tricalcium;diarsorate | 7778-44-1

• 物质功能分类: 有机原料 - 羧酸类化合物及衍生物
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 碱土金属氧阴离子化合物
• 英文名称: tricalcium;diarsorate
• 英文别名: Calcium arsenate
• CAS: 7778-44-1；10103-62-5
• 化学式: As₂Ca₃O₈
• 分子量: 398.07
• InChiKey: RMBBSOLAGVEUSI-UHFFFAOYSA-H

物化性质

• 熔点：
  1455℃ [CRC10]
• 密度：
  3,62 g/cm3
• 溶解度：
  溶于稀酸溶液
• 暴露限值：
  ACGIH: TWA 0.01 mg/m3NIOSH: IDLH 5 mg/m3; Ceiling 0.002 mg/m3
• 物理描述：
  Calcium arsenate is a white powder. Slightly soluble in water. Toxic by inhalation and ingestion. Used as an insecticide and germicide.
• 颜色/状态：
  White powder
• 气味：
  Odorless
• 沸点：
  Decomposes (NIOSH, 2016)
• 蒸汽压力：
  0 mm Hg @ 20 °C (approx)
• 稳定性/保质期：

  Moisture and carbon dioxide cause slow decomp to calcium carbonate and (phytotoxic) dicalcium hydrogen arsenate. In the presence of acids, water sol, strongly phytotoxic arsenic acid is produced.

• 分解：
  WHEN HEATED TO DECOMP IT EMITS TOXIC FUMES OF ARSENIC.
• 腐蚀性：
  Slight corrosive action on metals

计算性质

• 辛醇/水分配系数(LogP)：
  -9.28
• 重原子数：
  13
• 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：
  173
• 氢给体数：
  0
• 氢受体数：
  8

ADMET

代谢

砷主要通过吸入或摄入进入人体，其次是皮肤接触。进入人体后，砷会在全身分布，根据需要被还原成亚砷酸盐，然后通过亚砷酸盐甲基转移酶被甲基化成单甲基砷（MMA）和二甲基硅酸（DMA）。砷及其代谢物主要通过尿液排出体外。已知砷能诱导金属结合蛋白金属硫蛋白，通过绑定砷和其他金属并使其生物活性失效，以及作为抗氧化剂的作用，从而减少砷和其他金属的毒性效应。

Arsenic is absorbed mainly by inhalation or ingestion, as to a lesser extent, dermal exposure. It is then distributed throughout the body, where it is reduced into arsenite if necessary, then methylated into monomethylarsenic (MMA) and dimethylarsenic acid (DMA) by arsenite methyltransferase. Arsenic and its metabolites are primarily excreted in the urine. Arsenic is known to induce the metal-binding protein metallothionein, which decreases the toxic effects of arsenic and other metals by binding them and making them biologically inactive, as well as acting as an antioxidant. (L20)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

砒霜及其代谢物通过多种机制干扰ATP的产生。在柠檬酸循环层面，砒霜抑制了丙酮酸脱氢酶，并通过与磷酸竞争解耦了氧化磷酸化，从而抑制了与能量相关的NAD+还原、线粒体呼吸和ATP合成。过氧化氢的产生也增加了，这可能会形成活性氧物种和氧化应激。砒霜的致癌性受到砒霜与微管蛋白结合的影响，导致非整倍体、多倍体和有丝分裂停滞。其他砒霜蛋白靶点的结合也可能导致DNA修复酶活性改变、DNA甲基化模式改变和细胞增殖。

Arsenic and its metabolites disrupt ATP production through several mechanisms. At the level of the citric acid cycle, arsenic inhibits pyruvate dehydrogenase and by competing with phosphate it uncouples oxidative phosphorylation, thus inhibiting energy-linked reduction of NAD+, mitochondrial respiration, and ATP synthesis. Hydrogen peroxide production is also increased, which might form reactive oxygen species and oxidative stress. Arsenic's carginogenicity is influenced by the arsenical binding of tubulin, which results in aneuploidy, polyploidy and mitotic arrests. The binding of other arsenic protein targets may also cause altered DNA repair enzyme activity, altered DNA methylation patterns and cell proliferation. (T1, A17)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌性证据

致癌性分类：1）人类证据：充分；2）动物证据：有限。对人类致癌风险的总体评估为第1组：对人类致癌。注意：此评估适用于整个化学物质组，而不一定适用于组内所有单个化学物质。/砷和砷化合物/

