溴化钛(IV) | 7789-68-6

• 物质功能分类: 无机化工 - 无机盐 - 金属卤化物及卤酸盐
• 分子结构分类: 无机化合物 - 混合金属/非金属化合物 - 过渡金属盐
• 中文名称: 溴化钛(IV)
• 中文别名: 溴化钛；四溴化钛
• 英文名称: titanium(IV) bromide
• 英文别名: titanium tetrabromide；titanium bromide；titanium(IV) tetrabromide；titanium(4+);tetrabromide
• CAS: 7789-68-6
• 化学式: Br₄Ti
• 分子量: 367.496
• InChiKey: UBZYKBZMAMTNKW-UHFFFAOYSA-J

物化性质

• 熔点：
  38-40 °C(lit.)
• 沸点：
  230 °C(lit.)
• 密度：
  3.25 g/mL at 25 °C(lit.)
• 闪点：
  233°C
• 溶解度：
  与H2O反应
• 稳定性/保质期：
  如果遵照规格使用和储存，则不会分解。避免接触氧化物。 四溴化钛有两种变体：α变体在低于-15℃时稳定，β变体在高于-15℃时稳定。它具有潮解性，遇水分解，并且可溶于乙醇和乙醚。

计算性质

• 辛醇/水分配系数(LogP)：
  3.38
• 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：
  0
• 氢给体数：
  0
• 氢受体数：
  0

ADMET

代谢

溴主要通过吸入进入人体，但也可以通过皮肤接触。溴盐可以摄入。由于溴的活性，它会迅速形成溴化物并可能沉积在组织中，取代其他卤素。

Bromine is mainly absorbed via inhalation, but may also enter the body through dermal contact. Bromine salts can be ingested. Due to its reactivity, bromine quickly forms bromide and may be deposited in the tissues, displacing other halogens. (L626)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 毒性总结

溴是一种强大的氧化剂，能够从粘膜的水分中释放出氧自由基。这些自由基也是有力的氧化剂，能够造成组织损伤。此外，氢溴酸和溴酸的形成将导致二次刺激。溴离子还已知会影响中枢神经系统，导致溴中毒。这被认为是溴离子取代神经递质和传输系统中的氯离子的结果，从而影响许多突触过程。（L626, L627, A543）

Bromine is a powerful oxidizing agent and is able to release oxygen free radicals from the water in mucous membranes. These free radicals are also potent oxidizers and produce tissue damage. In additon, the formation of hydrobromic and bromic acids will result in secondary irritation. The bromide ion is also known to affect the central nervous system, causing bromism. This is believed to be a result of bromide ions substituting for chloride ions in the in actions of neurotransmitters and transport systems, thus affecting numerous synaptic processes. (L626, L627, A543)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 致癌物分类

对人类不具有致癌性（未被国际癌症研究机构IARC列名）。

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

溴蒸气会引起刺激和对粘膜的直接损害。元素溴也会烧伤皮肤。溴化物离子是一种中枢神经系统抑制剂，长期暴露会产生神经元效应。这被称为溴中毒，可能导致从中睡意到昏迷、恶病质、昏迷、反射丧失或病理反射、阵挛性癫痫、震颤、共济失调、神经敏感性丧失、瘫痪、眼乳头水肿、言语异常、脑水肿、谵妄、攻击性和精神病的中心反应。

Bromine vapour causes irritation and direct damage to the mucous membranes. Elemental bromine also burns the skin. The bromide ion is a central nervous system depressant and chronic exposure produces neuronal effects. This is called bromism and can result in central reactions reaching from somnolence to coma, cachexia, exicosis, loss of reflexes or pathologic reflexes, clonic seizures, tremor, ataxia, loss of neural sensitivity, paresis, papillar edema of the eyes, abnormal speech, cerebral edema, delirium, aggressiveness, and psychoses. (L625, L626, L627)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 暴露途径

口服（L626）；吸入（L626）；皮肤给药（L626）

Oral (L626) ; inhalation (L626) ; dermal (L626)

来源:Toxin and Toxin Target Database (T3DB)

