Vacuum Atmospheres Company

Lithium was weighed out and charged into reaction flasks under argon in a Vacuum Atmospheres Company dry box. (The checkers did not use a dry box Lithium was freshly cut in air, rinsed in hexane, and charged into reaction flasks under argon.) Biphenyl was purchased from, Aldrich Chemical Company, Inc. Tetrahydrofuran anhydrous, 99.9% purity, was purchased from Aldrich Chemical Company, Inc. It was freshly distilled over Na/K alloy under argon before use. 

Vacuum Atmospheres Company glove box equipped with a HE-493 purifier unit. The checker reports that he did not use a glove box to load the reaction flask, since KH is used in excess and OsH fPMei Phlj is reasonably air stable and can be weighed and handled in the atmosphere. 

General procedure A sealable Schlenk tube was charged with Ni(cod)2 (6 mg, 0.02 mmol, 2 mol%), dppf (22 mg, 0.04 mmol, 4 mol%), and sodium tert-butoxide (135 mg, 1.4 mmol) under Ar in a Vacuum Atmospheres Company (Hawthorne, CA) glove box. Toluene (1 mL) was added, followed by the aryl chloride (1.0 mmol), amine (1.2 mmol), and additional toluene (3 mL). The tube was sealed, removed from the... 

Figure 7.1 Example of two-port stainless steel glove box suitable for a catalyst development laboratory. Source www.vac-atm.com. From Vacuum Atmospheres Company 458 Boston Street, Topsfield, MA. 978-561-1763.

Reaction mixtures were formulated within a Vacuum Atmospheres Company Dri-Lab glove-box under an inert N2 atmosphere prior to reaction and data collection. 

Sodium tert-butoxide is purchased from Aldrich Chemical Company, Inc., and used without further purification. The bulk of this material is stored under nitrogen in a Vacuum Atmospheres Glovebox. Small portions (10-15 g) were removed from the glovebox in glass vials and weighed in the air. The checkers stored sodium tert-butoxide, purchased in 5-g bottles, in a desiccator and weighed it out in air. 

General Methods. Methanol used in kinetic runs was distilled from sodium methoxide or calcium hydride in a nitrogen atmosphere before use. Freshly distilled cyclohexanol was added to the methanol in the ratio 6.0 ml cyclohexanol/200 ml MeOH and was used as an internal standard for gas chromatographic (GC) analysis. Benzaldehyde was distilled under vacuum and stored under nitrogen at 5°. Other aldehydes (purchased from Aldrich) were also distilled before use. The corresponding alcohols (purchased from Aldrich) were distilled and used to prepare GC standards. All metal carbonyl cluster complexes were purchased from Strem Chemical Company and used as received. Tetrahydrofuran (THF) was distilled from sodium benzophenone under nitrogen before use. 

Cyclobutanecarboxylic acid, 98%, is from Aldrich Chemical Company, Inc., and is vacuum distilled before use. Tetrahydrofuran is freshly distilled from sodium-benzophenone under nitrogen. N-Methyiraorpholine, 99%, is from Aldrich Chemical Company, Inc., and is pre-dried over barium oxide, distilled from ninhydrin, and stored over sodium hydroxide pellets. Ethyl chloroformate, 97%, is from Aldrich Chemical Company, Inc., and is freshly distilled prior to use under a nitrogen atmosphere. Anhydrous ammonia (99.99% min) is from a Matheson lecture bottle. The silica gel used for flash chromatography is... 

Available from Alfred Bader Chemicals, Aldrich Chemical Company, Inc., 940 West St. Paul Ave., Milwaukee, WI 53233. Prior to use the compound should be purified on the vacuum line by fractional condensation at -45° (chlorobenzene slush) to eliminate any dimethylamine formed through possible exposure to atmospheric moisture. 

Sparteine is liberated from the commercially available sulfate salt (Aldrich Chemical Company, Inc.) as follows Sparteine sulfate pentahydrate (100 g, 240 mmol) is dissolved in deionized water (125 mL), and to this solution is slowly added aqueous 20% NaOH (100 mL). The resulting milky-white, oily mixture is then extracted with ether (4 x 150 mL). The combined ethereal extracts are dried over anhydrous K2CO3, filtered, and the solvent is removed under reduced pressure. Vacuum distillation of the residual oil from CaH2 affords 52 g (92%) of sparteine as a clear, colorless to slightly yellow, viscous oil (bp 115-120°C/0.3 mm). The sparteine free base readily absorbs atmospheric carbon dioxide (CO2) and should be stored under argon at -20°C in a freezer. 

The polyester resin used in this study, MR 13006 (Aristech Corporation), was supplied as a 60-wt% solution in styrene monomer. The epoxy resin, a digly-cidyl ether of bisphenol A (Epon 828), was obtained from Shell Chemical Company. The reactive liquid rubber, an amino-terminated butadiene-acrylonitrile copolymer (ATBN 1300 x 16), was provided by the BFGoodrich Company. The resin was mixed with additional styrene monomer to maintain the ratio of reactive unsaturation in the polyester-to-styrene monomer at 1 to 3. We added 1.5 wt% of tert-butylperbenzoate initiator to the solution, which we then degassed under vacuum. The mixture was poured between vertical, Teflon-coated, aluminum plates and cured under atmospheric pressure at 100 °C. In the modified compositions, the rubber was first dissolved in the styrene monomer, and then all the other components were added and the solution cured as described. In all the compositions, the ratio of the amine functions with respect to the epoxy functions was kept at 1 to ensure complete cure of the epoxy. 

All solvents and monomers were purified and stored under nitrogen atmosphere. The r-butyl chloride (r-BuCl, Eastman) was distilled from calcium hydride under nitrogen atmosphere prior to use. Diethylaluminum chloride (Et2 A1C1, Texas Alkyls Co.) was purified by vacuum distillation (bp °C/mm Hg 110/25). Ethyl chloride (EtCl, Linde Division, Union Carbide Co.) was purified by passing through a column packed with Molecular Sieves and barium oxide. The m-3-hexene (Chemical Samples Company) was distilled under nitrogen prior to use. The polybutadiene, Diene 35, from the Firestone Tire and Rubber Company and high 1,2-polybutadiene were purified by reprecipitations from benzene into excess acetone. 

The author believes that "low-molecular-weight hydrocarbons refers to light hydrocarbons at atmospheric conditions or vmder vacuum. The foaming tendency of light hydrocarbon distillation at medium pressure (>100 psia) is medium at high pressvu (>3(X) psia) is high. soubce Bolles, W. L. (Monsanto Company), private communication, 1977. 

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