Acid chloride, alcohols from hydrolysis

Acid anhydride-diol reaction, 65 Acid anhydride-epoxy reaction, 85 Acid binders, 155, 157 Acid catalysis, of PET, 548-549 Acid-catalyzed hydrolysis of nylon-6, 567-568 of nylon-6,6, 568 Acid chloride, poly(p-benzamide) synthesis from, 188-189 Acid chloride-alcohol reaction, 75-77 Acid chloride-alkali metal diphenol salt interfacial reactions, 77 Acid chloride polymerization, of polyamides, 155-157 Acid chloride-terminated polyesters, reaction with hydroxy-terminated polyethers, 89 Acid-etch tests, 245 Acid number, 94 Acidolysis, 74 of nylon-6,6, 568... 

The dibenzosuberyl ether is prepared from an alcohol and the suberyl chloride in the presence of triethylamine (CH2CI2, 20°, 3 h, 75% yield). It is cleaved by acidic hydrolysis (1 N HCl/dioxane, 20°, 6 h, 80% yield). This group has also been used to protect amines, thiols, and carboxylic acids. The alcohol derivative can be cleaved in the presence of a dibenzosuberylamine. ... 

Examples for necessary process improvements through catalyst research are the development of one-step processes for a number of bulk products like acetaldehyde and acetic acid (from ethane), phenol (from benzene), acrolein (from propane), or allyl alcohol (from acrolein). For example, allyl alcohol, a chemical which is used in the production of plasticizers, flame resistors and fungicides, can be manufactured via gas-phase acetoxylation of propene in the Hoechst [1] or Bayer process [2], isomerization of propene oxide (BASF-Wyandotte), or by technologies involving the alkaline hydrolysis of allyl chloride (Dow and Shell) thereby producing stoichiometric amounts of unavoidable by-products. However, if there is a catalyst... 

Dimethylaminoethane-2-ol (20) is a compound that, by virtue of its nucleophilic center (Me2NH+C2H40), is employed to convert protected segments bound to supports as benzyl esters into acids by transesterification into dimethylaminoethyl esters [C(=0)0C2H4NMe2] that are hydrolyzable by a dimethylformamide-water (1 1) mixture. Compound 20 readily forms esters from acid chlorides. The hydrolysis and esterification are facilitated by anchimeric assistance by the adjacent nitrogen atom (see Section 2.10). The amino alcohol also reacts with dichloromethane. 

Dinitrocubane (28) has been synthesized by Eaton and co-workers via two routes both starting from cubane-l,4-dicarboxylic acid (25). The first of these routes uses diphenylphos-phoryl azide in the presence of a base and tert-butyl alcohol to effect direct conversion of the carboxylic acid (25) to the tert-butylcarbamate (26). Hydrolysis of (26) with mineral acid, followed by direct oxidation of the diamine (27) with m-CPBA, yields 1,4-diiutrocubane (28). Initial attempts to convert cubane-l,4-dicarboxylic acid (25) to 1,4-diaminocubane (27) via a Curtins rearrangement of the corresponding diacylazide (29) were abandoned due to the extremely explosive nature of the latter. However, subsequent experiments showed that treatment of the acid chloride of cubane-l,4-dicarboxylic acid with trimethylsilyl azide allows the formation of the diisocyanate (30) without prior isolation of the dangerous diacylazide (29) from solution. Oxidation of the diisocyanate (30) to 1,4-dinitrocubane (28) was achieved with dimethyldioxirane in wet acetone. Dimethyldioxirane is also reported to oxidize both the diamine (27) and its hydrochloride salt to 1,4-dinitrocubane (28) in excellent yield. ... 

Numerous methods for the synthesis of salicyl alcohol exist. These involve the reduction of salicylaldehyde or of salicylic acid and its derivatives. The alcohol can be prepared in almost theoretical yield by the reduction of salicylaldehyde with sodium amalgam, sodium borohydride, or lithium aluminum hydride by catalytic hydrogenation over platinum black or Raney nickel or by hydrogenation over platinum and ferrous chloride in alcohol. The electrolytic reduction of salicylaldehyde in sodium bicarbonate solution at a mercury cathode with carbon dioxide passed into the mixture also yields saligenin. It is formed by the electrolytic reduction at lead electrodes of salicylic acids in aqueous alcoholic solution or sodium salicylate in the presence of boric acid and sodium sulfate. Salicylamide in aqueous alcohol solution acidified with acetic acid is reduced to salicyl alcohol by sodium amalgam in 63% yield. Salicyl alcohol forms along with -hydroxybenzyl alcohol by the action of formaldehyde on phenol in the presence of sodium hydroxide or calcium oxide. High yields of salicyl alcohol from phenol and formaldehyde in the presence of a molar equivalent of ether additives have been reported (60). Phenyl metaborate prepared from phenol and boric acid yields salicyl alcohol after treatment with formaldehyde and hydrolysis (61). 

