JPS58144377A - Preparation of 5-mercaptotetrazolyl-1-acetic acid - Google Patents
Preparation of 5-mercaptotetrazolyl-1-acetic acidInfo
- Publication number
- JPS58144377A JPS58144377A JP2562382A JP2562382A JPS58144377A JP S58144377 A JPS58144377 A JP S58144377A JP 2562382 A JP2562382 A JP 2562382A JP 2562382 A JP2562382 A JP 2562382A JP S58144377 A JPS58144377 A JP S58144377A
- Authority
- JP
- Japan
- Prior art keywords
- low polarity
- organic solvent
- acid
- mercaptotetrazolyl
- 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.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は工業的に容易に製造可能な収率尚く、純度穴な
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。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel method for producing 5-mercaptotetrazolyl-1-acetic acid with a high yield and purity that can be easily produced industrially.
従来の5−メルカプトテトラゾリル−1−ば[酸の製造
法は
げ) 原料が高価である。Conventional 5-mercaptotetrazolyl-1-ba [method for producing acid] Raw materials are expensive.
(ロ)危険な原料薬品上使用するため工業的でない。(b) It is not suitable for industrial use because it is used as a dangerous raw material for chemicals.
eフ 製造工程が複雑なうえ非常に困難な単位操作が
ある。eF The manufacturing process is complex and there are extremely difficult unit operations.
に)収率が低い。) low yield.
(ホ)製品の純度が低く、また肴色の度合が大きい。(e) The purity of the product is low and the degree of discoloration is large.
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(欠点がめった。Due to these problems, it may not be possible to actually industrialize it, or the cost is extremely high (shortcomings are rare).
本発明者等は上記の問題を解決すべく鋭息吋光した結果
、炙くべきことに純度、収率共に篩く、工業的に容易に
製造り能な本発明を完1祝するに至った。The inventors of the present invention have worked hard to solve the above problems, and as a result have completed the present invention, which has excellent purity and yield, and can be easily manufactured industrially. Ta.
本発明はカルボキシメチルジチオカルパミ/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
して便用し、先づアルカリ水溶液Vこエステルを溶解し
、ついでトルエン等の極性が低く、副生ずるペンジルメ
ル力プタ/倉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、更に反り後水層と有機溶
媒屑とを分離し、水層全塩酸等の鉱酸又は@濃酸で中和
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。The present invention conveniently uses carboxymethyldithiocarpami/acid benzyl ester (hereinafter simply referred to as ester) as a starting material, first dissolves the ester in an alkaline aqueous solution, and then uses low polarity such as toluene to dissolve the by-produced pennzyl ester. Add the organic solvent to be dissolved and the alkali metal azide, heat to react, and after warping, separate the aqueous layer and organic solvent waste, and soak the entire aqueous layer with a mineral acid such as hydrochloric acid or @concentrated acid. It provides a method for producing 5-mercaptotetrazolyl-1-acetic acid by neutralization, and the chemical reaction formula is as follows.
HOOC(!H2NHCB2CH2C6H5+M(工’
、)Oi4→M(I)001:’CH,NHC62C!
H2C6H5+H20(1)CM(1): ア・レカリ
金属〕
M(I)QOCCH2NHC82C12L”6H5+M
(1)N3→ N −N
II If +C6H5σu2sH(2
1CH2COOCH2C
0ON N−N+
1
0H2COO14I) C!H2COO
H以下上記反応式(す、(2)、(3)に従って本発明
を更に詳細に説明する。HOOC(!H2NHCB2CH2C6H5+M(工'
,)Oi4→M(I)001:'CH,NHC62C!
H2C6H5+H20(1) CM(1): A Recari Metal〕 M(I)QOCCH2NHC82C12L"6H5+M
(1) N3→ N −N II If +C6H5σu2sH(2
1CH2COOCH2C 0ON N-N+
1 0H2COO14I) C! H2COO
The present invention will be explained in more detail according to the reaction formulas (2) and (3) below.
(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20Q〜4oop1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。In the reaction of formula (1), ester crystals are added and dissolved in an alkaline aqueous solution having an equimolar amount as the ester (the amount of water is preferably 1 mole of 20Q to 4oop).
(2)式の反応ではペンジルメルカプク〉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、
50〜1so’C(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。In the reaction of formula (2), a low polarity (low dielectric constant) organic solvent that dissolves Penzylmercapuc well and an alkali metal azide in an amount of 1.0 to 1.5 times the mole of the ester are added.
Raise the temperature to 50 to 1so'C (preferably 70 to 100℃) and keep at the same temperature for 30 minutes or more (preferably 3 hours to 10
time), cool to room temperature, and separate to obtain an aqueous layer.
本発明においては上記有機溶媒の適訳が本発明の重要な
部分の一つであって、有機溶媒としてはトルニジ、キシ
レン、メシチレシなと及び極性の低いハロゲン化炭化ボ
索、極性の低いケト/類、極性の低いエステル蛸など力
r有効である。In the present invention, an appropriate translation of the above-mentioned organic solvent is one of the important parts of the present invention, and examples of organic solvents include torundi, xylene, mesitire, halogenated carbide with low polarity, ketone with low polarity, etc. It is effective to use esters such as esters with low polarity.
また本発明に使用の上記有機溶媒と(り式の反応におけ
るアルカリ水溶液中の水の重量比の割合は(95: 5
)〜(s:「s)であシ、好ましくは(80:20)
〜(20:80)である。Furthermore, the weight ratio of the organic solvent used in the present invention to water in the alkaline aqueous solution in the reaction of formula (2) is (95:5).
) ~ (s: “s)”, preferably (80:20)
~(20:80).
