Dinitriles imides

Diphenyl- -dinitril 508 -diphenylmethylimid 255 2-Fluor-3-oxo- -diathylester 2/7 2-Hydroxy- -dimethylester 204 2-Hydroxy- -propylimid 257 -imide 255... 

The efficient conversion of the furazans (70) into 1,4-dinitriles (71) is thought to occur via the nitrile oxides (72). Thermal decomposition of the diaziridones (73) in the presence of triethyl phosphite gives the phosphine-imine (75) and the isocyanate (74), which subsequently react together to give the carbodi-imide (76). ... 

Carbonsaure-nitrile konnen mit starken Alkylierungsmitteln [z. B. Trifluor-methansulfonsaure-methylester222,223, Eisen(IIl)-chlorid/2-Chlor-propan224] zu den entsprechenden Nitrilium-Sal-zen umgesetzt werden. Aus N-Methyl-acetnitrilium-trifluormethansulfonat und Diamino-ma-leinsaure-dinitril erhalt man je nach Reaktionsbedingungen 5-Amino-4-aminocarbonyl-l,2-dimethyl-, 5-Amino-4-cyan-l,2-dimethyl- oder 5-Amino-4-(cyan-imino-methyl)-l,2-dimethyl-imid-azol222 223. 

When dinitrile 19 was subjected to Pinner reaction conditions, and the imidate was then hydrolyzed, the desired 7 was obtained quantitatively and as a single diastereomer (Scheme 7). Only the equatorial CN group of 19 underwent the Pinner reaction the axial CN group remained complete-... 

The preparation of amide hydrazones is quite simple, by mixing corresponding nitriles (or dinitriles) and hydrazine (1 1.5 molar ratio) in ethanol at room temperature and then allowing the mixture to stand overnight. This is called the direct method. The yield by this method is normally good (>90%). If this method does not work, the so-called indirect method can be used, in which a nitrile, e.g., malononitrile, is converted into its imidate then reacted with hydrazine. In early references (e.g., Case, 1965150), anhydrous or 95% hydrazine was employed. We have found that 85% hydrazine hydrate still works without any difference in yield. Common recrystallization solvents are benzene or toluene. The amide hydrazones are stable to moisture, and so some amide hydrazones can be recrystallized from water, but they are sensitive to light and heat. As an example, we observed that picolinamide hydrazone (white crystals) partially turns into an orange compound, which has been identified as 3,6-picolin-(2H)-tetrazine. 

Diamino-1 H-pyrazole sind aus Malonsaure-dinitril und Hydrazinen direkt nicht er-haltlich. Zur Synthese geht man von Malonsaure-bis-[imid]-diestern aus, die durch Pinner-Reaktion aus Malonsaure-dinitril zuganglich sind438 439. 

Dichlor-6-hydroxy-2-acctoxv- -dinitril 971 -[2-inethoxy-oxiranyl-(2)-imid] 1177... 

By heating 4-amino-6-(cyanomethyl)-2-(trichloromethyl)pyrimidine-5-carbonitrile in a mixture of acetic and sulfuric acid the conversion into 4-aminopyrido[4,3-ring closure to the cyclic imide together with the substitution of the trichloromethyl group.516... 

Aromatic nitriles can be thermally selectively polymerized in pyrrolidin-2-one at temperatures above 200 C. Between 200 and 350 °C trimerization to 2,4,6-triaryl-l,3,5-triazines occurs, while at temperatures above 300 °C imidization occurs resulting in nonmelting, linear polyaryl-carbimine. Mixtures of trimers and polymeric imines are separable by sublimation or extraction with aromatic hydrocarbons.180 Since aryltriazines and polymeric aryltriazines have various industrial applications, several catalytic systems have been developed for the trimerization of aromatic nitriles and dinitriles, e.g. metal chlorides,181 iron(II) or iron(lll) cyanide,182 cop-per(II) carbonate,183 and molten zinc(II) chloride.184... 

