JP3150192B2 - Anthranilic acid derivatives - Google Patents
Anthranilic acid derivativesInfo
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- JP3150192B2 JP3150192B2 JP10819192A JP10819192A JP3150192B2 JP 3150192 B2 JP3150192 B2 JP 3150192B2 JP 10819192 A JP10819192 A JP 10819192A JP 10819192 A JP10819192 A JP 10819192A JP 3150192 B2 JP3150192 B2 JP 3150192B2
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Description
【0001】[0001]
【産業上の利用分野】本発明は、金属イオン遮蔽剤、特
に、ハロゲン化銀写真感光材料分野における金属イオン
遮蔽剤、また、ハロゲン化銀カラー写真感光材料用の漂
白能を有する処理液や黒白ハロゲン化銀写真感光材料用
の減力液に使用される酸化剤の中間体として、さらに、
洗剤組成物、クリーニング組成物、医療用、化粧用製剤
組成物、金属材料の被覆剤組成物として有用でかつ新規
なアントラニル酸誘導体及びキレート化剤に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal ion shielding agent, particularly a metal ion shielding agent in the field of silver halide photographic light-sensitive materials, a processing solution having a bleaching ability for a silver halide color photographic light-sensitive material, and a black and white. As an intermediate of an oxidizing agent used in a reducer for a silver halide photographic light-sensitive material,
The present invention relates to a novel anthranilic acid derivative and a chelating agent which are useful as detergent compositions, cleaning compositions, medical and cosmetic preparation compositions, and coating compositions for metallic materials.
【0002】[0002]
【従来の技術】従来、この種の化合物としては下記の化
合物が知られている。2. Description of the Related Art Heretofore, the following compounds have been known as such compounds.
【0003】[0003]
【化2】 Embedded image
【0004】( J.Phys.Chem.,61,694(1957)、Ber.28,1
686(1895) 参照) この化合物を金属イオン遮蔽剤として利用する場合、水
に対する溶解性が低く、高濃度で使用しようとすると、
化合物そのものとしても、また金属キレート化合物とし
た場合においても析出し、問題となる場合がある。また
金属イオンとの錯安定度定数が小さく、金属イオン遮蔽
剤としての性能は不十分である。(J. Phys. Chem., 61 , 694 (1957), Ber. 28 , 1)
686 (1895)) When this compound is used as a metal ion shielding agent, its solubility in water is low,
Even when the compound itself is used or when it is used as a metal chelate compound, it may precipitate and cause a problem. Further, the complex stability constant with metal ions is small, and the performance as a metal ion shielding agent is insufficient.
【0005】又、感光材料用酸化剤(例えば漂白剤)の
中間体として利用する場合、この化合物の金属キレート
化合物は溶液中経時で分解し、長期使用に適していな
い。When used as an intermediate of an oxidizing agent (for example, a bleaching agent) for a light-sensitive material, a metal chelate compound of this compound is decomposed with time in a solution and is not suitable for long-term use.
【0006】[0006]
【化3】 Embedded image
【0007】この化合物は金属遮蔽剤として多く使用さ
れているが、廃棄する場合、化合物そのものも金属キレ
ート化合物も生分解されにくく問題となっている。ま
た、この化合物の金属キレート化合物を感光材料用酸化
剤(例えば漂白剤)の中間体として利用する場合、酸化
力が弱く、銀の酸化過程に時間がかかるという問題があ
る。This compound is widely used as a metal shielding agent, but when discarded, both the compound itself and the metal chelate compound are difficult to biodegrade. Further, when a metal chelate compound of this compound is used as an intermediate of an oxidizing agent for a light-sensitive material (for example, a bleaching agent), there is a problem that the oxidizing power is weak and a long time is required for the silver oxidation process.
【0008】[0008]
【化4】 Embedded image
【0009】( Z.Anorg.Allgem.Chem.,314 ,321,(1962)
参照 ) この化合物は、合成の際に中間体となる2,5−ビス
(β−アミノエチルアミノ)テレフタル酸の合成が困難
という問題を有している。(Z. Anorg. Allgem. Chem., 314 , 321, (1962)
This compound has a problem that it is difficult to synthesize 2,5-bis (β-aminoethylamino) terephthalic acid, which is an intermediate during synthesis.
【0010】また、この化合物の金属キレート化合物を
感光材料用漂白剤の中間体として利用する場合、金属イ
オン(例えば鉄(3価)イオン等)2個と錯体形成をす
るので、従来の単核錯体(例えば上記〔化2〕の鉄錯体
あるいは〔化3〕の鉄錯体)よりも錯体分子が大きくな
り、多孔性のゼラチン膜で形成されるような感光材料中
での拡散速度が遅くなり、これにより感光材料中の銀の
酸化過程に時間がかかるという問題がある。When a metal chelate compound of this compound is used as an intermediate of a bleaching agent for a light-sensitive material, it forms a complex with two metal ions (for example, iron (trivalent) ions, etc.). The complex molecule becomes larger than the complex (for example, the iron complex of the above [Chemical formula 2] or the iron complex of the [Chemical formula 3]), and the diffusion rate in a photosensitive material formed by a porous gelatin film becomes slow. As a result, there is a problem that the oxidation process of silver in the photosensitive material takes a long time.
【0011】[0011]
【発明が解決しようとする課題】本発明は、金属イオン
遮蔽剤、特に、ハロゲン化銀写真感光材料分野における
金属イオン遮蔽剤、また、ハロゲン化銀カラー写真感光
材料用の漂白能を有する処理液や黒白ハロゲン化銀写真
感光材料用の減力液に使用される酸化剤の中間体とし
て、さらに、洗剤組成物、クリーニング組成物、医療
用、化粧用製剤組成物、金属材料の被覆剤組成物として
有用で、かつ生分解容易な新規なアントラニル酸誘導体
及びキレート化剤を提供するものである。The present invention relates to a metal ion shielding agent, particularly a metal ion shielding agent in the field of silver halide photographic light-sensitive materials, and a processing solution having a bleaching ability for silver halide color photographic light-sensitive materials. Intermediates of oxidizing agents used in reducers for black and white and silver halide photographic light-sensitive materials, further include detergent compositions, cleaning compositions, medical and cosmetic preparation compositions, and coating compositions for metal materials The present invention provides a novel anthranilic acid derivative and a chelating agent which are useful as a biodegradable and easily biodegradable.
