Chlorocarbonylation

Chlorocarbonyl, see Chlo-roformyl Chloroformyl Chlorosyl Chloro thio Chloryl... 

Table 34. Properties of Trimellitic Acid Esters and the Chlorocarbonyl Anhydride...

AminothiaZoles. In contrast to the pyrazolones, pyridones, and indoles just described, aminotliiazoles are used as diazo components. As such they provide dyes that ate more bathochromic than their benzene analogues. Thus aminothiazoles are used chiefly to provide dyes in the red-blue shade areas. The most convenient synthesis of 2-aminothiazoles is by the condensation of thiourea with an a-chlorocarbonyl compound for example, 2-aminothiazole [96-50A-] (94) is prepared by condensing thiourea [62-56-6J with a-chloroacetaldehyde [107-20-0J both readily available intermediates. 

Bielectrophiles have found appreciable applications in the synthesis of ring-fused systems, especially those involving [5,6] fused systems. The following serve to illustrate these applications. Reaction of pyrazole with (chlorocarbonyl)phenyl ketene (214) (Type 1, Scheme 6) readily formed the zwitterionic pyrazolo[l,2-a]pyrazole derivative (215) (80JA3971). With l-methylimidazole-2-thione (216), anhydro-2-hydroxy-8-methyl-4-oxo-3-phenyl-4//-imidazo[2,l-6][l,3]thiazinium hydroxide (217) was obtained (80JOC2474). 

Dipoles can also be built into heterocyclic systems, and though of limited use, they may also be utilized for the synthesis of [5,6] ring-fused systems. Reaction of 2 3H)-benzothiazolethione with (chlorocarbonyl)phenylketene in warm anhydrous benzene gave the heteroaromatic betaine (416). On heating with DMAD in boiling toluene the tricyclic pyridinone (418) was obtained, presumably by elimination of COS from the intermediate cycloadduct (417) (80JOC2474). 

Aziridine, cis-7V-t-butyl-3-ethynyl-2-vinyl-rearrangement, 7, 540 Aziridine, 2-chlorocarbonyl-ring expansion, 7, 42 Aziridine, 2-chloromethyl-synthesis, 7, 42 Aziridine, Mcyanodiphenyl-irradiation, 7, 61 Aziridine, dihalo-reduction, 7, 74 thermolysis, 7, 73... 

Recently a-chloro-)3-chlorocarbonyl enamines have been obtained from ynamines and phosgene (121a). 

Chlorkohlen-oxyd, n. carbonyl chloride, -oxyd-ather, m. ethyl chloroformate. -saure, /. chlorocarbonic acid (chloroformic acid, CICOOH). -sMureamtd, n. chlorocarbonyl amide (carbamyl chloride, H2NCOCI). -stoff, m. carbon chloride, carbon tetrachloride (sometimes with the adj. vierfach). 

A novel application of a phenyl aryldiazosulfone was found by Kessler et al. (1990). l-[4-(7V-Chlorocarbonyl-7V-methylamino)phenyl]-2-(phenylsulfonyl)diazene (6.18) is an acid chloride with a potential diazonio group. The above authors showed that in organic solvents (THF, etc.) this compound reacts easily, as expected, with nucleophiles (HNu), e.g., with aliphatic, aromatic, or heterocyclic amines, with cystine dimethyl ester, or with 4-methoxyphenol at the carbonyl function, yielding... 

C4H7CI2NO2 53726-30-0) see Sulfaperin, a-(chlorocarbonyl)-3-thiopheneacetic acid (C,H5C103S 60822-08-4) see Ticarcillin... 

C14H20CINO2) see Bietamiverine phenyl(chlorocarbonyl)ketene (QHjCIOj 17118-70-6) see Carindacillin phenyl chloroformate... 

Reaction of equimolar amounts of the thiocarbamate (91) with (chlorocarbonyl)sulphenyl chloride gave l,2,4-dithiazoline-5-one (92) and the 1,2,4-thiadiazole (93) the relative amounts of (92) and (93) being very dependent on the solvent used in the reaction. The mechanism of formation of both (92) and (93) was discussed <96JOC6639>. 

