Polymerization of Aniline Derivatives to Yield Poly[<i>N</i>,<i>N</i>-(phenylamino)disulfides] as Polymeric Auxochromes

Grace, James P.; Flitz, Evan; Hwang, Dae Sun; Bowden, Ned B.

doi:10.1021/acs.macromol.1c01548

Cited by 4 publications

(2 citation statements)

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“…These polymers were similar to polythiazyl, but they possess two sulfur atoms for every nitrogen atom. 58 In prior work, we reported the synthesis of poly[N,N-(phenylamino)disulfides] by the reaction of anilines with sulfur monochloride (S 2 Cl 2 ). The backbone of these polymers was the NSS functional group with anilines bonded to the nitrogen.…”

Section: Introductionmentioning

confidence: 99%

Polymerization of Primary Amines with Sulfur Monochloride to Yield Red Polymers with a Conjugated SN Backbone

et al. 2023

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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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Section: Introductionmentioning

confidence: 99%

Polymerization of Primary Amines with Sulfur Monochloride to Yield Red Polymers with a Conjugated SN Backbone

et al. 2023

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“…In materials chemistry, aminodisulfides have found applications as near-IR dyes and radical conductors . Furthermore, the aminodisulfide structure has received significant attention as the constituent element of functional polymers. , Due to the low bond dissociation energy and the dynamic covalent character of the S–S bond, such polymers are used as healable and reprocessable materials . They are also expected to have potential applications as biodegradable polymers for drug/gene delivery due to their degradability in reductive and acidic environments …”

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Amination of N-(Organodithio)phthalimides for the Modular Synthesis of Aminodisulfides

Asanuma,

Kanemoto

2023

Org. Lett.

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Synthetic methods for unsymmetrical aminodisulfides are greatly needed due to their applications in drug discovery, linker chemistry, and materials sciences. In this study, an amination reaction of N-dithiophthalimides has been developed for the divergent synthesis of unsymmetrical aminodisulfides. The reaction proceeds under mild conditions and provides the aminodisulfides in excellent yields without cleavage of the disulfide bond. The Ndithiophthalimides are readily available from several bilateral disulfurating reagents, and the broad substrate scope of this reaction allows for the modular synthesis of a variety of unsymmetrical aminodisulfides in two-step operations.

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Polymerization of Diamines with Sulfur Monochloride To Yield Bright, Conjugated Polymers

Wickremasinghage,

Breuer,

Bowden

2024

Macromolecules

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Highly conjugated polymers possessing the NSS functional group were synthesized to investigate the colors obtained from polymers with this understudied functional group. Five aromatic diamines were polymerized with sulfur monochloride (S2Cl2) to yield high molecular weight cross-linked polymers. The polymerizations were completed with ratios of amine to sulfur monochloride of 1.5:1, 1:1, 1:1.5, and 1:2 to yield polymers with different levels of cross-linking and molecular weights from 15 to 5100 kg mol–1. The compositions were investigated by elemental analysis to confirm that the amount of sulfur within the polymers agreed with predictions based on the ratio of monomers used in their synthesis. These polymers were brightly colored with colors from yellow, red, brown, green, and blue, and their UV–vis spectra were measured to determine the absorption maxima. Several control experiments were completed that demonstrated that the reactions between monomers occurred between the amines and S2Cl2 rather than electrophilic aromatic substitution reactions. The polymers were air stable but completely degraded in the presence of 2-mercaptoethanol. In each of these degradations, the diamine monomer was isolated without any evidence of a thiol on the ring, as would be expected for electrophilic aromatic substitution. These polymers were investigated for their ability to act as sensors for 2-mercaptoethanol by exposing them to 2-mercaptoethanol and measuring the change in the color. The reactions between the amines and S2Cl2 were rapid and used to print 2D objects with a variety of colors.

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Polymerization of Aniline Derivatives to Yield Poly[N,N-(phenylamino)disulfides] as Polymeric Auxochromes

Cited by 4 publications

References 60 publications

Polymerization of Primary Amines with Sulfur Monochloride to Yield Red Polymers with a Conjugated SN Backbone

Polymerization of Primary Amines with Sulfur Monochloride to Yield Red Polymers with a Conjugated SN Backbone

Amination of N-(Organodithio)phthalimides for the Modular Synthesis of Aminodisulfides

Polymerization of Diamines with Sulfur Monochloride To Yield Bright, Conjugated Polymers

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