2-氯萘 | 91-58-7

• 物质功能分类: 化学试剂 - 有机试剂 - 多环化合物
• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: 2-氯萘
• 中文别名: 1-氯化萘；Α-氯化萘；β-氯萘
• 英文名称: 2-chloronaphthalene
• 英文别名: 2-naphthyl chloride；2-monochloronaphthalene；2-chloronapthalene
• CAS: 91-58-7；51569-12-1
• 化学式: C₁₀H₇Cl
• mdl: MFCD00035731
• 分子量: 162.619
• InChiKey: CGYGETOMCSJHJU-UHFFFAOYSA-N

物化性质

• 熔点：
  57-60 °C
• 沸点：
  256 °C
• 密度：
  1.1377
• 闪点：
  125 °C
• 溶解度：
  Soluble in chloroform, carbon disulfide (Windholz et al., 1983), and many other halogenated liquid solvents (e.g., methylene chloride).
• 介电常数：
  5.0（24℃）
• 物理描述：
  Monoclinic plates or off-white crystalline powder. Melting point 59.5°C.
• 颜色/状态：
  Monoclinic plates, leaflets from dil alcohol
• 蒸汽密度：
  Relative vapor density (air = 1): 5.6
• 蒸汽压力：
  0.0122 mm Hg @ 25 °C
• 亨利常数：
  3.20e-04 atm-m3/mole
• 分解：
  When heated to decomposition it emits toxic fumes of /hydrogen chloride/.
• 折光率：
  Index of refraction: 1.60787 @ 70.7 °C/D
• 保留指数：
  1353 ;1343 ;1359.1 ;1348

计算性质

• 辛醇/水分配系数(LogP)：
  4.1
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

2-氯萘在玉米油中通过猪的逆颈动脉注射给药。尿液样本分析显示存在一种单羟基化合物，被鉴定为3-氯-2-萘酚。

2-chloronaphthalene in corn oil was admin by retrocarotid injection in pigs. Analysis of urine samples showed presence of monohydroxy compd, identified as 3-chloro-2-naphthol.

来源:Hazardous Substances Data Bank (HSDB)

代谢

产生 (+)-反式-7-氯-1,2-二氢-1,2-二氢氧萘在假单胞菌中。

Yields (+)-trans-7-chloro-1,2-dihydro-1,2-dihydroxynaphthalene in pseudomonas. /from table/

来源:Hazardous Substances Data Bank (HSDB)

代谢

在用单氯萘处理大鼠、猪和青蛙后，尿液和/或粪便中鉴定出的代谢物大多数是羟基化的多氯萘（酚型和共轭型），有证据表明是通过芳香环氧化物进行的代谢。

Most of the metabolites identified in urine and/or feces of rats, pigs, and frogs after treatment with monochloronaphthalenes were hydroxylated PCNs (phenolic and conjugated forms), with evidence for metabolism via arene oxide.

