65325-66-8

Upstream product

• 7205-88-1 1-[(chloromethyl)sulfanyl]-4-nitrobenzene 
• 593-70-4 R₃₂ 
• 1849-36-1 para-nitrobenzenethiol 
• 24067-17-2 4-nitrophenylboronic acid 
• 373-53-5 fluoroiodomethane 
• 100-01-6 4-nitro-aniline 
• 701-57-5 1-methylthio-4-nitro-benzene 

Downstream Products

• 39547-81-4 1-((fluoromethyl)sulfonyl)-4-nitrobenzene 
• 65325-70-4 1-((fluoromethyl)sulfinyl)-4-nitrobenzene 

Relevant academic research and scientific papers

Direct and Chemoselective Electrophilic Monofluoromethylation of Heteroatoms (O-, S-, N-, P-, Se-) with Fluoroiodomethane

The commercially available fluoroiodomethane represents a valuable and effective electrophilic source for transferring the CH2F unit to a series of heteroatom-centered nucleophiles under mild basic conditions. The excellent manipulability offered by its liquid physical state (bp 53.4 °C) enables practical and straightforward one-step nucleophilic substitutions to retain the chiral information embodied, thus allowing it to overcome de facto the requirement for fluoromethylating agents with no immediate access. The high-yielding methodology was successfully applied to a variety of nucleophiles including a series of drugs currently in the market.

Anodic fluorination of aromatic thioethers substituted by strongly electron-withdrawing groups

Arylalkylthioethers (aryl substituted by efficiently withdrawing groups) were anodically oxidized in the presence of Et3N, 3HF. Monofluorinations occuring often in good yield were found to be regiospecific onto the α-carbon of the aliphatic cha

Method for synthesizing aromatic monofluoromethylthio compound through one-pot method

The invention discloses a method for synthesizing an aromatic monofluoromethylthio compound through a one-pot method. The method comprises the following steps of: reacting aromatic amine serving as a raw material in an ice bath to generate corresponding diazonium salt under the effect of tert-butyl nitrite and tetrafluoroboric acid by taking anhydrous acetonitrile as a solvent; under the effect of copper chloride, cuprous chloride and 1, 10-phenanthroline, reacting in the ice bath by using potassium thiocyanate as a sulfur source to introduce sulfur atoms; and finally, under the effect of potassium hydroxide, reacting monofluoromethyl iodide in the ice bath to introduce monofluoromethyl, thereby obtaining the aromatic monofluoromethylthio compound. The method has the advantages of simple and safe steps, high reaction conversion rate, less three waste water, gas and solid and, environmental friendliness.

Monofluoromethyl-Substituted Sulfonium Ylides: Preparation, Structure-Reactivity Study and Substrate Scope?

Structure-reactivity study of a family of electrophilic monofluoromethylating reagents based on sulfonium ylide skeleton with different steric hindrance and electron-withdrawing properties was described. These studies led us to discover two highly reactive reagents 3 with a cyclic malonate backbone and 6 with an electron-poor 1,1,1,5,5,5-hexafluoropentane-2,4-dione backbone. The high reactivity of reagent 6 allowed to highly selectively access either C-monofluoromethylated or O-monofluoromethylated β-ketoesters in high yields by the use of different bases. In addition, reactions of reagent 3 with a variety of nucleophiles including phenols, carboxylic acids, thiophenols or heteroaryl nucleophiles occurred in full conversion within 10 min at room temperature and the scopes for these reactions were reported in detail.

Bunte Salt CH2FSSO3Na: An Efficient and Odorless Reagent for Monofluoromethylthiolation

A practical and efficient monofluoromethylthiolation that employs the typical Bunte salt, sodium S-(fluoromethyl) sulfurothioate, as the sulfur source is described. This reagent reacts readily with a variety of aryl amines and aryl thiols. The high tolerance of functional groups demonstrates the potential of this reaction. In addition, this method is suitable for the late-stage monofluoromethylthiolation of complex bioactive molecules.

Monofluoromethyl-Substituted Sulfonium Ylides: Electrophilic Monofluoromethylating Reagents with Broad Substrate Scopes

Two electrophilic monofluoromethylating reagents, monofluoromethyl(phenyl)sulfonium bis(carbomethoxy)methylide (3 a) and monofluoromethyl(4-nitrophenyl)sulfonium bis(carbomethoxy)methylide (3 b), and their reactions under mild conditions with a variety of nucleophiles, such as alcohols and malonate derivatives, sulfonic and carboxylic acids, phenols, amides, and N heteroarenes, are described. Mechanistic studies with deuterated reagents [D2]3 a/[D2]3 b suggest that these monofluoromethylation reactions proceed through an electrophilic substitution pathway.

Direct Monofluoromethylthiolation with S-(Fluoromethyl) Benzenesulfonothioate

An electrophilic shelf-stable monofluoromethylthiolating reagent S-(fluoromethyl) benezenesulfonothioate (1) was developed. In the presence of a copper catalyst, reagent 1 coupled with a variety of aryl boronic acids to give the corresponding monofluoromethylthiolated arenes in high yields. In addition, addition of reagent 1 to alkyl alkenes in the presence of a silver catalyst gave alkyl monofluoromethylthioethers in high yields.

Radical Fluoroalkylation of Isocyanides with Fluorinated Sulfones by Visible-Light Photoredox Catalysis

The radical fluoroalkylation of isocyanides with fluorinated sulfones is enabled by visible-light photoredox catalysis. A wide range of readily available mono-, di-, and trifluoromethyl heteroaryl sulfones can thus be used as efficient radical fluoroalkylation reagents under mild conditions. This method not only describes a new synthetic application of fluorinated sulfones, but also provides a new route to fluoroalkyl radicals.

Direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs)CH2F: The accelerating effect of α-fluorine substitution

An efficient and direct monofluoromethylation of O-, S-, N-, and P-nucleophiles with PhSO(NTs)CH2F 1 has been developed. In contrast to the previously known detrimental effect of α-fluorine substitution on SN2 reactions, the current monofluoromethylation is accelerated by the α-fluorine substitution. Based on a mechanistic study, a new reactivity of sulfoximine (as a radical monofluoromethylation reagent) is disclosed.

Electrophilic monofluoromethylation of O-, S-, and N-nucleophiles with chlorofluoromethane

CH2ClF has been found to be a useful electrophilic monofluoromethylating agent for a variety of O-, S-, and N-nucleophiles. The reaction is not sensitive to the radical scavenger such as nitrobenzene, which strongly supports an SN2 m