(2R)-2-phenyl-2-[(2R,4R,5S)-3,4,5-trihydroxy-6-[[(2R,4R,5S)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxymethyl]oxan-2-yl]oxyacetonitrile | 29883-15-6

• 物质功能分类: 生物化工 - 糖类化合物 - 双糖
• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (2R)-2-phenyl-2-[(2R,4R,5S)-3,4,5-trihydroxy-6-[[(2R,4R,5S)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]oxymethyl]oxan-2-yl]oxyacetonitrile
• CAS: 29883-15-6
• 化学式: C₂₀H₂₇NO₁₁
• 分子量: 457.4
• InChiKey: XUCIJNAGGSZNQT-ZPVJLWCPSA-N

物化性质

• 熔点：
  223-226 °C
• 比旋光度：
  -38.5 º (c=4, H2O)
• 沸点：
  563.27°C (rough estimate)
• 密度：
  1.4474 (rough estimate)
• 溶解度：
  在热水中的溶解度0.1 g/mL，清澈至微浑浊，无色
• LogP：
  -2.237 (est)
• 旋光度：
  SPECIFIC OPTICAL ROTATION (WATER, C= 1): -42 DEG @ 20 °C/D; SADTLER REF NUMBER: 16450 (IR, PRISM); 5152 (UV)

计算性质

• 辛醇/水分配系数(LogP)：
  -2.7
• 重原子数：
  32
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  202
• 氢给体数：
  7
• 氢受体数：
  12

ADMET

代谢

苦杏仁苷是一种由葡萄糖、苯甲醛和氰化物组成的化学复合物，后者可以通过β-葡萄糖苷酶或乳化酶的作用释放出来。尽管这些酶在哺乳动物组织中不存在，但人类的肠道微生物群似乎拥有这些或类似的酶，能够促使氰化物的释放，导致人类中毒。因此，与静脉注射相比，通过口服途径摄入的苦杏仁苷可能毒性高达40倍。

AMYGDALIN IS A CHEMICAL COMBINATION OF GLUCOSE, BENZALDEHYDE, & CYANIDE FROM WHICH THE LATTER CAN BE RELEASED BY THE ACTION OF BETA-GLUCOSIDASE OR EMULSIN. ALTHOUGH THESE ENZYMES ARE NOT FOUND IN MAMMALIAN TISSUES, THE HUMAN INTESTINAL MICROFLORA APPEARS TO POSSESS THESE OR SIMILAR ENZYMES CAPABLE OF EFFECTING CYANIDE RELEASE RESULTING IN HUMAN POISONING. FOR THIS REASON AMYGDALIN MAY BE AS MUCH AS 40 TIMES MORE TOXIC BY THE ORAL ROUTE AS COMPARED WITH IV INJECTION.

来源:Hazardous Substances Data Bank (HSDB)

代谢

植物苷类通过酶促或酸性水解产生氰化物，同时伴随着糖和芳香醛的产生。常见的例子是苦杏仁中的苦杏仁苷（龙胆二糖+苯甲醛+氢氰酸）。在植物组织中，存在一种酶复合物，名为乳糖酶，它与苷类共存，并催化苷类的水解，首先转化为 mandelonitrile 或 p-羟基mandelonitrile，然后转化为苯甲醛或 p-羟基苯甲醛，以及氢氰酸。这些醛被氧化成相应的芳香酸，并以肽结合物的形式排出体外。

...PLANT GLYCOSIDES ARE CHARACTERIZED BY PRODN OF CYANIDE, TOGETHER WITH A SUGAR & AROMATIC ALDEHYDE, ON ENZYMIC OR ACID HYDROLYSIS. COMMON EXAMPLES ARE AMYGDALIN (GENTIOBIOSE + BENZALDEHYDE + HCN) WHICH IS PRESENT IN BITTER ALMONDS... AN ENZYME COMPLEX, EMULSIN, IS PRESENT TOGETHER WITH GLYCOSIDES IN PLANT TISSUES & CATALYZES THE HYDROLYSIS OF GLYCOSIDES, FIRST TO MANDELONITRILE OR P-HYDROXYMANDELONITRILE, & THEN TO BENZALDEHYDE OR P-HYDROXYBENZALDEHYDE, & HCN. ... THE ALDEHYDES ARE OXIDIZED TO CORRESPONDING AROMATIC ACIDS & EXCRETED AS PEPTIDE CONJUGATES.

