1072-72-6

Usage

Uses

Used in Pharmaceutical Industry:
Tetrahydrothiopyran-4-one is used as a reactant for the stereoselective preparation of [aryl(nitro)ethyl] carbonyl compounds. This application is particularly relevant in the pharmaceutical industry, where the compound serves as a catalyst in asymmetric Michael addition to nitroolefins, facilitated by chiral pyrrolidine-pyridine conjugate bases. This process is crucial for the synthesis of various pharmaceutical compounds with specific stereochemistry, which can significantly impact their efficacy and safety.
Used in Chemical Research:
In the field of chemical research, Tetrahydrothiopyran-4-one is utilized to study the diastereoselectivity of the aldol reaction. Understanding the selectivity of this reaction is essential for developing new synthetic methods and improving the efficiency of existing ones, ultimately contributing to the advancement of chemical science and technology.

Purification Methods

Purify it by recrystallisation from diisopropyl ether or pet ether and dry it in air. If too impure, then dissolve it in Et2O, wash with aqueous NaHCO3, then H2O, dry (MgSO4), filter, evaporate and the residue is recrystallised as before. [Cardwell J Chem Soc 715 1949.] The oxime can be recrystallised from CHCl3/pet ether (at -20o) and has m 84-85o [Barkenbus et al. J Org Chem 20 871 1955]. The 2,4-dinitrophenylhydrazone has m 186o (from EtOAc) [Barkenbus et al. J Org Chem 16 232 1951]. The S-dioxide is recrystallised from AcOH, m 173-174o [Fehnel & Carmack J Am Chem Soc 70 1813 1948, Beilstein 17 II 287, 17 III/IV 4172, 17/1 V 21].

InChI:InChI=1/C5H8OS/c6-5-1-3-7-4-2-5/h1-4H2

Upstream product

• 4160-61-6 3-methoxycarbonyltetrahydropyran-4-one 
• 673-79-0 diethyl 3,3'-thiobispropionate 
• 140200-77-7 1-bromo-5-chloro-3-pentanone 
• 29683-23-6 tetrahydrothiopyran-4-ol 
• 50289-18-4 4-hydroxytetrahydro-2H-thiopyran-4-carbonitrile 
• 126573-38-4 tetrahydrothiopyran-4-one-3-carboxylic acid allyl ester 
• 140200-76-6 α,α'-dibromopentan-3-one 
• 139732-48-2 3,6-dihydrothiopyran 4-(trimethylsilyloxy)-2H-thiopyran 
• 98-86-2 acetophenone 
• 111-17-1 4-thiaheptane-1,7-dioic acid 
• 39557-51-2 diallyl 3,3'-thiodipropanoate 
• 4131-74-2 Dimethyl 3,3'-thiodipropionate 
• 137909-90-1 1,4-dioxa-8-thiaspiro<4.5>decane-6-carboxaldehyde 
• 17396-36-0 tetrahydro-4H-thiopyran-4-one 1-oxide 

Downstream Products

• 22072-22-6 thiepan-4-one 
• 185-73-9 1-oxa-6-thiaspiro<2.5>octane 
• 38447-82-4 4-methyltetrahydro-2H-thiopyran-4-ol 
• 62040-99-7 3,5-bis-((Ξ)-4-methyl-benzylidene)-tetrahydro-thiopyran-4-one 
• 101936-54-3 3,5-bis-((Ξ)-4-nitro-benzylidene)-tetrahydro-thiopyran-4-one 
• 28612-36-4 3,5-dibenzylidene-tetrahydro-thiopyran-4-one 
• 61448-77-9 3,5-bis-((Ξ)-4-methoxy-benzylidene)-tetrahydro-thiopyran-4-one 
• 102657-39-6 3,5-bis-(3,4-dimethoxybenzylidene)tetrahydrothiopyran-4-one 
• 102654-78-4 3,5-bis-((Ξ)-4-dimethylamino-benzylidene)-tetrahydro-thiopyran-4-one 
• 38486-19-0 tetrahydro-thiopyran-4-one-(2,4-dinitro-phenylhydrazone) 
• 103169-58-0 3,5-bis-((Ξ)-4-isopropyl-benzylidene)-tetrahydro-thiopyran-4-one 
• 6309-59-7 tetrahydro-4H-thiopyran-4-one oxime 
• 17396-35-9 1,1-dioxotetrahydrothiopyran-4-one 
• 65961-01-5 7a-morpholin-4-yl-1-(4-nitro-phenyl)-1,3a,4,6,7,7a-hexahydro-thiopyrano[3,4-d][1,2,3]triazole 

