JPH0359059B2 - - Google Patents
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- JPH0359059B2 JPH0359059B2 JP24219987A JP24219987A JPH0359059B2 JP H0359059 B2 JPH0359059 B2 JP H0359059B2 JP 24219987 A JP24219987 A JP 24219987A JP 24219987 A JP24219987 A JP 24219987A JP H0359059 B2 JPH0359059 B2 JP H0359059B2
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- Prior art keywords
- acid
- hydroxythiobenzoic
- compound
- formula
- present
- Prior art date
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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、チオ安息香酸誘導体及びその製造
法、更に詳しくは４−ヒドロキシチオ安息香酸又
はその塩及び製造法に関する。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to thiobenzoic acid derivatives and methods for producing the same, and more particularly to 4-hydroxythiobenzoic acid or salts thereof and methods for producing the same.
発明の開示
従来、４−ヒドロキシチオ安息香酸の製造法と
しては、４−ヒドロキシチジオ安息香酸エチルエ
ステルを2N−苛性ソーダ溶液と煮沸する方法が
知られており（Beilstein Ｅ10、110）、該文献
によれば、上記方法で得られる４−ヒドロキシチ
オ安息香酸の融点は208℃であるとされている。
しかしながら、本発明者が上記方法を実施して得
られた化合物を調べたところ、該化合物が沃素を
消費しないこと及びIRスペクトルにてSH基の特
性吸収ピーク（2550cm-1）が検出されないことか
ら、該化合物は上記文献に記載されているような
４−ヒドロキシチオ安息香酸ではないことが判明
した。DISCLOSURE OF THE INVENTION Conventionally, as a method for producing 4-hydroxythiobenzoic acid, a method of boiling 4-hydroxythidiobenzoic acid ethyl ester with a 2N caustic soda solution has been known (Beilstein E10, 110), and is described in this document. According to the above, the melting point of 4-hydroxythiobenzoic acid obtained by the above method is 208°C.
However, when the present inventor investigated the compound obtained by carrying out the above method, it was found that the compound did not consume iodine and the characteristic absorption peak (2550 cm -1 ) of the SH group was not detected in the IR spectrum. It was found that the compound is not 4-hydroxythiobenzoic acid as described in the above-mentioned document.
そこで本発明者は、下記に示す別途方法により
目的とする４−ヒドロキシチオ安息香酸の合成を
試み、この合成された化合物を調べたところ、そ
の融点は96℃であり、IRスペクトル及び元素分
析により該化合物は４−ヒドロキシチオ安息香酸
であることを確認した。また同時に、この４−ヒ
ドロキシチオ安息香酸をメタノール水溶媒中過酸
化水素で酸化すれば融点208℃の酸化物が得られ
ることから、上記文献の方法で得られた化合物は
４−ヒドロキシチオ安息香酸の酸化物であること
を確認した。 Therefore, the present inventor attempted to synthesize the target 4-hydroxythiobenzoic acid by the separate method shown below, and when the synthesized compound was examined, its melting point was 96°C, and the IR spectrum and elemental analysis showed that the synthesized compound had a melting point of 96℃. The compound was confirmed to be 4-hydroxythiobenzoic acid. At the same time, if this 4-hydroxythiobenzoic acid is oxidized with hydrogen peroxide in a methanol/water solvent, an oxide with a melting point of 208°C can be obtained. It was confirmed that it was an oxide of
本発明は、融点96℃を有する文献未記載の４−
ヒドロキシチオ安息香酸及びその塩並びにその製
造法を提供するものである。 The present invention utilizes 4-
The present invention provides hydroxythiobenzoic acid, its salts, and a method for producing the same.
本発明の４−ヒドロキシチオ安息香酸及びその
塩は、下記に示す方法に従い製造される。 4-Hydroxythiobenzoic acid and its salt of the present invention are produced according to the method shown below.
即ち、式
〔式中Ｒはアシル基を示す。〕
で表わされる４−アシルオキシ安息香酸クロリド
に硫化水素のアルカリ金属塩を反応させ、次いで
必要に応じ酸析することにより、式
で表わされる４−ヒドロキシチオ安息香酸及びそ
の塩が製造される。 That is, the expression [In the formula, R represents an acyl group. ] By reacting 4-acyloxybenzoic acid chloride represented by the formula with an alkali metal salt of hydrogen sulfide, and then acidifying if necessary, 4-hydroxythiobenzoic acid and its salts are produced.
