Silicon tetrachloride

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: This material is prepared after the manner of Chappelow et al. (J. Org. Chem. 1960, 25, 435-459.) 2-Propanol (887 g, 14.8 mol) was added slowly over a period of three hours under an atmosphere of Ar to SiCl4 (1475 g, 8.7 mol) at 0° C. The vented HCl gas from the reaction was neutralized by bubbling through a 25% (w/v) solution of KOH in water. The solution was allowed to react for 3 h whereupon, Ar was bubbled through the solution for 30 min. The solution was then distilled through a 30 cm Hemple column packed with 3 mm glass beads (Pot Temp: 180° C., Vapor Temp: 120° C.). The resulting fractions were analyzed by 1H NMR. Fraction A: 411 g (95% Mono: 5% Di); Fraction B: 184 g (22% Mono, 76% Di, 2% Tri); Fraction C: 511 g—27% yield, (95% Di, 5% Tri); and Fraction D: 393 g (50% Di, 50% Tri). Fractions B and D were pooled with other impure cuts from other runs and redistilled at a latter date. 1H NMR (CDCl3, 300 mHz) δ Mono: 4.53 (h, J=6.2 Hz, 1 H), 1.31 (d, J=6.2 Hz, 6 H). Di: 4.41 (h, J=6.2 Hz, 2 H), 1.26 (d, J=6.2 Hz, 12 H); Tri: 4.29 (h, J=6.2 Hz, 3 H), 1.21 (d, J=6.2 Hz, 12 H). 13C NMR (CDCl3, 75.5 mHz) δ Di: 69.27, 24.85. by bubbling through a 25% (w/v) solution of KOH in water to react for 3 h whereupon, Ar was bubbled through the solution for 30 min The solution was then distilled through a 30 cm Hemple column packed with 3 mm glass beads (Pot Temp: 180° C., Vapor Temp: 120° C.) redistilled at a latter date

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of 17.2 g of ethyl 4-hydroxy-3-methoxy-5-nitrophenylglyoxylate in 100 ml of dry acetonitrile and 100 ml of dry toluene is treated with 10.53 g of sodium iodide and 11.9 g of silicon tetrachloride and heated under reflux for 47 hours. The reaction mixture is then evaporated and the residue is distilled six times with 200 ml of toluene each time. The residue obtained is partitioned between water and ether and filtered through a filter aid of diatomaceous earth. The ethereal phase is washed four times with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. The oily residue is treated three times with ether and active carbon. There is obtained ethyl 3,4-dihydroxy-5-nitrophenylglyoxylate of m.p. 77°-79° (from ether/n-hexane). heated under reflux for 47 hours The reaction mixture is then evaporated the residue is distilled six times with 200 ml of toluene each time The residue obtained is partitioned between water and ether filtered through a filter aid of diatomaceous earth The ethereal phase is washed four times with saturated sodium chloride solution dried over sodium sulfate filtered evaporated The oily residue is treated three times with ether and active carbon

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A suspension of 17.2 g of ethyl 4-hydroxy-3-methoxy-5-nitrophenylglyoxylate in 100 ml of dry acetonitrile and 100 ml of dry toluene is treated with 10.53 g of sodium iodide and 11.9 g of silicon tetrachloride and heated under reflux for 47 hours. The reaction mixture is then evaporated and the residue is distilled six times with 200 ml of toluene each time. The residue obtained is partitioned between water and ether and filtered through a filter aid of diatomaceous earth. The ethereal phase is washed four times with saturated sodium chloride solution, dried over sodium sulfate, filtered and evaporated. The oily residue is treated three times with ether and active carbon. There is obtained ethyl 3,4-dihydroxy-5-nitrophenylglyoxylate of m.p. 77°-79° (from ether/n-hexane). heated under reflux for 47 hours The reaction mixture is then evaporated the residue is distilled six times with 200 ml of toluene each time The residue obtained is partitioned between water and ether filtered through a filter aid of diatomaceous earth The ethereal phase is washed four times with saturated sodium chloride solution dried over sodium sulfate filtered evaporated The oily residue is treated three times with ether and active carbon

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A series of 75/25 butadiene/styrene random copolymers were prepared according to Polymerization Recipe III by a continuous polymerization process using a reactor train consisting of a 3-pint, round bottomed glass reactor with stirring means, a 20 feet by 1/2 inch copper tube, and inlet for the 1,3-butadiene coupling adjuvant, a 65-ml. Kenics Static Mixer, a silicon tetrachloride inlet, a gear pump to move the polymer cement and to provide some mixing of the silicon tetrachloride coupling agent with the polymer cement, and a 425-ml Kenics Static Mixer. to provide