The development of chemicals to slowly release hydrogen sulfide would aid the survival of plants under environmental stressors as well as increase harvest yields. We report a series of dialkyldithiophosphates and disulfidedithiophosphates that slowly degrade to release hydrogen sulfide in the presence of water. Kinetics of the degradation of these chemicals were obtained at 85 °C and room temperature, and it was shown that the identity of the alkyl or sulfide group had a large impact on the rate of hydrolysis, and the rate constant varied by more than 10 4 ×. For example, using tert -butanol as the nucleophile yielded a dithiophosphate ( 8 ) that hydrolyzed 13,750× faster than the dithiophosphate synthesized from n -butanol ( 1 ), indicating that the rate of hydrolysis is structure-dependent. The rates of hydrolysis at 85 °C varied from a low value of 6.9 × 10 –4 h –1 to a high value of 14.1 h –1 . Hydrogen sulfide release in water was also quantified using a hydrogen sulfide-sensitive electrode. Corn was grown on an industrial scale and dosed with dibutyldithiophosphate to show that these dithiophosphates have potential applications in agriculture. At a loading of 2 kg per acre, a 6.4% increase in the harvest yield of corn was observed.
A series of polymers that possessed a backbone solely composed of alternating nitrogen and sulfur single bonds were synthesized for the first time. The structures of these polymers were based on polythiazyl (SN)x, which only possesses nitrogen and sulfur and is electrically conducting at room temperature in the absence of doping and superconducting at low temperatures. The polymers reported in this manuscript were synthesized using the reaction between sulfur dichloride (SCl2) and either anilines or octylamine. The isolated yields ranged from 48% to 74%, and the molecular weights were found using light scattering and refractive index detectors to be 6,200–35,000 g mol–1. The UV–vis spectra of the polymers were obtained, and the polymers possessed peak maxima around 450 nm and appeared red. The poly[(N,N-amino)sulfide] (polyNAS) synthesized from octylamine also was red, which demonstrated that the color was due to conjugation along the NS backbone. These polymers are the first polymers containing a backbone of alternating N and S, and are easily processed due to the groups attached to the nitrogens.
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