Benzene reaction+carbonyls

The Dewar-benzene iron carbonyl derivative [97], like perfluorobicyclo[2,2,0]hexa-2,5-diene itself, undergoes Diels-Alder addition to give [98a and b], with the chemical shifts shown. (53) [98a] is also formed, although in low yield, by the reaction of the preformed Diels-Alder adduct [99] with Na[(7r-C5H5)Fe(CO)2], confirming the stereochemistry of the addition. 

The disproportionation (or alkyl exchange) and the alkylation reactions of alkylsilanes have been carried out in a closed recirculation reactor at 373 - 623 K and 373 - 473 K, respectively, by using 100 - 200 mg of catalysts. For the disproportionation reaction, 30 Torr of diethylsilane (E2), diethyidimethylsilane (E2M2), and triethylsilane (E3) were used. For the alkylation reaction, 30 Torr of E2 and 30 Torr of alkylating reagents (propene, 1- and c/s-2-butene, 2-methyl-1-butene, 1,3-butadiene, methylacetylene, ethylacetylene) were used. Cyclic olefins, nitriles, benzene and carbonyl compounds were also tested. 

This preparation illustrates the Reformatsky reaction, which consists in the interaction of a carbonyl compound, an a-halogen ester (e.g., ethyl bromo-acetate) and zinc In the presence of ether or benzene, followed by hydrolysis. 

In a Lewis-acid catalysed Diels-Alder reaction, the first step is coordination of the catalyst to a Lewis-basic site of the reactant. In a typical catalysed Diels-Alder reaction, the carbonyl oxygen of the dienophile coordinates to the Lewis acid. The most common solvents for these processes are inert apolar liquids such as dichloromethane or benzene. Protic solvents, and water in particular, are avoided because of their strong interactions wifti the catalyst and the reacting system. Interestingly, for other catalysed reactions such as hydroformylations the same solvents do not give problems. This paradox is a result of the difference in hardness of the reactants and the catalyst involved... 

The first report of oxidative carbonylation is the reaction of alkenes with CO in benzene in the presence of PdCh to afford the /3-chloroacyl chloride 224[12,206]. The oxidative carbonylation of alkene in alcohol gives the q, f3-unsaturated ester 225 and /3-alkoxy ester 226 by monocarbonylation, and succinate 111 by dicarbonylation depending on the reaction conditions[207-209]. The scope of the reaction has been studied[210]. Succinate formation takes... 

In addition to benzene and naphthalene derivatives, heteroaromatic compounds such as ferrocene[232, furan, thiophene, selenophene[233,234], and cyclobutadiene iron carbonyl complexpSS] react with alkenes to give vinyl heterocydes. The ease of the reaction of styrene with sub.stituted benzenes to give stilbene derivatives 260 increases in the order benzene < naphthalene < ferrocene < furan. The effect of substituents in this reaction is similar to that in the electrophilic aromatic substitution reactions[236]. 

Benzoic acid and naphthoic acid are formed by the oxidative carbonylation by use of Pd(OAc)2 in AcOH. t-Bu02H and allyl chloride are used as reoxidants. Addition of phenanthroline gives a favorable effect[360], Furan and thiophene are also carbonylated selectively at the 2-position[361,362]. fndole-3-carboxylic acid is prepared by the carboxylation of 1-acetylindole using Pd(OAc)2 and peroxodisulfate (Na2S208)[362aj. Benzoic acid derivatives are obtained by the reaction of benzene derivatives with sodium palladium mal-onate in refluxing AcOH[363]. 

The carbonylation of 2-methyl-3-butyn-2-oI (50) in benzene gives teraconic anhydride (51). Fulgide (53) (a dimethylenesuccinic anhydride derivative), which is a photochromic compound, can be prepared by the carbonylation of 2,5-dimethyl-3-hexyne-2,5-diol (52)[21], The reaction proceeds under milder conditions when PdlOAc) is used as a catalyst in the presence of iodine [23],... 

