三叔丁基膦

三叔丁基膦 基本信息
CAS号 13716-12-6 分子式 C12H27P
分子量 202.31700 精确质量  202.18500
PSA  13.59000 LogP  4.86380

基本信息 展开↓

CAS号:
13716-12-6
3D弹球模型:
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分子式:
C12H27P
分子量:
202.31700
中文名称:
三叔丁基膦
英文名称:
Tri-tert-butylphosphine
中文别名:
三叔丁基膦;
三特丁基膦
英文别名:
Tri-tert-butylphosphine;
Tri-t-Butylphosphine;
tritert-butylphosphane;
P(t-Bu)3 P(t-Bu)3
精确分子量/精确质量:
202.18500
极性分子表面积/PSA:
13.59000
油水分配系数/LogP:

LogP值指的是某物质在正辛醇/水两相体系中的分配系数的对数值,反映了物质在油水两相中的分配情况。其中、LogP值越大,说明该物质越亲油;反之,LogP值越小,则说明该物质越亲水。
贝尔斯坦号/MDL:
MFCD00015006
EINECS:
237-266-4
PubChem:
24880600
BRN:
1738613
InChI:
InChI=1/C12H27P/c1-10(2,3)13(11(4,5)6)12(7,8)9/h1-9H3

生产制备方法及用途展开↓

制备方法


通过叔丁基氯化镁与三氯化磷在乙醚中反应,然后用叔丁基锂处理制备而来 (式1) 。

合成制备方法


通过叔丁基氯化镁与三氯化磷在乙醚中反应,然后用叔丁基锂处理制备而来 (式1)[1]

用途简介


医药中间体合成,金属催化剂配体等。

用途


P(t-Bu)3是一个应用于钯试剂催化的交叉偶联反应的电富性配体。钯试剂催化的芳基卤代物与芳基或烷基金属化合物 (M = B、Sn、Zn、Si、Mg) 之间的交叉偶联反应是形成C-C键的一种非常重要、有效地方法。传统的催化剂体系很容易实现钯对芳基C-Br键或C-I键的插入反应,而对于价格更为便宜、性质却更为惰性的芳基C-Cl键的活化则非常困难。研究发现,加入电负性大的P(t-Bu)3配体能够很有效地实现金属钯对芳基C-Cl键的插入反应,这无疑为C-C键形成反应注入了新的活力。除了P(t-Bu)3配体外,能够活化C-Cl键的有机配体还有由Milstein提出的体积大、电富性高的螯合双膦配体,Buchwald提出的体积大、电富性强的膦配体,Herrmann提出的N-杂环卡宾配体,以及Beller提出的亚磷酸盐配体。

P(t-Bu)3能够将钯试剂催化的卤代芳烃与苯胺底物的胺化反应扩展到氯代芳烃 (式2)[2],同时P(t-Bu)3也能促进芳基金属试剂如B、Zn、Sn、Si与卤代芳烃或芳基磺酰氯之间的交叉偶联反应 (式3)[3]

传统钯试剂催化的端炔与溴代芳烃之间的Sonogashira反应都是在高温以及加入共催化剂CuI条件下完成的。加入电负性配体P(t-Bu)3,不但可以使反应在室温下进行,还能避免CuI的使用,同时也能在高温下实现氯代芳烃与端炔的反应 (式4)[4]

氯代芳烃与单取代或双取代烯烃也能在Pd/P(t-Bu)3体系下、在二环己基甲基胺存在下发生Heck-Mizoroki交叉偶联反应 (式5)[5]

近年来,1-芳基三氮烯作为亲电试剂也能与芳基金属试剂 (如芳基硼、芳基硅) 在Pd/P(t-Bu)3催化体系作用下发生交叉偶联反应 (式6)[6]

物化性质展开↓

外观与性状:
透明液体(在10%己烷)
密度:
0.861 g/mL at 25 °C
熔点:
30-35 °C(lit.)
沸点:
102-103 °C13 mm Hg(lit.)
闪点:
1 °F
水溶解性:
insoluble
蒸汽压:
0.105mmHg at 25°C
存储条件/存储方法:

在低温下隔绝空气保存。

稳定性相关:

对空气非常敏感,必须在低温下隔绝空气保存。对它的操作必须在手套箱或惰性气体保护下进行。

其它信息:

