Secondary alcohol system

The secondary alcohol system provides an unexpectedly high resist sensitivity although the degree of expected dehydration is very small. In order to elucidate the imaging mechanism, we carried out model reactions in solution and analyzed the products by NMR. When a-methylbenzyl alcohol was treated with triflic acid in CDQ3 at room temperature for 1 hr, the alcohol was completely consumed and almost quantitativefy converted to an enantiomeric mixture of... 

S. Thus, the imaging mechanisms for the tertiary and secondary alcohol systems are much different. The former is based on the reverse polarity change induced by intramolecular dehydration and the latter relies on crosslinldng through intermolecular dehydration. 

Sulfation andSulfamation. Sulfamic acid can be regarded as an ammonia—SO. complex and has been used thus commercially, always in anhydrous systems. Sulfation of mono-, ie, primary and secondary, alcohols polyhydric alcohols unsaturated alcohols phenols and phenolethylene oxide condensation products has been performed with sulfamic acid (see Sulfonation and sulfation). The best-known appHcation of sulfamic acid for sulfamation is the preparation of sodium cyclohexylsulfamate [139-05-9] which is a synthetic sweetener (see Sweeteners). 

Vinyllithium [917-57-7] can be formed direcdy from vinyl chloride by means of a lithium [7439-93-2] dispersion containing 2 wt % sodium [7440-23-5] at 0—10°C. This compound is a reactive intermediate for the formation of vinyl alcohols from aldehydes, vinyl ketones from organic acids, vinyl sulfides from disulfides, and monosubstituted alkenes from organic halides. It can also be converted to vinylcopper [37616-22-1] or divinylcopper lithium [22903-99-7], which can then be used to introduce a vinyl group stereoselectively into a variety of a, P-unsaturated systems (26), or simply add a vinyl group to other a, P-unsaturated compounds to give y, 5-unsaturated compounds. Vinyllithium reagents can also be converted to secondary alcohols with trialkylb o r ane s. 

Secondary alcohols ate oxidi2ed to ketones in good yields under mild conditions in a triphasic system using an inert solvent, soHd Ca(OCl)2, and a hypochlorite resin as catalyst (175). 

A water-reducible coating or resin is one that is diluted with water before use. Water-reducible alkyds give comparable drying performance to solvent-bome alkyds. However, they are not widely used because film properties tend to be poorer than those of solvent-bome alkyds, especially in air-dry systems (26). This is pardy because of alcoholysis of the alkyd by primary alcohols such as 1-butanol [71-36-3] C H qO, a common solvent in water-reducible alkyds (27,28) secondary alcohols such as 2-butanol [78-92-2] C qH O, minimize this problem (27). In any case, the slow loss of amine or ammonia leads to short-term high sensitivity to water. Even in the fully dry films, the presence of unreacted carboxyHc acid groups leads to films having comparatively poor water resistance limiting their usehilness. 

All secondary alcohols are not dehydrated by this system instead, formates are sometimes produced, presumably by reaction with DMF ... 

The solvent for ammonia may have an important influence. In reduction of C,o unsaturated dinitriles to primary amines over ruthenium-on-alumina, ammonia-/-butanol proved the preferred system normal alcohols gave poor rates and secondary alcohols produced N-alkylated products 18). 

A method has been developed which determines the amount of residual alk-ene and secondary alcohol in AOS using an aqueous-organic extraction solvent system followed by GC analysis. Alkanes present (impurities in the feedstock) will also be determined with the unreacted alkene. 

An alternative approach to the microbial deracemization of secondary alcohols is to use two different microorganisms with complementary stereoselectivity. Fantin et al. studied the stereoinversion of several secondary alcohols using the culture supernatants of two microorganisms, namely Bacillus stearothermophilus and Yarrowia lipolytica (Figure 5.18) [31]. The authors tested three main systems for deracemization. First, they used the supernatant from cultures of B. stearothermophilus, to which they added Y. lipolytica cells and the racemic alcohols. Secondly, they used the culture supernatant of Y. lipolytica and added B. stearothermophilus cells and the racemic alcohols. Finally, they resuspended the cells of both organisms in phosphate buffer and added the racemic alcohols. The best results were obtained in the first system with 6-penten-2-ol (26) (100% ee and 100% yield). The phosphate buffer system gave... 

