Dicarboxylic acids unsaturated

A dispersant that can be used in drilling fluids, spacer fluids, cement slurries, completion fluids, and mixtures of drilling fluids and cement slurries controls the rheologic properties of and enhances the filtrate control in these fluids. The dispersant consists of polymers derived from monomeric residues, including low-molecular-weight olefins that may be sulfonated or phosphonated, unsaturated dicarboxylic acids, ethylenically unsaturated anhydrides, unsaturated aliphatic monocarboxylic acids, vinyl alcohols and diols, and sulfonated or phosphonated styrene. The sulfonic acid, phosphonic acid, and carboxylic acid groups on the polymers may be present in neutralized form as alkali metal or ammonium salts [192,193]. 

R. A. Grey. Process for preparing alternating copolymers of olefini-cally unsaturated sulfonate salts and unsaturated dicarboxylic acid anhydrides. Patent US 5210163, 1993. 

The reactivity of microgels resides in terminal carboxyl acid groups and in residual unsaturated dicarboxylic acid groups of the EUP-component. Due to sterical hindrance, presence of less reactive maleic acid units and deactivation of termi-... 

This technique has been used to obtain many liquid polyester resins based on glycols and unsaturated dicarboxylic acids. In... 

A few important unsaturated dicarboxylic acids are shown in Figure 12-3. The position of the acid groups in a dicarboxylic acid is significant ... 

A variety of dicarboxylic acids have been measured in air, including, for example, oxalic acid [(COOH)2], succinic acid [HOOCCH2CH2COOH], and malonic acid [HOOCCH2COOH], as well as larger straight-and branched-chain carboxylic acids unsaturated and aromatic acids such as phthalic acid are also observed in smaller concentrations (e.g., see Kawamura et al., 1996a, 1996b). Because of their lower vapor pressures, they are found predominantly in particles (see Chapter 9). 

An unsaturated dicarboxylic acid is doubly esterified with a chiral diol, leading to the macro-cyclic diolidc 1. Sequential formation of both enolates and methylation proceeds with high diastereofacial selectivity, which is induced by the relatively rigid conformation of the 12-mem-... 

MixedPhosphonate Esters. Unsaturated, mixed phosphonate esters have been prepared from monoesters of 1,4-cyclohexanedimethanol and unsaturated dicarboxylic acids. For example, maleic anhydride reacts with this diol to form the maleate, which is treated with benzenephosphonic acid to yidd an unsaturated product. These esters have been used as flame-retardant additives for thermoplastic and thermosetting resins (97). 

Saturated monobasic Tally adds Unsaturated monobasic fatly acids Propioloic acid series Dicarboxylic acids, where n = 0 for oxalic acid... 

Reaction XXXm. (b) Condensation of Malonic Adds with Aldehydes or some Ketones under the influence of Primary or Secondary Amines. (B., 35,1143.)—This is an example of the activating effect of two 1 3 oxy groups on a methylene group between them. In the presence of primary or secondary amines—e.g., ethylamine, di-ethylamine, piperidine— malonic acid condenses with aldehydes and some ketones to give unsaturated dicarboxylic acids. It is probable that the amine reacts first with the aldehyde, water being eliminated. 

The stereochemistry of addition to unsaturated dicarboxylic acids has also been examined (equations 93 and 94).130,143... 

As for the unsaturated carbonyl compounds, the most significant groups are the oc,/ -unsaturated acids or esters. Some of their methods of formation are closely analogous, for example, (a) the Horner-Emmons or Wadsworth-Emmons reaction, and (b) the aldol-type reactions. Rather more specific methods are considered below for the formation of a,/ -acetylenic acids, and for the conversion of the unsaturated dicarboxylic acid, maleic acid, into its anhydride or into fumaric acid. 

The simplest unsaturated dicarboxylic acids are maleic acid and fumaric acid, both of which are cheap, commercially available, materials. They are geometric isomers maleic acid is the (Z) isomer (19), and fumaric acid is the (E) isomer (20). Maleic acid forms an internal anhydride, maleic anhydride (21), which is widely used to form adducts with conjugated dienes (the Diels-Alder reaction, Section 7.6). The formation of the anhydride from maleic acid and the conversion of maleic acid into fumaric acid are described in Expt 5.218. The hydrogenation of maleic acid to succinic acid is of value as a means of evaluating the activity of a catalyst for use in hydrogenations at atmospheric pressure the experimental procedure is given in Section 2.17.1, p. 87. 

