Primary 1 Alcohols

Dehydration of alcohols (Sections 5 9-5 13) Dehydra tion requires an acid catalyst the order of reactivity of alcohols IS tertiary > secondary > primary Elimi nation is regioselective and proceeds in the direction that produces the most highly substituted double bond When stereoisomeric alkenes are possible the more stable one is formed in greater amounts An El (elimination unimolecular) mechanism via a carbo cation intermediate is followed with secondary and tertiary alcohols Primary alcohols react by an E2 (elimination bimolecular) mechanism Sometimes elimination is accompanied by rearrangement... 

Nitro alcohols react with amines to form nitro amines. Such a reaction can be carried out with a wide variety of primary and secondary amines, both ahphatic and aromatic a basic catalyst is requited if aromatic amines are involved. The products of reactions between dihydric nitro alcohols and amines are nitrodiamines, many of which are good fungicides (qv). Dihydric nitro alcohols, primary amines, and formaldehyde react to yield nitrohexahydropyrimidines (4). Nitrohexahydropyrimidines can be reduced to the corresponding amines, some of which are good fungicides or bactericides, eg, hexetidine [141-94-6] (5-amino-l,3—bis(2-ethylhexyl)-5-methylhexahydropyrimidine). 

Nitroparaffins are classed as primary, RCH2NO2, secondary, R2CHNO2, and tertiary, R2CNO2, by the same convention used for alcohols. Primary and secondary nitroparaffins exist ia tautomeric equiUbtium with the enoHc or aci forms. 

Steric factors are important ia transesterification reactions. With a given alcohol, primary alkyl borates react at a rate too fast to measure, secondary alkyl borates react at measurable rates, and tert-huty borate reacts very slowly. 

Primary Amyl Alcohols. Primary amyl alcohols (qv) are manufactured by hydroformylation of mixed butenes, followed by dehydrogenation (114). Both 1-butene and 2-butene yield the same product though in slightly different ratios depending on the catalyst and conditions. Some catalyst and conditions produce the alcohols in a single step. By modifying the catalyst, typically a cobalt carbonyl, with phosphoms derivatives, such as tri( -butyl)phosphine, the linear alcohol can be the principal product from 1-butene. 

Perhaps the most valuable reaction of alcohols is their oxidation to yield car-bony compounds—the opposite of the reduction of carbonyl compounds to yield alcohols. Primary alcohols yield aldehydes or carboxylic acids, secondary alcohols yield ketones, but tertiary alcohols don t normally react with most oxidizing agents. 

Like alcohols, amines with fewer than five carbon atoms are generally water-soluble. Also like alcohols, primary and secondary amines form hydrogen bonds and are highly associated. As a result, amines have higher boiling points than alkanes of similar molecular weight. Diethylamine (MW = 73 amu) boils at 56.3 °C, for instance, while pentane (MW = 72 amu) boils at 36.1 °C. 

Ethers and alcohols (m/z 31. 45, and 59)t Primary straight-chain alcohols Primary alcohols bonded at the y-carbon Formates... 

NITRO-, ETHYL ESTER, ( >], 65 Adipic acid [Hexanedioic acid], 70 DL-Alanine, jV-(tnfluoroacetyl)-, 125 Alcohols, primary, 40... 

Steinle et al. [426] studied the primary biodegradation of different surfactants containing ethylene oxide, such as sulfates of linear primary alcohols, primary oxoalcohols, secondary alcohols, and primary and secondary alkyl-phenols, as well as sulfates of all these alcohols and alkylphenols with different degrees of ethoxylation. Their results confirm that primary linear alcohol sulfates are slightly more readily biodegradable than primary oxoalcohol sulfates and that secondary alcohol sulfates are also somewhat worse than the corresponding linear primary. 

Alkylbenzenes are the commonest organic feedstocks found in the detergent industry, followed by ethoxylated alcohols, primary alcohols, and, Finally, a-olefins. Methylesters have been minimally applied so far. 

Alcohols can also be reduced indirectly by conversion to a sulfonate and reduction of that compound (10-80). The two reactions can be carried out without isolation of the sulfonate if the alcohol is treated with pyiidine-S03 in THF, and then LiAlH4 added. Another indirect reduction that can be done in one step involves treatment of the alcohol (primary, secondary, orbenzylic) with Nal, Zn, and Me3SiCl. In this case the alcohol is first converted to the iodide, which is reduced. For other indirect reductions of OH, see 10-86. 

Alcohols, primary, 56,40 ALDEHYDES, acetylenic, 55, 52 aromatic, aromatic hydrocarbons from, 55,7... 

The products from the reagent and alcohols depend on the nature of the alcohol. Primary alcohols yield the esters (202) from which several derivatives have been obtained. When the p-toluidine salts of (202) are heated in xylene, the phosphonamidodithioates (203) and the phosphonodiamidothioate (204) are formed. Tert-butyl alcohol presumably yields (202 R=CMe2) initially but at the reaction temperature butene is evolved... 

A new interesting branch of the modern antioxidant chemistry deals with the cyclic mechanisms involving acid catalysis. The first inhibiting system of this type was discovered in 1988 [44]. It consisted of an alcohol (primary or secondary), a stable nitroxyl radical TEMPO, and... 

