氰化汞 | 592-04-1

• 分子结构分类: 有机化合物 - 有机盐 - 有机金属盐
• 中文名称: 氰化汞
• 中文别名: 氰化高汞
• 英文名称: mercury(II) cyanide
• 英文别名: mercuric cyanide
• CAS: 592-04-1
• 化学式: C₂HgN₂
• mdl: MFCD00011037
• 分子量: 252.625
• InChiKey: FQGYCXFLEQVDJQ-UHFFFAOYSA-N

物化性质

• 物理描述：
  Mercuric cyanide appears as odorless tetragonal crystals or white powder. Toxic by inhalation (dust, and the hydrogen cyanide from decomposition) and by ingestion. Toxic oxides of nitrogen are produced in fires.
• 颜色/状态：
  Colorless, tetragonal crystals or white powder
• 气味：
  Odorless
• 沸点：
  Decomposes
• 熔点：
  Decomposes at 320 °C
• 溶解度：
  9.3 G SOL IN 100 ML WATER @ 14 °C
• 密度：
  4.00 g/cu cm @ 20 °C
• 分解：
  WHEN HEATED TO DECOMPOSITION IT EMITS VERY TOXIC FUMES OF /MERCURY, NITROGEN OXIDES AND HYDROGEN CYANIDE/.
• 折光率：
  INDEX OF REFRACTION: 1.645
• 稳定性/保质期：
  1. **稳定性**：稳定。 2. **禁配物**：强氧化剂、酸类。 3. **避免接触的条件**：潮湿空气、光照。 4. **聚合危害**：不聚合。

计算性质

• 辛醇/水分配系数(LogP)：
  -0.07
• 重原子数：
  5
• 可旋转键数：
  0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  47.6
• 氢给体数：
  0
• 氢受体数：
  2

ADMET

代谢

氰离子与硫结合形成硫氰酸盐。这种结合是由广泛分布于大多数动物组织/尤其是肝脏/中的硫氰酸酶催化的。硫氰酸酶的机制只能对有限的氰化物进行解毒，例如在正常代谢过程中形成的那些。另一个硫供体是3-巯基丙酮酸。该酶，巯基硫酸转移酶定位于细胞质中。/氰化物/

... CYANIDE ION IS CONJUGATED WITH SULFUR TO FORM THIOCYANATE. ... CONJUGATION IS CATALYZED BY ... RHODANESE WHICH IS WIDELY DISTRIBUTED IN MOST ANIMAL TISSUES ... /LIVER/ PARTICULARLY ACTIVE. ... RHODANESE MECHANISM IS CAPABLE OF DETOXICATING ONLY LIMITED AMT OF CYANIDE, SUCH AS ARE FORMED DURING NORMAL METAB. /SRP: ANOTHER SULFUR DONOR IS 3-MERCAPTOPYRUVATE. THE ENZYME, MERCAPTOSULFUR TRANSFERASE IS LOCALIZED IN CYTOSOL./ /CYANIDE/

来源:Hazardous Substances Data Bank (HSDB)

代谢

氰化物从体内移除的主要机制之一是其通过线粒体酶rhodanese（转硫酶）进行酶促转化，生成相对毒性较低的超氰酸盐。

/ONE OF/ THE MAJOR MECHANISM/S/ FOR REMOVING CYANIDE FROM THE BODY IS ITS ENZYMATIC CONVERSION, BY THE MITOCHONDRIAL ENZYME RHODANESE (TRANSSULFURASE), TO THIOCYANATE, WHICH IS RELATIVELY ... /LESS TOXIC/. /CYANIDE/

来源:Hazardous Substances Data Bank (HSDB)

代谢

汞主要通过摄入和吸入被吸收，然后通过血液流布全身，其中一部分会与血红蛋白上的巯基团结合。汞可以经过氧化变成汞离子，这一过程通过过氧化氢酶-过氧化氢途径进行。汞原子能够扩散到过氧化氢酶酶隙中，到达含有血红素环的活性位点。由于过氧化氢酶-过氧化氢途径普遍存在，氧化过程很可能发生在所有组织中。氧化后，汞倾向于在肾脏中积累。汞主要通过呼气和粪便排出体外。氰化物通过口服、吸入和皮肤途径迅速被吸收并在全身分布。氰化物主要通过罗丹酶或3-巯基丙酸硫转移酶代谢成硫氰化物。氰化物的代谢物通过尿液排出体外。(A6, L7, L96)