1.       性状:无色刺激性气味

2.       密度(g/mL,25/4℃):0.83-0.84

3.       相对蒸汽密度(g/mL,空气=1):未确定

4.       熔点(ºC):30

5.       沸点(ºC,常压):未确定

6.       沸点(ºC,5.2kPa):102-103

7.       折射率:未确定

8.       闪点(ºC):未确定

9.       比旋光度(º):未确定

10.    自燃点或引燃温度(ºC):-16

11.    蒸气压(kPa,25ºC):未确定

12.    饱和蒸气压(kPa,60ºC):未确定

13.    燃烧热(KJ/mol):未确定

14.    临界温度(ºC):未确定

15.    临界压力(KPa):未确定

16.    油水(辛醇/水)分配系数的对数值:未确定

17.    爆炸上限(%,V/V):未确定

18.    爆炸下限(%,V/V):未确定

19.    溶解性:不能拌和或难以拌和的。

安全信息展开↓

包装等级:
I
风险类别:
4.2
海关代码:
2931900090
WGK_Germany:
3
德国有关水污染物质的分类清单
危险类别码:
R17;R34
安全说明:
S26-S45-S62-S36/37/39-S25-S43-S27-S16
安全标志:
S16:远离火源。
S26:万一接触眼睛,立即使用大量清水冲洗并送医诊治。
S27:立刻除去所有污染衣物。
S43:灭火时使用...(某种合适的灭火装置名称)。
S45:出现意外或者感到不适,立刻到医生那里寻求帮助(最好带去产品容器标签)。
:
危险标志:
F:Flammable;C:Corrosive;

合成路线查看所有的合成路线

  • 13716-10-4

    二叔丁基氯化膦

  • +

  • 677-22-5

    叔丁基氯化镁

  • ~92%

  • 13716-12-6

    三叔丁基膦

  • 677-22-5

    叔丁基氯化镁

  • +

  • 7719-12-2

    三氯化磷

  • ~88%

  • 13716-12-6

    三叔丁基膦

  • 93646-62-9

    93646-62-9

  • 13716-12-6

    三叔丁基膦

  • +

  • 79593-41-2

    tetrakis(1,1-dimethylethyl)-Hexaphosphabicyclo(3.1.0)hexane

毒理性展开↓

毒理学数据:

 

生态数据:

通常对水是不危害的,若无政府许可,勿将材料排入周围环境。

MSDS 展开↓

Name: Tri-tert-butylphosphine 95% Material Safety Data Sheet
Synonym:
CAS: 13716-12-6
Section 1 - Chemical Product   MSDS Name:Tri-tert-butylphosphine 95% Material Safety Data Sheet
Synonym:

Section 2 - COMPOSITION, INFORMATION ON INGREDIENTS
CAS# Chemical Name content EINECS#
13716-12-6 Tri-tert-butylphosphine 95% 237-266-4
Hazard Symbols: F C
Risk Phrases: 17 34

Section 3 - HAZARDS IDENTIFICATION
  EMERGENCY OVERVIEW
Spontaneously flammable in air. Causes burns.Air sensitive.
Potential Health Effects
Eye:
Causes eye burns. Lachrymator (substance which increases the flow of tears).
Skin:
Causes skin burns.
Ingestion:
Causes gastrointestinal tract burns.
Inhalation:
Causes chemical burns to the respiratory tract.
Chronic:
Not available.

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.
Ingestion:
Do not induce vomiting. If victim is conscious and alert, give 2-4 cupfuls of milk or water. Get medical aid immediately.
Inhalation:
Remove from exposure and move to fresh air immediately. If not breathing, give artificial respiration. If breathing is difficult, give oxygen. Get medical aid.
Notes to Physician:

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. Material can spontaneously ignite (pyrophoric) when exposed to air at normal or slightly elevated temperatures.
Extinguishing Media:
Use foam, dry chemical, or carbon dioxide.

Section 6 - ACCIDENTAL RELEASE MEASURES
  General Information: Use proper personal protective equipment as indicated in Section 8.
Spills/Leaks:
Absorb spill with inert material (e.g. vermiculite, sand or earth), then place in suitable container. Remove all sources of ignition.
Use a spark-proof tool.

Section 7 - HANDLING and STORAGE
  Handling:
Use spark-proof tools and explosion proof equipment. Do not breathe dust, vapor, mist, or gas. Do not get in eyes, on skin, or on clothing. Use only in a chemical fume hood. Store and handle protected from air.
Storage:
Store in a cool, dry place. Store in a tightly closed container.
Flammables-area. Do not expose to air. Store under an inert atmosphere.

