Aldehydes in ether

Chiral homoallylic alcohols. The borane 1 reacts with aldehydes in ether at - 78° to furnish, after oxidation, chiral secondary homoallylic alcohols (2) with enantiomeric excesses of 83-96%. The addition occurs in all six cases examined in the same stereochemical sense. 

Boron Azaenolates from Oxazolines. The reagent is useful for asymmetric aldol condensations of achiral oxazolines. Treatment of 2-ethyl-4-dimethyl-2-oxazoline with IpC2BOTf in the presence of a tertiary amine furnishes a boron azaenolate. Without isolation, treatment with an aldehyde in ether at —78 °C provides an alkylated oxazoline, which is hydrolyzed and converted to p-hydroxy ester via treatment with Diazomethane. Although the yields for the four-step sequence are only moderate, the anti selectivities of the hydroxy acids are excellent with enantioselec-tivities of 77-85% ee (eq 1). ... 

Nickel peroxide, obtained by oxidation of nickel sulfate hydrate with an alkaline 6% solution of sodium hypochlorite, oxidizes alcohols either to aldehydes, when benzene is used as a solvent, or to acids, when the reaction is done in aqueous alkaline solution (equation 215) [932]. Allenic alcohols are converted into the aldehydes in ether at 20 °C in good yields [1137]. 

Synthesis of fi-lactones. Dichloroketene (generated in situ from dichloroacetyl chloride and triethylamine) reacts with aliphatic and aromatic aldehydes in ether at low temperatures (<20°) to give a,a-dichloro-/3-lactones.4 Esters of a-keto-carboxylic acids also undergo the reaction. 

Before commencing this discussion, it is appropriate to consider briefly the issue of kinetic versus thermodynamic control in the reactions of preformed Group I and Group II enolates and to summarize the structure-stereoselectivity generalizations that have emerged to date. It is now welt established that preformed lithium, sodium, potassium and magnesium enolates react with aldehydes in ethereal solvents at low temperatures (typically -78 °C) with a very low activation barrier. For example, reactions can often be quenched within seconds of the addition of an aldehyde to a solution of a lithium enolate. ... 

In 1981 Meyers and Yamamoto reported the use of an external reagent in the construction of a 2,3-anti unit. The boron azaenolate (85), prepared from the chiral boron reagent (86 diisopinocampheylbotyl triflate lpc2BOTf) and the achiral oxazoline derivative (87), reacts with aldehydes in ether at -78 C (Scheme 36). The direct products (88) are converted, after hydrolysis and esterification, to the corresponding a-methyl-P-hydroxycarboxyl derivatives (89), which are rich in the anti isomer (antiisyn... 

The presence of peroxide and aldehyde in ether is of more importance as they represent oxidation products, the aldehyde probably being formed by hydrolysis of the peroxide. King in an investigation on the products of autoxidation considered the peroxide present to be probably monacetaldehyde hydrogen peroxide together with hydrogen peroxide, but the constitution is still in doubt. A rapid method was devised for the estimation of peroxide in deteriorated ethers. 

From nitriles by treatment with anhydrous Stannous chloride dissolved in ether saturated with hydrogen chloride the resulting crystaUine aldimine stannichloride, [(RCH=NHj)2] SnCl, or (RCH=NH,HCl)2SnCl4, is hydrolysed by warm water, and the aldehyde is isolated by distillation with steam or by extraction with a solvent (Stephen reaction), for example, for R = CH3(CH2)4, i.e., n-amyl ... 

Owing to the instability of a-halogenoaldehydes it is occasionally preferable to use more stable derivatives, such as enol acetate prepared according to Bedoukian s method (204) and a-bromoacetals (4, 8, 10, 16, 22, 67, 101, 426). An advantage is said to be in the yield however, this appears to be slight. The derivatives react in the same sense as the aldehydes themselves, that is, the acetal group as the more polarized reacts first and enters the C-4 position. It is likely that the condensation and cyclization occur by direct displacement of alkoxide ions. Ethyl-a,/3-dihalogeno ethers (159, 164, 177, 248) have also been used in place of the free aldehydes in condensation with thioamides. 

