Fluoromethylenation

Donald J Burton and Jerry L Halinfeld, The Preparation and Reactions of Fluoromethylenes... 

Monofluoroalkenes have been prepared by the addition of fluoromethylene-triphenylphosphorane generated m situ by treatment of fluoroiodomethyltri-phenylphosphomum iodide with zinc-copper couple in dimethylformamtde [49] (equation 47) (Table 181. 

Table 18. Synthesis of Fluoroolefins via Reaction of Fluoromethylene-triphenylphosphorane with Carbonyl Compounds [49]...

Whereas access to fluoromethylene ylides is easy, higher homologues are more difficult to prepare because ot the facile (1-elimination of fluorine However hexafluoroisoprapylidene ylides may be prepared in situ from tetrakisftnfluoro-methyl)-l,3-dithietane and tnphenylphosphme [54 (equation 51) or 2,2-dichloro-hexafluoropropane and tnphenylphosphme [55, 56, 57 (equation 52) (Table 21) Pcrfluoro-2-buteiie reacts with tnbutylphosphine to cleanly form a solution of a fluonnated ylide [5/ ] (equation 53)... 

In table I we present the molar Kerr constants and mean square dipole moments of three fluorinated polymers, poly (trifluoroethylene) (PFjE), polylvinylidene fluoride) (PVF2) and poly(fluoromethylene) (PFM), dissolved in p-dioxane. The results show the sensitivity of mK to the degree and type of fluorination varying over an order of magnitude and also changing sign. Calculations of mK and for comparison are in progress (5). 

An efficient synthetic route to (10Z)- and (10 )-19-lluoro-la,25-dihydroxy vitamin D3 has been developed (488). The key feature of this pathway is the introduction of a 19-fluoromethylene group to a (5 )-19-nor-10-oxo-vitamin D derivative. The 10-oxo compound 445 has been obtained via a 1,3-dipolar cycloaddition reaction of (5 )-la,25-dihydroxyvitamin D with in situ generated nitrile oxide, followed by ring cleavage of the formed isoxazoline moiety with molybdenum hexacarbonyl. Conversion of the keto group of (5 )-19-nor-10-oxo-vitamin D to the E and Z fluoromethylene group has been achieved via a two-step sequence, involving a reaction of lithiofluoromethyl phenyl sulfone, followed by the reductive de-sulfonylation of the u-lluoro-j3-hydroxysulfone. The dye-sensitized photoisomerization of the (5 )-19-fluorovitamin D affords the desired (5Z)-19-fluorovitamin D derivatives, (10Z)- and (10 )-19-fluoro-la,25-dihydroxy-vitamin D3. 

Figure 2.1. Fluoromethylene cyanate ester structures and curing reaction.

The NCO—CH2(CF2) CH2—OCN monomer series have been characterized by DSC, IR, H-NMR, 19F-NMR, 13C-NMR, and elemental analysis.8 Table 2.1 summarizes the characterization most pertinent to these cyanate ester monomers. The n = 5,1, and 9 members are missing. This is a reflection of the difficulty in obtaining the odd hydrocarbon diol precursors. The trend of a rapid melting point increase with increasing fluoromethylene sequence length is an indication that monomers with n > 10 will probably not be melt-processible since the onset of the cure exotherm in most purified monomers occurs at 200°C. 

The hydrolytic susceptibility of the fluoromethylene cyanate ester is greater than that of the aromatic cyanate ester. Direct contact with water results in measurable hydrolysis to the carbamate in a 24-h period for the former while the latter is unaffected.9... 

It has been established by a variety of techniques that aromatic cyanate esters cyclotrimerize to form cross-linked cyanurate networks.1 Analogously, the fluoromethylene cyanate monomers cure to cyanurate networks. In addition to the 19F-NMR spectra shown in Figure 2.3, evidence includes an up-field shift of the methylene triplet (1H-NMR, 0.21 ppm 13C-NMR, 9.4 ppm), the disappearance of the cyanate functional group (IR, 2165 cm4 13C-NMR, 111.9ppm) and the appearance of the cyanurate functional group (IR, 1580 and 1370 cm4 13C-NMR, 173.6 ppm).9 Typically, monomers are advanced to prepolymers by thermal treatment at 120°C or just above the melting point. The prepolymers are then cured at 175°C and are postcured at 225°C. 

The curing reaction can be carried out thermally or with the addition of a catalyst. The thermal cure is strongly influenced by impurities associated with the synthesis. The greater the degree of monomer purity, the more slowly the thermal cure proceeds. If the monomer is sufficiently purified, the cure rate can be predictably controlled by the addition of catalysts. As with the aromatic cyanate esters, the fluoromethylene cyanate esters can be cured by the addition of active hydrogen compounds and transition metal complexes. Addition of 1.5 wt% of the fluorinated diol precursor serves as a suitable catalyst.9 The acetylacetonate transition metal salts, which work well for the aromatic cyanate esters,1 are also good catalysts. 