Section 8 - EXPOSURE CONTROLS, PERSONAL PROTECTION
  Engineering Controls:
Use adequate ventilation to keep airborne concentrations low.
Exposure Limits CAS# 13716-12-6: Personal Protective Equipment Eyes: Not available.
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.

Section 9 - PHYSICAL AND CHEMICAL PROPERTIES
 
Physical State: Solid
Color: colorless
Odor: unpleasant odor
pH: Not available.
Vapor Pressure: Not available.
Viscosity: Not available.
Boiling Point: 102 - 103 deg C @ 13.00mm Hg
Freezing/Melting Point: Not available.
Autoignition Temperature: Not available.
Flash Point: -17 deg C ( 1.40 deg F)
Explosion Limits, lower: Not available.
Explosion Limits, upper: Not available.
Decomposition Temperature:
Solubility in water: Insoluble.
Specific Gravity/Density: .8200g/cm3
Molecular Formula: C12H27P
Molecular Weight: 202.32

Section 10 - STABILITY AND REACTIVITY
  Chemical Stability:
Not available.
Conditions to Avoid:
Incompatible materials, ignition sources, exposure to air.
Incompatibilities with Other Materials:
Strong oxidizing agents.
Hazardous Decomposition Products:
Carbon monoxide, oxides of phosphorus, carbon dioxide.
Hazardous Polymerization: Has not been reported

Section 11 - TOXICOLOGICAL INFORMATION
  RTECS#:
CAS# 13716-12-6 unlisted.
LD50/LC50:
Not available.
Carcinogenicity:
Tri-tert-butylphosphine - Not listed by ACGIH, IARC, or NTP.

Section 12 - ECOLOGICAL INFORMATION
 

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

Section 14 - TRANSPORT INFORMATION
 
IATA
Shipping Name: PYROPHORIC LIQUID, ORGANIC, N.O.S.*
Hazard Class: 4.2
UN Number: 2845
Packing Group: I
IMO
Shipping Name: PYROPHORIC LIQUID, ORGANIC, N.O.S.
Hazard Class: 4.2
UN Number: 2845
Packing Group: I
RID/ADR
Not regulated as a hazardous material.

Section 15 - REGULATORY INFORMATION
 
European/International Regulations
European Labeling in Accordance with EC Directives
Hazard Symbols: F C
Risk Phrases:
R 17 Spontaneously flammable in air.
R 34 Causes burns.
Safety Phrases:
S 25 Avoid contact with eyes.
S 36/37/39 Wear suitable protective clothing, gloves
and eye/face protection.
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# 13716-12-6: No information available.
Canada
None of the chemicals in this product are listed on the DSL/NDSL list.
CAS# 13716-12-6 is not listed on Canada's Ingredient Disclosure List.
US FEDERAL
TSCA
CAS# 13716-12-6 is not listed on the TSCA inventory.
It is for research and development use only.


SECTION 16 - ADDITIONAL INFORMATION
N/A

海关数据查看详细

中国海关编码:2931900090

概述:
2931900090. 其他有机-无机化合物. 增值税率:17.0%. 退税率:13.0%. 监管条件:AB(入境货物通关单,出境货物通关单). 最惠国关税:6.5%. 普通关税:30.0%
摘要/Summary:
2931900090. other organo-inorganic compounds. VAT:17.0%. Tax rebate rate:13.0%. Supervision conditions:AB(certificate of inspection for goods inward,certificate of inspection for goods outward). MFN tariff:6.5%. General tariff:30.0%

分子结构与计算化学数据展开↓

分子结构数据


1、摩尔折射率:无可用的

2、摩尔体积(cm3/mol):无可用的

3、等张比容(90.2K):无可用的

4、表面张力(dyne/cm):无可用的

5、介电常数:无可用的

6、极化率(10-24cm3):无可用的

7、单一同位素质量:202.185037 Da

8、标称质量:202 Da

9、平均质量:202.3165 Da

计算化学数据


1.疏水参数计算参考值(XlogP):2.9

2.氢键供体数量:0

3.氢键受体数量:0

4.可旋转化学键数量:3

5.互变异构体数量:无

6.拓扑分子极性表面积0

7.重原子数量:13

8.表面电荷:0

9.复杂度:128

10.同位素原子数量:0

11.确定原子立构中心数量:0

12.不确定原子立构中心数量:0

13.确定化学键立构中心数量:0

14.不确定化学键立构中心数量:0

15.共价键单元数量:1

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