Butylphenols, solid

In a 200-ml, three-necked flask equipped with a mechanical stirrer, a thermometer, and a gas-inlet tube are placed 41.2 g. (0.2 mole) of 2,6-di- er/-butylphenol (Note 1) in 75 ml. of dimethylformamide (Note 2) and 2.5 g. (0.0075 mole) of salcomine (Note 3). With stirring, oxygen is introduced at such a rate that the temperature does not exceed 50°. This is continued for 4 hours. At the end of the reaction the temperature drops to about 25°. The reaction mixture is then poured onto 500 g. of crushed ice and 15 ml. of 4N hydrochloric acid. A yellow-brown precipitate is formed. The solid material is collected by suction filtration and washed on the filter three times with 50-ml. portions of IN hydrochloric... 

Fig. 8. Constant acid-constant base frequency shift-enthalpy relations. Solid lines are constant acid lines. The phenol line also contains values for p-t-butylphenol, 4-, phenol, 0, p-chlorophenol, , m-trifluormethylphenyl, A. The acid butanol is H...

A similar reaction of i -Bu2Mg with 2,6-di-fert-butylphenol in the presence of 18-crown-6 affords i-BuMgOC6H3Bu-r-2,6(18-crown-6) (209) as a crystalline solid. An X-ray crystal-structure determination showed that this compound in the solid state also exists as a monomer with a a-bonded i-butyl group and a a-bonded phenoxy oxygen atom. Three adjacent oxygen atoms of the crown-ether are involved in coordination to magnesium, resulting in penta-coordination. 

A novel mesoporous intercalate belonging to the class of mesostructured solid acids known as porous clay heterostructures (PCH) has been synthesized through the surfactant - directed assembly of silica in the two - dimensional galleries of saponite. The new saponite PCH, denoted SAP-PCH, exhibits a basal spacing of 32.9 A, a BET surface area of 850 m2/g and pore volume of 0.46 cm3/g. SAP-PCH is an effective catalyst for the condensed phase Friedel-Crafts alkylation of bulky 2,4-di-tert-butylphenol (DBP) with cinnamyl alcohol to produce a large flavan, namely, 6,8-di-tert-butyl-2,3-dihydro[4H]benzopyran. 

Here we report the synthesis and catalytic application of a new porous clay heterostructure material derived from synthetic saponite as the layered host. Saponite is a tetrahedrally charged smectite clay wherein the aluminum substitutes for silicon in the tetrahedral sheet of the 2 1 layer lattice structure. In alumina - pillared form saponite is an effective solid acid catalyst [8-10], but its catalytic utility is limited in part by a pore structure in the micropore domain. The PCH form of saponite should be much more accessible for large molecule catalysis. Accordingly, Friedel-Crafts alkylation of bulky 2, 4-di-tert-butylphenol (DBP) (molecular size (A) 9.5x6.1x4.4) with cinnamyl alcohol to produce 6,8-di-tert-butyl-2, 3-dihydro[4H] benzopyran (molecular size (A) 13.5x7.9x 4.9) was used as a probe reaction for SAP-PCH. This large substrate reaction also was selected in part because only mesoporous molecular sieves are known to provide the accessible acid sites for catalysis [11]. Conventional zeolites and pillared clays are poor catalysts for this reaction because the reagents cannot readily access the small micropores. 

Dealkylation of 2,6-di-ferf-butylphenol takes place at 403—423 K in the presence of solid H3PW 2O40. H3PWi2O40 is two orders of magnitude more active than aluminum sulfate for this reaction (205). 

The milled stock (111 parts) was dispersed in CH2C12 and a solution of f-butylphenolic resin (40 parts) in CH2C12 was stirred in. Additional CH2C12 was added so that the final slurry had 20% solids. The solvent was then evaporated and a thin film was produced. This film was pressed against the prepared substrate and covered with a sheet of finely-woven cotton cloth. The final sandwich was first pressed in a mold for 30 min at room temperature and 25,000 lb on a 5 in. ram and then cured for 40 min at 150°C and 30,000 lb on a 5 in. ram. The thickness of the elastomer layer in the resulting cloth-elastomer-substrate sandwich was 0.4 mm. Peeling experiments were carried out on strips of cloth-backed elastomer layer after trimming them to a uniform width on the substrate of 2 cm. 

