JPS639511B2 - - Google Patents
Info
- Publication number
- JPS639511B2 JPS639511B2 JP16203780A JP16203780A JPS639511B2 JP S639511 B2 JPS639511 B2 JP S639511B2 JP 16203780 A JP16203780 A JP 16203780A JP 16203780 A JP16203780 A JP 16203780A JP S639511 B2 JPS639511 B2 JP S639511B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- mercaptothiazoline
- carbon disulfide
- mol
- temperature
- 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
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- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 63
- 238000006243 chemical reaction Methods 0.000 claims description 31
- -1 sulfuric acid ester Chemical class 0.000 claims description 22
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 claims description 21
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 17
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 17
- 150000008051 alkyl sulfates Chemical class 0.000 claims description 7
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 claims description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 238000001308 synthesis method Methods 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 39
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 4
- 238000010517 secondary reaction Methods 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Chemical compound [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- UEBVBGGMLGIXTI-UHFFFAOYSA-N 1-aminoethyl hydrogen sulfate Chemical compound CC(N)OS(O)(=O)=O UEBVBGGMLGIXTI-UHFFFAOYSA-N 0.000 description 1
- OUIAITHYQOIRPM-UHFFFAOYSA-N 4-methyl-1,3-thiazolidine-2-thione Chemical compound CC1CSC(=S)N1 OUIAITHYQOIRPM-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Landscapes
- Thiazole And Isothizaole Compounds (AREA)
Description
【発明の詳細な説明】
本発明は、アミノアルキル硫酸エステルを出発
原料とし、２−メルカプトチアゾリン系含硫黄化
合物を高収率で合成する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for synthesizing a 2-mercaptothiazoline-based sulfur-containing compound in high yield using an aminoalkyl sulfate as a starting material.
これまで、アミノアルキル硫酸エステルと二硫
化炭素とから２−メルカプトチアゾリンを製造す
る方法が知られているが、従来の方法ではいずれ
も高収率で２−メルカプトチアゾリンを得ること
は困難であつた。 Until now, methods for producing 2-mercaptothiazoline from aminoalkyl sulfate and carbon disulfide have been known, but it has been difficult to obtain 2-mercaptothiazoline in high yield with any of the conventional methods. .
その理由としては、二硫化炭素が水あるいは水
酸化アルカリ水溶液に難溶でアミノアルキル硫酸
エステルとは異相反応となるため、反応に長時間
を要し二硫化炭素、アミノアルキル硫酸エステル
の分解のみならず、生成した２−メルカプトチア
ゾリンとの副反応などが起こり、その結果収率の
低下を招いていることが考えられる。 The reason for this is that carbon disulfide is poorly soluble in water or an aqueous alkali hydroxide solution and undergoes an out-of-phase reaction with the aminoalkyl sulfate, so the reaction takes a long time and only decomposes the carbon disulfide and the aminoalkyl sulfate. First, it is thought that side reactions with the generated 2-mercaptothiazoline occur, resulting in a decrease in yield.
特に中間体であるジチオカルバミン酸のアルキ
ル硫酸エステルの生成に必要な化学量論量の水酸
化アルカリが系内に最初から存在すると、原料の
アミノアルキル硫酸エステルが加水分解してアミ
ノアルキルアルコールとなる。そして、このアミ
ノアルキルアルコールが２−メルカプトチアゾリ
ンとなるためには、二硫化炭素がアミノアルキル
硫酸エステルと反応させる場合の２倍当量必要な
ため、必然的に収率が低下することになる。 In particular, if a stoichiometric amount of alkali hydroxide necessary for producing the intermediate alkyl sulfate of dithiocarbamic acid is present in the system from the beginning, the raw material aminoalkyl sulfate will be hydrolyzed to form aminoalkyl alcohol. In order for this aminoalkyl alcohol to become 2-mercaptothiazoline, twice the equivalent amount of carbon disulfide is required than when reacting with the aminoalkyl sulfate ester, which inevitably lowers the yield.
