Fluorine carbonyl chloride

It was important to determine whether the fluorine atom must be attached directly to the phosphorus atom in order to produce phosphorofluoridate-like activity. For this purpose we treated the toxic di-sec.-butyl phosphorofluoridate1 with diazomethane and obtained a compound which was undoubtedly di- ec.-butyl fluoromethylphosphonate (XIX). Unlike the parent phosphorofluoridate, the fluoromethylphosphonate was only slightly toxic and produced negligible myosis. (It may be mentioned here that thionyl chloride and carbonyl chloride were converted by means of diazomethane into bis-(chloromethyl)-sulphoxide and S-dichloroacetone respectively.)... 

Quinomethionate (91) (60AG973) is made by reaction of 6-methylquinoxaline-2,3-dithiol with carbonyl chloride. It is used to control spider mites, and also has fungicidal properties. An experimental acaricide containing the unusual trifluoromethylimino group is the thiazolidine (92) (72GEP2062348). It is made by reaction of Af.fV -diphenylthiourea with the highly fluorinated intermediate (93). 

Chlorodifluoroamine has been prepared by reaction of difluoro-amine with boron trichloride,1 phosgene (carbonyl chloride),2 or hydrogen chloride 2 treating a mixture of sodium azide and sodium chloride with fluorine 3 reaction of chlorine trifluoride with ammonium fluoride 4 reaction of chlorine with diflu oro-amine in the presence of potassium fluoride 5 and photolysis of tetrafluorohydrazine and sulfinyl chloride (thionyl chloride).6... 

Carbonyl fluoride can be prepared by any of several methods, including the conversion of carbonyl chloride to the fluoride by such reagents as hydrogen fluoride1 and antimony (III) fluoride.2 The direct combination of carbon monoxide and fluorine is another route to this fluoride, but carbon tetrafluoride is a by-product of the reaction.8 A particularly suitable laboratory preparation of carbonyl fluoride is the fluorination of carbon monoxide by silver (II) fluoride.4 This method, described below, gives directly carbonyl fluoride of rather high purity without recourse to a low-temperature distillation. 

Chloroformates, carbonyl chlorides and acid chlorides are converted into the corresponding fluorides 1 in excellent yield upon treatment with potassium fluoride in the presence of 18-crown-6 at room temperature. Fluoroformates are also synthesized from chloroformates by fluorination with potassium fluoride in acetylacetone at 60"C under UV irradiation, with potassium fluoride in nitrobenzene,- with potassium fluoride in the absence of a solvent at temperatures in the range 100-250 and with thallium(I) fluoride. 

Likewise, the competitive reaction of aldehydes 23 and 24 with allyltributylstannane gives homoallylic alcohol (25) exclusively (Scheme 1.18). In contrast, nonfluorinated cycloadduct is produced mainly under the catalysis of BF3 etherate in methylene chloride. These results clearly demonstrate that fluorinated carbonyl compounds are more reactive however, there is a turnabout in the reactivity under the Lewis acid catalytic conditions because of the lower basicity of the carbonyl group than that of the nonfluorinated one. 

Leckta has developed a catalytic asymmetric a-fluorination of acid chlorides utilising a dual activation strategy. " Treatment of an acid chloride with both quinidine and either a Ni(ii) or Pd(ii) source in the presence of NFSI and Hunig s base resulted in the formation of an unactivated, a-fluorinated carbonyl which could be subsequently captured by a range of nucleophiles resulting in the formation of densely functionalised products with excellent enantioselectivity (Scheme 15.40). 

Sulfur tetrafluoride [7783-60-0] SF, replaces halogen in haloalkanes, haloalkenes, and aryl chlorides, but is only effective (even at elevated temperatures) in the presence of a Lewis acid catalyst. The reagent is most often used in the replacement of carbonyl oxygen with fluorine (15,16). Aldehydes and ketones react readily, particularly if no alpha-hydrogen atoms are present (eg, benzal fluoride [455-31-2] from benzaldehyde), but acids, esters, acid chlorides, and anhydrides are very sluggish. However, these reactions can be catalyzed by Lewis acids (HP, BF, etc). 

Nickel carbonyl Niobium Nitrates Air, bromine, oxidizing materials Bromine trifluoride, chlorine, fluorine Aluminum, BP, cyanides, esters, phosphorus, tin(II) chloride, sodium hypophos-... 

The bifunctional chlorocarbonylsulfenyl chloride, obtainable through partial hydrolysis of trichlorotnethanesulfenyl chloride (162), is fluorinated by SbFg at the carbonyl group (66, 67) ... 

In the binding assay of the derivatives, it is shown that both fluoride 14 and chloride 15 [60] strongly bind to EP2 receptor. In contrast to chlorinated derivative 15, which also has some affinities to EP1 and EP4 receptors, the fluoride 14 showed any significant affinities to EP1, EP3, or EP4 receptors at 10 pM [59], From these results, it seems that )S-fluoride or )S-chloride can be substituted for the carbonyl group at C-9 of PGE structure, and the substitution by a fluorine atom is more suitable for binding selectively to the EP2 receptor. The fluorinated... 

The synthesis of AFP-07 is shown in Scheme 9 [107], The enone 59 prepared from the Corey lactone was reduced with aluminum reagent and protected with f-butyidimethylsilyl chloride. Fluorination of the lactone 60 under the standard conditions gave the difluorolactone 61. The carbonyl group of the difluorolactone... 

Many reagents convert primary amines into nitriles. Some of these have been mentioned above and represent serious limitations on methods for generating carbonyl compounds. Other ways of oxidizing amines to nitriles are the use of nickel peroxide,lead tetraacetate," copper(I) chloride plus oxygen and pyridine," iodine pentafluoride and benzeneseleninic anhydride. double bromination-dehy-drobromination can be effected for the preparation of nitriles with 2 equiv. of NBS and trimethyl-amine. Likewise, fluorination and elimination of HP gives nitriles." ... 

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