本発明において、出発原料として用いられる一
般式(2)で表わされる４−アシルオキシ安息香酸ク
ロリドは、入手容易な公知の化合物である。該化
合物は、例えば対応する４−アシルオキシ安息香
酸から後記参考例に示す方法によつても容易に製
造され得る。一般式(2)の化合物の具体例として
は、４−アセチルオキシ安息香酸クロリド、４−
プロピオニルオキシ安息香酸クロリド等の４−低
級アルカノイルオキシ安息香酸クロリド、ベンゾ
イルオキシ安息香酸クロリド等のアロイルオキシ
安息香酸クロリド等を例示できる。 In the present invention, 4-acyloxybenzoic acid chloride represented by general formula (2) used as a starting material is a known compound that is easily available. The compound can also be easily produced, for example, from the corresponding 4-acyloxybenzoic acid by the method shown in Reference Examples below. Specific examples of the compound of general formula (2) include 4-acetyloxybenzoic acid chloride, 4-
Examples include 4-lower alkanoyloxybenzoic acid chloride such as propionyloxybenzoic acid chloride, and aroyloxybenzoic acid chloride such as benzoyloxybenzoic acid chloride.
また、本発明で用いられる硫化水素のアルカリ
金属塩としては、従来公知のものを広く使用で
き、例えば水硫化ナトリウム、水硫化カリウム等
を挙げることができる。 Furthermore, as the alkali metal salt of hydrogen sulfide used in the present invention, a wide variety of conventionally known salts can be used, such as sodium bisulfide, potassium bisulfide, and the like.
斯かる硫化水素のアルカリ金属塩の使用量は、
特に制限されるものではないが、一般式(2)の化合
物１モル当り通常４〜７モル程度、好ましくは４
〜５モル程度とするのがよい。 The amount of alkali metal salt of hydrogen sulfide used is
Although not particularly limited, it is usually about 4 to 7 mol, preferably 4 to 7 mol per mol of the compound of general formula (2).
The amount is preferably about 5 moles.
一般式(2)の化合物の上記塩との反応は、通常適
当な溶媒中で行なわれる。用いられる溶媒として
は、例えば水、メタノール、エタノール、プロパ
ノール、イソプロパノール、ブタノール等の低級
アルコール、エチレングリコール、プロピレング
リコール、グリセリン等の多価アルコール等が挙
げられる。上記反応は、室温下及び加温下のいず
れでも行ない得るが、通常30〜100℃程度、好ま
しくは40〜90℃程度にて好適に進行し、該反応は
一般に１〜２時間程度で完結する。斯くしてSH
化反応と加水分解反応とが同時に行なわれ、目的
とする式(1)の化合物が塩の形態で生成する。 The reaction of the compound of general formula (2) with the above salt is usually carried out in a suitable solvent. Examples of the solvent used include water, lower alcohols such as methanol, ethanol, propanol, isopropanol, and butanol, and polyhydric alcohols such as ethylene glycol, propylene glycol, and glycerin. The above reaction can be carried out either at room temperature or under heating, but it usually proceeds suitably at about 30 to 100°C, preferably about 40 to 90°C, and the reaction is generally completed in about 1 to 2 hours. . Thus SH
The oxidation reaction and the hydrolysis reaction are carried out simultaneously, and the target compound of formula (1) is produced in the form of a salt.
式(1)で表わされる４−ヒドロキシチオ安息香酸
は、上記で生成する塩の形態の本発明化合物を酸
析（酸析化）することにより製造される。酸析
は、従来公知の方法に従い、例えば鉱酸水溶液、
好ましくは濃塩酸を使用して行ない得る。鉱酸水
溶液の使用量としては、酸の添加後の酸析処理す
べき液のPHが２以下、好ましくは０〜１になるよ
うに用いるのがよい。酸析は、冷却下、室温下及
び加温下のいずれでも行なわれるが、通常０〜50
℃程度、好ましくは20〜30℃程度の温度条件下が
よい。 4-Hydroxythiobenzoic acid represented by formula (1) is produced by acid precipitation (oxidation) of the compound of the present invention in the form of a salt produced above. Acid precipitation is performed according to a conventionally known method, for example, using a mineral acid aqueous solution,
Preferably, this can be carried out using concentrated hydrochloric acid. The amount of the mineral acid aqueous solution to be used is preferably such that the pH of the solution to be subjected to acid precipitation treatment after addition of the acid is 2 or less, preferably 0 to 1. Acid precipitation is carried out under cooling, at room temperature, or under heating, but is usually 0 to 50
Temperature conditions of about 0.degree. C., preferably about 20 to 30.degree. C. are preferable.