Mercury is absorbed mainly via ingestion and inhalation, then distributed throughout the body via the bloodstream, where a portion binds to sulfhydryl groups on haemoglobin. Mercury can undergo oxidation to mercuric mercury, which takes place via the catalase-hydrogen peroxide pathway. The mercury atom is able to diffuse down the cleft in the catalase enzyme to reach the active site where the heme ring is located. Oxidation most likely occurs in all tissue, as the catalase hydrogen peroxide pathway is ubiquitous. Following oxidation, mercury tends to accumulate in the kidneys. Mercury is excreted mainly by exhalation and in the faeces. Cyanide is rapidly alsorbed through oral, inhalation, and dermal routes and distributed throughout the body. Cyanide is mainly metabolized into thiocyanate by either rhodanese or 3-mercaptopyruvate sulfur transferase. Cyanide metabolites are excreted in the urine. (A6, L7, L96)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

汞离子与蛋白质的巯基或硫醇基团的高亲和力结合被认为是汞活性的主要机制。通过改变细胞内巯基状态，汞可以促进氧化应激、脂质过氧化、线粒体功能障碍和血红素代谢的改变。已知汞能与微囊和线粒体酶结合，导致细胞损伤和死亡。例如，汞可以抑制水通道蛋白，阻止细胞膜上的水流。它还抑制LCK蛋白，导致T细胞信号传导减少和免疫系统抑制。汞还被认为是通过作用于突触后神经元的膜来抑制神经兴奋性。它还通过抑制蛋白激酶C和碱性磷酸酶来影响神经系统，这会损害脑微血管的形成和功能，以及改变血脑屏障。汞还能产生自身免疫反应，可能是通过修饰主要组织相容性复合物（MHC）II类分子、自身肽、T细胞受体或细胞表面粘附分子。有机腈在体内和体外都会分解成氰化物离子。因此，有机腈的主要毒性机制是它们产生有毒的氰化物离子或氢氰酸。氰化物是电子传递链第四个复合体（存在于真核细胞线粒体膜中）的细胞色素c氧化酶的抑制剂。它与这种酶中的铁原子结合。氰化物与这种细胞色素的结合阻止了电子从细胞色素c氧化酶传递到氧气。结果，电子传递链被中断，细胞无法再通过有氧呼吸产生ATP能量。主要依赖有氧呼吸的组织，如中枢神经系统和心脏，受到特别影响。氰化物还通过结合过氧化氢酶、谷胱甘肽过氧化物酶、高铁血红蛋白、羟钴胺素、磷酸酶、酪氨酸酶、抗坏血酸氧化酶、黄嘌呤氧化酶、琥珀酸脱氢酶和Cu/Zn超氧化物歧化酶来产生一些毒性效应。氰化物与高铁血红蛋白中的铁离子结合形成无活性的氰化高铁血红蛋白。（L7, A8, A25, A26, L97）

High-affinity binding of the divalent mercuric ion to thiol or sulfhydryl groups of proteins is believed to be the major mechanism for the activity of mercury. Through alterations in intracellular thiol status, mercury can promote oxidative stress, lipid peroxidation, mitochondrial dysfunction, and changes in heme metabolism. Mercury is known to bind to microsomal and mitochondrial enzymes, resulting in cell injury and death. For example, mercury is known to inhibit aquaporins, halting water flow across the cell membrane. It also inhibits the protein LCK, which causes decreased T-cell signalling and immune system depression. Mercury is also believed to inhibit neuronal excitability by acting on the postsynaptic neuronal membrane. It also affects the nervous system by inhibiting protein kinase C and alkaline phosphatase, which impairs brain microvascular formation and function, as well as alters the blood-brain barrier. Mercury also produces an autoimmune response, likely by modification of major histocompatibility complex (MHC) class II molecules, self peptides, T-cell receptors, or cell-surface adhesion molecules.Organic nitriles decompose into cyanide ions both in vivo and in vitro. Consequently the primary mechanism of toxicity for organic nitriles is their production of toxic cyanide ions or hydrogen cyanide. Cyanide is an inhibitor of cytochrome c oxidase in the fourth complex of the electron transport chain (found in the membrane of the mitochondria of eukaryotic cells). It complexes with the ferric iron atom in this enzyme. The binding of cyanide to this cytochrome prevents transport of electrons from cytochrome c oxidase to oxygen. As a result, the electron transport chain is disrupted and the cell can no longer aerobically produce ATP for energy. Tissues that mainly depend on aerobic respiration, such as the central nervous system and the heart, are particularly affected. Cyanide is also known produce some of its toxic effects by binding to catalase, glutathione peroxidase, methemoglobin, hydroxocobalamin, phosphatase, tyrosinase, ascorbic acid oxidase, xanthine oxidase, succinic dehydrogenase, and Cu/Zn superoxide dismutase. Cyanide binds to the ferric ion of methemoglobin to form inactive cyanmethemoglobin. (L7, A8, A25, A26, L97)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

