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Trimethylsilyl trifluoromethanesulfonate (TMSOTf) is a widely used reagent in organic synthesis. It combines the reactivity of the trimethylsilyl group with the electrophilic nature of the triflate anion, making it a powerful catalyst and activating agent in a variety of chemical reactions.
Chemical Structure and Properties
Chemical Name: Trimethylsilyl trifluoromethanesulfonate
Abbreviation: TMSOTf
Molecular Formula: C₄H₉F₃O₃SSi
Molecular Weight: 218.27 g/mol
CAS Number: 27607-77-8
Physical Properties:
The molecule consists of a highly electrophilic triflate group (-OSO₂CF₃) and a trimethylsilyl (TMS) group, making it highly reactive in polar and anhydrous conditions.
Synthesis
TMSOTf is typically prepared by reacting trimethylsilyl chloride (TMSCl) with silver trifluoromethanesulfonate (AgOTf) under anhydrous conditions:
TMSCl+AgOTf→TMSOTf+AgCl\text{TMSCl} + \text{AgOTf} \rightarrow \text{TMSOTf} + \text{AgCl}TMSCl+AgOTf→TMSOTf+AgCl
The reaction must be performed in the absence of moisture because TMSOTf is hydrolytically unstable.
Applications
Advantages
Safety and Handling
TMSOTf is a highly reactive compound and must be handled with care.
Hazards:
Safety Precautions:
First Aid:
Storage:
Environmental Impact
TMSOTf is potentially hazardous to aquatic environments and should not be released into the environment. Disposal must comply with local environmental regulations.
Conclusion
Trimethylsilyl trifluoromethanesulfonate (TMSOTf) is a versatile and powerful reagent widely used in organic synthesis, particularly in electrophilic activation and silylation reactions. Its high reactivity and selectivity make it invaluable for various chemical processes, although its handling requires careful precautions due to its corrosive and moisture-sensitive nature.
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2-bromophenol
ChatGPT said:
ChatGPT 2-Bromophenol: Overview and Applications
2-Bromophenol is an aromatic halogenated phenol compound commonly used as a building block in organic synthesis. It is an ortho-substituted bromophenol, where a bromine atom is attached to the benzene ring at the second position relative to the hydroxyl group (-OH). The presence of both hydroxyl and halogen groups makes it a versatile reagent in the synthesis of pharmaceuticals, agrochemicals, and fine chemicals.
Chemical Structure and Properties
Chemical Structure
The structure of 2-bromophenol consists of a benzene ring with two functional groups:
This combination gives the molecule unique chemical and physical properties, including polarity, reactivity, and solubility.
Synthesis of 2-Bromophenol
2-Bromophenol can be synthesized by:
Chemical Structure and Properties
Chemical Name: Trimethylsilyl trifluoromethanesulfonate
Abbreviation: TMSOTf
Molecular Formula: C₄H₉F₃O₃SSi
Molecular Weight: 218.27 g/mol
CAS Number: 27607-77-8
Physical Properties:
| Appearance | Colorless to pale yellow liquid |
| Boiling Point | 109–111°C (at 20 mmHg) |
| Density | ~1.29 g/cm³ |
| Solubility | Miscible with most organic solvents |
| Stability | Reacts with water and alcohols |
Synthesis
TMSOTf is typically prepared by reacting trimethylsilyl chloride (TMSCl) with silver trifluoromethanesulfonate (AgOTf) under anhydrous conditions:
TMSCl+AgOTf→TMSOTf+AgCl\text{TMSCl} + \text{AgOTf} \rightarrow \text{TMSOTf} + \text{AgCl}TMSCl+AgOTf→TMSOTf+AgCl
The reaction must be performed in the absence of moisture because TMSOTf is hydrolytically unstable.
Applications
- Catalyst in Organic Synthesis:
- TMSOTf is an effective Lewis acid and is used to catalyze reactions requiring electrophilic activation.
- It is widely employed in Friedel-Crafts alkylations, acylations, and other electrophilic aromatic substitution reactions.
- Silylation Agent:
- It is used to introduce trimethylsilyl (TMS) groups into alcohols, phenols, and carboxylic acids, protecting these functional groups during multistep syntheses.
- Example: R−OH+TMSOTf→R−OTMS+HOTfR-OH + \text{TMSOTf} \rightarrow R-OTMS + \text{HOTf}R−OH+TMSOTf→R−OTMS+HOTf
- Activation of Nucleophiles and Electrophiles:
- TMSOTf enhances the reactivity of carbonyl compounds and other electrophiles, making it useful in reactions such as aldol condensations and Mukaiyama reactions.
- It can also activate certain nucleophiles like enol ethers, dienes, and ketene acetals.
