Succinic anhydride preparation

Block (cap) residual lysine residues with a carboxylic acid by acylation using succinic anhydride prepared in l-methyl-2-pyrrolidinone,... 

TABLE 1. Selected polypropylene succinic anhydrides prepared using polypropylene containing an ene terminus and maleic anhydride. 

In the following preparation, this reaction is exemplified by the union of anthracene with maleic anhydride, to form 9,io-dihydroanthracene-9,io-e do-a -succinic anhydride note that as a result of this reaction both the outer rings of the anthracene system become truly aromatic in character. 

The preparation of the cyclic ketone a-tetralone possesses a number of interesting features. Succinic anhydride is condensed with pure benzene in the presence of anhydrous aluminium chloride (slightly over two equivalents see 1 above) to yield (3-benzoylpropionlc acid ... 

Friedel-Crafts acylation of 3,3-dimethyl-2-indolinone by succinic anhydride gives 3,3-dimethyl-5-(3-catboxyptopionyl)-2-indoline, which is used as an intermediate in the preparation of inotropic agents for treatment of heart failure (94). Antibacterial phlotophenone derivatives have been prepared by Friedel-Crafts acylation with ptopanoyl chlotide (95). 

Typical reaction conditions are 150 to 300°C and up to 2 MPa pressure. Polyalkenyl succinic anhydrides are prepared under these conditions by the reaction of polyalkenes in a nonaqueous dispersion of maleic anhydride, mineral oil, and surfactant (33). 

V-Alkyl or A/-aryl succinimides can be prepared from the corresponding amines (107) or from succinic anhydride, ammonia, and the corresponding alcohol (108). Succinimides are also obtained by vapor-phase hydrogenation of the corresponding maleimides ia the presence of a catalyst (109). 

Succinic anhydride can be prepared from succinic acid by dehydration it operates in high boiling solvent (31), in the presence of clays as a catalyst (32), or at room temperature with triphosgene (33). 

The total consumption of succinic acid and succinic anhydride in 1990 was 1,500 t in the United States, 2,500 t in Europe, 7,500 t in Japan, and 1,500 t in other countries. Production was 500 t in the United States, 2,500 t in Europe, and 11,000 t in Japan. The total installed capacity is in the 18,000—20,000-t/yr range. The total consumption decreased slightly between 1990 and 1994 mainly because of the replacement of succinic acid by fumaric acid in bath preparations, which is one of the main uses of succinic acid in Japan. The principal producers are Buffalo Color in the United States, Lon2a SpA and Chemie Tin 2 in Europe, Kawasaki Kasei, Nippon Shokubai, Takeda Chemical, Kyowa Hakko, and New Japan Chemical in Japan. 

Friedel-Crafts Acylation. The Friedel-Crafts acylation procedure is the most important method for preparing aromatic ketones and thein derivatives. Acetyl chloride (acetic anhydride) reacts with benzene ia the presence of aluminum chloride or acid catalysts to produce acetophenone [98-86-2], CgHgO (1-phenylethanone). Benzene can also be condensed with dicarboxyHc acid anhydrides to yield benzoyl derivatives of carboxyHc acids. These benzoyl derivatives are often used for constmcting polycycHc molecules (Haworth reaction). For example, benzene reacts with succinic anhydride ia the presence of aluminum chloride to produce P-benzoylpropionic acid [2051-95-8] which is converted iato a-tetralone [529-34-0] (30). 

Cellulose esters of aromatic acids, aUphatic acids containing more than four carbon atoms and aUphatic diacids are difficult and expensive to prepare because of the poor reactivity of the corresponding anhydrides with cellulose Httle commercial interest has been shown in these esters. Of notable exception, however, is the recent interest in the mixed esters of cellulose succinates, prepared by the sodium acetate catalyzed reaction of cellulose with succinic anhydride. The additional expense incurred in manufacturing succinate esters is compensated by the improved film properties observed in waterborne coatings (5). 

Alkyl-substituted succiiiimides are prepared by reaction of alkyleneamines such as TETA or TEPA with the corresponding alkyl substituted succinic anhydride (43). 

