101373-67-5

Basic information

• Product Name: anti-3-Hydroxy-2-methyl-3-phenyl-propandithiosaeure-methylester
• CAS NO: 101373-67-5
• Molecular Weight: 226.364
• Mol File: 101373-67-5.mol
• Article Data: 3

Chemical Properties

• CAS DataBase Reference: anti-3-Hydroxy-2-methyl-3-phenyl-propandithiosaeure-methylester(CAS DataBase Reference)
• NIST Chemistry Reference: anti-3-Hydroxy-2-methyl-3-phenyl-propandithiosaeure-methylester(101373-67-5)
• EPA Substance Registry System: anti-3-Hydroxy-2-methyl-3-phenyl-propandithiosaeure-methylester(101373-67-5)

Safety Data

• Hazardous Substances Data: 101373-67-5(Hazardous Substances Data)

Upstream product

• 5415-95-2 methyl dithiopropionate 
• 100-52-7 benzaldehyde 
• 1892-30-4 dithiopropionic acid 
• 74-88-4 methyl iodide 

Relevant articles and documents

Dithio and thiono esters, LX: Addition of dithioic acid dianions to aldehydes and ketones

Aliphatic dithiocarboxylic acids such as dithioethanoic acid (1a), dithiopropanoic acid (10a) or 2-methyl-dithiopropanoic acid (10e) react with 2 moles of n-BuLi to form the corresponding dilithium dithioenolates 2a, 11a or 11e. These add to aldehydes and ketones to give the aldol adducts 3a-f and 12a-e. Methylation with methyl iodide leads to the more stable β-hydroxy dithioesters 4 and 13. The esters 4 have been dehydrated to yield the α,β-unsaturated dithioesters 5. Addition of the dilithium dithioenolate 2a to methylvinyl ketone, cyclohexenone or cyclopentenone followed by methylation gives rise to the δ,ε-unsaturated dithioesters 6-8.

STEREOCHIMIE DE LA DEPROTONATION ET DE LA REACTION D'ALDOLISATION DES DITHIOESTERS.

Cis lithium thioenolates are preferentially formed by deprotonation of dithiopropanoates with lithium diisopropylamide in tetrahydrofuran at -78deg C.The cis selectivity observed, is improved by increasing the alkylthio group size or by the ability of this group to chelate the lithium cation.When more bulkier bases such as lithium 2,2,6,6-tetramethylpiperidide or lithium hexamethyldisilazane are used, the selectivity is lowered.This lowering of selectivity is suppressed when the deprotonation is performed in presence of 12-crown-4.Addition of hexamethyl phosphoramide to the base does not invert the selectivity as it was reported for the deprotonation of esters ; a rather better cis selectivity is reached in the case of methoxymethyl dithiopropanoate.These original results are well understood in terms of an open transition state model.Preformed lithium thioenolates are reacted with a variety of aldehydes and affored stereospecifically syn aldols.The influence of hexamethylphosphoramide and reaction time is also examined.