Ketenes trimerization reactions

The cycloaddition reactions are subdivided into di-, tri- and oligomerization reactions, [2-1-1]-, [2-1-2]-, [3-1-2]- and [4- -2] cycloaddition reactions and other cycloaddition reactions. The insertion reactions into single bonds are also discussed. The cyclodimerization or cyclotrimerization reactions are special examples of the [2-1-2] and the [2-I-2-I-2] cycloaddition reactions, respectively. The cumulenes vary in their tendency to undergo these reactions. The highly reactive species, such as sulfines, sulfenes, thioketenes, carbon suboxide and some ketenes, are not stable in their monomeric form. Other cumulenes have an intermediate reactivity, i.e. they can be obtained in the monomeric state at room temperature and only heat or added catalysts cause di- or trimerization reactions. In this group, with decreasing order of reactivity, are allenes, phosphorus cumulenes, isocyanates, carbodiimides and isothiocyanates. 

Many examples of the usual route to /S-lactams via imines and acid chlorides, ketens, or keten equivalents have appeared.These include syntheses of 3-[bis(alkylthio)methylenamino]-2-azetidinones, ° of spiro-azetidinones and bis-azetidinones, and the use of l-methyl-2-halogenopyridinium salts to activate carboxylic acids towards coupling with imines. A non-hazardous alternative route to 3-amido-2-azetidinones, avoiding the use of azidoacetyl chloride, involves the reaction of Schiff bases with salts of [(a-methyl-/3-methoxycar-bonyl)vinylamino]acetic acid, e.g. (20), in the presence of ethyl chloroformate, as shown in Scheme 5. Formaldimines can be generated from their trimers by treatment with Lewis acids immediately prior to reaction with acid chlorides, so allowing the formation of the nocardicin nucleus which is unsubstituted at C-4. ... 

The synthesis of monocyclic 3-amino-P-lactams by the photolytic reaction of imines with pentacarbonyl[(dibenzylamino)carbene]chromium(0) was developed by Hegedus and co-workers [74]. These reactions are closely related to the previously described [2 -h 2]-cycloaddition reactions in that they are thought to involve attack of the imine nitrogen on a photogenerated, metal-bound ketene, followed by ring closure (Scheme 15). In a synthesis of a nocardicin precursor, optically active imine trimer 122 was photolyzed with carbene complex 123 providing a 46% yield of a 1 1 diastereomeric mixture of lactams... 

Formaldehyde is a strong electrophile, allowing acetal to polymerize by nucleophilic, anionic, or cationic addition of an alcohol to ketene carbonyl groups. Relatively weak bases such as pyridine initiate anionic addition polymerization cationic addition polymerization is catalyzed by strong acids. When the cyclic trimer trioxane is used as a copolymer to polymerize acetal copolymers, Lewis acids such as boron tiifluoride promote copolymerization. A more fundamental description is polymerization of an aldehyde or ketone -l- alcohol -i- an acid or base catalyst to form hemiac-etal, which further converts to acetal. The hemiacetal reaction is reversible to aldehyde and alcohol. 

The cyclotrimerization of carbon cumulenes is usually initiated by heat or catalysis. Especially, the use of a catalyst assures that trimerization can be accomplished in quantitative yields. The base catalyzed cyclotrimerization reaction seems to be limited to ketenes, isocyanates, isothiocyanates and carbodiimides. In the trialkylphosphine catalyzed trimerization of methyl isocyanate an asymmetric trimer is obtained. 

At 26.7 mbar pressure 40% weight toss main product is 2,4-diphenyl thiophene at least 11 unidentified minor products CO2, H2O, butene, isobutene, dimethyl ketene, styrene, methacrylic acid, succinic-type 5-membered cyclic anhydrides Chlorotrifluoroethylene, styrene, HQ, chloropentafluoropropene, ethene, chloroethene, totuene, a-melhylstyiene, dimer and trimer structures with some unsaturation S1F4 (fiom reaction of HF with glass). Distribution of products varies with polymer composition CO, CO2, propene, isobutene, dimethyl ketene, acrolein, allyl alcohol, toluene, styrene, cl-methylstyrene, ethylbenzene, glycidol, glycidylmethacrylate product distribution depends on copolymer composition... 

C, respectively, to (lS)-7,7-dimethyl-l-vinyl-2-norbamanone (112). The reaction of anhydride (113) with bis(trifluoromethyl)keten gave a trimer and a 15% yield of thiiran 1,1-dioxide (114). ... 

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