JPS5929659A - Preparation of thiosalicylic acid and dithiosalicylic acid - Google Patents
Preparation of thiosalicylic acid and dithiosalicylic acidInfo
- Publication number
- JPS5929659A JPS5929659A JP57140375A JP14037582A JPS5929659A JP S5929659 A JPS5929659 A JP S5929659A JP 57140375 A JP57140375 A JP 57140375A JP 14037582 A JP14037582 A JP 14037582A JP S5929659 A JPS5929659 A JP S5929659A
- Authority
- JP
- Japan
- Prior art keywords
- acid
- reaction
- alkali metal
- dithiosalicylic
- metal hydroxide
- 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
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
本発明はチオサリチル酸およびジチオサリチル酸の製造
方法に関する。さらに詳しくは０−ハロ安息香酸と硫黄
とを直接反応させるチオサリチル酸およ鉢ジチオサリチ
ル酸の新規な製造法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing thiosalicylic acid and dithiosalicylic acid. More specifically, the present invention relates to a novel method for producing thiosalicylic acid and dithiosalicylic acid by directly reacting 0-halobenzoic acid and sulfur.
チオサリチル酸およびジチオサリチル酸は農薬医薬など
の中間原料として有効な化学物質である。Thiosalicylic acid and dithiosalicylic acid are effective chemical substances as intermediate raw materials for pesticides and medicines.
従来チオサリチル酸を製造する方法としては例えば Ｉ
ｎｄｉａｎ、Ｊ、Ｐｈａｒｍ、 １９６８．３０（５
） １２４にはチオフェノールを高温高圧下Ｇこ炭酸ガ
スと反応させ、チオサリチル酸を製造する方法が記載さ
れているが、
工業的実施には経済的でなく適当でない。Conventional methods for producing thiosalicylic acid include, for example, I
ndian, J. Pharm, 1968.30 (5
) No. 124 describes a method for producing thiosalicylic acid by reacting thiophenol with carbon dioxide gas at high temperature and high pressure, but this method is uneconomical and unsuitable for industrial implementation.
またＯｒｇ、５ｙｎｔｈ 、 Ｃｏ１１ Ｖｏｌ ２
、５８０ にはアントラニル酸を原料とする方法が記載
されているが原料のアントラニル酸が高価であるばかり
でなく、ジアゾ化反応は濃度が低く容積効率が悪いので
工業的実施には適しない。Org, 5ynth, Co11 Vol 2
, 580 describes a method using anthranilic acid as a raw material, but not only is the raw material anthranilic acid expensive, but the diazotization reaction has a low concentration and poor volumetric efficiency, so it is not suitable for industrial implementation.
ＶｏｌＪ′二２２０ などの反応が知られているが、
本発明る収率では生成しない。例えばＣａｄｉ塩触媒の
存在これまでにまだ知られていない。Although reactions such as VolJ'2220 are known,
It is not produced at the yield according to the present invention. For example, the existence of Cadi salt catalysts is not yet known so far.
このような状況に鑑み本発明者らはチオサリチル酸およ
びジチオサリチル酸の製造方法について鋭意検討の結果
、０−ノ１０安息香酸をアルカリ金゛３−
属水酸化物の存在下硫黄と直接反応させる方法を発明し
た。In view of this situation, the present inventors have conducted intensive studies on methods for producing thiosalicylic acid and dithiosalicylic acid, and have developed a method in which 0-10 benzoic acid is directly reacted with sulfur in the presence of an alkali metal hydroxide. invented.
すなわち本発明の目的はチオサリチル酸およびジチオサ
リチル酸を工業的に収率よく製造する方法を提供する番
こあり、その要旨はＯ−ノ）口安息香酸をアルカリ水酸
化物の存在下硫黄と反応させることを特徴とするチオサ
リチル酸およびジチオサリチル酸の製造方法である。That is, an object of the present invention is to provide a method for industrially producing thiosalicylic acid and dithiosalicylic acid with good yield, and the gist thereof is to react O-benzoic acid with sulfur in the presence of an alkali hydroxide. This is a method for producing thiosalicylic acid and dithiosalicylic acid.
