Dinitriles anhydrides

Naphthalic anhydride has been prepared by the hydrolysis of the dinitrile of ,2-naphthaIic acid,1 by the oxidation of suitably substituted hydrocarbons or ketones,2 or by the dehydrogenation of the 3,4-dihydro compound with bromine 3 or with sulfur.4... 

The synthesis of dithienyl photochromes containing a maleic anhydride fragment (a furan-2,5-dione fragment) as the ethene bridge was a difficult problem. Initially, vicinal dinitriles 160 and 162 were used as the starting compounds (Scheme 49). But the latter compounds give a maleic anhydride only in the cis conformations. The separation of the cis and trans isomers is an additional time-consuming laborious problem. 

Cyclic amino acids 139, when heated in acetic anhydride, probably form initially mesoionic oxazolium 5-oxides (munchnones) subsequent 1,3-dip olar cycloaddition of 1,2-dicyanocyclobutene, loss of carbon dioxide, and opening of the cyclobutane ring lead to dinitriles 140 (80JHC1593). Pyridone 141 is the by-product (together with an indolizine) of the mono-cyclic pyridone dicarboxylate and acrylic ester (73JHC77). 

The synthesis of l,2-bis(thiophen-3-yl)maleic anhydride involves the dimerisation of a 3-cyanomethyl derivative of thiophene (1.45) by reaction with aqueous NaOH in the presence of CCl. Alkaline hydrolysis of the dinitrile (1.46) and dehydration produces the anhydride (1.47) as shown in Figure 1.12. ... 

The chemical transformation must not affect the stereogenic centers. Suitable acyclic candidates are compounds with easily convertible functional groups, such as diols, diamines, amino alcohols, dicarboxylic acids and so on. A number of procedures known before 1973 have been compiled, including conversion of diols and amino alcohols into sulfites or 1,3-dioxolanes by thionyl chloride, or acetalization with ketones31,1"319, as well as the conversions of dinitriles into imides320, dicarboxylic acids into cyclic anhydrides or imides321, and hydroxy acids into oxazolidones 322. 

Quinoxaline-2-carboxylic acid with thionyl chloride gives the acid chloride (79%), which undergoes the expected reactions.166 The gas-phase pyrolysis of quinoxaline-2,3-dicarboxylic anhydride (157) over a Nichrome coil gives o-phthalonitrile (158) (72%), probably via 2,3-quinoxalyne (159) which ring-cleaves, and the diisocyanide subsequently rearranges thermally to the dinitrile.167... 

History. Braun and Tschemak [23] obtained phthalocyanine for the first time in 1907 as a byproduct of the preparation of o-cyanobenzamide from phthalimide and acetic anhydride. However, this discovery was of no special interest at the time. In 1927, de Diesbach and von der Weid prepared CuPc in 23 % yield by treating o-dibromobenzene with copper cyanide in pyridine [24], Instead of the colorless dinitriles, they obtained deep blue CuPc and observed the exceptional stability of their product to sulfuric acid, alkalis, and heat. The third observation of a phthalocyanine was made at Scottish Dyes, in 1929 [25], During the preparation of phthalimide from phthalic anhydride and ammonia in an enamel vessel, a greenish blue impurity appeared. Dunsworth and Drescher carried out a preliminary examination of the compound, which was analyzed as an iron complex. It was formed in a chipped region of the enamel with iron from the vessel. Further experiments yielded FePc, CuPc, and NiPc. It was soon realized that these products could be used as pigments or textile colorants. Linstead et al. at the University of London discovered the structure of phthalocyanines and developed improved synthetic methods for several metal phthalocyanines from 1929 to 1934 [1-11]. The important CuPc could not be protected by a patent, because it had been described earlier in the literature [23], Based on Linstead s work the structure of phthalocyanines was confirmed by several physicochemical measurements [26-32], Methods such as X-ray diffraction or electron microscopy verified the planarity of this macrocyclic system. Properties such as polymorphism, absorption spectra, magnetic and catalytic characteristics, oxidation and reduc-... 

Two processes are commonly used for the production of copper phthalocyanine the phthalic anhydride-urea process patented by ICI [33,34] and the I.G. Farben dinitrile process [48], Both can be carried out continuously or batchwise in a solvent or by melting the starting materials together (bake process). The type and amount of catalyst used are crucial for the yield. Especially effective as catalysts are molybdenum(iv) oxide and ammonium molybdate. Copper salts or copper powder is used as the copper source [35-37] use of copper(i) chloride results in a very smooth synthesis. Use of copper(i) chloride as starting material leads to the formation of small amounts of chloro CuPc. In the absence of base, especially in the bake process, up to 0.5 mol of chlorine can be introduced per mole of CuPc with CuCl, and up to 1 mol with CuCl2. 

