JPS6155914B2 - - Google Patents
Info
- Publication number
- JPS6155914B2 JPS6155914B2 JP2562382A JP2562382A JPS6155914B2 JP S6155914 B2 JPS6155914 B2 JP S6155914B2 JP 2562382 A JP2562382 A JP 2562382A JP 2562382 A JP2562382 A JP 2562382A JP S6155914 B2 JPS6155914 B2 JP S6155914B2
- Authority
- JP
- Japan
- Prior art keywords
- low polarity
- organic solvent
- mercaptotetrazolyl
- acid
- acetic acid
- 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.)
- Expired
Links
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- -1 Benzyl carboxymethyl dithiocarbamate Chemical compound 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 150000008282 halocarbons Chemical class 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 1
- 239000012990 dithiocarbamate Substances 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- DKIJKONRLAWKDS-UHFFFAOYSA-N 2-(benzylsulfanylcarbothioylamino)acetic acid Chemical compound OC(=O)CNC(=S)SCC1=CC=CC=C1 DKIJKONRLAWKDS-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000010977 unit operation Methods 0.000 description 1
Description
本発明は工業的に容易に製造可能な収率高く、
純度大なる５−メルカプトテトラゾリル−１−酢
酸の新規な製造法に関するものである。
従来の５−メルカプトテトラゾリル−１−酢酸
の製造法は
(イ) 原料が高価である。
(ロ) 危険な原料薬品を使用するため工業的でな
い。
(ハ) 製造工程が複雑なうえ非常に困難な単位操作
がある。
(ニ) 収率が低い。
(ホ) 製品の純度が低く、また着色の度合が大き
い。
などの問題があり、実際に工業化できないか又
はコストが著しく高くつく欠点があつた。
本発明者等は上記の問題を解決すべく鋭意研究
した結果、驚くべきことに純度、収率共に高く、
工業的に容易に製造可能な本発明を完成するに至
つた。
本発明はカルボキシメチルジチオカルバミン酸
ベンジルエステル（以下単にエステルと略称す
る）を出発原料として使用し、先づアルカリ水溶
液にエステルを溶解し、ついでトルエン等の極性
が低く、副生するベンジルメルカプタンを溶解す
る有機溶媒とアルカリ金属のアジ化物を加え、加
熱して反応させ、更に反応後水層と有機溶媒層と
を分離し、水層を塩酸等の鉱酸又は有機酸で中和
して５−メルカプトテトラゾリル−１−酢酸を製
造する方法を提供するもので化学反応式で示すと
下記の通りである。
HOOCCH2NHCS2CH2C6H5＋Ｍ（Ｉ）OH
→Ｍ（Ｉ）OOCCH2NHCS2CH2C6H5＋H2O (1)
〔Ｍ（Ｉ）：アルカリ金属〕
以下上記反応式(1)、(2)、(3)に従つて本発明を更
に詳細に説明する。
(1)式の反応ではエステルと等モルのアルカリ水
溶液（水の量は200〜400ｇ／モルが好ましい）の
中に、エステルの結晶を加えて溶解する。
(2)式の反応ではベンジルメルカプタンをよく溶
解する極性の低い（誘電率の小さい）有機溶媒と
エステルの1.0〜1.5倍モルのアルカリ金属アジ化
物を加え、50〜150℃（好ましくは70〜100℃）ま
で昇温し、同温度で30分間以上（好ましくは３時
間〜10時間）保ち、室温まで冷却し、分液して水
層を得る。
本発明においては上記有機溶媒の選択が本発明
の重要な部分の一つであつて、有機溶媒としては
トルエン、キシレン、メシチレンなど及び極性の
低いハロゲン化炭化水素、極性の低いケトン類、
極性の低いエステル類などが有効である。
また本発明に使用の上記有機溶媒と(1)式の反応
におけるアルカリ水溶液中の水の重量比の割合は
（95：５）〜（５：95）であり、好ましくは
（80：20）〜（20：80）である。
(3)式の反応では水層を塩酸で中和（PH2.0〜
0.5）する。
次にエステル又はケトン等の適当な有機溶媒で
抽出後蒸発乾固して５−メルカプトテトラゾリル
−１−酢酸を得た。この５−メルカプトテトラゾ
リル−１−酢酸の結晶は必要に応じて精製すれば
よい。
次に実施例によつて本発明を説明する。
実施例 １
水80ｇに水酸化ナトリウム12ｇ（0.30モル）を
溶解した後、室温でカルボキシメチルジチオカル
バミン酸ベンジルエステルの結晶72.3（0.3モ
ル）を撹拌しながら溶解する。
次にトルエン120ｇ、アジ化ソーダ21.5ｇ
（0.33モル）を加え、80℃まで昇温後、同温度で
５時間保つ、室温まで冷却後、トルエン層と水層
とを分離する。
水層を塩酸でPH1.0に調整し、活性炭で処理す
る。
次に酢酸エチル150mlで４回抽出し、無水硫酸
ナトリウムで脱湿後、減圧で蒸発乾固し、ほぼ白
色の５−メルカプトテトラゾリル−１−酢酸の結
晶37ｇを得た。収率は75.6％であつた。
この結晶のアルカリ滴定による純度は98.1％で
ある。
実施例 ２
実施例１の反応溶媒組成を変えた場合の結果を
第１表に示した。
The present invention is industrially easy to produce, has a high yield,
