2-cyanoethyl phenyl

Cyanoethyl -Phenyl acid -Diphenyl hydrogen -Di-p-nitrophenyl — PhgPSe (RO)gPS... 

PhS(0)(0Ph)Me + RLi and LiX - PhSOCH X + PhSO Me]/ or reduction with homologation (with RjCuLi and LiX)/ Standard sulphinylation procedures reported include electrophilic substitution of phenols with ArSOCl and AlClj and the preparation of optically active sulphoxides from resolved (—)-menthyl sulphinates with ( )-l-alkenylmagnesium bromides or arylthiomethyl- or arylsulphonylmethyl-lithium compounds/ A practical route to 1-alkenyl sulphoxides uses non-activated alkynes and sulphenic acids, generated in situ from the thermolysis of 2-cyanoethyl phenyl sulphoxides/ ... 

Hartung et al. [102] described the crystal structure of 4 -(/i-cyanoethyl)-phenyl-4- -pentoxybenzoate which exhibits a monotropic nematic phase. The crystal structure of the compound shows a parallel arrangement of the molecules. 

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). 

When large groups, such as phenyl, bromo, ethoxycarbonyl or nitro are attached at position 3, the principal products are l-alkylcinnolin-4(l/f)-ones. Cyanoethylation and acetylation of cinnolin-4(l/f)-one takes place exclusively at N-1. Phthalazin-l(2/f)-ones give 2-substituted derivatives on alkylation and acylation. Alkylation of 4-hydroxyphthala2in-l(2/f)-one with an equimolar amount of primary halide in the presence of a base leads to 2-alkyl-4-hydroxyphthalazin-l(2/f)-one and further alkylation results in the formation of 4-alkoxy-2-alkylphthalazinone. Methylation of 4-hydroxy-2-methyl-phthalazinone with dimethyl sulfate in aqueous alkali gives a mixture of 4-methoxy-2-methylphthalazin-l(2/f)-one and 2,3-dimethylphthalazine-l,4(2//,3//)-dione, whereas methylation of 4-methoxyphthalazin-l(2/f)-one under similar conditions affords only 4-methoxy-2-methylphthalazinone. 

Condensation of the TV-substituted p-aminocrotonic acid ester 15 with p-benzoquinone (4) has been successfully carried out to furnish the 5-hydroxyindole 29 when the substituent R on the nitrogen of the aminocrotonic acid ester was methyl, ethyl, -propyl, isopropyl, or -butyl, -hexyl, p-cyanoethyl, p-hydroxyethyl, carbethoxymethyl, benzyl, phenyl, o-tolyl, dimethylaminopropyl, y-hydroxypropyl etc ... 

Synthetic Method 9 N-[8-bis(2-cyanoethyI) -9-[4- (phenylsulfonyl) -benzoyl]-9, 10-dihydro-1 0-phenyl-2-phenazinyl]-4-phenylsulfonylbenzamide (53) (procedure from US. Patent 4,889,932).18 A 3-liter round-bottom flask fitted with a mechanical stirrer was loaded with 16.6 g (0.066 mol) of 4-[di(2-cyanoethyl)amino]aniline in 800 ml of deionized water. A 10% excess of aniline (13.56 g, 0.1456 mol) and 100ml of deionized water were added to the mixture. The mixture was cooled to 0°C in an ice bath, and... 

Preparation of phenyl(mesitylyl)( 3-cyanoethyl)phosphine — Addition of a secondary phosphine to an unsaturated nitrile under aqueous basic conditions... 

An aqueous 50% KOH solution (0.5 ml) was added to a solution of phenyl(mesitylyl)phosphine (1.0 g, 4.4 mmol) and acrylonitrile (400 mg, 7.5 mmol) in acetonitrile (10 ml). The flask was heated at 50°C for 2 h, producing a yellow solution. Extraction with ether caused separation of a yellow insoluble material and gave a clear solution that, upon cooling to -25°C, gave white crystals of the product, which were washed with a small amount of petroleum ether. An additional crop was obtained from the mother liquor to provide pure phenyl(mesitylyl)((3-cyanoethyl)phosphine (857 mg, 70%), which exhibited spectra and analytical data in accord with the proposed structure. 

On the other hand, reaction of 5-acetyl-2-methyl-4-nitro-6-phenyl-3(2//)-pyridazinone 287 with A -methyl-/3-alaninenitrile afforded the 4-(2-cyanoethyl) derivative 288, which was cyclized by heating with sodium ethoxide in ethanol to the pyrido[2,3-rflpyridazine 289 (Equation 22) <1994S669>. 

To a refluxing solution of 9.73 gm (0.047 mole) of l-phenyl-3-(2-cyanoethyl)-thiourea in 75 ml of absolute methanol is added dropwise 7.4 gm (0.052 mole) of methyl iodide over a 5 min period. After refluxing for 3 hr the solution is evaporated to dryness under reduced pressure to give an oil. The oil is triturated with 50 ml of acetone to afford 15.1 gm (93%). Three recrystallizations from 3 1 absolute ethanol-ether solution raised the melting point from 152°-159°C to 165°-167°C (picrate derivative, m.p. 139°-141°C). 

B. Preparation of 4-Amino-1,2,5,6-tetrahydro-l-phenyl-phosphorin-3-carbonitrile. To a nitrogen-flushed 1-1. threenecked flask equipped with a mechanical stirrer, a pressure-equalizing addition funnel, and a reflux condenser are added 25 g. (0.22 mole) of potassium room temperature, 250 ml. of water is added, and the resulting mixture is stirred for 30 minutes while the product crystallizes. The mixture is filtered, and the solid product is washed on the filter with two 50-ml. portions of cold ethanol to give, after drying at 78° (1 mm.), 36-38 g. (84-88%) of 4-amino-1,2,5,6-tetrahydro-1 -phenylphosphorin- 3-carboni-trile, m.p. 134.5-137° (Note 9). A small amount of product can be recovered from the filtrate (Note 10). 

The intermediates, bis(2-cyanoethyl)phenylphosphine and 4-amino-l,2,5,6-tetrahydro-l-phenylphosphorin-3-carbonitrile, are easily isolated and characterized and show little or no oxidation when exposed to the air. l-Phenyl-4-phosphorinanone is a highly-crystalline material which is more sensitive to air oxidation than its two precursors. However, l-phenyl-4-phosphorinanone may be stored in a well-capped bottle for several months without appreciable oxidation. It is best stored in a dark bottle in a dry box under nitrogen. 

A further extension of this type of synthetic sequence is illustrated by the cyclization of 2-cyanoethyl(o-cyanophenyl)-phenylphosphine to the corresponding o-enaminenitrile followed by hydrolysis with acid to form 2,3-dihydro-l-phenyl-4(lH)-phosphinolinone.8 The only other reported synthesis of this... 

S-(2-Nitro-l-phenyl)ethyl, 678 S-2-(2,4-Dinitrophenyl)ethyl, 678 S-2-(4 -Pyridyl)ethyl, 679 S-2-Cyanoethyl, 679 S-2-(Trimethylsilyl)ethyl, 680 S-2,2-Bis(carboethoxy)ethyl, 681 S- (1-w -N itrophenyl-2- benzoyl) ethyl, 681 S-2-Phenylsulfonylethyl, 681... 

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