Monocarboxylic acid ester

Esters for lubricant applications are divided into five groups monocarboxylic acid esters (monoesters), dicarboxylic acid esters (diesters), glycerol esters, polyol esters, and complex esters. 

Acutally, better yields of the monocarboxylic acid esters are obtained by pyrolyzing the half-neutralized acid instead of the dipotassium salt. Even so, the yield of ester is only about 25%. 

Beilstein Handbook Reference) BRN 2004306 Caswell No. 715 Chrysanthemum mono-carboxylic acid pyrethrolone ester EINECS 204-455-8 EPA Pesticide Chemical d)de 069001 HSDB 6302 Piretrina 1 Pyrethrin I Pyrethrine I Pyrethrins Pyrethrolone, chrysanthemum monocarboxylic acid ester Pyrethronyl (+)-trans-chrysanthemate Pyrethrum RCRA waste number POOS. Registered by EPA as an insecticide. Viscous liquid bpo.1 = 170° d = 1.5192 [a]8 -14° (isooctane) km = 225 nm (e 36400 95% EtOH) insoluble in H2O, soluble in ElOH, petroleum ether, kerosene, CCI4, ethylene dichloride, nitromethane LDso (rat orl) = 584 - 900 mg/kg, (mus orl) = 273 - 796 mg/kg, (rat der) > 1500 mg/kg, (rbt der) = 5000 mg/kg highly toxic to fish toxic to bees, with repellent effect. 

GC of pyrrolizidine alkaloids was extensively investigated by Chalmers et al. (1965) using packed columns. They described the analysis of 58 underivatized monocarboxylic acid esters and macrocyclic diester alkaloids and derivatives. 

Synonyms Chrysanthemum monocarboxylic acid pyrethrolone ester Cyclopropanecarboxylic acid, 2,2-dimethyl-3-(2-methylpropenyl)-, ester with 4-hydroxy-3-methyl-2-(2,4-pentadienyl)-2-cyclopenten-1-one Pyrethrolone, chrysanthemum monocarboxylic acid ester (+)-Pyrethronyl (+)-trans-chrysanthemate Classification Pyrethrins (natural)... 

Pyrethrins. See Pyrethrum Pyrethrolone, chrysanthemum dicarboxylic acid methyl ester ester. See Pyrethrin II Pyrethrolone, chrysanthemum monocarboxylic acid ester. See Pyrethrin I Pyrethrolone ester of chrysanthemum dicarboxylic acid monomethyl ester. See Pyrethrin ii... 

In the case of reactions of halo-p-monocarboxylic acid esters with tinfoil, on the other hand, the carbonyl oxygen coordinates to the tin atom as the first step. It is considered that the coordination to the metal causes metal activation in the tin atom. C-Br activation and a cychzation reaction then proceed with the oxidative addition reactions of C and Br with the tin atom, as shown in Eq. (6.8) [26]. 

Besides nickel and cobalt, almost all of the catalysts discussed in the last chapter which were suited for the formation of free acids can be applied, e. g. rhodium, palladium and, with certain restrictions, iron. Cobalt hydrocarbonyl catalyzes the stoichiometric ester synthesis at mild reaction conditions [35, 121]. The initially formed acylcobalt carbonyls react rapidly with alcohols even at 50 °C and, in the presence of Na-alcoholate, even at 0 °C to give esters [121]. Dienes with isolated double bonds react with carbon monoxide and alcohols at mild reaction conditions in the presence of Pd/HCl to give unsaturated monocarboxylic acid esters and at more severe conditions to give saturated dicarboxylic acid esters [508]. 

Also trienes such as cyclododecatriene-1,5,9 yield mono- and dicarboxylic acid esters [488, 509]. Cyclododecane tricarboxylic acid esters are formed with bis-triphenyl phosphine palladium dichloride as catalyst [448]. The catalyst can be recycled [517]. Nearly quantitative syntheses of monocarboxylic acid esters of cyclododecadiene and of tricarboxylic acid esters of cyclododecane can be achieved with complex Pd-catalysts. 

By increasing the molar proportion of the monocarboxylic acid, the yield of (II) is improved. Thus electrolysis of a mixture of decanoic acid (n-decoic acid capric acid) (V) (2 mols) and methyl hydrogen adipate (VI) (1 mol) in anhydrous methanol in the presence of a little sodium methoxide gives, after hydrolysis of the esters formed, n-octadecane (VII), tetradecanoic or myristic acid (VIH) and sebacic acid (IX) ... 

Hydrogenolysis of the diallyl alkylmalonate 757 with formic acid in boiling dioxane affords the monocarboxylic acid 758. Allyl ethyl malonates are converted into ethyl carboxylates[471]. The malonic allyl ester TV-allylimide 759 undergoes smooth deallylation in refluxing dioxane to give the simple imide 760(472]. The allyl cyanoacetate 761 undergoes smooth decarboxylation to give... 

Esters of nonenolizable monocarboxylic acids such as ethyl benzoate give p diketones on reaction with ketone enolates... 

Constitution of Yohimbine and its Isomerides. The yohimb alkaloids are methyl esters of acids. Yohimbine, yohimbene, mesoyohimbine (isoyohimbine) and y-yohimbine (table, p. 502) are hydrolysed to four, distinct, monocarboxylic acids, C2,yH2402N2, each of which on decarboxylation by heating with soda-lime yields yohimbol, long supposed to be a secondary alcohol, Ci,yH240N2, but which Witkop has shown to be a ketone and has re-named yohimbone, C18H22ON2, m.p. 307° (dec.),... 