来源:Hazardous Substances Data Bank (HSDB)

代谢

各种李属植物含有...苦杏仁苷，它可以通过酶类乳化酶水解...在完整的植物中不会发生此类反应；只有在植物组织受损或开始腐烂时，才会开始释放氢氰酸。

...VARIOUS PRUNUS SPECIES CONTAIN...AMYGDALIN, WHICH IS HYDROLYZED BY ENZYME EMULSIN... IN INTACT PLANT NO SUCH ACTION TAKES PLACE; IT IS NOT UNTIL PLANT TISSUE IS DAMAGED OR STARTS TO DECAY THAT LIBERATION OF HCN BEGINS.

来源:Hazardous Substances Data Bank (HSDB)

代谢

糖苷的分解在瘤胃中通常比单胃动物的消化道更容易或更快发生。此外，小分子可以在瘤胃中被吸收，从而迅速进入血液循环。来自蔷薇科成员的氰苷糖苷，如苦杏仁苷的分解就是一个例子。

BREAKDOWN /OF GLYCOSIDES/ OFTEN OCCURS MORE READILY OR MORE RAPIDLY IN RUMEN THAN IN DIGESTIVE TRACT OF MONOGASTRIC ANIMALS. ALSO, SMALL MOLECULES CAN BE ABSORBED AT THE RUMEN & THUS ENTER CIRCULATION RAPIDLY. BREAKDOWN OF CYANOGENIC GLYCOSIDES, SUCH AS AMYGDALIN, FROM MEMBERS OF ROSE FAMILY...IS AN EXAMPLE.

来源:Hazardous Substances Data Bank (HSDB)

代谢

在蓖麻、曼陀罗、玫瑰、酵母和牛肉中产生普鲁纳斯:铃木H;生物化学与生物物理学年鉴99:476 (1962)。/来自表格/

YIELDS PRUNASIN IN BIDENS, DATURA, ROSE, YEAST, & BEEF: SUZUKI H; ARCHS BIOCHEM BIOPHYS 99: 476 (1962). /FROM TABLE/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

两例苦杏仁苷（杏仁苷）毒性报告，一例为48岁患有淋巴瘤的妇女，另一例为46岁患有大细胞未分化肺癌的男子。这名妇女在每周静脉注射6毫克和每日三次口服500毫克后，出现了发热、不适、头痛、严重腹部绞痛、弥漫性斑疹样红斑皮疹、淋巴结病和肝脾肿大。这名男子在每日口服500毫克杏仁苷后，出现了双下肢和上肢进行性神经肌肉无力。两例由口服引起的毒性在停药后得到解决。

TWO CASES OF LAETRILE (AMYGDALIN) TOXICITY WERE REPORTED IN A 48-YR-OLD WOMAN WITH LYMPHOMA & A 46-YR-OLD MAN WITH A LARGE CELL ANAPLASTIC CARCINOMA OF THE LUNG. THE WOMAN EXHIBITED FEVER, MALAISE, HEADACHE, SEVERE ABDOMINAL CRAMPS, A DIFFUSE MACULAR ERYTHEMATOUS RASH, LYMPHADENOPATHY & HEPATOSPLENOMEGALY FOLLOWING A WEEKLY 6 MG IV INJECTION & 5OO MG 3 TIMES DAILY ORALLY. THE MAN PRESENTED WITH PROGRESSIVE NEUROMUSCULAR WEAKNESS OF BOTH LOWER & UPPER EXTREMITIES FOLLOWING ORAL ADMIN OF 500 MG OF AMYGDALIN DAILY. BOTH CASES OF TOXICITY RESULTING FROM ORAL ADMIN WAS RESOLVED FOLLOWING DISCONTINUATION OF THE DRUG.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

