Alkyls fluoro

For all the olefins studied, alkyl-, fluoro-, or chloro-substituted, three binary, mononuclear species were observed. It now seems that it is a general property of Ni and Pd atom-olefin reactions at cryogenic temperatures to form complexes that have a maximum coordination of three olefin molecules per metal atom, regardless of the electronic or steric attributes of the substituent(s). As intimated previously, the absence of higher stoichiometry species, even for unsubstituted ethylene, is, most probably, the result of steric interactions (54). 

Ctther substituents, such as alkyl, fluoro, chloro and bromo show much weaker effects. 

Alkyl Fluoro- ElOa, 182 (H — F) Alkyl 2-Fluoro-2-nitro- ElOa. 184 (H - F)... 

Z = H, halo, C1-C20 alkyl, cycloalkyl, lower alkoxy, cyano R = Cj-C25 alkyl, cycloalkyl or halo-lower alkyl, fluoro-lower alkyl, aryl, lower alkoxy, hydroxy, carboxy, lower-alkyl carbonyl or lower alkoxy-carbonylo3Qr or (CRiR2)p-(CR3=CR4) j Q or (CRiR2)p-... 

Reaction (C) The reaction is important in a chain mechanism during the auto oxidization process. Direct observation of the reaction was successfully carried out by Hori et al. [32] for a urea-polyethylene complex (UPEC). Figure 7.30 shows the variations of ESR spectra for peroxy radicals in the UPEC due to heat treatment in vacuum at 361 K. Spectrum (a) was obtained from peroxy radicals and spectrum (d) was that obtained from alkyl radicals as shown in Section 7.4.1. Figure 7.31 shows the variation of the concentrations of various radicals with the time of heat treatment at 361 K. It was found that 20% of the radicals decayed, but ca. 80% of the decaying peroxy radicals were converted into alkyl radicals. A few authors reported that peroxy radicals trapped in polytetraflu-oroethylene converted into alkyl fluoro radicals by heat treatment in a similar manner. Some authors claimed that the back reaction of Eq. (7.16) occurred in that case ... 

A high-yield, efficient procedure to synthesize functionahzed alkyl/fluoro-alkyl-containing triazolium quaternary salts and triazolium ionic Uquids led to triazolium cations that contained covalently bound anionic sites, such as, fluorocarboxy, sulfonate, fluorohomoallyhc, and fluoroalkanol groups [43, 44]. These were converted by metathetical reactions with fluorine-containing anions to low-melting salts (26a,b, 27,28a,b, 29c,d, 30) (Scheme 8) [43]. These functionalized triazolium salts exhibit many characteristics associated with excellent ionic liquids with respect to stability in air and water, and when heated. All are liquids at 25 °C. 

Amino) (alkyl) (fluoro)[bis(trimethylsilyl)methyl]silanes [365] have been obtained by allowing the lithiated tris(trimethylsilyl)methane to react first with trifluoroorga-nosilane and then with lithium bromide. 

Scope and Limitations. Carbonyl Component. For practice purposes this reaction is limited to aromatic aldehydes, of which a wide variety has been studied, and to a,/3-unsaturated aliphatic aldehydes. The sub-stitutents on the ring of the aromatic aldehydes include alkyl, fluoro, chloro, bromo, iodo, hydroxyl, alkoxy, acyloxy, carbethoxy, nitro, and various combinations of two or more of these groups. Aldehydes of the naphthalene, pyrene, biphenyl, thiophene, furmi, pyrrole, indole, chro-mane, coumarane, and thiazole series also have been employed. 

Berthon-CedUle L, Leguem M (2008) Process for the preparation of fluoroquinolone-3-carboxylic adds via amination of alkyl fluoro(htdoquinolone)carboxylates with eunines. US Patent 54643,28 Nov 2008... 

Substitutive nomenclature of alkyl halides treats the halogen as a halo—(fluoro chloro bromo or lodo ) substituent on an alkane chain The carbon chain is numbered m the direction that gives the substituted carbon the lower number... 

