2- benzoyl chloride, ring

Acylations were often carried out with diaziridines. Twofold acylation is normally observed when two NH groups are present. Most acylations were performed with benzoyl chloride, acetyl chloride or phenyl isocyanate (B-67MI50800). Ring opening reactions during acylation, foreseeable for intermediates of electrophilic attack on nitrogen, were observed only seldom, provided mild conditions were used. 

The A -oxide reactions in quinazoline 3-oxide are, however, modified to a certain extent by the aforementioned properties. Thus, whereas it can be reduced to quinazoline with phosphorus trichloride or iron and ferrous sulfate in ethanol, reactions with alkali, acetic anhydride, and benzoyl chloride in the presence of cyanide result in ring fission (Scheme 4). 

Reaction of tryptamine with simple ketones has not been widely explored. Acetone in the presence of benzoyl chloride has been reported to yield 2-benzoyl-1,1 -dimethyl-1,2,3,4-tetrahydro-j8-carbo-line. That the keto group is much less reactive than the aldehyde group is indicated by the fact that j8-keto aldehydes, in the form of their acetals or sodium salts, react with tryptamine at the aldehyde function to yield the conjugated enamine 24, which undergoes ring closure via an intramolecular Michael addition. The potentialities of this interesting modification of the Pictet-Spengler reaction have not yet been fuUy explored. 

The hydroxy group undergoes 0-acylation and deacylation (79JHC689). These reactions of functionalized hydroxyfurazans are valuable methods for modification of these compounds. Thus, hydroxybifurazan 248 was aroylated with benzoyl chloride in the presence of pyridine with concomitant cleavage of the unsubstituted furazan ring to give nitrile 262 (Scheme 170) (75LA1029). 

Another approach for anchoring the carboxyl groups to the aromatic ring of PS is to use a two-step method [35]. In this method, first, the reaction of PS with 2-chloro-benzoylchloride is carried out. The product can then be followed as shown in Scheme (8). If chloro atom is as o-position on benzoyl chloride the reaction occurred as (a). If there is no substitute group o-position on benzoyl chloride, the preferred is reaction (b). 

Treatment of aziridine 137 (Scheme 3.64) with benzoyl chloride in the presence of pyridine and DMAP afforded ring-expansion product 179 in 90% yield [45], The reaction was believed to proceed through the intermediate N-acylaziridine 178. 

Sometimes acylium ions lose carbon monoxide to generate an ordinary carbonium ion. It will be recalled that free acyl radicals exhibit similar behavior at high temperatures. Whether or not the loss of carbon monoxide takes place seems to depend on the stability of the resulting carbonium ion and on the speed with which the acylium ion is removed by competing reactions. Thus no decarbonylation is observed in Friedel-Crafts reactions of benzoyl chloride, the phenyl cation being rather unstable. But attempts to make pivaloyl benzene by the Friedel-Crafts reaction produce tert-butyl benzene instead. With compound XLIV cyclization competes with decarbonylation, but this competition is not successful in the case of compound XLV in which the ring is deactivated.263... 

An interesting observation was made by Ferrier and coworkers61 during the acylation of 2,4-boronic esters of methyl a- and /3-d-xylopyranosides, in both of which the pyranoid ring must be in the C.,(d) conformation, and the 3-hydroxyl group must be axially attached. On treatment with benzoyl chloride in pyridine, the a-d-xyloside derivative gave 37% of the 3-benzoate and 19% of unreacted starting-material, but the /3-D-xyloside derivative yielded... 

Ti(OPr1)4-mediated nucleophilic ring opening of 2,3-epoxy-alcohol with primary amine requires more rigorous conditions, and the product is a complex mixture. Lin and Zeng22 found that this problem could be overcome and moderate to good yields could be obtained under weak base conditions by in situ /V-acylation of the aminolysis product with benzoyl chloride. 

Benzoylacetanilide couplers, 79 253 Benzoyl chloride, 3 595, 634 end use of chlorine, 6 134t physical constants of ring-chlorinated derivatives, 6 333t Benzoylcyclohexane-diones, 73 294 Benzoyloxy radicals, 74 281 Benzoyl peroxide (BPO), 3 634 20 105 hazards associated with, 78 491 uses for, 78 496... 