【0012】[0012]
【課題を解決するための手段】本発明のアントラニル酸
誘導体は、The anthranilic acid derivative of the present invention comprises:
【0013】[0013]
【化5】 Embedded image
【0014】(式中Zはアルキル基、ニトロ基、及びカ
ルボキシル基よりなる群から選ばれた基で置換されても
よいベンゼン環あるいはナフタレン環を完成するために
必要な原子群を表す。Xは水素原子または−L1 COO
M1 を表わす。M1 、M2 、M3 及びM4 はそれぞれ水
素原子あるいはカチオンを表す。L1 、L2 及びL
3 は、それぞれアルキレン基を表す。W1 は下記一般式
(W1 )で示される炭素数2以上のアルキレン基を含む
2価の連結基を表す。)で表される。 一般式(W1 ) −(Wa −Y)m −Wb − 式中、Wa 及びWb は同じであっても異なっていてもよ
く、炭素数2〜10のアルキレン基を表す。Yは単なる
結合、−O−、−S−を表す。mは0〜3の整数を表
し、mが2又は3の時には、(Wa −Y)は同じであっ
ても異なっていてもよい。W1 で表される連結基はアル
キル基、ヒドロキシ基を置換基として有していてもよ
く、置換基で炭素原子を有する場合、炭素数1〜10の
ものである。(In the formula, Z represents an atomic group necessary for completing a benzene ring or a naphthalene ring which may be substituted with a group selected from the group consisting of an alkyl group, a nitro group and a carboxyl group. Hydrogen atom or -L 1 COO
Representing the M 1. M 1 , M 2 , M 3 and M 4 each represent a hydrogen atom or a cation. L 1 , L 2 and L
3 represents an alkylene group. W 1 represents a divalent linking group containing an alkylene group having 2 or more carbon atoms represented by the following general formula (W 1 ). ). Formula (W 1) - (W a -Y) m -W b - wherein, W a and W b are individually selected from the same, represents an alkylene group having 2 to 10 carbon atoms. Y represents a mere bond, -O-, -S-. m represents an integer of 0 to 3, and when m is 2 or 3, (W a -Y) may be the same or different. The linking group represented by W 1 may have an alkyl group or a hydroxy group as a substituent, and when the substituent has a carbon atom, it has 1 to 10 carbon atoms.
【0015】式中、Zで形成されるベンゼン環及びナフ
タレン環のうち、好ましくはベンゼン環である。このベ
ンゼン環あるいはナフタレン環はアルキル基、ニトロ
基、カルボキシル基で置換されていてもよい。In the formula, among the benzene ring and naphthalene ring formed by Z, a benzene ring is preferred. This benzene ring or naphthalene ring may be substituted with an alkyl group, a nitro group or a carboxyl group.
【0016】Xで表される水素原子または−L1 COO
M1 (L1 はアルキレン基、M1 はカチオンを表わ
す。)のうち、好ましくは−L1 COOM1 である。A hydrogen atom represented by X or -L 1 COO
Of M 1 (L 1 represents an alkylene group and M 1 represents a cation), it is preferably -L 1 COOM 1 .
【0017】M1 、M2 、M3 及びM4 で表されるカチ
オンとしてはアルカリ金属(Li、Na、Kなど)、ア
ルキル土類金属(Mg、Caなど)、アンモニウム(ア
ンモニウム、トリエチルアンモニウム)などが例示でき
る。また、M1 、M2 、M3 及びM4 は同一又は互いに
異なっていてもよい。The cations represented by M 1 , M 2 , M 3 and M 4 include alkali metals (Li, Na, K, etc.), alkyl earth metals (Mg, Ca, etc.), ammonium (ammonium, triethylammonium) And the like. M 1 , M 2 , M 3 and M 4 may be the same or different from each other.
【0018】L1 、L2 及びL3 で表されるアルキレン
基は直鎖状、分岐状又は環状であってもよく、好ましく
は炭素数1〜5のアルキレン基、例えばメチレン基、エ
チレン基、トリメチレン基、プロピレン基等であり、特
にメチレン基が好ましい。L1 、L2 及びL3 は、同一
または互いに異なっていてもよい。The alkylene group represented by L 1 , L 2 and L 3 may be linear, branched or cyclic, and is preferably an alkylene group having 1 to 5 carbon atoms, for example, a methylene group, an ethylene group, Examples thereof include a trimethylene group and a propylene group, and a methylene group is particularly preferable. L 1 , L 2 and L 3 may be the same or different from each other.
【0019】W1 で表される炭素数2以上のアルキレン
基を含む2価の連結基は、好ましくは下記の一般式(W
1 )で表すことができる。The divalent linking group containing an alkylene group having 2 or more carbon atoms represented by W 1 is preferably represented by the following general formula (W
1 ).
【0020】一般式(W1 ) −(Wa −Y)m −Wb − 式中、Wa 及びWb は同じであっても異なっていてもよ
く、炭素数2〜10のアルキレン基(例えば炭素数2〜
10の直鎖、分岐アルキレン基、炭素数5〜10のシク
ロアルキレン基など)を表す。In the formula (W 1 )-(W a -Y) m -W b-wherein W a and W b may be the same or different and have an alkylene group having 2 to 10 carbon atoms ( For example, carbon number 2
10 linear or branched alkylene groups, cycloalkylene groups having 5 to 10 carbon atoms, etc.).
【0021】Yは単なる結合、−O−、−S−を表す。
mは0〜3の整数を表し、mが2又は3の時には、(W
a −Y)は同じであっても異なっていてもよい。Y represents a mere bond, -O- or -S-.
m represents an integer of 0 to 3. When m is 2 or 3, (W
a- Y) may be the same or different.
