JPH0333705B2 - - Google Patents
Info
- Publication number
- JPH0333705B2 JPH0333705B2 JP57141540A JP14154082A JPH0333705B2 JP H0333705 B2 JPH0333705 B2 JP H0333705B2 JP 57141540 A JP57141540 A JP 57141540A JP 14154082 A JP14154082 A JP 14154082A JP H0333705 B2 JPH0333705 B2 JP H0333705B2
- Authority
- JP
- Japan
- Prior art keywords
- benzyl
- added
- oocch
- surfactant
- carboxymethyldithiocarbamate
- 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 - Lifetime
Links
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 9
- DKIJKONRLAWKDS-UHFFFAOYSA-N 2-(benzylsulfanylcarbothioylamino)acetic acid Chemical compound OC(=O)CNC(=S)SCC1=CC=CC=C1 DKIJKONRLAWKDS-UHFFFAOYSA-N 0.000 claims description 8
- -1 benzyl halide Chemical class 0.000 claims description 7
- 239000004471 Glycine Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 239000003444 phase transfer catalyst Substances 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims description 2
- 230000003472 neutralizing effect Effects 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000002798 polar solvent Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 description 2
- 229940073608 benzyl chloride Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002334 glycols Chemical class 0.000 description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001515 polyalkylene glycol Polymers 0.000 description 2
- CSEIULCPGRDIPD-UHFFFAOYSA-N 9-chloro-9-octylheptadecane Chemical compound CCCCCCCCC(Cl)(CCCCCCCC)CCCCCCCC CSEIULCPGRDIPD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Substances CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- VANLTUPWUSFZOU-UHFFFAOYSA-N chloromethane;n,n-dioctyloctan-1-amine Chemical compound ClC.CCCCCCCCN(CCCCCCCC)CCCCCCCC VANLTUPWUSFZOU-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は５−メルカプトテトラゾリル−１−酢
酸
The present invention relates to 5-mercaptotetrazolyl-1-acetic acid
【式】を製造する原料と
して非常に有用なカルボキシメチルジチオカルバ
ミン酸ベンジルと名づけられる化合物の製造法に
関するものである。
本発明の化合物の製造方法を反応式で示すと次
の通りである。
HOOCCH2NH2＋Ｍ（）OH
→Ｍ（）OOCCH2NH2＋H2O (1)
（Ｍ（）：アルカリ金属）
Ｍ（）OOCCH2NH2＋CS2＋Ｍ（）OH
→Ｍ（）OOCCH2NHCS2M（）＋H2O (2)
Ｍ（）OOCCH2NHCS2M（）
＋C6H5CH2X→Ｍ（）OOCCH2
NH2CS2CH2C6H5＋Ｍ（）Ｘ (3)
（Ｘ ハロゲン原子）
Ｍ（）OOCCH2NHCS2CH2C6H5
＋Ｈ
→HOOCCH2NHCS2CH2
（C6H5）＋Ｍ（）
(4)
先づ(1)の反応式で示すように水系でグリシンを
アルカリで中和し、アルカリ金属塩を生成させ
る。
次に(2)の反応式に示すようにCS2の反応促進の
ため、界面活性剤ポリアルキレングリコール誘導
体（この場合、日本油脂株式会社製、商品名、ニ
ツサンデイスホームCK−140使用）又は／及び相
間移動触媒トリ−ｎ−オクチルアミンメチルクロ
ライド（広栄化学工業株式会社製、商品名、
TOMACを使用）を加える。
この界面活性剤又は／及び相間移動触媒の添加
は本発明物質製造法の特徴の一つである。
即ちグリシンアルカリ金属塩（１重量部）、ア
ルカリ（１重量部）と上記添加剤の入つた水溶液
にグリシンと等モルのCS2を０〜50℃、好ましく
は25〜35℃で滴下する。滴下後同温度で30分間以
上熟成する。０℃以下では反応が遅くまたCS2が
50℃以上の温度では沸騰するため使用することが
困難である。
次に(3)の反応式に示すようにハロゲン化ベンジ
ルの滴下前に、アルコール等のハロゲン化ベンジ
ルを溶解し、かつ安定な極性溶媒を添加する。極
性溶媒としては沸点が50〜100℃／760mmＨｇのも
のが好ましい。
なお、この極性溶媒は(1)又は(2)の反応式の段階
で入れておいてもよい。
ハロゲン化ベンジルは塩化ベンジルが好まし
く、その使用量はグリシンの0.8〜1.2倍モルが好
適で、温度は０〜80℃、好ましくは10〜30℃で滴
下する。滴下後30分間以上熟成するのが好まし
い。
次に必要に応じて水を加える。水の添加量が少
ないと極性溶媒の溜去の後期に反応液が激しく泡
立ち、容器から溢出する恐れがある。ついで70℃
以下（温度は低いほどよい）で極性溶媒を減圧下
で溜去する。
ただし、カルボキシメチルジチオカルバミン酸
ベンジルが不溶な極性溶媒の場合は溜去しなくて
もよい。
更に(4)の反応では、先づ必要に応じて水もしく
は有機溶媒を加える。この場合有機溶媒の量が少
ないと鉱酸滴下時、撹拌が困難になる。
次に鉱酸でPHを2.5付近にする。反応母液から
結晶を分離後乾燥してカルボキシメチルジチオカ
ルバミン酸ベンジルの結晶が得られた。収率は80
％以上である。この結晶を必要に応じて精製す
る。
本発明の精製した試料について、
(イ) 本発明物質の融点は測定の結果162.5〜166.6
℃であつた。