A4：无法归类为人类致癌物。/汞，元素和无机形态，作为汞/

A4: Not classifiable as a human carcinogen. /Mercury, elemental and inorganic forms, as Hg/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌物分类

对人类无致癌性（未列入国际癌症研究机构IARC清单）。

No indication of carcinogenicity to humans (not listed by IARC).

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 健康影响

水银主要影响神经系统。长期暴露在高水平的金属汞、无机汞或有机汞中，可能会永久性地损害大脑、肾脏和发育中的胎儿。对大脑功能的影响可能导致易怒、害羞、震颤、视力或听力改变以及记忆问题。儿童的水俣病是一种由汞中毒引起的疾病，其特点是手和脚疼痛和粉红色色素沉着。汞中毒还可能引起亨特-拉塞尔综合症和米纳特病。短时间内接触高水平的氰化物会损害大脑和心脏，甚至可能导致昏迷、癫痫、呼吸暂停、心脏骤停和死亡。长期吸入氰化物会导致呼吸困难、胸痛、呕吐、血细胞变化、头痛和甲状腺肿大。皮肤接触氰化物盐可能会引起刺激和产生溃疡。

Mercury mainly affects the nervous system. Exposure to high levels of metallic, inorganic, or organic mercury can permanently damage the brain, kidneys, and developing fetus. Effects on brain functioning may result in irritability, shyness, tremors, changes in vision or hearing, and memory problems. Acrodynia, a type of mercury poisoning in children, is characterized by pain and pink discoloration of the hands and feet. Mercury poisoning can also cause Hunter-Russell syndrome and Minamata disease. Exposure to high levels of cyanide for a short time harms the brain and heart and can even cause coma, seizures, apnea, cardiac arrest and death. Chronic inhalation of cyanide causes breathing difficulties, chest pain, vomiting, blood changes, headaches, and enlargement of the thyroid gland. Skin contact with cyanide salts can irritate and produce sores. (L7, L96, L97)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L7）；吸入（L7）；皮肤给药（L7）

Oral (L7) ; inhalation (L7); dermal (L7)

来源:Toxin and Toxin Target Database (T3DB)

吸收、分配和排泄

氰化物离子在口服或肠道外给药后容易被吸收。长时间接触氰化物溶液或氢氰酸可能导致通过皮肤吸收有毒量的氰化物...部分吸收的氰化物会通过肺部以原形排出。更大的一部分...通过...硫转移酶转化为相对无毒的硫氰酸盐离子。/氰化物/

CYANIDE ION IS READILY ABSORBED AFTER ORAL OR PARENTERAL ADMIN. PROLONGED LOCAL CONTACT WITH CYANIDE SOLN OR WITH HYDROGEN CYANIDE MAY RESULT IN ABSORPTION OF TOXIC AMT THROUGH SKIN. ... PART OF ABSORBED CYANIDE IS EXCRETED UNCHANGED BY THE LUNG. LARGER PORTION ... CONVERTED BY ... SULFURTRANSFERASE TO RELATIVELY NONTOXIC THIOCYANATE ION. /CYANIDE/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在30天内，给小鼠注射的碳-14标记氰化物中，有72%通过尿液和粪便排出，25%通过呼出的空气排出，3%被保留……呼出的空气中的排出高峰发生在10分钟内，而尿液和粪便中的排出高峰发生在6-24小时内。/氰化物/