【0022】これらW1 で表される連結基は、置換基を
有していもよく、置換基としては例えばアルキル基(例
えばメチル基、エチル基)、ヒドロキシ基が挙げられ
る。上記置換基で炭素原子を有する場合、好ましくは炭
素数1〜10のものであり、より好ましくは1〜4のも
のである。W1 としては上記一般式(W1 )においてm
=0又は1で、Wa 及びWb が炭素数2〜4のアルキレ
ン基又はシクロヘキシレン基のものが好ましい。特に好
ましくはm=0で、Wb が炭素数2〜4のアルキレン基
である。The linking group represented by W 1 may have a substituent. Examples of the substituent include an alkyl group (eg, a methyl group and an ethyl group) and a hydroxy group. When the substituent has a carbon atom, it preferably has 1 to 10 carbon atoms, and more preferably has 1 to 4 carbon atoms. W 1 is m in the above general formula (W 1 )
In = 0 or 1, W a and W b is preferably from alkylene or cyclohexylene group having 2 to 4 carbon atoms. Particularly preferably in the m = 0, W b is an alkylene group having 2 to 4 carbon atoms.
【0023】W1 の具体例としては例えば以下のものが
挙げられる。Specific examples of W 1 include the following.
【0024】[0024]
【化6】 Embedded image
【0025】本発明の一般式(1)で表される化合物の
具体例としては、下記化合物が挙げられるが、これに限
定されるものではない。Specific examples of the compound represented by the general formula (1) of the present invention include, but are not limited to, the following compounds.
【0026】[0026]
【化7】 Embedded image
【0027】[0027]
【化8】 Embedded image
【0028】[0028]
【化9】 Embedded image
【0029】[0029]
【化10】 Embedded image
【0030】上記一般式(1)で表される化合物は、例
えば下記に示すように、1−カルボキシ−2−ハロゲン
置換芳香族誘導体のハロゲン原子をジアミン誘導体で置
換した後、ハロゲン置換アルキルカルボン酸と反応させ
ることにより合成できる。The compound represented by the above general formula (1) is obtained, for example, by substituting a halogen atom of a 1-carboxy-2-halogen-substituted aromatic derivative with a diamine derivative and then subjecting the compound to a halogen-substituted alkyl carboxylic acid as shown below. Can be synthesized by reacting
【0031】[0031]
【化11】 Embedded image
【0032】式中、Zは一般式(1)のそれと同義であ
る。MはM1 〜M3 と同義、LはL1 〜L3 と同義、
M′はMと同義である。nは0、1、2を表わす。In the formula, Z has the same meaning as in formula (1). M is synonymous with M 1 to M 3 , L is synonymous with L 1 to L 3 ,
M 'is synonymous with M. n represents 0, 1, and 2.
【0033】1−カルボキシ−2−ハロゲン置換芳香族
誘導体におけるハロゲン原子をジアミン誘導体で置換す
るには、ジャーナル オブ ザ アメリカン ケミカル
ソサイエティ、第80巻、800頁(1958)を参
考にして合成でき、例えば、溶媒中、1−カルボキシ−
2−クロル置換芳香族誘導体とジアミン誘導体とを混合
し、炭酸カリウムと触媒量の銅を加え、加熱還流して対
応するジアミン誘導体が得られる。原料の芳香族誘導体
のハロゲン原子がヨードの場合には銅触媒を加えなくと
も目的物が得られる。In order to replace a halogen atom in a 1-carboxy-2-halogen-substituted aromatic derivative with a diamine derivative, it can be synthesized with reference to Journal of the American Chemical Society, Vol. 80, p. 800 (1958). , In a solvent, 1-carboxy-
The 2-chloro-substituted aromatic derivative and the diamine derivative are mixed, potassium carbonate and a catalytic amount of copper are added, and the mixture is heated to reflux to obtain the corresponding diamine derivative. When the halogen atom of the aromatic derivative as the raw material is iodine, the desired product can be obtained without adding a copper catalyst.
【0034】ここで使用する溶媒としては反応に関与し
ない限り限定されないが、例えばアルコール(例えばメ
タノール、エタノール、イソプロパノール、ブタノー
ル、ペンタノール等)、またジオキサン、ジメチルホル
ムアミド等が挙げられる。この反応は溶媒を使用しなく
とも目的物を得ることが出来る。The solvent used here is not limited as long as it does not participate in the reaction, and examples thereof include alcohols (eg, methanol, ethanol, isopropanol, butanol, pentanol, etc.), dioxane, dimethylformamide and the like. In this reaction, the desired product can be obtained without using a solvent.
【0035】触媒としては、銅粉の他にCuCl、Cu
Br、CuI、CuO、Cu2 O等の銅塩を用いること
も出来る。その量は、1−カルボキシ−2−ハロゲン置
換芳香族誘導体に対して、モル濃度で2%以上、10%
以下が望ましい。As a catalyst, CuCl, Cu
Copper salts such as Br, CuI, CuO, and Cu 2 O can also be used. The amount is 2% or more and 10% or more in molar concentration with respect to the 1-carboxy-2-halogen-substituted aromatic derivative.
The following is desirable.
【0036】ジアミン誘導体とハロゲン置換アルキルカ
ルボン酸との反応は、導入するアルキルカルボン酸数を
反応温度により制御した。In the reaction between the diamine derivative and the halogen-substituted alkyl carboxylic acid, the number of alkyl carboxylic acids to be introduced was controlled by the reaction temperature.
【0037】反応は通常0〜100℃で行なうが、アル
キルカルボン酸をフェニル基置換されていない窒素原子
上にのみ2個導入する場合には、約70℃以下で反応さ
せることが好ましい。また両窒素原子上にアルキルカル
ボン酸を導入する場合にはそれ以上の温度で反応させる
ことが好ましい。The reaction is usually carried out at 0 to 100 ° C., but when two alkylcarboxylic acids are introduced only on nitrogen atoms not substituted with a phenyl group, the reaction is preferably carried out at about 70 ° C. or lower. When an alkylcarboxylic acid is introduced on both nitrogen atoms, it is preferable to carry out the reaction at a higher temperature.