(ロ) 元素分析の結果を第１表に示したThis invention relates to a method for producing a compound named benzyl carboxymethyldithiocarbamate, which is very useful as a raw material for producing the formula. The method for producing the compound of the present invention is shown in the following reaction formula. HOOCCH 2 NH 2 +M()OH →M()OOCCH 2 NH 2 +H 2 O (1) (M(): Alkali metal) M()OOCCH 2 NH 2 +CS 2 +M()OH →M()OOCCH 2 NHCS 2 M()+H 2 O (2) M()OOCCH 2 NHCS 2 M() +C 6 H 5 CH 2 X→M()OOCCH 2 NH 2 CS 2 CH 2 C 6 H 5 +M()X (3) (X halogen atom) M()OOCCH 2 NHCS 2 CH 2 C 6 H 5 +H → HOOCCH 2 NHCS 2 CH 2 (C 6 H 5 ) + M() (4) As shown in the reaction formula in (1) Glycine is neutralized with an alkali in an aqueous system to generate an alkali metal salt. Next, as shown in reaction formula (2), to accelerate the reaction of CS 2 , a surfactant polyalkylene glycol derivative (in this case, Nitsusan Dice Home CK-140, manufactured by NOF Corporation) or / and phase transfer catalyst tri-n-octylamine methyl chloride (manufactured by Koei Chemical Industry Co., Ltd., trade name,
(using TOMAC). Addition of this surfactant and/or phase transfer catalyst is one of the characteristics of the method for producing the substance of the present invention. That is, to an aqueous solution containing an alkali metal salt of glycine (1 part by weight), an alkali (1 part by weight), and the above-mentioned additives, an equimolar amount of CS 2 as glycine is added dropwise at 0 to 50°C, preferably 25 to 35°C. After dropping, mature at the same temperature for 30 minutes or more. Below 0°C, the reaction is slow and CS 2
It is difficult to use at temperatures above 50°C as it boils. Next, as shown in reaction formula (3), before the benzyl halide is added dropwise, the benzyl halide is dissolved, such as alcohol, and a stable polar solvent is added. The polar solvent preferably has a boiling point of 50 to 100°C/760 mmHg. Note that this polar solvent may be added at the stage of reaction formula (1) or (2). The benzyl halide is preferably benzyl chloride, the amount used is preferably 0.8 to 1.2 times the mole of glycine, and the temperature is 0 to 80°C, preferably 10 to 30°C. It is preferable to ripen for 30 minutes or more after dropping. Then add water if necessary. If the amount of water added is small, the reaction solution will foam violently in the latter stage of distillation of the polar solvent, and there is a risk that it will overflow from the container. Then 70℃
The polar solvent is distilled off under reduced pressure (the lower the temperature, the better). However, in the case of a polar solvent in which benzyl carboxymethyldithiocarbamate is insoluble, distillation may not be performed. Furthermore, in reaction (4), water or an organic solvent is first added as necessary. In this case, if the amount of organic solvent is small, stirring becomes difficult when the mineral acid is added dropwise. Next, adjust the pH to around 2.5 with mineral acid. Crystals were separated from the reaction mother liquor and dried to obtain crystals of benzyl carboxymethyldithiocarbamate. Yield is 80
% or more. The crystals are purified if necessary. Regarding the purified sample of the present invention, (a) The melting point of the substance of the present invention was measured to be 162.5 to 166.6.
