Stannous Chloride as a Versatile Catalyst in Organic Synthesis

Singh, Okram Mukherjee; Devi, Laishram Ronibala

doi:10.2174/1570193x11310010007

Cited by 15 publications

(3 citation statements)

References 49 publications

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“…Organotin molecules are used widely, as the diverse ligand arrangements and complexing available to tin atoms promote an equally diverse set of uses. − Tin species are used to stabilize polyvinylchloride against degradation, − vulcanize silicone, and catalyze production of polyurethane. , Homogeneous organotin catalysts have particular capabilities in the realm of ester formation and exchange reactions that participate in polyester preparations: esterification, − transesterification, − polycondensation, , and ring-opening polymerization . The use of tin catalysts in these processes has been incorporated into continuing advancements in polyester polymer development with new monomers and for displacing bisphenol A residues from consumer products. − …”

Section: Introductionmentioning

confidence: 99%

Molecular Carbonyl Insertion as the Homogeneous Catalysis Mechanism for Transesterification of Dimethyl Terephthalate with Ethylene Glycol

McGill

Westmoreland

2021

Ind. Eng. Chem. Res.

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Carbonyl insertion is identified and computationally quantified as a mechanism for homogeneous organotin catalysis of transesterification. Organotin species are widely used catalysts for reactions of ester exchange, such as the transesterification of dimethyl terephthalate with ethylene glycol that is at the center of polyethylene terephthalate production. The mechanism proceeds by pericyclic reactions, inserting the ester carbonyl into a tin−alkoxide bond and forming an orthoester intermediate before that decomposes to release the product ester. To propose reaction steps and reaction rates for both dibutyl tin(IV) oxide and tin(II) acetate systems, computational quantum chemistry is applied at a B3LYP/def2-TZVPD level with Grimme dispersion and implicit ethylene glycol solvent and transition-state theory. Ligand-exchange reaction rates are orders of magnitude faster than the core mechanism, justifying equilibrium assumptions for the ligand state of the tin. The multiple reaction steps fit simple Arrhenius forms well when consolidated using a quasi-steady-state simplification, giving activation energies of 65.9 and 61.4 kJ/mol for dibutyltin oxide (DBTO) and tin(II) acetate, respectively. Analogous reaction mechanisms would apply in esterification, ester hydrolysis, and polycondensation reaction types as well. There is reasonable agreement with experimentally based rate constants at 197 °C. On the basis of tin−alkoxide bonds reacting with esters, the overall predicted rate constant is 180 cm 3 /(mol s) for DBTO versus 88 cm 3 /(mol s) obtained experimentally. For tin(II) acetate, the comparison is 1130 cm 3 /(mol s) predicted versus 392 and 57 cm 3 /(mol s) inferred from experiments.

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Section: Introductionmentioning

confidence: 99%

Molecular Carbonyl Insertion as the Homogeneous Catalysis Mechanism for Transesterification of Dimethyl Terephthalate with Ethylene Glycol

McGill

Westmoreland

2021

Ind. Eng. Chem. Res.

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“…We anticipated that depending on the reaction condition, the dealkylation might happen if an electron‐withdrawing group is present either at the ortho or para position of the O ‐alkyl group. The reagent has been used as a potential and inexpensive reagent in many chemical transformations, for example, cyclization, [6] multicomponent reactions, [7] preparation of heterocycles, [8] esterification, [9] etc. Many research groups reported nitro group reduction with stannous chloride dihydrate or with anhydrous form [10–13] .…”

Section: Introductionmentioning

confidence: 99%

Debenzylation or Demethylation in Methyl Ester of O‐Alkyl Nitrophenols with Stannous Chloride Dihydrate

Karmakar,

Patel,

Shah

et al. 2023

ChemistrySelect

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Stannous chloride dihydrate (SnCl2.2H2O) is an inexpensive and commonly used reagent for nitro group reduction. We observed partial O‐demethylation or O‐debenzylation of O‐alkylated nitrobenzene derivatives when subjected to the nitro reduction with the reagent in ethyl acetate at heating, a generally employed reaction condition. A neat reaction at 80 °C afforded the debenzylated product. Reactions at room temperature yielded corresponding O‐alkylated anilines only. The results show the effect of electron‐withdrawing groups on dealkylation; when at the ortho or para position to the alkoxy group, they enhanced the possibility of dealkylation, and no dealkylation was observed in meta‐oriented substrates. The systematic study may help researchers to choose the proper conditions to prevent undesired products.

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“…To the best of our knowledge, the use of tin(II) chloride in a three‐component coupling reaction of an aldehyde, amine, and alkyne has never been reported. Tin chloride is an inexpensive, easily available, mild Lewis acid that can be used for various organic transformations …”

Section: Introductionmentioning

confidence: 99%

Tin(II) Chloride Catalyzed Multicomponent Synthesis of Propargylamines and Intramolecular [3+2] Cycloaddition

Afraj

Chen

2016

Asian J Org Chem

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As imple method to synthesize propargylamines along with the highly diastereoselective synthesis of as eries of 4,6,7,8,8a,9-hexahydropyrrolo[1,2-a][1,2,3]triazolo[1,5-d]pyrazines has been developed. The three-component coupling of aldehydes,a mines,a nd alkynes (A 3 -coupling), which proceeds throughaC ÀHa ctivationp rocess with tin(II) chloride as the catalyst, and am etal-free [3+ +2] cycloaddition reaction were used to prepare the propargylamines and fused heterocycles, respectively,w ithoutt he need of ac ocatalyst or activator. The coupling reaction is applicable to variousaldehydes, amines, anda lkynes and provides the propargylamines in good to excellent yields with excellent distereoselectivities. The cycloaddition reaction also provides various tricyclicf used triazole derivatives in excellent yields with high distereoselectivities. Am echanism is proposed for the tin(II) chloride catalyzed three-component coupling as well as the [3+ +2] cycloaddition reaction.

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Stannous Chloride as a Versatile Catalyst in Organic Synthesis

Cited by 15 publications

References 49 publications

Molecular Carbonyl Insertion as the Homogeneous Catalysis Mechanism for Transesterification of Dimethyl Terephthalate with Ethylene Glycol

Molecular Carbonyl Insertion as the Homogeneous Catalysis Mechanism for Transesterification of Dimethyl Terephthalate with Ethylene Glycol

Debenzylation or Demethylation in Methyl Ester of O‐Alkyl Nitrophenols with Stannous Chloride Dihydrate

Tin(II) Chloride Catalyzed Multicomponent Synthesis of Propargylamines and Intramolecular [3+2] Cycloaddition

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