- Carbocation Generation:
- TMSOTf is frequently used to generate carbocations under mild conditions, which are crucial intermediates in cationic polymerization and rearrangement reactions.
- Glycosylation Reactions:
- It is a reagent of choice for glycosylation in carbohydrate chemistry, enabling the coupling of sugar donors with acceptors to form glycosidic bonds.
- Example: Sugar donor+Sugar acceptor+TMSOTf→Glycoside\text{Sugar donor} + \text{Sugar acceptor} + \text{TMSOTf} \rightarrow \text{Glycoside}Sugar donor+Sugar acceptor+TMSOTf→Glycoside
- Ring-Closing Reactions:
- TMSOTf is used in cyclization reactions, such as in the synthesis of heterocyclic compounds and lactones.
- Reagent for Selective Reactions:
- Due to its mild reactivity, TMSOTf is often used for selective transformations where harsher conditions may lead to unwanted side reactions.
Advantages
- High Electrophilicity: Enables efficient activation of substrates.
- Mild Reaction Conditions: Operates under relatively low temperatures and pressures.
- Versatility: Useful across a range of organic transformations.
Safety and Handling
TMSOTf is a highly reactive compound and must be handled with care.
Hazards:
- Reacts violently with water to release toxic gases, such as hydrogen fluoride (HF) and triflic acid.
- Causes severe burns upon skin or eye contact.
- Vapors are corrosive to the respiratory system.
Safety Precautions:
- Work in a well-ventilated fume hood.
- Use proper PPE: gloves, goggles, and lab coats.
- Avoid contact with moisture and incompatible substances like strong bases and oxidizers.
First Aid:
- Inhalation: Move to fresh air immediately; seek medical attention.
- Skin/Eye Contact: Wash thoroughly with water; for eye exposure, rinse for at least 15 minutes and seek immediate medical assistance.
- Ingestion: Do not induce vomiting; seek medical help immediately.
Storage:
- Store in a tightly sealed container under anhydrous conditions.
- Keep away from moisture, acids, and bases.
Environmental Impact
TMSOTf is potentially hazardous to aquatic environments and should not be released into the environment. Disposal must comply with local environmental regulations.
Conclusion
Trimethylsilyl trifluoromethanesulfonate (TMSOTf) is a versatile and powerful reagent widely used in organic synthesis, particularly in electrophilic activation and silylation reactions. Its high reactivity and selectivity make it invaluable for various chemical processes, although its handling requires careful precautions due to its corrosive and moisture-sensitive nature.
4o You said:
2-bromophenol
ChatGPT said:
ChatGPT 2-Bromophenol: Overview and Applications
2-Bromophenol is an aromatic halogenated phenol compound commonly used as a building block in organic synthesis. It is an ortho-substituted bromophenol, where a bromine atom is attached to the benzene ring at the second position relative to the hydroxyl group (-OH). The presence of both hydroxyl and halogen groups makes it a versatile reagent in the synthesis of pharmaceuticals, agrochemicals, and fine chemicals.
Chemical Structure and Properties
| Chemical Name | 2-Bromophenol |
| Molecular Formula | C₆H₅BrO |
| Molecular Weight | 173.01 g/mol |
| CAS Number | 95-56-7 |
| Appearance | White to pale yellow crystalline solid |
| Boiling Point | 210°C |
| Melting Point | 7°C |
| Density | 1.77 g/cm³ |
| Solubility | Slightly soluble in water, soluble in organic solvents like ethanol, ether, and chloroform |
Chemical Structure
The structure of 2-bromophenol consists of a benzene ring with two functional groups:
- Hydroxyl group (-OH) at the first position.
- Bromine atom (Br) at the second position (ortho position).
This combination gives the molecule unique chemical and physical properties, including polarity, reactivity, and solubility.
Synthesis of 2-Bromophenol
2-Bromophenol can be synthesized by:
- Bromination of Phenol:
- Phenol undergoes electrophilic aromatic substitution with bromine in the presence of a catalyst (like FeBr₃), resulting in bromophenol. By controlling the reaction conditions, the ortho isomer (2-bromophenol) can be selectively produced.
Reaction:
C6H5OH+Br2→C6H4BrOH+HBr\text{C}_6\text{H}_5\text{O H} + \text{Br}_2 \rightarrow \text{C}_6\text{H}_4\text{BrOH} + \text{HBr}C6H5OH+Br2→C6H4BrOH+HBr - Direct Bromination with NBS (N-Bromosuccinimide):
- NBS is used as a brominating agent in the presence of a radical initiator (like light or peroxide) to selectively brominate phenol derivatives at the ortho position.