Ethyl ethylthiomethyl

The anions of alkyl alkylthiomethyl sulphoxides have found a much broader application. Methyl methylthiomethyl sulphoxide 324 was first introduced by Ogura and Tsuchihashi in 1971412 and ethyl ethylthiomethyl sulphoxide 325 was synthesized by Schlessinger and coworkers in 1973413. Ogura and Tsuchihashi performed alkylation of 324 and obtained a series of substituted dithioacetal monoxides 326 which were then hydrolysed to the corresponding aldehydes (equation 181 Table 17)412. 

The use of ethyl ethylthiomethyl sulphoxide in this reaction leads to the desired addition products in much better yields (95-97%). These products were then converted into ketene dithioacetal monoxide derivatives 430 by a sequence of reactions (equation 258)505. Reaction of 2-lithio-l,3-dithiane-l-oxide with benzophenone affords a mixture of the diastereoisomeric tertiary alcohols 431 in a ratio which is temperature dependent (cis trans changes from 3 1 at — 78 °C to 1 1 at room temperature)268. 

Ethyl ethylthiomethyl sulphoxide anion 325 has been found to give better yield of 1,4-adducts compared with its methyl analogue . This anion has been used by Schlessinger and coworkers as a key reagent in the synthesis of 1,4-dicarbonyl precursors of naturally occurring cyclopentenones, e.g. dihydrojasmone 379 (equation 219). Michael addition of the anion of optically active (-l-)-(S)-p-tolyl p-tolylthiomethyl sulphoxide 380 to the properly substituted cyclopentenone constitutes an important step in the asymmetric synthesis of optically active cyclopentenone 381, which is a precursor of 11-deoxy-ent-prostanoids (equation 220). The reaction proceeds with a high and y-asymmetric induction (92%), but with a poor a-stereoselection (52 48). 

Unlike the carbanions from 1,3-dithians (see Chapter 3, p. 31 and Chapter 6, p. 90), the sulfinyl carbanions have the ability to undergo Michael additions (conjugate or 1,4-additions) with a,p-unsaturated carbonyl compounds. For instance, the secondary carbanion (44) from the ethyl ethylthiomethyl sulfoxide (45) may be sucessively reacted with ethyl iodide and 3-butene-2-one to give heptan-2,5-dione (46) via the tertiary carbanion (47), as shown in Scheme 23. The carbanion (47) may also be condensed with propyl bromide, and hydrolysis of the product yields ethyl propyl ketone (48) (Scheme 23). 

Als Synthesebausteinc fiir die Aldehyd-Herstellung (Ubersicht s. Lit.360) haben Methyl-(methylthio-methyl)-(V)360"362, Ethyl-ethylthiomethyl-sulfoxid(VI)295,363,364 bzw. l,3-Dithian-S-oxid(VII)295,364-366 Anwendung gefunden. 

Aq.30%-H2O2 added with ice-cooling to a soln. of formaldehyde diethyl mercaptal in acetic acid, and stirred 2 hrs. at room temp. -> ethyl ethylthiomethyl sulfoxide. Y 83%. - Other oxidants did not give satisfactory results. F. e. s. K. Ogura and G. Tsudiihashi, Bull. Chem. Soc. Japan 45, 2203 (1972). 

Closely related procedures are based on z-a I kyIthiosu Ifoxidcs, with ethylthiomethyl ethyl sulfoxide being a particularly convenient example.119 120... 

DITHIOPHOSPHATE de 0,0-DIETHYLE et de S-(2-ETHYLTHIO-ETHYLE) see DXH325 DITHIOPHOSPHATE de 0,0-DIETHYI.E et d ETHYLTHIOMETHYLE (FRENCH) see PGSOOO DITHIOPHOSPHATE de-0,0-DIETHYLE et de S(2,5-DICHLOROPHENYL) THIOMETHYLE (FRENCH) see PDC750... 

Phorate can be prepared by the reaction of diethyl phosphorodithioic acid, ethyl mercaptan and formaldehyde (Hook and Moss, 1948), or by the reaction of sodium 0,0-diethyl phosphorodithioate with ethylthiomethyl chloride (Lorenz and Schrader, 1952). 

Preparation of Ethylthiomethyl Ethyl Sulfoxide and Methyl Phenyl Sulfoxide... 

Synonyms AC 3911 American Cyanamid 3911 (9,(9-Diethyl 5 -ethylmercaptomethyl dithiophosphonate (9,(9-Diethyl 5 -ethylthiomethyl dithiophosphonate (9,(9-Diethyl iS-eth-ylthiomethyl phosphorodithioate El-3911 ENT 24042 Experimental insecticide 3911 Granutox L 11/6 Phorate-IOG Phosphorodithioic acid 0,0-diethyl 5 -((ethyl-thio)methyl) ester Rampart RCRA waste number P094 Thimet Timet Vegfm Vergfm foratox. 

---