The carry-over of Campylobacter isolates between sequential poultry flocks.

The carry-over of Campylobacter strains from one flock to a subsequent flock in the same broiler house has been studied using molecular epidemiological techniques. In all, 524 Campylobacter strains, isolated from two sequential broiler flocks from 60 broiler houses, were typed by restriction fragment polymorphism of the polymerase chain reaction (PCR) product of the flaA and flaB genes (fla typing). Selected strains were also typed using pulsed field gel electrophoresis (PFGE).

Polyfluoroether derivatives via nucleophilic fluorination of glyoxal hydrates with deoxofluor.

Various glyoxal hydrates have been reacted with Deoxofluor [(CH(3)OCH(2)CH(2))(2)NSF(3)]. In concentrated solutions of dichloromethane, Deoxofluor (1) efficiently fluorinates a variety of glyoxal hydrates, RCOCHO.H(2)O (R = 4-methoxyphenyl, 3,4-methylenedioxyphenyl, 4-methylphenyl, 4-fluorophenyl, phenyl, 2-thienyl, methyl) (6a-g) to form polyfluoroethers 7a-g and 8a-g as meso and racemic mixtures (approximately 1:1) in good yields.

Syntheses, derivatives, solubility, and interfacial properties of 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: potential building blocks for syntheses of amphiphatic macromolecules.

2-Hydroxymethyl-2-methyl-1,3-propanediol (A) was reacted with (Me(3)Si)(2)NH and toluenesulfonyl chloride (TsCl) to give mainly CH(3)C(CH(2)OSiMe(3))(3) (1), and CH(3)C(CH(2)OTs)(3) (2), respectively. With allyl bromide, the products were CH(3)C(CH(2)OCH(2)CH[double bond]CH(2))(2)(CH(2)OH) (3) and CH(3)C(CH(2)OCH(2)CH[double bond]CH(2))(CH(2)OH)(2) x H(2)O (4). The reactions of 4 with perfluoroalkyl iodides (R(f)I) were catalyzed by Cu(I)Cl to form 2-methyl-2-polyfluoroalkenyloxymethyl-1,3-propanediols: (R(f)CH=CHCH(2)OCH(2))C(Me)(CH(2)OH)(2) [R(f) = C(4)F(9) (5), C(8)F(17) (6), and (CF(2)CF(2))(4)OCF(CF(3))(2) (7)].

Cesium Fluoride Catalyzed Trifluoromethylation of Esters, Aldehydes, and Ketones with (Trifluoromethyl)trimethylsilane.

The low reactivity of carboxylic esters toward (trifluoromethyl)trimethylsilane (TMS-CF(3)) was investigated. A universal cesium fluoride catalyzed procedure for nucleophilic trifluoromethylation was developed. At room temperature (25 degrees C), with catalytic amounts of cesium fluoride, carboxylic esters were found to react to give the silyl ether intermediates, which afforded the trifluoromethyl ketones after hydrolysis.

New Electrophilic Trifluoromethylating Agents.

Synthetic routes to S-(trifluoromethyl)phenyl-4-fluorophenylsulfonium triflate (8), S-(trifluoromethyl)phenyl-2,4-difluorophenylsulfonium triflate (9), S-(trifluoromethyl)phenyl-3-nitrophenylsulfonium triflate (10), and S-(trifluoromethyl)-4-fluorophenyl-3-nitrophenylsulfonium triflate (11) are described. They are stable molecules and conveniently prepared by treating phenyl trifluoromethyl sulfoxide with benzene and its derivatives. These novel electrophilic trifluoromethylating agents react under mild conditions with a variety of aromatic rings (p-hydroquinone, pyrrole, and aniline) to give trifluoromethylated compounds (2-trifluoromethyl-p-hydroquinone, 2-trifluoromethylpyrrole, 2-trifluoromethylaniline, and 4-trifluoromethylaniline) in moderate to high yields.

Reactions of Iodoperfluoro-3-oxaundecylsulfonyl Fluoride with Halohydrocarbons through Organometallic Intermediates.

