2-Phenyl-3- acrylonitrile

When 3-chloro-3-phenyl acrylonitrile was involved in this reaction, a bi-cyclic product, 6,6 -diphenyl-4,4 -bis(l,2,3-dithiazine) was formed in good yield [262]. Five-membered cyclic disulfides were obtained in this reaction when ethylenic esters or ketones were taken as an unsaturated substrate (Scheme 61) [263]. 

Some results on thermal stability and thermal decomposition products of other acrylic acid derivatives including poly(a-chloro-acrylonitrile), poly(a-phenyl acrylonitrile), and poly(acryloyl chloride) as reported in literature are given in Table 6.7.17 [6]. 

The synthesis of fludioxonil is shown in Scheme 11.9. The key intermediate 3-phenyl-acrylonitrile 32 is prepared by Meerwein arylation of acrylonitrile using the diazonium salt of 2,3-(difluoromethylenedioxy)aniline (31). Treatment of intermediate 32 with/i-toluenesulfonyl methylisocyanide (TOSMIC) in the presence of strong base gives fludioxonil. The key intermediate 31 is available from several vendors. It is also prepared from 2,2-difluoro-l,3-benzodioxole (30), commercially available in bulk, by metalation at the 4-position of compound 30 followed by either direct conversion to aniline 31 using lithium methoxyamide or conversion to an azido... 

The enantioselective organocatalytic rearrangement of a-acyloxy-j8-keto sulfides to a-acyloxy thioesters has been developed. " 2-Cyano- and 2-carbethoxy-3-[2-(pyrrolidin-l-ylmethyl)phenyl]acrylonitriles undergo interconversion with l-(pyrrolidin-l-yl)indane-2-carbonitriles (Scheme 76). " ... 

Properties of trans-3-(4-Monomethylamino-phenyl)-acrylonitrile Evidence of Twisted Intramolecular Gharge Transfer (TICT) Process. 

Dry HCl bubbled through a well-stirred ice-cold soln. of resorcinol and a-phenyl-acrylonitrile in dry ether with portionwise addition of ZnClg, stirred 2-3 hrs. in the cold, kept 3-5 days in the refrigerator, the ether decanted off, the residue treated with cold dil. HCl, heated on a steam bath, and the resulting 3-phenyl-7-hydroxy-3,4-dihydrocoumarin refluxed 5-6 hrs. with 10%-Pd-C in diphenyl ether 3-phenyl-7-hydroxycoumarin. Overall Y 60-65%. F. e. s. A. K. Das Gupta and M. S. Paul, J, Indian Chem. Soc. 47, 1017 (1970) s. a. D. K. Chatterjee and K. Sen, ibid. 48, 387 (1971),... 

Tetrazole, 2-methyl-5-(4 -vinyl)phenyl-Tetrazole, 2-methyl-5-(4 -vinyl)phenyl- Acrylonitrile 1.1 0.42 583... 

Acrylonitrile reacts with the sodium salt of 4.5-dimethvl-A-4-thiazoline-2-thione (73J (R4 = R5 = Me) to yield 3-(2-cyanoethyl)-4.5-dimethyl-A-4-thiazoline-2-thione (74) (R4 = R, = Me) (Scheme 35 (160). Humphlett s studies of this reaction showed that the size of the R4 substituent is a determinant factor for the S versus N ratio (161. 162). If R4 == H, 100% of the N-substituted product (74) is obtained this drops to 50% when R4 = methyl, and only the S-substituted product (75) is obtained when R4 = phenyl. The same trend is observed with various CH2 = CH-X (X = C00CH3. COCH3) reagents (149). The S/N ratio also depends on the electrophilic center for CH2 = CH-X systems thus S-reaction occurs predominantly with acrylonitrile, whereas N-substitution predominates with methvlvinvlketone (149). 