（Ｘ：ハロゲン）
上式のよう（こアルカリ金属水酸化物の存在下にる。両
者はチオサリチル酸を酸化するとジチオサリチル酸が生
じ、ジチオサリチル酸を還元すれば直ちをこチオサリチ
ル酸が生じる平衡関係曇こあるので本発明では両者を合
わせて収率を考える。本発明の反応機構については充分
審かではないが、〇４−
一ハロ安息香酸と硫黄がアルカリ金属水酸化物の存在下
に直接反応してチオサリチル酸およびジテオサリチル酸
が生成するものと推定される。(X: Halogen) As shown in the above formula (in the presence of an alkali metal hydroxide), the two have an equilibrium relationship in which oxidizing thiosalicylic acid produces dithiosalicylic acid, and reducing dithiosalicylic acid immediately produces thiosalicylic acid. Therefore, in the present invention, the yield is considered by combining the two.Although the reaction mechanism of the present invention is not completely clear, 〇4- Monohalobenzoic acid and sulfur are directly reacted in the presence of an alkali metal hydroxide. It is estimated that the reaction produces thiosalicylic acid and diteosalicylic acid.
本発明で用いる０−ハロ安息香酸としては〇−ソ
クロル安息香酸が経済的に有利であるが、０−ブロモ安
息香酸、０−ヨード安息香酸なども場合によっては使用
できる。As the 0-halobenzoic acid used in the present invention, 0-sochlorobenzoic acid is economically advantageous, but 0-bromobenzoic acid, 0-iodobenzoic acid, etc. can also be used depending on the case.
アルカリ金属の水酸化物としては水酸化リチウム、水酸
化ナトリウム、水酸化カリウム、水酸化セシウムなどが
あるが、水酸化ナトリウム、またはないが、多分共融現
象によって融点降下が起り記載反応温度において反応物
を溶解し易くなるものと考えられ、その結果高収率を与
えるので好ましい。Alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, etc. However, sodium hydroxide or not reacts at the stated reaction temperature due to a melting point depression, probably due to a eutectic phenomenon. It is considered that it becomes easier to dissolve substances, and as a result, it gives a high yield, so it is preferable.
本発明の反応温度は０−ハロ安息丼酸の種類。The reaction temperature of the present invention is the type of 0-halobenzoic acid.
アルカリ金属水酸化物の種類や量２反応時間その他の反
応条件により異なり一義的に限定できないが、反応速度
の遅いことを許容すれば１００℃程度の低温でも可能で
あり、ある程度の分解などの削反応を許容するならば３
５０℃以上の如き高温でも反応させることも可能である
が１通常は２００℃〜３５０℃の範囲が適当であり１．
さらに好ましくは２５０°Ｃ〜３００℃ の温度範囲に
保持して反応を行なわせると良好な結果が得られる。温
度が低くすぎると反応速度が遅いばかりか反応収率が低
く、反応温度その他の反応条件によって一義的に限定す
ることはできないが、後記実施例に示すように反応温度
によって最適な範囲が存在するのでこれを選定すべきで
ある。It depends on the type and amount of alkali metal hydroxide, 2 reaction time, and other reaction conditions, but it cannot be definitively determined, but if the slow reaction rate is accepted, it is possible to do it at a low temperature of about 100°C, and it is possible to reduce decomposition to some extent. 3 if you allow the reaction
Although it is possible to carry out the reaction at a high temperature such as 50°C or higher, 1. Usually, the range of 200°C to 350°C is suitable.
More preferably, good results can be obtained by carrying out the reaction while maintaining the temperature within the range of 250 DEG C. to 300 DEG C. If the temperature is too low, not only the reaction rate is slow but also the reaction yield is low, and it cannot be uniquely limited by the reaction temperature and other reaction conditions, but as shown in the examples below, there is an optimal range depending on the reaction temperature. Therefore, this should be selected.
本発明の反応は２００℃以下の低温では溶媒を用いない
と固結して反応が進まないが、これ以上の温度では溶媒
を用いず、熱溶媒で反応させるのが操作も簡単であり経
済的でもあるので通常無溶媒で反応させる場合が多い。The reaction of the present invention solidifies and does not proceed at low temperatures below 200°C unless a solvent is used, but at temperatures higher than this, it is easy to operate and economical to carry out the reaction with a hot solvent without using a solvent. Therefore, the reaction is usually carried out without a solvent.