Relevant academic research and scientific papers

Synthesis and characterization of sulfide, sulfoxide and sulfone derivatives of thiopyran: antimicrobial evaluation

Abstract: A series of thiopyran derivatives and their oxidized analogous forms were synthesized and characterized by FT-IR, 1H, 13C, 31P NMR and mass spectroscopy techniques. The antibacterial and antifungal activities of these synthesized materials were evaluated against Staphylococcus aureus and Bacillus subtilis, as Gram-positive bacteria, and Escherichia coli and Pseudomonas aeruginosa, as Gram-negative bacteria, as well as the fungus Candida albicans. The results revealed that thiopyran S,S-dioxides are the most effective against all the bacteria studied in this work. Furthermore, thiopyran S-oxides showed excellent antifungal activity against Candida albicans.

Simple and efficient preparation of reagents for thiopyran introduction: Methyl tetrahydro-4-oxo-2H-thiopyran-3-carboxylate, tetrahydro-4H-thiopyran-4- one, and 3,6-dihydro-4-trimethylsilyloxy-2H-thiopyran

Tetrahydro-4H-thiopyran-4-one was prepared in >75% yield by treatment of dimethyl 3,3′-thiobispropanoate with NaOMe (generated in situ) in THF solution and decarboxylation of the resulting methyl tetrahydro-4-oxo-2H- thiopyran-3-carboxylate in refluxing 10% aqueous H2SO4. Reaction of tetrahydro-4H-thiopyran-4-one with Me3SiCl and Et 3N in CHCl3 gave the corresponding trimethylsilyl enol ether in near quantitative yield. The prepared reagents are useful for the synthesis of thiopyran-containing compounds. Georg Thieme Verlag Stuttgart.

HCl-catalyzed stereoselective Mannich reaction in H2O-SDS system

HCl-catalyzed Mannich reaction of cyclic ketone, aromatic aldehyde, and aromatic amine proceeded smoothly in water in the presence of SDS to afford the corresponding β-amino ketone with high anti selectivity.

Influence of the β-alkoxy group on the diastereoselectivity of aldol reactions of tetrahydro-4H-thiopyran-4-one with 4-alkoxytetrahydro-2H-thiopyran-3-carboxaldehydes

The diastereoselectivity of the aldol reaction of tetrahydro-4H-thiopyran-4-one (3) with 1,4-dioxa-8-thiaspiro[4.5]decane-6-carboxaldehyde (9a) under a variety of conditions is examined. Under optimized conditions, three of the four possible diastereomers from this aldol reaction can be obtained selectively (3-16:1). Reactions of 9a with the Li, B, Mg(II), and Ti(IV) enolates of 3 and with the corresponding trimethylsilyl enol ether 4b in the presence of BF3·OEt2, SnCl4, or TiCl4 as promoters gave the Felkin adducts exclusively (>95%) as mixtures of syn (11a) and anti (12a) diastereomers. Use of the "amine-free" Li enolate of 3 gave 12a with a much higher diastereoselectivity (9:1) and yield (70%) than that obtained using the lithium diisopropylamide-generated Li enolate of 3 (2-3:1; 15-40%). The TiC14-promoted reaction of 4b with 9a gave 11a with excellent selectivity (16: 1). In contrast, the MgBr2·OEt2-promoted reaction of 4b with 9a gave the anti-Felkin adducts exclusively as a 3:1 mixture of syn (13a)/anti (14a) diastereomers. Similar aldol reactions of 3 with the cis and trans isomers of 4-(methoxy)methoxytetrahydro-2H-thiopyran-3-carboxaldehyde (9b and 9c) were examined to probe the influence of the ketal protecting group in 9a on the observed aldol diastereoselectivity. The results are rationalized by applying Evans' stereochemical model for merged 1,2- and 1,3-asymmetric induction (nonchelation), with the exception of the MgBr2· OEt2-promoted reactions of 4b with 9a, 9b, and 9c, which are accommodated by assuming chelation control. Comparison of the reactions of 9a, 9b, and 9c suggests that the ketal group in 9a uniquely allows high levels of either Felkin or anti-Felkin selectivity to be achieved.