An interesting illustration of a bielectrophile contributing two heteroatoms to the resultant five-membered ring is the 2-alkyl-2-chloro- (or fluoro-) sulfonylcarbamoyl chlorides (212). With methylhydrazine initial attack by the more basic nitrogen occurred on the carbamoyl chloride, and this was followed by base-induced cyclization to 1,2,3,5-thiatriazolidine derivative (213) (77JCR(S)238, 77JCR(M)2813). Other reactions of this type are discussed in Chapter 4.28. 

Chroman-2-ylmethanol, (5)-6-hydroxy-2,5,7,8-tetramethyl-synthesis, 3, 779 Chromene, 3-acetyl-2-methoxy-synthesis, 3, 750 Chromene, 2-alkyl-synthesis, 3, 749 Chromene, 4-aryloxymethyl-synthesis, 3, 742-743 Chromene, bis(2,2-dimethyl-mass spectra, 3, 604 Chromene, 2,3-dichloro-synthesis, 3, 753 Chromene, 2,2-dimethyl-IR spectra, 3, 594 mass Spectra, 3, 604 molecular dimensions, 3, 621 synthesis, 3, 743, 749, 751 Chromene, 3-fluoro-2,2-dimethyl-synthesis, 3, 748 Chromene, 5-hydroxy-synthesis, 3, 745... 

Purine, 6-bromo-9-/3-D-(2,3,5-tri-0-acetyl)ribofuranosyl-synthesis, 5, 598 Purine, 6-carboxy-reactions, 5, 549 Purine, 8-carboxy-reactions, 5, 549 Purine, 2-chloro-reactions, 5, 561 synthesis, 5, 597 Purine, 6-chloro-alkylation, 5, 529 glycosylation, 5, 529 oxidation, 5, 539 3-oxides reactions, 5, 554 synthesis, 5, 595 reactions, 5, 561, 595 with ammonia, 5, 562 with fluorides, 5, 563 with trimethylamine, 5, 562 9- -D-ribofuranoside synthesis, 5, 560 synthesis, 5, 597, 598 Purine, 8-chloro-amination, 5, 542 Purine, 6-chloro-8-ethoxy-synthesis, 5, 591 Purine, 6-chloro-9-ethyl-dipole moment, 5, 522 Purine, 6-chloro-2-fluoro-riboside... 

Purine, 2,6-dithioxo-1,2,3,6-tetrahydro-dethiation, 5, 558 Purine, 8-ethoxy-synthesis, 5, 577, 596 Purine, 6-ethoxycarbonylmethyl-nucleoside synthesis, 5, 561 Purine, 8-ethoxy-7-methyl-synthesis, 5, 577 Purine, 9-ethyl-synthesis, 5, 593 Purine, 6-fonnyl-reactions, 5, 547 synthesis, 5, 593 Purine, 8-fonnyl-reactions, 5, 547 Purine, 2-fluoro-synthesis, 5, 597 Purine, 6-fluoro-alkylation, 5, 529 synthesis, 5, 563, 573 Purine, 6-fluoro-9-methyl-reactions, with ammonia, 5, 562 Purine, 6-furfurylamino- — see Kinetin Purine, 9-glycofuranosyl-synthesis, 5, 572 Purine, 2-glycosyl-synthesis, 5, 587 Purine, 8-glycosyl-synthesis, 5, 585 Purine, 9-glycosyl-synthesis, 5, 572 Purine, 8-halo-synthesis, 5, 598 Purine, 2-hydrazino-synthesis, 5, 593 Purine, 8-o -hydroxyethyl-synthesis, 5, 574... 

Electrochemical fluorination of a-cyclohexenyl-substituted carboxylic (acetic, propanoic, butanoic, and pentanoic) acid esters (methyl, ethyl, and propyl) results in a series of both perfluoro-9-alkyl-7-oxabicyclo[4 3 OJnonanes and per-fluoro-8-alkoxy-9-alkyl-7-oxabicyclo[4.3.0]nonanes [<8S] (equation 19)... 

