Dichlorobenzene, synthesis

Dichlorobenzene synthesis of toluene diisocyanate, dyestuffs, herbicides, and degreasers... 

In another process for the synthesis of PPS, as well as other poly(arylene sulfide)s and poly(arylene oxide)s, a pentamethylcyclopentadienylmthenium(I) TT-complex is used to activate -dichlorobenzene toward displacement by a variety of nucleophilic comonomers (92). Important facets of this approach, which allow the polymerization to proceed under mild conditions, are the tremendous activation afforded by the TT-coordinated transition-metal group and the improved solubiUty of the resultant organometaUic derivative of PPS. Decomplexation of the organometaUic derivative polymers may, however, be compHcated by precipitation of the polymer after partial decomplexation. 

Kyba and eoworkers prepared the similar, but not identical compound, 26, using quite a different approach. In this synthesis, pentaphenylcyclopentaphosphine (22) is converted into benzotriphosphole (23) by reduction with potassium metal in THF, followed by treatment with o "t/20-dichlorobenzene. Lithium aluminum hydride reduction of 23 affords l,2-i>/s(phenylphosphino)benzene, 24. The secondary phosphine may be deprotonated with n-butyllithium and alkylated with 3-chlorobromopropane. The twoarmed bis-phosphine (25) which results may be treated with the dianion of 24 at high dilution to yield macrocycle 26. The overall yield of 26 is about 4%. The synthetic approach is illustrated in Eq. (6.16), below. 

Installation of a different side chain completely alters the pharmacological profile leading to a new class of muscle relaxants. The synthesis begins with copper(II)-promoted di-azonium coupling between furfural (j ) and 3,4-dichlorobenzene-diazonium chloride (15) to give bi aryl aldehyde Next, condensation with 1-aminohydantoin produces the muscle relaxant clodanolene (17). ... 

Fig. 39 Microwave-assisted synthesis of pyridinones from resin-bonnd 2(iH)-pyrazinones. Reagents and conditions a dimethyl acetylenedicarboxylate, chlorobenzene, reflux (132 °C), 1-2 days or 1,2-dichlorobenzene, MW 220 °C, 20-40min b bromobenzene, reflux (156 °C), 2h or 1,2-dichlorobenzene, MW 220 °C, 10min R = OC2H4C2H c TFA, reflux (72 °C), 20-24 h or TFA/Ch2Cl2, MW 120 °C, 10-40min. R=OMe or Ph, R = methoxyphenyl. All microwave-assisted reactions were rim in sealed vessels...

A new heterocyclic system, 1,6-diphosphatriptycene (119), has been prepared in a one-step synthesis by treating o-dichlorobenzene with white phosphorus in the presence of ferric chloride. ... 

Reductive dechlorination in combination with the elimination of chloride has been demonstrated in a strain of Clostridium rectum (Ohisa et al. 1982) y-hexachlorocyclohexene formed 1,2,4-trichlorobenzene and y-l,3,4,5,6-pentachlorocyclohexene formed 1,4-dichlorobenzene (Figure 7.69). It was suggested that this reductive dechlorination is coupled to the synthesis of ATP, and this possibility has been clearly demonstrated during the dehalogenation of 3-chlorobenzoate coupled to the oxidation of formate in Desulfomonile tiedjei (Mohn and Tiedje 1991). Combined reduction and elimination has also been demonstrated in methanogenic cultures that transform 1,2-dibromoethane to ethene and 1,2-dibromoethene to ethyne (Belay and Daniels 1987). 

The fullerene C o was used as the Unking agent for the synthesis of (PCHD-fc-PS)6 and (PS-fc-PCHD)6 star-block copolymers [154], The polymers were then aromatized with 2,3-dichloro-5,6-dicyano-l,4-benzoquinone, DDQ, in 1,2-dichlorobenzene to yield the corresponding copolymers containing poly(l,4-phenylene) blocks. In order to achieve high 1,4-isomer contents and to avoid termination reactions, the polymerization of CHD was conducted in toluene at 10 °C without the presence of any additive to yield products with low molecular weights. Coupling of the PCHD-fo-PSLi to C60... 

An example of solid-phase microwave synthesis where the use of open-vessel technology is essential is shown in Scheme 4.10. The transesterification of /3-keto esters with a supported alcohol (Wang resin) is carried out in 1,2-dichlorobenzene (DCB) as a solvent under controlled microwave heating conditions [22], The temperature is kept constant at 170 °C, ca. 10 degrees below the boiling point of the solvent, thereby allowing safe processing in the microwave cavity. In order to achieve full conversion to the desired resin-bound /3-keto ester, it is essential that the methanol formed can be removed from the equilibrium [22]. 

Another important reaction principle in modem organic synthesis is carbon-hydrogen bond activation [159]. Bergman, Ellman, and coworkers have introduced a protocol that allows otherwise extremely sluggish inter- and intramolecular rhodium-catalyzed C-H bond activation to occur efficiently under microwave heating conditions. In their investigations, these authors found that heating of alkene-tethered benzimidazoles in a mixture of 1,2-dichlorobenzene and acetone in the presence of di-//-... 

The synthesis of /Mactams from diazoketones and imines can be realized not only by using photochemical reaction conditions but also under the action of microwave irradiation. When the reaction was performed in o-dichlorobenzene at 180 °C, however, the rates of thermal and microwave-assisted formations of -lactams were shown to be identical within the limits of experimental error (80-85% conversion after 5 min) [30]. 