【0038】ジアミン誘導体とハロゲン置換アルキルカ
ルボン酸との反応は、通常溶媒中で行われる。溶媒とし
ては反応に関与しない限り限定されないが、水、アルコ
ール(メタノール、エタノール、イソプロパノール等)
等を用いると有利に進行する。反応は、塩基存在下で行
うことが好ましく塩基としては、アルカリ(水酸化ナト
リウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウ
ム等)または三級アミン(トリエチルアミン等)が挙げ
られる。The reaction between the diamine derivative and the halogen-substituted alkylcarboxylic acid is usually performed in a solvent. The solvent is not limited as long as it does not participate in the reaction, but water, alcohol (methanol, ethanol, isopropanol, etc.)
The use of such a method advantageously proceeds. The reaction is preferably performed in the presence of a base, and examples of the base include alkalis (such as sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate) and tertiary amines (such as triethylamine).
【0039】また、一般式(1)において、L1 、
L2 、L3 がエチレンの場合、その合成にはハロゲン置
換アルキルカルボン酸の代わりに、アクリル酸を用いる
こともできる。In the general formula (1), L 1 ,
When L 2 and L 3 are ethylene, acrylic acid can be used in the synthesis instead of halogen-substituted alkyl carboxylic acid.
【0040】[0040]
【作用及び発明の効果】本発明の化合物は水溶性であ
り、金属イオン遮蔽剤として、例えば写真用処理液、キ
レート滴定用または医療用の分析試薬、医薬等への使用
に適している。The compound of the present invention is water-soluble and is suitable for use as a metal ion shielding agent, for example, in a photographic processing solution, a chelate titration or medical analysis reagent, a medicine, and the like.
【0041】次に、本発明を具体的に説明するため、実
施例を挙げる。Next, examples will be given to specifically explain the present invention.
【0042】[0042]
【実施例】以下、代表的な化合物について具体的合成例
をもって説明するが、本発明はこれらに限定されるもの
ではない。EXAMPLES Hereinafter, typical compounds will be described with reference to specific synthetic examples, but the present invention is not limited thereto.
【0043】実施例1 化合物1の合成法を下記に示す。Example 1 A method for synthesizing Compound 1 is shown below.
【0044】[0044]
【化12】 Embedded image
【0045】化合物1aの合成 o−ヨード安息香酸10.3g(4.15×10-2 mo
l)、炭酸カリウム10.3g(7.45×10-2 mo
l)をエチレンジアミン97g(1.61 mol)に懸濁
させ、4時間加熱還流した。反応液に水30mlを加
え、ナスフラスコに移し、溶媒を減圧留去した。水40
mlを加え、ビーカーに移し、濃塩酸でpH9に調整し
た。生じた沈殿を濾取し、ビーカーに入れ、水200m
lを加えて濃塩酸でpH1に調整した。生じた沈殿を濾
取し、水で洗浄後、減圧乾燥を行ない、灰色結晶1aを
4.9g(2.26×10-2 mol)を得た。収率54%
また化合物1aは別の合成法でも得られる。その合成法
を以下に示す。Synthesis of Compound 1a 10.3 g of o-iodobenzoic acid (4.15 × 10 −2 mo
l), 10.3 g of potassium carbonate (7.45 × 10 -2 mo
l) was suspended in 97 g (1.61 mol) of ethylenediamine and heated under reflux for 4 hours. 30 ml of water was added to the reaction solution, transferred to an eggplant flask, and the solvent was distilled off under reduced pressure. Water 40
Then, the mixture was transferred to a beaker and adjusted to pH 9 with concentrated hydrochloric acid. The resulting precipitate was collected by filtration, put into a beaker, and poured into 200 m of water.
and adjusted to pH 1 with concentrated hydrochloric acid. The resulting precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 4.9 g (2.26 × 10 -2 mol) of gray crystal 1a. 54% yield
Compound 1a can also be obtained by another synthesis method. The synthesis method is described below.
【0046】[0046]
【化13】 Embedded image
【0047】o−クロル安息香酸31.4g(2.01
×10-1 mol)、炭酸カリウム25.6g(1.85×
10-1 mol)、エチレンジアミン32ml(4.79×
10-1 mol)を1−ペンタノール68mlに懸濁させ、
銅粉0.3g(4.72×10-3)を加えて5時間加熱
還流した。水200mlを反応液に加え、溶媒を共沸さ
せ取り除いた。熱いうちに濾過し、冷却後に1:1(v
ol比)塩酸水溶液でpH7.8に調整した。生じた沈
殿を濾取し、200mlのエタノールで洗浄した。熱い
1:1塩酸水溶液に溶解した後、濾過し冷却した。生じ
た沈殿を濾取し、ビーカーにあけ、水100ml、28
%アンモニア水100ml及び活性炭0.5gを加えて
良く撹拌した。溶液を濾過した後、濃塩酸でpH1.6
に調整した。生じた沈殿を濾取し、水で洗浄後、乾燥す
ることにより灰色結晶1aを15.7g(7.25×1
0-2mol )得た。収率36%。31.4 g (2.01) of o-chlorobenzoic acid
× 10 -1 mol), 25.6 g of potassium carbonate (1.85 ×
10 -1 mol), 32 ml of ethylenediamine (4.79 ×
10 -1 mol) in 68 ml of 1-pentanol,
0.3 g (4.72 × 10 −3 ) of copper powder was added, and the mixture was heated under reflux for 5 hours. 200 ml of water was added to the reaction solution, and the solvent was removed by azeotropic distillation. Filter while hot and after cooling 1: 1 (v
pH ratio was adjusted to 7.8 with an aqueous hydrochloric acid solution. The resulting precipitate was collected by filtration and washed with 200 ml of ethanol. After dissolving in hot 1: 1 aqueous hydrochloric acid, the mixture was filtered and cooled. The resulting precipitate was collected by filtration and poured into a beaker.
% Ammonia water and activated carbon 0.5 g were added and stirred well. After the solution was filtered, the pH was adjusted to 1.6 with concentrated hydrochloric acid.
Was adjusted. The resulting precipitate was collected by filtration, washed with water, and dried to give 15.7 g of gray crystals 1a (7.25 × 1
0 -2 mol). Yield 36%.
