JPH10259172A - Production of alkyl 3-amino-4-substituted benzoate - Google Patents
Production of alkyl 3-amino-4-substituted benzoateInfo
- Publication number
- JPH10259172A JPH10259172A JP172898A JP172898A JPH10259172A JP H10259172 A JPH10259172 A JP H10259172A JP 172898 A JP172898 A JP 172898A JP 172898 A JP172898 A JP 172898A JP H10259172 A JPH10259172 A JP H10259172A
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- Prior art keywords
- alkyl
- amino
- pref
- group
- alkali metal
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【0001】[0001]
【発明の属する技術分野】本発明は、銀塩写真用材料な
どの中間体として有用なアルキル 3−アミノ−4−置
換ベンゾエイトを高純度、高収率で且つ簡単な方法で製
造する方法を提供するものである。The present invention provides a method for producing an alkyl 3-amino-4-substituted benzoate useful as an intermediate for silver salt photographic materials and the like in a high purity, a high yield and a simple method. Is what you do.
【0002】[0002]
【従来の技術】従来、アルキル 3−アミノ−4−クロ
ロベンゾエイトの合成法としては、3−ニトロ−4−置
換安息香酸をアルキルエステルとし、これを還元により
アミノ化する方法が検討されてきた。しかしながら、3
−ニトロ−4−ハロゲノ安息香酸の場合、接触還元を適
用しようとするとニトロ基の隣にある活性なハロゲン原
子の離脱が起きて、高収率で目的物を得ることは困難で
あった。また、3−ニトロ−4−アルコキシ安息香酸の
場合には、定法である鉄粉による還元法で目的物は得ら
れるが、鉄粉の処理などの工程上の煩雑な操作を必要と
した。このため工業的に安易に入手可能な3−アミノ−
4−置換安息香酸のFischer法によるエステル化
を試みたが、アミノ基のアルキル化が並行して起こり、
目的物は低収率でしか得られなかった。2. Description of the Related Art Hitherto, as a method for synthesizing alkyl 3-amino-4-chlorobenzoate, a method has been studied in which 3-nitro-4-substituted benzoic acid is converted to an alkyl ester and this is aminated by reduction. . However, 3
In the case of -nitro-4-halogenobenzoic acid, an attempt to apply catalytic reduction results in the elimination of an active halogen atom next to the nitro group, making it difficult to obtain the desired product in high yield. In addition, in the case of 3-nitro-4-alkoxybenzoic acid, the target product can be obtained by a conventional reduction method using iron powder, but complicated operations such as treatment of iron powder are required. For this reason, industrially easily available 3-amino-
An attempt was made to esterify the 4-substituted benzoic acid by the Fischer method, but alkylation of the amino group occurred in parallel,
The desired product was obtained only in low yield.
【0003】[0003]
【本発明が解決しようとする課題】本発明は、上記のよ
うな問題のない、アルキル 3−アミノ−4−置換ベン
ゾエイトを高純度、高収率で且つ簡単な方法で製造する
ことができる新規な方法の提供を目的とするものであ
る。SUMMARY OF THE INVENTION The present invention provides a novel method for producing an alkyl 3-amino-4-substituted benzoate having a high purity, a high yield and a simple method without the above-mentioned problems. It is intended to provide a simple method.
【0004】[0004]
【課題を解決するための手段】本発明者らは、鋭意検討
した結果、下記構成の製造方法によって、上記目的が見
事に達成されることを見いだした。 (1)下記一般式(I)で示される3−アミノ−4−置
換安息香酸又はそのアルカリ金属塩を炭酸塩塩基存在
下、ハロゲン化アルキルと反応させることを特徴とする
下記一般式(II)で示されるアルキル 3−アミノ−4
−置換ベンゾエイトの製造方法。Means for Solving the Problems As a result of intensive studies, the present inventors have found that the above-mentioned object can be achieved satisfactorily by the manufacturing method having the following structure. (1) A 3-amino-4-substituted benzoic acid represented by the following general formula (I) or an alkali metal salt thereof is reacted with an alkyl halide in the presence of a carbonate base. An alkyl 3-amino-4 represented by
-A process for producing substituted benzoates.