With the saturated analogs, i.e. succinic anhydride and its derivatives, pyridazines are formed in only a few cases. The reaction has been applied to the preparation of perhydro-pyridazines and their 3,6-diones (68MI21200, 70JOC1468). For the synthesis of 4,5-dihalopyridazinones, /3-formylacrylic acids, for example mucochloric acid, are useful syn-thons (Scheme 80). 

Furazan 1 was first prepared and characterized in 1964 by melting glyoxime 2 with succinic anhydride in 57% yield (64JA1863, 65JOC1854). Its A-oxide, furoxan 3, has been in a focus of attention for chemists for more than a century, but was synthesized only in 1994 by oxidation of 2 with dinitrogen tetroxide in dichloromethane in 45% yield (94MC7) (Scheme 1). The A-oxide cannot be prepared by direct oxidation of furazan. 

E) Preparation of 2-( 1-Succinyloxyethyl)-3-Methyl-5-(2-Oxo-2,5-Dihydro-4-Furyl)Bemo[b] -Furan (409 CBj 8.65 grams of compound 3574 CB in 43 ml of pyridine are warmed for 30 minutes, on a water bath, with succinic anhydride. At the end of this, the pyridine is stripped off in vacuo. The mixture is treated with dilute sulfuric acid and with ether, the crystalline product filtered off, washed with water and with ether, and recrystallized from ethyl acetate (9.35 grams). MPq = 144°C (measured after drying at 90°C and 0.1 mm). Yield 77%. The product yields an equimolecular compound with morpholine. MPc= 136°C (from ethyl acetate). 

Greco et al. [50] studied the effect of the reactive compatibilization technique in ethylene propylene rubber-polyamide-6 blends. Binary blends of polyamide-6-ethylene propylene rubber (EPR) and a ternary blend of polyamide-6-EPR-EPR-g-succinic anhydride were prepared by the melt mixing technique, and the influence of the degree of grafting of (EPR-g-SA) on morphology and mechanical properties of the blends was studied. 

Aroylation of 3-arylhydrazonoisatin with aroyl chlorides gave 1043, which cyclized with ammonium acetate to give [1,2,4]triazino[5,6-A>]indole 1044 (92MI1). Derivatives of 1045 were prepared (92MI1). Cyclocondensation of 5-ethyl-3-hydrazino-5/f[l,2,4]triazino[5,6-b]indole 165 with succinic anhydride in acetic acid gave pyridazinedione derivative 1046 (90MI7) (Scheme 197). 

FIGURE 8 Cumulative release of methylene blue (o), [1,4 - 14c] succinic acid (a), and polymer weight loss ( ) from polymer discs prepared from 3,9-bis(ethylidene-2,4,8,10-tetraoxaspiro[5,5Jundecane) and a 50 50 mole ratio of trans - cyclohexane dimethanol and 1,6-hexanediol at pH 7.4 and 37°C. Polymer contains 0.1 wt% [1,4 — [succinic anhydride and 0.3 wt% methylene blue. (From Ref. 

Hydroxamic acids are an important class of compounds targeted as potential therapeutic agents. A-Fmoc-aminooxy-2-chlorotrityl polystyrene resin 61 allowed the synthesis and subsequent cleavage under mild conditions of both peptidyl and small molecule hydroxamic acids (Fig. 14) [70]. An alternative hydroxylamine linkage 62 was prepared from trityl chloride resin and tV-hydroxyphthalimide followed by treatment with hydrazine at room temperature (Scheme 30) [71]. A series of hydroxamic acids were prepared by the addition of substituted succinic anhydrides to the resin followed by coupling with a variety of amines, and cleavage with HCOOH-THF(l 3). 

PLLA-fr-PCL) multiblock copolymers were prepared from the coupling reaction between the bischloroformates of carboxylated PLLA with diol-terminated PCL in the presence of pyridine [140]. LLA was polymerized with SnOCt2 and 1,6-hexanediol followed by the reaction with succinic anhydride to provide the dicarboxylated PLLA. The carboxyl end groups were subsequently transformed to acid chloride groups by the reaction with thionyl chloride (Scheme 65). As expected, the molecular weight distributions were broad for all samples (1.84 < Mw/Mn < 3.17). 

