14225-56-0

Upstream product

• 7473-99-6 α-chloroisobutyrophenone 
• 14225-53-7 2-isopropyl-5,5-dimethyl-2,4-diphenyl-2,5-dihydro-thiazole 
• 10409-54-8 2-bromo-2-methyl-1-phenyl-propan-1-one 

Downstream Products

• 14229-86-8 2-isopropyl-2,5,5-trimethyl-4-phenyl-2,5-dihydro-thiazole 
• 14229-89-1 2-ethyl-5,5-dimethyl-4-phenyl-2,5-dihydro-thiazole 
• 14229-91-5 2-isopropyl-5,5-dimethyl-4-phenyl-2,5-dihydro-thiazole 
• 14229-85-7 2,2-diethyl-5,5-dimethyl-4-phenyl-2,5-dihydro-thiazole 
• 611-70-1 phenyl isopropyl ketone 
• 14225-58-2 S-α,α-dimethylphenacyl thioacetate 
• 14229-65-3 Bis-<1-phenyl-isobutanon-(1)-yl-(2)>-trisulfid 
• 14229-87-9 2-ethyl-2,5,5-trimethyl-4-phenyl-2,5-dihydro-thiazole 
• 14229-90-4 5,5-dimethyl-4-phenyl-2-propyl-2,5-dihydro-thiazole 
• 14236-74-9 2,2-dimethyl-3-phenyl-1-thia-4-aza-spiro[4.5]dec-3-ene 

Relevant academic research and scientific papers

α-Methylphenacyl thioesters as convenient thioacid precursors

α-Methylphenacyl (Mpa) thioesters are described as precursors of thioacids. Mpa thioesters are accessible via the condensation of carboxylic acids and phenacyl thiol, which is easily prepared without column chromatography. The Mpa thioesters are selectively deprotected by reduction with zinc dust in the presence of conventional thioacid protecting groups. In addition, the Mpa group exhibits orthogonal reactivity to the Boc group. These features are expected to facilitate the preparation of complex thioacids, including those in peptides.

Sulfuranes with Oximate Axial Ligands

New sulfuranes having one or two axial oximate (R2C=NO) ligands were synthesized.An improved sulfurane-forming step, involving a rapidly stirred suspension of NaHCO3, is described.The failure of sulfide oximes in which sulfur bears one or two tertiary carbons to form sulfuranes is explained by a C-S bond cleavage leading to tertiary carbocations.This represents a hitherto unanticipated limitation to the standard method of sulfurane synthesis.The X-ray crystal structure of one of the new sulfuranes, namely 2,2'-spirobi(4-phenyl-3H-1,2,5-oxathiazoline), is reported (R = 0.0368).An unusual feature was the quite compressed equatorial (C-S-C) angle, 102.6(1) deg.The S-O bond length, 1.846(2) Angstroem, was similar to S-O bond lenghths of sulfuranes having two axial carboxylate ligands.Since the oximate ligand has not been used previously in a 10-S-4 species, an assessment of its apicophilicity relative to other more common axial ligands was made by considering X-ray structural data, IR data, and ab initio calculations.These suggest that the R2C=NO ligand is as apicophilic as the hexafluorocumyloxy (ArC(CF3)2O) ligand.

A facile, high-yielding method for the conversion of halides to mercaptans

An efficient, high-yield, one-pot preparation of alkyl and activated aryl mercaptans is presented. The method relies on sodium thiophosphate displacement of the halide, followed by mild hydrolysis of the intermediate phosphorothioate.

On the Joint Reaction of Elemental Selenium with Gaseous Ammonia and Ethylenimine, respectively in the Presence of Ketones. Joint Reaction of Elementary Sulfur and Gaseous Ammonia with Ketones, 96.

Elemental sulfur reacts with ketones and gaseous ammonia at room temperature yielding thiazoline-3 in excellent yields.Under the same conditions elemental selenium does not react at all.Attempts using the known techniques which have been applied in improving the reactivity of slowly reacting ketones in thiazoline-3-synthesis have been unsuccessful (Exp.No. 1-17).The reaction of α-halogenketones with sodiumhydrogenselenide to synthesize α-hydroselenoketones gives only the original ketones and selenium in almost quantitative yields (No. 18-23).The same is observed with α-haloketones and sodium ore magnesium-diselenides (No. 24-45).The explanation of these unexpected results is the strong reducing power of the hydrogenselenide (No. 46-52).Even α-bromoketones with activated bromine (i.g. by phenyl groups) were reduced by sodiumhydrogensulfide giving red undefinite oils.However, α-chloroketones give α-mercaptoketones in excellent yields (No. 53-61).Hydrogenselenide reduces α-mercaptoketones to sulfur and ketones in the presence of triethylamine (No. 62-67).Also the transformation of α-selenocyanketones to α,α'-diketodiselenides by alkali or the oxidative hydrolysis of selenium-"BUNTE" salts does not work and gives elementary selenium only.Studies about the concomitant reaction of elementary selenium and ethylenimine on ketones were continued (No. 68-83). - Keywords: Dihydro-p-selenazine, α-Haloketones, Hydrogenselenide reducing Action, α-Mercaptoketones