Chlorocarbonyl)nethoxy] 4-nethylcounarin CMMC Primary and secondary alcohols 592... 

Based on the well-known reaction of phenoxazine with phosgene,15 leuco Basic Blue 3 was treated with phosgene to form the stable 10-chlorocarbonyl-3,7-diethylaminophenoxazine (39) which can be isolated and further reacted with alcohol or amine.16... 

Leuco Methylene Blue, Basic Blue 3, or phenazine dyes are capped with a dye bearing acid chloride or chlorocarbonyl functionality. Normal procedures employed for the synthesis of benzoyl leuco Methylene Blue can be utilized except that a dye chloroformate (69) replaces the benzoyl chloride. 

C-branched sugars or C-oligosaccharides are obtainable through indium-promoted Barbier-type allylations in aqueous media.151 Indium-mediated allylation of a-chlorocarbonyl compounds with various allyl bromides in aqueous media gave the corresponding homoallylic chlorohydrins, which could be transformed into the corresponding epoxides in the presence of a base (Eq. 8.62).152... 

These results were explained by the discovery that the chloro-ruthenium complexes are not the primary photoproducts under CO in 1.0 M CCl /octane solution. Instead Ru(CO>5 proved to be the initial product even after nearly complete photofragmentation of the starting material, and the chlorocarbonyl ruthenium products to be the result of a secondary, dark reaction between the Ru(C0)5 and CCI4 (3) ... 

A one-pot synthesis of pyrano[3,2-c]quinolin-2,5(<5/7)-dione 107 was reported through the condensation reaction of chlorocarbonyl ketenes 108 with 4-hydroxyquinolin-2(l//)-ones 109. This simple procedure was shown to be a convenient synthesis of pharmacologically active compounds in high yields <06S435>. 

Photoresponsive systems incorporating an azobenzene moiety. The capped crown ether (196), shown as the (E) isomer, was synthesized initially by a high-dilution condensation between diaza-18-crown-6 and 3,3 -bis(chlorocarbonyl)azobenzene (Shinkai et al., 1980). Extraction patterns for the alkali metals differed between the (E) and (Z) isomers giving a clear example of photochemical control of the complexation behaviour. Subsequently, the analogue (197) was synthesized in which 2,2 -azopyridine was used for the cap (Shinkai Manabe, 1984). Photo-... 

I.3.4.2.4. Heterocumulenes The 1,3-dipolar cycloaddition of substituted ben-zonitrile oxides to the C=N group of chlorocarbonyl isocyanate C1C(0)N=C=0 gives 3-aryl-4-chlorocarbonyl-5-oxo-4,5-dihydro-l,2,4-oxadiazoles 172 in 75%-80% yield (340). A similar reaction with chlorosulfonyl isocyanate, C1S02N=C=0, affords 4-unsubstituted oxadiazolinones 173 (341). 

The reaction of dimethyl amino(butylamino)methylenemalonate (1364) and Af-(chlorocarbonyl)isocyanate in benzene afforded (l,3,5-triazin-2-ylidene)malonate (1365) in 52% yield and the hydrochloride salt of the starting material (1364 x HC1) (76ZOR2253). 

A wide range of organic substrates can undergo an oxidative carbonylation reaction. Depending on reaction conditions, alkenes have been converted into -chloroalkanoyl chlorides (oxidative chloro-chlorocarbonylation) [1,2], succinic diesters (oxidative dialkoxycarbonylation) [3-20], a,/J-unsaturated esters [21,22] (oxidative monoalkoxycarbonylation), or /J-alkoxyalkanoic esters [11] (oxidative alkoxy-alkoxycarbonylation), according to Eqs. 10-13. 

The compounds [9] and [10] were synthesized in an effort to increase the through-space interaction between the ferrocene moiety and the bound cation (Scheme 3). These ligands were prepared by reaction of two equivalents of the corresponding mono-azacrown ether with bis(chlorocarbonyl)ferrocene. 

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