The chiral siloxycyclopropane 106 undergoes carbonylative homocoupling to form the 4-ketopimelate derivative 108 via the palladium homoenolate 107 without racemization. The reaction is catalytic in CHCI3, but stoichiometric in benzene[93]. 

The thermal decomposition of thia2ol-2-yl-carbonyl peroxide in benzene, bromobenzene, or cumene affords thiazole together with good yields of 2-arylthiazoles but negligible amounts of esters. Thiazol-4-ylcarbonyl peroxide gives fair yields of 4-arylthiazoles, but the phenyl ester is also a major product in benzene, indicating reactions of both thiazol-4-yl radicals and thiazol-4-carbonyloxy radicals. Thiazole-5-carbonyl peroxide gives... 

Because the carbon atom attached to the ring is positively polarized a carbonyl group behaves m much the same way as a trifluoromethyl group and destabilizes all the cyclo hexadienyl cation intermediates m electrophilic aromatic substitution reactions Attack at any nng position m benzaldehyde is slower than attack m benzene The intermediates for ortho and para substitution are particularly unstable because each has a resonance structure m which there is a positive charge on the carbon that bears the electron withdrawing substituent The intermediate for meta substitution avoids this unfavorable juxtaposition of positive charges is not as unstable and gives rise to most of the product... 

In a polluted or urban atmosphere, O formation by the CH oxidation mechanism is overshadowed by the oxidation of other VOCs. Seed OH can be produced from reactions 4 and 5, but the photodisassociation of carbonyls and nitrous acid [7782-77-6] HNO2, (formed from the reaction of OH + NO and other reactions) are also important sources of OH ia polluted environments. An imperfect, but useful, measure of the rate of O formation by VOC oxidation is the rate of the initial OH-VOC reaction, shown ia Table 4 relative to the OH-CH rate for some commonly occurring VOCs. Also given are the median VOC concentrations. Shown for comparison are the relative reaction rates for two VOC species that are emitted by vegetation isoprene and a-piuene. In general, internally bonded olefins are the most reactive, followed ia decreasiag order by terminally bonded olefins, multi alkyl aromatics, monoalkyl aromatics, C and higher paraffins, C2—C paraffins, benzene, acetylene, and ethane. 

Benzene Nucleus Reactions. Ring substitutions, such as sulfonation and nitration, can be effected without destmction of the carbonyl group. Under the influence of the carbonyl group, meta substitution usually occurs. 

Reactions of acetylene and iron carbonyls can yield benzene derivatives, quinones, cyclopentadienes, and a variety of heterocycHc compounds. The cyclization reaction is useful for preparing substituted benzenes. The reaction of / fZ-butylacetylene in the presence of Co2(CO)g as the catalyst yields l,2,4-tri-/ f2 butylbenzene (142). The reaction of Fe(CO) and diphenylacetylene yields no less than seven different species. A cyclobutadiene derivative [31811 -56-0] is the most important (143—145). 

Friedrich et al. also used XPS to investigate the mechanisms responsible for adhesion between evaporated metal films and polymer substrates [28]. They suggested that the products formed at the metal/polymer interface were determined by redox reactions occurring between the metal and polymer. In particular, it was shown that carbonyl groups in polymers could react with chromium. Thus, a layer of chromium that was 0.4 nm in thickness decreased the carbonyl content on the surface of polyethylene terephthalate (PET) or polymethylmethacrylate (PMMA) by about 8% but decreased the carbonyl content on the surface of polycarbonate (PC) by 77%. The C(ls) and 0(ls) spectra of PC before and after evaporation of chromium onto the surface are shown in Fig. 22. Before evaporation of chromium, the C(ls) spectra consisted of two components near 284.6 eV that were assigned to carbon atoms in the benzene rings and in the methyl groups. Two additional... 

In view of the excellent donor properties of tertiary arsines, it is of interest to inquire whether these cyc/o-polyarsanes can also act as ligands. Indeed, (MeAs)s can displace CO from metal carbonyls to form complexes in which it behaves as a uni-, bi- or triden-tate ligand. For example, direct reaction of (MeAs)5 with M(CO)6 in benzene at 170° (M = Cr, Mo, W) yielded red crystalline compounds [M(CO)3( -As5Me5)] for which the structure... 

