CN1030581A - 新颖抗氧化剂和其制备方法 - Google Patents

新颖抗氧化剂和其制备方法 Download PDF

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CN1030581A
CN1030581A CN88104330.3A CN88104330A CN1030581A CN 1030581 A CN1030581 A CN 1030581A CN 88104330 A CN88104330 A CN 88104330A CN 1030581 A CN1030581 A CN 1030581A
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xitix
sulfinyl
steric isomer
sulfenylation
antioxidant
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霍斯特·波林
克里斯托夫·韦尔利
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F Hoffmann La Roche AG
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/3463—Organic compounds; Microorganisms; Enzymes
    • A23L3/3544—Organic compounds containing hetero rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/45—Heterocyclic compounds having sulfur in the ring
    • C08K5/46—Heterocyclic compounds having sulfur in the ring with oxygen or nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/12—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing sulfur and oxygen

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  • Anti-Oxidant Or Stabilizer Compositions (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Furan Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Food Preservation Except Freezing, Refrigeration, And Drying (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明是涉及新颖的5，6-亚磺酰-L-抗坏血酸 和其立体异构体，通过对L-抗坏血酸或相应的立体 异构体进行亚磺酰化的制备方法，含有5，6-亚磺酰 -L-抗坏血酸或其立体异构体，具有抗氧化性能的组 合物，以及5，6-亚磺酰-L-抗坏血酸或其立体异构 体作为抗氧化剂的用途。

Description

本发明涉及新颖的抗氧化剂，即下式Ⅰ的5，6-亚磺酰-L-抗坏血酸化合物和其具有下式Ⅱ，Ⅲ和Ⅳ的立体异构体
（5，6-亚磺酰-D-抗坏血酸）
Figure 881043303_IMG2
（5，6-亚磺酰-D-异抗坏血酸）
Figure 881043303_IMG3
（5，6-亚磺酰-L-异抗坏血酸）
本发明还涉及5，6-亚磺酰-L-抗坏血酸和其立体异构体的制备方法。该方法包括对L-抗坏血酸或其相应的立体异构即D-抗坏血酸，D-异抗坏血酸或L-异抗坏血酸进行亚磺酰化。
最后，本发明还涉及化合物Ⅰ至Ⅳ作为抗氧化剂的用途，以及含有5，6-亚磺酰-L-抗坏血酸或其一个立体异构体的，具有抑制氧化性能的组合物。
通常把亚磺酰氯用作为亚磺酰基来进行L-抗坏血酸或其立体异构体的亚磺酰化。反应试剂通常按近似等摩尔量进行反应，最好尽可能接近等摩尔量。另外，亚磺酰化反应通常在约-20℃至约50℃的温度下进行，较佳温度范围是约-10℃至约25℃。
亚磺酰化反应通常在隋性溶剂，尤其极性非质子传递溶剂存在下进行。这类溶剂的例子有：无环的二醚和多醚例如单甘醇二甲醚（1，2-二甲氧乙烷）和二甘醇二甲醚;环状一醚和二醚例如四氢呋喃和二噁烷;环丁砜（四氢噻吩砜）;二甲基甲酰胺;二甲基乙酰胺;N-甲基吡咯烷酮和乙腈。
该新颖化合物显示出有价值的抑制氧化性能，能在大范围的基质中使用，例如：
食品〔酒（尤其酒的硫化），醋，食用油和脂肪，啤酒，水果和疏菜汁，糖浆，肉类和腊肠制品，果脯，疏菜干，坚果，蜜饯和保藏疏菜，马铃薯制品，糊，沙司，蛋黄酱等〕
-饲料
-锅炉给水
-用水胶片制造和冲洗的物质
-印染物质
-用于织物制造和处理的物质
-塑料
-润滑油和润滑脂
-橡胶
在每个应用中，常规所用的化合物Ⅰ，Ⅱ，Ⅲ或Ⅳ的量可为少量的。其较好使用相应为其它所用的亚硫酸盐型抗氧化剂的量，也就是说，例如常用约1-700ppm，特别是约20-约2000ppm。较好是按用途来定其用量。在食品工业中，例如下面的量较好：
酒：约50-300ppm
果脯：约1000-7000ppm
果汁和疏菜汁：约80-300ppm
新颖化合物Ⅰ至Ⅳ除了本身能加到需保护的基质中处，还能在合适情况下以稀释形式例如用作为溶液，尤其作为水或醇溶液。
在高浓度（≥2mg/ml基质）情况下，化合物Ⅰ至Ⅳ还具有细菌学和真菌作用。
实施例
于装有温度计和搅拌器的350ml四颈磺化烧瓶中在充有保护气氛（N2）下，加入17.6g（200mmol）晶体的L-抗坏血酸和50ml四氢呋喃。在0℃下，加入7.42ml（102mmol）亚硫酰氯，并且0℃搅拌混合物24小时，当抗坏血酸完全溶介后，把溶液注入到200g冰/水中，然后在4个分液漏斗用4×200ml乙酸乙酯萃取。有机相经8×50ml的20%氯化钠溶液洗涤。合并乙酸乙酯相，硫酸钠干燥，并用旋转式汽化器于喷水真空下浓缩至干燥。将剩余物（21，2g）溶于45ml乙酸乙酯，空吸过滤除去少量不溶沉淀物，用5ml乙酸乙酯冲洗。滤液在搅拌下慢慢滴加入100ml甲苯。在加入晶种后搅拌混合物18小时。空吸过滤产物，并且45℃于喷水真空下干燥8小时至恒定重量，从而得到17.6g    5，6-亚磺酰-L-抗坏血酸（79%理论得率），熔点150-151℃（分解）;
〔α〕20 365＝+246.2°（于H2O的1%）
元素分析：C%    H%    S%
计算值：32.44    2.72    14.43
实侧值：32.68    2.66    14.00
使用D-抗坏血酸，D-导抗坏血酸或L-异抗坏血酸，按相似方法进行相应的5，6-亚磺酰化衍生物的合成。

