592-94-9

Upstream product

• 124-07-2 Octanoic acid 
• 455-32-3 benzoyl fluoride 
• 111-64-8 n-octanoic acid chloride 
• 19886-81-8 isopropenyl octanoate 
• 111-87-5 octanol 
• 124-13-0 Octanal 
• 5457-66-9 tert-butyl octanoate 

Downstream Products

• 335-57-9 perfluoroheptane 
• 335-67-1 Perfluorooctanoic acid 
• 335-66-0 perfluorooctanoyl fluoride 
• 335-35-3 perfluoro-2-butyl-tetrahydrofuran 
• 335-36-4 2,2,3,3,4,4,5-heptafluoro-5-nonafluorobutyl-tetrahydro-furan 
• 5457-66-9 tert-butyl octanoate 

Relevant academic research and scientific papers

Gram-Scale Preparation of Acyl Fluorides and Their Reactions with Hindered Nucleophiles

A series of acyl fluorides was synthesized at 100 mmol scale using phase-transfer-catalyzed halogen exchange between acyl chlorides and aqueous bifluoride solution. The convenient procedure consists of vigorous stirring of the biphasic mixture at room temperature, followed by extraction and distillation. Isolated acyl fluorides (usually 7-20 g) display excellent purity and can be transformed into sterically hindered amides and esters when treated with lithium amide bases and alkoxides under mild conditions.

A protocol for amide bond formation with electron deficient amines and sterically hindered substrates

A protocol for amide coupling by in situ formation of acyl fluorides and reaction with amines at elevated temperature has been developed and found to be efficient for coupling of sterically hindered substrates and electron deficient amines where standard methods failed.

Analogs of 2-arachidonoylglycerin containing the no-donor group

1, 3-Dinitroglyceryl esters of fatty acids, analogs of endocannabinoid 2-arachidonoylglycerin, were synthesized. Various methods for esterifying fatty acids with glycerine dinitrate were developed.

PROCESSES FOR PRODUCTION OF FLUORINE-CONTAINING COMPOUNDS

This process for producing fluorine-containing compounds includes liquid-phase fluorination by introducing a raw material compound and fluorine gas into a solvent to replace hydrogen atoms in the raw material compound with fluorine atoms. More specifically, the process for producing fluorine-containing compounds includes (1) promoting fluorination by dissolving the raw material compound in anhydrous hydrofluoric acid and introducing into a liquid-phase fluorination solvent, or (2) promoting fluorination by dissolving the raw material compound in a perfluoro compound having a plurality of polar groups in a molecule thereof and introducing into a liquid-phase fluorination solvent. According to these processes, a fluorination reaction can be carried out at high yield and without containing hardly any isomers while using a hydrocarbon compound as is for the raw material.

A convenient, one-pot procedure for the preparation of acyl and sulfonyl fluorides using Cl3CCN, Ph3P, and TBAF(t -BuOH) 4

Various carboxylic acids were converted into acyl fluorides in excellent yields by treatment with trichloroacetonitrile, triphenylphosphine, and TBAF(t-BuOH)4 at room temperature. The reaction was applicable to the preparation of acid-sensitive amino acid fluorides without deprotection or rearrangement

A new method for making acyl fluorides using BrF3

While many carboxylic acids could be converted directly to acyl fluorides by using BrF3, the reaction with acyl chlorides was found to be of a more general nature and yields better results. Surprisingly, reacting t-butyl esters with bromine trifluoride also resulted in acyl fluorides in reasonable yields. The reactions were completed in a few seconds at 0°C.