Classification of carcinogenicity: 1) evidence in humans: sufficient; 2) evidence in animals: limited. Overall summary evaluation of carcinogenic risk to humans is Group 1: Carcinogenic to humans. NOTE: This evaluation applies to the group of chemicals as a whole and not necessarily to all individual chemicals within the group. /Arsenic and arsenic compounds/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

分类：A；人类致癌物。分类依据：基于足够的人类数据。在主要通过吸入暴露的多个人类群体中观察到了肺癌死亡率的增加。此外，在饮用富含无机砷的饮用水的人群中，观察到多种内部器官癌症（肝脏、肾脏、肺和膀胱）的死亡率增加，以及皮肤癌发病率的增加。人类致癌性数据：充足。动物致癌性数据：不足。/无机砷/ /基于先前的分类系统/

CLASSIFICATION: A; human carcinogen. BASIS FOR CLASSIFICATION: Based on sufficient evidence from human data. An increased lung cancer mortality was observed in multiple human populations exposed primarily through inhalation. Also, increased mortality from multiple internal organ cancers (liver, kidney, lung, and bladder) and an increased incidence of skin cancer were observed in populations consuming drinking water high in inorganic arsenic. HUMAN CARCINOGENICITY DATA: Sufficient. ANIMAL CARCINOGENICITY DATA: Inadequate. /Inorganic Arsenic/ /Based on former classification system/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

A1：确认的人类致癌物。/砷和无机砷化合物/

A1: Confirmed human carcinogen. /Arsenic and inorganic compounds, as As/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 致癌性证据

评估：有足够的人类证据表明饮用水中的砷可导致膀胱癌、肺癌和皮肤癌...总体评估：饮用水中的砷对人类具有致癌性（第1组）。/饮用水中的砷/

Evaluation: There is sufficient evidence in humans that arsenic in drinking-water causes cancers of the urinary bladder, lung and skin ... Overall evaluation: Arsenic in drinking-water is carcinogenic to humans (Group 1). /Arsenic in drinking-water/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

在给予大鼠215毫克/公斤剂量的钙砷酸作为饮食，持续多达52天的情况下，砷含量最高的部位在肾脏和肝脏（干组织含量为146-537微克/克），而在毛发、大脑、骨骼、肌肉和皮肤中的含量相对较低。与给予砷三氧化物相比，给予钙砷酸后，肝脏和肾脏中的砷含量更高。

FOLLOWING DIETARY ADMIN OF 215 MG/KG OF DIET AS CALCIUM ARSENATE ... FOR UP TO 52 DAYS IN RATS, HIGHEST ARSENIC LEVELS (146-537 UG/G DRY TISSUE) ... IN KIDNEYS & LIVER & RELATIVELY LOWER LEVELS IN HAIR, BRAIN, BONE, MUSCLE, & SKIN. LIVER & KIDNEY LEVELS WERE GREATER AFTER ADMIN OF CALCIUM ARSENATE THAN OF ARSENIC TRIOXIDE.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

仓鼠每周接受气管内滴注...钙砷酸尘悬浮液。每周间隔处死动物，并通过湿法消解和砷化氢生成后的原子吸收光谱法测定肺、肝和毛发中的砷含量。接受钙砷酸盐处理的动物，其肺部砷含量约为接受砒霜处理的动物的100倍，比接受三氧化二砷处理的动物的1000倍。...这些无机砷化合物在肺部保留量的显著差异对于涉及呼吸道的动物致癌性测试的设计和解释具有重要意义，也可能对人类暴露情况有影响。

Hamsters were given weekly intratracheal instillations of ... calcium arsenate dust suspensions. Animals were killed at weekly intervals and the concn of arsenic was determined in lung, liver, and hair by atomic absorption spectrophotometry following wet digestion and arsine generation. Animals treated with calcium arsenate had concn of As in the lung about 100 times higher than that of animals given arsenic trisulfide and 1000 times higher than that of animals receiving arsenic trioxide. ... The substantial differentration in lung retention between these inorganic As cmpd is of importance for the design and interpretation of animal carcinogenicity tests involving the respiratory tract and could also have significance in human exposure situations.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

动物数据显示，在气管内滴注砒霜、亚砷酸钙和三氧化二砷后，肺内保留量有显著差异。砒霜的保留量比三氧化二砷高出10倍。

Animal data have shown substantial differences in lung retention after intratracheal instillations of arsenic trisulfide, calcium arsenate and arsenic trioxide. Retention of ... arsenic trisulfide was 10 times higher compared to arsenic trioxide.