【0005】[0005]
【化2】 Embedded image
【0006】式中、Rはアルキル基を表す。Xはアルカ
リ金属原子、水素原子を表し、Yはアルコキシ基、ハロ
ゲン原子を表す。 (2) 前記一般式(I)におけるXが水素原子、Yが
塩素原子である前記(1)に記載のアルキル 3−アミ
ノ−4−置換ベンゾエイトの製造方法。 (3) 前記アルキル基が、炭素数6ないし18個の非
置換又は置換アルキル基である前記(1)又は(2)に
記載のアルキル 3−アミノ−4−置換ベンゾエイトの
製造方法。In the formula, R represents an alkyl group. X represents an alkali metal atom or a hydrogen atom, and Y represents an alkoxy group or a halogen atom. (2) The method for producing an alkyl 3-amino-4-substituted benzoate according to the above (1), wherein X in the general formula (I) is a hydrogen atom and Y is a chlorine atom. (3) The method for producing an alkyl 3-amino-4-substituted benzoate according to the above (1) or (2), wherein the alkyl group is an unsubstituted or substituted alkyl group having 6 to 18 carbon atoms.
【0007】[0007]
【発明の実施の形態】Rは好ましくは炭素数6ないし1
8個、より好ましくは炭素数10〜16個の非置換又は
置換アルキル基を表す。上記の反応は一般的な非置換又
は置換アルキル基の導入に対して適用可能であるが、特
に長鎖アルキル基の導入に有効である。それらのアルキ
ル基の例としてはデシル基、ドデシル基、テトラデシル
基、ヘキサデシル基等の脂肪族アルキル基、2−エチル
シクロヘキシル基、シクロヘキシルメチル基等の環状ア
ルキル基、デシルオキシカルボニルメチル基、ドデシル
オキシカルボニルメチル基、1−オクチルオキシカルボ
ニルエチル基、1−デシルオキシカルボニルエチル基、
1−ドデシルオキシカルボニルエチル基等のアルコキシ
カルボニルアルキル基、ドデシルアミノカルボニルカル
ボニルメチル基、N−メチル−N−ドデシルアミノカル
ボニルメチル基等のアルキルアミノカルボニルアルキル
基が挙げられ、好ましくはデシル基、ドデシル基、テト
ラデシル基、1−ドデシルオキシカルボニルエチル基で
ある。これらのアルキル基は直鎖のものでも分岐のもの
でもよい。また、ハロゲン化アルキルの好ましい例とし
ては、臭化アルキル、塩化アルキルが挙げられる。DETAILED DESCRIPTION OF THE INVENTION R is preferably a compound having 6 to 1 carbon atoms.
Represents an unsubstituted or substituted alkyl group having 8, more preferably 10 to 16 carbon atoms. The above reaction is applicable to the introduction of general unsubstituted or substituted alkyl groups, but is particularly effective for the introduction of long-chain alkyl groups. Examples of such alkyl groups include aliphatic alkyl groups such as decyl group, dodecyl group, tetradecyl group, hexadecyl group, cyclic alkyl groups such as 2-ethylcyclohexyl group and cyclohexylmethyl group, decyloxycarbonylmethyl group, dodecyloxycarbonyl Methyl group, 1-octyloxycarbonylethyl group, 1-decyloxycarbonylethyl group,
Examples thereof include an alkoxycarbonylalkyl group such as a 1-dodecyloxycarbonylethyl group, an alkylaminocarbonylalkyl group such as a dodecylaminocarbonylcarbonylmethyl group and an N-methyl-N-dodecylaminocarbonylmethyl group, and a decyl group and a dodecyl group are preferable. , A tetradecyl group and a 1-dodecyloxycarbonylethyl group. These alkyl groups may be linear or branched. Preferred examples of the alkyl halide include alkyl bromide and alkyl chloride.