Bis ( -arene) metal complexes have been made for many transition metals by the AI/AICI3 reduction method and cationic species [M( j -Ar)2]"" " are also well established for n = 1, 2, and 3. Numerous arenas besides benzene have been used, the next most common being l,3,5-Mc3C6H3 (mesitylene) and CeMce. Reaction of arenas with metal carbonyls in high-boiling solvents or under the influence of ultraviolet light results in the displacement of 3CO and the formation of arena-metal carbonyls ... 

Modification of the Erlenmeyer reaction has been developed using imines of the carbonyl compounds, obtained with aniline," benzylamine or n-butylamine. Ivanova has also shown that an A-methylketimine is an effective reagent in the Erlenmeyer azlactone synthesis. Quantitative yield of 19 is generated by treatment of 3 equivalents of 2-phenyl-5(4ff)-oxazolone (2) (freshly prepared in benzene) with 1 equivalent of iV-methyl-diphenylmethanimine (18) in benzene. Products resulting from aminolysis (20), alkali-catalyzed hydrolysis (21), and alcoholysis (22) were also described. 

The carbonyl group reactivities in thiophenes and benzenes are very similar, as shown by the similar rates of alkaline hydrolysis of esters and by the great similarity of the thiophenealdehydes to benzaldehyde in numerous carbonyl group reactions. This has been ascribed to the counteracting —I- -M effects of the thienyl group in this kind of reactions. ... 

The same insertion of a methylene group between a benzene ring and carbonyl group is also found in the reaction of coumarandione (105 106 107). (The reaction course described by Schonbcrg et could not be confirmed. )... 

Depending on the specific reaction conditions, complex 4 as well as acylium ion 5 have been identified as intermediates with a sterically demanding substituent R, and in polar solvents the acylium ion species 5 is formed preferentially. The electrophilic agent 5 reacts with the aromatic substrate, e.g. benzene 1, to give an intermediate cr-complex—the cyclohexadienyl cation 6. By loss of a proton from intermediate 6 the aromatic system is restored, and an arylketone is formed that is coordinated with the carbonyl oxygen to the Lewis acid. Since a Lewis-acid molecule that is coordinated to a product molecule is no longer available to catalyze the acylation reaction, the catalyst has to be employed in equimolar quantity. The product-Lewis acid complex 7 has to be cleaved by a hydrolytic workup in order to isolate the pure aryl ketone 3. 

Since various substituents are tolerated, the Friedlander reaction is of preparative value for the synthesis of a large variety of quinoline derivatives. The benzene ring may bear for example alkyl, alkoxy, nitro or halogen substituents. Substituents R, R and R" also are variable. The reaction can be carried out with various carbonyl compounds, that contain an enolizable a-methylene group. The reactivity of that group is an important factor for a successful reaction. 

The carbonyl compound to be reduced (0.1 mole) is placed in a 250-ml round-bottom flask with 13.5 g of potassium hydroxide, 10 ml of 85% hydrazine hydrate, and 1(X) ml of diethylene glycol. A reflux condenser is attached and the mixture is heated to reflux for I hour (mantle). After refluxing 1 hour, the condenser is removed and a thermometer is immersed in the reaction mixture while slow boiling is continued to remove water. When the pot temperature has reached 200°, the condenser is replaced and refluxing is continued for an additional 3 hours. The mixture is then cooled, acidified with concentrated hydrochloric acid, and extracted with benzene. The benzene solution is dried, and the benzene is evaporated to afford the crude product, which is purified by recrystallization or distillation. 

Methods of synthesis for carboxylic acids include (1) oxidation of alkyl-benzenes, (2) oxidative cleavage of alkenes, (3) oxidation of primary alcohols or aldehydes, (4) hydrolysis of nitriles, and (5) reaction of Grignard reagents with CO2 (carboxylation). General reactions of carboxylic acids include (1) loss of the acidic proton, (2) nucleophilic acyl substitution at the carbonyl group, (3) substitution on the a carbon, and (4) reduction. 

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