Bis(diethylaluminum) Sulfate


[13747-43-8]  · C8H20Al2O4S  · Bis(diethylaluminum) Sulfate  · (MW 266.27)

(a Lewis acid catalyst for alkene polymerization1-4 and for promotion of allylstannane additions to various carbon electrophiles5,6)

Physical Data: none reported.

Solubility: sol hexanes, benzene, and n-heptane.

Form Supplied in: white solid; not widely available.

Analysis of Reagent Purity: by elemental analysis.

Preparative Method: the following procedure has proven most efficacious:3 a flask containing dry pulverized Na2SO4 is charged with a solution of Diethylaluminum Chloride (2 equiv) in n-heptane (or benzene). The stirred mixture is heated at reflux for 1 day. The liquid phase is removed by syringe and concentrated under reduced pressure to afford bis(diethylaluminum) sulfate as a white solid.

Handling, Storage, and Precautions: decomposes in air and reacts violently with moisture with evolution of ethane.3 Use in a fume hood.

Catalyst for Alkene Polymerization.

Bis(diethylaluminum) sulfate has been used in combination with other organometallic complexes to catalyze different types of alkene polymerizations.1-4 A 1:2 combination of this catalyst and cobalt(II) thiocyanate-bis(triphenylphosphine) effectively polymerizes 1,3-butadiene (and isoprene) to 1,2-syndiotactic polyisobutadiene.1 A three-component catalyst system containing bis(diethylaluminum) sulfate, Tris(acetylacetonato)iron(III) and Triphenylphosphine promotes the production of linear dimers of butadiene.2 The title reagent has also proven effective as a powerful activator of Titanium(III) Chloride in the polymerization of propylene.4

Catalyst for Allylstannane Addition.

Bis(diethylaluminum) sulfate is a good Lewis acid catalyst for promoting the coupling of allylstannanes with various electrophiles. For example, it catalyzes the addition of an allyl unit to acetals (eq 1), carbonyl compounds (eq 2), and a,b-unsaturated ketones (eq 3).5

Bis(diethylaluminum) sulfate also promotes the coupling of allylstannanes with various allylic species, such as allylic halides (eq 4), ethers (eq 5), and acetates (eq 6).6 The 1,5-diene products are obtained in good yield, albeit with modest regioselectivity. Many of these allylations are also catalyzed by Boron Trifluoride Etherate, but the yields are generally lower.5,6

1. Iwamoto, M.; Yuguchi, S. J. Polym. Sci., Polym. Lett. 1967, 5, 1007.
2. Iwamoto, M. BCJ 1968, 41, 2188.
3. Matsumura, K.; Atarashi, Y.; Fukumoto, O. JOM 1970, 25, 345.
4. Matsumura, K.; Atarashi, Y.; Fukumoto, O. J. Polym. Sci., Part A-1 1971, 9, 485.
5. Hosomi, A.; Iguchi, H.; Endo, M.; Sakurai, H. CL 1979, 977.
6. Hosomi, A.; Imai, T.; Endo, M.; Sakurai, H. JOM 1985, 95.

Robert F. Monestel & Viresh H. Rawal

The Ohio State University, Columbus, OH, USA

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