斯くして得られる本発明の化合物は、慣用の分
離手段に従い反応混合物から容易に単離、精製さ
れる。斯かる分離手段としては、例えば取等を
挙げることができる。また、斯くして単離された
式(1)の４−ヒドロキシチオ安息香酸を当モルの苛
性ソーダ水溶液に溶解後、少量の不溶分を別
し、液を再度酸析することにより、特に純度の
高い目的化合物とすることができる。 The compounds of the present invention thus obtained are easily isolated and purified from the reaction mixture according to conventional separation means. Such a separation means may include, for example, a trap. In addition, after dissolving the thus isolated 4-hydroxythiobenzoic acid of formula (1) in an equimolar aqueous solution of caustic soda, a small amount of insoluble matter is separated and the solution is precipitated again to obtain a particularly high purity. It can be a highly targeted compound.
本発明の化合物は、下記に示す有用性を備えた
ものである。例えば本発明化合物に塩化ベンジル
を縮合させることにより、４−ヒドロキシチオ安
息香酸ベンジルエステルに誘導できる。このベン
ジルエステルは、発色特性に優れ、また発色され
た画像に優れた安定性を与え得ることから、顕色
剤として好適に使用され得る。 The compounds of the present invention have the following utility. For example, by condensing benzyl chloride with the compound of the present invention, benzyl 4-hydroxythiobenzoate can be derived. This benzyl ester has excellent color-forming properties and can impart excellent stability to a colored image, so it can be suitably used as a color developer.
本発明の化合物に類似する化合物として４−ヒ
ドロキシ安息香酸が知られているが、これに塩化
ベンジルを縮合させて得られる４−ヒドロキシ安
息香酸ベンジルエステルは、発色特性に優れてい
るものの、発色された画像に優れた安定性を与え
得ないことから、顕色剤として単独では使用され
難いもである。 4-Hydroxybenzoic acid is known as a compound similar to the compound of the present invention, but 4-hydroxybenzoic acid benzyl ester obtained by condensing benzyl chloride with it has excellent coloring properties, but it does not develop color. It is difficult to use it alone as a color developer because it cannot provide excellent stability to the resulting image.
実施例
以下に参考例及び実施例を掲げて本発明をより
一層明らかにする。Examples Reference examples and examples are given below to further clarify the present invention.
参考例
トルエン720ml、４−アセチルオキシ安息香酸
108.1ｇ及びピリジン（触媒）0.3ｇを仕込み、撹
拌下常温で塩化チオニル78.5ｇを約１時間要して
滴下した。滴下後70〜80℃に昇温し、同温度で２
時間反応を行なつた。反応終了後、トルエンを回
収し、次いで真空蒸留して４−アセチルオキシ安
息香酸クロリドを得た。Reference example: 720ml of toluene, 4-acetyloxybenzoic acid
108.1 g and 0.3 g of pyridine (catalyst) were charged, and 78.5 g of thionyl chloride was added dropwise over about 1 hour at room temperature while stirring. After dropping, raise the temperature to 70-80℃, and at the same temperature
A time reaction was performed. After the reaction was completed, toluene was collected and then vacuum distilled to obtain 4-acetyloxybenzoic acid chloride.
沸点：111〜112℃／３mmHg
収量：108.4ｇ、収率：91％
実施例 １
フレーク水硫化ソーダ（70％）80.1ｇを水200
mlに加え、溶解後40〜50℃に保持し、上記参考例
で得られた４−アセチルオキシ安息香酸クロリド
39.7ｇを約1.5時間要して滴下した。滴下後、同
温度で1.5時間反応後、20℃に冷却し、濃塩酸に
て酸析した。析出した結晶を取し、水洗後乾燥
して４−ヒドロキシチオ安息香酸24.9ｇを得た。Boiling point: 111-112℃/3mmHg Yield: 108.4g, Yield: 91% Example 1 80.1g of flaked sodium bisulfide (70%) was mixed with 200 g of water.
ml of 4-acetyloxybenzoic acid chloride obtained in the above reference example.
39.7g was added dropwise over about 1.5 hours. After the dropwise addition, the mixture was reacted at the same temperature for 1.5 hours, cooled to 20°C, and acid-precipitated with concentrated hydrochloric acid. The precipitated crystals were collected, washed with water, and dried to obtain 24.9 g of 4-hydroxythiobenzoic acid.
上記で得られた４−ヒドロキシチオ安息香酸
24.9ｇを３％の水酸化ナトリウム水溶液215mlに
溶解し、微量の不溶分を別し、液を再度濃塩
酸にて酸析した。析出した結晶を取し、水洗、
乾燥して精製４−ヒドロキシチオ安息香酸を得
た。 4-hydroxythiobenzoic acid obtained above
24.9 g was dissolved in 215 ml of 3% aqueous sodium hydroxide solution, trace amounts of insoluble matter were separated, and the solution was acid-precipitated again with concentrated hydrochloric acid. Collect the precipitated crystals, wash with water,
After drying, purified 4-hydroxythiobenzoic acid was obtained.
