Formaldehyde acetals

Tertiary amines have been shown to react with isocyanates ia an analogous fashion to form ureas (41—43). Similarly, a2iridines (three-membered rings containing nitrogen) are found to react with isocyanates to yield cycHc ureas. Tertiary amines have also been shown to form labile dipolar 1 1 adducts with isocyanates reminiscent of salt formation. In contrast, formaldehyde acetal aminals form iasertion products with sulfonyl isocyanates (44,45). 

The Prins reaction with formaldehyde, acetic acid, acetic anhydride, and camphene gives the useful alcohol, 8-acetoxymethyl camphene, which has a patchouli-like odor (83). Oxidation of the alcohol to the corresponding aldehyde also gives a useful iatermediate compound, which is used to synthesize the sandalwood compound dihydo- P-santalol. 

The oxidation of n-butane represents a good example illustrating the effect of a catalyst on the selectivity for a certain product. The noncatalytic oxidation of n-butane is nonselective and produces a mixture of oxygenated compounds including formaldehyde, acetic acid, acetone, and alcohols. Typical weight % yields when n-butane is oxidized in the vapor phase at a temperature range of 360-450°C and approximately 7 atmospheres are formaldehyde 33%, acetaldehyde 31%, methanol 20%, acetone 4%, and mixed solvents 12%. 

Add excess of chloral hydrate (or of formaldehyde-acetic acid solution, 3 1) to the titrated solution in order to liberate the Zn from the cyanide complex, and titrate until the indicator turns blue. This gives the Zn only. The Cu content may then be found by difference. 

Finally, reaction of primary, secondary, or tertiary alcohols 11 with Me3SiCl 14 in the presence of equivalent amounts of DMSO leads via 789 and 790 to the chloro compounds 791 [13]. n-Pentanol, benzyl alcohol, yS-phenylefhanol or tert-butanol are readily converted, after 10 min reaction time, into their chloro compounds, in 89-95% yield, yet cyclohexanol affords after reflux for 4 h cyclohexyl chloride 784 in only 6% yield [13] (Scheme 6.5). 1,4-Butanediol is cyclized to tetrahydrofuran (THF) [13a], whereas other primary alcohols are converted in 90-95% yield into formaldehyde acetals on heating with TCS 14 and DMSO in benzene [13b] (cf also the preparation of formaldehyde di(n-butyl)acetal 1280 in Section 8.2.1). 

DMSO or other sulfoxides react with trimethylchlorosilanes (TCS) 14 or trimefhylsilyl bromide 16, via 789, to give the Sila-Pummerer product 1275. Rearrangement of 789 and further reaction with TCS 14 affords, with elimination of HMDSO 7 and via 1276 and 1277, methanesulfenyl chloride 1278, which is also accessible by chlorination of dimethyldisulfide, by treatment of DMSO with Me2SiCl2 48, with formation of silicon oil 56, or by reaction of DMSO with oxalyl chloride, whereupon CO and CO2 is evolved (cf also Section 8.2.2). On heating equimolar amounts of primary or secondary alcohols with DMSO and TCS 14 in benzene, formaldehyde acetals are formed in 76-96% yield [67]. Thus reaction of -butanol with DMSO and TCS 14 gives, via intermediate 1275 and the mixed acetal 1279, formaldehyde di-n-butyl acetal 1280 in 81% yield and methyl mercaptan (Scheme 8.26). Most importantly, use of DMSO-Dg furnishes acetals in which the 0,0 -methylene group is deuter-ated. Benzyl alcohol, however, affords, under these reaction conditions, 93% diben-zyl ether 1817 and no acetal [67]. 

Figure 39.1. Reaction between PYC and formaldehyde acetals to form MDB. Experimental...

The catalytic tests [temperature = 543-703 K liquid hourly space velocity (LHSV) = 2,0 h gas hotuly space velocity (GHSV) (if not differently reported) = 510 h PYC/formaldehyde acetal =1 1 moEmol were carried out in... 

An environmentally friendly synthesis of 1,2-methylenedioxybenzene (MDB) can be efficiently carried out in the gas phase, by feeding pyrocatechol (PYC) and formaldehyde acetals and using a catalyst containing weak acid sites and redox sites. The Ti-silicalite (TS-1) was identified as the most active and selective catalyst, indicating the role of well-dispersed octahedrally-coordinated Ti" ions in comparison with some model catalysts. 