The starting material was prepared with the modification on the epibatidine bicychc ring system by repositioning the nitrogen atom to a methylene group. We carried out the Hetero-Diels Alder reaction of cyclopentadiene and iminium ion generated from ammonium chloride and formaldehyde in the aqueous medium and protected resulted unstable secondary amine with benzoyl chloride to provide (3) in good yields [5] (Scheme 38.1). 

The bicyclic tropane ring of cocaine of course presented serious synthetic difficulties. In one attempt to find an appropriate substitute for this structural unit, a piperidine was prepared that contained methyl groups at the point of attachment of the deleted ring. Condensation of acetone with ammonia affords the piperidone, 17. Isophorone (15) may well be an intermediate in this process conjugate addition of ammonia would then give the aminoketone, 16. Further aldol reaction followed by ammonolysis would afford the observed product. Hydrogenation of the piperidone (18) followed then by reaction with benzoyl chloride gives the ester, 19. Ethanolysis of the nitrile (20) affords alpha-eucaine (21), an effective, albeit somewhat toxic, local anesthetic. 

The amine is then used to introduce a nitrile by diazotization followed by treatment of the diazonium salt with cuprous cyanide (180) the methyl ether is then cleaved by means of aluminum chloride. Treatment of the phenolic ketone 181 with benzoyl chloride and sodium benzoate serves to build up the chromone ring (182). The nitrile is next hydrolyzed to the acid with sulfuric acid. Esterification of the carboxyl as—its acid chloride—with N-(2-hydroxyethyl)piperi-... 

The triacyl compound (30) is obtained when an excess of benzoyl chloride is used in the acylation of 3-amino-5-methylamino-l,2,4-thiadiazole (29). However, when acetic anhydride is used no ring nitrogen acylated product is obtained <84CHEC-i(6)463>. Acetylation of 3-hydroxy-5-phenyl-1,2,4-thiadiazole (23) with acetic anhydride and dbu at room temperature gives a small amount of the N-2 compound (28) (Equation (6)) <85JHC1497>. 

Moreover, Wilde (9) also found that N-acyl mtinchnones are prone to equihbrate through ring-chain tautomerism, a process well known for N-alkyl mtinchnones (10-13). Thus, as shown in Scheme 10.1, oxazole 22 reacts with benzoyl chloride in the presence of DMAD to give a mixture of pyrroles 24 and 27 presumably via ketene 25, which (slowly) equilibrates mtinchnones 23 and 26. Capture of mtinchnone 23 by DMAD is faster than equihbration to mtinchnone 26. 

The Reissert-Henze and the Feely-Beavers-Tani reactions are considered together in this section because of their similarity. The former involves cyanation of acyloxy (formed in situ) (Scheme 113), and the latter alkoxy (Scheme 114), quaternary salts. The Reissert-Henze reaction is a facile, fairly general reaction for quinoline and isoquinoline AT-oxides (Table 19) with cyanation occurring a to the ring nitrogen. Certain substituents inhibit reaction, for example a 1-methyl group (equation 125), and others undergo replacement (Scheme 130) (81H(15)98l). Reaction of 1-methylisoquinoline 2-oxide with benzoyl chloride... 

Only one nonazapteridine (pyrimido[4,5- ]-l,2,4-triazine) derivative has been synthesized by the methods covered in this section. Thus, the reaction of the 5-amino-l,2,4-triazine-6-carboxylate 128a with triphenylphosphine/hexa-chloroethane produced the iminophosphorane 133 which underwent aza-Wittig reaction in hot benzoyl chloride in the presence of catalytic 4-dimethylaminopyridine (DMAP) to give the oxazino[6,5-< ]-l,2,4-triazine 134 as shown in Scheme 22 <2003ARK98>, which, as discussed in Section 10.20.1, constitutes an addition to the 44 ring systems covered by the remit of this chapter that were known at the time of CHEC-II(1996) <1996CHEC-II(7)785>. 

---