Carbonyl chloride reactions

Chromone-2-carbaldehyde, 3-methyl-synthesis, 3, 709 Chromonecarbaldehydes Knoevenagel condensation, 3, 711 Chromone-3-carbaldehydes mass spectra, 3, 615 oxidation, 3, 709 reactions, 3, 712 Schiff bases, 3, 712 synthesis, 3, 821 Chromone-2-carbonyl chloride Grignard reaction, 3, 711 Chromonecarboxamide, N-tetrazolyl-antiallergic activity, 3, 707 Chromone-2-carboxylic acid, 3-chloro-ethyl ester... 

Furan-2-carbonyl chloride, 5-alkyl-3,4-dichloro-synthesis, 4, 690 Furancarboxamides rotational isomerism, 4, 543 Furan-2-carboxylic acid, 5-acetylamino-ethyl ester reactions, 4, 647 Furan-2-carboxylic acid, amino-properties, 4, 708 Furan-2-carboxylic acid, 5-bromo-nitration, 4, 603, 711 Furan-2-carboxylic acid, 3-methyl-methyl ester bromination, 4, 604 Furan-2-carboxylic acid, 5-methyl-nitration, 4, 602... 

The early literature on the reactions of the indole Grignard reagents with the simple diacid chlorides, in particular with carbonyl chloride and oxalyl chloride (see Section III,C,4,b), is both conflicting and confusing and much of the work reported warrants repetition since the evidence presented in support of many of the structural assignments made is not entirel3 convincing. 

Related reactions are those of sodium azide with carbon disulflde to give 5-mercapto-l,2,3,4-thiatriazole (see 8ection IV) and with thio-carbonyl chloride to give 5-chloro-l,2,3,4-thiatriazole. ... 

The reaction between 6-aminopenicillanic acid (6.5 g) and 3-o-chlorophenyl-5-methyllsoxa2ole-4-carbonyl chloride (7.66 g) gave the sodium salt of 3-o-chlorophenyl-5-methyl4-isoxa2olyl-penicillin (9.9Bg) asa pale yellow solid. Colorimetric assay with hydroxy lamina against a ben2-ylpenicillin standard indicated a purity of 6B%. 

Ketone 13 possesses the requisite structural features for an a-chelation-controlled carbonyl addition reaction.9-11 Treatment of 13 with 3-methyl-3-butenylmagnesium bromide leads, through the intermediacy of a five-membered chelate, to the formation of intermediate 12 together with a small amount of the C-12 epimer. The degree of stereoselectivity (ca. 50 1 in favor of the desired compound 12) exhibited in this substrate-stereocontrolled addition reaction is exceptional. It is instructive to note that sequential treatment of lactone 14 with 3-methyl-3-butenylmagnesium bromide and tert-butyldimethylsilyl chloride, followed by exposure of the resultant ketone to methylmagnesium bromide, produces the C-12 epimer of intermediate 12 with the same 50 1 stereoselectivity. 

A similar reaction of 5-oxo-4-phenyl-4,5-dihydro-l//-l,2.4-bcnzotriazepine-3-carbonyl chloride with 2-(dimethylamino)ethanol gave 2-(dimcthylamino)elhyl 5-oxo-4-phenyl-4,5-dihydro-l U-, 2,4-benzotri-azcpine-3-carboxylate (11c) yield 54% mp 130-132 C. 

Self-Test 13.4B The highly toxic gas carbonyl chloride, COCl2 (phosgene), is used to synthesize many organic compounds. Use the following data to write the rate law and determine the value of k for the reaction used to produce carbonyl chloride ... 

Other examples are given by the reaction of rra j-10-bromo-10,ll-dihydro-ll-hydroxy-5H-dibenz[b,f]azepine-5-carbonyl chloride with gaseous HBr in CCI4 to give the expected trans dibromide and the corresponding olefin in an about 3 7 ratio (Table 6) (ref. 20). The same reaction of 10-bromo-10,11-dihydro-11-... 

Most carbonyl-ene reactions used in synthesis are intramolecular and can be carried out under either thermal or catalyzed conditions,43 but generally Lewis acids are used. Stannic chloride catalyzes cyclization of the unsaturated aldehyde 5. 

With the free amine 36 and carbonyl chloride 2 in hand, the coupling of these two fragments was achieved in the presence of 4-methylmorpholine (NMM) to afford the desired free phenol 1 and the ester 43 in about 10 1 ratio. The reaction mixture was directly treated with aqueous MeNH2 to cleave the ester of 43. Acidification with HC1 provided free phenol 1 in 88% isolated yield after crystallization and filtration. Raltegravir (1) was isolated as a crystalline potassium salt (1 1 molar ratio) by addition of KOEt to a solution of the free phenol 1 in a 93% yield, and 99.5% purity (Scheme 6.12). 

The preparation of 3-vinylpyrroles was investigated utilizing the Horner-Wads worth-Emmons reaction with 3-formyl-lV-tosylpyrrole <06S1494>. The intramolecular acylation of pyrrole-2-Weinreb amides provided access to novel indolizinone derivatives <06T6182>. The amidation of pyrrole-2-carbonyl chloride was utilized as a key step in the preparation of pyrrole-oxazole analogue 90 of the insecticide Pirate <06S1975>. 

For reaction of benzoyl chlorides in water, reactivity follows the electronreleasing ability of p-substituents, and there are striking differences in the micellar effects (Table 7). With electron-withdrawing substituents k+/k > 1, but its value progressively decreases with increasing electron release from a p-substituent. Thus an increase in electron release changes k+/k from values characteristic of a carbonyl addition reaction to values characteristic of SN reactions at saturated carbon. This classification also... 

The syntheses of these three compounds share a common route as described by Brickner et al. [53] and Barbachyn et al. [54]. Namely, the coupling reaction of 3,4-difluoronitrobenzene (82) with piperazine, morpholine, or thiomorpholine to yield the corresponding 4-substituted 3-fluoro-nitrobenzene (83), which upon reduction gives rise to the aniline derivative (84). Carbobenzoxy protection of the active nitrogen of 84 using benzyloxy-carbonyl chloride (CbzCl) results in the formation of carbamates 85a and 85b. Treatment of 85a,b with n-BuLi and (i -glycidyl butyrate yields a 5-(R)-... 

Weinreb et al86 have also studied the participation of allenes in imino-ene and carbonyl-ene reactions. Gycloisomerization of imine 133 in the presence of stannic chloride gave exclusively the m-substituted cyclopentyl isomer 135 (Scheme 27). The thermal imino-ene reaction of 136 was equally effective. More highly substituted... 

A similar reaction of dibenzothiophene with 1,8-naphthoylenebenzimi-dazole-4-carbonyl chloride has also been described. ... 

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