Tertiary protection

This reaction can also be utili2ed to prepare functionali2ed initiators by reaction of butyUithium with a substituted 1,1-diphenylethylene derivative. For example, polymers end functionali2ed with primary amine, tertiary amine, phenol, and bis(phenol) groups have been prepared in essentiaUy quantitative yield by using the reaction of butyUithium with the corresponding substituted (or protected) 1,1-diphenylethylene (87). 

Other Specialty Chemicals. In fuel-ceU technology, nickel oxide cathodes have been demonstrated for the conversion of synthesis gas and the generation of electricity (199) (see Fuel cells). Nickel salts have been proposed as additions to water-flood tertiary cmde-oil recovery systems (see Petroleum, ENHANCED oil recovery). The salt forms nickel sulfide, which is an oxidation catalyst for H2S, and provides corrosion protection for downweU equipment. Sulfur-containing nickel complexes have been used to limit the oxidative deterioration of solvent-refined mineral oils (200). 

Tertiary Amine Catalysts. The Hquid tertiary aHphatic amines used as catalysts in the manufacture of polyurethanes can cause contact dermatitis and severe damage to the eye. Inhalation can produce moderate to severe irritation of the upper respiratory tracts and the lungs. Ventilation, protective clothing, and safety glasses are mandatory when handling these chemicals. 

TtM use of vinyl chloroformate tor N-dealkytatlon of tertiary amines, protection of amino groups, protection of hydroxyl groups or formation of Z-ketoimidazoles. Synthesis of vtnyl cartxjnates by means of fluoro or chiorofonnates. 

Aminoboranes can be prepared from diborane to protect a tertiary amine during oxidation they are cleaved by refluxing in ethanol or methanolic sodium carbonate. ... 

Amine oxides, prepared to protect tertiary amines during methylation and to prevent their protonation in diazotized aminopyridines, can be cleaved by reduction (e.g., SO2/H2O, 1 h, 22°, 63% yield H2/Pd-C, AcOH, AC2O, 7 h, 91% yield Zn/HCl, 30% yield). Photolytic reduction of an aromatic amine oxide has been reported [i.e., 4-nitropyridine A-oxide, 300 nm, (MeO)3PO/CH2Cl2, 15 min, 85-95% yieldl. ... 

The front of the transferred surge will, however, be less steep and dampened than on the primary side due to capacitive dampening. But sometimes this may also exceed the BIL, particularly of the tertiary (if provided) and also the secondary windings of the transformer, as well as the cable and the terminal equipment connected on the lower voltage side. This is especially the case when the primary side voltage is very high compared to the secondary. Protection of the secondary windings, in all probability, will be sufficient for all the cables and terminal equipment connected on the secondary side. 

Note Even then a surge protection is essential for the tertiary if the tertiary is provided. 

The U.S. Clean Air Amendments of 1977 define two kinds of air quality standards primary standards, levels that will protect health but not necessarily prevent the other adverse effects of air pollution, and secondary standards, levels that will prevent all the other adverse effects of air pollution (Table 22-7). The amendments also define air quality levels that cannot be exceeded in specified geographic areas for "prevention of significant deterioration" (PSD) of the air of those areas. Although they are called "increments" over "baseline air quality" in the law, they are in effect tertiary standards, which are set at lower ambient levels than either the primary or secondary standards (Table 22-8). 

The reactivity of various steroid alcohols decreases in the order primary > secondary (equatorial) > secondary (axial) > tertiary. The only systematic investigation relating to the selective protection of steroidal hydroxyl functions has been carried out with the cathylate (ethyl carbonate) group. Since only equatorial hydroxyl groups form cathylates this ester has been used as a diagnostic tool to elucidate the configuration of secondary alcohols. 

While the reductive procedure appears simpler, it also provides a higher proportion of the A -double bond isomer on dehydration than is obtained from the tertiary carbinol. This may be a consequence of the lower steric requirements of a A -olefin having only one alkyl group attached to C-20. In either case, all other double bonds must be protected before the ozonolysis and other free hydroxyls should be esterified prior to dehydration at C-20. 

The conversion of 3 to 8 is summarized in Scheme 2. The trityl group (too large and too acid sensitive for the ensuing steps) was removed from N, and both N s were protected by Cbz (benzyloxycarbonyl) groups. Protection of the tertiary OH specifically as the robust TBS (f-butyldimethylsilyl) group was found to be necessary for the sequence involving the electrophilic aromatic substitution step, 5 to 6, and the Stille coupling steps (6 + 7 —> 8). 

Nal increases the reactivity of MOMCl by the in situ preparation of MOMI, which facilitates the protection of tertiary alcohols. ... 

In this case, the tertiary and electron-deficient MPM group is retained. " A very slow cleavage of an MPM protected adenosine was attributed to its reduced electron density as a result of n stacking with the adenine. Typically, these reactions are complete in < 1 h, but in this case complete cleavage required 41 h. 

Six categories of A/-hetero atom derivatives are considered N-M (M = boron, copper) N-N (e.g., A/-nitro, A-nitroso) A-oxides (used to protect tertiary amines) N-P (e.g., phosphinamides, phosphonamides) N-SiR3 (R = CH3), and N-S (e.g., sulfonamides, sulfenamides). 

In an interesting analogy to the penicillin series, acylation of 7-ACA with the phenylglycine moiety affords a compound with oral activity. Thus, phenylglycine is first protected as the carbo tertiary butyloxy derivative (45). Reaction of this with isobutyloxy chloroformate affords the mixed anhydride (46). Condensation of that with 7-ACA gives the intermediate, 47. Treatment with either trifluoroacetic or formic acid provides the free amine cephaloglycin (48). ... 

An ester of alanine with an arylaliphatic alcohol has shown promise as a non-tricyclic antidepressant. It may be speculated that the hindered milieu of the ester linkage protects the compound from hydrolysis by endogenous esterases. The preparation starts by reaction of pheny-lacctate 83 with methyl magnesium iodide to give tertiary carbinol 84. Acylation with 2-bromo-]>ropionyl bromide leads to ester 85 displacement of halogen with ammonia leads to alaproclate ( 6) [211. 

Step 2 The second step is removal of the DMT protecting group by treatment with dichloroacetic acid in CH2CI . The reaction occurs by an S -l mechanism and proceeds rapidly because of the stability of the tertiary, benzylic dimethoxytrityl cation. 

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