Phthaloyl dichloride

Polyester carbonate resins are made by the interfacial process described for standard PC resins. The phthalate units are introduced by reaction of the appropriate phthaloyl dichlorides concurrent with the phosgenation. At present, Bayer, GE, and Miles produce polyester carbonate resins (47) sales volume is low, probably ca 100 t/yr. Polyester carbonates are used primarily in appHcations requiring 5—25°C higher heat-deflection temperature and better hydrolytic performance than are provided by standard PC resins. Properties are given in Table 9. 

Anthracyclinones.1 Phthaloyl dichlorides undergo Friedel Crafts reactions with hydroquinones or the dimethyl ethers to give 1,4-dihydroxyanthraquinones in one step. 

Phenylacetyl chloride and hydrocin-namoyl chloride are reduced at mercury to form both acyl radicals and acyl anions as intermediates [76]. From electrolyses of phenylacetyl chloride, the products include 1,4-diphenyl-2-butene-2,3-diol diphenylac-etate, phenylacetaldehyde, toluene, 1,3-diphenylacetone, and l,4-diphenyl-2,3-butanediol, and analogous species arise from the reduction of hydrocinnamoyl chloride. Reduction of phthaloyl dichloride is a more complicated system [77] the electrolysis products are phthalide, biph-thalyl, and 3-chlorophthalide, but the latter compound undergoes further reduction to give phthalide, biphthalyl, and dihydrobi-phthalide. 

Phthalic anhydride is converted to phthaloyl dichloride by reaction with phosgene1084. 

Electrochemical reduction of phthaloyl dichloride (73) at a carbon or mercury cathode in acetonitrile containing TEAP led to a complex array of products. Six cathodic waves observed in the CV for the reduction of phthaloyl dichloride arise from the reductions of different electrolysis products, as well as from hydrolytically formed phthalic anhydride (74),. caused by the presence of residual water in the solvent/supporting electrolyte (equation 45). From controlled potential electrolyses of phthaloyl dichloride, a variety of products including 3-chlorophthalide (75), phthalide (76), biphthalyl (77) and dihydrobiph-thalide (78) can be obtained69,70. Reduction of glutaryl dichloride (79) at a mercury cathode in acetonitrile containing 0.1M TEAP results in the formation of 5-chlorovalerolactone (80) and valerolactone (81) as minor products, and a polymeric material (equation 46)68. 

Alternatively, they have been synthesized by the polycondensation of 3-chlorophthalides or phthaloyl dichloride with aromatic hydrocarbons [Eq. (16)] [94]. However, polymers with irregular structural units were produced. The irregular structure is the result of para- and meta-substitution of the oxydiphenylene unit. 

The reagent converts phthaloyl dichloride (I) into biphthalidylidene (2) in 23% yield. ... 

Upon being electrolyzed at carbon or mercury in MeCN containing TEAP, phthal-oyl dichloride [224] is converted into 3-chlorophthalide, phthalide, and biphthalyl. However, this system is complicated by the fact that 3-chlorophthalide can itself be reduced (at a potential only slightly more negative than that needed for reduction of phthaloyl dichloride) to afford phthalide, biphthalyl, and dihydrobiphthalide. 

Compounds with enato 1,3-diaza chelate rings, e.g., (138) (cf. (37) and (38)), are oxidized to radical species which form 6,6 -C—C (139), and 6,6 -C=C linked bismacrocycles, which can be reduced to form 6,6 -biscyclams (140) (Scheme 33).177 [Ni(cyclam)]2+ and [Fe(cyclam)(MeCN)2]3+ are aerially oxidized to the 6-6 -ethylidene linked cations (141) which reduce to the 6,6 -biscyclam cations. Reaction of (138) with bifunctional o-phthaloyl dichloride gave bisacyl-linked macrocycles (142).178... 

Treatment of 11 with excess aroyl chloride ArCOCl followed by hydrolysis gives a mixture of ArCONH2 and (ArCO)2NH, while the reaction of 12 with phthaloyl dichloride or phthalic anhydride results in the formation of phthalim-ide. Aroylpalladium complexes, prepared from ArX (X=Br, I) and [Pd(PPh3)4] under CO, also react with 12 to yield the aroylimides and/or aroylamides aifter... 

C-sodium acetate is produced by the reaction of the Grignard reagent, methylmagnesium bromide in diethyl ether, with cyclotron-produced nC-carbon dioxide at -15°C (Oberdorfer et al, 1996). After reaction, the product is allowed to react with O-phthaloyl dichloride to produce nC-acetyl chloride, which is then hydrolyzed to 11C-acetate with saline. The solution is filtered through a 0.22-pm membrane filter. 11C-acetate has been found to be stable at pH between 4.5 and 8.5 for up to 2 h at room temperature. The overall yield is about 10-50%. It is used for the measurement of oxygen consumption (oxidative metabolism) in the heart, since acetyl CoA synthetase converts 11C-acetate to acetyl coenzyme A after myocardial uptake, which is metabolized to 11C-C02 in the tricarboxylic acid cycle. 