IN 30 DAYS, 72% OF (14)C FROM IP DOSE OF (14)C-CYANIDE TO MICE WAS EXCRETED IN URINE & FECES, 25% IN EXPIRED AIR, & 3% WAS RETAINED ... PEAK EXCRETION OCCURRED WITHIN 10 MIN IN EXPIRED AIR & WITHIN 6-24 HR IN URINE & FECES. /CYANIDE/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

氰化物会迅速从皮肤和所有粘膜表面被吸收，并且在吸入时最为危险，因为有毒的量会通过支气管粘膜和肺泡被吸收。

CYANIDES ARE RAPIDLY ABSORBED FROM SKIN & ALL MUCOSAL SURFACES & ARE MOST DANGEROUS WHEN INHALED, BECAUSE TOXIC AMT ARE ABSORBED THROUGH BRONCHIAL MUCOSA & ALVEOLI. /CYANIDES/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

氰化物通过血液分布到所有器官和组织，其在红细胞中的浓度比血浆中的浓度高出两到三倍。据推测，红细胞中氰化物的积累反映了它与变性血红蛋白的结合。/氰化物/

Cyanide is distributed to all organs and tissues via the blood, where its concn in red cells is greater than that in plasma by a factor of two or three. Presumably, the accumulation of cyanide in erythrocytes is a reflection of its binding to methemoglobin. /Cyanides/

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 海关编码：
  2837199090
• 储存条件：
  储存注意事项：应储存在阴凉、通风良好的专用库房内，并实行“双人收发、双人保管”制度。远离火种和热源，避免光照，包装需密封。应与氧化剂、酸类及食用化学品分开存放，严禁混合存储。储区应备有适当的材料以处理泄漏物。

SDS

Name:	Mercury(II) cyanide, 99% Material Safety Data Sheet
Synonym:	Mercuric cyanide.
CAS:	592-04-1

Section 1 - Chemical Product MSDS Name: Mercury(II) cyanide, 99% Material Safety Data Sheet
Synonym: Mercuric cyanide.

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SECTION 2 - COMPOSITION, INFORMATION ON INGREDIENTS

CAS#	Chemical Name	content	EINECS#
592-04-1	Mercury(II) cyanide	99	209-741-6

Hazard Symbols: T+
Risk Phrases: 26/27/28 33

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SECTION 3 - HAZARDS IDENTIFICATION EMERGENCY OVERVIEW Very toxic by inhalation, in contact with skin and if swallowed. Danger of cumulative effects.Hygroscopic (absorbs moisture from the air).Light sensitive. Potential Health Effects
Eye:
Exposure to mercury or mercury compounds can cause discoloration on the front surface of the lens, which does not interfere with vision. Causes eye irritation and possible burns.
Skin:
Causes skin irritation and possible burns.
Ingestion:
May be fatal if swallowed. Causes gastrointestinal irritation with nausea, vomiting and diarrhea. Metabolism may release cyanide, which may result in headache, dizziness, weakness, collapse, unconsciousness and possible death. Inorganic mercury compounds may cause central and peripheral nervous system effects.
Inhalation:
Causes respiratory tract irritation with possible burns. Acute exposure to high concentrations of mercury vapors may cause severe respiratory tract irritation.
Chronic:
Chronic ingestion may cause accumulation of mercury in body tissues. Chronic exposure to mercury compounds may produce immunologic glomerular disease. Chronic exposure to cyanide solutions may lead to the development of a "cyanide" rash, characterized by itching, and by macular, papular, and vesicular eruptions, and may be accompanied by secondary infections.

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SECTION 4 - FIRST AID MEASURES
Eyes:
Immediately flush eyes with plenty of water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical aid immediately.
Skin:
Get medical aid immediately. Immediately flush skin with plenty of water for at least 15 minutes while removing contaminated clothing and shoes. Wash clothing before reuse.
Ingestion:
If victim is conscious and alert, give 2-4 cupfuls of milk or water. Never give anything by mouth to an unconscious person. Get medical aid immediately.
Inhalation:
Get medical aid immediately. Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen.
Notes to Physician:

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SECTION 5 - FIRE FIGHTING MEASURES
General Information:
As in any fire, wear a self-contained breathing apparatus in pressure-demand, MSHA/NIOSH (approved or equivalent), and full protective gear. During a fire, irritating and highly toxic gases may be generated by thermal decomposition or combustion.
Extinguishing Media:
Use agent most appropriate to extinguish fire. Use water spray, dry chemical, carbon dioxide, or appropriate foam.

