Catalysis alkylation

Uses are for fluorocarbons (66%), alumina (14%), petroleum alkylation catalysis (4%), stainless steel pickling (4%), and uranium chemical production (2%). 

Alkylation Catalysis are used to make carbon-carbon bonds, as in the liquid phase alkylation of benzene to ethylbenzene, a styrene precursor. The catalyst used in this case is aluminum chloride. 

The formation of allenylidene derivatives from ethynyl-hexanol and alkenyl-vinylidene mononuclear complexes (9), the formation of mononuclear ruthenium allenyl complexes from terminal alkynes (10), the intermediacy of ruthenium-allenylidene complexes in forming propargylic alcohols (II), and in the cyclization of propargyl alcohols (12), and the use of mononuclear ruthenium compounds in allylic alkylation catalysis (13) have also been reported. 

Sun. N Klabiindc. KJ. High activiiy solid super base catalysts employing nanocrystuis of metal oxides isomerization and alkylation catalysis, including conversion of... 

Boger, D.L. and Turnbull, P (1998) Synthesis and evaluation of a carbocyclic analogue of the CC-1065 and doucarmycin alkylation subunits role of the vinylogous amide and implications on DNA alkylation catalysis. J. Org. Chem., 63, 8004-11. 

Alkylation catalysis is generally performed by H2SO4 and may produce discharges rich in sulfonic acids as mentioned earlier. Any use of HF may create problems of eliminating fluorides that are more or less easy to precipitate depending on whether NaF or NH4F is involved (F" precipitation as CaF2). 

The copolymers of ethylene and propylene (OCVP) are obtained by coordination catalysis using a derivative of vanadium and a derivative of an aluminum alkyl. Molar compositions of ethylene and propylene are usually on the order 45 and 55%. 

With the catalysis of strong Lewis acids, such as tin(IV) chloride, dipyrromethenes may aiso be alkylated. A very successful porphyrin synthesis involves 5-bromo-S -bromomethyl and 5 -unsubstituted 5-methyl-dipyrromethenes. In the first alkylation step a tetrapyrrolic intermediate is formed which cyclizes to produce the porphyrin in DMSO in the presence of pyridine. This reaction sequence is useful for the synthesis of completely unsymmetrical porphyrins (K.M. Smith, 1975). 

The thioboration of terminal alkynes with 9-(alkylthio)-9-borabicyclo[3.3.1]-nonanes (9-RS-9-BBN) proceeds regio- and stereoselectively by catalysis of Pd(Ph,P)4 to produce the 9-[(Z)-2-(alkylthio)-l-alkeny)]-9-BBN derivative 667 in high yields. The protonation of the product 667 with MeOH affords the Markownikov adduct 668 of thiol to 1-alkyne. One-pot synthesis of alkenyl sulfide derivatives 669 via the Pd-catalyzed thioboration-cross-coupling sequence is also possible. Another preparative method for alkenyl sulfides is the Pd-catalyzed cross-coupling of 9-alkyl-9-BBN with l-bromo-l-phe-nylthioethene or 2-bromo-l-phenylthio-l-alkene[534]. 

Sulfides (172) in which Rj = alkyl can be obtained also by direct alkylation of the 2-mercaptothiazoles either in alcaline medium (156, 597) or by phase-transfer catalysis in better yield (824). 

I ovolac Synthesis and Properties. Novolac resins used in DNQ-based photoresists are the most complex, the best-studied, the most highly engineered, and the most widely used polymers in microlithography. Novolacs are condensation products of phenoHc monomers (typically cresols or other alkylated phenols) and formaldehyde, formed under acid catalysis. Figure 13 shows the polymerization chemistry and polymer stmcture formed in the step growth polymerization (31) of novolac resins. 

Friedel-Crafts alkylation using alkenes has important industrial appHcations. The ethylation of benzene with ethylene to ethylbenzene used in the manufacture of styrene, is one of the largest scale industrial processes. The reaction is done under the catalysis of AlCl in the presence of a proton source, ie, H2O, HCl, etc, although other catalysts have also gained significance. 

Reactions 33 and 35 constitute the two principal reactions of alkyl hydroperoxides with metal complexes and are the most common pathway for catalysis of LPOs (2). Both manganese and cobalt are especially effective in these reactions. There is extensive evidence that the oxidation of intermediate ketones is enhanced by a manganese catalyst, probably through an enol mechanism (34,96,183—185). 