一位57岁的女性乳腺癌患者因摄入致死剂量的苦杏仁苷（杏仁苷）被送往医院。入院时，她的氰化物水平为29.0微克/分升。患者在接受对症治疗后有所改善，并被转移到另一家医院，三天后出院。十二天后，患者无生命迹象被送回急诊科。尸检显示氰化物水平为218微克/分升，并将死因记录为氰化物中毒。

A FATAL LAETRILE (AMYGDALIN) INGESTION BY A 57-YR-OLD FEMALE WITH BREAST CARCINOMA WAS PRESENTED. CYANIDE LEVEL ON ADMISSION TO HOSPITAL WAS 29.0 MCG/DL. THE PT IMPROVED WITH SYMPTOMATIC THERAPY & WAS TRANSFERRED TO ANOTHER HOSPITAL FROM WHICH SHE WAS DISCHARGED 3 DAYS LATER. TWELVE DAYS LATER, THE PT WAS RETURNED TO THE EMERGENCY DEPARTMENT WITH NO SIGN OF LIFE. AN AUTOPSY REVEALED A CYANIDE LEVEL OF 218 MCG/DL & DOCUMENTED THE CAUSE OF DEATH AS CYANIDE POISONING.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

一名48岁的女性在连续9天服用杏仁苷（苦杏仁苷）后，发生了一起严重的氰化物中毒案例，几乎致命。杏仁苷通过静脉、肌肉注射、口服和直肠给药，同时配合了“排毒饮食”。入院时血液中的氰化物水平为116微克/分升。

A NEAR FATAL CASE OF CYANIDE POISONING IS REPORTED IN A 48-YR-OLD WOMAN AFTER A 9 DAY COURSE OF LAETRILE (AMYGDALIN). LAETRILE WAS ADMIN IV, IM, ORALLY, & RECTALLY ALONG WITH A "DETOXIFICATION DIET". BLOOD LEVELS OF CYANIDE ON ADMISSION WERE 116 MUG/DL.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

两起儿童苦杏仁苷中毒事件在食用杏核后发生。第一起事件涉及8名儿童，在大量摄入后2小时表现出典型的苦杏仁苷中毒迹象和症状；其中7名儿童康复，1名儿童死亡。第二起事件涉及16名儿童，他们食用了用杏核制成的糖果。症状和体征与第一组相同，但在摄入后半小时出现，并且非常严重。其中三名儿童死亡。

TWO EPISODES OF CYANIDE POISONING OCCURRED IN CHILDREN AFTER INGESTION OF APRICOT KERNELS. THE 1ST EPISODE INVOLVED 8 CHILDREN WHO EXHIBITED TYPICAL SIGNS & SYMPTOMS OF CYANIDE POISONING 2 HR AFTER INGESTION OF LARGE AMOUNTS; 7 CHILDREN RECOVERED & 1 DIED. THE 2ND EPISODE INVOLVED 16 CHILDREN WHO HAD EATEN SWEETS PREPARED FROM KERNELS. SYMPTOMS & SIGNS WERE THE SAME AS THOSE IN THE 1ST GROUP BUT APPEARED 1/2 HR AFTER INGESTION & WERE VERY SEVERE. THREE OF THE CHILDREN DIED.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 人类毒性摘录

苦杏仁苷是由葡萄糖、苯甲醛和氰化物组成的化学复合物，其中的氰化物可以被释放出来。苦杏仁苷是苦杏仁素的主要成分，这种据称具有抗癌作用的药物也曾导致人类氰化物中毒。

AMYGDALIN IS A CHEMICAL COMBINATION OF GLUCOSE, BENZALDEHYDE, & CYANIDE FROM WHICH THE LATTER CAN BE RELEASED... AMYGDALIN IS THE MAJOR INGREDIENT OF LAETRILE, & THIS ALLEGED ANTICANCER DRUG HAS ALSO BEEN RESPONSIBLE FOR HUMAN CYANIDE POISONING.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

