A SO2F2-mediated ring-opening cross-coupling of cyclobutanone oxime derivatives with alkenes was developed for the construction of a range of δ-olefin-containing aliphatic nitriles with (E)-configuration selectivity. This new method features wide substrate scope, mild conditions, and direct N-O activation.

BACKGROUND: Managing resistance to phosphine (PH3 ) in rusty grain beetle, Cryptolestes ferrugineus, is challenging, as strongly resistant insects of this species require very high concentrations over lengthy exposure periods (>10 days). Recently, approaches that enhance the efficacy of PH3 have gained momentum to control this pest, especially co-fumigations. In this study, efficacy of co-fumigating PH3 with another commercially available fumigant, sulfuryl fluoride (SF), has been evaluated against adults and eggs of two PH3 -resistant strains of C. ferrugineus. Concentrations of the mixture, representing lower than current application rates of both fumigants, were tested towards its field use.
RESULTS: Co-fumigation of PH3 with SF was achieved in two patterns: over a continuous exposure period of 168 h simultaneously and sequentially over two periods of 78 h, in which insects were exposed to SF first followed by PH3 with 12 h aeration in-between. Results of simultaneous fumigations identified two effective co-fumigation rates, SF 185 + PH3 168 g hm-3 and SF 370 + PH3 84 g hm-3 that yielded complete control of adults and eggs. These two rates also were equally effective when they were applied sequentially and produced consistent results. Irrespective of application methods, concentrations of both PH3 and SF failed individually in achieving complete mortality of either adults or eggs or both.
CONCLUSIONS: Our results confirmed that a co-fumigation strategy involving half the current standard rate of PH3 (84 g hm-3 ) with one-fourth of the current maximal registered rate of SF (370 g hm-3 ) can provide effective control of strongly PH3 -resistant C. ferrugineus.

This study investigated the efficacy of using Vikane gas fumigant (sulfuryl fluoride) at the 1.9× dosage rate for eliminating bed bugs (Cimex lectularius L.) in two challenging infestation situations: personal vehicles, and confined spaces densely packed with personal belongings. The vehicles used in this study were large minivans with seating that folded into the floor. The confined spaces were cargo trailers filled to 85% capacity with books, furniture, and other household items. Each van and trailer was equipped with ~90 sentinel bed bugs consisting of three groups of 9-11 bed bug eggs, 10 nymphs, and 10 adults. The Vikane Fumiguide calculator was used to determine the target dosage (g-h/m3) to apply in each replicate (e.g., one van or trailer). Sulfuryl fluoride concentrations were measured throughout the fumigation process using a Spectros SF-ReportIR. Concentration readings were input into the Fumiguide to determine when the accumulated dosage (g-h/m3) was achieved, and when aeration should be initiated. After aeration was complete, the sentinel bed bugs were removed from the replicates and bed bug nymph and adult mortality was recorded. Bed bug eggs were monitored for 23 d to determine latent mortality. Fumigated bed bug mortality for each replication was 100% regardless of life stage. Latent mortality was observed in a single bed bug egg, but the first instar never fully eclosed. This study determined that fumigation with sulfuryl fluoride at the 1.9× dosage factor is an effective method for eliminating resistant bed bugs from vehicles and personal belongings in densely packed situations.

According to Article 12 of Regulation (EC) No 396/2005, EFSA has reviewed the maximum residue levels (MRLs) currently established at European level for the pesticide active substance sulfuryl fluoride. To assess the occurrence of sulfuryl fluoride and fluoride ion residues in plants, processed commodities and livestock, EFSA considered the conclusions derived in the framework of Directive 91/414/EEC, the MRLs established by the Codex Alimentarius Commission as well as the European authorisations reported by Member States (including the supporting residues data). Based on the assessment of the available data, MRLs were calculated, but a consumer risk assessment could be carried out for sulfuryl fluoride only. Although no apparent risk to consumers was identified for sulfuryl fluoride, a standard consumer risk assessment to fluoride ion could not be performed, lacking information on the toxicological reference values for fluoride. Hence, an \'overall\' consumer risk assessment could not be performed, only tentative MRLs proposal could be derived and measures for reduction of the consumer exposure should also be considered. Nevertheless, considering that fluoride ion is naturally occurring in food of plant and animal origin, EFSA performed an indicative calculation of the consumer exposure to estimate whether the uses currently authorised will contribute significantly to the overall consumer exposure to fluoride.

The Mitsunobu reaction is a powerful transformation for the one-pot activation and substitution of aliphatic alcohols. Significant efforts have focused on modifying the classic conditions to overcome problems associated with purification from phosphine-based byproducts. Herein, we report a phosphine free method for alcohol activation and substitution that is mediated by sulfuryl fluoride. This new method is effective for a wide range of primary alcohols using phthalimide, di-tert-butyl-iminodicarboxylate, and aromatic thiol nucleophiles in 74 % average yield. Activated carbon nucleophiles and a deactivated phenol were also effective for this reaction in good yields. Secondary alcohols were also successful substrates using aryl thiols, affording the corresponding sulfides in 56 % average yield with enantiomeric ratios up to 99:1. This new protocol has a distinct synthetic advantage over many existing phosphine-based methods as the byproducts are readily separable. This feature was exploited in several examples that did not require chromatography for purification. Furthermore, the mild reaction conditions enabled further in situ derivatization for the one-pot conversion of alcohols to amines or sulfones. This method also provides a boarder nucleophile scope compared to existing phosphine-free methods.