毒理性

• 症状

溴蒸气会引起刺激和对粘膜的直接损害。症状包括流泪、流鼻涕、眼部刺激伴有来自咽和上呼吸道的粘液分泌、咳嗽、呼吸困难、窒息、喘息、鼻出血和头痛。溴离子是一种中枢神经系统抑制剂，会引起共济失调、言语不清、震颤、恶心、呕吐、乏力、眩晕、视觉障碍、不稳、头痛、记忆和注意力受损、定向障碍和幻觉。这被称为溴中毒。

Bromine vapour causes irritation and direct damage to the mucous membranes. Symptoms include lacrimation, rhinorrhoea, eye irritation with mucous secretions from the oropharyngeal and upper airways, coughing, dyspnoea, choking, wheezing, epistaxis, and headache. The bromide ion is a central nervous system depressant producing ataxia, slurred speech, tremor, nausea, vomiting, lethargy, dizziness, visual disturbances, unsteadiness, headaches, impaired memory and concentration, disorientation and hallucinations. This is called bromism. (L626, L627)

来源:Toxin and Toxin Target Database (T3DB)

安全信息

• TSCA：
  No
• 危险等级：
  8
• 危险品标志：
  C
• 安全说明：
  S26,S36/37/39,S45
• 危险类别码：
  R14
• WGK Germany：
  3
• 海关编码：
  28275900
• 危险品运输编号：
  UN 3260 8
• 包装等级：
  II
• 危险标志：
  GHS05
• 危险性描述：
  H314
• 危险性防范说明：
  P280,P305 + P351 + P338,P310
• 储存条件：
  请将贮藏器密封，并将其存放在阴凉、干燥的地方，最好放置在紧密封装的容器中。

SDS

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Section 1: Product Identification
Chemical Name: Titanium (IV) bromide, min. 98%
CAS Registry Number: 7789-68-6
Formula: TiBr4
EINECS Number: 232-185-0
Chemical Family: metal halide
Synonym: Titanium tetrabromide

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Section 2: Composition and Information on Ingredients
Ingredient CAS Number Percent ACGIH (TWA) OSHA (PEL)
Title Compound 7789-68-6 100% no data no data

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Section 3: Hazards Identification
With moisture, this material becomes a strong, corrosive acid. The liquid and its vapor are extremely corrosive
Emergency Overview:
to skin, eyes, mucous membranes and respiratory tract.
Primary Routes of Exposure: Ingestion, inhalation, eyes and skin
Eye Contact: Severe corrosive to the eyes. Exposure can lead to permanent eye damage.
Skin Contact: Corrosive to skin. Contact can lead to redness, pain, blistering, ulceration, and scar formation.
Material releases corrosive fumes, causing burns of the mucous membranes and lungs.Pulmonary edema
Inhalation:
may occur.
Product is a highly corrosive acid. Ingestion may cause pain, vomiting, burns of mouth and throat, and
Ingestion:
ulceration of gastrointestinal tract.
Acute Health Affects: Severe corrosive to eyes, skin, mucous membranes and respiratory tract. Ingestion may be fatal.
Repeated or prolonged exposure to bromides by any route may cause skin rashes (bromaderma) and central
Chronic Health Affects:
nervous system depression, including ataxia, psychoses, memory loss, irritability, and headache.
NTP: No
IARC: No
OSHA: No

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SECTION 4: First Aid Measures
Immediately flush the eyes with copious amounts of water for at least 10-15 minutes. A victim may need
Eye Exposure:
assistance in keeping their eye lids open. Get immediate medical attention.
Wash the affected area with water. Remove contaminated clothes if necessary. Seek medical assistance if
Skin Exposure:
irritation persists.
Remove the victim to fresh air. Closely monitor the victim for signs of respiratory problems, such as difficulty
Inhalation:
in breathing, coughing, wheezing, or pain. In such cases seek immediate medical assistance.
Seek medical attention immediately. Keep the victim calm. Give the victim water (only if conscious). Induce
Ingestion:
vomiting only if directed by medical personnel.