【0048】化合物1の合成 上記で合成した化合物1a4.9g(2.26×10-2
mol)、クロル酢酸10.0g(1.06×10-1 mo
l)を水30mlに懸濁させ、5N水酸化ナトリウム5
5ml(0.275 mol)を徐々に加えpH9〜11に
保った。内温60℃で5時間、90℃で3時間撹拌し
た。冷却後、反応液をビーカーに移し、濃塩酸でpH1
に調整した。生じた沈殿を濾取し、再びビーカーに入
れ、水100mlを加えた。5N水酸化ナトリウムを加
えてpH4に調整後、濾過し、濃塩酸でpH1.6に調
製した。生じた沈殿を濾取し、水で洗浄後減圧乾燥する
ことにより、白色結晶1を2.8g(7.90×10-3
mol )得た。収率35%。融点222〜224℃(分
解)。Synthesis of Compound 1 4.9 g of the compound 1a synthesized above (2.26 × 10 −2)
mol), 10.0 g of chloroacetic acid (1.06 × 10 −1 mo
l) was suspended in 30 ml of water, and 5N sodium hydroxide 5
5 ml (0.275 mol) was gradually added to keep the pH at 9-11. The mixture was stirred at an internal temperature of 60 ° C for 5 hours and at 90 ° C for 3 hours. After cooling, transfer the reaction solution to a beaker, and add concentrated hydrochloric acid to pH 1
Was adjusted. The resulting precipitate was collected by filtration, placed again in a beaker, and 100 ml of water was added. After adjusting the pH to 4 by adding 5N sodium hydroxide, the mixture was filtered and adjusted to pH 1.6 with concentrated hydrochloric acid. The resulting precipitate was collected by filtration, washed with water, and dried under reduced pressure to give 2.8 g of white crystals 1 (7.90 × 10 −3).
mol). Yield 35%. 222-224 ° C (decomposition).
【0049】 元素分析値 C15H18N2 O8 ・1/2H2 O H C N 計算値(%) 5.12 50.85 7.81 実測値(%) 5.13 50.79 7.88 1HNMR (D2 O+NaOD) δppm δ2.67 (t 2H) δ3.12 (s 4H) δ3.23 (t 2H) δ3.68 (s 2H) δ6.93−7.01(m 2H) δ7.25−7.40(m 2H) 実施例2 また、化合物1は、化合物1aの2塩酸塩1bによって
も同様に得ることができる。[0049] Elemental analysis C 15 H 18 N 2 O 8 · 1 / 2H 2 O H C N Calculated (%) 5.12 50.85 7.81 Found (%) 5.13 50.79 7. 88 1 H NMR (D 2 O + NaOD) δ ppm δ 2.67 (t 2H) δ 3.12 (s 4H) δ 3.23 (t 2H) δ 3.68 (s 2H) δ 6.93-7.01 (m 2H) δ 7. 25-7.40 (m2H) Example 2 Compound 1 can also be obtained in the same manner by dihydrochloride 1b of compound 1a.
【0050】[0050]
【化14】 Embedded image
【0051】但し、化合物1bとクロロ酢酸の反応の際
には、塩酸中和分のアルカリを化合物1aのときよりも
余分に添加する必要がある。However, in the reaction of the compound 1b with chloroacetic acid, it is necessary to add an excess of alkali neutralized with hydrochloric acid as compared with the case of the compound 1a.
【0052】化合物1bは以下の合成法によって得られ
る。500mlの三つ口フラスコに、無水炭酸カリウム
25.6g(0.184mol )、o−クロル安息香酸3
1.4g(0.201 mol)、エチレンジアミン28.
8g(0.479 mol)、n−アミルアルコール68m
l、銅粉0.3g(4.72×10-3)を加え、5時間
加熱還流した。その反応液に水200mlを添加し、攪
拌後、濾過した。アミルアルコールと残りのエチレンジ
アミンを除去するため、減圧蒸留した。残渣に水300
mlを加えて溶解し、氷浴で冷却しながら、1:1塩酸
水溶液でpH7.8に調整した。析出した黄色沈澱を濾
取し、エタノール160mlで洗浄した。少量の1:1
塩酸水溶液で再結晶させ、目的物1bを38.7g(収
率76%)得た。Compound 1b is obtained by the following synthesis method. In a 500 ml three-necked flask, 25.6 g (0.184 mol) of anhydrous potassium carbonate, o-chlorobenzoic acid 3
1.4 g (0.201 mol), ethylenediamine 28.
8 g (0.479 mol), n-amyl alcohol 68 m
1, 0.3 g (4.72 × 10 −3 ) of copper powder was added, and the mixture was heated under reflux for 5 hours. 200 ml of water was added to the reaction solution, and the mixture was stirred and filtered. Vacuum distillation was performed to remove amyl alcohol and residual ethylenediamine. Water 300 in the residue
The mixture was dissolved by adding an ice bath to adjust the pH to 7.8 with a 1: 1 aqueous hydrochloric acid solution while cooling in an ice bath. The deposited yellow precipitate was collected by filtration and washed with 160 ml of ethanol. Small 1: 1
The crystal was recrystallized with an aqueous hydrochloric acid solution to obtain 38.7 g (yield: 76%) of the target product 1b.
【0053】実施例3 化合物2を下記のようにして合成した。Example 3 Compound 2 was synthesized as follows.
【0054】[0054]
【化15】 Embedded image
【0055】化合物2aの合成 o−ヨード安息香酸25.3g(0.102 mol)、炭
酸カリウム17.0g(0.123mol )を1,3−プ
ロパンジアミン166g(2.24mol )に懸濁させ、
15時間加熱還流した。水30mlを加え、溶媒を減圧
留去した後、水を150ml加えてビーカーに移した。
濃塩酸でpH1に調整した後、生じた結晶を濾取し、乾
燥させることにより白色結晶2aを6.25g(2.7
1×10-2mol)を得た。収率27%。Synthesis of Compound 2a 25.3 g (0.102 mol) of o-iodobenzoic acid and 17.0 g (0.123 mol) of potassium carbonate were suspended in 166 g (2.24 mol) of 1,3-propanediamine.