Iodoperfluoro-3-oxaundecylsulfonyl fluoride reacted with Cu, Zn, or Grignard reagent to produce the respective organometallic species, which was further reacted with halohydrocarbons 4-ClC(6)H(4)Br, 4-CH(3)C(O)C(6)H(4)Br, CH(2)=CHCH(2)Br, and CH(3)SiCl, to give derivatives of R(CF(2))(8)O(CF(2))(2)SO(2)F [R = 4-ClC(6)H(4) (7), 4-CH(3)C(O)C(6)H(4) (5), CH(2)=CHCH(2) (3), and CH(3)Si (13)], in moderate yields. The compounds were characterized by NMR, infrared, and mass spectroscopy as well as elemental analyses. The addition product of trichlorosilane and 3 was reacted with sodium methoxide to give (12H,12H,13H,13H,14H,14H-hexahydroperfluoro-3-oxatetradecyl methylsulfonate) trimethoxysilane, [(CH(3)O)(3)Si(CH(2))(3)(CF(2))(8)O(CF(2))(2)SO(3)Me] (11).

Tetrameric fluorophosphazene, (NPF(2))(4), planar or puckered?

The results obtained in a comprehensive experimental study on the redetermination of the structure of N(4)P(4)F(8) with single-crystal X-ray diffraction, gas electron diffraction (GED), and differential scanning calorimetry (DSC) establish clearly that, in contrast to the previous report, the eight-membered heterocycle is not planar. Above the phase transition temperature of -74 degrees C, the ring appears pseudoplanar. However, the N(4)P(4) ring is disordered and is puckered above the phase transition when the disorder is modeled correctly.

Nucleophilic di- and tetrafluorination of dicarbonyl compounds.

Reactions of various diketo compounds with Deoxofluor [(CH(3)OCH(2)CH(2))(2)NSF(3)] have been investigated. When reacted with Deoxofluor, alpha-diketones, R(1)COCOR(2) (R(1) = R(2) = Ph; R(1) = R(2) = 4-Me-C(6)H(4); R(1) = Ph, R(2) = Me; R(1) = Me, R(2) = Et) (1a-d) formed difluoro derivatives (2a-d) in the presence of a catalytic amount of HF and/or tetrafluoro (3a-d) products depending on the reaction conditions and stoichiometry used. Reactions of beta-diketones, R(3)COCH(2)COR(4) (R(3) = R(4) = Ph; R(3) = R(4) = Me; R(3) = Me, R(4) = Ph) (4e-g), with Deoxofluor in the presence of a catalytic amount of HF led to the formation of difluoroalkenones as a mixture of E (5e-g) and Z (6e-g) isomers in good yield.

Concentration-dependent reactions of deoxofluor with arylglyoxal hydrates: a new route to polyfluoro ethers.

[reaction: see text]. In concentrated solutions (CH2Cl2) at 25 degrees C, arylglyoxal hydrates, ArCOCHO*H2O (Ar = 4-MeO-C6H4-, 4-Me-C6H4-, 4-F-C6H4-, Ph-, (2a-f) with Deoxofluor gave fluorinated ethers, ArCF2CHFOCHFCF2Ar, (3a-f) in >90% yields as meso/racemic mixtures (approximately 1:1). Under very dilute conditions, mixtures of ArCF2CHO (major) (4a-f) and ArCF2CF2H (6a-f) (minor) were obtained.

Changes in the carriage of Campylobacter strains by poultry carcasses during processing in abattoirs.

The recent development of simple, rapid genotyping techniques for Campylobacter species has enabled investigation of the determinative epidemiology of these organisms in a variety of situations. In this study we have used the technique of fla typing (PCR-restriction fragment length polymorphism analysis of the flaA and flaB genes) to identify the sources of strains contaminating the carcasses of five campylobacter-positive and two campylobacter-negative broiler flocks during abattoir processing. The results confirmed that, in the United Kingdom, individual broiler flocks are colonized by a limited number of subtypes of Campylobacter jejuni or C.

Syntheses and reactions of the fluorinated cyclic thionylphosphazene NSO(Ar)[NPF(2)]2(Ar = 4-t-BuC(6)H(4)-) with difunctional reagents.

The S-aryl substituted thionylphosphazene (Cl(2)PN)(2)[4-t-BuC(6)H(4)(O)SN] (1) was prepared by Friedel-Craft's reaction of NSOCl(NPCl(2))(2) with tert-butylbenzene. When it reacted with excess KSO(2)F at 110 degrees C, the P-Cl bonds of 1 were fluorinated, yielding the tetrafluorothionylphosphazene, (F(2)PN)(2)[4-t-BuC(6)H(4)(O)SN] (2). An equimolar reaction of 2 with dilithiated 1,3-propanediol in THF at -78 degrees C resulted in the formation of the ansa-substituted compound CH(2)(CH(2)O)(2)[FPN](2)[4-t-BuC(6)H(4)(O)SN] (3).

