Formate ester formic acid

Linalyl Formate.—The formic acid ester of linalol, CjqHj OOCHj, has a distinctive odour somewhat resembling that of the acetate. It is an oil boiling at 189° to 192°, and is prepared by treating linalol with formic acid, but the reaction is not complete and commercial samples are never pure esters. 

Terpinyl Formate.—The formic acid ester of terpineol, CjeHj-OOCH, occurs naturally in Ceylon cardamom oil. It is prepared artificially by... 

Other complications can also arise. For example, in the separation of anthocyanins and anthocyanin-rich fractions, it is advisable to avoid acetonitrile and formic acid — acetonitrile is difficult to evaporate and there is a risk of ester formation with formic acid. 

Alkyl formates or formic acid and its esters can be converted to trialkyl orthothioformates [74-77] which in turn can be converted to trialkyl orthoformates in good yields [78, 79], It has been reported that acid chlorides of higher carboxylic acids can also be converted to trialkyl orthothioformates [80], but thus far no reports appear in the literature on attempts to convert them to trialkyl ortho esters. 

Synonyms Formic acid 2-Propenyl ester Formic acid Allyl ester Allyl alcohol Formate... 

The ammonium formate in formic acid procedure has rendered possible the first preparation of isomeric 4,5-disubstituted oxazoles.03101 Bredereck, Gompper, and Reich101 have reported the anomalous behavior of certain long-chain a-bromo ketones a single a-bromo ketone on reaction with ammonium formate in formic acid gives a mixture of two isomeric oxazoles. Refluxing of a-bromo ketones or of a-chloro-/3-keto esters with ammonium acetate in acetic acid results in the formation of substituted 2-methyl-oxazoles.40 102 Ethyl a-chloroacetoacetate on heating with ammonium carbonate or formamide in formic acid yields 4-methyloxazole-5-carboxylic ester.40 103... 

Beilstein Handbook Reference) AI3-24240 BRN 1738888 EINECS 208-818-1 FEMA No. 2197 Formic acid, 2-methylpropyl ester Formic acid, isobutyl ester Iso-butyl formate Isobutyl formate Isobutyl methanote Isobutylester kyseliny mravenci 2-Methylpropyl formate 2-Methyl-1-propyl formate NSC 6958 Tetryl formate UN2393. Industrial solvent. Liquid mpn-95.8° bp = 98.2° d O = 0.8776 slightly soluble in H2O (1 g/100 ml), CHCI3, very soluble in MezCO, freely soluble in EtOH, Et20. 

Beilstein Handbook Reference) AI3-15407 BRN 1735844 EINECS 210-901-2 FEMA No. 2944 Formic acid, 1-methylethyi ester Formic acid, isopropyl ester HSDB 6401 Isopropyl formate Isopropyl methanoate 1-Methylethyl formate NCI-C60106. Liquid bp = 68.2 d O = 0.8728 Am = 213 nm (e = 65, MeOH) slightly soluble in H2O, CCI4, soluble in CHCI3, very soluble in Me2CO, freely soluble in EtOH, EtzO. 

Synonyms Benzyl alcohol formate Benzyl methanoate Formic acid benzyl ester Formic acid phenylmethyl ester... 

Synonyms Citronellyl methanoate 3,7-Dimethyl-6-octen-1-ol formate 2,6-Dimethyl-2-octen-8-yl formate 3,7-Dimethyl-6-octen-1-yl formate Formic acid, citronellyl ester Formic acid-3,7-dimethyl-6-octen-1-yl ester Empirical C11H20O2 Formula C10H19OOCH... 

Formic acid, citronellyl ester Formic acid-3,7-dimethyl-6-octen-1-yl ester. See Citronellyl formate... 

Reduction of the double bond of (2-pyridyl)acrylates (XI-53) without reducing the ester group in order to obtain 2-pyridylpropionates (XI-54) was accomplished in good yields by using either a mixture of phosphorus with 57% hydriodic acid in acetic acid" or by hydrogenation over platinum oxide" or 10% palladium-on-carbon in acetic acid. Treatment of the betaine of either the 2- or 4-pyridineacrylate (XI-S5) with fused potassium formate in formic acid also... 

The hydrolysis of carboxylic esters (RCOOR ) is one of the most intensively studied classes of chemical reaction due to its interest in chemistry, biology, and industrial processes [1]. Methyl formate (HCOOCH3) is the simplest of these esters, and has found major appUcations. Due to its small size, this ester has been employed as a test case in both experimental and theoretical investigations. The reaction in a neutral aqueous medium [2], studied in the present work, leads to the formation of formic acid and methanol via different pathways. Since most hydrogen transfers occur in aqueous solution, one must consider the role of water molecules in this... 

A considerable amount of the formic acid, however, still remains behind in the distilling-flask as the unhydrolysed monoformate. Therefore, if time allows, dilute the residue in the flask with about an equal volume of water, and then steam-distil, the monoformate ester being thus completely hydrolysed and the formic acid then driven over in the steam. Collect about 400 ml. of distillate. Add this distillate to that obtained by direct heating of the reaction mixture and then treat with lead carbonate as described above. Total yield of lead formate is now about 40 g. 

