Ureas, Alkyl

Coil coating finishes—titanium extender in urea-alkyl with 75% rutile and 25% anatase titanium dioxide. 

A 2- or 6-hydroxy-substituted purine can be prepared from the corresponding 4,5-diamino-pyrimidinol by cyclization with an acid, ester, ortho ester, or amide. If the ring closure is performed with reagents such as urea, alkyl chloroformates, urethanes, phosgene, and alkyl isocyanates, the 8-hydroxypurines are formed. Various xanthine and uric acid derivatives have been prepared by the condensation of 5,6-diaminopyrimidine-2,4-diols with formic acid. Purin-2-ol (1) was prepared by this route from 4,5-diaminopyrimidin-2-ol and ethyl orthoformate. ... 

Thiourea, unlike urea, readily reacts in the tautomeric form (I) in the presence of suitable reagents, particularly alkyl halides thus benzyl chloride reacts with... 

Chapter III. 1 Heptene (111,10) alkyl iodides (KI H3PO4 method) (111,38) alkyl fluorides (KF-ethylene glycol method) (111,41) keten (nichrome wire method) (111,90) ion exchange resin catalyst method for esters (111,102) acetamide (urea method) (111,107) ethyl a bromopropionate (111,126) acetoacetatic ester condensation using sodium triphenylmethide (111,151). 

Urea derivadves are of general interest in medicinal chemistry. They may be obtained cither from urea itself (barbiturates, sec p. 306) or from amines and isocyanates. The latter are usually prepared from amines and phosgene under evolution of hydrogen chloride. Alkyl isocyanates are highly reactive in nucleophilic addidon reactions. Even amides, e.g. sulfonamides, are nucleophilic enough to produce urea derivatives. 

Reaction of 2-aminothiazoles with alkyl isocyanates yields 2-thiazolylureas (256) (Scheme 153) (479-483). This reaction is general and works with acyl isocyanates (484. 485). These heterocyclic ureas are also prepared by the reaction of H2O on 2-thia2olylcyanamide (486) or by action of HjOj on the corresponding thiourea (303, 481). 

Alkylation of bis(4-methyl-2-thiazolyl)urea (257) with dimethyl sulfate gives product 258 dimethylated on the ring nitrogens (Scheme 154) (488). Alkylation of l-alkyl-3-(2-thiazolyl)urea from its derived anion formed by NaH gives 259 (Scheme 155). 

Reaction of 2-imino-3-alkyl-4-thiazolines with alkyl isocyanates gives the ureas (382), which when nitrated on C-5 give the schistosomicide class of compounds (383) (Scheme 219), When nitration takes place on the ring... 

These compounds are prepared m a manner analogous to that of barbituric acid itself Diethyl malonate is alkylated twice then treated with urea... 

Thiourea (H2NCNH2) reacts with diethyl malonate and its alkyl derivatives in the same way that urea does Give the structure of the product obtained when thiourea is used instead of urea in the synthesis of pentobarbital The anesthetic thiopental (Pentothal) sodium is the sodium salt of this product yWhat IS the structure of this compound ... 

Section 21 8 Alkylation of diethyl malonate followed by reaction with urea gives derivatives of barbituric acid called barbiturates, which are useful sleep promoting drugs... 

A/B = alkylated ben2enes TBU = tetrabutyl urea TOP = trioctyl phosphate and DIBC = diisobutyl carbinol. See text. 

Reportedly, simple alkyl isocyanates do not dimerize upon standing. They trimerize to isocyanurates under comparable reaction conditions (57). Aliphatic isocyanate dimers can, however, be synthesized via the phosgenation of A[,A[-disubstituted ureas to yield /V-(ch1orocarhony1)ch1oroformamidine iatermediates which are subsequendy converted by partial hydrolysis and base catalyzed cycUzation. This is also the method of choice for the synthesis of l-alkyl-3-aryl-l,3-diazetidiones (mixed dimers of aromatic and aUphatic isocyanates) (58). 

Commercially important arenesulfonyl isocyanates are not directly accessible from the corresponding sulfonamides via phosgenation due to lack of reactivity or by-product formation at elevated temperatures. A convenient method for their preparation consists of the reaction of alkyl isocyanates with sulfonamides to produce mixed ureas which, upon phosgenation, yield a mixture of alkyl and arenesulfonyl isocyanates. The desired product can be obtained by simple distillation (16). Optionally, the oxalyl chloride route has been employed for the synthesis of arenesulfonyl isocyanate (87). 

A wide selection of amino resin compositions is commercially available. They are all alkylated to some extent in order to provide compatibiUty with the other film formers, and formulation stabiUty. They vary not only in the type of amine (melamine, urea, ben2oguanamine, and glycolutil) used, but also in the concentration of combined formaldehyde, and the type and concentration of alkylation alcohol (/ -butanol, isobutyl alcohol, methanol). 

Alkyl carbamates (urethanes) ate formed from reaction of alcohols with isocyanic acid or urea (see Urettpane polymers). 

A/-substituted, long-chain alkyl monomethylol cycHc ureas have also been used to waterproof cotton through etherification. Other water repellent finishes for cotton are produced by cross-linked siHcone films (56). In addition to the polymeri2ation of the phosphoms-containing polymers on cotton to impart flame retardancy and of siHcone to impart water repeUency, polyduorinated polymers have been successfuUy appHed to cotton to impart oil repeUency. Chemical attachment to the cotton is not necessary for durabUity oU repeUency occurs because of the low surface energy of the duorinated surface (57). 

IV-Alkyl substituted ureas usually eliminate the IV-substituted amine (80JHC235), but IV-arylthioureas may give ring IV-aryl derivatives 66UC447). 

Typical of these materials are the poly(vinyl thioethers), the poly(vinyl isocyanates), the poly(vinyl ureas) and the poly(alkyl vinyl ketones). Methyl isopropenyl ketone and certain vinylpyridine derivatives have been copolymerised with butadiene to give special purpose rubbers. 

Modified melamine resins are also employed commercially. Alkylated resins analogous to the alkylated urea-formaldehyde resins provide superior coatings but are more expensive than the urea-based products. 

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