Although harmine 52 is frequently obtained by isolation (or purchase order), a synthesis of this compound as well as a number of analogs has recently appeared [47,48]. The key step to this synthesis was the thermal electrocyclization of oxime intermediate 55, which was prepared by acylation of vinylindole derivative 54 followed by treatment with hydroxylamine hydrochloride. Neither oxime 55 nor its ketone precursor were isolated— instead, the crude reaction mixture was heated at reflux in o-dichlorobenzene to ultimately yield harmine in 56% yield overall starting from 54 (Fig. 18). 

The synthetic route to tetrachlorothioindigo may serve as an example for an industrial scale synthesis. Starting material is 2,5-dichlorothiophenol, which is obtained by reduction of 2,5-dichlorobenzene sulfochloride or by reaction of the 2,5-dichlorobenzene diazonium salt with potassium-o-ethyldithiocarbonate and hydrolysis or with disodium sulfide and subsequent reduction ... 

Miscellaneous. A number of reports of the synthesis of unusual heterocyclic phosphines have appeared. Improved procedures for the synthesis of l,3,5-triaza-7-phospha-adamantane (48) have been reported,40-41 and the triazaphosphahomo-adamantane (49) has also been prepared.42 Routes to the large ring phosphacyclo-alkanes (50) have been described,43 and the bicyclic diphosphine (51) has been isolated from the reaction of white phosphorus with o-dichlorobenzene in the presence of transition-metal halides.44... 

Venkatachaliah, V.R., Kuppusamy, R., and Pamulaparti, S.R. Solubility of o-dichlorobenzene under isoproturon synthesis conditions, J. Chem. Eng. Data, 38(2) 245-246, 1993. 

Chlorinated aromatics, including monochlorobenzene (MCB), o-dichloroben-zene (o-DCB), and p-dichlorobenzene (p-DCB), are the major chlorinated aromatic species produced on an industrial scale. MCB is used as both a chemical intermediate and a solvent. As an intermediate, it is used to produce chloroni-trobenzene, pesticides, and pharmaceutical products. In solvent applications, MCB is used in the manufacture of isocyanates. Its high solvency allows it to be used with many types of resins, adhesives, and coatings. The o-dichlorobenzene is used primarily for organic synthesis, especially in the production of 3,4-dichlo-roaniline herbicides. Like MCB, it can be used as a solvent, especially in the production of isocyanates. It is also used in motor oil and paint formulations. The p-dichlorobenzene is used as a moth repellent and for the control of mildew and fungi. It also is used for odor control. It is a chemical intermediate for the manufacture of pharmaceuticals and other organic chemicals. 

Instituto di Ricerche Biomediche. 1986a. Study of the capacity of the test article para-dichlorobenzene to induce "unscheduled DNA synthesis" in cultured HeLa cells. Experiment Nos. M1032/1-2. 

Steinmetz KL, Spanggord RJ. 1987a. Examination of the potential of p-dichlorobenzene to induce unscheduled DNA synthesis or DNA replication in the in vivo - in vitro mouse hepatocyte DNA repair assay. 

Isomeric l,3a,4,6a- (220) and l,3a,6,6a- (91) dibenzotetraazapentalenes can be prepared from the thermal decomposition of 2-((9-azidophenyl)-2//-benzotriazole (224) and - o-azidophenyl)-2//-benzotriazole (230), respectively, in high boiling solvents such as 0-dichlorobenzene and decalin. This synthesis was improved upon when it was found that (220) and (91) can be prepared from the reactions of 2-((9-nitrophenyl)-2//-benzotriazole (226) and l-(o-nitrophenyl)-2//-benzotriazole (229), respectively, with triethyl phosphite in refluxing xylene. ... 

A free radical cyclization of oxime ethers tethered to an aldehyde has been used in the synthesis of azepine derivatives . For example, oxime ether 389 is cyclized to azepine 390 by reaction with Sml2 in HMPA and f-BuOH at —78°C (equation 170) . Similar free radical cyclization of oxime ethers can be carried out also in the presence of Bu3SnH/AIBN in benzene . Oxime 0-methyl ether 391 underwent thermal cyclization in refluxing o-dichlorobenzene (ODCB) leading to the mixture of two products 392 and 393 in ratio 69 31 in overall yield of 91% (equation 171) °. Rearrangement of oxime 0-tosylates in the presence of piperidine also leads to azepine ring formation . ... 

Ackermann and Althammer reported an efficient synthesis of murrayafoline A (7) starting from the easily accessible 2-methoxy-4-methylaniline (598) (see Scheme 5.33) (898). This methodology involves a Pd(0)-catalyzed domino N-H/C-H bond activation to afford the carbazole framework directly. Thus, in a one-pot operation, 2-chloro-bromobenzene (1573) and the aniline 598 were directly transformed into murrayafoline A (7) in 74% yield by reacting with a catalytic amount of Pd(ll) acetate in the presence of K3PO4, PCys, and N-methylpyrrolidone (NMP). This reaction also proceeds with 1,2-dichlorobenzene, albeit in 72% yield (898) (Scheme 6.4). 

The synthesis of a diphenylmethano-bridged fuUerene derivahve with reactive functional groups on the phenyl rings is exemplified by the preparahon of the diphenol derivative 118 (Scheme 4.23). It can be obtained from the corresponding methyl ether by treatment with BBrj in o-dichlorobenzene at 0 °C to room temperature in 94% yield. In contrast to the non-polar diphenyl-methano bridged fullerenes, 118 is soluble and stable in pyridine but sparingly soluble in benzene or toluene. 

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