Phthaloyl chlorides

Acid Chloride Formation. Monoacid chlorides of maleic and fumaric acid are not known. Treatment of maleic anhydride or maleic acid with various reagents such as phosgene [75-44-5] (qv), phthaloyl chloride [88-95-9] phosphoms pentachloride [10026-13-8] or thionyl chloride [7719-09-7] gives 5,5-dichloro-2(5JT)furanone [133565-92-1] (4) (26). Similar conditions convert fumaric acid to fumaryl chloride [627-63-4] (5) (26,27). NoncycHc maleyl chloride [22542-53-6] (6) forms in 11% yield at 220°C in the reaction of one mole of maleic anhydride with six moles of carbon tetrachloride [56-23-5] over an activated carbon [7440-44-4] catalyst (28). 

Cychc diacyl peroxides can be generated from suitable dibasic acid chlorides and sodium or hydrogen peroxide, especially in dilute solutions (187,205), eg, 2,3-ben2odioxin-l,4-dione [4733-52-2] from phthaloyl chloride ... 

Phthalic anhydride and diethyl phthalate are easily converted with hydrazine into 4-hydroxyphthalazin-l(2/f)-one. Its substituted derivatives have been prepared using substituted hydrazines, substituted phthalic anhydrides, or diesters or disodium salts of substituted phthalic acids (Scheme 81). However, condensation of phenylhydrazine with phthalic anhydride gives only a small amount of the corresponding phthalazine, the main product being 2-anilinophthalimide. This can be rearranged in the presence of base into the phthalazine derivative. For the preparation of 2,3-disubstituted derivatives, 1,2-disub-stituted hydrazines are reacted with the appropriate phthalic anhydrides or phthaloyl chlorides. Derivatives of 4-amino- or 4-hydrazino-phthalazin-l(2iT)-one have been prepared either from the corresponding monothiophthalimide and 3-aminoisoindolin-3-one (1S4) or from ethyl 2-cyanobenzoate (155) and hydrazine hydrate (Scheme 82). Similarly,... 

Freshly opened bottles of diehloroacetyl chloride from Aldrich Chemical Company, Inc., were used. The acid chloride can also be prepared by the dropwiae addition of 1 volume of dichloroacetic acid to 2.5 volumes of phthaloyl chloride heated to 140°. After the addition is complete, the solution is vigorously heated and diehloroacetyl chloride, b.p. 106-108°, is distilled through a 30-cm. column packed with glass beads the yield is 85%. 

Adriamycin release from BSA chemically crosslinked with tere-phthaloyl chloride was studied by Sawaya et al. (113). The unusual aspect of these studies is that incorporation was accomplished by immersing the crosslinked microspheres in a solution of the drug. 

A hydrolysis of seven tons of phthaloyl chloride that was carried out in a herbicide synthesis workshop went out of control and detonated, causing the workshop to be destroyed. 

Interfacial or solution polycondensation, with or without stirring, was the general procedure utilized for the preparation of the polyamides and polyureas.l a Details are given in Table I. An important point to be noted is that, in the unstirred interfacial condensation polymerization of 1 with sebacoyl chloride or tere-phthaloyl chloride in the organic phase and triethylamine as the proton acceptor, immediate film formation took place at the interface. The polyamide films were removed after 1 h, dried, and utilized for taking electron micrographs. 

Finally, in the presence of triethylamine as the base, phthaloyl chloride has been used with a primary phosphine (1-adamantylphos-phine) for the preparation of a diacylphosphine that is an analogue of an iV-substituted phthalimide.358... 

Phthalocyanine blues, 14 318 Phthalocyanine Green, pigment for plastics, 7 367t Phthalocyanine green, 14 318 Phthaloyl chlorides, 19 715 pH values... 

Commercial phthaloyl chloride contains about 94 per cent of halide and some phthalic anhydride. The amount of chloride specified corresponds to a slight molar excess. 

According to the submitters, yields of the order of 95 per cent of other acid chlorides can be obtained by the use of phthal-oyl chloride (1 mole of chloride to 1 mole of a monobasic acid, 2 moles of chloride to 1 mole of a dibasic acid). Zinc chloride, as catalyst, is not necessary in the reaction of most acids and their anhydrides with phthaloyl chloride. When acids are used, it is best to add one of the components slowly, in order to avoid a too violent evolution of hydrogen chloride on wanning. 