口服苦杏仁苷给小鼠后，苦杏仁苷释放的氰化物的最大浓度在大约1.5-2小时达到，并且与注射KCN（氰化钾）后观察到的值范围相似。评估了消化道各个区域内容物以及肿瘤组织从苦杏仁苷中释放氰化物的能力。胃和上肠的活性较低，而小肠和粪便则释放了大量氰化物。小鼠之间的差异很大。

THE MAX CYANIDE LEVEL AFTER ORAL ADMIN OF AMYGDALIN TO MICE WAS REACHED AT ABOUT 1 1/2-2 HR & WAS WITHIN THE RANGE OF VALUES SEEN AFTER KCN ADMIN. THE ABILITY OF THE CONTENTS OF VARIOUS REGIONS OF THE GI TRACT & OF TUMOR TISSUE TO RELEASE CYANIDE FROM AMYGDALIN WAS ASSESSED. THE STOMACH & UPPER INTESTINE HAD LITTLE ACTIVITY WHILE THE LOWER INTESTINE & FECES RELEASED LARGE AMOUNTS. THERE WAS A LARGE VARIATION BETWEEN MICE.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险等级：
  6.1(b)
• 危险品标志：
  Xn
• 安全说明：
  S26,S36/37/39,S45
• 危险类别码：
  R22
• WGK Germany：
  3
• 海关编码：
  29389090
• 危险品运输编号：
  2811
• 危险类别：
  6.1(b)
• RTECS号：
  OO8450000
• 包装等级：
  III
• 危险性防范说明：
  P280,P305+P351+P338
• 危险性描述：
  H302

制备方法与用途

苦杏仁苷简介

苦杏仁中含有一种β-生氰的糖苷，分子中含有氰基(CN)。食用后，该化合物会释放自由的氰基，导致中毒现象；它实际上是苦杏仁中苯丙氨酸代谢的一种产物。

来源

苦杏仁苷（Amygdalin）又名苦杏仁苷，是一种在许多植物中发现的有毒氰苷，尤其以杏、苦杏仁、苹果、桃及梅子等植物种子中最为突出。此外，该物质还存在于其他李属植物如杏和黑樱桃，以及枇杷的叶、果和核里。

配糖物

许多植物根部的细胞含有配糖物，在水解后会产生有毒物质，导致细胞死亡。以桃根中的扁桃苷为例，它是一种氰化糖苷，在水解作用下会产生氢氰酸（HCN）和苯甲醛两种毒素。穿刺短体线虫能够促使这种化学反应发生。

功效与作用

杏仁含有3%的苦杏仁甙。经酶分解后产生氢氰酸，虽然毒性较强但少量使用对呼吸中枢有镇静效果，因此被认为具有一定的镇咳平喘功效，并且具备杀死伤寒杆菌及其他菌类的能力。近年来的研究还发现氢氰酸具有抗癌作用。

化学性质

苦杏仁苷来源于蔷薇科植物东北苦杏仁的干燥成熟种子。

用途

作为一种含葡糖苷的氰化物，它可以作为基质用于鉴别、区分和表征麦芽糖酶、杏仁酪以及β-葡萄糖苷酶等。此外，它还可以用作底物来鉴定、鉴别并表征麦芽糖酶、乳清酶和β-葡萄糖苷酶等多种酶。

类别

有毒物品

毒性分级

高毒

急性毒性

口服 - 大鼠LD50: 522毫克/公斤；口服 - 小鼠LD50: 443毫克/公斤

可燃性危险特性

可燃；受热会产生有毒氮氧化物烟雾

储运特性

库房通风、低温干燥

灭火剂

干粉、泡沫、砂土、二氧化碳