3-Butenamides

Palladium complexes effectively catalyze the three-component coupling reactions of CC>2461 or isocyanates,462 462 allyltributyltin, and allyl chloride to afford allyl 3-butenoate or iV-tosyl-iV-allyl-3-butenamides, respectively (Equations (104) and (105)). 

The reaction of diethylamine or alcohol with 2,3-allenamide 551 affords /3-diethyl-amino-a,/3-unsaturated enamide 555, indicating the migration of the C=C bond under basic conditions. The corresponding reaction of 551 with benzyl thiol proceeded to afford /j-thiobenzy 1-/1,y-unsatu rated enamide 556 the /i,y-C=C bond can migrate to the a,/3-position on the treatment with DBU in THF to afford 557 [257]. In reactions of 4,4-dichloro-2,3-butenamide 558 with amines, thiolates and alcohols, ce,/j-unsaturated enamides 560-564 are always formed on treatment with a base [258, 259]. 

The reaction of HC1 with 2,3-butadienamide afforded 3-chloro-3-butenamide [261]. 

Caution. Allylcyanide (3-butenenitrile) is toxic. The procedure for preparing 3-butenamide below should be carried out in a well-ventilated hood. 

Butenamide is prepared according to the literature.6 A mixture of 3-butenenitrile (10mL), H20 (2.2 mL), and cone H2S04 (6.9 mL) is prepared at... 

C4H602, 2-Propenoic acid, methyl ester platinum complex, 26 138 C4H7NO, 3-Butenamide nickel complex, 26 206 C4HsO, Furan, tetrahydro-iron complex, 26 232 magnesium complex, 26 147 neodymium and samarium complexes, 26 20... 

NO, Nitrosyls, molybdenum and tungsten, 26 132, 133 NOC, Cyanate tungsten complex, 26 42 NOC4H7, 3-Butenamide nickel complex, 26 206 NOC4H , 2-Propenamide, 2-methyl-nickel complex, 26 205 NOC H, Benzoyl isocyanide chromium complex, 26 32, 34, 35 N04ReC16H, Perrhenate, tetrabutylam-monium, 26 391... 

The cycloaddition reaction is accompanied by another reaction giving about 30% of 3-methyl-3-butenamide-N-sulfonyl chloride which is readily hydrolyzed during the aqueous work-up. The /3-lactam-N-sulfonyl chloride which is the major product of the reaction is relatively stable to hydrolysis under the conditions of its isolation. 

Plants. The primary metabolites are (1-carboxy-l-methyl) allyl 3,5-dichlorophenylcarbamate and Af-(3,5-dichlorophenyl)-2-hydroxy-2-methyl-3-butenamide. Alkaline hydrolysis leads to loss of 3,5-dichloroaniline from vinclozolin and its metabolites. 

Himbert reported that ynamine 95 reacts with aiylsulfonylazides 96 to give 2-oxo-3-siloxy N-sulfinyl-3-butenamides 98 in fair to good yields.65,66 The reaction was thought to involve initial formation of diazo compound 97 which gives on elimination of N2 and migration of one of the sulfonyl oxygens, the sulfinimine. 

C11H11N02 1 -benzyl-2,5-pyrrolidinedione 2142-06-5 25.00 1.1619 2 21959 C11H13NO 3-methyl-4-phenyi-3-butenamide 7236-47-7 25.00 1.0340 2... 

C11H12N20 2,2-dimethyl-4-phenyl-2H-imidazole-1-oxide 23557-86- 592.15 52.805 2 21959 C11H13NO 3-methyl-4-phenyl-3-butenamide 7236-47-7 521.82 45.984 2... 

NOC. Cyanate, tungsten complex, 26 42 NOC4H7, 3-Butenamide, nickel complex, 26 206... 

In the cobalt-catalyzed photochemical carbonylation of olefins, hydroformyla-tion can be performed easily at ambient temperature (and high pressure) with high primary aldehyde selectivities (cf. Section 2.1.1) [59]. Under comparable conditions allylic amines are carbonylated to 2-pyrrolidinone, Al,/V -diallylurea, and A -allyl-3-butenamide [60]. Photochemical methoxycarbonylation of olefins is possible at ambient conditions, i.e., at room temperature and atmospheric pressure [61]. 

The reaction also works with cyclic amides to afford bicyclic heterocycles [84]. The 3-butenamide 135 (n=l, R=H) also undergoes a consecutive process which affords compounds 136 or the dimer 138 depending on the ligand used (Table 6) [84, 85], Large excess ofPPhs affords almost exclusively the linear aldehyde and further to the pyrrolidone 136 by cyclization, water elimination to give 140, and double bond isomerization. 

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