Half-esters

Diacids and Half-esters. - A research group led by Gais has given full accounts of their work on the PLE-catalysed asymmetric 

A new route to racemic 2-arylsuccinic acids consists of condensations between 3-nitrostyrenes (33) and the enamine (34) subsequent acidic hydrolysis of the resulting adducts (cone. HC1, reflux) then gives the diacids (35) in good to excellent yields.  

A milder hydrolysis procedure would clearly extend the scope of this method. Dye-sensitised photo-oxygenation in methanol can be used to 

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Cool the flask in ice, acidify with 10 ml. of cold 1 1-hydro-chloric acid and distil under reduced pressure (water pump) until most of the alcohol is removed. Add water to the residue, extract several times with ether, wash the combined ethereal extracts with N ammonia solution until a test portion gives no precipitate upon acidification. Extract the combined alkahne solutions once with a fresh portion of ether, and add the aqueous solution to an excess of dilute hydrochloric acid the final mixture should still be acidic to Congo red. Collect the crystalhne half-ester by filtration at the pump, wash it with water and dry at 100°. The yield is 14-5 g., m.p. 122-125°. Recrystallise by dissolving in about 40 ml. of warm benzene and adding an equal volume of petroleum ether (b.p. 40- 60°) 13 -5 g. of the colourless half-ester, m.p. 125-126°, are obtained. 

Electrolysis, under similar conditions, of a mixture of two carboxylic acids RCOOH and R COOH leads, in addition to normal coupling products R—R and R —R, to cross coupling R—R. If a mixture of a saturated carboxylic acid and a half ester of an ato-dicarboxylic acid is electrolysed, there are three main products, viz., a hydrocarbon (I), a mono-ester (II), and a di-ester (HI) and these are readily separable by distillation. Some unsaturated ester (IV) is often present in small quantity. 

The organotin maleate and maleate half-ester derivatives also exhibit this bleaching effect reportedly by a Diels-Alder addition reaction (18). The reaction is specific to the organotin maleates other organotin carboxylates containing normal dieneopltiles fail to produce similar results (19). 

Phtha/k anhydride is the most important type of dibasic acid derivative ki alkyd preparation because of its low cost and the excellent overall properties it imparts to the reski. The anhydride stmcture allows a fast esterification to form half-esters at relatively low reaction temperatures without hberatkig water, thereby avoiding the danger of excessive foaming ki the reactor. However, skice the two carboxyl groups of phthaUc anhydride are ki the ortho position to each other on the benzene ring, cycHc stmctures may and do occur ki the reski molecules. 

Studies of reaction mechanisms ia O-enriched water show the foUowiag cleavage of dialkyl sulfates is primarily at the C—O bond under alkaline and acid conditions, and monoalkyl sulfates cleave at the C—O bond under alkaline conditions and at the S—O bond under acid conditions (45,54). An optically active half ester (j -butyl sulfate [3004-76-0]) hydroly2es at 100°C with iaversion under alkaline conditions and with retention plus some racemization under acid conditions (55). Effects of solvent and substituted stmcture have been studied, with moist dioxane giving marked rate enhancement (44,56,57). Hydrolysis of monophenyl sulfate [4074-56-0] has been similarly examined (58). 

Sulfated Natural Oils and Fats. Sulfated natural triglycerides were the first nonsoap commercial surfactants introduced in the middle of the nineteenth century. Since then sulfates of many vegetable, animal, and fish oils have been investigated (see also Fats AND FATTY oils). With its hydroxyl group and a double bond, ricinoleic acid (12-hydroxy-9,10-octadecenoic acid) is an oil constituent particularly suited for sulfation. Its sulfate is known as turkey-red oil. Oleic acid is also suited for sulfation. Esters of these acids can be sulfated with a minimum of hydrolysis of the glyceride group. Polyunsaturated acids, with several double bonds, lead to dark-colored sulfation products. The reaction with sulfuric acid proceeds through either the hydroxyl or the double bond. The sulfuric acid half ester thus formed is neutralized with caustic soda ... 

PMVEMA, supphed as a white, fluffy powder, is soluble in ketones, esters, pyridine, lactams, and aldehydes, and insoluble in aUphatic, aromatic, or halogenated hydrocarbons, as well as in ethyl ether and nitroparaffins. When the copolymer dissolves in water or alcohols, the anhydride group is cleaved, forming the polymers in free acid form or the half-esters of the corresponding alcohol, respectively. Table 7 illustrates the commercially available alternating copolymers and derivatives. 

International Specialty Products (ISP) suppHes ethyl, isopropyl, and -butyl half-esters of PMVEMA as 50% solutions in ethanol or 2-propanol. Typical properties are shown in Table 8. These half-esters do not dissolve in water but are soluble in dilute aqueous alkaU and in aqueous alcohoHc amine solutions. The main appHcation for the half-esters is in hairsprays where they combine excellent hair-holding properties at high humidity without making the hair stiff or harsh. These half-esters are easily removed during shampooing, have a very low order of toxicity, and form tack-free films that exhibit good gloss, luster, and sheen (see Hair preparations). 