Claims (8)

1、具有抗氧化性能的组合物，其含有5，6-亚磺酰-L-抗坏血酸或其立体导构体。
2、根据权利要求1的组合物，其含有5，6-亚磺酰-L-抗坏血酸。
3、制备5，6-亚磺酰-L-抗坏血酸和其立体异构体的方法，该方法包括亚磺酰化L-抗坏血酸或相应的立体异构体。
4、根据权利要求3的方法，其中对L-抗坏血酸进行亚磺酰化得到5，6-亚磺酰L-抗坏血酸。
5、根据权利要求3或4的方法，其中所说的亚磺酰化是通过亚磺酰氯来进行的。
6、防止基质空气氧化的方法，其包括所说基质与有效量的5，6-亚磺酰-L-抗坏血酸或其立体异构体的掺合。
7、5，6-亚磺酰-L-抗坏血酸或其立体异构体作为抗氧化剂的用途。
8、5，6-亚磺酰-L-抗坏血酸作为抗氧化剂的用途。
CN88104330.3A 1987-07-09 1988-07-08 新颖抗氧化剂和其制备方法 Pending CN1030581A (zh)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1044907C (zh) * 1994-03-24 1999-09-01 陕西省西安制药厂 异维生素c钠制取异维生素c工艺
CN1045292C (zh) * 1994-07-22 1999-09-29 郑州市生物化工厂 异抗坏血酸的制备方法
CN108497104A (zh) * 2018-05-02 2018-09-07 贵州芳瑞堂生物科技有限公司 一种抗氧化剂组合物的制备工艺

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5336683A (en) * 1992-01-24 1994-08-09 Hoffmann-La Roche Inc. Antioxidants
US10663218B2 (en) 2017-11-17 2020-05-26 Omnicell, Inc. Dispensing system with temperature controlled drawers
US10596319B2 (en) 2017-11-23 2020-03-24 Aesynt Incorporated Compounding device system
US11335444B2 (en) 2017-11-30 2022-05-17 Omnicell, Inc. IV compounding systems and methods

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DE1217970B (de) * 1964-08-05 1966-06-02 Basf Ag Verfahren zur Herstellung von Schwefligsaeure-1, 2-alkylenestern
JPS60130582A (ja) * 1983-12-19 1985-07-12 Takeda Chem Ind Ltd 食品用酸化防止剤，アスコルビン酸誘導体およびその製造法
JPS61227578A (ja) * 1985-03-30 1986-10-09 Neos Co Ltd １，３，２―ジオキサチオラン―２―オキシド誘導体およびその製法
JPH01227578A (ja) * 1988-03-08 1989-09-11 Konica Corp 電子スチルカメラ

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1044907C (zh) * 1994-03-24 1999-09-01 陕西省西安制药厂 异维生素c钠制取异维生素c工艺
CN1045292C (zh) * 1994-07-22 1999-09-29 郑州市生物化工厂 异抗坏血酸的制备方法
CN108497104A (zh) * 2018-05-02 2018-09-07 贵州芳瑞堂生物科技有限公司 一种抗氧化剂组合物的制备工艺

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AU1866788A (en) 1989-01-12
US4841070A (en) 1989-06-20
JPS6445383A (en) 1989-02-17
IL86970A0 (en) 1988-12-30
AU602593B2 (en) 1990-10-18
EP0298399A1 (de) 1989-01-11
DK331388A (da) 1989-01-10

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