---

SECTION 5: Fire Fighting Measures
Flash Point: not applicable
Autoignition Temperature: none
Explosion Limits: none
Extinguishing Medium: None. Material is non-flammable.
If this product is involved in a fire, fire fighters should be equipped with a NIOSH approved positive pressure
Special Fire Fighting Procedures:
self-contained breathing apparatus and full protective clothing.
Hazardous Combustion and none
Decomposion Products:
Unusual Fire or Explosion Hazards: No unusual fire or explosion hazards.

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SECTION 6: Accidental Release Measures
Small spills can be mixed with powdered sodium bicarbonate, lime, or calcium carbonate and swept up. Avoid
Spill and Leak Procedures:
raising dust.

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SECTION 7: Handling and Storage
Store solid in a tightly sealed container away from moisture. Handle in a fume hood under a dry atmosphere of
Handling and Storage:
air or nitrogen. Prolonged exposure to the atmosphere may degrade the product.

---

SECTION 8: Exposure Controls and Personal Protection
Eye Protection: Always wear approved safety glasses when handling a chemical substance in the laboratory.
Skin Protection: Wear protective clothing and gloves. Consult with glove manufacturer to determine the proper type of glove.
Ventilation: The solid may form corrosive vapors. It should be handled in an efficient fume hood.
If in form of fine dust and ventilation is not available a respirator should be worn. The use of respirators
Respirator:
requires a Respirator Protection Program to be in compliance with 29 CFR 1910.134.
Ventilation: The solid may form corrosive vapors. It should be handled in an efficient fume hood.
Additional Protection: No additional protection required.

---

SECTION 9: Physical and Chemical Properties
Color and Form: orange xtl.
Molecular Weight: 367.54
Melting Point: 39°
Boiling Point: 230°C
Vapor Pressure: no data
Specific Gravity: 2.6
Odor: pungent odor
Solubility in Water: decomposes

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SECTION 10: Stability and Reactivity
Stability: moisture sensitive
Hazardous Polymerization: no hazardous polymerization
Conditions to Avoid: contact with moisture
Incompatibility: water, alcohols, oxidizing agents, oxygen and active metals
Decomposition Products: none

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SECTION 11: Toxicological Information
RTECS Data: No information available in the RTECS files.
Carcinogenic Effects: no data
Mutagenic Effects: no data
Tetratogenic Effects: no data

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SECTION 12: Ecological Information
Ecological Information: No information available

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SECTION 13: Disposal Considerations
Disposal: Dispose of according to local, state and federal regulations.

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SECTION 14: Transportation
Shipping Name (CFR): Corrosive solids, N.O.S.
Hazard Class (CFR): 8
Additional Hazard Class (CFR): NA
Packaging Group (CFR): II
UN ID Number (CFR): UN# 1759
Shipping Name (IATA): Corrosive solid, N.O.S.
Hazard Class (IATA): 8
Additional Hazard Class (IATA): NA
Packaging Group (IATA): II
UN ID Number (IATA): UN# 1759

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SECTION 15: Regulatory Information
TSCA: Not listed in the TSCA inventory
SARA (Title 313): Title compound not listed.
Second Ingredient: none

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SECTION 16 - ADDITIONAL INFORMATION
N/A

制备方法与用途

理化性质

四溴化钛是一种黄色单斜或立方晶体，易潮解。其相对密度分别为2.6（单斜）或3.24（立方），熔点为39℃，沸点为230℃。该物质能溶于乙醇、乙醚、四氯化碳和氯仿以及盐酸和氢溴酸中。遇水则分解，并能被碱的水溶液完全分解。作为一种不稳定的金属溴化物，它介于四碘化钛和四氯化钛之间，具有较高的路易士酸性并易于溶解在非极性有机溶剂中。TiBr4为抗磁性物质，中心原子的外层电子组态为d0。

应用

四溴化钛可作为钛源制备其他物质，例如用于汽车工业中的燃油深度脱氮、制备氮化钛陶瓷粉末以及碳化钛陶瓷粉末等。

生态学数据

对水稍微有害。未经许可，请勿将材料排入环境。

结构与制备

该四配物的结构为正四面体，可通过多种方法合成：

• 由单质直接合成
• 让二氧化钛、碳和溴反应（即克罗尔法）
• 让四氯化钛和溴反应

反应信息

• 作为反应物：
  描述：

  溴化钛(IV) 在 氢气 作用下， 生成 四氢化物钛
  参考文献：
  名称：

  Smatko, J. S., British Intelligence Objectives Subcommittee (Met. Ind. London 70 {1947} 363/4)