Diphenylacetic acid has been obtained by the reduction of benzilic acid with hydriodic acid and red phosphorus by the treatment of phenylbromoacetic acid with benzene and zinc dust, or with benzene and aluminum chloride by the hydrolysis of diphenylacetonitrile by heating a-diphenyldichloroethyl-ene with alcoholic sodium ethylate by heating benzilic acid from diphenylmethane, mercury diethyl, sodium and carbon dioxide by the oxidation of a,a,S,S-tetraphenyl- 8-butine by the decomposition of some complex derivatives obtained from diphenylketene by the hydrolysis of diphenyl-5,5-hydan-toin 0 by the treatment of diphenylbromoacetic acid with copper by the oxidation of dichlorodiphenylcrotonic acid. ... 

Bromo-2-isopropylanisole (191) was prepared from p-bromoanisole (190). It was caused to react with magnesium and ethylene oxide to obtain the alcohol (192). Its bromoderivative on heating with diethylmalonate and sodium ethoxide followed by hydrolysis with alcoholic potassium hydroxide yielded the substituted malonic acid. This on heating furnished acid (193). Its acid chloride in benzene underwenr cyclization with aluminium chloride to yield tetralone (194). It was... 

Homophthalic acid has been prepared from naphthalene via phthalonic acid 1 from hydrindone by nitrosation, hydrolysis, and hydrogen peroxide oxidation 2 from hydrindene by oxidation with chromic and sulfuric acids 3 and from o-toluic acid by bromination of the acid chloride followed by treatment with alcohol and sodium cyanide and hydrolysis with 50 per cent sulfuric acid.4 Since phthalide has become commercially available, the preparation outlined above, essentially that described by Wis-licenus 5 fifty-six years ago, is by far the simplest and most economical. 

N-Acylsaccharins (13) possess a certain potential as acylating agents. They will acylate amines, but will react with water or alcohols only when acid or base is present.167 The method was used to acylate a-amino-penicillanic acid.170 Micheel162-165 has based a peptide (38) synthesis on the acyl transfer from 31 [Z = carbobenzoxy, obtained through reaction with DCC or with pseudosaccharin chloride (6) or with thionyl chloride and imidazole] to amino acids. Pseudosaccharin anhydride 323, lee js thg product of a condensation between 6 and 1, mostly from hydrolysis of 6. Formation of 32 tends to occur in nonprotic solvents with base catalysis, even when practical precautions are taken to exclude moisture. Water and protic solvents seem to shield the anion 19 and prevent attack on 6. 

Other functional groups may be present in the molecule containing the double bond. Methallyl alcohol, H2C = C(CHjX HjOH, is hydrated by a mixture of 25% sulfuric acid in the presence of isobutyraldehyde to give the cyclic acetal of isobutylene glycol with the aldehyde. Hydrolysis of the acetal by dilute mineral acid gives isobutylene glycol (94%). Hydration of the double bond by aqueous sulfuric acid has been used to make chloro-i-butyl alcohol from methallyl chloride and /S-hydroxybutyric acid from crotonic acid. ... 

Aluminum chloride and its derivatives are the most familiar Lewis acids and are routinely employed in many Lewis acid-promoted synthetic transformations. The first polymer-supported metal Lewis acids to be studied were polymers attached by weak chemical or physical interactions to a Lewis acid. In the 1970s Neckers and coworkers reported the use of styrene-divinylbenzene copolymer-supported AlCl,- or BF3 as catalyst in condensations, esterifications, and acetalization of alcohols [11,12]. This type of polymer-supported AICI3 (1) is readily prepared by impregnation of a polystyrene resin with AICI3 in a suitable solvent. Subsequent removal of the solvent leaves a tightly bound complex of the resin and AICI3. The hydrophobic nature of polystyrene protects the moisture-sensitive Lewis acid from hydrolysis, and in this form the Lewis acid is considerably less sensitive to deactivation by hydrolysis. This polymer complex could be used as a mild Lewis acid catalyst for condensation of relatively acid-sensitive dicyclopropylcarbinol to an ether (Eq. 1) [13],... 

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