Reactions of alcohols with cesium fluoroxysulfate

The reactions of alcohols with cesium fluoroxysulfate (CsSO4F) in MeCN suspension were studied, and the role of the structure of the alcohol and the reaction conditions on the course of reaction was determined. Secondary benzyl alcohols bearing a nonactivating aromatic ring were selectively oxidized to the corresponding ketones, while the CsSO4F-mediated reaction of phenyl-1-naphthylmethanol resulted in the formation of 1-fluoronaphthalene and benzaldehyde. Cyclic and noncyclic secondary alcohols were readily converted to ketones, as well as 1-hydroxybenzecyclanes to benzocyclanones- 1, without any further fluorination or oxidation under the reaction conditions. On the other hand, reactions of primary alcohols with CsSO4F resulted in the formation of acid fluorides derived from further fluorination of aldehydes. Another type of transformation was observed in the case of alcohols bearing a benzyl functional group attached geminal to a hydroxy group, where decarbanylation of reactive intermediates resulting in the formation of benzyl fluoride derivatives became the main process. 2- Phenylethanol was so converted to benzyl fluoride and phenylacetyl fluoride in a 3:1 relative ratio, while 2-phenyl-1-propanol was selectively transformed to 1-phenyl-1-fluoroethane. The presence of the radical inhibitor nitrobenzene in the reaction mixture considerably inhibited conversion of the starting material. The same effect was observed by lowering the solvent polarity. Hammett correlation analysis of the effect of substituents on the reaction rates of oxidation of a set of substituted 1-phenyl-1-ethanols to acetophenones gave the reaction constant p+ = -0.32, while analysis of analogous data for the transformations of benzyl alcohols to benzoyl fluorides gave the value of -0.54. A mechanism including radical intermediates was proposed for the transformation of alcohols by CsSO4F.

Oxidation of primary alcohols to acyl fluorides using BrF3

Aliphatic and alicyclic primary alcohols when treated with BrF3 were rapidly oxidized to the corresponding acyl fluorides. The reaction is of an ionic nature. The main by-product was found to be the symmetrical ester which originates from the reaction between the acyl fluoride and unreacted starting alcohol.

The effect of heteroatoms on the reactions of organic molecules with caesium fluoroxysulphate

CsSO4F reacted at room temperature, or at 35°C in acetonitrile with various heteroatom-containing organic molecules, and three types of transformations have been observed. Fluoro substitution process took place with triphenylmethane, triphenylsilane, triphenylchlorosilane, 4-tert-butylphenol, benzaldehyde, and octanol, thus forming fluorotriphenylmethane, fluorotriphenylsilane, 2-fluoro-4-tert-butylphenol, benzoyl fluoride, or octanoyl fluoride in high yields. Substitution reaction was accompanied by fluoroaddition process in the case of 2-fluoro-4-tert-butylphenol, where 2,2-difluoro-4-tert-butylcyclohexadienon-4,6- was isolated. CsSO4F easily oxidised secondary alcohols to ketones, and 1,2-dihydro-4-tert-butylbenzene to quinone derivate. Oxygenation process was observed in the case of triphenylphosphine, and dibenzothiophene, while ethyl iodide was transformed to ethyliodo(III) difluoride. Solvent plays an important role in these reactions, being successfully performed in CH3CN, and completely inhibited in CH2Cl2, while different shapes of the effect on fluorination of various organic molecules were observed by altering solvent nature by successive mixing of CH3CN with CH2Cl2.

Reactions of Aldehydes with Cesium Fluoroxysulfate

Various aromatic and aliphatic aldehydes reacted at 35-40 deg C in CH3CN with CsSo4F giving acid fluorides in a good yield.In some cases formation of fluorohydrocarbons was also observed.Hammett correlation analysis of the transformation of various substituted benzaldehydes (p-OCH3, p-CH3, p-F, p-CF3, m-NO2) gave the reaction constant ρ+ = -0.38.Solvent polarity strongly influenced the conversion of aldehydes into acid fluorides, being in acetonitrile almost quantitative and completely halted in CH2Cl2, n-hexane, or tetrahydrofuran.The presence of nitrobenzene, often used as a radical scavenger, considerably reduced the acid fluoride formation.Based on experimental observations was concluded that the main intermediates involved in the conversion of aldehydes into acid fluorides with CsSO4F must be of a radical nature.