It was warm at ℃. (b) The results of elemental analysis are shown in Table 1.
【表】
理論値は
として計算した。第１表より測定値は理論とよく
一致していることがわかる。
(ハ) 次にNMRスペクトルを第１図に示した。
第１図より、[Table] Theoretical values are It was calculated as It can be seen from Table 1 that the measured values are in good agreement with the theory. (c) Next, the NMR spectrum is shown in Figure 1. From Figure 1,
【表】
なお、第１図のNMRスペクトルにはカルボキ
シル基の−OHの化学シフトがもう少し高く、第
１図には示されていないが上記以外のピークは見
られなかつた。
(イ)〜(ハ)の結果より本願発明の化合物は前記した
ように[Table] In addition, in the NMR spectrum shown in Figure 1, the chemical shift of -OH of the carboxyl group was a little higher, and although not shown in Figure 1, no peaks other than the above were observed. From the results of (a) to (c), the compound of the present invention is found to be as described above.
【式】であ
ることがわかる。
本発明によつて得られた化合物は収率が高く、
製造の操作が簡単で、かつ製造コストが安価な利
点がある。
実施例 １
苛性曹達40ｇ（1.0モル）を水90ｇに溶解し、
室温でグリシン37.5ｇ（0.5モル）を溶解する。
次に界面活性剤ポリアルキレングリコール誘導
体（日本油脂株式会社製ニツサンデイスホーム
CK−140使用）を１ｇ加える。二硫化炭素38ｇ
（0.5モル）を30〜35℃で30分にわたり加え、同温
度で３時間撹拌する。
メタノール125mlを加えた後、塩化ベンジル
63.3ｇ（0.5モル）を15〜20℃で30分間にわたり
加え、同温度で３時間撹拌する。
次に水100ｇを加え、減圧でメタノールを溜去
後、水150ｇを加える。冷却しながら濃塩酸を加
え、PH2.5の酸性にする。遠心分離し、真空乾燥
してカルボキシメチルジチオカルバミン酸ベンジ
ルの結晶110ｇを得た。
この結晶のアルカリ滴定による純度は92.8％で
収率は84.3％であつた。
比較例 １
実施例１と同様な方法で界面活性剤ニツサンデ
イスホームCK−140を加えない場合のカルボキシ
メチルジチオカルバミン酸ベンジルの収率は55.0
％で収率は著しく低い。
実施例 ２
実施例１と同様にして、同様の反応で界面活性
剤の代りに相間移動触媒としてトリ−ｎ−オクチ
ルメチルクロライド（広栄化学工業株式会社製商
品名TOMAC使用）を１ｇ添加して行つた。
その結果得られたカルボキシメチルジチオカル
バミン酸ベンジルの純度は92.0％で収率は85.0％
であつた。
上記より本発明において界面活性剤又は相間移
動触媒の添加は共に同様な純度と収率でカルボキ
シメチルジチオカルバミン酸ベンジルが得られる
ことが分つた。
実施例 ３
実施例１の場合と同様にして、界面活性剤の代
りに実施例１使用の界面活性剤0.5ｇと実施例２
使用の相間移動触媒0.5ｇとを併用して同様の反
応を行わせた。
その結果得られたカルボキシメチルジチオカル
バミン酸ベンジルの純度は94.3％、収率は82.5％
であつた。It can be seen that [Formula]. The compound obtained by the present invention has a high yield;
It has the advantage of easy manufacturing operations and low manufacturing costs. Example 1 40g (1.0 mol) of caustic soda was dissolved in 90g of water,
Dissolve 37.5 g (0.5 mol) of glycine at room temperature. Next, surfactant polyalkylene glycol derivative (Nitsu Sun Day Home, manufactured by NOF Corporation)
Add 1 g of CK-140). Carbon disulfide 38g
(0.5 mol) over 30 minutes at 30-35°C and stirred at the same temperature for 3 hours. After adding 125ml of methanol, benzyl chloride
63.3 g (0.5 mol) is added over 30 minutes at 15-20°C and stirred at the same temperature for 3 hours. Next, add 100 g of water, distill off methanol under reduced pressure, and then add 150 g of water. While cooling, add concentrated hydrochloric acid to make it acidic to pH 2.5. The mixture was centrifuged and dried under vacuum to obtain 110 g of benzyl carboxymethyldithiocarbamate crystals. The purity of the crystals determined by alkaline titration was 92.8%, and the yield was 84.3%. Comparative Example 1 The yield of benzyl carboxymethyldithiocarbamate when the surfactant Nitsusan Daishome CK-140 was not added was 55.0 in the same manner as in Example 1.
