Aliphatic alcohol-substituted

Aliphatic Alcohol-Substituted Sulfonamides. Several monahydroxy alcohols were tested (Table 4) and gave Class III or IV delayed activity however, the toxicity was delayed to a greater extent than the corresponding compound without the alcohol group. 

AM toxin, 151 Acetylenic ketone, 148 Active sulfonamides, 234 Aedes aegypti L., 275 Agrochemicals historical view, 1 side effects, 2 Alectra orobanchoides, 448 Alectra vogelii, 448 Aliphatic alcohol-substituted sulfonamides, 232... 

Amyl alcohol describes any saturated aliphatic alcohol containing five carbon atoms. This class consists of three pentanols, four substituted butanols, and a disubstituted propanol, ie, eight stmctural isomers four primary, three secondary, and one tertiary alcohol. In addition, 2-pentanol,... 

The actual mechanism or process involved in the operation of smelling is not exactly known. The most important investigation in this direction is that of Backmann. He observed that in order that a substance may be odorous it must be sufficiently soluble in both water and in the lipoid fats of the nose cells. The odours of the saturated aliphatic alcohols first increase as the molecular weight increases and then decrease. The lower alcohols are comparatively odourless because of their low degree of solubility in the lipoid fats, while on the other hand the highest members are odourless because of their insolubility in water. The intermediate alcohols which are soluble in both fats and water have powerful odours. Backmann used olive oil in his experiments as a substitute for the lipoid fats. 

The soft heavier odours of the cyclo substituted aliphatic alcohols such as benzyl and phenyl-ethyl alcohols. 

Up to now, nine classes of different polyphosphazenes are known and characterized substituted with aliphatic alcohols [40,41,262-281] or phenols [41,95, 277,282-297],with aliphatic [42,298-300] or aromatic [301-304] amino groups, with di-functional spiro hydroxy (e.g. dihydroxybiphenyl [305] or di hydroxy-... 

The aralkyl alcohols and more highly substituted aliphatic alcohols (Fig. 10.2) are used mostly as preservatives. These include ... 

The oxidation of a series of meta- and para-substituted a-phenylethanols shows that electron-donating substituents facilitate reaction (p = —1.01) . A similar study of primary aliphatic alcohols confirmed this trend p = —1.06 + 0.06). 

A heterobimetallic BINOL-Ga/Li complex 53 has been developed for the enantioselective ARO of meso-cpoxides (BINOL = l,T-bi(2-naphthol)).278 Using />-methoxyphenol as the nucleophile, this etherification reaction was observed to take place with a high level of asymmetric induction. An improved catalyst 54 has also been reported that exhibits greater stability under the reaction conditions and delivers higher yields and ee s (Equation (78)).279 A simple catalyst derived from Sc(OTf)3 and the chiral bipyridine ligand 52 has been shown to be effective for the ARO of aryl-substituted /// -epoxides with aliphatic alcohols to give high ee s (Equation (79)).280... 

Scheme 19 Allylic substitution reactions between aliphatic alcohols and allylic carbonates...

A similar calculation was performed for the aliphatic alcohols. Some subclustering could be seen In this case, but In general the aliphatic alcohols cluster at dot product levels around 0.90 or higher regardless of chain length and substitution pattern. 

Depending on the alcohol moieties present (i.e., quality of leaving group(s), presence of an aliphatic alcohol moiety), the neutral reaction as well as reactions with soft nucleophiles (e.g. HS-, CN, see Box 13.1) may also proceed by nucleophilic substitution at a carbon atom (C-0 cleavage). This is the case for trialkyl phosphates such as trimethyl and triethyl phosphate ... 

In some cases, the effect of reactant structure may outweigh the influence of catalyst nature. This is seen by comparison with the dehydration of aliphatic secondary alcohols and substituted 2-phenylethanols on four different oxide catalysts (Table 4). With aliphatic alcohols, the slope of the Taft correlation depended on the nature of the catalyst (A1203 + NaOH 1.2, Zr02 0.3, Ti02—0.8, Si02—2.8 [55]) whereas for 2-phenyl-ethanols, the slope of the corresponding Hammett correlation had practically the same value (from —2.1 to —2.4) for all catalysts of this series [95]. The resonance stabilisation of an intermediate with a positive charge on Ca clearly predominates over other influences. 