This tendency is related to the polarization properties of the monomer substituents (42). Monomers that are dissimilar in polarity tend to form alternating monomer sequences in the polymer chain. An example is the monomer pair acrylonitrile—styrene. Styrene, with its pendent phenyl group, has a relatively electronegative double bond whereas acrylonitrile, with its electron-withdrawing nitrile group, tends to be electropositive. 

Styrene readily copolymerizes with many other monomers spontaneously. The styrene double bond is electronegative on account of the donating effect of the phenyl ring. Monomers that have electron-withdrawiag substituents, eg, acrylonitrile and maleic anhydride, tend to copolymerize most readily with styrene because their electropositive double bonds are attached to the electronegative styrene double bond. Spontaneous copolymerization experiments of many different monomer pair combiaations iadicate that the mechanism of initiation changes with the relative electronegativity difference between the monomer pairs (185). 

Nitrones or aci-nitro esters react with alkenes to give in some cases A/-substituted isoxazolidines and in others 2-isoxazolines. When the intermediate isoxazolidines were observed, a number of procedures transformed them into the 2-isoxazolines. Acrylonitrile and phenyl rzcf-nitrone esters produced an A/-methoxyisoxazolidine. Treatment with acid generated a 2-isoxazole while treatment with base generated an oxazine (Scheme 118) (68ZOR236). When an ethoxycarbonyl nitrone ester was reacted with alkenes, no intermediate isoxazolidine was observed, only A -isoxazolines. Other aci-mtro methyl esters used are shown in Scheme 118 and these generate IV-methoxyisoxazolidines or A -isoxazolines which can be further transformed (72MI41605). 

The enamines derived from cyclic ketones give the normal alkylated products, although there is some evidence that unstable cycloadducts are initially formed (55b). Thus the enamine (28) derived from cyclohexanone and pyrrolidine on reaction with acrylonitrile, acrylate esters, or phenyl vinyl sulfone gave the 2-alkylated cyclohexanones (63) on hydrolysis of the intermediates (31,32,55,56). These additions are sensitive to the polarity of the solvent. Thus (28) in benzene or dioxane gave an 80% yield of the... 

Giese and Kretzschmar7j found the rate of addition of hexenyl radicals to methyl acrylate increased 2-fold between aqueous tetrahydrofuran and aqueous ethanol, Salikhov and Fischer74 reported that the rate constant for /-butyl radical addition to acrylonitrile increased 3.6-fold between tetradecane and acetonitrile. Bednarek et al75 found that the relative reactivity of S vs MMA towards phenyl radicals was ca 20% greater in ketone solvents than it was in aromatic solvents. 

Recently Mosher and Driscoll 2 have noted that the polymerization of acrylonitrile can be observed during the chromic acid oxidation of 2,2-dimethyl-l-phenyl-l-propanol. The polymerization is caused by radicals formed during the oxidation of benzaldehyde (which is one of the cleavage product of phenyl-1-butylcarbinol). The oxidation of benzaldehyde is due to the chromium(IV), most probably, or chromiun(V) intermediates. 

The following syntheses all proceeded regioselectively 4,6-diaryl-3,4-dihydropyrimidine-2-thiones with 3-bromopropionic acid in a Ac20/AcOH system <2001MI407, 2000IJH49>, or with acrylonitrile in pyridine followed by hydrolysis <1996IJB915> resulted 6,8-diaryl-2,3-dihydro+//,6//-pyrirnido[2,l+][l,3]thiazin-4-ones in good yield 4-phenyl-5-carbethoxy-3,4-dihydropyrimidine-2-thiones with benzylidenemalonitrile in a NaOAc/AcOH system... 

Acrylic acid, /ro i-/3-(o-NiTROPHEira.)-a-PHENYL-, 35, 89 Acrylonitrile, 30, 80 36, 6 Acrylonitrile, triphenyl-, 31, 52 Acylation of ethanolamine with phthalic anhydride, 32, 19 Acyloin reaction, 36, 79 2-Acylpyridines, phenylhydrazones of,... 

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