Ethyl formate. Reflux a mixture of 61 g. (50 ml.) of A.R. formic acid (98/100 per cent.) and 31 g. (39-5 ml.) of absolute ethyl alcohol for 24 hours. Transfer to a Claisen flask with fractionating side arm (or attach a fractionating column to the flask), distil and collect the liquid passing over below 62°. Wash the distillate with saturated sodium bicarbonate solution and saturate with salt before removing the ester layer. Dry with anhydrous sodium or magnesium sulphate, filter, and distil. The ethyl formate passes over at 53-54°. The yield is 36 g. 

J-unsaturated ester is formed from a terminal alkyne by the reaction of alkyl formate and oxalate. The linear a, /J-unsaturated ester 5 is obtained from the terminal alkyne using dppb as a ligand by the reaction of alkyl formate under CO pressure. On the other hand, a branehed ester, t-butyl atropate (6), is obtained exclusively by the carbonylation of phenylacetylene in t-BuOH even by using dppb[10]. Reaction of alkynes and oxalate under CO pressure also gives linear a, /J-unsaturated esters 7 and dialkynes. The use of dppb is essen-tial[l 1]. Carbonylation of 1-octyne in the presence of oxalic acid or formic acid using PhiP-dppb (2 I) and Pd on carbon affords the branched q, /J-unsatu-rated acid 8 as the main product. Formic acid is regarded as a source of H and OH in the carboxylic acids[l2]. 

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) ... 

This reaction occurs readily ia the presence of sulfuric or hydrofluoric acid. In the absence of such strong acids, formic acid reacts readily with olefins to give formate esters (21). 

Formic acid is currently produced iadustriaHy by three main processes (/) acidolysis of formate salts, which are ia turn by-products of other processes (2) as a coproduct with acetic acid ia the Hquid-phase oxidation of hydrocarbons or (3) carbonylation of methanol to methyl formate, followed either by direct hydrolysis of the ester or by the iatermediacy of formamide. 

Formic acid is used as an intermediate in the production of a number of dmgs, dyes, flavors, and perfume components. It is used, for example, in the synthesis of aspartame and in the manufacture of formate esters for flavor and fragrance appHcations. 

Uses ndReactions. Dihydromyrcene is used primarily for manufacture of dihydromyrcenol (25), but there are no known uses for the pseudocitroneUene. Dihydromyrcene can be catalyticaUy hydrated to dihydromyrcenol by a variety of methods (103). Reaction takes place at the more reactive tri-substituted double bond. Reaction of dihydromyrcene with formic acid gives a mixture of the alcohol and the formate ester and hydrolysis of the mixture with base yields dihydromyrcenol (104). The mixture of the alcohol and its formate ester is also a commercially avaUable product known as Dimyrcetol. Sulfuric acid is reported to have advantages over formic acid and hydrogen chloride in that it is less compUcated and gives a higher yield of dihydromyrcenol (105). 

When dihydromyrcene is treated with formic acid at higher temperatures (50°C) than that required to produce dihydromyrcenol and its formate, an unexpected rearrangement occurs to produce a,3,3-trimethylcyclohexane methanol and its formate (106). The product is formed by cyclization of dihydromyrcene to the cycloheptyl carbonium ion, which rearranges to give the more stable cyclohexyl compound (107). The formate ester, a,3,3-trimethylcyclohexane methanol formate [25225-08-5] (57) is a commercially avaUable product known as Aphermate. 

Acid moieties include formic acid itself, formates and orthoesters, formamide, DMF dimethyl acetal and ethyl diethoxyacetate, acids, acid chlorides and anhydrides, the last including a rare [3,4-oxalate esters, 2-acyl or 2-ethoxycar-bonyl derivatives e.g. 180) are formed. 

The stereoselective reactions in Scheme 2.10 include one example that is completely stereoselective (entry 3), one that is highly stereoselective (entry 6), and others in which the stereoselectivity is modest to low (entries 1,2,4, 5, and 7). The addition of formic acid to norbomene (entry 3) produces only the exo ester. Reduction of 4-r-butylcyclohexanone (entry 6) is typical of the reduction of unhindered cyclohexanones in that the major diastereomer produced has an equatorial hydroxyl group. Certain other reducing agents, particularly sterically bulky ones, exhibit the opposite stereoselectivity and favor the formation of the diastereomer having an axial hydroxyl groi. The alkylation of 4-t-butylpiperidine with benzyl chloride (entry 7) provides only a slight excess of one diastereomer over the other. 

The formate ester of phenol is rarely formed, but can be prepared from the phenol, formic acid, and DCC, 94-99% yield. The formate ester is not very stable to basic conditions or to other good nucleophiles. ... 

The common name of an ester consists of two words. The first word (methyl, ethyl,...) is derived from that of the alcohol the second word (formate, acetate,...) is the name of the acid with the -ic suffix replaced by -ate. Thus ethyl formate (Table 22.4) is made from ethyl alcohol and formic acid ... 

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