Secondary 2 Alcohols

Like tertiary alcohols secondary alcohols normally undergo dehydration by way of carbocation intermediates... 

Most higher alcohols of commercial importance are primary alcohols secondary alcohols have more limited specialty uses. Detergent range alcohols are apt to be straight chain materials and are made either from natural fats and oils or by petrochemical processes. The plasticizer range alcohols are more likely to be branched chain materials and are made primarily by petrochemical processes. Whereas alcohols made from natural fats and oils are always linear, some petrochemical processes produce linear alcohols and others do not. Industrial manufacturing processes are discussed in Synthetic processes. 

The above procedure describes the only known preparation of the inner salt of methyl (carboxysulfamoyl)triethylammonium hydroxide and illustrates the use of this reagent to convert a primary alcohol to the corresponding urethane.2 Hydrolysis of the urethane would then provide the primary amine. The method is limited to primary alcohols secondary and tertiary alcohols are dehydrated to olefins under these conditions, often in synthetically useful yields.2... 

Allyl Alcohols. Secondary cyclic allylic alcohols are reduced with the combination of Et3SiH and ethereal LiC104, even in the presence of a tertiary alcohol (Eq. 35) or ketal function.173 Primary allylic alcohols do not undergo deoxygenation under similar conditions.173... 

N) [W3V18042(H20)12(X04)]-24H20 alcohols, secondary alcohols Sorption of water [184, 185]... 

Normal butyl alcohol + Secondary butyl alcohol... 

In the absence of primary alcohols, secondary alcohols participate in transesterification reactions to provide good yields for most alcohols. No significant electronic effect is observed when electron-releasing and electron-withdrawing substitutents on aromatic secondary alcohols (Table 22, entries 2-4). A steric effect is observed with cyclohexanol derivatives. Increasing the a-substituent from hydrogen to methyl or teri-butyl dramatically decreases efficiency of transesterifi-... 

Propanol, 2 Isopropyl Alcohol Isopropanol Secondary Alcohols Secondary Aliphatic Amines... 

Butyl Alcohol, Secondary (For Use in Org Coatings) sec-C4HgOH TT- B-848B Dec 1959... 

Primary alcohol Secondary alcohol Carboxyhc acid... 

Alcohols such as methanol, 2-propanol, and benzhydrol are cleanly oxidized to the corresponding carbonyl compounds upon photoexcitation with Na3PWi2O40 in water or with (n-P NfoPW C in CH3CN (406). The quantum yields appear to be governed by the oxidation potential of the alcohol, the availability of a-hydrogens, and the tightness of complexation with the photocatalyst The reactivity order is primary alcohol > secondary alcohol > tertiary alcohol. 

Aldehydes Ketones alcohols, secondary nitro amines. Aliphatic aromatic Aromatic aldehydes and... 

Selective oxidation of sec-alcohols. Secondary alcohols can be oxidized selectively in the presence of primary ones by NaBrO, (1 equiv.) in the presence of CAN or Ce(S04)2 (0.1 equiv.) with 80-90% yields. 

Reaction kinetics with the various reagents becomes faster as their nucleophilicity is increased. The following order of reactivity can be given primary aliphatic amine > primary aromatic amine > secondary aliphatic amine primary alcohol > secondary alcohol > water > tertiary alcohol phenol > mercaptan. 

A limited number of studies have considered the use of surfactant and cosolvent mixtures to enhance the recovery of NAPLs (Martel et al., 1993 Martel and Gelinas, 1996). Martel et al. (1993) and Martel and Gelinas (1996) employed ternary phase diagrams to select surfactant+cosolvent formulatons for treatment of NAPL-contaminated aquifers. The surfactant+cosolvent formulations used in their work, which included lauryl alcohol ethersulfate/n-amyl alcohol, secondary alkane sulfonate/n-butanol, and alkyl benzene sulfonate/n-butanol, were shown to be effective solubilizers of residual trichloroethene (TCE) and PCE in soil columns (Martel et al., 1993). However, very little information is available regarding the effect of cosolvents on the solubilization capacity and phase behavior of ethoxylated nonionic surfactants. 

Recently, Bode et al. were able to demonstrate that the products formed after generation of the homoenolate equivalents 67 are determined by the catalytic base [64]. Strong bases such as KOt-Bu led to carbon-carbon bond-formation (y-butyrolactones), while weaker bases such as diisopropylethylamine (DIPEA) allowed for protonation of the homoenolate and the subsequent generation of activated carboxylates. The combination of triazolium catalyst 72 and DIPEA in THF as solvent required no additional additives and enabled milder reaction conditions (60 °C), accompanied by still high conversions in the formation of saturated esters out of unsaturated aldehydes (Scheme 9.21). Aliphatic and aromatic enals 62, as well as primary alcohols, secondary alcohols and phenols, are suitable substrates. a-Substituted unsaturated aldehydes did not yield the desired products 73. 

Primary alcohol Secondary alcohol Tertiary alcohol Phenol... 

The classical method for the introduction of the trityl group involved the reaction of a primary alcohol (secondary alcohols react very slowly — if at all) with triphenylmethyl chloride (mp 110-112 °C) in pyridine [Scheme 4.209).3S3-394 The reaction can be slow and a more convenient procedure using DMAP9 or DBU395 to accelerate the reaction is applicable to large scale as shown in the... 

Seven noncommercial acid-labile linkers have been reported recently in the literature and are shown in Figs. 1.8. (1.7-1.10) and 1.9 (1.11-1.13). The THP (tetrahy-dropyran) linker 1.7 (63), which is easily grafted onto Merrifield resin, has been used to support primary alcohols, secondary alcohols, hydroxylamines, and carboxylic acids. It is stable to strong nucleophiles and basic conditions and can be cleaved by... 

Primary drug ALCOHOL Secondary drug ANALGESICS Effect Mechanism Precautions... 

Grignard reagents readily deprotonate alcohols, secondary amines, and secondary amides in certain snbstrates, the resnlt-ing magnesiated species can nndergo inter- or intramolecnlar addition, or intramolecnlar rearrangement. ... 

Quinolinium dichromate (17) shows the solubility profile common to most chromium based oxidants—sparingly soluble in chlorinated solvents, but more soluble in more polar solvents. It has been mainly used in dichloromethane at reflux, or in DMF at 30 C to oxidize primary alcohols. Secondary alcohols are also oxidized reasonably well. 

Oxidation of alcohols. Secondary alcohols are oxidized to ketones in 85-95% yield by dibenzoyl peroxide in the presence of catalytic amounts of NiBr2 or the soluble complex with dimethoxyethane, NiBrj (CH20CH3)2 (Alfa), in acetonitrile. Under the same conditions, primary alcohols are oxidized to esters. However if 1.5-2.5 equiv. of NiBr2 is used, aldehydes can be obtained in reasonable yield. 

Compared with primary alcohols, secondary alcohols underwent competitive dehydration to yield olefins in addition to O-benzylation products in the presence of KY. 

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