Table 8. Typical Properties of Alcohol Solutions of the Half-Esters of PMVEMA...

Industrial Synthetic Improvements. One significant modification of the Stembach process is the result of work by Sumitomo chemists in 1975, in which the optical resolution—reduction sequence is replaced with a more efficient asymmetric conversion of the meso-cyc. 02Lcid (13) to the optically pure i7-lactone (17) (Fig. 3) (25). The cycloacid is reacted with the optically active dihydroxyamine [2964-48-9] (23) to quantitatively yield the chiral imide [85317-83-5] (24). Diastereoselective reduction of the pro-R-carbonyl using sodium borohydride affords the optically pure hydroxyamide [85317-84-6] (25) after recrystaUization. Acid hydrolysis of the amide then yields the desired i7-lactone (17). A similar approach uses chiral alcohols to form diastereomic half-esters stereoselectivity. These are reduced and direedy converted to i7-lactone (26). In both approaches, the desired diastereomeric half-amide or half-ester is formed in excess, thus avoiding the cosdy resolution step required in the Stembach synthesis. 

Starch succinates [39316-70-6] are also used as thickening agents in foods. The 1-octenylsuccinate half-ester [52906-93-17, sold as its sodium salt [66829-29-6], has surface active (emulsifying) properties. 

From the presence of uronic acid, sulfate half-ester, pymvyl cycUc acetal, or succinate half-ester groups. 

Use of an intermediate as a starting reactant. Again taking Scheme IX as an example, if intermediate B is stable enough to be isolated or synthesized, its reaction to give C ean be studied independently of its formation from A. (This requires that the A —> B step be irreversible). For example, in the overall hydrolysis of a diester, the intermediate is the half-ester, which usually can be synthesized to serve as a reactant in a separate study,... 

One of the few nonnitrogenous compounds to show spasmolytic activity is a rather simple chromone. Acylation of the phenolic ketone, 31, with the half ester-half acid chloride from oxalic... 

Catalytic reduction of the nitrile 79 in the presence of semicarbazide affords initially the semicarbazone of 80. Hydrolysis-interchange, for example in the presence of pyruvic acid, gives the aldehyde 80. Condensation with the half ester of malonic acid leads to the acrylic ester 81 the double bond is then removed by means of catalytic reduction (82). Base catalyzed reaction of the... 

One such compound, bropirimine (112), is described as an agent which has both antineo-plastic and antiviral activity. The first step in the preparation involves formation of the dianion 108 from the half ester of malonic acid by treatment with butyllithium. Acylation of the anion with benzoyl chloride proceeds at the more nucleophilic carbon anion to give 109. This tricarbonyl compound decarboxylates on acidification to give the beta ketoester 110. Condensation with guanidine leads to the pyrimidone 111. Bromination with N-bromosuccinimide gives bropirimine (112) [24]. 

The reactions of olefins with peracids to form epoxides allows for the selective oxidation of carbon-carbon double bonds in the presence of other functional groups which may be subject to oxidation (for example, hydroxyl groups). The epoxides that result are easily cleaved by strong acids to diols or half-esters of diols and are therefore useful intermediates in the synthesis of polyfunctional compounds. 

The general procedures for the preparations of half-esters of diols are not usually very efficient in that both unreacted diol and diester are present along with the desired half-ester. Unfortunately, the present example is no exception but is included as an illustration of the type of results that can be expected under these circumstances. The diol employed for this reaction is prepared in Chapter 5, Section II. 

Docosanedioic acid has been prepared by Wolff-Kishner reduction of 6,17-diketodocosanedioic acid, formed by reaction of the half-ester acid chloride of adipic acid with the a,co-cadmium derivative of decane (%26 overall yield).3 Reduction of Wolff-Kishner method, followed by simultaneous reduction and desulfurization with Raney nickel of the 2,5-bis(co-carboxyoctyl)thiophene pro-... 

Primary alcohol sulfates are half esters of sulfuric acid. These substances are relatively simple organic molecules and have been known for a long time. The first alcohol sulfate was prepared by Dumas in 1836 [1] but long-chain alcohol sulfates were not used as surfactants until the 1930s [2]. 

Basically, the production of half esters of sulfuric acid involves the introduction of the -S03H group by replacement of the O-H bond with an O-S bond, according to the general reaction [Eq. (1)] ... 

Alcohol sulfates are half esters of sulfuric acid and contain a C-O-S bond in the molecule. This bond is only relatively stable in water and can hydrolyze, mainly under acidic conditions. The hydrolysis is favored by temperature as was proven in the study of Maurer et al. with octadecyl sulfuric acid [57]. They found that a 0.05 M solution in distilled water at 100°C hydrolyzed to 50% in less than 30 min, whereas at 60°C the hydrolysis was 10% after 3 h and 16% after 7 h. 

Scheme 6 Regioisomeric possibilities during sulfosuccinate formation of the maleic half ester.

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