  摘要：

  DOI：
• 作为产物：
  描述：

  dilithiumtrisbutane-1,4-diyl-titanium(IV)(ether)2 在 溴 作用下， 以 甲苯 为溶剂， 生成 溴化钛(IV)
  参考文献：
  名称：

  Schreer, Heike; Froehlich, Hans-Otto, Zeitschrift fur Chemie, 1989, vol. 29, p. 414 - 415

  摘要：

  DOI：
• 作为试剂：
  描述：

  methyl 4,5,7,8-tetra-O-acetyl-3-deoxyl-alpha-D-manno-2-octulopyranosonate 在 溴化钛(IV) 作用下， 以 二氯甲烷 为溶剂， 生成 Methyl (4,5,7,8-tetra-O-acetyl-3-deoxy-α-D-manno-2-octulopyranosyl bromide)-onate
  参考文献：
  名称：

  Synthese von 3-Desoxy-d-manno-2-octulosonsäure (KDO)-Oligosacchariden

  摘要：

  DOI：

  10.1016/0008-6215(83)88319-0

文献信息

• Synthesis and Reactivity of Cyclopentadienyl and Indenyl Ligands Bearing ω-Fluorinated Pendant Groups. Crystal Structure of (ortho-F-C₆H₄)-CPh₂-C₅H₄SiMe₃
  作者：A. Khvorost、D. Lemenovskii、N. Ustynyuk、K. Rufanov、J. Kipke

  DOI：10.1515/znb-2002-1104

  日期：2002.11.1

  A series of cyclopentadienes and indenes with ω-fluorinated pendant groups have been synthesised and their reactivity towards metallating agents n-BuLi, NaH, TlOEt, Me3SiCl, Me3SnCl, TiHal4, ZrX4 (X = Cl, NMe2) has been investigated. The crystal structure of 1-trimethylsilyl- 3-(diphenyl-ortho-fluorophenyl-methyl)-cyclopentadiene (3) was determined.

  已经合成了一系列带有 ω-氟化侧基的环戊二烯和茚，并研究了它们对金属化剂 n-BuLi、NaH、TlOEt、Me3SiCl、Me3SnCl、TiHal4、ZrX4（X = Cl、NMe2）的反应性。确定了1-三甲基甲硅烷基-3-(二苯基-邻-氟苯基-甲基)-环戊二烯(3)的晶体结构。
• INSIGHTS into the structures adopted by titanocalix[6 and 8]arenes and their use in the ring opening polymerization of cyclic esters
  作者：Orlando Santoro、Mark R. J. Elsegood、Elizabeth V. Bedwell、Jake A. Pryce、Carl Redshaw

  DOI：10.1039/d0dt02130j

  日期：——

  In the case of [TiI4], the ladder [(TiI)2(TiINCMe)2(μ3-O)2(L2)]·7.25CH2Cl2 (11·7.25CH2Cl2) was isolated. These complexes have been screened for their potential to act as catalysts in the ring opening polymerization (ROP) of ε-caprolactone (ε-CL), δ-valerolactone (δ-VL) and rac-lactide (r-LA), both in air and N2. For ε-CL and δ-VL, moderate activity at 130 °C over 24 h was observed for 1, 9 and 11; for

  对叔丁基杯[6] areneH 6，L 1 H 6与[TiCl 4 ]的相互作用提供了络合物[Ti 2 Cl 3（MeCN）2（OH 2）（L 1 H）] [Ti 2 Cl 3（MeCN）3（L 1 H）]·4.5MeCN（1 ·4.5MeCN），其中两个假八面体钛中心与一个杯[6]芳烃键合。类似的反应，但使用THF导致THF开环产物钛[Ti 4氯2（μ 3 -O）2（NCMe）2（L）2（O（CH 2）4 Cl）2 ]·4MeCN（2 ·4MeCN），其中LH 4 =对叔丁基杯[4] areneH 4。处理后，L 1 H 6与[TiF 4 ]（3当量）的相互作用导致形成[[TiF）2（μ-F）L 1 H] 2 ·6.5MeCN（3 ·6.5MeCN）的络合物。用[TiCl 4 ]处理对叔丁基杯[8] areneH 8，L 2 H 8导致分离出复合物[（TiCl）2（TiClNCMe）2（μ
• Isolable and Readily Handled Halophosphonium Pre-reagents for Hydro- and Deuteriohalogenation
  作者：Florian T. Schevenels、Minxing Shen、Scott A. Snyder