Fumaryl chloride has been prepared from fumaric acid and phthaloyl chloride,3 from maleic acid by the action of thionyl chloride in the presence of zinc chloride, and from maleic anhydride by the use of phthaloyl chloride in the presence of zinc chloride.4... 

Phenylbenzbyldiazomethane, 48 Phenyl cinnamate, 77 o-Phenylenediamine, 10 Phosphorus oxychloride, 11 Phosphorus trichloride, 106 Photoflood lamps, 84, 104 Phthalic anhydride, 70 Phthalic monoperacid, 70 Phthaloyl chloride, 51 a-Picoline, 79... 

With some lots of phthaloyl chloride, owing to the presence of an unknown impurity, the first few drops of the distillate have a reddish color. If the distillation is interrupted and air admitted... 

The proposed formation of 2,5-benzothiazocine-l,6-diones (114 R = Pr) from the reaction of phthaloyl chloride (112) and amidino thioamides (113 R = Pr, Ar = 4-O2NC6H4, 4-MeOC6H4) in pyridine has been disproved. Instead, supported by an X-ray structure, the products have been shown to be spiro[4,4]lactones (116 R = Pr, Ar = 4-O2NC6H4, 4-MeOCeH4). The proposed mechanism of formation of... 

Although a two-step synthesis of l,l -(l,3-phenylene)bis-(3-phenyl-2-propyn-l-one) (1,3-PPPO) has been reported [8], we found that 1,3-PPPO could also be prepared from a one-step route, starting from iso-phthaloyl chloride and phenylacetylene, employ-... 

Both phthaloyl chloride and the unsymmetrical isomer 38 give an almost quantitative yield of the two isomers 39 and 40 on reduction [174, 175], Each of these... 

Heterocyclic secondary enamines and dicarboxylic acid dichlorides undergo complex, ring-size-dependent annulation reactions that, in the case of ester 238 and phthaloyl chloride (Scheme 57), lead to lactone-containing derivative 239 (02T2821). 

An interesting formation of a 1,3-dioxan -one from a geminal dichloride and salicylic acid is displayed in Scheme 103. Langer et al. have found that phthaloyl chloride cleanly reacted with salicylic acid. The product was not the expected nine-membered ring but spirotetracycle 219 in 82% yield. The product formation can be explained by assuming an initial equilibration of phthaloyl chloride and 3,3-dichloro-3//-isobenzofuran-l-one <2001EJ01511>. 

Benzodiazocine and dibenzo[Z>,/][ 1,4]diazocine-diones (220) and (218) are obtained by condensation of diethyl succinate and phthalate, respectively, with o-phenylenediamine (69JOC2138). Contrary to an early report, the use of phthaloyl chloride leads to other products and not the tricyclic diazocine. The dibenzo derivative is also formed in the oxidation of diazabiphenylene (219) (78T495). Ring contraction of (218) occurs readily on heating or on treatment with PCI5 or with base. 

Much better yields have been obtained by using phthaloyl chloride to trap the eliminated nitrite ion and tetraphenylphosphonium bromide as a catalyst in the fluoride substitution reactions.140 The less easily accessible 3-fluorobenzonitrile derivatives have been prepared this way. Table 6 illustrates some of the nitro derivatives which have been transformed into fluoro analogs in good yield.140... 

Similarly, only by using phthaloyl chloride as the trapping agent for the eliminated nitrite ion, could 3,5-dinitro-l-(trifluoromethyl)benzene (13) be converted to 3-fluoro-5-nitro-l-(trif-luoromethyl)benzene (14) in good yield.141... 

Disodium hexafluorosilicate converts phthaloyl chloride into phthaloyl fluoride in 51.5 % yield.15 Disodium and barium hexafluorosilicate can be used for the preparation of chloro-fluoromethanes. Thus, heating carbon tetrachloride with disodium hexafluorosilicate or barium hexafluorosilicate in an autolave under high pressure gives a mixture where dichlorodi-... 

Hydroperoxide groups can be generated previously on the Nylon monomer, e.g. oxidizing the tertiary carbon atom of the isopropyl group of the 5-isopropyl phthaloyl chloride with potassium permanganate. The corresponding polyamide can be grafted with styrene in a redox system (151). 

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