The present invention relates to a novel method for producing 5-mercaptotetrazolyl-1-acetic acid with high purity. In the conventional method for producing 5-mercaptotetrazolyl-1-acetic acid, (a) raw materials are expensive; (b) It is unindustrial because it uses dangerous raw materials. (c) The manufacturing process is complex and requires extremely difficult unit operations. (d) Yield is low. (e) The purity of the product is low and the degree of coloration is large. There were problems such as these, and the drawback was that it could not be commercialized or the cost would be extremely high. As a result of intensive research to solve the above problems, the present inventors found that both purity and yield were surprisingly high.
The present invention has been completed, which can be easily manufactured industrially. The present invention uses carboxymethyldithiocarbamic acid benzyl ester (hereinafter simply referred to as ester) as a starting material, first dissolves the ester in an alkaline aqueous solution, and then dissolves a by-product benzyl mercaptan with low polarity such as toluene. An organic solvent and an alkali metal azide are added, heated to react, and after the reaction, the aqueous layer and organic solvent layer are separated, and the aqueous layer is neutralized with a mineral acid such as hydrochloric acid or an organic acid to produce 5-mercapto. A method for producing tetrazolyl-1-acetic acid is provided, and the chemical reaction formula is as follows. HOOCCH 2 NHCS 2 CH 2 C 6 H 5 +M(I)OH →M(I)OOCCH 2 NHCS 2 CH 2 C 6 H 5 +H 2 O (1) [M(I): Alkali metal] The present invention will be explained in more detail below according to the above reaction formulas (1), (2), and (3). In the reaction of formula (1), ester crystals are added and dissolved in an alkaline aqueous solution (the amount of water is preferably 200 to 400 g/mol) in equimolar proportions to the ester. In the reaction of formula (2), a low polarity (low dielectric constant) organic solvent that dissolves benzyl mercaptan well and an alkali metal azide in an amount of 1.0 to 1.5 times the mole of the ester are added, ℃), maintained at the same temperature for 30 minutes or more (preferably 3 to 10 hours), cooled to room temperature, and separated to obtain an aqueous layer. In the present invention, the selection of the above organic solvent is one of the important parts of the present invention, and organic solvents include toluene, xylene, mesitylene, etc., halogenated hydrocarbons with low polarity, ketones with low polarity,
Esters with low polarity are effective. In addition, the weight ratio of water in the alkaline aqueous solution in the reaction of the organic solvent used in the present invention and formula (1) is (95:5) to (5:95), preferably (80:20) to (20:80). In the reaction of equation (3), the aqueous layer is neutralized with hydrochloric acid (PH2.0 ~
0.5). Next, the mixture was extracted with a suitable organic solvent such as ester or ketone, and then evaporated to dryness to obtain 5-mercaptotetrazolyl-1-acetic acid. The crystals of 5-mercaptotetrazolyl-1-acetic acid may be purified as necessary. Next, the present invention will be explained with reference to Examples. Example 1 After dissolving 12 g (0.30 mol) of sodium hydroxide in 80 g of water, 72.3 (0.3 mol) of crystals of carboxymethyldithiocarbamic acid benzyl ester are dissolved at room temperature with stirring. Next, 120g of toluene and 21.5g of soda azide.