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 毒性总结

识别：氯代萘共有75种可能的同系物。商业产品通常是几种同系物的混合物，从稀薄液体到硬蜡再到高熔点固体不等。它们的主要用途包括电缆绝缘、木材防腐、发动机油添加剂、电镀遮蔽化合物、电容器以及折射率测试油，并作为染料生产的原料。人类暴露：氯代萘进入环境的主要来源可能是废物焚烧和含有氯代萘的物品填埋处理。过去，工作场所中氯代萘的浓度曾达到14.5毫克/立方米，而在制造站点附近室外空气中的水平为25-2900纳克/立方米。最近的研究监测表明，在半农村地区氯代萘的浓度可达150皮克/立方米，而在偏远地区为1-40皮克/立方米。一项关于氯代自来水的研究发现，单氯萘的浓度为0.44纳克/升。氯代萘可以通过口服、吸入和皮肤途径吸收，口服给药后会在全身吸收和分布。氯代萘，尤其是具有二噁英样结构的同系物，已经在普通人群的脂肪组织、肝脏、血液和母乳样本中检出，浓度在纳克/千克脂质范围内。职业暴露于氯代萘后，报告了严重的皮肤反应（氯痤疮）和肝病。在20世纪30至40年代，处理氯代萘的工人中氯痤疮很常见。对电缆制造厂接触氯代萘的工人进行的一项队列研究发现，死于肝硬化的工人数过多。然而，患有氯痤疮的个体并没有显示出与非氯痤疮工人相比更高的因肝硬化死亡的风险。所有接触男性的癌症总死亡率略有但显著升高（标准化死亡率=1.18），但在患有氯痤疮的亚队列中并没有更高。这个亚队列显示出食管癌和良性及未指定肿瘤的死亡率有统计学意义的升高。接触氯代萘的工人描述的症状包括眼睛刺激、疲劳、头痛、贫血、血尿、阳痿、厌食、呕吐和严重的腹痛。动物研究：氯代萘在鱼类中表现出高度生物累积性，但在虾类和藻类中则累积性较低。生物累积的程度随着氯代萘氯化度的增加而增加。最高氯化度的萘似乎不生物累积。单氯萘在土壤和水微生物的需氧条件下似乎容易被降解。鱼类中氯代萘的浓度最高可达大约300微克/千克脂质重量。对海鸟蛋的监测研究发现，1974年至1987年间氯代萘水平有所下降。已知的羟基代谢物主要是在实验动物中发现的较低氯代萘（单至四氯代）。还有初步迹象表明，在大鼠粪便中存在甲基硫代或甲基亚砜氯萘代谢物。父母化合物和/或代谢物的消除通过粪便和尿液进行。较高氯代的同系物似乎比较低氯代的毒性更大。氯代萘的长期和致癌性研究尚未进行。1-单氯萘在沙门氏菌Ames试验中不具有致突变性。与相关化合物一样，氯代萘已被证明是细胞色素p450（CYP）依赖性微粒体酶的诱导剂。氯代萘还发现能改变大鼠的脂质过氧化和抗氧化酶活性，表明氧化应激。至少氯代萘的一些生物学和毒性反应被认为是通过细胞质Ah受体介导的，类似于2,3,7,8-四氯二苯并-p-二噁英（TCDD）及相关化合物的反应。所有测试的氯代萘都会在实验动物中引起皮肤刺激。氯代萘对水生生物表现出中等至高急性毒性。/氯代萘，单氯萘/

