Methoxyacetyl chloride

Electron-rich aromatic substrates can react without a catalyst present. Modern variants of the Blanc reaction use chloromethyl ether" (e.g. (C1CH2)20, ClCH20Me) or methoxyacetyl chloride, since those reagents are more reactive and give higher yields. 

Benzodiazepines react with methoxyketene, generated from methoxyacetyl chloride by the action of triethylamine (see Houben-Weyl, Vol. El 5, p2827fi), to give mixtures of cycloadducts and their acylation products, e.g. formation of 29 and 30.302... 

Isophthaloyl chloride, 2888 f Isopropyl chloroformate, 1560 Methanesullinyl chloride, 0435 Methoxyacetyl chloride, 1165 4-Methoxybenzoyl chloride, 2930 f Methyl chloroformate, 0599 Oleoyl chloride, 3772 Oxalyl dibromide, 0583 Oxalyl dichloride, 0605... 

Methanol, Hydrogen, Raney nickel catalyst, 0484 Methoxyacetyl chloride, 1165 4-Methoxy-3-nitrobenzoyl chloride, 2916 Methyl formate, Methanol, Sodium methoxide, 0834 3-Methyl-2-penten-4-yn-l-ol, 2384 Nitric acid, 4436... 

Chloromethyl methyl ether. A new synthesis1 from methoxyacetic add involves chlorination with thionyl chloride followed by decarbonylation of the methoxyacetyl chloride catalyzed by aluminum chloride ... 

The synthesis of antiviral spiro-(3-lactam 51 begins with the benzylation of isatin 45 to give 1-benzylisatin 46, which affords Schiff s base 47 on reaction with anisidine in ethanol. The Schiff s base 47 on treatment with methoxyacetyl chloride by the chloride-imidate cycloaddition [85] route afforded a mixture of spiro E- and Z-azetidin-2-ones 48 and 49, which were separated by chromatography. The (Z)-N-arylazetidin-2-one 49 was further converted to desired 4-spiro-(3-lactam 51 by treatment with ceric ammonium nitrate and subsequently with tetrabutylammonium bromide in THF in the presence of pulverized KOH (Scheme 13). 

Recently two alternative procedures have been described. In one case14 methoxyacetyl chloride (MeOCH2 COCl) in the presence of anhydrous aluminium chloride is thought to provide the source of the cation (4), which substitutes in the aromatic nucleus to give the benzyl methyl ether (5), which is subsequently converted into the chloromethylated product (6). 

A wide range of substituted aromatic systems have been chloromethylated by this procedure, the only disadvantage being the expense of the methoxyacetyl chloride. 

Isophthaloyl chloride, 2883 f Isopropyl chloroformate, 1555 Methanesulfinyl chloride, 0434 Methoxyacetyl chloride, 1161 4-Methoxybenzoyl chloride, 2925 f Methyl chloroformate, 0732 Oleoyl chloride, 3766 Oxalyl dibromide, 0580 Oxalyl dichloride, 0602... 

Fithium tetrahydroaluminate, Fluoroamides, 0075 Lithium tetrahydroaluminate, Water, 0075 Lithium, 1,2-Diaminoethane, Tetralin, 4675 Magnesium, Barium carbonate, Water, 4685 Maleic anhydride, Bases, or Cations, 1400 Mercaptoacetonitrile, 0763 t Methanol, Hydrogen, Raney nickel catalyst, 0482 4-Methoxy-3-nitrobenzoyl chloride, 2911 Methoxyacetyl chloride, 1161 t Methyl formate, Methanol, Sodium methoxide, 0830 3-Methyl-2-penten-4-yn-l-ol, 2378 Nitric acid, 4430... 

To the mixture of 41.0 g (lS,2S)-2-[2- [3-(lH-benzimidazol-2-yl)propyl]methylmethylamino ethyl]-6-fluoro-l-isopropyl-l,2,3,4-tetrahydronaphthalen-2-ol, 240 mL water, and 240 mL toluene were added 22.4 g potassium hydroxide, and the mixture heated to 45-50°C for one hour. The resulting two-phase mixture was separated. To the organic phase was added 39.4 g (4.0 eq.) potassium carbonate sesquihydrate then a solution of 21.0 g (17.7 mL, 3.25 eq.) methoxyacetyl chloride in 33 mL toluene was added over two hours at 25-30°C, and the resulting mixture stirred for an additional 30 min. Water, 200 mL, was added to quench the reaction. The organic phase, containing mibefradil as the free base was added an ethanol. 

The product from Step 1 (8.0 mmol) was added to 75 ml CH2CI2 containing NEt3 (9.0 mmol) and thereafter methoxyacetyl chloride (10.0 mmol) dissolved in 20 ml CH2CI2 added. The reaction was stirred 30 minutes and was then poured into 75 ml 5% aqueous... 

This stable alkoxycarbenium salt can be prepared in about 90 % yield by the reaction of either methoxyacetyl chloride or chloromethyl methyl ether with anhydrous hexa-fluoroantimonic acid in sulfur dioxide or dichloromethane ... 

The reaction between methoxyacetyl chloride and (4/ )-155 or (4/ )-157 gave the corresponding bicyclic product in a moderate yield [58% in (4/ )-155] or in a very poor yield [5% in (4/ )-157] (compared to the 81% yield of 153a). Thus, a methylseleno substituent on the imine moiety promoted this ketene-imine cycloaddition reaction. 

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