さらにアミノアルキル硫酸エステルと二硫化炭
素はジチオカルバミン酸のアルキル硫酸エステル
を経由して２−メルカプトチアゾリンに至ると考
えられるが、反応に必要な水酸化アルカリが最初
から系内に全量存在する場合には生成したジチオ
カルバミン酸のアルキル硫酸エステルがただちに
２−メルカプトチアゾリンとなるため、２−メル
カプトチアゾリンの水酸化アルカリとの接触時間
が長くなり、加水分解による損失が多くなるばか
りでなく、前記分解生成物であるアミノアルキル
アルコールとの２次反応をも起し、著しく収率の
低下を来たすのである。また、水酸化アルカリが
最初から全量系内に存在すると、反応の進行につ
れて、急激に反応し、温度制御が不可能となる。
この傾向は大容量の反応になるほど装置の放熱率
が小さくなるので顕著となり、工業的に実施する
には危険が大きすぎる。さらに、局部的な激しい
温度上昇により、上述の副反応が増大し、一層収
率の低下を招くことになるのである。 Furthermore, the aminoalkyl sulfate and carbon disulfide are thought to reach 2-mercaptothiazoline via the alkyl sulfate of dithiocarbamic acid, but if the entire amount of alkali hydroxide necessary for the reaction is present in the system from the beginning, Since the generated alkyl sulfate of dithiocarbamic acid immediately becomes 2-mercaptothiazoline, the contact time of 2-mercaptothiazoline with alkali hydroxide becomes longer, and not only does the loss due to hydrolysis increase, but also the decomposition products A secondary reaction with certain aminoalkyl alcohols also occurs, resulting in a significant decrease in yield. Furthermore, if the entire amount of alkali hydroxide is present in the system from the beginning, it will react rapidly as the reaction progresses, making temperature control impossible.
This tendency becomes more pronounced as the reaction volume increases, as the heat dissipation rate of the device decreases, and it is too dangerous to carry out industrially. Furthermore, the localized severe temperature rise increases the above-mentioned side reactions, further reducing the yield.
本発明者らは、この従来の２−メルカプトチア
ゾリン化合物の合成法の欠点を克服するため鋭意
研究を重ねた結果、アミノアルキル硫酸エステル
と二硫化炭素を水酸化アルカリ存在下に反応させ
るに際し、水酸化アルカリを分割添加しつつ反応
を行わせることにより、上記目的を達成し得るこ
とを見出し、この知見に基づき本発明をなすに至
つた。 The present inventors have conducted intensive research to overcome the drawbacks of this conventional method for synthesizing 2-mercaptothiazoline compounds. As a result, when reacting aminoalkyl sulfate and carbon disulfide in the presence of an alkali hydroxide, the present inventors found that It has been discovered that the above object can be achieved by carrying out the reaction while adding alkali oxide in portions, and based on this knowledge, the present invention has been accomplished.
すなわち本発明は、
一般式
（式中、R1、R2、R3及びR4は水素原子又は低級
アルキル基を示す）
で表わされるアミノアルキルアルコールの硫酸エ
ステルを水酸化アルカリ存在下に二硫化炭素と反
応させ
一般式
（式中、R1、R2、R3及びR4は前記と同じ意味を
もつ）
で表わされる２−メルカプトチアゾリンを製造す
るに当り、ジチオカルバミン酸のアルキル硫酸エ
ステルを生成するにほぼ十分な水酸化アルカリを
系に存在させジチオカルバミン酸のアルキル硫酸
エステルを十分生成させたのち、残りの水酸化ア
ルカリを系に分割添加し、さらに反応を行うこと
を特徴とする上記一般式〔〕で表わされる２−
メルカプトチアゾリン系含硫黄化合物の合成法を
提供するものである。 That is, the present invention has the general formula (In the formula, R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or a lower alkyl group) A sulfuric acid ester of an aminoalkyl alcohol represented by the following formula is reacted with carbon disulfide in the presence of an alkali hydroxide. (In the formula, R 1 , R 2 , R 3 and R 4 have the same meanings as above.) In producing the 2-mercaptothiazoline represented by 2 represented by the above general formula [], characterized in that after alkali oxide is present in the system to sufficiently generate alkyl sulfate of dithiocarbamic acid, the remaining alkali hydroxide is added to the system in portions and further reaction is carried out. −
The present invention provides a method for synthesizing mercaptothiazoline-based sulfur-containing compounds.
