Acetyl chloride methylal reaction

Isotope labeling by derivative formation with deuterated reagents is useful for the preparation of analogs such as dg-acetonides, da-acetates, da-methyl ethers, dg-methyl esters, etc. The required reagents are either commercially available or can be easily prepared. (The preparation of da-methyl iodide is described in section IX-F. Various procedures are reported in the literature for the preparation of dg-acetone, da-diazometh-ane57.i63.i73 and da-acetyl chloride. ) These reactions can be carried out under the usual conditions and they need no further discussion. A convenient procedure has been reported for the da-methylation of sterically hindered or hydrogen bonded phenolic hydroxyl functions by using da-methyl iodide and sodium hydroxide in dimethyl sulfoxide solution. This procedure should be equally applicable to the preparation of estradiol da-methyl ether derivatives. 

The reactions of [PtMe2(/MCJo-dias)] (dias = PhMeAsCHjCHjAsMePh) with acetyl chloride, methyl iodide or allyl halides gives one isomer (Cheney and Shaw, 1971b). For acetyl chloride and methyl iodide the addition is trans, but it is impossible to distinguish between the isomers [8] and [9] on the basis of ir and nmr spectroscopy. With allyl halides the addition is cis, but again it is not possible to distinguish between the two isomers. 

TTie true ketones, in which the >CO group is in the side chain, the most common examples being acetophenone or methyl phenyl ketone, C HjCOCH, and benzophenone or diphenyl ketone, C HjCOC(Hj. These ketones are usually prepared by a modification of the Friedel-Crafts reaction, an aromatic hydrocarbon being treated with an acyl chloride (either aliphatic or aromatic) in the presence of aluminium chloride. Thus benzene reacts with acetyl chloride... 

Acetophenone. Acetophenone [98-86-2] (methyl phenyl ketone) is a colorless Hquid that forms laminar crystals at low temperature (mp 20°C). It has a characteristic sweet orange blossom odor, and is soluble in alcohols and ethers. It is found in nature in oil of casatoreum, obtained from beavers oil of labdanum, recovered from plants and in buds of balsam poplar. It can be prepared by the Friedel-Crafts reaction (qv) of acetyl chloride with benzene in the presence of aluminum chloride however, this route is of Htde commercial significance. 

Aminosodium salt and acylated with 1 H-tetrazole-1 -acetyl chloride. The acetoxy group is then displaced by reaction with 5-methyl-1,3-4-thi-adiazole-2-thiol in buffer solution. The product acid is converted to the sodium salt by NaHCOa. 

The chiral acetate reagent is readily prepared from methyl mandelate [methyl (A)-hydroxy-phenyl acetate] which is first converted by treatment with phcnylmagnesium bromide into the triphenylglycol783, c (see Section 1.3.4.2.2.2.) and subsequently transformed into the acetate by reaction with acetyl chloride in the presence of pyridine. Thereby, the secondary hydroxyl group of the glycol is esterified exclusively. Both enantiomers of the reagent are readily accessible since both (R)- and (5)-hydroxyphenylacelic acid (mandelic acids) arc industrial products. 

N-Methyl-N-f2-Nitroxy propyl) Nitramine. (Me2NENA N-(2-NitroxypropyI) methyl nitramine. (02N)N(CH3).(CH2CH(0N02).CH3, mw 179.16, N 23.46%, OB to C02 -66.80%, pale yellow oil, mp 22—23°, d 1.320g/cc at 25/4°, RI 1.478 at 25°. Prepn from 2-hydroxy-propylamine after nitration with 98% nitric acid at 10° by reaction of the amine-nitric acid mixt with acetic anhydride acetyl chloride at 35°. Reaction mixt poured on ice. Yield is 74%. No expl properties listed Reft 1) Beil - not found 2) Blomquist, OSRD 4134, 45 119 (1944)... 

A solution of 2-methyl-l-(trimethylsilyloxy)cyclohex-l-ene (10 mmol) in dichloromethane (8 ml) was added dropwise over 15 min with stirring to acetyl chloride (10 mmol) and TiCl4 (10 mmol) in dichloromethane (15 ml) at -78 °C. After 1 h at -78 °C, the reaction mixture was allowed to warm to ambient temperature over 2h. It was then diluted with ether (20ml), and poured into saturated sodium hydrogen carbonate solution (50 ml). Normal work-up, followed by chromatography on silica gel, gave the /1-diketone (9.1 mmol, 91%). 

The following reaction sequence was used to obtain methyl hydroxymethanediphosphonic acid. This compound is widely used as a water hardness sequestering agent and detergent builder. Triethyl chloride was reacted with acetyl chloride to give diethylacetylphosphonate, followed by a conversion with diethyl phosphite and sodium. After completion of this reaction the substance was hydrolyzed with HC1 to yield hydroxymethanediphosphonic acid, [93,94], as shown in Eqs. (49)-(51) ... 

Ab initio molecular orbital calculations are being used to study the reactions of anionic nucleophiles with carbonyl compounds in the gas phase. A rich variety of energy surfaces is found as shown here for reactions of hydroxide ion with methyl formate and formaldehyde, chloride ion with formyl and acetyl chloride, and fluoride ion with formyl fluoride. Extension of these investigations to determine the influence of solvation on the energy profiles is also underway the statistical mechanics approach is outlined and illustrated by results from Monte Carlo simulations for the addition of hydroxide ion to formaldehyde in water. 

Phenyl-l,2,3,6-tetrahydropyrido[2,l- ][l,3]thiazino[3,2- ]quinolin-6-ones were prepared by the reaction of 2-mercapto-5-phenyl-l,4-dihydroquinolin-4-ones with 1,3-dihalopropane <1997JAK97/278780>. 7-Acetyl-2-aryl-9-cyano-6-methyl-8-phenyl-3,4-dihydro-277,877-pyrido[2,l- ][l,3]thiazin-4-ones were obtained from 5-acetyl-3-cyano-6-methyl-4-phenyl-l,2,3,4-tetrahydropyridine-2-thione with 3-aryl-2-propenoyl chloride <2002CHE761>. Reaction... 

Apart from the reaction of cyclohexanecarboxylic acid with methyllithium, cyclohexyl methyl ketone has been prepared by the reaction of cyclohexylmagnesium halides with acetyl chloride or acetic anhydride and by the reaction of methylmagnesium iodide with cyclohexanecarboxylic acid chloride. Other preparative methods include the aluminum chloride-catalyzed acetylation of cyclohexene in the presence of cyclohexane, the oxidation of cyclohexylmethylcarbinol, " the decarboxylation and rearrangement of the glycidic ester derived from cyclohexanone and M)utyl a-chloroj)ropionate, and the catalytic hydrogenation of 1-acetylcycIohexene. "... 

The reaction with acetyl chloride affords the diagonal methyl derivative after CO deinsertion, as in the case of Mel (Scheme 17) ... 

For the synthesis of the natural blue pigment trichotomine dimethyl ester, L-Trp-OMe was used as a starting material. The first step of this synthesis was conversion into methyl l-methyl-3,4-dihydro-/8-carboline-3-carboxylate with acetyl chloride in TFA (85JOC3322). An improved method starts from the corresponding thioamides via thioiminium salts which cyclize spontaneously in refluxing solvent (82CPB4226). A-Formyl-tryptophan also cyclized readily with no side reactions (68CJC3404). 

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