Alcohols primary, secondary and tertiary

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). 

Interestingly, this strategy was applied to the more reactive propargyl alkoxides allowing for the simultaneously introduction of the three partners at the start of the reaction. In fact, in this case, no side reactions occurred [95]. This process is remarkably versatile, giving good yields of stereodefined 3-arylidene (and alkenyli-dene) tetrahydrofurans 105 with a variety of propargyl alcohols (primary, secondary, and tertiary) and unsaturated halides (aryl iodides, vinyl bromides, and tri-flates) (Scheme 8.45). 

Relative Stability of alcohol, primary, secondary and tertiary models for possible cyclic nitrosamine metabolites as proposed in figure 2. All energies are in kcal/mole. 

Methoxybenzyl ethers. Alcohols (primary, secondary, and tertiary) are derivatized under neutral conditions with the title reagent in the presence of AgOTf in dichloromethane. 

Methoxymethyl ethers. Etherification of alcohols with this reagent is mediated by AgOTf-NaOAc. This method is suitable for derivatizing acid-sensitive alcohols. Primary, secondary, and tertiary alcohols react at comparable rates, phenols slower. 

Bromination of alcohols. Primary, secondary, and tertiary alcohols are converted to bromides. 

Fluorination of alcohols. Primary, secondary, and tertiary alcohols are converted by (1) into the corresponding fluorides the reaction occurs readily at 10° or below. One advantage of this reagent is that products of dehydration and carbonium ion rearrangement are formed in smaller amounts than with SF4, SeF4 pyridine (5, 576-577), and (C2Hs)2NCF2CHClF (5,214-216). It is also useful for fluorination of aldehydes and ketones that are sensitive to acid. 

Alkyt iodides. Alcohols (primary, secondary, and tertiary) can be converted into iodides by reaction with this reagent. The reaction can be carried out on the free alcohol or on the trimethylsilyl ether of the alcohol. Yields of alkyl iodides are usually about the same for both methods. The conversion proceeds with inversion. ... 

Silylation of Alcohols. Primary, secondary, and tertiary alcohols are silylated by reaction with TBDMS triflate in excellent yields. For instance, treatment of r-butanol with 1.5 equiv of TBDMS triflate and 2 equiv of 2,6-lutidine in CH2CI2 at 25 °C for 10 min gives a 90% yield of (r-butoxy)-r-butyldimethylsilane. The following alcohols are similarly silylated in excellent yields (70-90%) 2-phenyl-2-propanol, ewufo-norbomeol, c/s-2,2,4,4-tetramethylcyclobutane-l,3-diol, and 9-O-methylmaytansinol (converted to the 3-TBDMS derivative) (eq I). ... 

The lower members of other homologous series of oxygen compounds— the acids, aldehydes, ketones, anhydrides, ethers and esters—have approximately the same limits of solubility as the alcohols and substitution and branching of the carbon chain has a similar influence. For the amines (primary, secondary and tertiary), the limit of solubility is about C whilst for the amides and nitriles it is about C4. 

The reason for this is that reaction (i) is usually much slower than (ii) and (iii) so that the main reaction appears to be (Iv) (compare the preparation of tertiary butyl chloride from tertiary butyl alcohol and concentrated hydrochloric acid, Section 111,33). If the reaction is carried out in the presence of P3rridine, the latter combines with the hydrogen chloride as it is formed, thus preventing reactions (ii) and (iii), and a good yield of the ester is generally obtained. The differentiation between primary, secondary and tertiary alcohols with the aid of the Lucas reagent is described in Section III,27,(vii). 