Sodium glycols Sodium nitrate Sodium nitrite Sodium sulphate Stearic acid Steaiyl alcohol Substituted aliphatics Substituted amides Sulphur... 

Phenols can be etherified with resin-bound benzyl alcohols by the Mitsunobu reaction [554,555], or, alternatively, by nucleophilic substitution of resin-bound benzyl halides or sulfonates [556,557], Both reactions proceed smoothly under mild conditions. Aliphatic alcohols have been etherified with Wang resin by conversion of the latter into a trichloroacetimidate (C13CCN/DCM/DBU (15 100 1), 0°C, 40 min), fol-... 

Aliphatic alcohols do not undergo solvolysis as readily as benzylic alcohols, and are generally converted into halides under basic reaction conditions via an intermediate sulfonate. Because of the hydrophobicity of polystyrene, however, nucleophilic substitutions with halides on this support do not always proceed as readily as in solution (Table 6.3). Alternatively, phosphorus-based reagents can also be used to convert aliphatic alcohols into halides. 

Bicyclic nitroso acetals were able to be synthesised by employing ethyl vinyl ether (dienophile), styrene (dipolarophile) and the previously discussed resin-bound ni-troalkenes in a one-pot tandem [4+2]/[3+2]. As illustrated in Scheme 7.30, several aromatic and aliphatic substituents could be introduced to the bicyclic scaffold. Reductive cleavage of the cycloadducts with lithium aluminium hydride (LLAIH4) gave rise to the 3a-methyl alcohol substituted nitroso acetals in moderate overall yields. All these examples demonstrate that resin-bound nitroalkenes can be readily synthesised by microwave synthesis and thereafter can be used as starting materials, in a variety of high pressure-promoted cycloadditions. 

When reaction (16) (X = Br) is carried out30 in the presence of small quantities (0.25-0.50 vol. %) of various aliphatic alcohols, aliphatic ethers, or water, the kinetic form becomes that of the second-order overall. Furthermore, the reaction rate does not depend on the illimination. It was suggested30,32 that in the presence of the above additives, reaction (16) (X = Br) is an electrophilic bimolecular substitution with a complex of the type Br-Br ORR as the electrophile. 

Unsubstituted aliphatic alcohols cannot usually be a-metalated by treatment with strong bases (to yield a dianion). Dilithiated methanol has been prepared by treatment of Bu3SnCH2OH with two equivalents of BuLi, and can be alkylated at carbon [287]. Treatment of allyl alcohol with excess BuLi/TMEDA in pentane at room temperature does not lead to formation of the dianion of allyl alcohol but to addition of BuLi to the C-C double bond [288] (Scheme 5.33). Benzylic alcohols, on the other hand, can be deprotonated twice and, depending on the substitution pattern at the... 

Interestingly, the corresponding azo dicarboxylate (DEAD) could be substituted to the hydrazide derivative (DEAD-H2) with equal efficiency. Unfortunately, both primary and secondary aliphatic alcohols proved to be poor substrates and only modest conversions could be achieved under these conditions, even when a larger amount of the CuCl Phen catalyst was employed (Table II, Entries 7 and 8). 

Unfortunately, even using this optimized procedure, we were not able to improve the conversion of primary alcohols into the corresponding aldehydes. However, close examination of the oxidation behavior of several primary aliphatic alcohols revealed intriguing features (Table VII). Whilst poor conversion of 1-decanol 23 to decanal 24 was achieved (Table VII, Entry 1), dibenzyl leucinol 25 and Boc-prolinol 27 were quantitatively transformed into the corresponding aldehydes (Table VII, Entries 2 and 3). The enhanced reactivity of 25 and 27 could be due either to an increased steric effect at the a-carbon center, to an electronic influence of the a-nitrogen substituent or to a combination of both. To test the importance of steric hindrance, the aerobic oxidation of cyclohexane methanol 29 and adamantane methanol 31 was carried out. Much to our surprise, oxidation of 29 afforded 30 in 70% conversion (Table VII, Entry 4) and transformation of 31 to 32 proceeded with 80% conversion (Table VII, Entry 5). Clearly increased substitution at the a-position favors the oxidation of primary aliphatic alcohols, although the conversions are still not optimum. 

For example, picric acid is a strong gas phase acid aliphatic alcohols are weak gas phase acids. Oxygen substitution reactions leading to phenolate ions occur for some substances. 

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