As a preliminary step in the manufacture of unsaturated polyester thermoset plastic one uses low molecular weight linear polyester (Mr 10,000) obtained by a polycondensation of polyglycols with saturated and unsaturated dicarboxylic acids. The precondensate can then be dissolved and stored in the stabilized comonomer, e.g. styrene, with which it will be crosslinked later. The crosslinking polymerization reaction between the polyester chains and the styrene bridges is initiated with the help of organic peroxides which are added dispersed in plasticizers. The reaction begins at 60-90 °C and then proceeds exothermally. In addition to this a cold hardening reaction can also be carried out. For this reaction cold accelerators are necessary, e.g. tertiary amines or cobalt naphthenate. 

This method also works well with unsaturated dicarboxylic acids containing odd carbon chains such as (271) which react with the benzene-1,2-dithiol (270) in the presence of phosphorus oxychloride and perchloric acid giving colored methine salts of type (272)... 

Fumaric acid (unsaturated C4 dicarboxylic acid) Universal - a tricarboxylic acid (TCA) cycle intermediate Helianthus annuus (Asteraceae), Pisum sativum (Fabaceae), Averrhoa carambola (Oxalidaceae), Glauciumflavum (Papaveraceae), Malus domestica (Rosaceae) LOX (wheat germ competitive)... 

The ability to accept electrons from donors is particularly pronounced in acrylic acid derivatives [85] its alkyl esters [78, 87, 88], acrylonitrile [88], acrylamide, hydroxylacrylates [85], and further in styrenes substituted with an electronegative atom or group m-nitrostyrene, 2,6-dichlorostyrene [86], / -nitrostyrene [89] bicyclobutane-1-carbonitrile [89] lactones /J-propio-Iactone [85], sulfolactone vinyl ketones [87] unsaturated dicarboxylic acids and their derivatives diethyl fumarate, fumaronitrile [90], ROOC—N— N—COOR [86], cyclic anhydrides of diacids [91 ], particularly maleic anhydride [78, 92] ethylenes substituted with electronegative groups [93, 95]... 

Asymmetric induction also takes place in the cinchona catalyzed addition of thioacetic acid to a,/3-unsaturated dicarboxylic acid esters. Both the reaction rate and optical purity of the addition products are influenced by the nature of the alkoxy or thioalkoxy group in the unsaturated substrate. Generally, thioesters are more reactive towards thioacetic acid and better enantioselectivities are observed for unhindered esters11. 

Ozonolysis as used below is the oxidation process involving addition of ozone to an alkene to form an ozonide intermediate which eventually leads to the final product. Beyond the initial reaction of ozone to form ozonides and other subsequent intermediates, it is important to recall that the reaction can be carried out under reductive and oxidative conditions. In a general sense, early use of ozonolysis in the oxidation of dienes and polyenes was as an aid for structural determination wherein partial oxidation was avoided. In further work both oxidative and reductive conditions have been applied . The use of such methods will be reviewed elsewhere in this book. Based on this analytical use it was often assumed that partial ozonolysis could only be carried out in conjugated dienes such as 1,3-cyclohexadiene, where the formation of the first ozonide inhibited reaction at the second double bond. Indeed, much of the more recent work in the ozonolysis of dienes has been on conjugated dienes such as 2,3-di-r-butyl-l,3-butadiene, 2,3-diphenyl-l,3-butadiene, cyclopentadiene and others. Polyethylene could be used as a support to allow ozonolysis for substrates that ordinarily failed, such as 2,3,4,5-tetramethyl-2,4-hexadiene, and allowed in addition isolation of the ozonide. Oxidation of nonconjugated substrates, such as 1,4-cyclohexadiene and 1,5,9-cyclododecatriene, gave only low yields of unsaturated dicarboxylic acids. In a recent specific example... 

Our know-how , achieved by the oxidative cleavage of 1-octene, was then used to convert co-unsaturated fatty acids to dicarboxylic acids. 

Carboxylic Acids and their Derivatives.—2,3-Seco-A -unsaturated dicarboxylic acids (443), obtained by ozonolysis of 2-hydroxymethylene-4-en-3-ones, have been considered rather resistant to cyclisation to form the A-nor-3-en-2-one system (444). Two convenient methods for achieving such a reaction are now described. Dieckmann condensation of the dimethyl ester (445) was successful with sodium hydride, in toluene containing a little methanol. The 5-methoxy-carbanion (446), resulting from conjugate addition of methoxide ion, is suggested as a possible activated intermediate. Alternatively, the diacid (in the B-nor-series)... 

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