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SECTION 6 - ACCIDENTAL RELEASE MEASURES
General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Clean up spills immediately, observing precautions in the Protective Equipment section. Sweep up or absorb material, then place into a suitable clean, dry, closed container for disposal. Avoid generating dusty conditions. Provide ventilation.

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SECTION 7 - HANDLING and STORAGE
Handling:
Wash thoroughly after handling. Use only in a well-ventilated area. Avoid contact with eyes, skin, and clothing. Avoid ingestion and inhalation. Store protected from light. Avoid mechanical shock and friction.
Storage:
Store in a cool, dry, well-ventilated area away from incompatible substances. Poison room locked. Keep containers tightly closed. Store protected from light.

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SECTION 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
Engineering Controls:
Use adequate general or local exhaust ventilation to keep airborne concentrations below the permissible exposure limits. Exposure Limits CAS# 592-04-1:
United States OSHA: 5 mg/m3 TWA (listed under Cyanide anion).0.1 mg/m3 Ceiling (listed under Mercury, aryl and inorganic compound Belgium - TWA: (listed as mercury inorganic compounds): 0.025 mg/ VLE (as Hg) France - VME: (listed as mercury inorganic compounds): 0.1 mg/m3 (as Hg)
Germany: (listed as mercury inorganic compounds): 0.1 mg/m3 VME ( Hg)
Germany: (listed as mercury inorganic compounds): Skin absorber
Malaysia: (listed as mercury, aryl and inorganic compounds): 0.1 mg/m3 TWA (as Hg)
Netherlands: (listed as mercury inorganic compounds): 0.15 mg/m3
Netherlands: (listed as mercury inorganic compounds): 0.05 mg/m3
Russia: (listed as mercury inorganic compounds): 0.2 mg/m3 TWA (a Hg)
Russia: (listed as mercury inorganic compounds): 0.05 mg/m3 STEL Hg)
Spain: (listed as mercury inorganic compounds): 0.025 mg/m3 VLA-E (as Hg) Personal Protective Equipment
Eyes:
Wear appropriate protective eyeglasses or chemical safety goggles as described by OSHA's eye and face protection regulations in 29 CFR 1910.133 or European Standard EN166.
Skin:
Wear appropriate protective gloves to prevent skin exposure.
Clothing:
Wear appropriate protective clothing to prevent skin exposure.
Respirators:
Follow the OSHA respirator regulations found in 29 CFR 1910.134 or European Standard EN 149. Use a NIOSH/MSHA or European Standard EN 149 approved respirator if exposure limits are exceeded or if irritation or other symptoms are experienced.

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SECTION 9 - PHYSICAL AND CHEMICAL PROPERTIES
Physical State: Crystals
Color: white
Odor: odorless
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: Not available.
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: 320 deg C ( 608.00 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature: 320 deg C
Solubility in water: Soluble.
Specific Gravity/Density: 3.996
Molecular Formula: C2HgN2
Molecular Weight: 252.63

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SECTION 10 - STABILITY AND REACTIVITY
Chemical Stability:
Stable under normal temperatures and pressures. Friction and impact sensitive explosive.
Conditions to Avoid:
Incompatible materials, light, friction.
Incompatibilities with Other Materials:
Strong oxidizing agents, acids.
Hazardous Decomposition Products:
Hydrogen cyanide, nitrogen oxides, carbon monoxide, carbon dioxide, mercury/mercury oxides.
Hazardous Polymerization: Has not been reported.

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SECTION 11 - TOXICOLOGICAL INFORMATION RTECS#: CAS# 592-04-1: OW1515000
LD50/LC50:
CAS# 592-04-1: Oral, mouse: LD50 = 33 mg/kg; Oral, rat: LD50 = 26 mg/kg.
Carcinogenicity:
Mercury(II) cyanide - Not listed by ACGIH, IARC, or NTP.
Other:
See actual entry in RTECS for complete information.

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SECTION 12 - ECOLOGICAL INFORMATION

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SECTION 13 - DISPOSAL CONSIDERATIONS Dispose of in a manner consistent with federal, state, and local regulations.