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 职业暴露限值：
  Ceiling: 0.002 mg/m3 [15-minute]
• TSCA：
  Yes
• 危险等级：
  6.1
• 立即威胁生命和健康浓度：
  5 mg As/m3
• 安全说明：
  S45,S53
• 危险类别码：
  R50/53,R45,R23/25
• 包装等级：
  II
• 危险类别：
  6.1
• 危险品运输编号：
  1573

制备方法与用途

水中溶解度(g/100ml)：每100毫升水中的溶解克数为3.629×10⁻³（20℃）

类别 有毒物品

毒性分级 剧毒

急性毒性

• 大鼠口服 LD₅₀: 20 毫克/公斤
• 小鼠口服 LD₅₀: 794 毫克/公斤

可燃性危险特性 不燃；受热分解产生有毒砷化物烟雾

储运特性 应存放在通风、低温和干燥的库房内，并与食品分开存放和运输

灭火剂 可用雾状水或砂土进行灭火

职业标准 时间加权平均容许浓度 (TWA): 0.01 毫克/立方米（砷）

反应信息

• 作为反应物：
  描述：

  tricalcium;diarsorate 在 ammonium molybdate 、 双氧水 、 对甲苯磺酸 作用下， 以 四氢呋喃 、 乙醇 、 水 为溶剂， 反应 20.0h， 以0.246 g的产率得到(苯基)甲基1-苯基-1H-四唑-5-基砜
  参考文献：
  名称：

  用醇一锅制备Julia-Kocienski硫化物和砜

  摘要：

  报道了一种从醇和硫醇单锅制备Julia-Kocienski硫化物和砜的方法。甲磺酸磺酰氯和三乙胺在THF中将各种伯醇转化为相应的甲磺酸酯。反应完成后，加入硫醇（1或10）和NaH或t- BuOK。茱莉亚-Kocienski所硫化物3，9和11分别通过一釜两步过程在76-96％的产率（16个实施例）制备由醇。此外，在硫化物形成后，将反应混合物用对甲苯磺酸中和并用H 2 O 2处理。和在EtOH中的钼酸铵，除反式-2-hexen-1-ol外，均以良好的收率得到Julia-Kocienski砜4。

  DOI：

  10.1016/j.tetlet.2019.151017
• 作为产物：
  描述：

  氢氧化钙 生成 tricalcium;diarsorate
  参考文献：
  名称：

  KUBO, XIROMI;SEHKIYA, TEHTSUO;MATSUGURA, OSAKU

  摘要：

  DOI：

文献信息

• Convenient synthesis of allylic sulfides and application to allylic carbon-carbon bond formation.
  作者：Kanoko TSUBOYAMA、Kazuyoshi TAKEDA、Katsumi TORII、Haruo OGURA

  DOI：10.1248/cpb.38.2357

  日期：——

  Allylic sulfides were synthesized from allylic alcohols 1 using S, S'-bis(1-phenyl-1H-tetrazol-5-yl) dithiocarbonate (2) by means of a single-step reaction. The allylic sulfides were coupled with a Grignard reagent or carbanion in the presence of a catalytic amount of copper(I) bromide or palladium(0).

  阿利基硫化物通过一步反应，由阿利基醇1与S,S'-双(1-苯基-1H-四唑-5-基)二硫代碳酸酯2合成。这些阿利基硫化物在催化量的铜(I)溴化物或钯(0)存在下，与格氏试剂或碳负离子进行偶联反应。
• Single-step preparation of allylic sulfides having 1-phenyltetrazole-5-thio group from allylic alcohols using ,′-BIS(1-phenyl-1-tetrazol-5-YL) dithiocarbonate and reactions involving the allylic sulfides
  作者：Kazuyoshi Takeda、Kanoko Tsuboyama、Katsumi Torii、Maki Murata、Haruo Ogura

  DOI：10.1016/s0040-4039(00)80428-1

  日期：1988.1

  The reaction of allylic alcohols and ,′-bis(1-phenyl-1-tetrazol-5-yl) dithiocarbonate () gave allylic sulfides having 1-phenyltetrazole-5-thio group in a single step. Furthermore, these allylic sulfides could be applied to carbon-carbon bond and carbon-sulfur bond formations by using Grignard reagents or carbanions in the presence of a catalytic amount of copper(I)bromide or palladium (0), respectively