SUCCINIC ACID DINITRILE see SNEOOO SUCCINIC ACID, HYDROXY- see MANOOO SUCCINIC ACID, O-ISOPROPYL-O -TRIBUTYLSTANNYL ESTER see TIE600 SUCCINIC ACID PEROXIDE (DOT) see SNC500 SUCCINIC ANHYDRIDE see SNCOOO SUCCINIC-1,1-DIMETHYL HYDRAZIDE see DQD400 SUCCINIC DINITRILE see SNEOOO SUCCINIC PEROXIDE see SNC500 SUCCINODINITRILE see SNEOOO... 

An alternative mechanism may include first an O-inserhon step, followed by the transformation of the oxidized compound into the cyano-containing compound. An example might be the oxidation of butadiene to maleic anhydride followed by hydrolysis to the acid, the formation of the diamide and the oxydehydrogenation to the dinitrile. 

Ammonia and amines react with partially or fully activated carboxylic acid derivatives (acylating reagents) like acid anhydrides, acid halides, ammonium salts of monoesters, monoamides with heating, diesters under basic conditions and dinitriles after partial hydrolysis. ... 

Magnetic field effects. 331 Magnetic moment, 77, 331-32, 385 z component. 161-63 p and ft" contributions, 164-65, 170 excited stale. 158-59 Magnetic optical rotary dispersion (MORD), 142 Maleic anhydride, 420 Maleic dinitrile. 434 Maleimide. 420... 

Keywords solid-solid reaction, Diels-Alder reactions, maleic anhydride, fumaro-dinitrile, fumarodinitrile, fulvenes, orthoquinone, 9-methylanthracene, ball mill, stereospecific, stereospecific... 

Fairly high yields of coumarins are obtainable by irradiation for 4-6 h of methoxycinnamic acids in acetonitrile-water saturated with oxygen and containing naphthalene-1,4-dinitrile. Further routes to the flavone ring system continue to appear. Flavone-3-carboxylic acids are ao ssible from fi-phenoxybenzylidenemalonic acids and either sulphuric acid or trifluoroacetic acid-trifluoroacetic anhydride. Attempts to cyclize the malonic esters were less... 

Pentyl- -4-amid-l-mcthylcstcr 1002 Phenyl- -dimethylester -[2-phenyl-propyl-(2)-oxycarbonylimid 706 Tetrahydrofuranyl-(2> -anhydrid 686 Tetramcthyl- -dinitril 1123... 

Treatment of quinoxaline-2,3-dicarboxylic acid anhydrides, diesters, or dinitriles with hydrazine monohydrate gives pyridazino[4,5-h]quin-oxalines (Scheme 7). ... 

Methyl-l,5-diaminopentane, 413 Methylene chloride, 17, 182, 265, 291 2-Methyleneglutaric dinitrile, 392 Methyl ethyl ketone, 260, 454 Methyl isobutyl ketone, 525 Methyl mercaptan, 240 Methyl methacrylate, 29, 254 a-Methylnadic anhydride, 452 4-(a-Methylnadimido)-benzoic acid, 452 2-Methyl-5-nitroaniline, 454 2-Methylpentamethylenediamine, 392, 393, 399, 409 A -Methyl-4-picolinium hexafluorophosphate, 157 Methylpiperidine, 399 4-Methyl-pyrazolo[3.4-b]quinoline, 37... 

The diamines were synthesized through the aromatic nucleophilic substitution of corresponding diols with / -chloronitrobenzene or /7-fluoronitrobenzene in the presence of potassium carbonate, followed by catalytic reduction with hydrazine monohydrate and Pd/C (such as synthesis of DBAPB and DBTFAPB in Scheme 2.6). As illustrated in Scheme 2.7, bis(ether anhydride)s were prepared by a three-stage synthetic procedure starting from the nucleophilic nitrodisplacement reaction of 4-nitrophthalonitrile with diols (15A 15F, Scheme 2.7) in dry DMF in the presence of potassium carbonate at room temperature. Use of high temperature (in excess of 100 °C) was avoided as it led to dark colored products in the case of 16A 16F. The nitrodisplacement reactions led to a series of new bis(ether nitrile)s (16A 16F, Scheme 2.7). The bis(ether dinitrile)s were then hydrolyzed in an alkaline solution in the presence of hydrogen peroxide to obtain the corre-... 

Succinic anhydride, (1-octenyl)-. See 1-Octenylsuccinic anhydride Succinic anhydride, (tetrapropenyl). See Tetrapropenyl succinic anhydride Succinic dialdehyde. See Succinaldehyde Succinic dinitrile. See Succinonitrile Succinic imide. See Succinimide Succinic peroxide. See Succinic acid peroxide Succinimide... 

When some heterocyclic dicarboxylic anhydrides are heated in contact with a glowing nichrome wire, the dinitrile is formed [167] probably via a heteryne, for example, o-phthalonitrile was obtained in 72% yield from quinoxaline-2,3-dicarboxylic anhydride. 

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