Reaction with NaOCl

Scheme 8.6. Jacobsen s approach to epoxidation of simple olefins, fa) A few examples of (salen)Mn(III) epoxidation catalysts prior to reaction with NaOCl.

Spectrophotometric determination by use of a modified Konig reaction with NaOCl as the chlorinating agent... 

Derivatization with p-nitrobenzaldehyde followed by reaction with o-dinitrobenzene to yield a purple color LOD = 10 pg/L Barbituric or N,N-dimethylbarbituric acid derivative Spectrophotometric determination by use of a modified Konig reaction with NaOCl as the chlorinating agent... 

The calcium chloride content of Ca(OCl)2 slurries or filter cakes can be reduced or eliminated by reaction with concentrated, low salt NaOCl solution (181). 

Sodium Hypochlorite—Acid—Sodium Chlorite System. In this method, hydrochloric or sulfuric acid is added into a sodium hypochlorite [7681 -52-9] NaOCl, solution before reaction with the sodium chlorite (118). 

Other metal chlorides and salts can also be used lea ding to formation of numerous other metal dichloroisocyanurates (34). Other routes to SDCC iuclude reaction of a moistened powdered mixture of TCCA, CA, and NaHCO (35), reaction of cmde CA with NaOCl (36), and reaction of NaH2 with HOCl (37) or CI2O (38). 

The benzo-fused 1,3-dithietane 6, from which the formation of two dithiiranes (7 and 8) is possible depending on the course of the reaction, only gave the alkylaryldithiirane 7 in 59% yield by treatment with NaOCl-NaC104 (97BCJ509). Tliis is suggestive of the intermediate formation of the more stable, diaryl-substituted carbocation 9 and not the other counterpart 10. 

The second analytical method uses a combustion system (O Neil et al. 1994) in place of reaction with BrF,. This method was used for the crocodiles because they were represented by very thin caps of enamel. The enamel was powdered and sieved (20 mg), pretreated in NaOCl to oxidize organic material and then precipitated as silver phosphate. Approximately 10-20 mg of silver phosphate were mixed with powdered graphite in quartz tubes, evacuated and sealed. Combustion at 1,200°C was followed by rapid cooling in water which prevents isotopic fractionation between the CO2 produced and the residual solid in the tube. Analyses of separate aliquots from the same sample typically showed precisions of 0.1%o to 0.4%o with 2 to 4 repetitive analyses even though yields are on the order of 25%. 

The versatility of the INOC reaction is evident from the synthesis of tetrahy-drofurans fused to an isoxazoline 22a-f (Eq. 3) [181. a-Allyloxyaldoximes 21, formed by the reduction of jS-nitrostyrenes 19 with SnCl2 2H2O in the presence of an unsaturated alcohol 20, are transformed to isoxazolines 22 in high yield on treatment with NaOCl via stereoselective ring closure of a nitrile oxide intermediate (Table 2). 

The reaction of the a-bromo aldoxime 52e (R = R = Me) with unsaturated alcohols has been extended to the heterocyclic systems furfuryl alcohols and 2-thiophene methanol [29b]. The furanyl and thiophenyl oximes 63a-c were treated with NaOCl and the resulting heterocyclic nitrile oxides were found to undergo spontaneous intramolecular dipolar cycloaddition to produce the unsaturated tricyclic isoxazolines 64a-c in high yield (Eq. 5). In these cases, the heterocyclic ring acts as the dipolarophile with one of the double bonds adding to the nitrile oxide [30]. 

The results obtained in reactions involving the two first examples showed a reduced catalytic activity compared to the homogeneous catalyst, a situation that may be due to diffusion problems. Enantioselectivity was similar or slightly lower than in solution, with 80% ee [21] and 58% ee [22] in the epox-idation of ds-/l-methylstyrene with NaOCl providing the best results. Only in the last example was an improvement in enantioselectivity reported from 51% to 91% ee in the epoxidation of a-methylstyrene. Recovery of the catalyst was only considered in one case [21] and a significant decrease in enantioselectivity was observed on reuse. 

Encapsulation in Y zeohte was also the method chosen to immobihze Mn complexes of C2-symmetric tetradentate hgands (Fig. 24) [75]. These materials were used as catalysts for the enantioselective oxidation of sulfides to sulfoxides with NaOCl. The lack of activity when the larger io-dosylbenzene was used as an oxidant was interpreted as an indication that the reaction took place inside the zeolite microporous system. Both the chemo- and enantioselectivity were dependent on the structure of the sulfide. (2-Ethylbutyl)phenylsulfide led to better results than methylphenylsulfide, although in all cases the enantioselectivity was low (up to 21% ee). 

Bicyclic derivatives of furazan A-oxide are prepared by nitrile oxide dimerization reaction. Dioxime 272 (R, R = Me) undergoes cyclization to the corresponding 4,4-tetramethylperhydrocycloocta[c]furazan A-oxide 273 (84% yield) by treatment with NaOCl/HaO/CHaCla at 0°C and then refuxing in toluene (equation 117). However, in the cases of sterically less hindered oximes 272 (R = H, Me R = H) only complex mixtures of oligomerization and cyclization products could be obtained ". Interestingly, the reaction of pyridyl oxime -274 with TsCl afforded 1,2,5-oxadiazole 275 as single product (equation 118). On the other hand, the reaction of Z-isomer of oxime 274 leads only to 0-tosylated oxime. ... 

KCN NaOCl KOCN NaCl Reaction with chlorine in alkaline medium also yields cyanate ... 

NaS03NH2 + 2 NaOCl - NaS03NCl2 + 2 NaOH Sulfamoyl chloride [7778-42-9] forms from reaction with thionyl chloride (15,16) ... 

The odor of skunks is caused by chemical compounds called thiols. These compounds, of which butanethiol (C4H ()S) is a representative example, can be deodorized by reaction with household bleach (NaOCl) according to the following equation ... 

How many grams of butanethiol can be deodorized by reaction with 5.00 mL of 0.0985 M NaOCl ... 

Dimethyl sulfide is toxic and possesses a very bad odour. Particularly, in reactions with activated DMSO on a very big scale, it may be advisable to destroy the dimethyl sulfide, generated during the reaction, by purging the reaction mixture with a nitrogen flow, and scrubbing the resulting gaseous mixture with aqueous NaOCl.5... 

E)-3-Arylidenethiochroman-4-oncs possess thioether and oi,[)-unsaturatcd ketone functionalities both of which are susceptible to oxidation by DMD. In fact, chemoselective oxidation at sulfur is observed with a separable mixture of the sulfoxide and sulfone being produced in >5 1 ratio. A similar situation holds for the related thioflavanones. Epoxidation of the alkenic double bond in the thiochromanone 1,1-dioxides alone can be achieved using methyl(trifluoromethyl)-dioxirane (Scheme 65) <1994T13113>. However, reaction of NaOCl with 3-arylidenethioflavanones gives the epoxide and subsequent oxidation with DMD then gives a mixture of the sulfoxide and sulfone <2003MRC193>. 

Very high yields of bis(a,a-dichloroethyl)benzenes are obtained by the reaction of NaOCl with diethylbenzenes at pH = 8 under phase transfer conditions (equation 106)792. 

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