  DOI：10.1021/jacs.6b12653

  日期：2017.5.10

  and acid-sensitive moieties, particularly polyenes prone to cyclization. The process is also challenging when conducted on a small scale, and moreover, methods for the addition of their deuterated counterparts typically require special techniques, especially when control of stoichiometry is required. Herein is described a readily synthesized and handled reagent class which can accomplish the controlled

  尽管对跨烯烃添加酰卤进行了充分研究，但许多具有离去基团、多不饱和度和酸敏感部分的底物类别仍然存在局限性，特别是易于环化的多烯。该过程在小规模进行时也具有挑战性，此外，添加氘代对应物的方法通常需要特殊技术，尤其是在需要控制化学计量时。本文描述了一种易于合成和处理的试剂类，它可以在耐受不同功能的温和反应条件下，完成 HCl 和 HBr 跨几个烯烃类的受控和选择性马尔可夫尼科夫加成。该过程在实验室规模上特别有价值，并提供了与其他方法的直接比较。
• Aqueous chemistry of Bis(cyclopentadienyl)dihalotitanium(IV)
  作者：Dina Nath、R.K. Sharma、A.N. Bhat

  DOI：10.1016/s0020-1693(00)94100-8

  日期：1976.1

  Abstract Bis(cyclopentadienyl)dibromotitanium(IV) and bis(cyclopentadienyl)diiodotitanium(IV) have been prepared by the reaction of cyclopentadienylthallium(I) and the appropriate titanium tetrahalide. The aqueous chemistry of (C 5 H 5 ) 2 TiX 2 has been reinvestigated. It has been found that compounds (C 5 H 5 ) 2 TiX 2 (X = F, Cl, Br, I) can be prepared in good yields by the action of haloacids on

  摘要通过环戊二烯基th（I）与适当的四卤化钛反应制得了双（环戊二烯基）二溴钛（IV）和双（环戊二烯基）二碘化钛（IV）。（C 5 H 5）2 TiX 2的水化学已经重新研究。已经发现，通过卤代酸对桥连化合物[（C 5 H 5）2 TiX的作用，可以高收率地制备化合物（C 5 H 5）2 TiX 2（X = F，Cl，Br，I）。 '] 2 O（X'= Cl，Br，I，NO 3）。也已经报道了涉及（C 5 H 5）2 TiX 2的其他卤素交换反应。
• Chemoselective Claisen–Schmidt bis-substitutional condensation catalyzed by an alkoxy-bridged dinuclear Ti(IV) cluster
  作者：Yufei Wu、Jie Hou、Yuliang Liu、Mingfu Zhang、Chen-Ho Tung、Yifeng Wang

  DOI：10.1016/j.tet.2016.01.055

  日期：2016.3

  The highly efficient and chemoselective α,α′-bis-substitution of alkanones is important in organic synthesis. Herein, a dimeric titanium cluster, Ti2Cl2(OPri)6·2HOPri (Ti2), is used in the Claisen–Schmidt condensation reaction, for the selectively activation of symmetrical ketones containing α,α′-methylene groups and production of α,α′-bis-substituted alkanones in high efficiency and chemoselectivity

  链烷酮的高效和化学选择性的α，α'-双取代在有机合成中很重要。在本文中，二聚物钛簇Ti 2 Cl 2（OPr i）6 ·2HOPr i（Ti 2）用于克莱森－施密特缩合反应，以选择性活化包含α，α'-亚甲基和高效和化学选择性生产α，α'-双取代链烷酮。高效和化学选择性可以扩展到各种典型的链烷酮和芳族醛。Ti 2的氧桥联二聚体基序 离子Ti-Cl键负责高效和化学选择性。