Variation of Equivalent Weight. In an attempt to produce more flexible coatings, the UPE A formulation was modified to increase the equivalent weight by substituting succinic anhydride for a portion of the maleic anhydride. These unsaturated polyesters were prepared by the same method as above and the compositions and their properties are summarized in Table II. 

Maleate/vinyl ether formulations based on a model unsaturated polyester prepared from maleic anhydride and 1,5-pentane diol and triethylene glycol divinyl ether were studied. At molecular weights of less than about 10,000 the cured films were extremely brittle. When the equivalent weight of the unsaturated polyester was increased by replacing some of the maleic anhydride with succinic anhydride, measurable values for film elongation could be obtained but the cure speed was definitely slower. When either diethyl maleate or isobutyl vinyl ether were added as monofunctional diluents the cure dose needed to obtain 200 MEKDR was increased and the flexibility measured by pencil hardness increased as the amount of diluent was increased. A urethane vinyl ether was synthesized and used to replace DVE-3 and films with increased elongation were obtained at equivalent at dosages as low as 1 J/cm2. 

Mitsubishi have reported several processes based on Ru-catalyzed hydrogenation of anhydrides and acids. Succinic anhydride can be converted into mixtures of 1,4-butane-diol and y-butyrolactone using [Ru(acac)3]/trioctylphosphine and an activator (often a phosphonic acid) [97]. Relatively high temperatures are required ( 200°C) for this reaction. The lactone can be prepared selectively under the appropriate reaction conditions, and a process has been developed for isolating the products and recycling the ruthenium catalyst [98-100]. 

While Diehl et al. (2001) agree that the addition of DMSO to print buffer improves spot uniformity, they argue that DMSO is also toxic and a good solvent for other materials. As a result, they explored alternative chemistries to replace DMSO and also to improve upon postprint blocking conditions in an effort to find a replacement for borate-NMP (l-methyl-2-pyrrolidinone) buffer used for preparing solutions of succinic anhydride for capping of residual amine groups. 

Octahydrodibenzothiophene (73) has been prepared by the following sequence. Friedel-Crafts acylation of 4,5,6,7-tetra-hydrobenzo[6]thiophene with succinic anhydride (87%) or with the ester chloride of succinic acid followed by hydrolysis (80%), yields the keto acid (74). Huang-Minlon reduction of 74 followed by cyclization of the derived acid chloride with stannic chloride yields l-keto-1,2,3,4,6,7,-8,9-octahydrodibenzothiophene (53) (Section V,A). Reduction of 53 gives 73 as a solid (overall yield 32%). 

The diacylation of isopropenyl acetate with anhydrides of dicarboxylic acids is applicable for the synthesis of several other cyclic jS-triketones in moderate yield. - It has been used for the synthesis of 2-acetylcyclohexane-l,3-dione (40% yield), 2-acetyl-4-methylcyclopentane-l,3-dione (10% yield), 2-acetyl-4,4-dimethylcyclopentane-l,3-dione (10% yield), 2-acetyl-5,5-dimethylcyclohexane-l,3-dione (10% yield), 2-acetylcyclo-heptane-l,3-dione (12% yield) and 2-acetylindane-l,3-dione (26% yield). Maleic anhydrides under more drastic conditions give acetylcyclopent-4-ene-l,3-diones in yields from 5% to 12%. The corresponding acylation of the enol acetate of 2-butanone with succinic anhydride has been used to prepare 2-methylcyclopentane-l,3-dione, an important intermediate in steroid synthesis. - ... 

The main group of methods for the preparation of a 1,2,4-oxadiazole ring is based on cyclization of amidoxime derivatives in the presence of acylating agents °. A surprisingly easy cyclization of O-benzoyl-/ -piperidinopropioamidoxime 247 to oxadiazole 248 in DMSO at room temperature was described (equation 107) . 3-(3-Aryl-1,2,4-oxadiazol-5-yl)propionic acids 250 were obtained by the reaction of amidoximes 249 with succinic anhydride under microwave irradiation or conventional heating (equation 108) °°. 

Other electrophiles such as succinic anhydride," imines," " or 2-(2-amino-methylene)-3-indolinones" have also been used to prepare 5(47f)-oxazolones. 

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