An efficient route to alkyl chlorides from alcohols using the complex TCT/DMF
Lidia De Luca1, Giampaolo Giacomelli, Andrea Porcheddu
1Dipartimento di Chimica, Università degli Studi di Sassari, Via Vienna 2, I-07100 Sassari, Italy.
Organic Letters
|February 15, 2002
Summary
This study introduces a new method for converting alcohols and beta-amino alcohols into chlorides and bromides efficiently. The room-temperature reaction uses readily available reagents, preserving optical activity in carbinols.
Area of Science:
- Organic Chemistry
- Synthetic Chemistry
Background:
- Efficient synthesis of alkyl halides from alcohols is crucial in organic chemistry.
- Existing methods may require harsh conditions or lack stereochemical control.
Purpose of the Study:
- To develop a mild and efficient method for converting alcohols and beta-amino alcohols to alkyl halides.
- To investigate the applicability of the method to optically active substrates.
Main Methods:
- Reaction of alcohols and beta-amino alcohols with 2,4,6-trichloro[1,3,5]triazine and N,N-dimethyl formamide.
- Conducting the reaction at room temperature in methylene chloride.
Main Results:
- High yields of corresponding chlorides and bromides were achieved.
- The procedure is effective for both simple alcohols and beta-amino alcohols.
- Optically active carbinols were converted without loss of stereochemical integrity.
Conclusions:
- A novel, efficient, and mild protocol for the synthesis of alkyl halides from alcohols has been established.
- The method offers a valuable alternative for halogenation reactions, particularly for stereochemically sensitive substrates.
More Related Videos
Related Concept Videos
02:46E1 Reaction: Kinetics and Mechanism
Here, in contrast to the E2 reaction mechanism, we delve into the aspects of the E1 reaction mechanism, which has two steps: rate-limiting loss of the leaving group and abstraction of the beta hydrogen by a weak base. Typically, the experimental proof for the E1 mechanism is via kinetic studies or isotope studies. While the former demonstrates the first-order kinetics—the dependence of the reaction solely on substrate concentration—the latter proves the abstraction of hydrogen only in the...
02:48Conversion of Alcohols to Alkyl Halides
This lesson delves into the conversion of alcohols to corresponding alkyl halides and the mechanism of action for different reagents. Typically, the hydroxyl group is first protonated to convert it to a stable leaving group. Consequently, based on the starting alcohol, the mechanism undergoes either of the nucleophilic substitution routes, SN1 or SN2. Tertiary alkyl halides are made using the two-step SN1 mechanism that occurs via a carbocation intermediate, which is stabilized by...
01:12Acid Halides to Esters: Alcoholysis
Alcoholysis is a nucleophilic acyl substitution reaction in which an alcohol functions as a nucleophile. Acid halides react with alcohol to produce esters. The mechanism proceeds in three steps:
01:15Acid Halides to Alcohols: Grignard Reaction
Organomagnesium halides, commonly known as Grignard reagents, convert acid halides to tertiary alcohols. The reaction requires two equivalents of the Grignard reagent and proceeds via a ketone intermediate.
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
Grignard reagents are a source of carbanions and function as nucleophiles. The mechanism begins with the nucleophilic attack by the carbanion at the carbonyl carbon of the acid halide to form a tetrahedral intermediate. Next, the carbonyl group is re-formed, and the halide ion departs,...
01:27Radical Substitution: Halogenation of Alkanes and Alkyl Substituents
In the presence of heat or light, alkanes react with molecular halogens to form alkyl halides by a substitution reaction called radical halogenation. This reaction has three steps: initiation, propagation, and termination, as seen in the radical chlorination of methane to produce methyl chloride.
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
In the initiation step of the reaction, the chlorine molecule undergoes homolytic cleavage in the presence of light or heat, forming two highly reactive chlorine radicals. Propagation occurs in two...
![[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F13097.jpg&w=3840&q=75)
01:24[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
The Claisen rearrangement is a [3,3] sigmatropic rearrangement of allyl vinyl ethers to unsaturated carbonyl compounds. The rearrangement is a concerted pericyclic reaction proceeding via a chair-like transition state.