1-氯萘 | 90-13-1

• 物质功能分类: 有机原料 - 烃类化合物及其衍生物 - 烃类卤化物
• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 中文名称: 1-氯萘
• 中文别名: α-氯代萘；氯萘；α-氯萘；1-氯代萘；a-氯代萘
• 英文名称: 1-Chloronaphthalene
• 英文别名: 1-naphthyl chloride
• CAS: 90-13-1；25586-43-0
• 化学式: C₁₀H₇Cl
• mdl: MFCD00003874
• 分子量: 162.619
• InChiKey: JTPNRXUCIXHOKM-UHFFFAOYSA-N

物化性质

• 熔点：
  −20 °C(lit.)
• 沸点：
  111-113 °C5 mm Hg(lit.)
• 密度：
  1.194 g/mL at 25 °C(lit.)
• 闪点：
  250 °F
• 溶解度：
  酒精：可溶
• 介电常数：
  5.0
• 物理描述：
  1-chloronaphthalene is a clear colorless to amber oily viscous liquid. (NTP, 1992)
• 颜色/状态：
  Oily liquid
• 味道：
  /1-Chloronaphthalene/ gives water a sweetish, astringent taste, the perception threshold for which is higher than for odor. /Odor threshold (0.01 mg/L)/.
• 蒸汽密度：
  5.6 (Air= 1)
• 蒸汽压力：
  0.029 mm Hg @ 25 °C
• 亨利常数：
  Henry's Law constant= 0.000355 atm-cu m/mole @ 25 °C
• 自燃温度：
  > 558 °C; 1036 °F
• 分解：
  When heated to decomposition it emits toxic fumes of /hydrogen chloride/.
• 气味阈值：
  0.01 mg/L
• 折光率：
  Index of refraction: 1.63321 @ 20 °C/D
• 保留指数：
  1356.1 ;1349

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 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

在大鼠中产生 S-(1-萘基)谷胱甘肽... 在兔中... /根据表格/

Yields s-(1-naphthyl)glutathione in rats ... in rabbits ... . /from table/

来源:Hazardous Substances Data Bank (HSDB)

代谢

1-... /氯萘被猪代谢成4-氯-1-萘酚.../

1-... /Chloronaphthalene is/ metabolized by pig to 4-chloro-1-naphthol... .

来源:Hazardous Substances Data Bank (HSDB)

代谢

氯化-α-萘酚通过体外预处理的大鼠肝微粒体转化为活性中间体，该中间体与标记有35硫的谷胱甘肽形成共价复合物。

Alpha-chloronaphthalene was converted by pretreated liver microsomes in vitro to active int which formed covalent complexes with (35)sulfur labeled glutathione.

来源:Hazardous Substances Data Bank (HSDB)

代谢

代谢途径：2-氯萘至D-8-氯-1,2-二羟基萘至3-氯水杨酸。

Metabolic pathway: 2-chloronaphthalene to d-8-chlor-1,2-dihydroxynaphthalene to 3-chlorosalicylic acid.

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

红斑。疼痛。

Redness. Pain.

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

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)

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 concentration 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)

安全信息

• TSCA：
  Yes
• 危险等级：
  9
• 危险品标志：
  Xn,N
• 安全说明：
  S26,S29,S36,S36/37,S37/39,S45,S61
• 危险类别码：
  R22,R51/53,R36/37/38
• WGK Germany：
  2
• 海关编码：
  29039990
• 危险品运输编号：
  3082
• RTECS号：
  QJ2100000
• 包装等级：
  III

制备方法与用途

化学性质

无色挥发性油状液体。不溶于水，但能溶于四氯化碳、二硫化碳、苯及氯苯中。

用途

用于制备1-萘酚，进而生产染料、木材防腐剂、杀菌剂和特种清洁剂等。 此外，也可用作油脂溶剂，并在有机合成过程中作为溶剂与分析试剂使用。

生产方法

由萘直接氯化获得。以锌为催化剂时，萘与氯的摩尔比为1：0.84-1.17，催化剂用量为萘重的0.4-0.5%，通氯时间为3至6小时，反应温度控制在90-95℃之间。此过程可得到平均81.7%产率的1-氯萘，并通过二次分馏提高产品纯度至96%。