(3)式の反応では水層を塩酸で中8](PH2,0〜
o、 s ) −’1;あさ。In the reaction of formula (3), the aqueous layer is diluted with hydrochloric acid.
o, s) -'1; morning.
次にエステル又はケトン等の適当な有機溶媒で抽出板蒸
発乾固して5−メルカプトテトラゾリル−1−酢11!
2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。Next, an extraction plate was evaporated to dryness using a suitable organic solvent such as an ester or ketone to obtain 5-mercaptotetrazolyl-1-vinegar 11!
I got 2. The crystals of 5-mercaptotetrazolyl-1-acetic acid may be purified as necessary.
次Vこ実施例によって本発明を説明する。The invention will now be described by way of examples.
ス施y1]1
7i(80yに水酸化ナトリウム12y(0,30モル
)f: tz;解した後、室温でカルボキシメチルジチ
オカルバミシeベア’;ルエステルの結晶72.3(0
,3モル)を攪拌しながら俗解する。After dissolving sodium hydroxide 12y (0.30 mol) in 80y, crystals of carboxymethyl dithiocarbamic acid ester 72.3(0
, 3 mol) while stirring.
次にトルエン120J/、アジ化ンーダ21.5y(O
,a3モルンを加え、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。Next, toluene 120J/, azide 21.5y (O
, a3 morn was added, the temperature was raised to 80°C, and kept at the same temperature for 5 hours. After cooling to room temperature, the toluene layer and the aqueous layer were separated.
水層を塩酸でPH1,Oに調整し、活性炭で処理する。The aqueous layer was adjusted to pH 1.0 with hydrochloric acid and treated with activated carbon.
次に酢酸エチル1s oml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、はぼ白色の5−
メルカプトテトラゾリル−1−酢酸の結晶379f得た
。収率は74%であった。Next, it was extracted four times with 1 s oml of ethyl acetate, dehumidified with anhydrous sodium sulfate, and evaporated to dryness under reduced pressure.
Crystals 379f of mercaptotetrazolyl-1-acetic acid were obtained. The yield was 74%.
この結晶のアルカリ滴定による純度は91.1%である
。The purity of this crystal determined by alkaline titration is 91.1%.
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
ボした。Example 2 Table 1 shows the results obtained when the reaction solvent composition of Example 1 was changed.
第 1 表
゛ズ施例 3
実施例1のトルエンの代9に他のイず機溶媒?用い、溶
媒組成が(sO: 50)の場合の結果を第2表しで示
した。Table 1 Example 3 Can other organic solvents be used in place of toluene in Example 1? Table 2 shows the results when the solvent composition was (sO: 50).
ただしメチルアルコールの場合は反応温度を650とし
だ。However, in the case of methyl alcohol, the reaction temperature should be 650.
第2表より啄性の嶋い溶媒の場合収率は低い。As shown in Table 2, the yield is low in the case of a flimsy solvent.
第 2 x
手続補正書(自発)
昭和57年4月ら日
持fF庁長官 島田春樹殿
工 事件の表示
!hイ相57年特許願第25623号
2、 発IJIの名称
5−メルカグトテトクゾリルー1−酢酸の製造法
3 補正音する者
事件との関係 特計出頗人
住所 大阪?i北区堂島浜1丁目2番6号氏名 東洋化
成工業林式会社
代表取締役社長 小林栄衛
り(細書の発明のsr: III ;%説チ]の欄6
補正の内容
明細書中
(1)4貝下から3行目
「遺沢」を「選択」に訂正
(2)6貝1行目
「トルエ」を「トルエン」に訂正
(3)6負10行目
「74%−1を「75.6%」に訂正
(4)6貝11行目No. 2 x Procedural Amendment (Voluntary) April 1980, Chief of Japan Agency, Haruki Shimada Indication of the incident! Patent Application No. 25623 of 1957 2, Name of IJI 5 - Process for producing mercagutotetoxolyl 1 - acetic acid 3 Relationship with the case of the amended person Address of the person making the special offer Osaka? i 1-2-6 Dojimahama, Kita-ku Name Eiri Kobayashi, President and Representative Director of Toyo Kasei Industrial Forestry Co., Ltd. Column 6 of Invention SR: III; % theory in the specification
Contents of amendment In the description (1) Corrected “Izawa” in the 3rd line from the bottom of the 4th shell to “selection” (2) Corrected “Tolue” in the 1st line of the 6th shell to “Toluene” (3) 6th negative line 10 Corrected ``74%-1'' to ``75.6%'' (4) 6 shells line 11
Claims (1)
ン酸ペンジルエステルヲ溶解し、ついで極性が低く、か
つ副生ずるペンジルメルカグク7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刹゛
機鍍によって中和して、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ずるペンジルメル力ブタソ全溶
解する有機酸媒としてトルエン1キシレン、メシチレ/
、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便用する持dF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. Carboxymethyldithiocarbamic acid pendyl ester is dissolved in an aqueous alkaline solution, then an organic solvent that has low polarity and dissolves by-produced pendyl merkagoku 7 and an alkali metal azide are added, and a heating reaction is carried out. After the reaction, the aqueous layer and the organic solvent layer are separated, and the aqueous layer is neutralized with a mineral acid or a chemical solution to form 5-mercaptotetrazolyl-
1-A method for producing acetic acid. 2 Toluene 1 xylene, mesitilene/
2. A method for producing 5-mercaptotetrazolyl-1-acetic acid according to claim 1, wherein halogenated hydrocarbons having low polarity, ketones having low polarity, and esters having low polarity are used.
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 true JPS58144377A (en) | 1983-08-27 |
JPS6155914B2 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) |
Families Citing this family (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
Also Published As
Publication number | Publication date |
---|---|
JPS6155914B2 (en) | 1986-11-29 |
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