A metal-free and redox-neutral method for Beckmann rearrangement employing inexpensive and readily available SO2 F2 gas is described. The reported transformation proceeds at ambient temperature and is compatible with a wide range of sterically and electronically diverse aromatic, heteroaromatic, aliphatic and lignin-like oximes providing amides in good to excellent yields. The reaction proceeds through the formation of an imidoyl fluoride intermediate that can also be used for the synthesis of amidines.

Structural fumigations using sulfuryl fluoride for the extermination of dry-wood termites are conducted by the thousands in California and other warm-weather states. Sulfuryl fluoride is an odorless gas that targets the nervous system and can cause respiratory irritation, pulmonary edema, nausea, vomiting, seizures, and death. Structural voids or compartments such as wall sockets, crawl spaces, cabinets, or cells in air mattresses may create ongoing exposure after a structure has been certified as safe. The authors describe a case of potential sulfuryl fluoride exposure to a family following home fumigation. Despite regulation, sulfuryl fluoride poisonings from structural fumigations continue to occur. This article examines the physical characteristics of sulfuryl fluoride and the regulatory oversight of its application, in an effort to understand how and why these poisonings happen. Increasing aeration times of fumigated structures, overseeing monitoring efficacy, and using technology to capture clearance data could reduce sulfuryl fluoride exposure and illness.

A catalyst-free novel and efficient methodology for the challenging synthesis of benzo-oxetes from 2\'-hydroxyacetophenones mediated by sulfuryl fluoride (SO2F2) gas has been realized. The combination of 2\'-hydroxyacetophenones and SO2F2 furnishes synthetically challenging benzo-oxetanes in moderate to excellent yields. The highlight of this work is the design and synthesis of strained four-membered oxete rings.

BACKGROUND: Susceptibility to phosphine (PH3 ) and sulfuryl fluoride (SF) and cross-resistance to SF were evaluated in two life stages (eggs and adults) of key grain insect pests, Rhyzopertha dominca (F.), Sitophilus oryzae (L.), Cryptolestes ferrugineus (Stephens), and Tribolium castaneum (Herbst). This study was performed with an aim to integrate SF into phosphine resistance management programmes in Australia.
RESULTS: Characterisation of susceptibility and resistance to phosphine in eggs and adults showed that C. ferrugineus was the most tolerant as well as resistant species. Mortality responses of eggs and adults to SF at 25 °C revealed T. castaneum to be the most tolerant species followed by S. oryzae, C. ferrugineus and R. dominica. A high dose range of SF, 50.8-62.2 mg L-1 over 48 h, representing c (concentration) × t (time) products of 2438-2985 gh m-3 , was required for complete control of eggs of T. castaneum, whereas eggs of the least tolerant R. dominca required only 630 gh m-3 for 48 h (13.13 mg L-1 ). Mortality response of eggs and adults of phosphine-resistant strains to SF in all four species confirmed the lack of cross-resistance to SF.
CONCLUSIONS: Our research concludes that phosphine resistance does not confer cross-resistance to SF in grain insect pests irrespective of the variation in levels of tolerance to SF itself or resistance to phosphine in their egg and adult stages. While our study confirms that SF has potential as a \'phosphine resistance breaker\', the observed higher tolerance in eggs stresses the importance of developing SF fumigation protocols with longer exposure periods. © 2016 Society of Chemical Industry.

Aryl sulfonyl chlorides (e.g. Ts-Cl) are beloved of organic chemists as the most commonly used S(VI) electrophiles, and the parent sulfuryl chloride, O2 S(VI) Cl2 , has also been relied on to create sulfates and sulfamides. However, the desired halide substitution event is often defeated by destruction of the sulfur electrophile because the S(VI) Cl bond is exceedingly sensitive to reductive collapse yielding S(IV) species and Cl(-) . Fortunately, the use of sulfur(VI) fluorides (e.g., R-SO2 -F and SO2 F2 ) leaves only the substitution pathway open. As with most of click chemistry, many essential features of sulfur(VI) fluoride reactivity were discovered long ago in Germany.6a Surprisingly, this extraordinary work faded from view rather abruptly in the mid-20th century. Here we seek to revive it, along with John Hyatt\'s unnoticed 1979 full paper exposition on CH2 CH-SO2 -F, the most perfect Michael acceptor ever found.98 To this history we add several new observations, including that the otherwise very stable gas SO2 F2 has excellent reactivity under the right circumstances. We also show that proton or silicon centers can activate the exchange of SF bonds for SO bonds to make functional products, and that the sulfate connector is surprisingly stable toward hydrolysis. Applications of this controllable ligation chemistry to small molecules, polymers, and biomolecules are discussed.