Substitution S reaction

The apphcation of bimolecular, nucleophilic substitution (S ) reactions to sucrose sulfonates has led to a number of deoxhalogeno derivatives. Selective displacement reactions of tosyl (79,85), mesyl (86), and tripsyl (84,87) derivatives of sucrose with different nucleophiles have been reported. The order of reactivity of the sulfonate groups in sucrose toward reaction has been found to be 6 > 6 > 4 > 1. ... 

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). 

As an illustration of the real complexity of Mill s reaction, when two molecules of heterocycloammoniums of different nature, one of them being thiazolium (2-substituted or not), are put together in a basic medium, nine dyes theoretically can be produced (depending on the nature of the substituent in the ring) three thiazolomonomethine cyanines (two symmetrical, one asymmetrical) and six trimethine cyanines (two symmetrical, two symmetrical mesosubstituted. one unsymmetrical, one unsymmetrical mesosubstituted). One cannot separate such a mixture by usual chromatographic means. 

The process involving aHyl alcohol has not been iadustriaHy adopted because of the high production cost of this alcohol However, if the aHyl alcohol production cost can be markedly reduced, and also if the evaluated cost of hydrogen chloride, which is obtained as a by-product from the substitutive chlorination reaction, is cheap, then this process would have commercial potential. The high temperature propylene—chlorination process was started by SheH Chemical Corporation ia 1945 as an iadustrial process (1). The reaction conditions are a temperature of 500°C, residence time 2—3 s, pressure 1.5 MPa (218 psi), and an excess of propylene to chlorine. The yield of aHyl chloride is 75—80% and the main by-product is dichloropropane, which is obtained as a result of addition of chlorine. Other by-products iaclude monochioropropenes, dichloropropenes, 1,5-hexadiene. At low temperatures, the amount of... 

Condensation of sodium phenoxide witli 2,2,2-trifluoroethyl iodide gives a product of direct substitution in a low yield, several other ethers are formed by eliminatton-addition reactions [7] Use of mesylate as a leaving group and hex amethyl phosphoramide (HMPA) as a solvent increases the yield of the substitution [S] Even chlorine can be replaced when the condensation is performed with potassium fluoride and acetic acid at a high temperature [9] (equations 6-8)... 

Applications of orgatiocopper reagents and reactions to natural product syndiesis ate dassified by reaction type conjugate addition, S 2 substitution, S 2 substitution, 1,2-metalate teariangemenp and catboctiptadon. 

In every chemical reaction, there is a direct relationship between the rate at which the reaction occurs and the concentrations of the reactants. When we measure this relationship, we measure the kinetics of the reaction. For example, let s look at the kinetics of a simple nucleophilic substitution—the reaction of CH3Br with OH- to yield CH3OH plus Br-—to see what can be learned. 

The reaction of thiyl radicals with silicon hydrides (Reaction 8) is the key step of the so-called polariiy-reversal catalysis in the radical chain reduction. The reaction is strongly endothermic and reversible with alkyl-substituted silanes (Reaction 8). For example, the rate constants fcsH arid fcgiH for the couple triethylsilane/ 1-adamantanethiol are 3.2 x 10 and 5.2xlO M s respectively. 

Since acidification liberates CO and the alcohol (45), the reaction is essentially reversible. The reaction presumably occurs via the substitution [usually a S, reaction 139)] of the coordinated alkoxide by CO, which then adds the alkoxide. In an extension of this reaction, the photolysis of solutions of [RCo(salen)H20] (R = Me, Et, n-Pr, n-Bu) in alcohols R OH (R = Me,... 

These hetero cycles, mainly Fx, are especially deactivated toward electrophilic substitution (S Ar) under standard conditions being the reaction with acid, FT as electrophile, also slow. However, some specific Bfxs have been depicted as nucleophile toward good electrophiles like NO2 and- = N (Fig. 6) [47,53]. 

Smooth COSMO solvation model. We have recently extended our smooth COSMO solvation model with analytical gradients [71] to work with semiempirical QM and QM/MM methods within the CHARMM and MNDO programs [72, 73], The method is a considerably more stable implementation of the conventional COSMO method for geometry optimizations, transition state searches and potential energy surfaces [72], The method was applied to study dissociative phosphoryl transfer reactions [40], and native and thio-substituted transphosphorylation reactions [73] and compared with density-functional and hybrid QM/MM calculation results. The smooth COSMO method can be formulated as a linear-scaling Green s function approach [72] and was applied to ascertain the contribution of phosphate-phosphate repulsions in linear and bent-form DNA models based on the crystallographic structure of a full turn of DNA in a nucleosome core particle [74],... 

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