Resting cell of G. candidum, as well as dried cell, has been shown to be an effective catalyst for the asymmetric reduction. Both enantiomers of secondary alcohols were prepared by reduction of the corresponding ketones with a single microbe [23]. Reduction of aromatic ketones with G. candidum IFO 5 767 afforded the corresponding (S)-alcohols in an excellent enantioselectivity when amberlite XAD-7, a hydro-phobic polymer, was added to the reaction system, and the reduction with the same microbe afforded (R)-alcohols, also in an excellent enantioselectivity, when the reaction was conducted under aerobic conditions (Figure 8.31). 

Later, in a modification to the above system, we reported the use of an indenylruthenium complex 2 as a racemization catalyst for the DKR of secondary alcohols, which does not require ketones but a weak base hke triethylamine and molecular oxygen to be achvated. The DKR with 2 in combination with immobilized Pseudomonas cepacia lipase (PCL, trade name. Lipase PS-C ) was carried out at a lower temperature (60°C) and provided good yields and high optical purities (Table 2). This paved the way for the omission of ketones as... 

Intermolecular hydroalkoxylation of 1,1- and 1,3-di-substituted, tri-substituted and tetra-substituted allenes with a range of primary and secondary alcohols, methanol, phenol and propionic acid was catalysed by the system [AuCl(IPr)]/ AgOTf (1 1, 5 mol% each component) at room temperature in toluene, giving excellent conversions to the allylic ethers. Hydroalkoxylation of monosubstituted or trisubstituted allenes led to the selective addition of the alcohol to the less hindered allene terminus and the formation of allylic ethers. A plausible mechanism involves the reaction of the in situ formed cationic (IPr)Au" with the substituted allene to form the tt-allenyl complex 105, which after nucleophilic attack of the alcohol gives the o-alkenyl complex 106, which, in turn, is converted to the product by protonolysis and concomitant regeneration of the cationic active species (IPr)-Au" (Scheme 2.18) [86]. 

Hj concentration as a function of time for various alcohols as electron donor. In the presence of primary and secondary alcohols the rates of Hj generation are equal although the induction periods at the start of illumination are different. In the presence of a tertiary alcohol the rate of formation is substantially lower. As mentioned in section 4.2 alcohols are not strongly adsorbed at the TiO particles and therefore do not react with the positive holes before they are trapped. The main scavenger in this system is the platinum deposit which scavenges electrons and catalyses the reduction of hydrogen ions 2 e" -I- 2 —> H2- A surprising observation was that the H2... 

Control experiments do not provide evidence for oxidation of the secondary alcohol groups in the glycoside or for degradation of the ligand backbone. A similar regioselectivity was also observed in a benzyl alcohol/1-phenylethanol model system that showed no proof for the oxidation of the secondary alcohol by formation of acetophenone (18, 23,26). 

Trifluoromethanesulfonates of alkyl and allylic alcohols can be prepared by reaction with trifluoromethanesulfonic anhydride in halogenated solvents in the presence of pyridine.3 Since the preparation of sulfonate esters does not disturb the C—O bond, problems of rearrangement or racemization do not arise in the ester formation step. However, sensitive sulfonate esters, such as allylic systems, may be subject to reversible ionization reactions, so appropriate precautions must be taken to ensure structural and stereochemical integrity. Tertiary alkyl sulfonates are neither as easily prepared nor as stable as those from primary and secondary alcohols. Under the standard preparative conditions, tertiary alcohols are likely to be converted to the corresponding alkene. 

A catalytic system that extends the reactivity of Mn02 to saturated secondary alcohols has been developed.15 This system consists of a Ru(II) salt, RuCl2(/i-cymene)2, and 2,6-di-r-butylbenzoquinone. 

One feature of this oxidation system is that it can selectively oxidize primary alcohols in preference to secondary alcohols, as illustrated by Entry 2 in Scheme 12.5. The reagent can also be used to oxidize primary alcohols to carboxylic acids by a subsequent oxidation with sodium chlorite.34 Entry 3 shows the selective oxidation of a primary alcohol in a carbohydrate to a carboxylic acid without affecting the secondary alcohol group. Entry 5 is a large-scale preparation that uses NaC102 in conjunction with bleach as the stoichiometric oxidant. 

Prevost, M., and R. Bugarel, 1981. Theoretical and technical aspects of a chemical heat pump Secondary alcohol-ketone-hydrogen system, Proc. 2nd World Cong. Chem. Eng.,... 

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