CN1218042A - 硫代乙酸的稳定化 - Google Patents

硫代乙酸的稳定化 Download PDF

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Publication number
CN1218042A
CN1218042A CN98120951A CN98120951A CN1218042A CN 1218042 A CN1218042 A CN 1218042A CN 98120951 A CN98120951 A CN 98120951A CN 98120951 A CN98120951 A CN 98120951A CN 1218042 A CN1218042 A CN 1218042A
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Prior art keywords
acid
thioacetic
thioacetic acid
stabilization
chloroacetic
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CN98120951A
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CN1130340C (zh
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Y·勒巴特
B·蒙圭隆
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Arkema France SA
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Elf Atochem SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C327/00—Thiocarboxylic acids
    • C07C327/02—Monothiocarboxylic acids
    • C07C327/04—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms
    • C07C327/06—Monothiocarboxylic acids having carbon atoms of thiocarboxyl groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of an acyclic saturated carbon skeleton

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

为了防止硫代乙酸在贮藏过程中的降解,向其中加入0.005%到0.5%的氯代乙酸,优选为二氯代乙酸。

Description

硫代乙酸的稳定化
本发明涉及硫代羧酸领域，尤其涉及硫代乙酸的稳定化。
由硫化氢与乙酸酐反应(专利FR1,417,154)制得的通式CH3-COSH的酸，在实际中被用作例如巯基甲基氧丙基左旋脯氨酸(抗高血压试剂)等药物合成中的中间体。
已知硫代乙酸倾向于水解形成多种含硫或含氧化合物，这会降低硫代乙酸商品的纯度。导致硫代乙酸不稳定性的一个原因尤其是它通过下述的反应在酸的催化下形成硫化氢和乙酸(《四面体》,1965，第21卷，第835页):
还生成二乙酰基硫(CH3CO-S-COCH3)和二乙酰基二硫化物(CH3CO-S-S-COCH3)。
为了使硫代乙酸稳定化，专利 JP1,345,605 业已建议向其中加入一种含磷无机酸或者有机强酸(pKa＜3.3)。除了草酸之外，其他列举的化合物(磷酸、柠檬酸和甲磺酸)不具有足够的稳定作用，不能使硫代乙酸在贮存时保存完好。
现已发现，令人惊异的是，氯代乙酸可以在50℃下使硫代乙酸在1-2个月的时间内保持稳定，这足以满足长途运输之需。
同样业已发现的是，在包括单氯代乙酸(pKa=2.9)、二氯代乙酸(pKa=1.3)和三氯代乙酸(pKa=0.7)的氯代乙酸系列中，二氯代乙酸表现出最有效的稳定作用。
因此本发明的第一个目标是稳定硫代乙酸的一种方法，其特征在于向其中加入足量的氯代乙酸，优选为二氯代乙酸。
本发明的再一个目标在于一种主要由硫代乙酸和少量氯代乙酸，优选为二氯代乙酸组成的组合物。
氯代乙酸稳定剂的用量可以为50～5,000ppm，然而优选为100～2,000ppm(0.01～0.2％(重量))。
为了获得最佳的稳定化效果，向新蒸馏尽量不含水(含水量＜0.5％)的硫代乙酸中加入氯代乙酸稳定剂是有利的。另外，为了防止空气的氧化作用，将贮藏的产品置于氮气隔离保护之下是希望的。
下述实施例说明本发明，而不对其构成限制。
实施例1(对比)
将新蒸馏的硫代乙酸(纯度99.27％)加入到几个玻璃安剖瓶中，密封，置于保持50℃的烘箱内。
定时将安剖瓶冷却和打开，以用气相色谱测量其中硫代乙酸的纯度。示于下表的数据结果表明，在贮存100天之后，产品的纯度降低到了63％。
实施例2(对比)
按照实施例1操作，但是向硫代乙酸中加入3,000ppm的草酸。在贮存100天之后，纯度下降约为10％。
实施例3和4
按照实施例1操作，但是向硫代乙酸中加入3,000ppm的二氯代乙酸(实施例3)或者仅仅加入1,000ppm的二氯代乙酸(实施例4)。
下表中的结果表明，二氯代乙酸比草酸要有效的多，因为在贮存100天之后硫代乙酸的纯度仅仅下降2～3％，即使在用量仅为其三分之一的时候亦是如此。
    50℃下的贮存时间(天)             硫代乙酸的纯度(％)
 实施例1(对比)   实施例2(对比) 实施例3 实施例4
    0   99.27    99.27    99.27    99.27
    20   93.60    98.80    98.85    99.0
    50   91.80    97.80    98.50    98.96
    80    80    94.20    97.10    98.40
    100    63    88.90    96.40    96.80

