Substituted anilides

Quinazolines 51 have been prepared by the condensation of A-aryl carbamates with hexamine, followed by aromatisation of the dihydro intermediate. A variety of mono- and di-substituted anilides were used, mefa-substituted starting materials giving 7-substituted quinazolines <06T12351>. Benzoquinazolines were also prepared similarly from naphthylamine carbamates <06OL255>. 

This procedure may be used to prepare other substituted anilides. If one of the components is a solid, it can be dissolved in an excess of the other. For instance, 46 g. of 2-amino-5-nitroanisole in 285 ml. of hot ethyl bcnzoylacetate is passed through in 30 minutes, with a transformer setting of 70 volts then the column is rinsed with 50 ml. of the ester. The product crystallizes in the receiver and is... 

The most important substituted anilide herbicides (Fig. 10, Table 3) are Propanil,Propachlor,and Alachlor [43,151,175-178]. 

Antiandrogens such as cyproterone acetate (5.54) or the nonsteroidal flutamide (5.55, a substituted anilide) are competitive antagonists on the cytosol receptor. They do not prevent DHT formation rather, they inhibit the nuclear retention of DHT in the prostate. They cause feminization in male fetuses and decrease libido in males. Cyproterone is also an active progestogen. In men, antiandrogens are used commonly in the treatment of prostatic cancer and uncommonly to inhibit sex drive in hypersexuality in women, antiandrogens are used to treat virilization. Bicalutamide (5.56) and nilutamide (5.57) are potent, orally active antiandrogens that may be used in the treatment of metastatic prostate carcinoma. 

The anilide 19 was also cyclized with ethyl cyanoacetate to give 20 (68JHC185 69USP3459754). Acid-catalyzed cyclization of suitably 2-substituted anilides such as 21 gave 22 [761JC(B)705 88M1405], The pyrrolo [1,2-a] quinazolone 24 was obtained by double ring closure of the... 

Starmer GA, McLean S, Thomas J. 1971. Analgesic potency and acute toxicity of substituted anilides and benzamides. Toxicol Appl Pharmacol 19 20-28. 

Table 2. Coupling of substituted anilide derivatives with n-butyl acrylate using Pd(OAc)2 in acetic acid.3...

If this mechanism is really operative, the "abstraction product" formed in benzene is not necessarily due to a triplet nitrene precursor. Recently a careful study of the thermolysis of methylazide in substituted benzenes demonstrated that the unsubstituted primary sulfonamide is a product of hydrogen abstraction by the nitrene 72). On the other hand there are remarkable differences in isomer ratios (o m p) of the ring-substituted anilides formed depending on the spin state of the reacting nitrene. The triplet was shown to attach the aromatic nucleus mainly in the o-position, as is expected from a highly electrophilic diradical. Dehydrogenations by carbonylnitrenes have been reported by several authors for a variety of systems. In the direct photolysis of ethylazidoformate 29 in cyclohexene, the amide 30 and the bicyclohexenyl 31 were isolated 35b Both products result from an abstraction reaction. 

Similarly, a series of m- and -substituted anilides 68 of thienoic acid were prepared and their H NMR spectroscopic characteristics were examined. In general, good correlations were observed between the chemical shifts of proton signals of the acyl aromatic rings and the Hammett . 

A rather different cyclization process occurs when (65) is treated with tri-flooroperacctic [172] or other peracids (Scheme 2.1.26) [173]. The acylamines appear to react most cleanly, with performic acid giving yields of (68) in the range 43-91% for a wide range of compounds. The o-substituted anilides (65) are made by treatment of o-chloronitrobenzene (1 mol) with the appropriate amine (2.1 mol) followed by reduction, and acylation with formic acid, acetic anhydride or benzoyl chloride [173]. 

Substituted anilide analogues Substituted anilinocarbonyl analogues 234... 

A potentially interesting advance for the treatment of urinary incontinence has been reported [53]. Although some of the analogues of a series of KCA substituted anilides lower blood pressure, others are stated to inhibit bladder contractions without cardiovascular effects. Thus, compound (41) increased the intercontraction interval of conscious rat bladder at a dose of... 

The anodic methoxylation of aromatic compounds such as naphthalene [41], anthracene [42], alkylbenzenes [31,43], phenols [44-46], anisoles [33,47-54] and other alkoxyben-zenes [53], methoxynaphthalenes [33], methoxyanthracenes [50,54], inden-l-ones [55], / a/r/-substituted anilides [56] and heterocyclic compounds, such as furans [57], thiophenes [58], and pyrroles [59], has received considerable attention. 

Description and classification of substances is of course not always easy, and the information provided in a UV spectrum is not always sufficient for identification, but it should be possible with the aid of this type of picture and information to classify quite rapidly some substances not included in the selection from their UV spectra, according to the chemical (and sometimes also the therapeutic) group defined by their chromophores. For example, it is logical to assume an analgesic/antipyretic classification from a pyrazolone spectrum, while conversely if a substance is thought to be a local anaesthetic, the analyst will consider p-aminobenzoic acid esters or base-substituted anilides, and will read the spectrum from this aspect. 

Bismuth(lll) salts such as BiCls, BiBrj, Bi(OCOR)3, and Bi (OTf), [166] have been widely used as Lewis acid catalysts to mediate C-C bond formation. Bi (OTf) 3, Bi2O3, and BiCl, catalyze Friedel-Crafts acylation with acyl chlorides or acid anhydrides [167]. Both electron-rich and electron-deficient arenes are acylated in high yields under catalysis by Bi(OTf)3 (Scheme 14.82). Under microwave irradiation the catalytic activity of BiX3 (X = C1, OTf) in the acylation of aromatic ethers is enhanced [168]. The N-acyl group of p-substituted anilides migrates to the ortho position of the aromatic nucleus under BiCls catalysis [169]. Treatment of 2,3-dichloroanisole with the ethyl glyoxylate polymer in the presence of a catalytic amount of Bi(OTf)3 affords an a,a-diarylacetic acid ester quantitatively (Scheme 14.83) [170]. 

Zikan and coworkers [35-37] have prepared substituted anilides of 3-benzyl-5-bromosalicylic acids (23), some of which exhibited high activity against H. nana and Aspicularis tetraptera in experimental animals. 

As part of our research work to achieve new, simple, non corrosive and environmentally friendly processes for the acid hydrolysis of aromatic amides, we report herein a study of the hydrolysis of substituted anilides (Scheme 1) in liquid phase using zeolites with different pore structures and framework Si-to-Al ratios, as acid catalysts. 

Anilides substituted in 2- or 3-positions are monoarylated. 4-Substituted anilides can be either mono- or diarylated. For slower reactions or diarylation, use of silver trifluoroacetate instead of silver acetate is beneficial by increasing the reaction rate. The products can be deprotected by base hydrolysis to afford 2-aryl- or 2,6-diarylanilines. 

The most important compounds are the N-substituted a-chloroacetamides, particularly the substituted anilides, which are used partly for preemergence treatment and partly for postemergence treatment of many kinds of crops. 

Fig. 13.22. Scattergram of the interplanar angle g) in carbon-substituted anilides between best planes through the atoms of the phenyl ring and the three atoms directly bonded to N versus the deviation d of N from the latter plane. The deviation of the interplanar angle from coplanarity is correlated with pyramidalization at N. The data scatter displays an approximately parabolic distribution. Similar results were described in a previous study [102]...

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