Succinic diesters

A wide range of organic substrates can undergo an oxidative carbonylation reaction. Depending on reaction conditions, alkenes have been converted into -chloroalkanoyl chlorides (oxidative chloro-chlorocarbonylation) [1,2], succinic diesters (oxidative dialkoxycarbonylation) [3-20], a,/J-unsaturated esters [21,22] (oxidative monoalkoxycarbonylation), or /J-alkoxyalkanoic esters [11] (oxidative alkoxy-alkoxycarbonylation), according to Eqs. 10-13. 

Succinic diesters and acrylic esters are formed through insertion of the olefin into the Pd-C bond of an alkoxycarbonylpalladium species X - Pd - C02R (ensuing from the reaction between PdX2, CO and an alcohol R OH used as an external nucleophile, Scheme 3). Further carbon monoxide insertion, followed by nucleophilic displacement by R OH, then leads to the succinic diester (Scheme 3, path a). /J-H elimination may also take place to give the a./J-unsaluralcd ester (Scheme 3, path b). This latter pathway is followed at low carbon monoxide partial pressures. 

A CH-group, which bears vinyl and sulfide substituents, is acidic enough to be metallated by strong bases. Other d3-synthons may contain two activating functional groups in Imposition ( homoenolate -equivalents). Only one of the a-carbons is deprotonated under appropiate conditions (e.g. succinic diesters). Ano ther possibility is an acidic carbon and a non-acidic functional group in 1,3-positions (e.g. propargyl derivatives). Silyl ethers of a, -unsaturated alcohols can also be converted to anions, which react as d3-synthons (W. Oppolzer, 1976). 

Route C (Fig. 2) starts from the extremely cheap bulk agents isobutylene and maleic anhydride 4 and provides diester 9 in two steps. When in the course of process development this attractive access to the potential enzyme substrate 9 could be established, work concentrated immediately on its enantio- and regioselective monohydrolysis. Thus, the sterically more hindered ester group had to be hydrolyzed to the target monoacid (R)-2 a. Protease-catalyzed reactions with the stated specificity had already been described for several 2-substituted succinate diesters, such as 2-... 

Dianion enolates of succinate diesters show the same stereochemical behavior as simple ester enolates deprotonation with LITMP in THF gives the ( , )-enolate and deprotonation in THF-HMPA gives the (Z,Z)-enolate (Scheme 4). No mixed enolates are observed. The corresponding diamides seem to give (ZZ)-enolates. ... 

Amidation of esters. Acrylic and )3-keto amides, protected dipeptides, as well as iV,iV -diacyldiamines are accessible by the enzymatic method. Succinic diesters are converted to V-aminosuccinimides by hydrazines. 

Details are given of the use of a series of alkyl pyridinium bromide maleate and succinate diester surfactants as stabihsers in the free radical emulsion polymerisation of styrene. Latexes were examined using surface tension and TEM. 26 refs. 

From succinate diesters (Eq. 23), dimerization is preferred, and esters of long-chain aliphatic alcohols condense to functional cyclohexanediones, used in the synthesis of new organic conductors. ... 

Substitution with a bifunctional snbstituent may either form a bridge across a CD end or link two CDs together in a dimer as shown in Figure The reaction of the succinate diester 5 with either 6 -amino-(6 -deoxy-j0-CD) 6 or 3 -amino-((2 S,3 S)-3 -deoxy-j0-CD) 7 or both prodnces three succinamide linked j0-CD dimers Af,A -bis(6 -deoxy- 0-CD-6 -yl)succinamide, 8, A/ A -bis((2 S,3 S)-3 -deoxy-j0-CD-3 -yl)succinamide, 9, and Af-((2 S,3 S)-3 -deoxy-y8-CD-3 -yl)-iV -(6 -deoxy-j6-CD-6 -yl) succinamide, 11, through 6 -(3-(4-nitrophenoxycarbonyl)-propionamido)-(6 -deoxy- S-CD), 10, in 70-85% yield. A snbstantial range of linked CD dimers has been stndied. ... 

Esterification. Succinic anhydride reacts readily with alcohols to give monoesters of succinic acid, which are readily esterified to diesters by the usual methods (34—37). 

Succinic acid diesters are also obtained by one-step hydrogenation (over Pd on charcoal) and esterification of maleic anhydride dissolved in alcohols (40) carbonylation of acrylates in the presence of alcohols and Co complex catalysts (41—43) carbonylation of ethylene in alcohol in the presence of Pd or Pd—Cu catalysts (44—50) hydroformylation of acetylene with Mo and W complexes in the presence of butanol (51) and a biochemical process from dextrose/com steep Hquor, using Jinaerobiumspirillum succiniciproducens as a bacterium (52). 

The synthesis of 2-hydroxycyclobutanone was chosen as a model for the use of a trapping agent because diethyl succinate was the most accessible of 1,2-diesters and because the hydrolysis step for this compound is more difficult than most. Procedures developed for succinoin have been found broadly applicable in preparation of other sensitive acy loins. 

Diesters dimethyl malonate, dimethyl succinate, dimethyl glu-tarate, and dimethyl adipate... 

Most researchers currently agree that the hydrido mechanism is more common than the alkoxycarbonyl path in the alkoxycarbonylation of alkenes with palladium systems. However, carbalkoxy complexes are putative intermediates in carbonylation reactions giving succinates and polyketone diesters, with metals like Co, Rh, or Pd.137... 

Diesters and even triesters have been converted to bis- and tris(cyclopropanol)s, respectively. Dimethyl succinate gave the bis (cyclopropanol) derivative 17 in 80% yield, while triethyl trans-cyclopropanetricarboxylate (18) yields the tris (cyclopropanol) 19 (90%) (Scheme 11.4 selected examples in Table 11.2) [77,78], Higher homologous dicarboxylic acid diesters are likewise smoothly converted with ethylmagnesium bromide in the presence of Ti(OiPr)4 to provide the corresponding bis (cyclopropanol) s [71,78]. 

We discovered another synthetic technique that involves the conversion by direct fluorination of hydrocarbon polyesters to perfluoropolyesters followed by treatment with sulfur tetrafluoride to produce new perfluoropolyethers.42 The first paper in this area ofreasearch reported that conversion of poly(2,2-dimethyl-1,3-propylene succinate) and poly( 1,4-butylene adipate) by using the direct fluorination to produce novel branched and linear perfluoropolyethers, respectively. The structures are shown in Figure 14.6. The second paper concerns the application of the direct fluorination technology base directed toward oligomers, diacids, diesters, and surfactants.43... 

Reactions of wood with cyclic anhydrides do not yield a by-product, leaving the modified wood polymers with a covalently bonded carboxylic group an example is reaction with succinic anhydride (SA) (Figure4.1a). With reactions above 100°C there is some formation of diester observed (Figure 4.1b), resulting in cross-linking within the cell wall matrix (Matsuda, 1987). 

Miscellaneous Compounds. A saturated spirocychc pyrrohdine serves as the nucleus for a diamine that has been described as a hypohpemic agent. Treatment of the carbanion of the substituted cylcohexane carboxyhc ester (20-1) with methyl bromoacetate leads to the alkylation and formation of the diester (20-2). Saponification of the ester groups followed by reaction with acetic anhydride leads to ring closure of the succinic anhydride (20-3). Condensation with ammonia leads to the succinimide (20-4). The side chain is then added by alkylation of the anion on nitrogen with l-bromo-4-dimethylaminobutane (20-5). Reaction of this last intermediate with lithium aluminum hydride leads to the reduction of the carbonyl groups to methylene. This affords the pyrrolidine (20-6) atiprimod [22]. 

---