The mixture was heated under reflux for 15 hours. After adding 30 ml of water and distilling off the solvent under reduced pressure, 150 ml of water was added and transferred to a beaker.
After adjusting the pH to 1 with concentrated hydrochloric acid, the resulting crystals were collected by filtration and dried to give 6.25 g (2.7) of white crystals 2a.
1 × 10 -2 mol). Yield 27%.
【0056】化合物2の合成 上記で合成した化合物2a6.25g(2.71×10
-2mol )、クロル酢酸15.0g(1.59×10-1mo
l )を水50mlに加え、水酸化ナトリウム9.17g
(2.29×10-1mol )を水50mlに溶解した溶液
を滴下してpH9〜11に保った。内温60℃で3時
間、90℃で3時間撹拌した。冷却後、反応液をビーカ
ーにあけpH1.6に調整し、冷蔵庫に放置した。二週
間後析出した結晶を濾取し、乾燥することにより、白色
結晶2を3.7g(9.58×10-3mol )得た。収率
43%。融点167〜170℃。Synthesis of Compound 2 6.25 g of the compound 2a synthesized above (2.71 × 10
-2 mol), 15.0 g of chloroacetic acid (1.59 × 10 -1 mo)
l) was added to 50 ml of water, and 9.17 g of sodium hydroxide was added.
A solution of (2.29 × 10 -1 mol) dissolved in 50 ml of water was added dropwise to keep the pH at 9-11. The mixture was stirred at an internal temperature of 60 ° C for 3 hours and at 90 ° C for 3 hours. After cooling, the reaction solution was poured into a beaker, adjusted to pH 1.6, and left in a refrigerator. Two weeks later, the precipitated crystals were collected by filtration and dried to obtain 3.7 g (9.58 × 10 −3 mol) of white crystals 2. 43% yield. Melting point 167-170 [deg.] C.
【0057】 元素分析値 C16H20N2 O8 ・H2 O H C N 計算値(%) 5.73 49.74 7.25 実測値(%) 5.61 49.92 7.41 1HNMR (D2 O+NaOD) δppm δ 1.95 (m 2H) δ 3.22 (t 2H) δ 3.53 (t 2H) δ 3.68 (s 4H) δ 3.98 (s 2H) δ 7.2−7.9 (m 4H) 実施例4 化合物15の合成法を下記に示す。Elemental analysis value C 16 H 20 N 2 O 8 · H 2 O H C N Calculated value (%) 5.73 49.74 7.25 Observed value (%) 5.61 49.92 7.41 1 HNMR (D 2 O + NaOD) δ ppm δ 1.95 (m 2H) δ 3.22 (t 2H) δ 3.53 (t 2H) δ 3.68 (s 4H) δ 3.98 (s 2H) δ 7. 2-7.9 (m 4H) Example 4 A method for synthesizing Compound 15 is shown below.
【0058】[0058]
【化16】 Embedded image
【0059】化合物1aを103g(4.75×10-1
mol)、クロル酢酸112g(9.62×10-1 mol)
を水100mlに懸濁させ、水酸化ナトリウム82g
(2.05 mol)を水100mlに溶解した水溶液を徐
々に加え、pH9〜11に保った。内温55〜60℃で
5時間撹拌した。冷却後、生じた沈澱を濾取し、水20
0mlに溶解させた。103 g (4.75 × 10 −1 ) of compound 1a
mol), 112 g of chloroacetic acid (9.62 × 10 -1 mol)
Was suspended in 100 ml of water, and 82 g of sodium hydroxide was added.
An aqueous solution of (2.05 mol) dissolved in 100 ml of water was gradually added to keep the pH at 9-11. It stirred at 55-60 degreeC of internal temperature for 5 hours. After cooling, the resulting precipitate was collected by filtration and washed with water 20
It was dissolved in 0 ml.
【0060】氷浴で冷却しながら、濃塩酸を加え、pH
3.6に調整した。30分程攪拌した後、生じた沈殿を
濾取し、水で洗浄後、減圧乾燥することにより、白色結
晶を38g(1.12×10-1mol )得た。収率24
%。融点185℃より徐々に分解。While cooling in an ice bath, concentrated hydrochloric acid was added,
Adjusted to 3.6. After stirring for about 30 minutes, the resulting precipitate was collected by filtration, washed with water, and dried under reduced pressure to obtain 38 g (1.12 × 10 -1 mol) of white crystals. Yield 24
%. Decomposes gradually from melting point 185 ° C.
【0061】 元素分析値 C13H14N2 Na2 O6 H C N 計算値(%) 4.15 45.89 8.23 実測値(%) 4.32 45.54 8.28 1HNMR (D2 O+NaOD) δppm δ2.93 (t 2H) δ3.35 (s 4H) δ3.37 (t 2H) δ6.70 (t 1H) δ6.82 (d 1H) δ7.35 (t 1H) δ7.71 (d 1H) 実施例5 化合物17を下記のように合成した。Elemental analysis value C 13 H 14 N 2 Na 2 O 6 HCN Calculated value (%) 4.15 45.89 8.23 Actual value (%) 4.32 45.54 8.28 1 HNMR ( D 2 O + NaOD) δ ppm δ 2.93 (t 2H) δ 3.35 (s 4H) δ 3.37 (t 2H) δ 6.70 (t 1H) δ 6.82 (d 1H) δ 7.35 (t 1H) δ 7.71 (D 1H) Example 5 Compound 17 was synthesized as follows.
【0062】[0062]
【化17】 Embedded image
【0063】化合物1aを30g(1.38×10-1 m
ol)を水50mlに懸濁させ、水酸化ナトリウム28g
(7.0×10-1 mol)を水100mlに溶解した水溶
液を加えた。さらに、アクリル酸27ml(3.94×
10-1 mol)を添加し、60℃で4時間攪拌した。冷却
後、濃塩酸を加えて、pH2〜3に調整した。攪拌後、
静置し、2層に分離した液の上層部を取り除き、残った
下層部に水を200ml加えて、よく攪拌した。生じた
沈殿を濾取し、水で洗浄後、減圧乾燥することにより、
白色結晶を23g(7.09×10-2mol )得た。収率
51%。融点183〜185℃。Compound 1a (30 g, 1.38 × 10 -1 m)
ol) in 50 ml of water and 28 g of sodium hydroxide
An aqueous solution in which (7.0 × 10 -1 mol) was dissolved in 100 ml of water was added. Further, 27 ml of acrylic acid (3.94 ×
10 -1 mol) and stirred at 60 ° C. for 4 hours. After cooling, concentrated hydrochloric acid was added to adjust the pH to 2-3. After stirring,
The solution was allowed to stand, the upper layer of the liquid separated into two layers was removed, and 200 ml of water was added to the remaining lower layer, followed by thorough stirring. The resulting precipitate was collected by filtration, washed with water, and then dried under reduced pressure.
