and the residue was extracted with chloroform. After drying the extract, the solvent was distilled off. The residue was crystallized by adding ether and recrystallized from dichloromethane-ether to give 1.2 g of the title compound as colorless crystals.
融点76〜78℃ 元素分析値C9H12N2Oとして 計算値:C,65.83;H,7.37;N,17.06 実測値:C,65.62;H,7.41;N,17.03 NMRスペクトル（CDCl3）δ： 2.85（3H,s）,2.98（3H,d,J＝4.8Hz）,3.49（1H,bs）,
5.96−6.33（1H,bs）,6.60−7.36（4H,m）。Melting point: 76-78 ° C Elemental analysis: C 9 H 12 N 2 O Calculated: C, 65.83; H, 7.37; N, 17.06 Found: C, 65.62; H, 7.41; N, 17.03 NMR spectrum (CDCl 3 ) δ: 2.85 (3H, s), 2.98 (3H, d, J = 4.8Hz), 3.49 (1H, bs),
5.96-6.33 (1H, bs), 6.60-7.36 (4H, m).
フロントページの続き (56)参考文献 特開 昭55−31027（ＪＰ，Ａ) 特開 昭57−91975（ＪＰ，Ａ) 特開 昭57−106649（ＪＰ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C07C 229/60,227/18,237/30 A61K 31/165,31/19,31/195 ＣＡ（ＳＴＮ) ＣＡＯＬＤ（ＳＴＮ) ＲＥＧＩＳＴＲＹ（ＳＴＮ)Continuation of the front page (56) References JP-A-55-31027 (JP, A) JP-A-57-91975 (JP, A) JP-A-57-106649 (JP, A) (58) Fields investigated (Int) .Cl. 6 , DB name) C07C 229 / 60,227 / 18,237 / 30 A61K 31 / 165,31 / 19,31 / 195 CA (STN) CAOLD (STN) REGISTRY (STN)
Claims (1)
ドロキシル基、アミノ基又は低級アルキルアミノ基を、
ｎは１〜４の整数を意味する。ただし、R1がカルボキシ
ル基であり、R2がヒドロキシル基で、ｎが１である場合
を除く。］で表される化合物、その塩又はそれらの水和
物を、有効成分とする抗潰瘍剤。1. The general formula (1) Wherein R 1 is a hydrogen atom or a carboxyl group, R 2 is a hydroxyl group, an amino group or a lower alkylamino group,
n means an integer of 1 to 4. However, this excludes the case where R 1 is a carboxyl group, R 2 is a hydroxyl group, and n is 1. An anti-ulcer agent comprising, as an active ingredient, the compound represented by the formula (1), a salt thereof or a hydrate thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053927A JP2810667B2 (en) | 1988-03-08 | 1988-03-08 | Aminobenzoic acid derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63053927A JP2810667B2 (en) | 1988-03-08 | 1988-03-08 | Aminobenzoic acid derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01226860A JPH01226860A (en) | 1989-09-11 |
| JP2810667B2 true JP2810667B2 (en) | 1998-10-15 |
Family
ID=12956360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63053927A Expired - Fee Related JP2810667B2 (en) | 1988-03-08 | 1988-03-08 | Aminobenzoic acid derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2810667B2 (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5531027A (en) * | 1978-08-25 | 1980-03-05 | Dai Ichi Seiyaku Co Ltd | N-phenetyl acetamide derivative |
| JPS5791975A (en) * | 1980-10-06 | 1982-06-08 | Doujin Kagaku Kenkyusho:Kk | Water-soluble heterocyclic azo compound and its application |
| JPS609744B2 (en) * | 1980-12-20 | 1985-03-12 | ライオン株式会社 | Dental adhesive consisting of N-methyl-N-(2-hydroxy-3-methacryloyloxypropyl)-m-aminobenzoic acid and this compound |
-
1988
- 1988-03-08 JP JP63053927A patent/JP2810667B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01226860A (en) | 1989-09-11 |
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| LAPS | Cancellation because of no payment of annual fees |