【0008】前記一般式(I)、一般式(II)において
Xは水素原子、ナトリウム、カリウム等のアルカリ金属
原子であり、好ましくは水素原子、ナトリウム、より好
ましくは水素原子である。Yは塩素原子、臭素原子、フ
ッ素原子等のハロゲン原子、炭素数1〜18個のアルコ
キシ基であり、好ましくは炭素数1〜6個のアルコキシ
基、フッ素原子、塩素原子であり、より好ましくはメト
キシ基、エトキシ基、ブトキシ基、フッ素原子、塩素原
子であり、更に好ましくはメトキシ基、エトキシ基、塩
素原子である。炭酸塩塩基の好ましい例としては、炭酸
カリウム、炭酸ナトリウム等が挙げられる。In the general formulas (I) and (II), X is a hydrogen atom, an alkali metal atom such as sodium or potassium, preferably a hydrogen atom, sodium, and more preferably a hydrogen atom. Y is a chlorine atom, a bromine atom, a halogen atom such as a fluorine atom, an alkoxy group having 1 to 18 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms, a fluorine atom, a chlorine atom, more preferably A methoxy group, an ethoxy group, a butoxy group, a fluorine atom and a chlorine atom, more preferably a methoxy group, an ethoxy group and a chlorine atom. Preferred examples of the carbonate base include potassium carbonate, sodium carbonate and the like.
【0009】本発明においては、前記一般式(I)で示
される3−アミノ−4−置換安息香酸又はそのアルカリ
金属塩と炭酸カリウム、炭酸ナトリウム等の炭酸塩塩基
と塩化アルキル、臭化アルキル等のハロゲン化アルキル
をほぼ化学量論的に反応させることにより、目的の一般
式(II)で示される化合物を得ることができる。反応モ
ル比として好ましくは、前記一般式(I)で示される3
−アミノ−4−置換安息香酸又はそのアルカリ金属塩1
モルに対して、炭酸塩塩基0.5〜2.0モル、ハロゲ
ン化アルキル1.0〜2.0モルであり、より好ましく
は3−アミノ−4−置換安息香酸又はそのアルカリ金属
塩1モルに対して、炭酸塩塩基0.9〜1.2モル、ハ
ロゲン化アルキル1.0〜1.3モルである。反応溶媒
としては、N,N−ジメチルホルムアミド、N,N−ジ
メチルアセトアミド、ジメチルスルホキシド、アセトン
等が挙げられるが、より好ましくはN,N−ジメチルホ
ルムアミド、ジメチルスルホキシドである。反応溶媒の
使用量は3−アミノ−4−置換安息香酸又はそのアルカ
リ金属塩1に対して、好ましくは2〜10倍容量の溶媒
を用いるが、より好ましくは2〜5倍容量である。溶媒
が多すぎると反応の進行が遅くなり、またコスト高とな
る。In the present invention, a 3-amino-4-substituted benzoic acid represented by the above general formula (I) or an alkali metal salt thereof, a carbonate base such as potassium carbonate or sodium carbonate, an alkyl chloride, an alkyl bromide or the like is used. Is reacted almost stoichiometrically to obtain the desired compound represented by the general formula (II). The reaction molar ratio is preferably 3 represented by the general formula (I).
-Amino-4-substituted benzoic acid or its alkali metal salt 1
The amount is 0.5 to 2.0 mol of a carbonate base and 1.0 to 2.0 mol of an alkyl halide, more preferably 1 mol of 3-amino-4-substituted benzoic acid or an alkali metal salt thereof, per mol. Are 0.9 to 1.2 mol of a carbonate base and 1.0 to 1.3 mol of an alkyl halide. Examples of the reaction solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethylsulfoxide, acetone and the like, and more preferred are N, N-dimethylformamide and dimethylsulfoxide. The amount of the reaction solvent used is preferably 2 to 10 times the volume of the 3-amino-4-substituted benzoic acid or its alkali metal salt 1, and more preferably 2 to 5 times the volume. If the amount of the solvent is too large, the progress of the reaction becomes slow, and the cost becomes high.