本発明においてはアミノアルキル硫酸エステル
を当量の水酸化アルカリ水溶液に溶解したのち、
これにその硫酸エステルと等モルの二硫化炭素を
加え、所定の温度で所定の時間反応させ（第１次
反応）その後さらにその硫酸エステルと当量の水
酸化アルカリを添加又は滴下しつつ反応を行わせ
る（第２次反応）ものである。その各反応は次式
で表わすことができる。 In the present invention, after dissolving the aminoalkyl sulfate in an equivalent amount of alkali hydroxide aqueous solution,
Add carbon disulfide in an amount equivalent to that of the sulfuric ester, and react at a specified temperature for a specified period of time (first reaction).Then, the reaction is further carried out while adding or dropping an equivalent amount of alkali hydroxide to the sulfuric ester. (secondary reaction). Each reaction can be expressed by the following formula.
（R1、R2、R3及びR4は前記と同じ意味をもつ）
第１次反応の反応温度は二硫化炭素の沸点以下
で行い、その温度により反応時間が決められるが
通常は１〜10時間の範囲である。また、第２次反
応は通常90℃以下で行うのが好ましい。これを越
えて加熱する場合には、２−メルカプトチアゾリ
ンの加水分解などの副反応を助長し収率低下を来
すので適当でない、又この２次反応時間としては
0.5〜５時間が採用されるが、温度と時間の関係
は希望する反応の反応速度及び分解反応の許容値
から自動的に決められるものである。 (R 1 , R 2 , R 3 and R 4 have the same meanings as above) The reaction temperature of the first reaction is carried out below the boiling point of carbon disulfide, and the reaction time is determined by the temperature, but usually 1~ The range is 10 hours. Further, it is preferable that the secondary reaction is usually carried out at a temperature of 90°C or lower. When heating beyond this time, it is not appropriate because it promotes side reactions such as hydrolysis of 2-mercaptothiazoline and reduces the yield.
A time of 0.5 to 5 hours is employed, but the relationship between temperature and time is automatically determined based on the desired reaction rate and decomposition reaction tolerance.
本発明方法に用いられる水酸化アルカリ水溶液
としては、NaOH、KOH、LiOH、RbOH、
CsOHなどの水溶液が好適であるが、これらは、
水酸化アルカリの対応の酸化物から調製したもの
でもよい。 The aqueous alkali hydroxide solutions used in the method of the present invention include NaOH, KOH, LiOH, RbOH,
Aqueous solutions such as CsOH are preferred;
It may also be one prepared from the corresponding oxide of alkali hydroxide.
以上のように本発明方法は、最初にジチオカル
バミン酸のアルキル硫酸エステルを生成するに足
るだけの水酸化アルカリを系内に存在させること
により、まずジチオカルバミン酸のアルキル硫酸
エステルを十分に生成させたのち、次いで残る水
酸化アルカリを添加しつつ２−メルカプトチアゾ
リンの生成反応を行わしめるものである。このよ
うな方法によれば、アミノアルキル硫酸エステル
及び２−メルカプトチアゾリンが多量の水酸化ア
ルカリと加熱下に長時間接触することを避けるこ
とができるので、分解などの副反応が最小限に抑
えられ、２−メルカプトチアゾリン系化合物を高
収率で得ることができる。 As described above, in the method of the present invention, sufficient alkali hydroxide is present in the system to generate the alkyl sulfate of dithiocarbamic acid, and then the alkyl sulfate of dithiocarbamic acid is sufficiently generated. Then, while adding the remaining alkali hydroxide, the reaction for producing 2-mercaptothiazoline is carried out. According to this method, the aminoalkyl sulfate ester and 2-mercaptothiazoline can be prevented from coming into contact with a large amount of alkali hydroxide for a long time under heating, so side reactions such as decomposition can be minimized. , 2-mercaptothiazoline compounds can be obtained in high yield.
