tert-Butyllithium solution
tert-Butyllithium
CAS: 594-19-4
Molecular Formula: C4H9Li
tert-Butyllithium solution - Names and Identifiers
| Name | tert-Butyllithium |
| Synonyms | tert-Butyllithium Nominally1.5Minn-Pentane tert-Butyllithium solution lithium 2-methylpropan-2-ide TERT-BUTYLLITHIUM SOLUTION IN HEPTANE ButyllithiuminpentaneMslightlycloudyliq TERT-BUTYLLITHIUM, 1.7M SOLUTION IN PENT TERT-BUTYLLITHIUM SOLUTION, ~1.5 M IN PE NTANE |
| CAS | 594-19-4 |
| EINECS | 209-831-5 |
| InChI | InChI=1/C4H9.Li/c1-4(2)3;/h1-3H3;/rC4H9Li/c1-4(2,3)5/h1-3H3 |
| InChIKey | BKDLGMUIXWPYGD-UHFFFAOYSA-N |
tert-Butyllithium solution - Physico-chemical Properties
| Molecular Formula | C4H9Li |
| Molar Mass | 64.06 |
| Density | 0.69g/mLat 20°C |
| Boling Point | 36-40 °C |
| Flash Point | 20°F |
| Vapor Density | ~3 (vs air) |
| Appearance | liquid |
| Color | slightly cloudy |
| Exposure Limit | ACGIH: TWA 1000 ppmOSHA: TWA 1000 ppm(2950 mg/m3)NIOSH: IDLH 1500 ppm; TWA 120 ppm(350 mg/m3); Ceiling 610 ppm(1800 mg/m3) |
| BRN | 3587204 |
| Storage Condition | 2-8°C |
| Sensitive | Air & Moisture Sensitive |
tert-Butyllithium solution - Risk and Safety
| Risk Codes | R11 - Highly Flammable R15 - Contact with water liberates extremely flammable gases R17 - Spontaneously flammable in air R34 - Causes burns R51/53 - Toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. R65 - Harmful: May cause lung damage if swallowed R66 - Repeated exposure may cause skin dryness or cracking R67 - Vapors may cause drowsiness and dizziness R50/53 - Very toxic to aquatic organisms, may cause long-term adverse effects in the aquatic environment. R38 - Irritating to the skin R14/15 - |
| Safety Description | S26 - In case of contact with eyes, rinse immediately with plenty of water and seek medical advice. S36/37/39 - Wear suitable protective clothing, gloves and eye/face protection. S43 - In case of fire use ... (there follows the type of fire-fighting equipment to be used.) S45 - In case of accident or if you feel unwell, seek medical advice immediately (show the label whenever possible.) S62 - If swallowed, do not induce vomitting; seek medical advice immediately and show this container or label. S61 - Avoid release to the environment. Refer to special instructions / safety data sheets. S16 - Keep away from sources of ignition. S33 - Take precautionary measures against static discharges. S9 - Keep container in a well-ventilated place. |
| UN IDs | UN 3394 4.2/PG 1 |
| WGK Germany | 1 |
| FLUKA BRAND F CODES | 3-10 |
| TSCA | Yes |
| HS Code | 29319090 |
| Hazard Class | 4.3 |
| Packing Group | I |
tert-Butyllithium solution - Reference Information
| EPA chemical information | Information provided by: ofmpub.epa.gov (external link) |
| Organolithium Reagent | Tert-butyl lithium is a commonly used organolithium reagent in the laboratory. The chemical properties are similar to n-butyl lithium, but the activity is higher. Soluble in pentane, ether, tetrahydrofuran and diethylene glycol dimethyl ether. It is stable to heat and rarely decomposes when heated at 100 ℃ for 20 hours. The products of tert-butyl lithium sold on the market are usually packaged in the form of 1.3M pentane solution. In the laboratory, tert-butyl chloride (containing tert-butyl alcohol) and sodium-containing lithium are reacted at a reflux temperature in n-pentane to prepare tert-butyl lithium finished products. Figure 1 shows: tert-butyl chloride reacts with metal lithium to prepare tert-butyl lithium Chemical reaction equation tert-butyl lithium is a super base in organic synthesis, and the activity order of the organic lithium reagent base commonly used in the laboratory: tert-butyl lithium> butyl lithium> ethyl lithium> pentyl lithium> phenyl lithium> methyl lithium. |
| Uses | tert-butyl lithium is mainly used as lithiation reagent, halogen-lithium exchange reagent, cyclization reagent and strong base, etc., to prepare various types of organic compounds. For example: (1) Through the halogen-metal exchange reaction, tert-butyl lithium can be used to prepare other organic Keng compounds, such as aryl Keng, trialkyl boron hydride file, vinyl file, a Keng alkyl phenyl sulfide, β-Keng enamine, etc. The laboratory is used as a polymerization initiator and metallization agent. Compared with n-butyl lithium and isobutyl lithium, tert-butyl lithium has stronger alkaline and metallization activities and weaker nucleophilicity, so it can be used for hydrocarbon substrates with weaker proton acidity Deprotonic lithiation reaction. Generally, simple alkanes can still remain inert to tert-butyl lithium, but for heteroatom-containing solvents such as THF, they will react with tert-butyl lithium. When the substrate is a compound containing heteroatoms such as oxygen, nitrogen, and sulfur, using tert-butyl lithium