Chromium compounds decompose primary and secondary hydroperoxides to the corresponding carbonyl compounds, both homogeneously and heterogeneously (187—191). The mechanism of chromium catalyst interaction with hydroperoxides may involve generation of hexavalent chromium in the form of an alkyl chromate, which decomposes heterolyticaHy to give ketone (192). The oxidation of alcohol intermediates may also proceed through chromate ester intermediates (193). Therefore, chromium catalysis tends to increase the ketone alcohol ratio in the product (194,195). 

Heterogeneous Catalysis. The main discovery of the 1980s was the use of titanium sihcaUte (TS-1) a synthetic zeoHte from the ZSM family containing no aluminum and where some titanium atoms replace siUcon atoms in the crystalline system (Ti/Si = 5%) (33). This zeoHte can be obtained by the hydrolysis of a siUcate and an alkyl titanate in the presence of quaternary ammonium hydroxide followed by heating to 170°C. Mainly studies have been devoted to the stmcture of TS-1 and its behavior toward H2O2 (34). The oxidation properties of the couple H2O2/TS-I have been extensively developed in... 

Catalysis. As of mid-1995, zeoHte-based catalysts are employed in catalytic cracking, hydrocracking, isomerization of paraffins and substituted aromatics, disproportionation and alkylation of aromatics, dewaxing of distillate fuels and lube basestocks, and in a process for converting methanol to hydrocarbons (54). 

In contrast to triphenylphosphine-modified rhodium catalysis, a high aldehyde product isomer ratio via cobalt-catalyzed hydroformylation requires high CO partial pressures, eg, 9 MPa (1305 psi) and 110°C. Under such conditions alkyl isomerization is almost completely suppressed, and the 4.4 1 isomer ratio reflects the precursor mixture which contains principally the kinetically favored -butyryl to isobutyryl cobalt tetracarbonyl. At lower CO partial pressures, eg, 0.25 MPa (36.25 psi) and 110°C, the rate of isomerization of the -butyryl cobalt intermediate is competitive with butyryl reductive elimination to aldehyde. The product n/iso ratio of 1.6 1 obtained under these conditions reflects the equihbrium isomer ratio of the precursor butyryl cobalt tetracarbonyls (11). 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

The most widely used process for the production of phenol is the cumene process developed and Hcensed in the United States by AHiedSignal (formerly AHied Chemical Corp.). Benzene is alkylated with propylene to produce cumene (isopropylbenzene), which is oxidized by air over a catalyst to produce cumene hydroperoxide (CHP). With acid catalysis, CHP undergoes controUed decomposition to produce phenol and acetone a-methylstyrene and acetophenone are the by-products (12) (see Cumene Phenol). Other commercial processes for making phenol include the Raschig process, using chlorobenzene as the starting material, and the toluene process, via a benzoic acid intermediate. In the United States, 35-40% of the phenol produced is used for phenoHc resins. 

Substituted Phenols. Phenol itself is used in the largest volume, but substituted phenols are used for specialty resins (Table 2). Substituted phenols are typically alkylated phenols made from phenol and a corresponding a-olefin with acid catalysts (13). Acidic catalysis is frequendy in the form of an ion-exchange resin (lER) and the reaction proceeds preferentially in the para position. For example, in the production of /-butylphenol using isobutylene, the product is >95% para-substituted. The incorporation of alkyl phenols into the resin reduces reactivity, hardness, cross-link density, and color formation, but increases solubiHty in nonpolar solvents, dexibiHty, and compatibiHty with natural oils. 

Alkylphenols containing 3—12-carbon alkyl groups are produced from the corresponding alkenes under acid catalysis. Alkylphenols containing the methyl group were traditionally extracted from coal tar. Today they are produced by the alkylation of phenol with methanol. 

In 1957 a procedure was described that selectively alkylated phenol in the ortho position (7). This approach, using aluminum catalysis, made a variety of 2,6-dialkylphenols accessible. The mechanism proposed for this ortho alkylation is outlined as follows ... 

The alkylation of phenol with an alkene using either acid or aluminum catalysis probably accounts for 95% of the commercially produced alkylphenols with alkyl groups of three carbons or larger. The alkenes are commercially available and environmentally kind. They do not produce by-products as do alkylations which use alcohols or alkyl haUdes. Together with an acid catalyst and the appropriate amount of phenol, mono-, di-, and trialkylphenols can be produced. 

Reactions with Aldehydes and Ketones. An important use for alkylphenols is ia phenol—formaldehyde resias. These resias are classified as resoles or aovolaks (see Phenolic resins). Resoles are produced whea oae or more moles of formaldehyde react with oae mole of pheaol uader basic catalysis. These resias are thermosets. Novolaks are thermoplastic resias formed whea an excess of phenol reacts with formaldehyde under acidic conditions. The acid protonates formaldehyde to generate the alkylating electrophile (17). 

---