With aldehydes, primary alcohols readily form acetals, RCH(OR )2. Acetone also forms acetals (often called ketals), (CH2)2C(OR)2, in an exothermic reaction, but the equiUbrium concentration is small at ambient temperature. However, the methyl acetal of acetone, 2,2-dimethoxypropane [77-76-9] was once made commercially by reaction with methanol at low temperature for use as a gasoline additive (5). Isopropenyl methyl ether [116-11-OJ, useful as a hydroxyl blocking agent in urethane and epoxy polymer chemistry (6), is obtained in good yield by thermal pyrolysis of 2,2-dimethoxypropane. With other primary, secondary, and tertiary alcohols, the equiUbrium is progressively less favorable to the formation of ketals, in that order. However, acetals of acetone with other primary and secondary alcohols, and of other ketones, can be made from 2,2-dimethoxypropane by transacetalation procedures (7,8). Because they hydroly2e extensively, ketals of primary and especially secondary alcohols are effective water scavengers. 

Formic acid forms esters with primary, secondary, and tertiary alcohols. The high acidity of formic acid makes use of the usual mineral acid catalysts unnecessary in simple esterifications (17). Formic acid reacts with most amines to form formylamino compounds. With certain diamines imida2ole formation occurs, a reaction that has synthetic utiHty (18) ... 

Sequential substitution reactions which transform alcohols into a family of primary, secondary, and tertiary amines. 

Miller and Kirchner [9] and Mathis and Ourisson [1] have both already demonstrated that esterification at the start can be employed to distinguish primary, secondary and tertiary alcohols. Tertiary alcohols react much more slowly... 

Rather similar was the paper [PolG36a] which also derives asymptotic formulae for the number of several kinds of chemical compounds, for example the alcohols and benzene and naphthalene derivatives. Unlike the paper previously mentioned, this one gives proofs of the recursion formulae from which the asymptotic results are derived. A third paper on this topic [PolG36] covers the same sort of ground but ranges more broadly over the chemical compounds. Derivatives of anthracene, pyrene, phenanthrene, and thiophene are considered as well as primary, secondary, and tertiary alcohols, esters, and ketones. In this paper Polya addresses the question of enumerating stereoisomers -- a topic to which we shall return later. 

Diethyl ether and other simple symmetrical ethers are prepared industrially by the sulfuric acid-catalyzed dehydration of alcohols. The reaction occurs by SN2 displacement of water from a protonated ethanol molecule by the oxygen atom of a second ethanol. Unfortunately, the method is limited to use with primary alcohols because secondary and tertiary alcohols dehydrate by an El mechanism to yield alkenes (Section 17.6). 

Primary, secondary, and tertiary alcohols can be converted to any of the four halides by treatment with the appropriate NaX, KX, or NH4X in polyhydrogen fluoride-pyridine solution." This method is even successful for neopentyl halides. Another reagent that converts neopentyl alcohol to neopentyl chloride, in 95% yield, is PPh3-CCl3CN." ... 

The reaction gives good yields with primary, secondary, and tertiary alcohols, and with alkyl and aryllithium reagents.Allylic alcohols also couple with certain... 

Thin-layer chromatography usually involves the adsorption chromatographic separation of substance mixtures into polarity groups. It is well known that clean looking chromatographic peaks can hide several substances. For instance, primary, secondary and tertiary alcohols are to be found at very nearly the same hRf. 

Dihydro-6,7-dijiethoxy-4- ethyl-3-oxo-quinoxaline-2-car]3onyl azide DMOQ-CON, Primary, Secondary and tertiary alcohols 594... 

NO Reactions. The most informative derivitization reaction of oxidized polyolefins that we have found for product identification is that with NO. The details of NO reactions with alcohols and hydroperoxides to give nitrites and nitrates respectively have been reported previously, and only the salient features are discussed here (23). The IR absorption bands of primary, secondary and tertiary nitrites and nitrates are shown in Table I. After NO treatment, y-oxidized LLDPE shows a sharp sym.-nitrate stretch at 1276 cm-1 and an antisym. stretch at 1631 cm-1 (Fig. 1), consistent with the IR spectra of model secondary nitrates. Only a small secondary or primary nitrite peak was formed at 778 cm-1. NO treatment of y-oxidized LLDPE which had been treated by iodometry (all -OOH converted to -OH) showed strong secondary nitrite absorptions, but only traces of primary nitrite, from primary alcohol groups (distinctive 1657 cm-1 absorption). However, primary products were more prominent in LLDPE after photo-oxidation. 

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