From both economic and ecological points of view, substances derived from esters of monocarboxylic acids sulfonated in the a position form an interesting class of surfactants [1]. The general formula of these a-sulfomonocarboxylic esters, also called a-sulfo fatty acid esters or, in short, a-ester sulfonates, is Rj-CH(S03Me)-C00-R2 (with Rj and R2 = alkyl groups, Me = alkali metal). 

If only the monocarboxylic acid is required, the ester after hydrolysis with potash may be strongly acidified with sulphuric acid and the mixture heated under reflux the mineral acid promotes decarboxylation at a temperature just above 100°. The net result is the replacement of the halogen atom of the alkyl halide by —CHjCOOH thus in the above example ... 

Esters of Q to Cn monocarboxylic acids [1288-1292], acid-methyl esters [1282], and polycarboxylic acid esters [1287], as well as oleophilic monomeric and oligomeric diesters [1293], have been proposed as basic materials for inverted emulsion muds. Natural oils are triglyceride ester oils [1844] and are similar to synthetic esters. Diesters also have been proposed [1293-1297]. 

The copolymers may be mixed with other demulsifiers, in particular with alkoxylated novolaks and copolymers that are obtainable by copolymerization of one or more polyoxyalkylene ethers of allyl or methallyl alcohol with vinyl esters of alkyl monocarboxylic acids. 

H. Muller, C. P. Herold, and S. von Tapavicza. Monocarboxylic acid-methyl esters in invert-emulsion muds (Monocarbonsaure-Methylester in Invert-Bohrspiilschlammen). Patent EP 382071,1990. 

Systematic studies150,153 with CLX50, (7), decyl esters of pyridine monocarboxylic acids (8)-(10), and dipentyl esters of pyridine dicarboxylic acids (11)—(15) showed that extraction of Cu11 is strongly dependent on the activity of water and the total concentration of ionic and molecular species in the aqueous phase. For the monoesters, copper distribution is dependent on... 

Reaction of malonic esters with 1,2-dibromoethane and 1,3-dibromopropane under liquiddiquid two-phase conditions produces the cyclopropane- and cyclobutane- 1,1 -dicarboxyl ic esters, which can be hydrolysed under the basic conditions (6.2.24.C) [e.g. 75, 109] and decarboxylated to give the monocarboxylic acid [e.g. 109]. 

Treatment of either the sc or the ap atropisomer of the diester (97) with potassium hydroxide effected the hydrolysis of only one of the ester groups for steric reasons, to afford monocarboxylic acid sc-98 and ap-98, respectively. The sc isomer was converted into a nienthyl ester (99) for resolution into optical isomers. Thus the three rotameric forms of the monocarboxylic acid ( + sc, -sc, ap) were isolated (142). 

Composition. Rosin is primarily a complex mixture of monocarboxylic acids of alkylated hydrophenanthrene nuclei. These constituents, known as resin acids, represent about 90% of rosin. The resin acids are subdivided into two types, based on their skeletal structure. The abietic-type acids contain an isopropyl group pendent from the carbon numbered 13. The pimaric-type acids have a methyl and vinyl group pendent from the same carbon atom. Figure 1 shows the structure of typical resin acids abietic acid, C20H30O2 (1) is predominant. The remaining 10% of commercial rosin consists of neutral materials that are either hydrocarbons or saponifiable esters. These materials are derived from resin acids by decarboxylation or esterification. 

Kolbe electrolysis is generally useful for the formation of hydrocarbons from monocarboxylic acids and for the preparation of many difunctional compounds as well. A specific illustration is the synthesis of esters of long-chain dicarboxylic adds from monoesters of appropriate dicarboxylic acids (see p. 33). A number of these syntheses are discussed by Fichter.4 In the present preparation, a two-compartment cell is employed to avoid, or at least greatly reduce, undesired reduction of the nitro group at the cathode. It seems likely that the procedure could be adapted to the preparation of other difunctional compounds containing groups that are easily reduced. 

Esters. The monoisobutyrate ester of 2,2,4-trimethyl- 1,3-pentanediol is prepared from isobutyraldehyde in a Tishchenko reaction (58,59). Diesters, such as trimethylpentane dipelargonate (2,2,4-trimethylpentane 1,3-dinonanoate), are prepared by the reaction of 2 mol of the monocarboxylic acid with 1 mol of the glycol at 150—200°C (60,61). The lower aliphatic carboxylic acid diesters of trimethylpentanediol undergo pyrolysis to the corresponding ester of 2,2,4-trimethyl-3-penten- l-ol (62). These unsaturated esters reportedly can be epoxidized by peroxyacetic acid (63). 

To a soln of the methyl ester of 13[120 (0.032-0.114 mmol) in 25% aq MeOH (1-2 mL) was added 1M LiOH (1.2 equiv). The resulting mixture was stirred at rt for 1-2 h and then concentrated under reduced pressure. The residue was dissolved in H20 (15 mL) and carefully acidified to pH 2 with 1 M HC1. The resulting soln was extracted with CH2C12 (3 x 15 mL), and the combined organic fractions were dried (MgS04) and concentrated in vacuo to give the monocarboxylic acid yield 61-88%. 

Kishner1 studied the reaction of the Orignard reagent sn the ester of cyclopropane monocarboxylic acid, he obtained a compound which ne considered to be cyclopropyldii.iethylcaJbinol.and from this ht obtained an uneaturated hydrocarbon,cyclop/opylmethyl-ethylene, CHg - CH - C CHS The cyclic struc-... 

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