本発明の方法により工業的に有用なチオサリチル酸およ
びジチオサリチル酸を工業的に有利奢こ製造することが
できる。By the method of the present invention, industrially useful thiosalicylic acid and dithiosalicylic acid can be produced in an industrially advantageous manner.
以下実施例および比較例を示して本発明をさらに詳卸目
こ説明する。EXAMPLES The present invention will be explained in more detail below with reference to Examples and Comparative Examples.
実施例１
’ｆｉ）０− りｏ ｑ安息香酸１ ｇ （６，３８ｍ
ｍｏｌｅ） 、粉末し
硫黄２ ｇ （６２，５ｍｍｏｌｅ） 、水酸化ナトリ
ウム２ｇ加熱し２７０℃に保持して３分間反応させた。Example 1 'fi) 0-ri oq benzoic acid 1 g (6,38 m
2 g (62.5 mmole) of powdered sulfur and 2 g of sodium hydroxide were heated and kept at 270° C. to react for 3 minutes.
反応生成物に水を加え、塩酸でＰＨ９〜１０に鯛整した
後、過剰のＮａＢＨ４を加えて完全に還元した。この溶
液を塩酸酸性とした後、エーテルで抽出しジアゾメタン
でメチル化してＳ−メチルチオ７−
安息香酸メチルとなし、ガスクロマトグラフで分析した
。生成したＳ−メチルチオ安息香酸メチルはＮＭ、Ｒ，
ＧＣ−ＭＳおよび元素分析により同定した。Ｓ−メチル
チオ安息香酸メチルの生成量は０．８４ｇ （４，６２
ｍｍｏｌｅ）テあり、Ｑ −りｏｏ安息香酸に対する収
率は７２．４％であった。これはチオサリチル酸および
ジチオサリチル酸の合計に相当する。Water was added to the reaction product, and the pH was adjusted to 9 to 10 with hydrochloric acid, followed by complete reduction by adding excess NaBH4. This solution was acidified with hydrochloric acid, extracted with ether, methylated with diazomethane to give methyl S-methylthio-7-benzoate, and analyzed by gas chromatography. The generated methyl S-methylthiobenzoate is NM, R,
Identified by GC-MS and elemental analysis. The amount of methyl S-methylthiobenzoate produced was 0.84 g (4,62
mmole) and the yield based on Q-rioo benzoic acid was 72.4%. This corresponds to the sum of thiosalicylic acid and dithiosalicylic acid.
実施例２〜５
第１表
２ ＮａＯＨ４，０２，５
ａＯＨ
３（ＫＯＨ（’２′、４２７０．０
４ （ＮａＯＨ（２，０７６０、
ＫＯＨ２，６
５ＫＯＨ４，０２９，４
８−
比較例１〜３
アルカリ金属の水酸化物と硫黄のかわりにアルカリ金属
の硫化物を使用した以外は実施例１と同様に実施し、第
２表をこ示す結果を得た。Examples 2-5 Table 1 2 NaOH4,02,5 aOH 3(KOH('2', 4270.0 4 (NaOH(2,0760, KOH2,6 5KOH4,029,4 8- Comparative Examples 1-3 Alkali The same procedure as in Example 1 was carried out except that an alkali metal sulfide was used instead of the metal hydroxide and sulfur, and the results shown in Table 2 were obtained.
第 ２ 表
Ｉ Ｎａ２Ｓ−９８ｆ） ５．０ ０３ Ｋ２Ｓ
２，５ １．１
実施例６〜１２
第３表に示す諸条件以外は実施例１と同様に実施し、第
３表に示す結果を得た。Table 2 I Na2S-98f) 5.0 03 K2S
2,5 1.1 Examples 6 to 12 The same procedure as in Example 1 was carried out except for the conditions shown in Table 3, and the results shown in Table 3 were obtained.