【0010】反応温度は余り低いと反応しにくく、また
高すぎると副生成物が生じるため、通常20〜120
℃、好ましくは60〜100℃が適用される。If the reaction temperature is too low, it is difficult to react, and if it is too high, by-products are formed.
C, preferably from 60 to 100C are applied.
【0011】更に、本発明においては、反応をより良好
に完結させる上で添加順序が肝要である。反応の好まし
い添加順序は、溶媒を入れた中にまず3−アミノ−4−
置換安息香酸又はそのアルカリ金属塩を投入し、次いで
炭酸塩塩基を加えて20〜40℃に加温し20分〜60
分、好ましくは30分〜40分攪拌する。最後にハロゲ
ン化アルキルを添加し反応させる方法が良好な結果を与
える。Furthermore, in the present invention, the order of addition is important for completing the reaction better. The preferred order of addition of the reaction is to first add 3-amino-4-
The substituted benzoic acid or an alkali metal salt thereof is charged, and then a carbonate base is added, and the mixture is heated to 20 to 40 ° C. and heated for 20 minutes to 60 minutes.
Minutes, preferably 30 to 40 minutes. Finally, a method in which an alkyl halide is added and reacted gives good results.
【0012】本発明の方法によって同一分子内にアミノ
基とカルボキシル基の2つの反応性基を有する化合物に
おいて、一方の基を保護することなくカルボキシル基を
選択的に反応させることが可能である。According to the method of the present invention, in a compound having two reactive groups, an amino group and a carboxyl group, in the same molecule, the carboxyl group can be selectively reacted without protecting one of the groups.
【0013】次に本発明の化合物の製造方法の一例を述
べる。N,N−ジメチルホルムアミドまたはジメチルス
ルホキシド中に、3−アミノ−4−置換安息香酸又はそ
のアルカリ金属塩を添加する。その後に炭酸カリウムを
徐々に添加し、20〜40℃の温度範囲で30分間攪拌
する。その溶液に臭化アルキルもしくは塩化アルキルを
注入し、80〜100℃で反応時間1〜8時間、好まし
くは1〜4時間反応させ、水を添加後酢酸エチルで抽出
し、濃縮後、メタノールで晶析させ目的物であるアルキ
ル 3−アミノ−4−置換ベンゾエイトを高収率、且つ
高純度で得ることができる。Next, an example of a method for producing the compound of the present invention will be described. In N, N-dimethylformamide or dimethylsulfoxide, 3-amino-4-substituted benzoic acid or its alkali metal salt is added. Thereafter, potassium carbonate is gradually added, and the mixture is stirred in a temperature range of 20 to 40 ° C. for 30 minutes. An alkyl bromide or alkyl chloride is poured into the solution, and the mixture is reacted at 80 to 100 ° C. for 1 to 8 hours, preferably 1 to 4 hours. After adding water, the mixture is extracted with ethyl acetate, concentrated, and crystallized with methanol. The alkyl 3-amino-4-substituted benzoate as a target product can be obtained in high yield and high purity.