Chemical Properties. A combination of excellent chemical and mechanical properties at elevated temperatures result in high performance service in the chemical processing industry. Teflon PEA resins have been exposed to a variety of organic and inorganic compounds commonly encountered in chemical service (26). They are not attacked by inorganic acids, bases, halogens, metal salt solutions, organic acids, and anhydrides. Aromatic and ahphatic hydrocarbons, alcohols, aldehydes, ketones, ethers, amines, esters, chlorinated compounds, and other polymer solvents have Httle effect. However, like other perfluorinated polymers,they react with alkah metals and elemental fluorine. 

An unusual method for the preparation of syndiotactic polybutadiene was reported by The Goodyear Tire Rubber Co. (43) a preformed cobalt-type catalyst prepared under anhydrous conditions was found to polymerize 1,3-butadiene in an emulsion-type recipe to give syndiotactic polybutadienes of various melting points (120—190°C). These polymers were characterized by infrared spectroscopy and nuclear magnetic resonance (44—46). Both the Ube Industries catalyst mentioned previously and the Goodyear catalyst were further modified to control the molecular weight and melting point of syndio-polybutadiene by the addition of various modifiers such as alcohols, nitriles, aldehydes, ketones, ethers, and cyano compounds. 

AC2O, FeCl3, It, <30 min, 60-93% yield. These conditions will selectively protect an aldehyde in the presence of a ketone. This combination also converts r-butyldimethylsilyl (TBDMS) ethers to acetates. 

Dobbie and Tinkler suggested that, sipce hydrastinine in solution in ether or chloroform has an absorption spectrum almost identical with that of hydrohydrastinine, whilst the absorption spectra of its solutions in water or alcohol resemble those of the salts, it may exist in two forms, represented by formula I (solid state or dissolved in ether or chloroform), and II (dissolved in water or alcohol) these conclusions have been confirmed by Steiner. No evidence for the existence of Roser s aldehydic form was obtained. 

Generally, isolated olefinic bonds will not escape attack by these reagents. However, in certain cases where the rate of hydroxyl oxidation is relatively fast, as with allylic alcohols, an isolated double bond will survive. Thepresence of other nucleophilic centers in the molecule, such as primary and secondary amines, sulfides, enol ethers and activated aromatic systems, will generate undesirable side reactions, but aldehydes, esters, ethers, ketals and acetals are generally stable under neutral or basic conditions. Halogenation of the product ketone can become but is not always a problem when base is not included in the reaction mixture. The generated acid can promote formation of an enol which in turn may compete favorably with the alcohol for the oxidant. 

Benzyloxy-2-fluoro-2-methylpropionaIdehyde was prepared in optically active form from (5)-monoethyl 2-fluoro-2-methylmalonate, which had itself been prepared by enzymatic hydrolysis A number of enol silyl ethers or enolates were added to the aldehyde in processes that occur with fair to good diastereoselectivity [6] (equation 6) (Table 2)... 

The Fisher oxazole synthesis involves condensation of equimolar amounts of aldehyde cyanohydrins (1) and aromatic aldehydes in dry ether in the presence of dry hydrochloric acid. ... 

In 1922 Majima and Kotake reported that 3-formylindole (209) could be obtained in yields of up to 40% by the action of a fivefold excess of ethyl formate on indole magnesium iodide in anisole at low temperatures. However, they also claimed that only traces of the aldehyde were obtained when the reaction was carried out in ether. ... 

Further substitution of benzoic acid leads to a drug with antiemetic activity. Alkylation of the sodium salt of p-hydroxy-benzaldehyde (8) with 2-dimethylaminoethyl chloride affords the so-called basic ether (9). Reductive amination of the aldehyde in the presence of ammonia gives diamine, 10. Acylation of that product with 3,4,5-trimethoxybenzoyl chloride affords trimetho-benzamide (11). ... 

Lithium aluminum hydride, LiAIH4/ is another reducing agent often used for reduction of aldehydes and ketones. A grayish powder that is soluble in ether and tetrabydrofuran, LiAlH4 is much more reactive than NaBH4 but also more dangerous. It reacts violently with water and decomposes explosively when heated above 120 °C. 

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