Claims (8)

1．稳定化硫代乙酸的方法，其特征在于向其中加入足量的氯代乙酸。
2．权利要求1的方法，其中的稳定剂是二氯代乙酸。
3．权利要求1或2的方法，其中稳定剂的用量为50～5,000ppm，优选为100～2,000ppm。
4．权利要求1至3之一的方法，其中稳定剂被加入到新蒸馏的硫代乙酸中，优选加入到含水量低于0.5％的硫代乙酸中。
5．权利要求1至4之一的方法，其中稳定化产品在隔绝空气的条件下贮存。
6．主要由硫代乙酸和50～5,000ppm氯代乙酸组成的组合物。
7．权利要求6的组合物，含有100～2,000ppm的氯代乙酸。
8．权利要求6或7的组合物，其中的氯代乙酸是二氯代乙酸。
CN98120951A 1997-10-15 1998-10-14 硫代乙酸的稳定化 Expired - Fee Related CN1130340C (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9712898A FR2769626B1 (fr) 1997-10-15 1997-10-15 Stabilisation de l'acide thioacetique
FR9712898 1997-10-15

Publications (2)

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CN1218042A true CN1218042A (zh) 1999-06-02
CN1130340C CN1130340C (zh) 2003-12-10

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CN98120951A Expired - Fee Related CN1130340C (zh) 1997-10-15 1998-10-14 硫代乙酸的稳定化

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US (1) US6011173A (zh)
EP (1) EP0909756B1 (zh)
JP (1) JPH11189583A (zh)
KR (1) KR19990037119A (zh)
CN (1) CN1130340C (zh)
AT (1) ATE203517T1 (zh)
BR (1) BR9804435A (zh)
CA (1) CA2246644A1 (zh)
DE (1) DE69801203T2 (zh)
FR (1) FR2769626B1 (zh)
IL (1) IL126127A0 (zh)
IN (1) IN187720B (zh)
TW (1) TW531528B (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314668C (zh) * 2003-03-03 2007-05-09 隆萨股份公司 硫代乙酸及其盐的制备方法

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090269390A1 (en) * 2008-04-25 2009-10-29 Medtronic, Inc. Medical devices, polymers, compositions, and methods for delivering a haloacetate
JP5553559B2 (ja) * 2009-09-04 2014-07-16 三協化成株式会社 チオカルボン酸類の製造方法
CN106187793A (zh) * 2016-01-26 2016-12-07 赵鸣 5‑氨基酮戊酸及其衍生物的盐化合物和应用

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1417154A (fr) * 1964-07-28 1965-11-12 Aquitaine Petrole Procédé de préparation des thioacides
JPS60142953A (ja) * 1983-12-28 1985-07-29 Toyo Kasei Kogyo Kk チオ酢酸の安定化法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1314668C (zh) * 2003-03-03 2007-05-09 隆萨股份公司 硫代乙酸及其盐的制备方法

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EP0909756B1 (fr) 2001-07-25
FR2769626B1 (fr) 1999-12-03
TW531528B (en) 2003-05-11
IN187720B (zh) 2002-06-15
FR2769626A1 (fr) 1999-04-16
US6011173A (en) 2000-01-04
IL126127A0 (en) 1999-05-09
JPH11189583A (ja) 1999-07-13
DE69801203D1 (de) 2001-08-30
BR9804435A (pt) 1999-12-07
CA2246644A1 (fr) 1999-04-15
CN1130340C (zh) 2003-12-10
KR19990037119A (ko) 1999-05-25
DE69801203T2 (de) 2002-05-16
EP0909756A1 (fr) 1999-04-21
ATE203517T1 (de) 2001-08-15

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