The methoxymethyl (MOM) and (3-methoxyethoxymethyl (MEM) groups are used to protect alcohols and phenols as formaldehyde acetals. These groups are normally introduced by reaction of an alkali metal salt of the alcohol with methoxymethyl chloride or (3-methoxyethoxymethyl chloride.157... 

The reversible acid-catalyzed transacetalation of the cyclophane formal 3 has been shown to undergo a ring-fusion/ring-fission process to generate a mixture of polymer cyclic formaldehyde acetals by means of oxonium ion intermediates <06CEJ8566>. The stepwise... 

Overman reported the synthesis of highly enantiopure 3-acyltetrahydrofurans with C5 substituents from formaldehyde acetals of allylic diols <00TL9431>. An example of Overman s procedure is depicted below, which involves the generation of a formaldehyde oxonium ion intermediate 92 before the cyclization. 

Fermentation of the wastes - conversion to acetates Acetogenesis - conversion to acids, formaldehyde and Hydrogen, and Methanogenesis - conversion of formaldehyde, acetates, and acids to CO2 and Methane... 

Methanol, CH3OH, the simplest alcohol, is made by reacting CO and H2 at high pressures over a catalyst. Methanol is a liquid at room temperature and is highly toxic. It is used to make formaldehyde, acetic acid, and other chemical intermediates. It is also used as a feedstock for MTBE (methyl tertiary butyl ether), a gasoline-blending component. 

Cacciapaglia, R. Di Stefano, S. Mandolini, L. Metathesis reaction of formaldehyde acetals An easy entry into the dynamic covalent chemistry of cyclophane formation. J. Am. Chem. Soc. 2005,127, 13666-13671. 

Ammonia Derivatives Methyl t-butyl ether -Butyraldehyde Dimethyl terephthalate Methanol Formaldehyde Acetic acid... 

This is the reason why, for example, the zero order formic acid dehydrogenation may easily be measured on bulk metal catalysts at 200-300°C. whereas the approximately first order ethanol dehydrogenation requires highly activated porous metals of large specific surface in order to become measurable under the same conditions. The same has been shown for the decomposition of formaldehyde, acetic acid, and hydrazine hydrate. In these cases, the fractional surface coverage is simply 1000 times lower than in the case of a zero order reaction. 

CH2O -I- Pb(CH3COO)2 -I- 2CH3COOH (formaldehyde) (acetic acid)... 

The benzylic alcohol 6-bromo-9-ethylcarbazole-3-ylcarbinol alkylated 3-bromo-9-ethylcarbazole at the 6-position generating 139 (R = Br). Dicarba-zol-3-ylmethanes also resulted from direct treatment of the 3-halo-9-ethylcar-bazoles with formaldehyde-acetic acid and sulfuric acid, presumably via the 3-carbinols. High yield 3-monoalkylation of 9-methylcarbazole was... 

Phenol aldehydes are generally pleasant-smelling products. Some of them are particularly important as fragrance and flavor materials. Anisaldehyde and certain derivatives of protocatechu aldehyde (3,4-dihydroxybenzaldehyde) are well-known representatives. The monomethyl ether of protocatechu aldehyde, vanillin, is perhaps the most widely used flavor material. Other important derivatives of this aldehyde are veratraldehyde (dimethyl ether) and heliotropin (formaldehyde acetal derivative) they are not only used as fragrance and flavor substances, but also are intermediates in many industrial processes. 

Detection and Determination of the Aldehydes.—The aldehydes present in spirits are mainly acetaldehyde, paraldehyde, formaldehyde, acetal and, in small quantities, higher homologous aldehydes (butyral-dehyde, valeraldehyde) and other aldehydes (acraldehyde, furfuraldehyde, etc.). They are detected and determined as follows ... 

Alkyl ethers of sucrose have been prepared by reaction with long-chain alkyl halides to provide mixtures of regioisomers and products of different degree of substitution.82,83 A similar reaction with chloromethyl ethers of fatty alcohols provides formaldehyde acetals.84,85 Alkenyl ethers of various carbohydrates, and notably of sucrose, can also be obtained by palladium-catalyzed telomerization of butadiene (Scheme 6).86 88 Despite a low-selectivity control, this simple and clean alternative to other reactions can be carried out in aqueous medium when sulfonated phosphines are used as water-soluble ligands. 

Methanol are commonly added Water formaldehyde, acetals, ... 

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