Diketo compounds with (trifluoromethyl)trimethylsilane: double nucleophilic trifluoromethylation reactions.

Reactions of various diketo compounds with (trifluoromethyl)trimethylsilane (Me3SiCF3) in the presence of catalytic amounts of cesium fluoride have been studied. gamma-Ketoesters, CH3COCH2CH2CO2R (R = Et, Bu), were reacted with 2 equiv of Me3SiCF3 at room temperature to give CH3C(OH)(CF3)CH2CH2COCF3 in good yield after hydrolysis. alpha-Diketones, R1COCOR2 (R1 = R2 = Ph; R1 = Ph, R2 = Me; R1 = R2 = Me; R1 = Me, R2 = Et), when reacted with Me3SiCF3, formed 1:1 or 1:2 addition products depending on the reaction conditions and stoichiometry used.

Syntheses and experimental studies on the relative stabilities of spiro, ansa, and bridged derivatives of cyclic tetrameric fluorophosphazene.

Reactions of (CF2CH2OSiMe3)2 and CF2(CF2CH2OSiMe3)2 with N4P4F8 (1) in a 1:2.5 molar ratio resulted in the formation of monospiro compounds [(CF2CH2O)2PN](F2PN)3 (2) and [CF2(CF2)CH2O)2PN](F2PN)3 (4) as well as the intermolecular bridged compounds F7N4P4OCH2CF2CF2CH2OP4N4)F7 (3) and F7N4P4OCH2CF2CF2CF2CH2OP4N4F7 (5). An equimolar reaction of dilithiated 1,3-propanediol with 1 resulted in the 1,3-ansa-substituted compound CH2(CH2O)2[P(F)N]2(F2PN)2 (6) as the major product in good yield.

A novel synthesis of hexakis(trifluoromethyl)cyclotriphosphazene. Single-crystal X-ray structures of N3P3(CF3)6 and N3P3F6.

Reaction of hexafluorocyclotriphosphazene (N3P3F6) with trimethyl(trifluoromethyl)silane in the presence of a catalytic amount of cesium fluoride in THF produced hexakis(trifluoromethyl)cyclotriphosphazene [N3P3(CF3)6] in 90% isolated yield. N3P3(CF3)6 is fully characterized by melting point, IR, NMR (19F, 13C, 31p), MS, and elemental analysis data. Single-crystal X-ray structures of N3P3(CF3)6 and N3P3F6 are reported.

Novel and versatile reactions of trifluoroamine oxide: a new route to polyfluorinated ethers.

A series of pyrimidine methyl and polyfluoroalkyl ethers were synthesized from the reactions of trifluoroamine oxide (1) with several 5-substituted uracils in the presence of tetrabutylammonium hydroxide and methanol, 2,2,2-trifluoroethanol (6), or 1H,1H-pentafluoropropanol (7). With 5-(trifluoromethyl)uracil (2), the new ethers formed were 5-fluoro-5-(trifluoromethyl)-6-methoxypyrimidine-2,4-dione (8), 5-fluoro-5-(trifluoromethyl)-6-(trifluoroethoxy)pyrimidine-2,4-dione (9), and 5-fluoro-5-(trifluoromethyl)-6-(1H,1H- pentafluoropropoxy)pyrimidine-2,4-dione (10). With 5-chlorouracil (3), the new ethers 5-chloro-5-fluoro-6-methoxypyrimidine-2,4-dione (11), 5-chloro-5-fluoro-6-(trifluoroethoxy)pyrimidine-2,4-dione (12), and 5-chloro-5-fluoro-6-(1H,1H-pentafluoropropoxy)pyrimidine-2,4-dione (13) were obtained.

Sequential spread of Campylobacter infection in a multipen broiler house.

Generally, colonization with Campylobacter jejuni is first detected in broilers 2-3 wk after hatching. Once introduced into a flock, this infection spreads very rapidly. The sources and routes of transmission of C.

Selective Reactivity of the Phosphorus-Chlorine and Carbon-Chlorine Bonds in Cyclic Chlorocarbaphosphazenes: An Unusual Activation of a Carbon-Nitrogen Bond in Trialkylamines.

