ChemInform Abstract: Synthesis of Dithioesters by Reaction of Dithioacids or Their Salts with Halides, Aldehydes and Epoxides.

Bonnans-Plaisance, C.; Gressier, J.C.; Lévesque, Guy; Mahjoub, Ali Reza

doi:10.1002/chin.198615098

Cited by 7 publications

(12 citation statements)

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“…To our knowledge, no crystal analysis of ammonium dithiocarboxylates has been reported. Since the first isolation of crystalline ammonium dithiocarboxylates in 1972, a variety of ammonium dithiocarboxylates have been prepared. − However, quaternary ammonium dithiocarboxylate has been limited to only tetramethylammonium 2-methylpropanecarbodithioate and benzenecarbodithioate and tetraethylammonium 2-hydroxybenzenecarbodithioate 43 and tetrathiooxalates, most likely due to the difficulty of preparation and purification. Their X-ray structural analyses have not been described.…”

Section: Resultsmentioning

confidence: 99%

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

et al. 1999

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Dithiocarboxylic acids and their trimethylsilyl esters were found to readily react with potassium, rubidium, and cesium fluorides to give the corresponding alkali metal dithiocarboxylates 3-5 in moderate to good yields. A series of tetramethylammonium dithiocarboxylates 8 have been prepared in good yields by the reaction of sodium dithiocarboxylates 7 with tetramethylammonium chloride. The structures of potassium (3b), rubidium (4g), cesium (5f), and tetramethylammonium 4-methylbenzenecarbodithioates (8e) and tetramethylammonium 2-methoxybenzenecarbodithioate (8f) were characterized crystallographically. These heavier alkali metal salts (3b, 4g, 5f) have a dimeric structure [(RCSSM)(2), M = K, Rb, Cs] in which the two dithiocarboxylate groups are chelated to the metal cations which are located on the upper and lower sides of the plane involving the two opposing dithiocarboxylate groups. The K(+) cations interact with the tolyl fragment of a neighboring molecule, while the Rb(+) and Cs(+) cations interact with two neighboring tolyl fragments, in which the ipso and ortho carbons are positioned close to the metals. The interaction number of the metals with surrounding atoms is 8 for K(+) and Rb(+) and 12 for Cs(+). The C-S distances of the dithiocarboxylate group are different for the potassium salt 3b. In contrast, those of the rubidium salt 4g and cesium salt 5f are equal. Similarly, the chelating sulfur-metal bond distances of 3b are different, while those of 4g and 5f are almost equal. The dihedral angles of the phenyl ring and dithiocarboxylate plane increase in the order of the K, Rb, and Cs salts. The structural analysis of sodium 4-methylbenzenecarbodithioate (7g) revealed the presence of 4-CH(3)C(6)H(4)CS(2)Na(0.36). In contrast, the tetramethylammonium salts 8 are monomeric where the cation moieties are located out of the dithiocarboxylate plane. The potassium 3, rubidium 4, and cesium dithiocarboxylates 5 readily reacted with methyl iodide or triorganotin chlorides at room temperature to give the corresponding methyl 9 and triorganotin dithioesters 10 in good yields. At 0 degrees C, the reactivity of the rubidium 4 and cesium salts 5 to methyl iodides decreases dramatically compared with those of the sodium salts 7 and potassium salts 3.

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Section: Resultsmentioning

confidence: 99%

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

et al. 1999

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“…The method is applicable to all forms of RAFT agents (i.e., dithioesters, trithiocarbonates, xanthates, and dithiocarbamates) but is mainly used for preparation of RAFT agents containing primary and secondary R groups. RAFT agents with tertiary R are more cumbersome to prepare via this method as nucleophilic substitution on tertiary halides is relatively slow, which results in lower yields of the desired product, requires extended reaction times (e.g., Tables and ), and elimination is a potential complication . Nonetheless, acceptable yields (70–80%) have been reported for some tertiary trithiocarbonates. − …”