(0.33 mol) was added, the temperature was raised to 80°C, kept at the same temperature for 5 hours, and after cooling to room temperature, the toluene layer and the aqueous layer were separated. The aqueous layer is adjusted to pH 1.0 with hydrochloric acid and treated with activated carbon. Next, the extract was extracted four times with 150 ml of ethyl acetate, dehumidified with anhydrous sodium sulfate, and evaporated to dryness under reduced pressure to obtain 37 g of almost white crystals of 5-mercaptotetrazolyl-1-acetic acid. The yield was 75.6%. The purity of this crystal determined by alkaline titration is 98.1%. Example 2 Table 1 shows the results when the reaction solvent composition of Example 1 was changed.
【表】
実施例 ３
実施例１のトルエンの代りに他の有機溶媒を用
い、溶媒組成が（50：50）の場合の結果を第２表
に示した。
ただしメチルアルコールの場合は反応温度を65
℃とした。
第２表より極性の高い溶媒の場合収率は低い。[Table] Example 3 Table 2 shows the results when another organic solvent was used in place of toluene in Example 1 and the solvent composition was (50:50). However, in the case of methyl alcohol, the reaction temperature is 65
℃. As shown in Table 2, the yield is low in the case of highly polar solvents.
Claims (1)
ルバミン酸ベンジルエステルを溶解し、ついで極
性が低く、かつ副生するベンジルメルカプタンを
溶解する有機溶媒とアルカリ金属アジ化物とを加
え、加熱反応させ、反応後水層と有機溶媒層とを
分離し、水層を鉱酸もしくは有機酸によつて中和
して、５−メルカプトテトラゾリル−１−酢酸を
製造する方法。 ２ 極性が低くかつ副生するベンジルメルカプタ
ンを溶解する有機溶媒としてトルエン、キシレ
ン、メシチレン、極性の低いハロゲン化炭化水
素、極性の低いケトン類、極性の低いエステル類
を使用する特許請求の範囲第１項記載の５−メル
カプトテトラゾリル−１−酢酸の製造法。[Scope of Claims] 1. Benzyl carboxymethyl dithiocarbamate is dissolved in an aqueous alkaline solution, and then an organic solvent that has low polarity and dissolves by-produced benzyl mercaptan and an alkali metal azide are added, and the mixture is heated and reacted. A method for producing 5-mercaptotetrazolyl-1-acetic acid by separating an aqueous layer and an organic solvent layer, and neutralizing the aqueous layer with a mineral acid or an organic acid. 2 Claim 1 in which toluene, xylene, mesitylene, a halogenated hydrocarbon with low polarity, ketones with low polarity, and esters with low polarity are used as organic solvents that have low polarity and dissolve the by-product benzyl mercaptan. A method for producing 5-mercaptotetrazolyl-1-acetic acid as described in Section 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2562382A JPS58144377A (en) | 1982-02-18 | 1982-02-18 | Preparation of 5-mercaptotetrazolyl-1-acetic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2562382A JPS58144377A (en) | 1982-02-18 | 1982-02-18 | Preparation of 5-mercaptotetrazolyl-1-acetic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58144377A JPS58144377A (en) | 1983-08-27 |
| JPS6155914B2 true JPS6155914B2 (en) | 1986-11-29 |
Family
ID=12170998
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2562382A Granted JPS58144377A (en) | 1982-02-18 | 1982-02-18 | Preparation of 5-mercaptotetrazolyl-1-acetic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58144377A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62179012U (en) * | 1986-05-01 | 1987-11-13 | ||
| JPH01228518A (en) * | 1988-03-09 | 1989-09-12 | Matsushita Seiko Co Ltd | Filter for ventilator |
-
1982
- 1982-02-18 JP JP2562382A patent/JPS58144377A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62179012U (en) * | 1986-05-01 | 1987-11-13 | ||
| JPH01228518A (en) * | 1988-03-09 | 1989-09-12 | Matsushita Seiko Co Ltd | Filter for ventilator |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58144377A (en) | 1983-08-27 |
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