Figure 2.3. Schematic 15F-NMR spectra illustrating effects of (a) fluoromethylene chain length on monomer resonances and (b) chemical transformation of cyanate functional group on fluoromethylene resonances of n = 6 monomer.

The fluorine content, density, critical surface energy, glass transitions, thermal expansion coefficient above and below the glass transition, and 300°C isothermal thermogravimetric stabilities of the fluoromethylene cyanate ester resin system with n = 3, 4, 6, 8, 10 are summarized Table 2.2. Also included for the purpose of comparison are the corresponding data for the aromatic cyanate ester resin based on the dicyanate of 6F bisphenol A (AroCy F, Ciba Geigy). 

The fluorine content for the fluoromethylene cyanate ester resin system is clearly significantly greater than that for AroCy F and also significantly less than that for PTFE (76.0%). Correspondingly, the density reflects the fluorine content. As a homologous series, the contribution of incremental CF2 units can be quantified. From the density data, the volume equivalent of 41. 0 A1 /CF, structural unit in an amorphous thermoset matrix has been determined.8... 

The surface properties are of particular interest for composites and coatings. The n = 6 monomer will wet Teflon, and PTFE filled composites can be prepared. The critical surface tension of wetting for the fluoromethylene cyanate ester resin series has been determined from contact-angle measurements on cured resin surfaces. As indicated in Table 2.2, it parallels the fluorine composition and begins to approach the PTFE value of 18 dyn/cm. 

The absorption of moisture critically affects other important resin properties, particularly those associated with low-dielectric and thermomechanical applications. Results of a 96-h boiling water immersion test are presented in Table 2.2. The moisture absorbed decreased substantially with fluoromethylene chain length from n = 3 to n = 6, followed by only modest decreases for n = 8 and 10. This latter behavior was somewhat unexpected and may be the effect of decreased cross-link density counteracting the increased fluorine content. These 100°C measurements are just above the glass transition and the situation may be different at room temperature. These measurements are in progress. 

Figure 2.4. Dielectric constant and tan delta (average values 0.5 to 1.5GHz) of fluoromethylene cyanate esterresin series.

As indicated above, the dielectric properties are the chief consideration for applications of these fluoromethylene cyanate ester resins. As such, processing as coatings for microelectronic applications and as nonstructural castings and composites for radome-related applications is being investigated. In this respect the n = 6 system has been identified as the best compromise for synthesis, properties, and processing. Results in this section pertain only to this member of the series, which is currently under evahation for the above applications.13... 

Figure 2.5. SEM photograph of a silicon wafer cross section illustrating gap fill quality of a cured, spin-coated fluoromethylene resin (n = 6) over aluminum features having width and spacing. 

The synthesis and properties of the fluoromethylene cyanate ester monomer series, NCOCH2(CF2) CH2OCN, n = 3, 4, 6, 8, 10, and corresponding resins... 

Coupling constants (4/f,h) have been observed in a few instances where fluorine is attached to sp2-hybridized carbon, as, for example, in derivatives of 3-deoxy-3-C-(fluoromethylene)-l,2 5,6-di-O-isopropyli-dene-a-D-ribo- and -xylo-furanose, where JF, h-2 and 4/F, h-4 occur254,264 in the range of 0.5-5.5 Hz, and in 5,6-dideoxy-6,6-difluoro-l,2-0-isopropylidene-3-0-methyl-a-D-xylo-hex-5-enofuranose,251 where 4JFete, h-4 = 2.0 Hz and VFtran. h-4 = 1.5 Hz (cis and trans, relative to H-5). 

A stereochemical dependence has been observed for the 5/f,h-i values observed for a number of 3-deoxy-3-C-(fluoromethylene)-l,2 5,6-di-0-isopropylidene-a-D-ribofuranose derivatives n. =... 

The 1,3-dipolar cycloaddition of diazomethane to MFA (24) occurred exclusively at the C2-C3 Jt-bond to give 4-(fluoromethylene)pyrazolines. The methylene group of diazomethane was regioselectively attached to the C2 carbon atom of 24 with a syw.anti ratio of 88 12 [72b], DFA (25) similarly reacted with diazomethane to give 4-(difluoromethylene)pyrazoline 89 selectively [72b, 86], The cycloaddition reaction of bulkier 2-diazopropane with DFA was less regioselective. 

In 1985, Fluck et al. reported that treatment of the P-fluoromethylene-phosphorane 3f with 2 equiv of butyllithium at -95°C gave the 1,1,3,3-tetrakis(dimethylamino)-lA5,3A5-diphosphete 5f in 34% yield.30 The formation of this four-membered ring could result from a [2 + 2] head-to-tail dimerization of the transient phosphinocarbene 2f. However, an alternative... 

METHYL]SULFONYL]BENZENE AND (Z)-[2-(FLUOROMETHYLENE)CYCLOHEXYL] BENZENE... 

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