另一种方法是在溶剂氯苯中以碘为催化剂进行反应，反应温度为60-70℃，通氯6小时后结束反应。该过程中会同时生成2-氯萘，占总量的2-20%，由于两种异构体沸点相近（2-氯萘沸点264-266℃），且化学性质较为相似，分离难度较大。

少量生产可通过甲萘胺经重氮化、置换而得。

类别

有毒物品

毒性分级

中毒

急性毒性

大鼠口服 LD50: 1540毫克/公斤；小鼠口服 LD50: 1091毫克/公斤

可燃性危险特性

遇明火或高温可燃，受高热分解产生有毒氯化物气体。

储运特性

库房需保持通风、低温和干燥，并与氧化剂及食品添加剂分开存放。

灭火剂

泡沫、二氧化碳、砂土、雾状水、干粉。

职业标准

时间加权平均浓度（TWA）: 0.2毫克/立方米；短时间接触限值（STEL）: 0.6毫克/立方米。

反应信息

• 作为反应物：
  描述：

  1-氯萘 在 silver(II) fluoride 作用下， 生成 十八氟十氢萘
  参考文献：
  名称：

  稠环碳氟化合物的制备

  摘要：

  DOI：

  10.1021/ie50447a630
• 作为产物：
  描述：

  烯丙苯 在 三氯溴甲烷 、 铁粉 作用下， 以 乙醇 为溶剂， 反应 2.0h， 以90%的产率得到1-氯萘
  参考文献：
  名称：

  使用烯丙基苯和多卤代甲烷的苯并苯胺化处理将光和铁介导的碳阳离子途径转变为多取代的1-卤代萘

  摘要：

  烯丙基苯与多卤代甲烷的偶联可得到各种各样的多取代的1-溴和氯萘。该反应在可见光辐射下由铁金属介导，并通过Kharasch加成中间体进行，然后进行分子内Fe III介导的Friedel-Crafts烷基化，在此过程中形成两个C sp 2 -C sp 2键。该方法可轻松获得具有C-5至C-8取代基的1-卤代萘，否则难以合成。

  DOI：

  10.1002/adsc.202001249
• 作为试剂：
  描述：

  光气 、 苯胺 在 1-氯萘 作用下， 生成 异氰酸苯酯
  参考文献：
  名称：

  Siefken, Justus Liebigs Annalen der Chemie, 1949, vol. 562, p. 75,1114

  摘要：

  DOI：

文献信息

• Synthesis of Aromatic Carboxylic Acids by Carbonylation of Aryl Halides in the Presence of Epoxide-Modified Cobalt Carbonyls as Catalysts
  作者：V. P. Boyarskii、T. E. Zhesko、S. A. Lanina

  DOI：10.1007/s11167-005-0619-y

  日期：2005.11

  A new procedure was developed for synthesis of aromatic and heteroaromatic acids and their derivatives (esters, salts) by carbonylation of the corresponding aryl halides. The acids are selectively formed in a high yield under very mild conditions. Highly active catalytic systems, base-containing alcoholic solutions of cobalt carbonyl modified with epoxides, were used to activate aryl halides.

  开发了一种新方法，用于通过相应的芳基卤化物的羰基化合成芳族和杂芳族酸及其衍生物（酯，盐）。在非常温和的条件下可以高产率选择性地形成酸。高活性的催化体系（用环氧化物改性的含羰基钴钴的含碱醇溶液）用于活化芳基卤化物。
• CuI/Oxalic Diamide-Catalyzed Cross-Coupling of Thiols with Aryl Bromides and Chlorides
  作者：Chia-Wei Chen、Yi-Ling Chen、Daggula Mallikarjuna Reddy、Kai Du、Chao-En Li、Bo-Hao Shih、Yung-Jing Xue、Chin-Fa Lee

  DOI：10.1002/chem.201701671

  日期：2017.7.26

  We report a general copper‐catalyzed cross‐coupling of thiols with aryl halides by using N‐aryl‐N′‐alkyl oxalic diamide (L3) or N,N′‐dialkyl oxalic diamide (L5) as the ligand. Both aryl and alkyl thiols can be coupled with unactivated aryl bromides and chlorides to give the desired products in good yields. Furthermore, this system features a broad substrate scope and good tolerance of functional groups