%, the yield is extremely low. Example 2 A similar reaction was carried out in the same manner as in Example 1, with the addition of 1 g of tri-n-octylmethyl chloride (trade name: TOMAC, manufactured by Koei Chemical Industry Co., Ltd.) as a phase transfer catalyst instead of the surfactant. Ivy. The purity of the resulting benzyl carboxymethyldithiocarbamate was 92.0% and the yield was 85.0%.
It was hot. From the above, it has been found that benzyl carboxymethyldithiocarbamate can be obtained with similar purity and yield when a surfactant or a phase transfer catalyst is added in the present invention. Example 3 In the same manner as in Example 1, 0.5 g of the surfactant used in Example 1 and Example 2 were added instead of the surfactant.
A similar reaction was carried out in combination with 0.5 g of the phase transfer catalyst used. The resulting benzyl carboxymethyl dithiocarbamate has a purity of 94.3% and a yield of 82.5%.
It was hot.
第１図は本発明物質のNMRスペクトルを示
す。
ａ、
FIG. 1 shows the NMR spectrum of the substance of the present invention. a,
【式】ｂ、CH2、ｃ、NH、ｄ、Ｎに
結合するCH2、の夫々のNMRスペクトルであ
る。[Formula] These are NMR spectra of b, CH 2 , c, NH, d, CH 2 bonded to N.
Claims (1)
は／及び相間移動触媒を加え、ついでCS2を加え
てＭ（）OOCCH2NHCS2M（）〔ここにＭ
（）はアルカリ金属〕を生成させ、次にハロゲ
ン化ベンジルを加えてＭ（）
OOCCH2NHCS2CH2C6H5を生成させ、更に鉱酸
で中和してカルボキシメチルジチオカルバミン酸
ベンジルを製造する方法。[Claims] 1 Glycine is dissolved in an alkali, a surfactant or/and a phase transfer catalyst is added, and then CS 2 is added to form M()OOCCH 2 NHCS 2 M() [where M
() is an alkali metal], then add benzyl halide to M()
A method for producing benzyl carboxymethyldithiocarbamate by producing OOCCH 2 NHCS 2 CH 2 C 6 H 5 and further neutralizing it with a mineral acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57141540A JPS5931759A (en) | 1982-08-14 | 1982-08-14 | Carboxymethyldithiocarbamic acid benzyl ester and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57141540A JPS5931759A (en) | 1982-08-14 | 1982-08-14 | Carboxymethyldithiocarbamic acid benzyl ester and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5931759A JPS5931759A (en) | 1984-02-20 |
| JPH0333705B2 true JPH0333705B2 (en) | 1991-05-20 |
Family
ID=15294342
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57141540A Granted JPS5931759A (en) | 1982-08-14 | 1982-08-14 | Carboxymethyldithiocarbamic acid benzyl ester and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5931759A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57174142A (en) * | 1981-03-02 | 1982-10-26 | Merck & Co Inc | Method of removing uniform catalyst eightth family metal from process current |
-
1982
- 1982-08-14 JP JP57141540A patent/JPS5931759A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS57174142A (en) * | 1981-03-02 | 1982-10-26 | Merck & Co Inc | Method of removing uniform catalyst eightth family metal from process current |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5931759A (en) | 1984-02-20 |
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