1.3- Dibenzoyl- -chlorid

Hsiao et al. prepared a series of fluorinated PHAs by low-temperature solution polycondensation of 4,4 -[isopropylidenebis( 1,4-phenylene)dioxy]diben-zoyl chloride and 4,4 -piexafluoroisopropylidenebis (l,4-phenylene)dioxy]dibenzoyl chloride with three... 

The wide angle X-ray diffraction pattern tom melt-drawn fiber of homopolyester, obtained from the reaction of l,3-bis(p-hydroxyphenyl)-l,3-propanedione and 4,4 -hexamethylenedioxy-dibenzoyl chloride, exhibits a typical smectic A mesophase, i. e., an inner reflection as spot at the meridional position and a diffuse outer reflection at the equatorial position (Figure 8.27). 

A) Benzoyl Derivative. Since acetylation and benzoylation do not always proceed smoothly with nitrophenols, it is best to reduce them to the aminophenol as in (3) above. Add an excess of 20% aqueous sodium hydroxide to the reaction mixture after reduction, cool and then add a small excess of benzoyl chloride, and shake in the usual way. The dibenzoyl derivative wiU separate. Filter, wash with water and recrystalUse. (M.ps., p. 551.)... 

The dibenzoyl derivatives can be prepared by the normal Schotten-Baumann method, using 10% aqueous sodium hydroxide and an excess of benzoyl chloride, but the m.ps. of the dibenzoyl derivatives are inconveniently high (p- ssO-... 

Rapid side-chain chlorination of toluene proceeds in the dark with sulphuryl chloride in the presence of dibenzoyl peroxide (0-001-0 005 mol per mol of SOjCl,) as catalyst ... 

Method 2. In a 500-ml. rovmd-bottomed flask, fitted with an efficient reflux condenser, place 92 g, (106 ml.) of toluene, 68 g. (41 ml.) of redistilled sulphuryl cldoride and 1 g, of dibenzoyl peroxide (Section IV,196). Reflux gently, when a vigorous reaction takes place the reaction is complete in 30 minutes. Isolate the benzyl chloride as described in Method 1. The yield is 50 g. 

Neutrahse about one third of the filtrate with 5N sodium hydroxide and add a further 2 ml. of the alkah solution. Add 1 ml. of benzoyl chloride and stir until the odour of the acid chloride disappears. Collect the solid by suction filtration, wash it with water until free from alkah, and then recrystalhse it from dilute alcohol. The product is the dibenzoyl derivative of hexamethylenediamine and melts at 159°. 

Acylation with aromatic acid chlorides was believed to occur on carbon 91). The dibenzoylation of the enamine (113) with benzoyl chloride in the presence of triethylamine has, however, been shown to give a mixture of three products (92). The major components are the cis and Irons isomers of the O-acylated enamino ketone (Ola and b) and the minor isomer is the 2,6-diacylated enamine (132). 

Dibenzoyl-2,2 -biindole (295) was obtained by the action of benzoyl chloride on the 2,2 -biindole Grignard reagent. ... 

Methyldiaziridine and 3-n-propyldiaziridine (45) give with benzoyl chloride the dibenzoyl compounds 48 and 49. Both compounds are shown to be true diaziridines by oxidizing iodide. This discovery was of special interest the sole compounds retained in recent literature- of those formerly formulated as diaziridines were supposedly 1,2-diacyl-diaziridines, e.g. 50 [compare Section I, Eq. (1)]. 

Pyridine has been phenylated with the following free-radical sources benzenediazonium chloride with aluminum trichloride the Gomberg reaction " phenylhydrazine and metal oxides A -nitroso-acetanilide dibenzoyl peroxide phenylazotriphenylmethane di-phenyliodonium hydroxide and electrolysis of benzoic acid. ° Although 2-phenylpyridine usually accounts for over 50% of the total phenylated product, each of the three phenyl derivatives can be obtained from the reaction by fractional recrystallization of the... 

There is an early report that thiophene reacts at the 3-position in phenylation with benzenediazonium chloride and aluminum trichloride, but in the Gomberg reaction thiophene has been found to substitute mainly at the 2-position both with p-tolyl and with p-chloro-phenyl radicals.Bcnzothiazole is phenylated at the 2-position in low yield by dibenzoyl peroxide a small quantity of the 4-isomcr is also obtained. ... 