In contrast to phosphorus esters, sulfur esters are usually cleaved at the carbon-oxygen bond with carbon-fluorine bond formation Cleavage of esteri nf methanesulfonic acid, p-toluenesidfonic acid, and especially trifluoromethane-sulfonic acid (tnflic acid) by fluoride ion is the most widely used method for the conversion of hydroxy compounds to fluoro derivatives Potassium fluoride, triethylamine trihydrofluoride, and tetrabutylammonium fluoride are common sources of the fluoride ion For the cleavage of a variety of alkyl mesylates and tosylates with potassium fluoride, polyethylene glycol 400 is a solvent of choice, the yields are limited by solvolysis of the leaving group by the solvent, but this phenomenon is controlled by bulky substituents, either in the sulfonic acid part or in the alcohol part of the ester [42] (equation 29)... 

Various sources of fluoride ion have been investigated, of which highly nucleophilic tetraalkylammonium fluorides ate the most effective Thuf, fluoro alkyl halides and N (fluoroalkyl)amines are efficiently synthesized by treatment of the corresponding trifluoromethanesulfonic esters with tetrabutylammonium fluoride trihydrate in aprotic solvents [5fl] (equation 34) The displacement reactions proceed quantitatively at room temperature within seconds, but tail with hydrogen fluoride-pyridine and give reasonable yields only with hydrogen fluo ride-alkylamine reagents... 

Tertiary Af-alkyl-Al,(V-bis(2-fluoro-2,2-dinitroethyl)atnines containing 77-methylene or A -methyl groups are oxidized by chromium trioxide in acetic acid to Af,Al-bis(2-fluoro-2,2-dimtroethyl)formamides [ 5] (equation 82)... 

Many Jluonnaled aromatic compounds are alkylated with alkyl halides under Fnedel-Crafis conditions For example, the intramolecular alkylation of 3-fluoro-At-(chloroaee-tyl)amhne with alununum chlonde gives 6-fluorooxmdole [5] (equation 5) Similarly, 3 -chloro-4-fluoropropiophenone affords 5-fluoromdanone [6] (equation 6)... 

Alkyl fluorides are more reactive than other alkyl halides under Friedel-Crafts conditions, whereas trifluoromethyl groups are less reactive than other trihalomethyl groups Thus, a bromoindane is prepared from 1-bromo-l-fluoro-2,2,3,3-tetramethylcyclopropane and benzene [5] (equation 8) whereas 3-tnfluo romethylphenyldiphenylchloromethane is obtained from 3-trifluoromethyl-benzotrichloride and benzene [9] (equation 9)... 

A fluorinated oxazine, prepared fromfluoroacetonitrile and 2 methyl-1,3-pen-tanediol, is alkylated at low temperature The resulting products furnish a fluoro aldehydes after botohydride reduction and hydrolysis [JJ4] (equation 99)... 

Alkyl diethylphosphononuoroacetates have been used extensively in ol fi-nanon procedures [69], principally forming the ffJ-a-fluoro-a.P-unsaturated esters with very high stereoselectivity [70] (equation 61) (Table 22). Preparation of the ethyl diethylphosphonofluoroacetate from ethyl fluoroacetate has obviated the necessity to prepare ethyl bromofluoroacetate from bromine fluoride and ethyl diazoacetate [71],... 

Extensive reviews of the effects of fluonnation on stmeture and bonding are available [75, 76, 77], and only the charactenstic trends in bond strengths will be covered here. The bond energies cited are average values corrected for the revised heats of formation of alkyl radicals [78], but their precision is seldom better than 2 kcal/mol for the fluoro compounds. 

The pyrrolidine enamines of /l -3.]cetosteroids (111), on alkylation with methyl iodide, gave mainly the N-alkylated product (5,55) in nonpolar solvents such as benzene. The reaction in more polar solvents gave the 4-methylated product (5.S). The reaction of (111) with perchloryl fluoride involves attack at the C-4 atom to give, after acid hydrolysis, either 4-fluoro-zJ -3-ketone (119) or 4,4-difluoro-zJ -3-ketone 120), depending on the reaction conditions (59). 

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