A reactor was charged with 4-t-butylphenol (199.7 mmol) and 100 ml of toluene and then heated to reflux under nitrogen during which time roughly 20 ml of toluene were removed by distillation. The mixture was then cooled to 100°C, treated with the syringe-addition of tetraisopropyl titanate (47.43 mmol), and refluxed 30 minutes. Isopropanol was then removed by distillation at up to 90°C. Thereafter an additional 50 ml of isopropanol was distilled over at 140°C, and a dark red liquid was isolated. Upon cooling the liquid crystallized to a red solid at ambient temperature. The crystals were dried overnight at 80°C, and the product was isolated in 94.8% yield. 

A dimeric zirconium(IV) trihydride complex has been synthesized by reaction of LiBHEt3 with the tridentate triaryloxide zirconium chloride complex ZrCl(THF)2(t-Bu-L) (H3(t-Bu-L) = 2,6-bis(4-t-butyl-6-methylsalicyl)-4-f-butylphenol) (equation 14). The solid-state structure shows each zirconium center adopts a trigonal prismatic stracture with a Zr-Zr separation of 3.163(1) A. In solution, the three resulting hydrides appear equivalent on the NMR timescale. Analogous reactivity was observed for the titanium conger. However, in the resulting titanium trihydride, the metals are assigned formal Ti(III) oxidation states. ... 

The effects of various parameters on the ferf-butylation of phenol on the ZeoUte-H-beta have been studied". Alkylation of phenol in the vapor phase using Zeolite SAP-11 and ferf-butyl alcohol gives the ortho- and para-ferf-butylphenols, together with the 2, 6-di-ferf-butylphenol (equation 22). Vapor-phase alkylation of phenol with tert-butyl alcohol over solid superacid catalysts, such as sulfated zirconia" and mesoporous H-AMCM-41, gives para-fert-butylphenol as a major product in high regioselectivity. 

Poly-rert-butylphenol disulfide Yellow to light Solid density at 20°C = 805 kg/m Nitrosamine-free... 

Amino-4-r-butylphenol and 2-amino-4-chlorophenol behaved similarly under identical conditions. A solid product was obtained in each case which melted at 205.5-207 C (4) and 206-207 C (5), respectively. A mixture melting point determination of a mixture of the two materials melted over a range (179-186 C) to confirm the individual identities. Spectral data for both products are in the Experimental. 

These results show an apparent activation energy for the hydrogenation of 4-t-butylphenol of 15kJ/mol, which indicates that the reaction is controlled by liquid/solid mass transfer. 

DIBUTYLPHENOL or 2,6-DI-/rrt-BUTYLPHENOL (26746-38-3) Combustible solid or liquid above 97°F/33°C (flash point >200 F/>93°C). Reacts with oxidizers, with a risk of fire or explosions. Reacts with boranes, alkalis, aliphatic amines, amides, nitric acid, sulfuric acid. 

Alkofen B 2,4,6-Tri-t-butylphenol 2,4,6-Tri-tert-butyl-1-hydroxybenzene 2,4,6-Tri-tert-butylphenol CCRIS 5845 2,4,6-Tris(1,1-dimethylethyl)phenol EINECS 211-989-5 NSC 14459 P 23 Phenol, 2,4,6-lri-tert-butyl- Phenol, 2,4,6-tris(1,1-dimethylethyl)- TM02 Tris(1,1-dimethyl-ethyl)phenol Voidox. Solid mp = 131° bp = 278° (P = 0.864 Xm = 280 nm (cyclohexane) insoluble in H2O, alkali, soluble in EtOH, Me2CO, CCI4. 

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