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SECTION 14 - TRANSPORT INFORMATION IATA
Shipping Name: MERCURY CYANIDE
Hazard Class: 6.1
UN Number: 1636
Packing Group: II IMO
Shipping Name: MERCURY CYANIDE
Hazard Class: 6.1
UN Number: 1636
Packing Group: II RID/ADR
Shipping Name: MERCURIC CYANIDE
Hazard Class: 6.1
UN Number: 1636
Packing group: II
USA RQ: CAS# 592-04-1: 1 lb final RQ; 0.454 kg final RQ

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SECTION 15 - REGULATORY INFORMATION European/International Regulations European Labeling in Accordance with EC Directives
Hazard Symbols: T+
Risk Phrases:
R 26/27/28 Very toxic by inhalation, in contact with skin and if swallowed. R 33 Danger of cumulative effects.
Safety Phrases:
S 13 Keep away from food, drink and animal feeding stuffs. S 28A After contact with skin, wash immediately with plenty of water. S 36 Wear suitable protective clothing. S 45 In case of accident or if you feel unwell, seek medical advice immediately (show the label where possible). WGK (Water Danger/Protection) CAS# 592-04-1: 3 Canada CAS# 592-04-1 is listed on Canada's NDSL List. CAS# 592-04-1 is listed on Canada's Ingredient Disclosure List. US FEDERAL TSCA CAS# 592-04-1 is listed on the TSCA inventory.

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SECTION 16 - ADDITIONAL INFORMATION
MSDS Creation Date: 7/16/1998 Revision #3 Date: 1/18/2005 The information above is believed to be accurate and represents the best information currently available to us. However, we make no warranty of merchantability or any other warranty, express or implied, with respect to such information, and we assume no liability resulting from its use. Users should make their own investigations to determine the suitability of the information for their particular purposes. In no way shall the company be liable for any claims, losses, or damages of any third party or for lost profits or any special, indirect, incidental, consequential or exemplary damages, howsoever arising, even if the company has been advised of the possibility of such damages.

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

合成制备方法：将1份质量的HgO和1份质量的普鲁士蓝溶入10份水中，在水浴上加热数小时。滤除沉淀后，蒸发溶液，即可得到晶体。

用途：该物质可用于医药、杀菌皂、照相以及作为分析试剂。[15]

反应信息

• 作为反应物：
  描述：

  氰化汞 在 六氯乙硅烷 作用下， 生成 三氯硅烷甲腈
  参考文献：
  名称：

  PREPARATION AND SOME PROPERTIES OF TRICHLOROCYANOSILANE¹

  摘要：

  DOI：

  10.1021/ja01524a078
• 作为产物：
  描述：

  氢氰酸 在 mercury dichloride 作用下， 以 水 为溶剂， 以>99的产率得到氰化汞
  参考文献：
  名称：

  Berthelot, Comptes Rendus Hebdomadaires des Seances de l'Academie des Sciences, 1873, vol. 77, p. 388 - 392

  摘要：

  DOI：
• 作为试剂：
  描述：

  ω-methoxycarbonyloctyl 2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside 在 calcium sulfate 、 4 A molecular sieve 、 sodium methylate 、 氰化汞 作用下， 以 甲醇 、 硝基甲烷 、 二氯甲烷 、 甲苯 为溶剂， 反应 22.0h， 生成 8-methoxycarbonyloctyl 3,4,6-tri-O-benzyl-β-D-galactopyranosyl-(1->3)-2-acetamido-4,6-O-benzylidene-2-deoxy-β-D-glucopyranoside
  参考文献：
  名称：

  Recognition of β-d-Gal p-(1 → 3)-β-d-Glc pNAc-OR acceptor analogues by the Lewis α-(1 → 34)-fucosyltransferase from human milk