IDENTIFICATION: There are 75 possible congeners of chlorinated naphthalenes. Commercial products are generally mixtures of several congeners and range from thin liquids to hard waxes to high melting point solids. Their main uses have been in cable insulation, wood preservation, engine oil additives, electroplating masking compounds, capacitors and refractive index testing oils and as a feedstock for dye production. HUMAN EXPOSURE: The major sources of release of chlorinated naphthalenes into the environment are likely from waste incineration and disposal of items containing chlorinated naphthalenes to landfill. In the past, chlorinated naphthalene concn of up to 14.5 mg/cu m have been measured in the workplace, while levels of 25-2900 ng/cu m have been recorded in out door air in vicinity of manufacturing sites. More recently, monitoring studies have revealed chlorinated naphthalene concn up to 150 pg/cu m at semirural sites and 1-40 pg/cu m at remote sites. A single study on chlorinated tap water revealed 0.44 ng monochloronaphthalene/l. Chlorinated naphthalenes can be absorbed via oral, inhalative and dermal routes, with absorption and distribution over the whole body after oral admin. Chlorinated naphthalenes, especially the dioxin-like congeners, have been detected in adipose tissue, liver, blood and breast milk samples from the general population at concn in the ng/kg lipid range. Severe skin reactions (chloracne) and liver disease have been reported after occupational exposure to chlorinated naphthalenes. Chloracne was common among workers who handling chlorinated naphthalenes in the 1930's to 1940's. A cohort study on workers exposed to chlorinated naphthalenes at a cable manufacturing plant found an excess of deaths from cirrhosis of the liver. However, individuals with chloracne did not show a higher mortality due to liver cirrhosis compared with other workers. The mortality from all cancers was slightly but significantly elevated among all exposed men (standardized mortality ratio =1.18), but was not more elevated in the subcohort with chloracne. This subcohort showed statistically significant excess mortality from cancer of the esophagus and from benign and unspecified neoplasms. Symptoms described in workers exposed to chlorinated naphthalenes included irritation of the eyes, fatigue, headache, anemia, hematuria, impotency, anorexia, vomiting and severe abdominal pain. ANIMAL STUDIES: Chlorinated naphthalenes have been shown to be highly bioaccumulative in fish, but less so in shrimp and algae. The amount of bioaccumulation observed incr with the degree of chlorination of the chlorinated naphthalenes. The most highly chlorinated naphthalenes do not appear to bioaccumulate. Monochloronaphthalenes appear to be readily degradable by soil and water microorganisms under aerobic conditions. Chlorinated naphthalene concn in fish range up to a maximum of around 300 ug/kg lipid weight. Monitoring studies with seabird eggs have revealed a decr in chlorinated naphthalene levels between 1974 and 1987. Hydroxy metabolites have been identified mostly for the lower chlorinated naphthalenes (mono- to tetra-) in experimental animals. There are also preliminary indications for the occurrence of methylthio- or methyl sulfoxide chloronaphthalene metabolites in the feces of rats. Elimination of the parent compounds and/or metabolites occurs via feces and urine. The higher chlorinated congeners appeared to be more toxic than the lower chlorinated ones. Long term and carcinogenicity studies with chlorinated naphthalenes have not been performed. 1-Monochloronaphthalene was not mutagenic in the Salmonella Ames test. Like related cmpd, chlorinated naphthalenes have been demonstrated to be inducers of the cytochrome p450 (CYP) dependent microsomal enzymes. Chlorinated naphthalenes were also found to change lipid peroxidation and antioxidant enzyme activities in rats in a manner indicative of oxidative stress. At least some of the biological and toxic responses of chlorinated naphthalenes are believed to be mediated via the cytosolic Ah receptor, resembling those of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) and related cmpd. All chlorinated naphthalenes tested cause skin irritations in laboratory animals. Chlorinated napthalenes appear to be of moderate to high acute toxicity to aquatic organisms. /Chlorinated naphthalenes, Monochloronaphthalenes/

来源:Hazardous Substances Data Bank (HSDB)

毒理性

• 暴露途径

这种物质可以通过吸入、皮肤接触和摄入被身体吸收。

The substance can be absorbed into the body by inhalation, through the skin and by ingestion.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 吸入症状

咳嗽。

Cough.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 皮肤症状

Redness.

Redness.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

毒理性

• 眼睛症状

Redness.

Redness.

来源:ILO-WHO International Chemical Safety Cards (ICSCs)

吸收、分配和排泄

在猪的后颈动脉给药1-氯萘10分钟后，血液中的浓度是5.1微克/克，并随时间降低。给药2-氯萘后，浓度与1-氯萘相似。其代谢物，3-氯萘酚，在血液中被检测到。在给药氯化萘6小时后，它们在大脑、肾脏、肝脏、肺、骨骼肌、心脏和脂肪中被发现，以大脑和肾脏的浓度最高。2-氯萘的脂肪浓度较低（0.6微克/克）。氯化萘分布在各种器官和组织中，而代谢物则集中在尿液、胆汁、肾脏和肝脏中。

In pigs 10 min after retrocarotid admin of 1-chloronaphthalene the blood concn was 5.1 ug/g & decreased with time. After admin of 2-chloronaphthalene, the concn was similar to 1-chloronaphthalene. Its metabolite, 3-chloro-naphthol, was detected in blood. 6-hr after admin of the chlorinated naphthalenes, they were found in the brain, kidney, liver, lung, skeletal muscle, heart & fat with highest concn in brain & kidney. Fat concn of 2-chloronaphthalene was low (0.6 ug/g). Chloronaphthalenes are distributed in various organs & tissues whereas metabolites were concentrated in urine, bile, kidney & liver.

