Isocyanato chloride

B. Polymeric Urea [Benzene, diethenyl-, polymer with ethenylbenzene, [[[[(1 methylethyl)amino]carbonyt]amino]methyl] deriv.] A 10.0-g. portion of benzylamine polymer beads prepared as in Part A and 125 ml. of tetrahydrofuran (Note 6) are combined in a 300-ml., three-necked, round-bottomed flask equipped with a magnetic stirrer, a dropping funnel, and a condenser fitted with a gas-inlet tube A nitrogen atmosphere is established in the system, and the slurry is stirred while 1.35 g. (0.0159 mole) of isopropyl isocyanate [Propane, 2-isocyanato-] is added. This causes an exothermic reaction, which subsides after about 20 minutes. The mixture is then stirred at room temperature for 22 hours and at reflux for an additional 4 hours. The beads are collected by filtration, washed with 150-ml. portions of tetrahydrofuran (Note 6) and methanol, and dried under reduced pressure over calcium chloride to yield 9.09 g, of the isopropyl urea polymer. 

Isocyanic acid, 2-(chIoroformyl)ethyl ester (8) Propanoyl chloride, 3-isocyanato- (9) (3729-19-9)... 

Iron tricarbonyl dieme complex, 57, 16 Isobutyl chloroform.ate, 59, 165 Isobutylene, 59, 164 Isobutyl fluoride, 5, 73 Isobutyryl chloride, 59, 29 Isocyanato acid chlotrides, from amino acids, 59, 200... 

Trichloromethyl chloroformate has proven effective in the preparation of N-carboxy-a-amino acid anhydrides from amino acids, and various compounds having isocyanate, acid chloride, and chloroformate groups.For example, trichloromethyl chloroformate may be used instead of phosgene in the preparation of 2-tert-butoxycarbonyloxyimino-2-phenylacetonitrile. The use of this reagent is illustrated here by the synthesis of 3-isocyanato-propanoyl chloride from 3-aminopropanoic acid hydrochloride. 

The isocyanato acid chloride 291 (X = CH2CH2, CH = CH), prepared through trimethylsilyl esters (Section II,A,4), reacts with aniline to give the isocyanato carboxamide 292, which readily yields the quinazolinedione 293 (73AG86 75LA1387). Armarego has prepared the quinazolindiones... 

Isoeyanato moaes. The first known member of this class, 2,5-dichloro-3,6-di-isocyanato-l,4-benzoquinone (2), was prepared by treating 2,S-diamino-3,6-dichloro-1,4-benzoquinone (I) with oxalyl chloride in butyl acetate and chlorobenzene. ... 

Isocyanato- and 2-isothiocyanatobenzonitriles 1 react with hydrogen halides in dibutyl ether to give 4-haloquinazolin-2(li/)-ones and -quinazoline-2(l//)-thiones 2, respectively. The ring closure is based on a nucleophilic attack of the intermediary nitrile-halide adducts at the carbamic or thiocarbamic acid chloride function. 

Carboxy includes carboxy (carboxylic acids), alkoxycarbonyl (esters), carbamoyl (amides), thiocarbamoyl, hydrazinocarbamoyl (hydrazides), guanidinocarbonyl, azidocarbonyl (azides), chlorocarbonyl (acid chlorides), amidino, C-hydrazino-C-iminomethyl, C-alkoxy-C-iminomethyl (imino ethers), C-alkylthio-C-iminomethyl (iminothioethers), cyano (nitriles), C-formyl(aldehydes), dialkoxymethyl (acetals of aldehydes), C-acyl (ketones), isocyanato, and thiocyanato groups. 

Attack on Unsaturated Carbon. Numerous reports of addition of tertiary phosphites, secondary phosphites, and silyl phosphites to activated olefins have appeared. The addition of secondary phosphites to acryloyl chloride in the presence of trimethylsilyl azide provides a route to 2-isocyanato-ethylphosphonates (13). ... 

Another interesting application of iminium chlorides in organic synthesis involves their use as catalysts in the conversion of carboxylic acids to carboxylic acid chlorides ( ), carbamates to isocyanates ( ), amino-acids to isocyanato acid chlorides and arylamine hydrochlorides to isocyanates In these reactions chlorodimethylformiminium chloride is being used, because it is readily available. However, other imidoyl halides could react in a like manner. 

In contrast, phosphoryl isocyanates are attacked by phosphorus pentachloride on the isocyanato group, with concomitant cleavage of the alkoxy groups by the generated hydrogen chloride. Thus, dichlorophos-phorylcarbonimidoyl dichloride (XXVIII) is obtained in the reaction of the phosphoryl isocyanate and phosphorus pentachloride ( " ). 

The phosgenation of isatoic anhydride and aminocarboxylic and amino-sulfonic acids, to afford isocyanatoarylcarbonyl chlorides and isocyanato-arlsylfonyl chlorides, is also catalyzed by iminium chlorides. 

Benzene carboxaldehyde. See Benzaldehyde Benzenecarboximidamide, 4,4 -[1,6-hexanediylbis (oxy) bis-. See Hexamidine Benzenecarboxylic acid. See Benzoic acid Benzene chloramine. See Chloramine-B Benzene chloride. See Chlorobenzene Benzene, 1-chloro-2-isocyanato-. See2-Chlorophenyl isocyanate Benzene, 1-chloro-3-isocyanato-. See3-Chlorophenyl isocyanate Benzene, 1-chloro-4-isocyanato-. See4-Chlorophenyl isocyanate Benzene, 2-chloro-4-isocyanato-1-methyl-. See 3-Chloro-4-methylphenyl isocyanate Benzene, (chloromercuho)-. See Phenylmercuric chloride Benzene, chloromethyl-. See Monochlorotoluene... 

Fiirstner reported that a low-valent iron(-II) complex catalyzed the crosscouplings of primary and secondary alkyl halides with various aryl Grignard reagents under such mild reaction conditions that chemoselective arylations would be feasible in the presence of potentially reactive functional groups, such as carbonyl, cyano and isocyanato groups. While aUcyl bromides and iodides showed excellent reactivities with this iron catalyst system, aUcyl chlorides were found to be inert under the reported reaction conditions (Equation 5.27) [35]. 

COOH Dioxane, PCls product 2-isocyanato-benzoyl chloride 161... 

Oxalyl chloride has been used as a phosgene substitute to prepare 4-jluorophmyl-S-isocyanato-pyridazin-S-yl methanone 448 [301] and 5-trijluoromethylmercapto-2,4-dichloro-6-isocyanato-pyrimidine 450 [302]. 

The reactions of amino acids or amino alcohols with phosgene are interesting since they provide in one step molecules with two different functional groups, namely isocyanato acid chlorides or isocyanato chloroformates. 

A procedure using trichloromethyl chloroformate (diphosgene) has been successfully applied in the synthesis of isocyanato acid chlorides and isocyanato chloroformates from amino acids and amino alcohols, respectively [161,1016]. 

All of the synthesized compounds described thus far in this chapter have been of monovalent reactivity, i.e. the compounds consist of one or more active functional groups of the same selectivity and, where appropriate, one or more further non-active functions. Difunctional compounds such as isocyanato-chloroformate 108 [60] (Section 4.2.1), 446 [300] (Section 4.3.1.4), isocyanato-carbamoyl chloride 179 [111, 112] (Section 4.2.2.2), isocyanato acid chloride 1231 [447] (Section 4.3.5.4), and 1343 [1016] (Section 4.4.2.3), also fall into this category because all of their functions are of the same selectivity, in these examples electrophiles. 

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