The parent imide 24 (R = H) has also been prepared by ammonolysis of the diester 26. The resultant diamide 27 gave the imide on pyrolysis. Reaction of the imide 24 (R = H) with isopropylamine is reported to give the diamide 28. No pyrolysis experiment has, however, been reported on this compound. Treatment of the dinitrile 29 with ammonia in the... 

Coumarin ring formation presumably by way of an intermediate imide accompanied the demethylation of the dinitrile shown with aluminium chloride in chlorobenzene by refluxing for 3.5 hours to afford a 96% yield of 3-cyano-5-hydroxy-7-pentylcoumarin (ref. 148). 

In addition, other preparation methods of polyimides use bis(methylol imide) in reaction with diamines, diisocyanates, or dinitrile compounds, according to the scheme shown in Figure 3.7. 

The dinitriles for the preparations of (320) to (323), were best obtained from the appropriate dibromoalkane and the sodium 4-cyanophenate. In the subsequent Pinner reaction it was found that an excess of ethanol was needed to get good yields of the ethyl imidate salt and a large excess of alcoholic ammonia ensured efficient conversion to the amidine since the imidate base reacts preferably with ammonia, but any traces of the salt tend to react with solvent to give the triethyl orthoester [39(U392], 4-Bromophenol reacted with K CN in the presence of copper(II) sulphate and sodium bicarbonate to give radioactive 4-hydroxybenzonitrile which was converted by the above procedure to pentamidine labelled at the... 

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... 

The first approach (i) is well applicable in most cases, since the phthalocyanine macrocycle is usually easily prepared by template cyclotetramerization of a suitable synthon 2 derived from phthalic acid 4 its anhydride 5, imide 6, diamide 7, or more reactive dinitrile 8 or diiminoimide 9 (Scheme 2). 

The precursor for a-octafluorophthalocyanines [MPc Fg], 3,6-difluorophtha-lonitrile 33 can be prepared starting from the commercially available 2,5-difluoro-benzoylchloride 27, which was hrst transformed to diethylamide 28 (80 %), then carboxylated to amidoacid 29 (80 %) and converted to 3,6-difluorophthalic anhydride 30 (62 %) [20] (Scheme 8). The latter was melted with urea at 125-130 °C to afford imide 31 (93 %), converted upon treatment with 25 % aqueous NH3 to diamide 32 (60 %), which was dehydrated with SOCI2 in DMF to dinitrile 33 (74 %) [16]. The Zn" complex [ZnPc Fg] (34) was then prepared by heating of the dinitrile 33 with Zn" acetate in DMF in the presence of DBU (29 %) [16]. 

Later a modified procedure for the preparation of 3,6-bis(trifluoromethyl) phthalodinitrile 83b was elaborated [67] (Scheme 23), which starts from 2,5-bis(trifluoromethyl)benzoyl chloride 86 and includes its conversion to N,N-diethylamide 87, carboxylation of the latter in the presence of 2,2,6,6-tetramethylpiperidine, followed by direct formation of the imide 81b ( 59 % overall yield). The diamide 82b obtained with liquid NH3 treatment (28 % yield), was then converted to dinitrile 83b with triflic anhydride in dioxane (yield... 

The dinitrile precursors for p-tetra- and p-octatrifluoromethylphlhalocyanines [MPcP(CF3)4] and [MPci (CF3)g] (Scheme 24) were obtained [69] starting from the mono(bis)trifluoromethyl substituted acetylenes 88a,b and 2,3-dimetylbutadiene 89 which easily give the Diels-Alder products 90a,b. These adducts were converted quantitatively upon dehydrogenation with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) to o-xylene derivatives 91a,b. Their oxidation Cr03 in a mixture of acetic and sulfuric acids affords the phthalic acids 91a,b (yield ca. 80 %) which were converted to dinitriles 96a,b and diiminoimides 97a,b in a common way through intermediate anhydrides 93a,b, imides 94a,b, diamides 95a,b. 

Milberger EC, Wong EKT (1983) Nitrogenation of hydrocarbons to produce cyclic imides and dinitriles. European Patent Applieation EP 82620 A2 19830629... 

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