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

氯萘可以通过皮肤、肺和肠道吸收，并倾向于储存在脂肪组织中。它们会在毛皮脂腺和脂肪组织中积累，并且在脑、肾和其他身体组织中也有一定程度的积累。排泄主要通过尿液中的代谢物以及胆汁进行。

Chloronaphthalenes can be absorbed through the skin, lung, and gut, and tend to deposit in fat depots. Accumulation occurs in pilosebaceous acini and adipose tissue and to a lesser degree in brain, kidney and other body tissues. Excretion occurs predominantly in urinary metabolites as well as in bile. /Chloronaphthalenes/

来源:Hazardous Substances Data Bank (HSDB)

吸收、分配和排泄

从对PCN代谢的研究中可以得出结论，单氯和二氯萘（>80-90%）以及四氯萘（>45%）能很好地被胃肠道吸收。更高氯化的PCN吸收较差，可能非常差……。

From studies on the metabolism of PCNs, it can be concluded that mono and dichloronaphthalenes (>80-90%) and tetrachloronaphthalenes (>45%) are well absorbed by the gastrointestinal tract. Higher chlorinated PCNs are less well absorbed, presumably very poorly absorbed ... .

来源:Hazardous Substances Data Bank (HSDB)

安全信息

• 危险品标志：
  Xi
• 安全说明：
  S16,S26,S36/37,S37/39,S45,S7
• 危险类别码：
  R36/37/38
• WGK Germany：
  3
• 海关编码：
  29039990
• 危险品运输编号：
  UN1230 3/PG 2
• RTECS号：
  QJ2275000

制备方法与用途

化学性质：

• 白色晶体粉末，熔点为57-60℃。

类别：有毒物质

毒性分级：中毒

急性毒性：

• 大鼠口服LD₅₀：2,078毫克/千克
• 小鼠口服LD₅₀：886毫克/千克

可燃性危险特性：可燃，燃烧时分解产生有毒氯化物气体。

储运特性：需存放在低温、通风且干燥的库房中。

灭火剂：可用清水、二氧化碳、泡沫或砂土扑灭。

职业标准：

• 时间加权平均容许浓度（TWA）：0.2毫克/立方米
• 短时间接触容许浓度（STEL）：0.6毫克/立方米

反应信息

• 作为反应物：
  描述：

  2-氯萘 在 乙醚 、 lithium 作用下， 生成 2-甲基萘
  参考文献：
  名称：

  Vesely; Stursa, Chemicke Listy, 1932, vol. 26, p. 490

  摘要：

  DOI：
• 作为产物：
  描述：

  2-naphthalenesulfonic acid sodium salt 在 五氯化磷 作用下， 生成 2-氯萘
  参考文献：
  名称：

  Rymarenko, Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1876, vol. 8, p. 139

  摘要：

  DOI：

文献信息

• Pd-Catalyzed Vinylation of Aryl Halides with Inexpensive Organosilicon Reagents Under Mild Conditions
  作者：Chu-Ting Yang、Jun Han、Jun Liu、Yi Li、Fan Zhang、Hai-Zhu Yu、Sheng Hu、Xiaolin Wang

  DOI：10.1002/chem.201802573

  日期：2018.7.20

  Pd‐catalyzed Hiyama vinylation reaction of non‐activated aryl chlorides and bromides under mild conditions was developed. The use of efficient vinyl donors and electron‐rich sterically hindered phosphine ligands was critical for the success of the reaction. The products of this transformation can be used for Am/Cm separation, an important challenge in nuclear fuel reprocessing. The substituent effect

  在温和条件下开发了钯催化未活化的芳基氯和溴化物的Hiyama乙烯基化反应。有效的乙烯基供体和富含电子的位阻膦配体的使用对于反应成功至关重要。这种转化的产物可用于Am / Cm分离，这是核燃料后处理中的一项重要挑战。还获得了取代基对Am / Cm分离选择性的影响，这可能有助于开发用于分离Am和Cm的新型色谱材料。
• Synthesis of α-Aryl Nitriles through Palladium-Catalyzed Decarboxylative Coupling of Cyanoacetate Salts with Aryl Halides and Triflates
  作者：Rui Shang、Dong-Sheng Ji、Ling Chu、Yao Fu、Lei Liu