次に本発明を実施例に基づきさらに詳細に説明
する。 Next, the present invention will be explained in more detail based on examples.
実施例 １
撹拌機、温度制御手段、還流器及び滴下漏斗を
備えた反応器に、２−アミノエタノールの硫酸エ
ステル0.2モルをとり、これを水酸化ナトリウム
0.2モル分含有の20％水酸化ナトリウム水溶液に
室温で溶解した。次にこれに二硫化炭素0.2モル
を加え十分に撹拌したのち、徐々に温度を上げ二
硫化炭素の沸点近くで２時間反応させた。次いで
20％水酸化ナトリウム水溶液を水酸化ナトリウム
として0.2モル分加え、さらに３時間反応を続け
た。２次反応中まだ若干の二硫化炭素が残つてい
て還流が起るが反応の後半では完全に消費され、
最終的に温度を60℃として反応を終了した。次に
40℃以上で熱時ろ過を行い、得られた粗結晶を冷
水でよく洗浄し、白色の２−メルカプトチアゾリ
ンの結晶を得た。純度は99.4％で仕込みの２−ア
ミノエタノール硫酸エステル基準の収率は93.3％
であつた。Example 1 Into a reactor equipped with a stirrer, a temperature control means, a reflux device, and a dropping funnel, 0.2 mole of sulfuric acid ester of 2-aminoethanol was placed, and this was added to sodium hydroxide.
It was dissolved in a 20% aqueous sodium hydroxide solution containing 0.2 mol at room temperature. Next, 0.2 mol of carbon disulfide was added to this, and after stirring thoroughly, the temperature was gradually raised and the reaction was carried out for 2 hours near the boiling point of carbon disulfide. then
A 20% aqueous sodium hydroxide solution was added in an amount of 0.2 mol as sodium hydroxide, and the reaction was continued for an additional 3 hours. During the secondary reaction, some carbon disulfide still remains and reflux occurs, but in the latter half of the reaction it is completely consumed.
The reaction was finally terminated at a temperature of 60°C. next
Filtration was performed while hot at 40° C. or higher, and the obtained crude crystals were thoroughly washed with cold water to obtain white crystals of 2-mercaptothiazoline. The purity is 99.4% and the yield based on the 2-aminoethanol sulfate ester used is 93.3%.
It was hot.
実施例 ２
実施例１と同じ装置を用い、水酸化ナトリウム
0.2モルを含有する20％水酸化ナトリウム水溶液
に２−アミノエタノールの硫酸エステル0.2モル
を室温で溶解し、これに二硫化炭素0.2モルを加
え十分撹拌した。次に徐々に温度を上げ、二硫化
炭素の沸点近くで２時間反応させた。次いで水酸
化ナトリウム0.2モルの20％水酸化ナトリウム水
溶液を滴下しながら、二硫化炭素還流下に２時間
反応させ、滴下終了後さらに２時間熟成反応を行
つた。反応の後半では二硫化炭素が完全に消費さ
れ、最終的に温度を70℃に高めたのち反応を終了
した。次に40℃以上で熱時ろ過を行い、得られた
粗結晶を冷水でよく洗い、２−メルカプトチアゾ
リンの白色結晶を得た。純度は99.2％で仕込み２
−アミノエタノール硫酸エステル基準の収率は
96.0％であつた。Example 2 Using the same equipment as in Example 1, sodium hydroxide
0.2 mol of sulfuric ester of 2-aminoethanol was dissolved in a 20% aqueous sodium hydroxide solution containing 0.2 mol at room temperature, 0.2 mol of carbon disulfide was added thereto, and the mixture was thoroughly stirred. Next, the temperature was gradually raised and the reaction was carried out for 2 hours near the boiling point of carbon disulfide. Next, a 20% aqueous sodium hydroxide solution containing 0.2 mol of sodium hydroxide was added dropwise, and the mixture was allowed to react for 2 hours under refluxing carbon disulfide, and after the completion of the addition, an aging reaction was further carried out for 2 hours. In the latter half of the reaction, carbon disulfide was completely consumed, and the reaction was finally terminated after raising the temperature to 70°C. Next, filtration was performed while hot at 40° C. or higher, and the obtained crude crystals were thoroughly washed with cold water to obtain white crystals of 2-mercaptothiazoline. Purity is 99.2% and preparation 2
-The yield based on aminoethanol sulfate is
It was 96.0%.