Another situation is observed when salts or transition metal complexes are added to an alcohol (primary or secondary) or alkylamine subjected to oxidation in this case, a prolonged retardation of the initiated oxidation occurs, owing to repeated chain termination. This was discovered for the first time in the study of cyclohexanol oxidation in the presence of copper salt [49]. Copper and manganese ions also exert an inhibiting effect on the initiated oxidation of 1,2-cyclohexadiene [12], aliphatic amines [19], and 1,2-disubstituted ethenes [13]. This is accounted for, first, by the dual redox nature of the peroxyl radicals H02, >C(0H)02 and >C(NHR)02 , and, second, for the ability of ions and complexes of transition metals to accept and release an electron when they are in an higher- and lower-valence state. 

Surfactants can be produced from both petrochemical resources and/or renewable, mostly oleochemical, feedstocks. Crude oil and natural gas make up the first class while palm oil (+kernel oil), tallow and coconut oil are the most relevant representatives of the group of renewable resources. Though the worldwide supplies of crude oil and natural gas are limited—estimated in 1996 at 131 X 1091 and 77 X 109 m3, respectively [28]—it is not expected that this will cause concern in the coming decades or even until the next century. In this respect it should be stressed that surfactant products only represent 1.5% of all petrochemical uses. Regarding the petrochemically derived raw materials, the main starting products comprise ethylene, n-paraffins and benzene obtained from crude oil by industrial processes such as distillation, cracking and adsorption/desorption. The primary products are subsequently converted to a series of intermediates like a-olefins, oxo-alcohols, primary alcohols, ethylene oxide and alkyl benzenes, which are then further modified to yield the desired surfactants. 

Synonyms AI3-15288 C-07328 EINECS 204-663-5 FEMA No. 2057 Fermentation amyl alcohol Fusel oil IP3 l-Hydroxy-3-methylbutane Isoamylol Isobutyl carbinol Isopentanol Isopentyl alcohol Methyl-3-butan-l-ol 2-Methyl-4-butanol 2-Methylbutan-4-ol 3-Methylbutanol 3-Methylbutan-l-ol 3-Methyl-l-butanol NSC 1029 Primary isoamyl alcohol Primary isobutyl alcohol UN 1105. 

Preventol CMK, see p-Chloro-/n-cresol Preventol I, see 2,4,5-Trichlorophenol Priltox, see Pentachlorophenol Primary amyl acetate, see Amyl acetate Primary isoamyl alcohol, see Isoamyl alcohol Primary isobutyl alcohol, see Isoamyl alcohol Prioderm, see Malathion Prist, see Methyl cellosolve Profume A, see Chloropicrin Profume R 40B1, see Methyl bromide Prokarbol, see 4,6-Dinitro-o-cresol... 

Entry Secondary alcohol Primary alcohol Catalyst (mol% Ir) Base Yield (%) ... 

Many transition-metal complexes have been reported as catalysts of this reaction, including [lr(g-Cl)(coe)2]2 [74] and [lrH2(solv.)(PPh3)][SbF6] [75]. The latter catalyst appeared to be a very active and highly selective. The hydroxyl group can be selectively silylated, even in the presence of other potentially reactive C=C and C=0 groups. The order of relative reactivities of alcohol isomers is secondary alcohol > primary alcohol > tertiary alcohol. 

The oxyfunctionalization of alkanes with H2O2 on TS-1 has only been reported very recently [113-114]. Linear or branched alkanes are oxidized to secondary and/or tertiary alcohols and ketones, the latter ones being formed by consecutive oxidation of the secondary alcohols. Primary alcohols are not detected. At 50°C maximum turn-overs of n-hexane of 35 mol/mol Ti were reported... 

In 1992, Hari Prasad Rao and Ramaswamy reported on the oxyfunctionalization of alkanes with H2O2 using a vanadium silicate molecular sieve s . With this catalyst acyclic and cyclic alkanes were oxidized to a mixture of the corresponding alcohols (primary and secondary ones), aldehydes and ketones. Unfortunately, most of the early attempts were of rather limited success due to low turnover frequencies and radical producing side reactions as observed, for example, by Mansuy and coworkers in 1988. ... 

Before the synthesis of the pseudoureas was published, Bernthsen and Klinger [6] reported a pseudothiourea synthesis involving the reaction of thioureas with alkyl halides. This reaction was briefly reviewed by Dains [16] and Stieglitz [49, 50], and it found many commercial applications [51-53]. The preparation of isothiouronium salts by the direct action of thiourea and halogen acids on alcohols (primary, secondary, and tertiary) was reported by Stevens [8] and further developed by Johnson and Sprague [54, 55] (Eq. 25). 

Again analogous to alcohols, primary mercaptans split out H2S to give a strong M - 34 peak, the resulting ion then eliminating ethylene thus the homologous series M - H2S - (CH2=CH2) arises. 

Selective oxidation of alcohols. Primary alcohols are oxidized by this RuCL complex about 50 times as rapidly as secondary alcohols. Use of benzene as solvent is critical lor this high selectivity. Little or no reaction occurs in CH3CN, THF, or DMF. Most oxidants, if they show any selectivity, oxidize secondary alcohols more rapidly than primary ones. However, ruthenium-catalyzed oxidations with N-mcthylmorpholine N-nxide and oxidations with PCC4 proceed about three times as rapidly with primary alcohols as with secondary ones. 

Oxidation of alcohols. Primary and secondary alcohols are oxidized under neutral conditions by this combination of reagents. An aci-nitro ester is the intermediate, which decomposes slowly when heated in THF (equation I).1... 

---