The explosive decomposition of the solid has been studied in detail [6], The effect of moisture upon ignitibility and explosive behaviour under confinement was studied. A moisture content of 3% allowed slow burning only, and at 5% ignition did not occur [7], Thermal instability was studied using a pressure vessel test, ignition delay time, TGA and DSC, and decomposition products were identified [8], The presence of acyl chlorides renders dibenzoyl peroxide impact-sensitive [9], There is a further report of a violent explosion during purification of the peroxide by Soxhlet extraction with hot chloroform [10], Residual traces of the peroxide in a polythene feed pipe exploded when it was cut with a handsaw [11]. The heat of decomposition has been determined as 1.39 kJ/g. The recently calculated value of 69° C for critical ignition temperature coincides with that previously recorded. 

A recent report indicates that thiophenes (not benzothiophenes) may be formed from alkyl phenyl ketones by treatment with a slight excess of thionyl chloride in the cold.58 Propiophenone, for example, yields 3,4-dibenzoyl-thiophene (47). Adipic acid and related carboxylic acids yield thiophene derivatives upon treatment with thionyl chloride in the presence of pyridine.59... 

The same authors have more recently described the synthesis of dibenzoyl diselenides by reaction of selenium with sodium hydroxide under PTC and MW irradiation conditions to afford sodium diselenides which react further with benzoyl chloride at 0 °C [81]. 

The 1,4-diketone 1,2-dibenzoylethane 151 can be transformed in one step into 3,4-dibenzoyl-l,2,5-thiadiazole 152 when treated either with preformed trithiazyl trichloride in tetrachloromethane (Equation 29) <1997J(P1)2831> or with urethane, thionyl chloride, and pyridine in benzene (Katz reagent) <2002ARK90> (see also Section 5.09.9.2.l(iii)(b)). Similarly, treatment of 1,3-diketones 153 with tetrasulfur tetranitride antimony pentachloride complex in toluene at 100 °C < 1998J(P 1 )2175 >, or trithiazyl trichloride in boiling tetrachloromethane < 1997J(P 1)2831 >, affords 4-substituted-3-aroyl-l,2,5-thiadiazoles 154 (Equation 30). 

Free-radical chain reactions have been reviewed60. The cyclization of dienes by the action of free radicals is illustrated for the case of the 1,6-heptadiene derivative 90 (E = CC Me) in equation 56. Treatment with tosyl radicals, produced from tosyl chloride and a catalytic amount of dibenzoyl peroxide, generates the radicals 91, which cyclize to 92. The latter reacts with tosyl chloride to form 93 and tosyl radicals are regenerated. The product is obtained in 85% yield as a 6 1 mixture of cis- and fraws-isomers61. 

The Reissert reaction of 3,4-dihydro-p-carboline (213) has also been studied 47,48). It has been shown that 3,4-dihydro-p-carboline (213) afforded 1-cyano-2,9-dibenzoyl-l,2,3,4-tetrahydro-P-carboline (214) with a phase-transfer catalyst and trimethylsilyl cyanide (Scheme 27). However, the normal Reissert product 2-benzoyl-l-cyano-l,2,3,4-tetrahydro-p-carboline (215) was obtained when a catalytic amount of anhydrous aluminum chloride was used in addition to the trimethylsilyl cyanide reagent. Reaction of 214 with sodium... 

Ornithine or a, h-diamimrvalerianic Acid.—In 1877 JafTe obtained from the urine of birds, which he had fed with benzoic acid, dibenzoyl ornithine or ornithuric acid, and from this substance he prepared ornithine chloride. He regarded it as a diaminovalerianic acid, the first known representative of the series of diamino acids, but only in 1898 was the position of the two amino groups definitely determined by Ellinger, who obtained putrescine from it by putrefaction the identity of putrescine with tetramethylenediamine had been previously shown by... 

The initial medicinal chemistry route to the azabicyclo[3.3.0]octane-3-carboxylic acid produced the azabicyclo system in a diastereoselective but racemic manner, and required a classical resolution to achieve enantioenriched material (Teetz et al., 1984a, b 1988). Reaction of (R)-methyl 2-acetamido-3-chloropropanoate (43) and 1-cyclopentenylpyrrolidine (44) in DMF followed by an aqueous acidic work-up provided racemic keto ester 45 in 84% yield (Scheme 10.11). Cyclization of 45 in refluxing aqueous hydrochloric acid provided the bicyclic imine, which was immediately reduced under acidic hydrogenation conditions. The desired cis-endo product 46 was obtained upon recrystaUization. The acid was protected as the benzyl ester using thionyl chloride and benzyl alcohol, providing subunit 47 as the racemate. Resolution of 47 was accomplished by crystallization with benzyloxy-carbonyl-L-phenylalanine or L-dibenzoyl-tartaric acid. 

---