61097-65-2

Upstream product

• 109142-68-9 2,2-dimethyl-4-isopropylidene-3-thietanone tosylhydrazone 
• 811-98-3 d⁽⁴⁾-methanol 
• 65927-08-4 3,5-Dihydro-3,3,5,5-tetramethyl-4H-pyrazole-4-thione 
• 1000-87-9 2,4-dimethyl-2,3-pentadiene 
• 565-80-0 2,4-dimethylpentan-3-one 
• 335293-36-2 2,2,4,4-Tetramethyl-3-thietanone acetylhydrazone 
• 89050-85-1 2,2,4,4-Tetramethylthietan-3-one Hydrazone 
• 17346-16-6 2,4-dibromo-2,4-dimethylpentan-3-one 
• 58721-01-0 2,2,4,4-Tetramethylthietan-3-one 

Downstream Products

• 109142-66-7 2,4-dimethyl-3-mercaptopenta-1,3-diene 
• 94398-17-1 (1-isopropenyl-2-methyl-1-propenyl) disulfide 
• 94398-15-9 4-Isopropylidene-5,5-dimethyl-2-p-tolyl-[1,3]oxathiolane 
• 94398-61-5 2-Benzhydrylidene-4-isopropylidene-5,5-dimethyl-[1,3]oxathiolane 
• 109142-67-8 (1-Isopropenyl-2-methyl-propenylsulfanylmethyl)-benzene 
• 94398-13-7 ((2S,3R)-5-Isopropylidene-4,4-dimethyl-2-phenyl-tetrahydro-thiophen-3-yl)-phenyl-methanone 
• 86748-25-6 2,5-diisopropylidene-3,3,6,6-tetramethyl-1,4-dithiane 
• 86766-00-9 6-isopropylidene-2,2,4,4,6,6-hexamethyl-thiane-3-thione 
• 94398-60-4 2,2-dimethyl-3-(2-propylidene)-5-phenyl-4-thioxolane 
• 94398-16-0 4-Isopropylidene-5,5-dimethyl-2-(4-nitro-phenyl)-[1,3]oxathiolane 
• 94398-14-8 3-Isopropylidene-2,2-dimethyl-6-phenyl-[1,4]oxathiane 

Relevant academic research and scientific papers

Direct episulfidation of alkenes and allenes with elemental sulfur and thiiranes as sulfur sources, catalyzed by molybdenum oxo complexes

The molybdenum oxo complexes 1a and 1b catalyze efficiently the sulfur transfer to a series of alkenes 4 and allenes 6, for which elemental sulfur, phenylthiirane, or methylthiirane have been employed as sulfur sources to afford the corresponding episulfi

Photochemistry of 2,2,4,4-tetramethyl-3-thietan-1-ylidene: A heterocyclic carbene with an unusually short lifetime and evidence for a nonclassical structure

Laser flash (308 nm) and steady-state photolysis (300 nm) of Δ3-1,3,4-oxadiazoline (3) produces a transient that can be trapped with pyridine to give an adduct with λmax = 350 nm, attributed to ylide 10. Laser flash photolysis (LFP) studies of the ylide indicate that the value of kpyrτ (where kpyr, is the absolute rate constant of carbene reaction with pyridine and τ is the carbene lifetime) of the reactive intermediate is 25 times smaller than that deduced for cyclobutylidene. The sulfur-containing transient may have a much shorter lifetime than cyclobutylidene or a much smaller value of kpyr. These experimental results, along with ab initio calculations, suggest that the structure of 2,2,4,4-tetramethyl-3-thietan-1-ylidene is best represented as nonclassical, bisected structure 2 and not classical structure 1.

Photolysis of Tetraalkyl-1-pyrazoline-4-thiones. - Diastereoselective Formation of (E)/(Z)-Alkylidenethiiranes from cis- and trans-Tetraalkyl-1-pyrazoline-4-thiones

The tetraalkyl-1-pyrazolin-4-ones 5 react with hydrazine to afford the hydrazones 6 which are transformed into the thiones 7 in high yields by treatment with disulphur dichloride in the presence of triethylamine.Selective excitation of the azo chromophor of 7a with 350-nm light gives rise to the isopropylidenethiirane 8, besides molecular nitrogen, in a very clean reaction; at almost quantitative conversions, less than 2percent of byproducts are observed, and about 10percent of 8 have isomerized to the pentadienethiol 9.Photolysis of the stereoisomers cis- and trans-7b yields mixtures of the alkylidenethiiranes (E)- and (Z)-10 with (E)/(Z) ratios of 35:65 and 49:51.The results are interpreted in terms of diastereomeric bis-orthogonal (cis- and trans-21) and mono-orthogonal thioxyallyl diradicals (E)- and (Z)-23 which cyclize to furnish (E)- and (Z)-10.There seems to be a qualitative resemblance between the photochemical and thermal stabilities in the series of 4-substituted tetramethyl-1-pyrazolines, viz. 7a oct-2-ene derivatives. Key Words: 4H-Pyrazole-4-thiones, 3,3,5,5-tetraalkyl-3,5-dihydro- / Thiiranes, 3,3-dialkyl-2-alkylidene/ 1,3-Pentadiene-3-thiol, 2,4-dimethyl- / Photolysis/ Extrusion of molecular nitrogen/ (E)/(Z) Stereoselectivity

Gas-Phase Thermolysis of 4-substituted 3,5-Dihydro-3,3,5,5-tetramethyl-4H-pyrazoles Studied by Photoelectron Spectroscopy and Flash Vacuum Pyrolysis

Gas-phase thermolysis of the 3,5-dihydro-4H-pyrazoles 1-4 have been studied by photoelectron spectroscopy and flash vacuum pyrolysis.In the PE-controlled thermolysis, 1-4 extrude molecular nitrogen, and the fragments cyclize immediately to different three-membered rings.In the case of 2 and 3, the former 4-substituent becomes part of the three-membered ring, whereas 1 and 4 afford short living oxo- and iminocyclopropanes.At higher temperatures and in flash vacuum pyrolysis, acyclic compounds and smaller molecules are formed in a second step.Based on MNDO, AM1, and PM3 calculations, the ionization potentials of 3,5-dihydro-3,3,5,5- tetramethyl-4-methylene-4H-pyrazole (3) have been assigned to molecular orbitals.To aid the identificaion of the pyrolysis products, PE spectra of the methylenethiirane 9 and the methylenecyclopropanes 11 and 13 have been measured and interpreted with the aid of SCF calculations.

NATURE OF THYOXYALLYL INTERMEDIATE IN THE DECOMPOSITION OF ALLENE EPISULFIDE AND PYRAZOLINE-4-THIONE

Thermolysis of tetramethylallene episulfide (10) gave 2,4-dimethyl-3-mercaptopenta-1,3-diene(12) via thioxyallyl intermediate(13) by unimolecular C-S bond cleavage. 3,3,5,5-Tetramethylpyrazoline-4-thione(11) also gave 12 probably via the same intermediate(13), which has a biradical character.