Thiomethyl alcohol

Chemical Designations - Synonyms Mercaptomethane Methanethiol Methyl sulfidrate Thiomethyl alcohol Chemical Formula CH3SH. 

Synonyms BME BRN 1696840 CS EINECS 200-822-1 FCY FEMA No. 2716 Mercapto-methane Methanethiol Methyl sulfhydrate Methyl thioalcohol RCRA waste number U153 Thiomethanol Thiomethyl alcohol UN 1064. 

Synonyms Methanethiol mercaptomethane thiomethyl alcohol methyl sulfhydrate... 

METHYL MERCAPTAN Metlianethlol, Methyl sulfhydrate, Thiomethyl alcohol, Mercaptoinethane Flammable Compressed Gas 2 4 0... 

Beilstein Handbook Reference) BRN 1696840 EINECS 200-822-1 FEMA No. 2716 HSDB 813 Mercaptan methylique Mercaptomethane Methaanthiol Methanethiol Methanthiol Methvtiolo Methyl mercaptan Methyl sulfhydrate Methyl-mercaptaan Methylmercaptan Metilmercaptano RCRA waste number U153 Thiomethanol Thiomethyl alcohol UN 1064. Used in manufacture of pesticides, plastics and jet fuels. Odiferous gas mp = -123° bp = -5.9° = 0.8665 soluble in organic... 

SYNONYMS mercaptomethane, methanethiol, methyl sulfhydrate, thiomethanol, thiomethyl alcohol. 

Synonyms Mercaptomethane Methanethiol Methyl sulfidrate Thiomethyl alcohol Chemical Formula CHjSH (ii) Observable Characteristics — Physical State (as shipped) Liquefied compressed gas Color Colorless Odor Garlic foul strong offensive (Iii) Physical and Chemical Properties — Physical State at 15 C and I atm. Gas Molecular Weight 48.1 Boiling Point at I atm. 43.2, 6.2, 279.4 Freezing Point -189, -123, 150 Critical Temperature 386.2, 196.8, 470.0 Critical Pressure 1,050, 71.4, 7.25 Specific Gravity 0.892 at 6 C (liquid) Vapor (Gas) Specific Gravity 1.66 Ratio of Specific Heats of Vapor (Gas) 1.1988 Latent Heat of Vaporization 220, 122, 5.10 Heat of... 

The cyclization of y -hydroxy ketones is useful for the formation of pyrans,306,403 both directly and via rearrangement, as illustrated in Eq. 231.153 As with their acyclic counterparts, these cyclizations also occur with the silyl ethers of the hydroxy ketones where Et3SiH/BiBr3 is used with the TBS and TES ethers.342,404 A methyl thiomethyl ether is also capable of undergoing the reductive cyclization 405 In like manner, 1,4-diols and e-hydroxy ketones provide oxepanes, with I ds Si H or PhMe2SiH/TMSOTf being especially effective (Eqs. 232 and 233).336,406 The trimethylsilyl ether of the alcohol also provides the oxepane.306... 

Phenylthio)carbene,18 a heteroatom-substituted carbene, reacts similarly with a variety of alkoxides to give a-thiomethyl-substituted alcohols 14 (Scheme 8... 

Reaction of 56 with thiols in dichloromethane gives the analogous alkyl-thiomethyl and cycloalkylthiomethyl derivatives [e.g., treatment with ethanethiol gives A -(2-hydroxyethylthiomethyl)vinblastine (57)] (75). Compound 56 is also a useful intermediate for the preparation of N-1-furanyl derivatives. For example, treatment of 56 with furfuryl alcohol in methylene chloride in the presence of trace acid gives N -[(5-hydroxy-methyOfurfuryl]vinblastine (58). 

In comparison to some of the other activation methods however, the dimethyl sulfoxide-acetic anhydride procedure has certain disadvantages. The method often requires the use of long reaction times (1 24 h), which can result in many side reactions, especially with sensitive substrates. Notable in this respect is that it is not uncommon for this procedure to result in the formation of substantial yields of the thiomethyl ethers obtained from the Pummerer rearrangement product as described above. In fact upon attempted oxidation of cholesterol with this system, the major product obtained was the corresponding (methylthio)methyl ether. Acetates may also be formed if the alcohol is unhindered. For example the sugar derivative (9) reacts under these conditions to form an enol acetate (derived from the requir carbonyl compound) in 40% yield contaminated with 30% of the acetate (10 equation S). ... 

A mechanism suggested for Swern-Moffatt oxidation with TFAA is shown in Scheme 8.6. In the first step, DMSO reacts with TFAA to form cationic reactive species I, which is known to be stable only below —At higher temperatures, rearrangement of I takes place to give species II. The reaction of II with an alcohol IQ upon treatment with a base leads to formation of a major by-product, trifluoroacetic acid (TFA) ester VII. Therefore, the first step should be carried out below —50 °C. In the second step, reactive species I is allowed to react with an alcohol HI at or below —50°C to obtain intermediate IV. IV may also undergo the Pummerer rearrangement to give a methyl thiomethyl (MTM) ether VI upon treatment with a base. In the third step, IV is treated with a base (usually triethylamine) to obtain the desired carbonyl compound V and dimethyl sulfide. 

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