実施例 ３
実施例１と同様の装置を用い、２−アミノ−１
−プロパノールの硫酸エステル0.2モルを、水酸
化カリウム0.2モル含有の25％水酸化カリウム水
溶液に室温で溶解したのち、冷却しながら二硫化
炭素0.2モルを加え十分に撹拌した。次に徐々に
温度を上げ、二硫化炭素の沸点近くで２時間反応
させたのち、水酸化カリウム0.2モル含有の25％
水酸化カリウム水溶液を滴下しながら２時間反応
を行い、さらに２時間後反応を行つた。最後に70
℃まで温度を高め二硫化炭素が残つていないこと
を確認してから実施例１と同様の後処理を行い、
４−メチル−２−メルカプトチアゾリンの結晶を
得た。仕込基準の収率は95.7％であつた。Example 3 Using the same apparatus as in Example 1, 2-amino-1
- After 0.2 mol of propanol sulfate ester was dissolved in a 25% aqueous potassium hydroxide solution containing 0.2 mol of potassium hydroxide at room temperature, 0.2 mol of carbon disulfide was added while cooling and the mixture was thoroughly stirred. Next, the temperature was gradually raised, and after reacting for 2 hours near the boiling point of carbon disulfide, 25% of potassium hydroxide containing 0.2 mol of potassium hydroxide
The reaction was carried out for 2 hours while dropping an aqueous potassium hydroxide solution, and the reaction was further carried out after 2 hours. 70 at the end
After increasing the temperature to ℃ and confirming that no carbon disulfide remains, the same post-treatment as in Example 1 was carried out.
Crystals of 4-methyl-2-mercaptothiazoline were obtained. The yield based on the preparation was 95.7%.
比較例 １
実施例１と同様の装置を用い、２−アミノエタ
ノールの硫酸エステル0.2モル及び二硫化炭素0.2
モルを水50ｇに懸濁し、これに水酸化ナトリウム
0.4モルの45％水酸化ナトリウム水溶液を滴下し
ながら温度を高め二硫化炭素の沸点近くで４時間
反応を行つたのち、さらに２時間熟成反応を行い
最終的に温度を70℃に上げて反応を終了した。後
処理を実施例１と同様に行い85.2％収率で２−メ
ルカプトチアゾリンを得た。Comparative Example 1 Using the same apparatus as in Example 1, 0.2 mol of 2-aminoethanol sulfate ester and 0.2 mol of carbon disulfide were added.
Suspend the mole in 50g of water and add sodium hydroxide to this.
The temperature was raised while 0.4 mol of 45% sodium hydroxide aqueous solution was added dropwise, and the reaction was carried out for 4 hours near the boiling point of carbon disulfide. After that, the reaction was aged for another 2 hours, and the temperature was finally raised to 70°C to terminate the reaction. finished. Post-treatment was performed in the same manner as in Example 1 to obtain 2-mercaptothiazoline with a yield of 85.2%.