  我们通过使用报告与芳基卤硫醇的一般铜-催化的交叉偶联ñ -芳基- N' -烷基草酸二酰胺（L3）或ñ，N' -二烷基二酰胺草酸（L5）作为配体。芳基和烷基硫醇都可以与未活化的芳基溴化物和氯化物偶合，以高收率得到所需的产物。此外，该系统具有广泛的底物范围和对官能团的良好耐受性。重要的是，草酸二酰胺是稳定的，并且可以容易地由市售和廉价的起始原料制备。
• Aromatic substitution in ball mills: formation of aryl chlorides and bromides using potassium peroxomonosulfate and NaX
  作者：Robert Schmidt、Achim Stolle、Bernd Ondruschka

  DOI：10.1039/c2gc16508b

  日期：——

  Aryl chlorides and bromides are formed from arenes in a ball mill using KHSO5 and NaX (X = Cl, Br) as oxidant and halogen source, respectively. Investigation of the reaction parameters identified operating frequency, milling time, and the number of milling balls as the main influencing variables, as these determine the amount of energy provided to the reaction system. Assessment of liquid-assisted grinding conditions revealed, that the addition of solvents has no advantageous effect in this special case. Preferably activated arenes are halogenated, whereby bromination afforded higher product yields than chlorination. Most often reactions are regio- and chemoselective, since p-substitution was preferred and concurring side-chain oxidation of alkylated arenes by KHSO5 was not observed.

  芳基氯和芳基溴是通过在球磨机中使用KHSO5和NaX（X=Cl，Br）分别作为氧化剂和卤素源，从芳烃形成的。对反应参数的调查确定操作频率、研磨时间和研磨球数为主要影响变量，因为这些变量决定了向反应系统提供的能量。对液体辅助研磨条件的评估揭示，在这种特殊情况下，溶剂的添加没有优势效应。优先激活的芳烃被卤化，其中溴化得到的产物收率高于氯化。大多数反应具有区域选择性和化学选择性，因为更喜欢对位取代，而且没有观察到KHSO5对烷基化芳烃侧链的氧化作用。
• Highly Active Monoligated Arylpalladacyles for Cross-Coupling Reactions
  作者：Chunming Zhang、Kelli Ogawa、Siyu Tu、Chengli Zu、Jim Ringer、Chris Derstine、Hien Do、Philip P. Fontaine、Jerzy Klosin

  DOI：10.1021/acs.oprd.9b00234

  日期：2019.10.18

  for a range of aryl halide and boronate coupling partners. Notably, aryl chlorides are viable coupling partners even under relatively mild conditions at short reaction times (e.g., 1 h at 60 °C). One of the best catalysts described here exhibits improved turnover frequency for a particularly difficult coupling reaction involving an aryl chloride and a sterically congested boronic ester.

  已经开发了一系列具有酰胺，尿素和氨基甲酸酯骨架的新型单连接芳基四环复合物，发现它们对Suzuki-Miyaura交叉偶联具有很高的活性。这些Palladacycle预催化剂衍生自简单，廉价的原料，并且对空气和湿气稳定。在测试的那些中最活跃的同类物是基于尿素的palladacycles，它与t Bu 3一起使用。P配体可诱导一系列芳基卤和硼酸酯偶联伙伴的高转化率。值得注意的是，即使在相对温和的条件下，较短的反应时间（例如，在60°C下1 h），芳基氯化物也是可行的偶合伴侣。这里描述的最好的催化剂之一对于特别困难的偶合反应表现出改善的周转频率，所述偶合反应涉及芳基氯和空间拥挤的硼酸酯。
• Use of N-oxide compounds in coupling reactions
  申请人：Fagnou Keith

  公开号：US20080132698A1

  公开（公告）日：2008-06-05

  Metal-catalyzed coupling process comprising reacting a compound of general formula 1 with a compound A-X, to obtain a compound of general formula 2, which may further be converted to a compound of general formula 3

  金属催化偶联过程包括将一般式1的化合物与化合物A-X反应，得到一般式2的化合物，该化合物可能进一步转化为一般式3的化合物。

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