  摘要：

  The Lewis alpha-(1 --> 3/4)-frucosyltransferase (E.C. 2.4.1.65) transfers L-fucose from GDP-fucose to OH-4 of the Glc pNAc residue in the disaccharide beta-D-Gal p-(1 --> 3)-beta-D-Glc pNAc-OR [R = (CH2)(8)COOMe] (1) to give the Lewis-A blood group determinant beta-D-Gal p-(1 --> 3)-[alpha-L-Fuc p-(1 --> 4)]-beta-D-Glc pNAc-OR. Five deoxy analogues of 1, as well as its N-propionyl derivative, were chemically synthesized and kinetically evaluated as both substrates and inhibitors for the enzyme from human milk. The unmodified acceptor 1 had K-m = 640 mu M with V-max set arbitrarily to 100. The 6-deoxy (K-m = 400 mu M, V-max = 90) and N-propionyl compounds (K-m = 330 mu M, V-max = 170) remained excellent substrates while the 4-deoxy compound was a very weak competitive inhibitor with K-i = 9 mM. Deoxygenation of OH-2' and OH-4' (of the Gal residue) in 1 had little effect on the activity. The OH-6 group of the Gal residue proved to be critical for recognition by the enzyme since substitution of this group with hydrogen led to an inactive compound. (C) 1996 Elsevier Science Ltd.

  DOI：

  10.1016/0008-6215(96)00047-x

文献信息

• Notes. Complexes containing mercury–molybdenum bonds: new compounds of the type [HgX{trans-Mo(CO)₂L(η⁵-C₅H₅)}](L = arsine or phosphine). Crystal and molecular structure of the complex [Hg(CN){trans-Mo(CO)₂(AsMe₂Ph)(η⁵-C₅H₅)}]
  作者：Geoffrey Salem、Brian W. Skelton、Allan H. White、Stanley Bruce Wild

  DOI：10.1039/dt9830002117

  日期：——

  SCN, or S2CNEt2). The molecular structure of the complex [Hg(CN)trans-Mo(CO)2(AsMe2Ph)(η5-C5H5)}] has been determined by single-crystal X-ray analysis. The crystals are monoclinic, space group P21/c, with a= 14.570(4), b= 12.457(3), c= 10.783(3)Å, β= 114.04(2)°, and Z= 4. The structure was solved by heavy-atom methods and refined by least squares to a residual of 0.037 for 2 218 reflections with |I0|

  该系列汞钼结合复合物的[汞柱（CN）反式-Mo（CO）2 L（η 5 -C 5 H ^ 5）}]（其中L = ASME 2 PH，PME 2 PH，PMePh 2，或PPH 3）已经从汞柱（CN）制备2及其盐的Na [沫（CO）2 L（η 5 -C 5 H ^ 5）]或二聚物[汞柱反式-Mo（CO）2 L（η 5 -C 5 H 5）} 2]。氰基汞络合物是轻松合成衍生物[HgX 反式-Mo（CO）2 L（η 5 -C 5 H ^ 5）}]（其中X =氯，溴，I，NO 3，O- 2 CME，OCN，SCN，或S 2 CNET 2）。该配合物的分子结构[汞柱（CN）反式-Mo（CO）2（ASME 2 PH）（η 5 -C 5 H ^ 5）}]已由单晶确定X射线分析。晶体是单斜晶体，空间群P 2 1 / c，其中a = 14.570（4），b = 12.457（3），c= 10.783（3）Å，β=
• Studies on transition-metal cyano-complexes. Part 4. Cyanide hydride complexes of Groups 6A and 8
  作者：M. Jane Mockford、William P. Griffith

  DOI：10.1039/dt9850000717

  日期：——

  The new complex K4[MoH(CN)7]·2H2O and its characterisation by 1H, 13C n.m.r. and vibrational spectra are reported. Vibrational and n.m.r. data are also presented for [MH(CN)5]3–(M = Rh or Ir). Attempts to prepare other cyanide hydride species are discussed. Reactions of the above species with small molecules and unsaturated hydrocarbons are reported.

  报道了新的络合物K 4 [MoH（CN）7 ]·2H 2 O以及通过1 H，13 C nmr和振动光谱表征的特征。还提供了[MH（CN）5 ] 3–（M = Rh或Ir）的振动和nmr数据。讨论了制备其他氰化物氢化物的尝试。报道了上述物质与小分子和不饱和烃的反应。
• Metal polypyrazolylborates
  作者：G Gioia Lobbia、C Santini、F Giordano、P Cecchi、K Coacci

  DOI：10.1016/s0022-328x(97)00485-3

  日期：1998.2

  X-ray crystal structure of the complex Et–Hg·TpPh2, which is here reported, represents the first case in which the Hg (bonded to an organic R-group and a tripodal N-donor ligand) is tetrahedrally coordinated (with some distortions), instead of being T-shaped. The compound is orthorhombic, space group P 212121 with a=12.966(3) Å, b=16.940(3) Å, and c=18.412(4) Å; V=4044(1) Å3; Z=4; R(Rw)=0.056(0.057).