  DOI：10.1002/anie.201006763

  日期：2011.5.2

  Worth its salt: The palladium‐catalyzed decarboxylative coupling of the cyanoacetate salt as well as its mono‐ and disubstituted derivatives with aryl chlorides, bromides, and triflates is described (see scheme). This reaction is potentially useful for the preparation of a diverse array of α‐aryl nitriles and has good functional group tolerance. S‐Phos=2‐(2,6‐dimethoxybiphenyl)dicyclohexylphosphine)

  值得其盐：描述了氰基乙酸盐及其与芳基氯化物，溴化物和三氟甲磺酸酯的钯催化的脱羧偶联反应（参见方案）。该反应对于制备各种α-芳基腈具有潜在的实用性，并具有良好的官能团耐受性。S-Phos = 2-（（2,6-二甲氧基联苯）二环己基膦），Xant-Phos = 4,5-双（二苯基膦基）-9,9-二甲基x吨。
• “One-pot” synthesis of amidoxime via Pd-catalyzed cyanation and amidoximation
  作者：Chu-Ting Yang、Jun Han、Jun Liu、Mei Gu、Yi Li、Jun Wen、Hai-Zhu Yu、Sheng Hu、Xiaolin Wang

  DOI：10.1039/c4ob02456g

  日期：——

  “One-pot” synthesis of amidoxime was developed for studies on the interactions between amidoxime and uranyl.

  “一锅法”合成酰胺肟，用于研究酰胺肟与铀酰之间的相互作用。
• Pd-Catalyzed α-Arylation of α,α-Difluoroketones with Aryl Bromides and Chlorides. A Route to Difluoromethylarenes
  作者：Shaozhong Ge、Wojciech Chaładaj、John F. Hartwig

  DOI：10.1021/ja501117v

  日期：2014.3.19

  α-difluoroketones with aryl and heteroaryl bromides and chlorides catalyzed by an air- and moisture-stable palladacyclic complex containing P(t-Bu)Cy2 as ligand. The combination of this Pd-catalyzed arylation and base-induced cleavage of the acyl–aryl C–C bond within the α-aryl-α,α-difluoroketone constitutes a one-pot, two-step procedure to synthesize difluoromethylarenes from aryl halides. A broad range

  我们报告了 Pd 催化的 α,α-二氟酮与芳基和杂芳基溴化物和氯化物的 α-芳基化反应，该反应由含有 P(t-Bu)Cy2 作为配体的空气和水分稳定的钯环络合物催化。这种 Pd 催化的芳基化和碱诱导的 α-芳基-α,α-二氟酮内酰基-芳基 C-C 键断裂的组合构成了从芳基卤化物合成二氟甲基芳烃的一锅两步法。广泛的电子变化芳基和杂芳基溴化物和氯化物经历了这两种转化，以高产率提供了 α-芳基-α,α-二氟酮、二氟甲基芳烃和二氟甲基杂芳烃。
• Synthesis of <i>N</i>-(Hetero)aryl Carbamates via CuI/MNAO Catalyzed Cross-Coupling of (Hetero)aryl Halides with Potassium Cyanate in Alcohols
  作者：S. Vijay Kumar、Dawei Ma

  DOI：10.1021/acs.joc.7b03175

  日期：2018.3.2

  to N-(hetero)aryl carbamates was developed through CuI/MNAO [2-((2-methylnaphthalen-1-yl)amino)-2-oxoacetic acid] catalyzed cross-coupling of (hetero)aryl chlorides with potassium cyanate in alcohols at 120–130 °C. This method utilizes broadly available substrates to afford various N-(hetero)aryl carbamates in good to excellent yields. Moreover, (hetero)aryl bromides and (hetero)aryl iodides were also

  通过CuI / MNAO [2-（（（2-甲基萘-1-基）氨基）-2-氧乙酸]]催化（杂）芳基氯化物与钾的交叉偶联，开发了一种N-（杂）芳基氨基甲酸酯的有效途径醇中的氰酸盐在120–130°C下。该方法利用广泛可用的底物以良好至优异的产率提供各种N-（杂）芳基氨基甲酸酯。此外，（杂）芳基溴化物和（杂）芳基碘化物也以低催化剂负载量和相对较低的温度反应以提供N-（杂）芳基氨基甲酸酯。

表征谱图