Ammonia, reaction with hydroxy-esters

Dihydrobenzo-TAs of this type may be obtained from 2-mercap-tobenzoic acid and its esters. The reaction with dimethyl-acetylenediear-boxylate affords acid 153, which is converted into a chloroanhydride. Further cyclization by the action of ammonia gives compound 152 (R3 = H) (67JOC2678 70JHC1007). TV-Hydroxy- (57USP2776281) and Tv-amino-... 

Theato et al. [19] studied the polymerization of activated esters such as 2,4,5-trichlorophenyl acrylate and endo-N-hydroxy-5-norbornene-2,3-dicarboxyimide acrylate (NORB, Fig. 1) using ATRP. They showed that the polymer side chains were reactive by performing a couphng reaction with ammonia. 

Pyrones, which are the ring-oxygen equivalents of pyridones, are simply a- and y-hydroxy-pyrylium salts from which an 0-proton has been removed. There is little to recommend that 2- and 4-pyrones be viewed as aromatic they are perhaps best seen as cyclic unsaturated lactones and cyclic p-oxy-a,P-unsaturated-ketones, respectively, for example 2-pyrones are hydrolysed by alkali, just like simpler esters (lactones). It is instructive that, whereas the pyrones are converted into pyridones by reaction with amines or ammonia, the reverse is not the case - pyridones are not transformed into pyrones by water or hydroxide. Some electrophilic C-substitutions are known for pyrones and benzopyrenes, the oxygen guiding the electrophile ortho or para, however there is a tendency for electrophihe addition to the C-C double bond of the heterocyclic ring, again reflecting their non-aromatic nature. Easy Diels-Alder additions to 2-pyrones are further evidence for diene, rather than aromatic, character. 

The first use of preformed enolates for synthesis appears to have been by Hauser and coworkers, who converted r-butyl and ethyl acetate into the lithium enolates by reaction with LiNH2 in liquid ammonia the resulting enolates were found to react with aldehydes and ketones to give 3-hydroxy esters (equations 1 and 2). ... 

PROPANOIC ACID, 2-HYDROXY-, BUTYL ESTER (79-09-4) Forms explosive mixture with air (flash point 126°F/52°C). Violent reaction with strong oxidizers, caustic substances. Incompatible with aliphatic amines, alkalis, alkanolamines, ammonia, alkylene oxides, epichlorohydrin, isocyanates, sulfuric acid. Attacks many metals, forming explosive hydrogen gas. Flow or agitation of substance may generate electrostatic charges due to low conductivity. 

Hydroxyphenamate. 2-Phenyl-l,2-butanediol 1-carbamate carbamic acid ft -ethyl -0-hydroxy phenethy] ester d-ethyl-p-hydroxyphenethy] carbamic acid ester 0-ethyl-0-hydroxy phenethyl carbemate 2-hydroxy-2-phenyl-butyl carbamate Al 0361 Listica. C.,H.sNOv mol wt 209.24. C 63.14%, H 7.23%, N 6.69%, O 22 94%. Prepd from d-ethyl -d-hydroxyphenethyl alcohol and ethyl chloro-formate followed by reaction with ammonia Sifferd, Brait-berg. U,S. pat. 3,066,164 (1962 to Armour-Pharm.). Pharmacology and toxicology Bastian, Clements, Di-V. Nerv. Sys. 22, 9 (1961). 

Yet a further reaction which forms three bonds is the use of imidic esters with suitably functionalized ketones (e.g. a-hydroxy, a-bromo). This method is exemplified by the synthesis of a new imidazole alkaloid (146), which had been isolated from a member of the Urticaceae family (80AHC(27)24l), and by the more general synthesis of 4-alkyl-5-methoxymethylimidazole (147) (79AP107). The cyclization process, which takes place in liquid ammonia, may be complicated by 2-alkylbutanamide by-products which result from Favorskii rearrangement of the bromomethoxy ketones (Scheme 83). 

Two different polyurethanes were used as starting materials a solid elastomer based on a trifunctional polyethertriol, 1,4-butanediol and methylenebis(phenyl isocyanate) and a flexible foam where the diol was replaced by water. The ammonolysis reactions were carried out at 139 °C and 140 atm for 120 min, and with a polyurethane/ammonia weight ratio of 1. Under these conditions the polyurethane conversion was practically total. The ammonolysis reaction transforms the CO group into urea and the ester groups and derivatives of carboxylic acids into amides, whereas ether and hydroxy groups are inert towards ammonia. Scheme 2.7 illustrates the stoichiometry proposed by the authors for the ammonolysis of the polyether urethane. 

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