  R–Hg +离子（R = Me，Et，Pr，i -Pr，Ph，p- Tol，苄基，5-Me-噻吩基或二茂铁基）配合物Tp Ph 2（hydrtritris（ 3,5-二苯基-1- ħ吡唑-1-基）borato）或TP 4BR（氢化三（4-溴-1- ħ吡唑-1-基）borato）这里报告。通过1 H，13 C和199 Hg NMR光谱的比较显示，配体Tp Ph 2比Tp 4Br更好。Et–Hg·Tp Ph 2复合物的X射线晶体结构此处报道的，是第一种情况，其中Hg（结合到有机R-基团和三脚架N-供体配体上）四面体配位（有些变形），而不是T形。该化合物是正交晶体，空间群P 2 1 2 1 2 1 1，其中a = 12.966（3）Å，b = 16.940（3）Å，c = 18.412（4）Å；V = 4044（1）埃3 ; Z = 4；R（R w）= 0.056（0.057）。
• Bis-cyclopentadienyl molybdenum and tungsten compounds with mercury-transition metalmercury bonds. Part I. Chemical, spectroscopic and structural studies of halogeno- and thiolato-derivatives
  作者：M.M Kubicki、R Kergoat、J.E Guerchais、C Bois、P L'Haridon

  DOI：10.1016/s0020-1693(00)90499-7

  日期：1980.1

  Cp 2 MH 2 (M = Mo and W) react with HgX 2 (X = Cl, Br, I, SCN, OAc and CN) salts, giving insoluble compounds which have the general formula Cp 2 M(HgX) 2 ·xHgX 2 (I) (x = 0, 1 3 , 1 2 , 2 3 and 1). These compounds were characterized by using IR and, for some of them, Raman spectroscopy. Frequencies of Hg-X vibrations are discussed in the light of an ‘adduct type’ structure. MoHg and WHg bands are

  摘要Cp 2 MH 2（M = Mo和W）与HgX 2（X = Cl，Br，I，SCN，OAc和CN）盐反应，得到通式为Cp 2 M（HgX）2·xHgX的不溶化合物2（I）（x = 0、1 3，1 2，2 3和1）。这些化合物的特征是使用红外光谱仪（对于其中一些光谱仪采用拉曼光谱法）。Hg-X振动的频率根据“加合物类型”结构进行了讨论。在130-140 cm -1附近的Ramam光谱中检测到MoHg和WHg谱带。分离出中间体聚合化合物（Cp 2 MoHg）n（II），并通过红外光谱和晶胞参数进行表征。所有化合物（I）和（II）与硫醇盐反应生成非加合物：i）化合物Cp 2 M（HgSR）2（R = Me，Et，i Pr和n Pr）（III）可溶于有机溶剂和ii）不溶性化合物[Cp 2 MHg 2（SR）] X（X = Cl，Br）（IV）。X ＝ Cl的化合物（IV）也从（III）的氯
• Slow complexation rates of crown ethers: what's taking so long?
  作者：Julius. Rebek、S. V. Luis、L. R. Marshall

  DOI：10.1021/ja00276a054

  日期：1986.8

  /Ma In the latter, octahedral Pt(IV) complex the formerly trans orientation of the carbon ligands has changed to a cis arrangement. IH NMR studies have revealed that the flat p-tolyl group is fixed in a position perpendicularly to the N-Pt-N axis. The mechanistic aspects of oxidative addition reactions of X2 and alkyl and aryl iodides to PtX(NCN) complexes are currently investigated.

  /Ma 在后者中，八面体 Pt(IV) 络合物之前的碳配体的反式取向已变为顺式排列。1H NMR 研究表明，平坦的对甲苯基固定在垂直于 N-Pt-N 轴的位置。目前正在研究 X2 和烷基碘和芳基碘与 PtX(NCN) 配合物的氧化加成反应的机理。