Phenol 4-cyano

Mild acid converts it to the product and ethanol. With the higher temperatures required of the cyano compound [1003-52-7] (15), the intermediate cycloadduct is converted direcdy to the product by elimination of waste hydrogen cyanide. Often the reactions are mn with neat Hquid reagents having an excess of alkene as solvent. Polar solvents such as sulfolane and /V-m ethyl -pyrrol i don e are claimed to be superior for reactions of the ethoxy compound with butenediol (53). Organic acids, phenols, maleic acid derivatives, and inorganic bases are suggested as catalysts (51,52,54,59,61,62) (Fig. 6). 

The mechanism of thermolysis and photolysis of ethers of 3-hydroxy-1,2-benzisoxazole has also been studied. Heating of the allyl ether (43) gave minor amounts of (44) and two benzoxazoles. Photolysis of (45) in methanol gave a benzisoxazole and an iminoester, via intermediate (46). Thermolysis at 600 °C gave a benzoxazole, a benzoxazolone and cyano-phenol (Scheme 16) (71DIS(D)4483). 

Phenol, Oms-2-(2-butenyl)-asymmetric intramolecular oxidative cyclization, 6,365 Phenol, 4-cyano-hydrolysis... 

Unlike 14-18, the Heck reaction is not limited to activated substrates. The substrate can be a simple alkene, or it can contain a variety of functional groups, such as ester, ether,carboxyl, phenolic, or cyano groups. It can also be a... 

Fig. 37 Addition of phenols, 2-cyano-pyrrol, or hydrazoic acid to ketenes...

A wide variety of aromatic compounds can be brominated. Highly reactive ones, such as anilines and phenols, may undergo bromination at all activated positions. More selective reagents such as pyridinium bromide perbromide or tetraalkylammonium tribromides can be used in such cases.18 Moderately reactive compounds such as anilides, haloaromatics, and hydrocarbons can be readily brominated and the usual directing effects control the regiochemistry. Use of Lewis acid catalysts permits bromination of rings with deactivating substituents, such as nitro and cyano. 

Entries 7 and 8 illustrate conversion of diazonium salts to phenols. Entries 9 and 10 use the traditional conditions for the Sandmeyer reaction. Entry 11 is a Sandmeyer reaction under in situ diazotization conditions, whereas Entry 12 involves halogen atom transfer from solvent. Entry 13 is an example of formation of an aryl iodide. Entries 14 and 15 are Schiemann reactions. The reaction in Entry 16 was used to introduce a chlorine substituent on vancomycin. Of several procedures investigated, the CuCl-CuCl2 catalysis of chlorine atom transfer form CC14 proved to be the best. The diazonium salt was isolated as the tetrafluoroborate after in situ diazotization. Entries 17 and 18 show procedures for introducing cyano and azido groups, respectively. 

AS1079 Sodium-4-cyano phenolate Cl, N03,Br, N03,HP042- S042- citrate, nucleotides... 

The intermediate N-acylpyridinium salt is highly stabilized by the electron donating ability of the dimethylamino group. The increased stability of the N-acylpyridinium ion has been postulated to lead to increased separation of the ion pair resulting in an easier attack by the nucleophile with general base catalysis provided by the loosely bound carboxylate anion. Dialkylamino-pyridines have been shown to be excellent catalysts for acylation (of amines, alcohols, phenols, enolates), tritylation, silylation, lactonization, phosphonylation, and carbomylation and as transfer agents of cyano, arylsulfonyl, and arylsulfinyl groups (lj-3 ). 

In this series, too, replacement of the N-methyl by a group such as cyclopropylmethyl leads to a compound with reduced abuse potential by virtue of mixed agonist-antagonist action. To accomplish this, reduction of 24 followed by reaction with tertiary butylmagnesium chloride gives the tertiary carbinol 27. The N-methyl group is then removed by the classic von Braun procedure. Thus, reaction with cyanogen bromide leads to the N-cyano derivative (28) hydrolysis affords the secondary amine 29. (One of the more efficient demethylation procedures, such as reaction with ethyl chloroformate would presumably be used today.) Acylation with cyclopropylcarbonyl chloride then leads to the amide 30. Reduction with lithium aluminum hydride (31) followed by demethylation of the phenolic ether affords buprenorphine (32).9... 

At moderate temperatures (T < 350 K), these peroxides are stable but readily decompose at elevated temperatures to form radicals [58 60]. Peroxyl radicals can add to phenoxyl radicals at both para- and ort/zo-positions with the proportion dependent on the substituent. Thus, the peroxyl radical adds to 2,4,6-tris(l,l-dimethylethyl)phenoxyl in the para-position by eight times more rapidly than in the ortho-position, whereas it adds to 2-methyl-4,6-bis(l,l-dimethylethyl)phenoxyl preferentially in the ortho-position [59], The rate constants of the reactions of the peroxyl radical with 2,6-bis(l,l-dimethylethyl)-4-substituted phenoxyl radicals in benzene were measured in the presence of respective phenol and AIBN as a source of 1-cyano-l-methylethylperoxyl radicals [60,61]. The concentration of the formed phenoxyl radical in these experiments peaked at [ArO ]max (k7/kx)[ArOH]. Using this expression and taking the known kn values, the values of ks for various phenoxyl radicals 4-Y-2,6-(Me3C)2. Q,H20 were estimated at T 353 K (see Database [52]) ... 

Variations in retention and selectivity have been studied in cyano, phenyl, and octyl reversed bonded phase HPLC columns. The retention of toluene, phenol, aniline, and nitrobenzene in these columns has been measured using binary mixtures of water and methanol, acetonitrile, or tetrahydrofuran mobile phases in order to determine the relative contributions of proton donor-proton acceptor and dipole-dipole interactions in the retention process. Retention and selectivity in these columns were correlated with polar group selectivities of mobile-phase organic modifiers and the polarity of the bonded stationary phases. In spite of the prominent role of bonded phase volume and residual silanols in the retention process, each column exhibited some unique selectivities when used with different organic modifiers [84],... 

Recently, the 2-[ F]fluoroethylation of a phenolic desalkyl precursor based on the jSi-AR-selective antagonist ICI 89,406 was realized via a two-step synthesis starting with the [ F]fluorination of ethylene glycol di-p-tosylate. The radiosynthesis yielded (S)-A/-[2-[3-(2-cyano-phenoxy)-2-hydroxy-propylamino]-ethyl]-A/ -[4-(2-[ F]fluoroethoxy)-phenyl]-urea 10, representing a potent F-labeled high affinity / i-AR-selective radioligand with a / i-AR-selectivity of >40.000 (Fig. 15) [107],... 

In the last years, ILs have been applied as matrices for matrix-assisted laser desorption/ionization (MALDI) MS [42], thus expanding the use of MALDI. In Ref. 38 the suitability of alkylammonium- and alkylimidazolium salts of a-cyano-4-hydroxycinnamic acid was investigated as a MALDI matrix and at the same time as the additive of BGE. The alkylammonium salt produced better separation of phenolic compounds than the alkylimidazolium salt. The investigation suggests that it is possible to synthesize ILs suitable for electrophoretic analysis as well as for online MALDI-MS analysis. 

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