【0014】[0014]
【実施例】以下、本発明を実施例によりさらに詳細に説
明するが、本発明はこれらに限定されるものではない。 実施例1 ドデシル 3−アミノ−4−クロロベンゾエイトの合
成:N,N−ジメチルホルムアミド50mlに3−アミ
ノ−4−クロロ安息香酸17.2g(0.1モル)を添
加した。その後炭酸カリウム13.8g(0.1モル)
を添加し、20〜30℃の温度範囲で30分間攪拌し
た。その溶液中に臭化ドデシル27.4g(0.11モ
ル)を注入し、80℃に昇温し同温度で1時間反応させ
る。反応終了後酢酸エチル50ml及び水50mlを添
加し有機層を分離し濃縮した。その後にメタノール10
0mlを添加し、冷却晶析、濾過、乾燥し、目的物3
2.3g(収率95%)を得た。純度99%以上、融点
58.3〜59.5℃、元素分析の結果は次の通りであ
った。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto. Example 1 Synthesis of dodecyl 3-amino-4-chlorobenzoate: 17.2 g (0.1 mol) of 3-amino-4-chlorobenzoic acid was added to 50 ml of N, N-dimethylformamide. Then 13.8 g (0.1 mol) of potassium carbonate
Was added, and the mixture was stirred at a temperature in the range of 20 to 30 ° C. for 30 minutes. 27.4 g (0.11 mol) of dodecyl bromide is poured into the solution, the temperature is raised to 80 ° C., and the mixture is reacted at the same temperature for 1 hour. After completion of the reaction, 50 ml of ethyl acetate and 50 ml of water were added, and the organic layer was separated and concentrated. Then methanol 10
0 ml was added, and the product was cooled, crystallized, filtered and dried to obtain the desired product 3
2.3 g (95% yield) were obtained. The purity was 99% or more, the melting point was 58.3-59.5 ° C., and the results of elemental analysis were as follows.
【0015】 [0015]
【0016】実施例2 ドデシル 3−アミノ−4−クロロベンゾエイトの合
成:ジメチルスルホキシド50mlに3−アミノ−4−
クロロ安息香酸17.2g(0.1モル)を添加した。
その後炭酸カリウム13.8g(0.1モル)を添加
し、20〜30℃の温度範囲で30分間攪拌した。その
溶液中に塩化ドデシル22.5g(0.11モル)を注
入し、100℃に昇温し同温度で1時間反応させた。反
応終了後酢酸エチル50ml及び水50mlを添加し有
機層を分離し濃縮した。その後メタノール100mlを
添加し、冷却晶析、濾過、乾燥し目的物32.3g(収
率95%)を得た。純度99%以上、融点58.0〜5
9.2℃。元素分析の結果は次の通りであった。Example 2 Synthesis of dodecyl 3-amino-4-chlorobenzoate: 3-Amino-4-amine was added to 50 ml of dimethyl sulfoxide.
17.2 g (0.1 mol) of chlorobenzoic acid were added.
Thereafter, 13.8 g (0.1 mol) of potassium carbonate was added, and the mixture was stirred for 30 minutes in a temperature range of 20 to 30 ° C. 22.5 g (0.11 mol) of dodecyl chloride was poured into the solution, the temperature was raised to 100 ° C., and the mixture was reacted at the same temperature for 1 hour. After completion of the reaction, 50 ml of ethyl acetate and 50 ml of water were added, and the organic layer was separated and concentrated. Thereafter, 100 ml of methanol was added, and the mixture was cooled, crystallized, filtered and dried to obtain 32.3 g (yield: 95%) of the desired product. Purity 99% or more, melting point 58.0-5
9.2 ° C. The results of the elemental analysis were as follows.
【0017】 [0017]
【0018】実施例3 テトラデシル 3−アミノ−4−メトキシベンゾエイト
の合成:N,N−ジメチルホルムアミド50mlに3−
アミノ−4−メトキシ安息香酸16.7g(0.1モ
ル)を添加した。その後炭酸カリウム13.8g(0.
1モル)を添加し、20〜30℃の温度範囲で30分間
攪拌した。その溶液中に臭化テトラデシル30.5g
(0.11モル)を注入し、80℃に昇温し同温度で1
時間反応させた。反応終了後酢酸エチル50ml及び水
50mlを添加し有機層を分離し濃縮した。その後メタ
ノール100mlを添加し、冷却晶析、濾過、乾燥し目
的物33.1g(収率91%)を得た。純度98%以
上、融点54.0〜56.0℃。元素分析の結果は次の
通りであった。Example 3 Synthesis of tetradecyl 3-amino-4-methoxybenzoate: 3-N-N-dimethylformamide in 50 ml
16.7 g (0.1 mol) of amino-4-methoxybenzoic acid were added. Thereafter, 13.8 g of potassium carbonate (0.