Acyclic tertiary amines such as triethylamine and tri-n-propylamine used as HCl scavengers in nucleophilic substitution reactions of cyclic chlorocarbaphosphazenes [N(3)PC(2)Cl(4) (I) and N(3)P(2)CCl(5) (II)] with (CF(2))(n)()(CF(2)CH(2)OH)(2) [n = 0 (III) or 1 (IV)] are found to undergo a facile C-N bond cleavage with the regiospecific substitution of the dialkylamino groups on the ring carbon atoms of the carbaphosphazene. In the case of cyclic amines such as 1-methylpiperidine and 4-methylmorpholine, the cleavage was found to occur regiospecifically at the N-CH(3) bond, resulting in the ring substitution of the cyclic secondary amino group on the dicarbaphosphazene ring carbon atoms. The polyfluoro diol III forms a spirocyclic ring exclusively at the phosphorus site in compounds [CF(2)CH(2)O](2)PN(3)C(2)[N(C(2)H(5))(2)](2) (1), [CF(2)CH(2)O](2)PN(3)C(2)[N(C(3)H(7))(2)](2) (2), [CF(2)CH(2)O](2)PN(3)C(2)[NCH(2)(CH(2))(3)CH(2)](2) (3), and [CF(2)CH(2)O](2)PN(3)C(2)[N(CH(2))(2)O(CH(2))(2)](2) (5) along with the formation of carbon-substituted carbaphosphazenes, Cl(2)PN(3)C(2)[NCH(2)(CH(2))(3)CH(2)](2) (4) and Cl(2)PN(3)C(2)[N(CH(2))(2)O(CH(2))(2)](2) (6).

Insertion of Fluoroalkenes into Activated C-H Bonds for the Preparation of Polyfluorinated Sulfanes, Alcohols, and Acyclic and Cyclic Ethers.

Free radical addition reactions of tetrahydrothiophene, pentamethylene sulfide, and 1,4-thioxane with various cyclic and acyclic per- and polyfluorinated olefins are readily initiated by di-tert-butyl peroxide, providing a convenient route for synthesizing cyclic sulfanes with fluorinated side groups. Tetrahydrothiophene reacts with hexafluoropropene, perfluoroallylbenzene, perfluorocyclobutene, and 1,2-dichlorotetrafluorocyclobutene in the presence of catalytic amounts of the peroxide to give the corresponding addition products CH(2)CH(2)CH(2)SCHCF(2)CHFCF(3) (1), CH(2)CH(2)CH(2)SCHCF(2)CHFCF(2)C(6)F(5) (2), CH(2)CH(2)CH(2)SCHCFCHFCF(2)CF(2) (3), and CH(2)CH(2)CH(2)SCHCClCHClCF(2)CF(2) (4), respectively. Pentamethylene sulfide reacts analogously with hexafluoropropene to give CH(2)CH(2)CH(2)CH(2)SCHCF(2)CHFCF(3) (8).

Synthesis of Cyclic Ethers with Fluorinated Side Chains.

Di-tert-butyl peroxide initiated free radical addition of THF to various fluorinated alkenes (CF(2)=CH(2), CF(2)=CFH, CH(2)=CHCF(3), CF(2)=CFCF(3), CF(2)=CFC(5)F(11), CF(2)=CFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F) gives either bidirectional addition products [CH(2)CH(2)CH(2)OCH(CF(2)CH(3)) (1), CH(2)CH(2)CH(2)OCH(CH(2)CHF(2)) (2), CH(2)CH(2)CH(2)OCH(CF(2)CH(2)F) (3), and CH(2)CH(2)CH(2)OCH(CFHCHF(2)) (4)] or unidirectional products [CH(2)CH(2)CH(2)OCH(CH(2)CH(2)CF(3)) (5), CH(2)CH(2)CH(2)OCH(CF(2)CHFCF(3)) (6), CH(2)CH(2)CH(2)OCH(CF(2)CHFC(5)F(11)) (7), and CH(2)CH(2)CH(2)OCH(CF(2)CHFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F) (8)] depending on the structure of the alkene. Reaction of dioxane with CF(2)=CFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F gives a single product, CH(2)OCH(2)CH(2)OCH(CF(2)CHFOCF(2)CF(CF(3))OCF(2)CF(2)SO(2)F) (9). In the case of hexafluoropropene or perfluoroallylbenzene, reaction with an excess of tetrahydrofuran gives only the monosubstituted products CH(2)CH(2)CH(2)OCH(CF(2)CHFCF(3)) (6) and CH(2)CH(2)CH(2)OCH(CF(2)CFHCF(2)C(6)F(5)) (11) respectively.