  烯丙醇和的反应，双（1-苯基-1-四唑-5-基）二硫代碳酸酯（），得到具有在一个单一的步骤1苯基四唑基-5-硫代基烯丙基硫化物。此外，在催化量的溴化铜（I）或钯（0）的存在下，分别使用格氏试剂或碳负离子，可以将这些烯丙基硫化物应用于碳-碳键和碳-硫键的形成。
• The influence of α-coordinating groups of aldehydes on <i>E</i>/<i>Z</i>-selectivity and the use of quaternary ammonium counter ions for enhanced <i>E</i>-selectivity in the Julia–Kocienski reaction
  作者：Mintu Rehman、Sravya Surendran、Nagendra Siddavatam、Goreti Rajendar

  DOI：10.1039/d1ob02126e

  日期：——

  Modified reaction conditions for improved E-selectivity of olefins in the Julia–Kocienski reaction of aldehydes having α-coordinating substituents are demonstrated. The chelating groups in aldehydes are expected to stabilize the syn-transition state with metal ions, whereas the weakly coordinating quaternary ammonium ions are devoid of all possible chelating interactions to enhance E-selectivity. A

  证明了在具有 α- 配位取代基的醛的 Julia-Kocienski 反应中改进的烯烃E选择性的改进反应条件。醛中的螯合基团有望稳定与金属离子的顺过渡态，而弱配位的季铵离子没有所有可能的螯合相互作用以增强E选择性。提出了一项系统研究，以研究醛的相邻保护基团的大小及其对 Julia-Kocienski 反应中E / Z选择性的螯合效应。
• Cytostatic tetrazole–butenolide conjugates: linking tetrazole and butenolide rings via stille coupling and biological activity of the target substances
  作者：Vojtěch Balšánek、Lucie Tichotová、Jiří Kuneš、Marcel Špulák、Milan Pour、Ivan Votruba、Vladimír Buchta

  DOI：10.1135/cccc2009040

  日期：——

  A series of tetrazoles linked to the butenolide core via benzene rings were prepared by the Stille coupling reaction of α-(tributylstannyl)butenolides and 5-(alkylsulfanyl)-1-(4-iodophenyl)tetrazoles, and the compounds were tested for antifungal and cytostatic activity. Interesting antifungal activities against the filamentous strain Absidia corymbifera, and cytostatic activities against leukemic cells HL-60 and CCRF-CEM were found. The cytostatic activity requires the presence of both the butenolide ring and the alkylsulfanyl group bound to tetrazole ring. In addition, the feasibility of Pd-coupling reactions with 5-iodotetrazoles was evaluated.

  一系列通过苯环连接到丁烯内酯核心的四唑类化合物，是通过α-(三丁基锡基)丁烯内酯和5-(烷基硫基)-1-(4-碘苯基)四唑的斯蒂尔偶联反应制备的，并且对这些化合物进行了抗真菌和细胞毒活性测试。有趣的抗真菌活性针对丝状菌株Absidia corymbifera，以及对白血病细胞HL-60和CCRF-CEM的细胞毒活性被发现。细胞毒活性需要丁烯内酯环和连接到四唑环的烷基硫基团同时存在。此外，还评估了与5-碘四唑进行Pd偶联反应的可行性。
• Neutral Sulfur Nucleophiles: Synthesis of Thioethers and Thioesters by Substitution Reactions of N-Heterocyclic Carbene Boryl Sulfides and Thioamides
  作者：Xiangcheng Pan、Dennis P. Curran

  DOI：10.1021/ol5010164

  日期：2014.5.16

  Newly discovered boryl sulfides and N-borylthioamides are shown to serve as neutral sources of sulfur nucleophiles in substitutions reactions. For example, heating of diMe-Imd-BH(SPh)2 with benzyl bromides, primary bromides, or acid chlorides provides the corresponding thioethers or thioesters in high yields. Likewise, N-phenyltetrazole thioethers/esters are made from a readily available N-borylthionotetrazole

  已显示新发现的硼烷基硫化物和N-硼烷基硫代酰胺可在取代反应中用作硫亲核试剂的中性来源。例如，将diMe-Imd-BH（SPh）2与苄基溴化物，伯溴化物或酰氯一起加热可提供高收率的相应硫醚或硫酯。同样地，Ñ -phenyltetrazole硫醚/酯由容易获得的制造Ñ -borylthionotetrazole。可以将硼烷基硫化物的形成及其向前的亲核取代反应向下进行一锅反应，该反应的成分为NHC-硼烷（NHC-BH 3），二硫化物和亲电试剂。