1 mol), and the mixture was stirred for 30 minutes in a temperature range of 20 to 30 ° C. 30.5 g of tetradecyl bromide in the solution
(0.11 mol), the temperature was raised to 80 ° C., and 1
Allowed to react for hours. After completion of the reaction, 50 ml of ethyl acetate and 50 ml of water were added, and the organic layer was separated and concentrated. Thereafter, 100 ml of methanol was added, and the mixture was cooled, crystallized, filtered and dried to obtain 33.1 g (yield 91%) of the desired product. Purity 98% or more, melting point 54.0-56.0 ° C. The results of the elemental analysis were as follows.
【0019】 [0019]
【0020】実施例1〜3と同様に本発明を用いること
により、例えばドデシルオキシカルボニルエチル基のご
とき置換アルキル基を導入したドデシルオキシカルボニ
ルエチル 3−アミノ−4−クロロベンゾエイトも容易
に製造することが可能である。By using the present invention in the same manner as in Examples 1 to 3, dodecyloxycarbonylethyl 3-amino-4-chlorobenzoate into which a substituted alkyl group such as a dodecyloxycarbonylethyl group has been introduced can be easily produced. It is possible.
【0021】[0021]
【発明の効果】本発明によれば、アルキル 3−アミノ
−4−置換ベンゾエイトを高収率且つ高純度でしかも簡
単な方法で効率的に製造することができる。According to the present invention, an alkyl 3-amino-4-substituted benzoate can be efficiently produced in a high yield and a high purity by a simple method.
Claims (3)
−4−置換安息香酸又はそのアルカリ金属塩を炭酸塩塩
基存在下、ハロゲン化アルキルと反応させることを特徴
とする下記一般式(II)で示されるアルキル 3−アミ
ノ−4−置換ベンゾエイトの製造方法。 【化1】 式中、Rはアルキル基を表す。Xはアルカリ金属原子、
水素原子を表し、Yはアルコキシ基、ハロゲン原子を表
す。1. A method of reacting a 3-amino-4-substituted benzoic acid represented by the following general formula (I) or an alkali metal salt thereof with an alkyl halide in the presence of a carbonate base: A method for producing an alkyl 3-amino-4-substituted benzoate represented by II). Embedded image In the formula, R represents an alkyl group. X is an alkali metal atom,
Y represents a hydrogen atom, and Y represents an alkoxy group or a halogen atom.
子、Yが塩素原子である請求項1に記載のアルキル 3
−アミノ−4−置換ベンゾエイトの製造方法。2. The alkyl 3 according to claim 1, wherein X in the general formula (I) is a hydrogen atom and Y is a chlorine atom.
A method for producing an amino-4-substituted benzoate.
個の非置換又は置換アルキル基である請求項1又は2に
記載のアルキル 3−アミノ−4−置換ベンゾエイトの
製造方法。3. The method according to claim 1, wherein the alkyl group has 6 to 18 carbon atoms.
The method for producing an alkyl 3-amino-4-substituted benzoate according to claim 1 or 2, which is an unsubstituted or substituted alkyl group.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP172898A JPH10259172A (en) | 1997-01-14 | 1998-01-07 | Production of alkyl 3-amino-4-substituted benzoate |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP466097 | 1997-01-14 | ||
JP9-4660 | 1997-01-14 | ||
JP172898A JPH10259172A (en) | 1997-01-14 | 1998-01-07 | Production of alkyl 3-amino-4-substituted benzoate |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH10259172A true JPH10259172A (en) | 1998-09-29 |
Family
ID=26335001
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP172898A Pending JPH10259172A (en) | 1997-01-14 | 1998-01-07 | Production of alkyl 3-amino-4-substituted benzoate |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH10259172A (en) |
-
1998
- 1998-01-07 JP JP172898A patent/JPH10259172A/en active Pending
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