比較例 ２
実施例１と同様の装置を用い水酸化ナトリウム
0.4モルの20％水酸化ナトリウム水溶液を仕込み、
これに２−アミノエタノールの硫酸エステル0.2
モルと二硫化炭素0.2モルを加えたのち、温度を
高め二硫化炭素の沸点で反応を開始した。30分後
二硫化炭素の激しい還流が起り、発泡により液面
が急上昇したので加熱を弱め還流が落付いてから
更に反応を４時間続けた。最終的に温度を70℃に
して反応を終了し実施例１と同様の後処理を行つ
た。得られた２−メルカプトチアゾリンの収率は
２−アミノエタノールの硫酸エステル基準で72.5
％であつた。Comparative Example 2 Using the same equipment as in Example 1, sodium hydroxide
Prepare 0.4 mol of 20% sodium hydroxide aqueous solution,
Add to this 0.2 sulfate of 2-aminoethanol.
After adding mol and 0.2 mol of carbon disulfide, the temperature was raised and the reaction started at the boiling point of carbon disulfide. After 30 minutes, intense reflux of carbon disulfide occurred and the liquid level rose rapidly due to foaming, so the heating was weakened and after the reflux had subsided, the reaction was continued for an additional 4 hours. Finally, the temperature was raised to 70°C to terminate the reaction, and the same post-treatment as in Example 1 was performed. The yield of the obtained 2-mercaptothiazoline was 72.5 based on the 2-aminoethanol sulfate ester.
It was %.
Claims (1)
ルキル基を示す） で表わされるアミノアルキルアルコールの硫酸エ
ステルを水酸化アルカリ存在下に二硫化炭素と反
応させ 一般式 （式中、R1、R2、R3及びR4は前記と同じ意味を
もつ） で表わされる２−メルカプトチアゾリンを製造す
るに当り、ジチオカルバミン酸のアルキル硫酸エ
ステルを生成するにほぼ十分な水酸化アルカリを
系に存在させジチオカルバミン酸のアルキル硫酸
エステルを十分生成させたのち、残りの水酸化ア
ルカリを系に分割添加し、さらに反応を行うこと
を特徴とする上記一般式〔〕で表わされる２−
メルカプトチアゾリン系含硫黄化合物の合成法。[Claims] 1. General formula (In the formula, R 1 , R 2 , R 3 and R 4 represent a hydrogen atom or a lower alkyl group) A sulfuric acid ester of an aminoalkyl alcohol represented by the following formula is reacted with carbon disulfide in the presence of an alkali hydroxide, and the general formula (In the formula, R 1 , R 2 , R 3 and R 4 have the same meanings as above.) In producing the 2-mercaptothiazoline represented by 2 represented by the above general formula [], characterized in that after alkali oxide is present in the system to sufficiently generate alkyl sulfate of dithiocarbamic acid, the remaining alkali hydroxide is added to the system in portions and further reaction is carried out. −
Synthesis method of mercaptothiazoline-based sulfur-containing compounds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16203780A JPS5788171A (en) | 1980-11-19 | 1980-11-19 | Synthetic method of compound containing sulfur |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16203780A JPS5788171A (en) | 1980-11-19 | 1980-11-19 | Synthetic method of compound containing sulfur |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5788171A JPS5788171A (en) | 1982-06-01 |
| JPS639511B2 true JPS639511B2 (en) | 1988-02-29 |
Family
ID=15746873
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16203780A Granted JPS5788171A (en) | 1980-11-19 | 1980-11-19 | Synthetic method of compound containing sulfur |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5788171A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH023258U (en) * | 1988-06-21 | 1990-01-10 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5256362A (en) * | 1989-07-14 | 1993-10-26 | Nippon Shokubai Co., Ltd. | Method for production of granular cysteamine hydrochloride |
| CN1049218C (en) * | 1995-02-22 | 2000-02-09 | 吉林大学 | Synthetic method for R-tetrahydro thiazole-2-thione-4-carboxylic acid |
-
1980
- 1980-11-19 JP JP16203780A patent/JPS5788171A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH023258U (en) * | 1988-06-21 | 1990-01-10 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5788171A (en) | 1982-06-01 |
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