Simultaneous C- and -acylation of an imidazole by phthaloyl dichloride occurs in the presence of TEA. 

These studies allow the efficient synthesis of anfhraquinones under mild conditions, including anthracyclinones, by direcf ortho-bisacylafion of aromatic compounds with orf/io-phthaloyl dichlorides a few examples are reported in Table 2.6. Similarly, aromatic cycloalkanediones can be easily prepared by bis-acylation of aromafic compounds wifh different aliphatic diacyl chlorides. ... 

The direct 1,4-dimethylanthraquinone 17 synthesis via double acylation of para-xylene with phthalic anhydride can be performed in 15% yield at 138°C, but an equimolecular amount of triflic acid is necessary (Scheme 3.3). Better results are achieved by using phthaloyl dichloride under triflic acid catalysis (5% mol) at the same temperature anthraqui-none 17 can be synthesized in 52% yield. Moreover, product 17 is obtained in 89% yield when the same reaction is carried out in 1,2-dichloroethane and a higher amount of triflic acid (10% mol). 

Phenylenedioarbonyl dichloride p-Phthaloyl chloride p-Phthaloyl dichloride p-Phthalyl diohloride Tere-phthalic acid chloride Terephthalic acid dichloride Terephthalio diohloride Terephthaloyl chloride Tere-phthalyl diohloride. Needies, mp = 83.5° bp = 258, bp9= 125° soluble in Et20. 

The last reaction illustrates how useful it can be to convert an acid first into its anhydride and then into its chloride. Most carboxylic anhydrides are relatively stable to inorganic acid chlorides cyclic anhydrides are even formed preferentially if a dicarboxylic acid such as maleic, tartaric, or phthalic acid is treated with an inorganic acid chloride such as SOCl2 under the usual conditions 1092 however, phthalic anhydride is converted by PC15 at higher temperatures into phthaloyl dichloride (A). 

Phthaloyl dichloride from phthalic anhydride and PC15 1039 Phthalic anhydride (1 mole sublimed) and pure PC15 (1.06 moles) are heated in a 500-ml round-bottomed flask fitted with a reflux condenser and a CaCl2 tube and placed in an oil-bath at 150°. After 12 h the reflux condenser is replaced by a downward water-condenser and the bath-temperature is raised gradually to 250°. Most of the POCl3 formed distils off. The residual crude dichloride, when distilled, has b.p. 131-133°/9-l 0 mm, the yield being 92%. The product contains a little phthalic anhydride. 

Phthaloyl chloride from phthalic anhydride and SOCl2 1093 Phthalic anhydride (300 g) and anhydrous ZnCl2 (1.5 g) are heated to 220° in a three-necked flask fitted with a reflux condenser and stirrer. Then SOCl2 (241 g) is allowed to run into the stirred mixture at such a rate that the temperature does not fall below 220°, after which the whole is distilled at greatly reduced pressure. At 119-122°/4.5 mm this gives 380 g of distillate, from which, on cooling, 22 g of phthalic anhydride crystallizes. Filtration from this gave phthaloyl dichloride that was shown by a Cl determination to be 94 % pure, which suffices for many purposes. 

Reaction of amides with phthaloyl dichloride to give A-acylphthalimides has sometimes been used to characterize them 624... 

For this purpose the amide is heated with phthaloyl dichloride, either without a solvent or in toluene, until evolution of hydrogen chloride ceases.624 This method is often superior to acylation of phthalimide625 if it is a question of synthesizing A-acylphthalimides N(p-toluenesulfonyl)phthalimide, for instance, can be obtained only by the phthaloyl dichloride method.624... 

Most such ring closures have therefore been treated in the preceding Chapters. On the other hand, cyclization of phthaloyl dichloride to dichlorophthalide (page 1067) has no analogy in the acyclic series and is therefore treated in the present Chapter. 

Interconversion of phthaloyl dichloride and its isomer, 3,3-dichloro-phthalide, has been studied in especial detail 67... 

At the boiling point the equilibrium lies completely towards the symmetrical phthaloyl dichloride however, this chloride can be rearranged by aluminum chloride to the unsymmetrical dichlorophthalide since that compound can be withdrawn as its stable complex with the metal salt. Detailed experimentation has been described in Organic Syntheses.68... 

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