as a deproton reagent can obtain high regioselectivity. For example, the reaction of vinyl ether or cyclic ether with tert-butyl lithium is a simple method for preparing α-lithiated vinyl ether. (2) Tert-butyl lithium is similar to other alkyl lithium reagents. The lithiation reaction of tert-butyl lithium on aromatic compounds containing heteroatom substituents also has ortho lithiation effect. In the lithium halogen exchange reaction, tert-butyl lithium has greater advantages over n-butyl lithium and isobutyl lithium due to its weak nucleophilicity. Among them, the lithium-iodine exchange reaction is the most complete and effective. For example, lithium-iodine exchange occurs when it first reacts with 6-iodo-1-hexene at low temperature, and then heats up to produce high stereoselectivity and regioselectivity. The 5-outer cyclic reaction is then attacked by electrophiles to obtain functionalized products (Formula 4)[4]. Similar isomeric reactions can also be used to prepare polycyclic compounds. |
| Safe access to tert-butyl lithium | tert-butyl lithium (tert-Butyllithium) is "famous" in organic chemistry ". On the one hand, because it is widely used and extremely alkaline, the hydrogen atom that is difficult to pull out by ordinary reagents is nothing in front of tert-butyl lithium. On the other hand, because this product has its own "flame" special effect, it can react violently and burn quickly when exposed to water and oxygen. A little carelessness can trigger a laboratory accident, which makes many organic "brick movers" frightened. There is a joke describing tert-butyl lithium, "It looks like a liquid, and when it is released, it is a flame". If the operation is not careful, the lighter will burn and the heavier may lose their lives. Tert-butyl lithium is an organometallic compound with very active chemical properties and easy to form tert-butyl carbanion. This carbanion is extremely alkaline (Lewis acid/alkaline, refers to the ability to accept/provide protons). Because of its strong ability to provide electrons, that is, it is extremely reducible, making tert-butyl lithium highly flammable and can ignite spontaneously when exposed to water or air. Usually the experiment needs to be operated very carefully, and the experiment often needs to be carried out in a high-purity inert gas environment. Although tert-butyl lithium is dangerous, it is also a very practical reagent in synthesis experiments, so how to safely use tert-butyl lithium is particularly important. Recently, the Mogens Hinge team from Aarhus University in Denmark wrote in the journal Org. Process Res. Dev. An article on how to safely access tert-butyl lithium was published on the website. The device used and the access process are shown in the figure. |
| quenching method | slowly pour into tetrahydrofuran with a small amount of dry ice, slowly add twice the excess amount of ethanol, then add water to dilute, finally add dilute HCl until the solution becomes clear, and pour into the corresponding waste liquid barrel in the floor fume hood. Problems to be considered in quenching treatment: 1) Choose a suitable quenching reagent, and fully consider the stability of the product and the difficulty of post-treatment; 2) If the quenching process will release a lot of heat, it must be quenched under cooling; 3) Don't rely too much on the literature without monitoring the reaction. Only when TLC or other analytical means show the end of the reaction can the reaction be quenched; 4) If possible, post-treatment should be carried out as soon as possible after quenching. |
| precautions | tert-butyl lithium solution is highly flammable and easy to catch fire when exposed to air or moisture. it must be protected by dry nitrogen during storage and must be very careful when using it. The operation of tert-butyl lithium should be carried out under anhydrous and oxygen-free conditions, and safety equipment such as goggles and anti-corrosion gloves should be worn. In case of fire, use a dry powder fire extinguisher to extinguish it. Never use a water-containing or chlorinated alkane fire extinguisher. The reaction involving tert-butyl lithium must be carried out under the protection of nitrogen or argon that insulates air and moisture. Since the reaction is exothermic, the reaction should be controlled to proceed at low temperatures. |
| category | spontaneous combustion substances in contact with water |
| flammability hazard characteristics | its heptane solution spontaneously ignites in the air; When exposed to heat, open flame is flammable; Reaction with water to spontaneously ignite |
| storage and transportation characteristics | warehouse ventilation and low temperature drying; Waterproof, anti-open flame |
| fire extinguishing agent | dry powder |
Last Update：2024-04-10 22:29:15