23 g (7.09 × 10 -2 mol) of white crystals were obtained. Yield 51%. 183-185 ° C.
【0064】 元素分析値 C15H20N2 O6 H C N 計算値(%) 6.21 55.55 8.64 実測値(%) 6.14 55.38 8.54 1HNMR (D2 O+NaOD) δppm δ2.40 (t 4H) δ2.77 (t 2H) δ2.82 (t 4H) δ3.48 (t 2H) δ6.77 (t 1H) δ6.89 (d 1H) δ7.40 (t 1H) δ7.77 (d 1H) 実施例6 化合物18を下記のようにして合成した。[0064] Elemental analysis C 15 H 20 N 2 O 6 H C N Calculated (%) 6.21 55.55 8.64 Found (%) 6.14 55.38 8.54 1 HNMR (D 2 O + NaOD) δ ppm δ 2.40 (t 4H) δ 2.77 (t 2H) δ 2.82 (t 4H) δ 3.48 (t 2H) δ 6.77 (t 1H) δ 6.89 (d 1H) δ 7.40 (t) 1H) δ 7.77 (d 1H) Example 6 Compound 18 was synthesized as follows.
【0065】[0065]
【化18】 Embedded image
【0066】(化合物18aの合成)2−クロロ−5−
ニトロ安息香酸20.2g(0.10 mol)をメタノー
ル50mlに懸濁させ、エチレンジアミン60.1g
(1.0 mol)、炭酸カリウム40.0g(0.29 m
ol)、銅粉0.30g(4.7×10-3mol )を加え、
6時間加熱還流した。水50mlを加え、濾過した後、
溶媒を減圧留去した。さらに、水100mlを加え、濃
塩酸でpH1に調整した。氷浴で冷却後、生じた沈澱を
濾取し、水、メタノールで洗浄した。減圧乾燥し、黄色
結晶を23.0g(8.79×10-2mol )得た。収率
88%。(Synthesis of Compound 18a) 2-Chloro-5-
Nitrobenzoic acid (20.2 g, 0.10 mol) was suspended in methanol (50 ml), and ethylenediamine (60.1 g) was suspended.
(1.0 mol), 40.0 g of potassium carbonate (0.29 m
ol) and 0.30 g (4.7 × 10 −3 mol) of copper powder were added,
The mixture was refluxed for 6 hours. After adding 50 ml of water and filtering,
The solvent was distilled off under reduced pressure. Further, 100 ml of water was added, and the pH was adjusted to 1 with concentrated hydrochloric acid. After cooling in an ice bath, the resulting precipitate was collected by filtration and washed with water and methanol. After drying under reduced pressure, 23.0 g (8.79 × 10 -2 mol) of yellow crystals were obtained. Yield 88%.
【0067】(化合物18の合成)上記で得た化合物1
8aを16.4g(6.27×10-2mol )を水30m
lに懸濁させ、水酸化ナトリウム6.6g(1.65×
10-1mol )と水30mlを加えて内温を50℃に保っ
た。クロル酢酸14.1g(1.21×10-1 mol)を
水30mlに溶解し、反応液に加えた。さらに、水酸化
ナトリウム4.9g(1.22×10-1 mol)と水25
mlの溶液を、反応液がpH9〜11に保たれるように
加えた。4時間撹拌後、氷冷し、濃塩酸を加え、pH1
に調整した。生じた沈澱を濾取し、ビーカーに移して、
水50mlを加えた。水酸化ナトリウム水溶液によりp
H12に調整し、濾過した後、濃塩酸でpH1に調整し
た。1時間加熱還流し、室温に冷却後、析出した結晶を
濾取し、減圧乾燥し、化合物18の1/2水和物を1
0.4g(2.97×10-2mol )得た。黄色結晶。収
率47%。融点約206℃より徐々に分解。(Synthesis of Compound 18) Compound 1 obtained above
16.4 g (6.27 × 10 -2 mol) of 8a was added to 30 m of water.
6.6 g of sodium hydroxide (1.65 ×
10 -1 mol) and 30 ml of water were added to maintain the internal temperature at 50 ° C. 14.1 g (1.21 × 10 -1 mol) of chloroacetic acid was dissolved in 30 ml of water and added to the reaction solution. Further, 4.9 g (1.22 × 10 -1 mol) of sodium hydroxide and 25
ml of solution was added so that the reaction was kept at pH 9-11. After stirring for 4 hours, the mixture was cooled on ice, concentrated hydrochloric acid was added,
Was adjusted. The resulting precipitate was collected by filtration and transferred to a beaker.
50 ml of water were added. P with sodium hydroxide solution
The mixture was adjusted to H12, filtered, and adjusted to pH 1 with concentrated hydrochloric acid. The mixture was heated under reflux for 1 hour, cooled to room temperature, and the precipitated crystals were collected by filtration and dried under reduced pressure.
0.4 g (2.97 × 10 -2 mol) was obtained. Yellow crystals. Yield 47%. Decomposes gradually from a melting point of about 206 ° C.