融点：96℃、色相：淡横色
収量：21ｇ、収率：68％
IRスペクトル（KBr錠）νnax：3250、2550、
1640、1220cm-1
元素分析値（C7H6OSとして）
Ｃ Ｈ Ｓ
分析値（％） 54.49 3.95 20.70
理論値（％） 54.52 3.92 20.80
実施例 ２
トルエン120ml、４−アセチルオキシ安息香酸
18ｇ及びピリジン（触媒）0.05ｇを仕込み、参考
例１と同様に反応を行ない、反応終了後減圧下で
トルエン55mlを回収した。Melting point: 96℃, Hue: Light yellow Yield: 21g, Yield: 68% IR spectrum (KBr tablet) ν nax : 3250, 2550,
1640, 1220cm -1 Elemental analysis value (as C 7 H 6 OS) C H S analysis value (%) 54.49 3.95 20.70 Theoretical value (%) 54.52 3.92 20.80 Example 2 Toluene 120ml, 4-acetyloxybenzoic acid
18 g and 0.05 g of pyridine (catalyst) were charged, and the reaction was carried out in the same manner as in Reference Example 1. After the reaction was completed, 55 ml of toluene was recovered under reduced pressure.
フレーク水硫化ソーダ（70％）40ｇを水100ml
に加え、溶解後85〜90℃に保持し、上記で得られ
た酸クロリドのトルエン溶液を約0.5時間要して
滴下した。滴下後、同温度で２時間反応後、冷
却、分液し、水層を取り出した。得られた水層を
20℃に冷却し、濃塩酸にて酸析した。析出した結
晶を取し、水洗後乾燥しえ４−ヒドロキシチオ
安息香酸13.7ｇを得た。 40g of flaked sodium bisulfide (70%) and 100ml of water
In addition, the solution was maintained at 85 to 90°C after dissolution, and the toluene solution of the acid chloride obtained above was added dropwise over about 0.5 hours. After the dropwise addition, the mixture was reacted at the same temperature for 2 hours, then cooled and separated, and the aqueous layer was taken out. The resulting aqueous layer
The mixture was cooled to 20°C and precipitated with concentrated hydrochloric acid. The precipitated crystals were collected, washed with water, and dried to obtain 13.7 g of 4-hydroxythiobenzoic acid.
上記で得られた４−ヒドロキシチオ安息香酸を
実施例１と同様に処理し、精製品を得た。 The 4-hydroxythiobenzoic acid obtained above was treated in the same manner as in Example 1 to obtain a purified product.
融点：96℃、色相：淡黄色
収量：10.3ｇ、収率66.8％
IRスペクトル及び元素分析値は、実施例１で
得られた化合物のそれと一致した。Melting point: 96°C, hue: pale yellow Yield: 10.3 g, yield 66.8% The IR spectrum and elemental analysis values were consistent with those of the compound obtained in Example 1.
Claims (1)
の塩。 ２ 式 〔式中Ｒはアシル基を示す。〕 で表わされる４−アシルオキシ安息香酸クロリド
に硫化水素のアルカリ金属塩を反応させ、次いで
必要に応じ酸析することを特徴とする式 で表わされる４−ヒドロキシチオ安息香酸及びそ
の塩の製造法。[Claims] 1 formula 4-hydroxythiobenzoic acid and its salts represented by: 2 formulas [In the formula, R represents an acyl group. ] A formula characterized by reacting 4-acyloxybenzoic acid chloride represented by the formula with an alkali metal salt of hydrogen sulfide, followed by acid precipitation as necessary. A method for producing 4-hydroxythiobenzoic acid and its salts represented by
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24219987A JPS6483061A (en) | 1987-09-25 | 1987-09-25 | Thiobenzoic acid derivative and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24219987A JPS6483061A (en) | 1987-09-25 | 1987-09-25 | Thiobenzoic acid derivative and production thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6483061A JPS6483061A (en) | 1989-03-28 |
| JPH0359059B2 true JPH0359059B2 (en) | 1991-09-09 |
Family
ID=17085745
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24219987A Granted JPS6483061A (en) | 1987-09-25 | 1987-09-25 | Thiobenzoic acid derivative and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6483061A (en) |
-
1987
- 1987-09-25 JP JP24219987A patent/JPS6483061A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6483061A (en) | 1989-03-28 |
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