Section: Raft Agent Synthesismentioning

confidence: 99%

RAFT Agent Design and Synthesis

et al. 2012

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This Perspective reviews the design and synthesis of RAFT agents. First, we briefly detail the basic design features that should be considered when selecting a RAFT agent or macro-RAFT agent for a given polymerization and set of reaction conditions. The RAFT agent should be chosen to have an optimal C tr (in most circumstances higher is better) while at the same time it should exhibit minimal likelihood for retarding polymerization or undergoing side reactions. The RAFT agent should also have appropriate solubility in the reaction medium and possess the requisite end-group functionality for the intended application. In this light we critically evaluate the various methods that have been used for RAFT agent synthesis. These methods include reaction of a carbodithioate salt with an alkylating agent, various thioacylation procedures, thiation of a carboxylic acid or ester, the ketoform reaction, thiol exchange, radical substitution of a bis(thioacyl) disulfide, and radical-induced R-group exchange. We also consider methods for synthesis of functional RAFT agents and the preparation of macro-RAFT agents by modification of, or conjugation to, existing RAFT agents. The most used methods involve esterification of a carboxy functional RAFT agent, azide–alkyne 1,3-dipolar cycloaddition, the active ester–amine reaction, and RAFT single unit monomer insertion. While some of these processes are described as “click reactions”, most stray from that ideal. The synthetic method of choice is strongly dependent on the structure of the desired RAFT agent. Finally, we outline some of the current challenges in RAFT agent design and synthesis.

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“…The afore‐mentioned synthesized polymer, DTB‐PAS‐diol, includes a dithiobenzoyl structure at the terminal, and this structure derived from the structure of the CTA used here. In general, thiobenzoyl compounds easily hydrolyze in an aqueous medium owing to their low thermodynamic stability (a formation enthalpy for the CS bond is 180 kJ/mol smaller than that for the CO bond). Thiobenzoyl compounds play an important role in RAFT polymerization, and research has reported their stability in an aqueous medium .…”

Section: Resultsmentioning

confidence: 99%

RAFT-based synthesis and the gelation property of telechelic polymers that can immobilize biomacromolecules

Kinoshita

Takami

Mori

et al. 2017

J. Polym. Sci. Part A: Polym. Chem.

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Telechelic polymers, macromolecules having two reactive end groups, can serve as building blocks for constructing polymers or polymeric materials that have complex architectures. Among the telechelic polymers, polymers bearing hydroxyl groups at two terminals have been used as components for preparation of functional materials. In the present study, RAFT polymerization of both N‐acryloylmorphorin and N‐succinimidyl acrylate by using a newly synthesized dithiobenzoate‐type chain transfer agent bearing hydroxyl groups at both terminals (HECPHD) was reported. After the acryloylation of the hydroxyl terminals of the obtained polymer, gelation was observed. Furthermore, the polymer could react with a protein via the conjugation of the succinimidyl esters‐containing polymers to the amino groups present on the protein surface. The results show that activated esters‐bearing polymers with hydroxyl groups at both terminals can be used as building blocks for constructing polymeric materials for an immobilization of biomacromolecules. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 1356–1365

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ChemInform Abstract: Synthesis of Dithioesters by Reaction of Dithioacids or Their Salts with Halides, Aldehydes and Epoxides.

Abstract: Quartäre Ammoniumsalze von Dithiobenzoesäuren reagieren mit Alkyl‐ bzw. Arylhalogeniden oder ‐dihalogeniden unter Bildung von symm. oder unsymm. Dithio‐ bzw. Bisdithioestern.

Cited by 7 publications

References 0 publications

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

Heavy Alkali Metal Arenedithiocarboxylates: A Facile Synthesis, Dimeric Structure, and Nonbonding Interaction between the Metals and Aromatic Ring Carbons

RAFT Agent Design and Synthesis

RAFT-based synthesis and the gelation property of telechelic polymers that can immobilize biomacromolecules

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