【0068】 元素分析値 C13H15N3 O8 ・1/2 H2 O H C N 計算値(%) 4.60 44.58 12.00 実測値(%) 4.58 44.61 11.94 1HNMR (D2 O+NaOD) δppm δ2.98 (t 2H) δ3.37 (s 4H) δ3.51 (t 2H) δ6.77 (d 1H) δ8.11 (dd 1H) δ8.60 (d 1H) δ7.71 (d 1H) 実施例7 上記で合成した化合物1と上述した〔化2〕で示される
比較化合物について、それぞれの鉄キレートを調製し、
その安定度定数を求めた。その結果を下記に示す。Elemental analysis value C 13 H 15 N 3 O 8 .1 / 2 H 2 O HCN Calculated value (%) 4.60 44.58 12.00 Actual value (%) 4.58 44.61 11 .94 1 H NMR (D 2 O + NaOD) δ ppm δ 2.98 (t 2H) δ 3.37 (s 4H) δ 3.51 (t 2H) δ 6.77 (d 1H) δ 8.11 (dd 1H) δ 8.60 (d 1H) δ7.71 (d 1H) Example 7 For the compound 1 synthesized above and the comparative compound represented by the above [Chemical Formula 2], respective iron chelates were prepared,
The stability constant was determined. The results are shown below.
【0069】[0069]
【表1】 [Table 1]
【0070】本発明の化合物は比較化合物よりも、錯安
定度定数が大きく、鉄(3価)イオンに対する遮蔽性能
は高い。The compound of the present invention has a larger complex stability constant than the comparative compound, and has a higher shielding performance against iron (trivalent) ions.
【0071】実施例8 上記で合成した化合物1及び化合物2と上述した〔化
3〕で示される比較化合物について、それぞれの鉄キレ
ートを調製し、その酸化還元電位を求めた。その結果を
下記に示す。Example 8 Iron chelates were prepared for the compounds 1 and 2 synthesized above and the comparative compound represented by the above formula [3], and the oxidation-reduction potential was determined. The results are shown below.
【0072】[0072]
【表2】 [Table 2]
【0073】 条件: 〔キレート剤〕=12mM 〔 Fe3+ 〕=10mM 支持電解質〔 KNO3 〕=1.0M 0.2M CH3 COOH−CH3 COONa buf
fer 参照電極:SSCE 作用電極:グラッシーカーボン電極 対照電極:白金電極 化合物1の鉄錯体は比較化合物の鉄錯体よりも酸化還元
電位は高く、その酸化力が強い。Conditions: [Chelating agent] = 12 mM [Fe 3+ ] = 10 mM Supporting electrolyte [KNO 3 ] = 1.0 M 0.2 M CH 3 COOH—CH 3 COONa buf
fer Reference electrode: SSCE Working electrode: Glassy carbon electrode Reference electrode: Platinum electrode The iron complex of compound 1 has a higher redox potential and stronger oxidizing power than the iron complex of the comparative compound.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 FI C11D 3/33 C11D 3/33 G03C 5/42 G03C 5/42 7/42 7/42 (58)調査した分野(Int.Cl.7,DB名) C07C 229/00 A61K 7/00 A61K 31/195 C09K 3/00 C11D 3/00 G03C 5/00 G03C 7/00 CA(STN) REGISTRY(STN)──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI C11D 3/33 C11D 3/33 G03C 5/42 G03C 5/42 7/42 7/42 (58) Investigation field (Int.Cl. . 7, DB name) C07C 229/00 A61K 7/00 A61K 31/195 C09K 3/00 C11D 3/00 G03C 5/00 G03C 7/00 CA (STN) REGISTRY (STN)
Claims (1)
よりなる群から選ばれた基で置換されてもよいベンゼン
環あるいはナフタレン環を完成するために必要な原子群
を表す。Xは水素原子または−L1 COOM1 を表わ
す。M1 、M2 、M3 及びM4 はそれぞれ水素原子ある
いはカチオンを表す。L1 、L2 及びL3 は、それぞれ
アルキレン基を表す。W1 は下記一般式(W1 )で示さ
れる炭素数2以上のアルキレン基を含む2価の連結基を
表す。)で表されるアントラニル酸誘導体。 一般式(W1 ) −(Wa −Y)m −Wb − 式中、Wa 及びWb は同じであっても異なっていてもよ
く、炭素数2〜10のアルキレン基を表す。Yは単なる
結合、−O−、−S−を表す。mは0〜3の整数を表
し、mが2又は3の時には、(Wa −Y)は同じであっ
ても異なっていてもよい。W 1 で表される連結基はアル
キル基、ヒドロキシ基を置換基として有していてもよ
く、置換基で炭素原子を有する場合、炭素数1〜10の
ものである。[Claim 1] (In the formula, Z represents a group of atoms necessary to complete a benzene ring or a naphthalene ring which may be substituted with a group selected from the group consisting of an alkyl group, a nitro group, and a carboxyl group. X represents a hydrogen atom or Represents L 1 COOM 1 , M 1 , M 2 , M 3 and M 4 each represent a hydrogen atom or a cation L 1 , L 2 and L 3 each represent an alkylene group W 1 represents the following general formula (This represents a divalent linking group containing an alkylene group having 2 or more carbon atoms represented by (W 1 ).) Formula (W 1) - (W a -Y) m -W b - wherein, W a and W b are individually selected from the same, represents an alkylene group having 2 to 10 carbon atoms. Y is just
Represents a bond, -O- or -S- . m represents an integer of 0 to 3, and when m is 2 or 3, (W a -Y) may be the same or different. The linking group represented by W 1 is
It may have a kill group or a hydroxy group as a substituent. When the substituent has a carbon atom, it has 1 to 10 carbon atoms.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP10819192A JP3150192B2 (en) | 1991-07-15 | 1992-04-28 | Anthranilic acid derivatives |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3-173601 | 1991-07-15 | ||
JP17360191 | 1991-07-15 | ||
JP10819192A JP3150192B2 (en) | 1991-07-15 | 1992-04-28 | Anthranilic acid derivatives |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH05178803A JPH05178803A (en) | 1993-07-20 |
JP3150192B2 true JP3150192B2 (en) | 2001-03-26 |
Family
ID=26448136
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP10819192A Expired - Fee Related JP3150192B2 (en) | 1991-07-15 | 1992-04-28 | Anthranilic acid derivatives |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3150192B2 (en) |
-
1992
- 1992-04-28 JP JP10819192A patent/JP3150192B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH05178803A (en) | 1993-07-20 |
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