第３表
６ １．５ ２７０ ３ ６３，２７
３．０ ２７０ ３ ３７，６８ ２
．０ ２７０ １ ２５．０９ ２．０
２７０ ５ ５０，０１０ ２．０
２４０ ３ ４５．０１１
２．０ ２９０ ３
７０．２１２ ２．０ ３１０
３ ５０．Ｑ実施例１３
実施例１と同様にして得られた反応生成物に水を加えて
均一水溶液とした後、これを高速液体クロマトグラフィ
ーにより分析した結果、チオサリチル酸０．７１ｇ （
４，０１ｍｍｏｌｅ ）とジチオサリチル酸０．０５９
ｇ （０，１９ｍｍｏｌｅ）の存在を確認シタ。チオ
サリチル酸とジチオサリチル酸を合わせた収率実施例１
の１０倍量スケール、すなわち０−り実施例１と同様の
条件で反応生成物に水を加え塩酸酸性として沈澱物を枦
取し水洗した。この沈澱物を炭酸す） ＩＪウム水溶液
をこ溶解、加熱、熱時枦遇して未反応硫黄を除去した後
、再度塩酸酸性として冷却しジチオサリチル酸を晶析し
た。得られた結晶を炉取、乾燥して高速液体クロマトグ
ラフィーで分析したところ高純度のジチオサリチル酸で
あることが判明した。その我社は６．８３ ｇ （２２
，３ｍｍｏｌｅ）であり、０−クロロ安息香酸に対する
収率は７０．０％であった。Table 3 6 1.5 270 3 63,27
3.0 270 3 37,68 2
．． 0 270 1 25.09 2.0
270 5 50,010 2.0
240 3 45.011
2.0 290 3
70.212 2.0 310
3 50. Q Example 13 After adding water to the reaction product obtained in the same manner as in Example 1 to make a homogeneous aqueous solution, this was analyzed by high performance liquid chromatography. As a result, 0.71 g of thiosalicylic acid (
4,01 mmole) and dithiosalicylic acid 0.059
Confirm the presence of g (0.19 mmole). Yield Example 1 of combined thiosalicylic acid and dithiosalicylic acid
The reaction product was acidified with hydrochloric acid by adding water under the same conditions as in Example 1 on a 10-fold scale, that is, under the same conditions as in Example 1. The precipitate was collected and washed with water. This precipitate was dissolved in an aqueous IJ solution, heated and heated to remove unreacted sulfur, and then acidified with hydrochloric acid again and cooled to crystallize dithiosalicylic acid. The obtained crystals were collected in a furnace, dried, and analyzed by high performance liquid chromatography, and were found to be highly pure dithiosalicylic acid. Our company is 6.83 g (22
, 3 mmole), and the yield based on 0-chlorobenzoic acid was 70.0%.
出願人製鉄化学工業株式会社 代表者 佐々木 浩 １１−Applicant Steel Chemical Industry Co., Ltd. Representative Hiroshi Sasaki 11-
Claims (4)
下に硫黄と反応させることを特徴とするチオサリチル酸
およびジチオサリチル酸の製造法。(1) A method for producing thiosalicylic acid and dithiosalicylic acid, which comprises reacting 0-halobenzoic acid with sulfur in the presence of an acyl metal hydroxide.
る特許請求の範囲（１）記載の方法。(2) The method according to claim (1), wherein the reaction is carried out while being maintained at a temperature of 200 to 350°C.
許請求の範囲（１）記載の方法。(3) The method according to claim (1), wherein the 0-halobenzoic acid is 0-chlorobenzoic acid.
５） アルカリ金属水酸化物が水酸化すｌ−ＩＪウム
と水酸化カリウムの等モル混合物である特許請求の範囲
（１）記載の方法。(4) The alkali metal hydroxide is sodium hydroxide (
5) The method according to claim (1), wherein the alkali metal hydroxide is an equimolar mixture of sulfur hydroxide and potassium hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57140375A JPS5929659A (en) | 1982-08-11 | 1982-08-11 | Preparation of thiosalicylic acid and dithiosalicylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57140375A JPS5929659A (en) | 1982-08-11 | 1982-08-11 | Preparation of thiosalicylic acid and dithiosalicylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5929659A true JPS5929659A (en) | 1984-02-16 |
| JPS6158471B2 JPS6158471B2 (en) | 1986-12-11 |
Family
ID=15267357
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57140375A Granted JPS5929659A (en) | 1982-08-11 | 1982-08-11 | Preparation of thiosalicylic acid and dithiosalicylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929659A (en) |
-
1982
- 1982-08-11 JP JP57140375A patent/JPS5929659A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6158471B2 (en) | 1986-12-11 |
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