Hydrogenation of sulfoxides to sulfides under mild conditions using ruthenium nanoparticle catalysts

The first demonstration of the hydrogenation of sulfoxides under atmospheric H2 pressure is reported. The highly efficient reaction is facilitated by a heterogeneous Ru nanoparticle catalyst. The mild reaction conditions enable the selective hydrogenation of a wide range of functionalized sulfoxides to the corresponding sulfides. The high redox ability of RuO x nanoparticles plays a key role in the hydrogenation.

Synthesis and reduction kinetics of sterically shielded pyrrolidine nitroxides

A series of sterically shielded pyrrolidine nitroxides were synthesized, and their reduction by ascorbate (vitamin C) indicate that nitroxide 3, a tetraethyl derivative of 3-carboxy-PROXYL, is reduced at the slowest rate among known nitroxides, i.e., at a 60-fold slower rate than that for 3-carboxy-PROXYL.

Synthesis of 5 H-Imidazo[1,2-a]thiopyrano-[4',3':4,5]thieno[2,3-d]pyrimidin-5-one

The enamino-ester, ethyl, 2-amino-4,7-dihydro-5H-thieno[2,3-c]thiopyrano-3-carboxylate (5) was prepared from tetrahydrothiopyran-4-one (4). Annelating reagent, 5-methyl-2-methylthioimidazoline (8) was prepared starting from 1, 2-diaminopropane (6) via 5-methyl-2-imidazolidinethione (7). The reaction of enamino-ester (5) with the annelating reagent (8) in HMPTA leaded to new 1,2,3,6,7,9-hexahydro-5H-imidazo[1,2-a]thiopyrano[4',3':4,5]thieno[2,3-d]pyrimidin-5-one (9) in good yield.

Aminooxyamide tricyclic inhibitors of farnesyl-protein transferase

Novel aminooxyamide tricyclic compounds and pharmaceutical compositions are disclosed which are inhibitors of the enzyme, farnesyl protein transferase. Also disclosed is a method of inhibiting Ras function and therefore inhibiting the abnormal growth of cells. The method comprises administering the novel aminooxyamide tricyclic compound to a biological system. In particular, the method inhibits the abnormal growth of cells in a mammals such as a human.

Syntheses of 4H-thiopyran-4-one 1,1-dioxides as precursors to sulfone-containing analogues of tetracyanoquinodimethane

Synthetic routes to the unsubstituted 4H-thiopynan-4-one 1,1-dioxide (5a), 2,6-dialkyl-substituted, 2-aryl- or 2-heteroaryl-6-alkyl-substituted, 2,6-diaryl- or diheteroaryl-substituted, and 2-heteroaryl-6-aryl-substituted 4H-thiopyran-4-one 1,1-dioxides 5b-s are described. Sodium hydrosulfide hydrate in buffered aqueous alcohol can be used as a substitute for hydrogen sulfide gas for the introduction of sulfur to methyl acrylate, to 1,5-disubstituted-1,4-pentadien-3-ones 13, or to 1,5-disubstituted-1,4-pentadiyn-3-ones 17. The double dehydrogenation of 2,3,5,6-tetrahydrothiopyran-4-one 1,1-dioxides 13 with iodine-DMSO-sulfuric acid gives thiopyran-4-one 1,1-dioxides 5 in good yield and small amounts of 1,4-pentadien-3-ones 13. 2,3,5,6-Tetrahydrothiopyran-4-one 1,1-dioxide (9) and 5,6-dihydrothiopyran-4-one 1,1-dioxide (12), which lack aryl or heteroaryl substituents, give poor yields of 4H-thiopyran-4-one 1,1-dioxide (5a) with iodine-DMSO-sulfuric acid.

A SIMPLE METHOD FOR THE PRODUCTION OF 1,5-DIHALOGENO-3-PENTANONES AND 1-BROMO-3-PENTANONE - PRECURSORS OF DIVINYL AND ETHYL VINYL KETONES

The reaction of methyl 3-halogenopropionates with ethylmagnesium bromide in the presence of catalytic amounts of tetraisopropoxytitanium gave the corresponding 1-(2-halogenoethyl)cyclopropanols, the bromination of which with N-bromosuccinimide led to high yields of 1,5-dihalogeno-3-pentanones. 1-Bromo-3-pentanone was obtained by the acid-catalyzed opening of the three-membered ring of 1-(2-bromoethyl)cyclopropanol and also by the bromination of 1-ethylcyclopropanol.The reactions of 1,5-dibromo-3-pentanone with sodium carbonate and sodium sulfide led to good yields of divinyl ketone and 4-tetrahydrothiopyrone respectively.