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Metal Hydrides, Metal Alkyls, Metal Aryls, and Silanes mixed with
Acetals, Ketals, Hemiacetals, and Hemiketals

Hazard Predictions

• Corrosive: Reaction products may be corrosive
• Flammable: Reaction products may be flammable
• Generates gas: Reaction liberates gaseous products and may cause pressurization
• Intense or explosive reaction: Reaction may be particularly intense, violent, or explosive

The combination of metal hydrides with acetals, hemiacetals, or ketals may result in reactions of the former with alcohols or ethers similar to the reactions described below:

ALCOHOLS: Interaction of methanol, ethanol, or 2-propanol with undiluted trialkylaluminum compounds is explosive, and tert-butanol reacts vigorously (Mirviss, S. B. et al., Ind. Eng. Chem., 1961, 53 (1), 54A).

The interaction of diethyl zinc and methanol is explosively violent and ignition ensues (Methoden der Organischen Chemie; Muller, E. (Ed.); Stuttgart, Thieme, 1973, Vol. 13.2a, p. 855).

Alcohols react with organolithium and organomagnesium compounds to liberate flammable hydrocarbon gases (Carey, Francis. "Organic Chemistry", 5th Edition, Chpt. 14. Accessed at: http://www.chem.ucalgary.ca/courses/351/Carey5th/Ch14/ch14-1.html#Reactivity).

Hydrides react spontaneously and irreversibly with proton donors, including alcohols, evolving flammable H2 gas (Rittmeyer, P., U. Wietelmann. 2002. Hydrides. In Ullmann's Encyclopedia of Industrial Chemistry. Wiley-VCH Verlag GmbH & Co. KGaA. (Online)).

Glycerol ignites on contact with NaBH4; the reaction between other glycols and NaBH4 is somewhat exothermic (Epshtein, N.A. et al. 1987. Chemical Abstracts 106:55145).

There is a violent reaction between methanol and BeH2, even at very low temperature (Barbaras, G.D. 1951. J. Am. Chem. Soc. 73:48).

Dialkylmagnesium compounds can react explosively with alcohols (Sidgwick, N. V., 1950, The Chemical Elements and their Compounds, Oxford, Oxford University Press, p. 233).

Glycerol undergoes an exothermic reaction with NaH (Urben, P.G. 1995. Bretherick's Handbook of Reactive Chemical Hazards, 5th Edition. Oxford: Butterworth-Heinemann. pp. 1501).

Alcohols can react violently with alkylaluminum solutions to produce a gas, likely H2 (MCA Case History No. 1778, Case Histories of Accidents in the Chemical Industry, Washington, MCA).

Sodium hydride reacts with alcohols to form corrosive and strongly basic sodium alkoxides (Klemm, A., Hartmann, G. and Lange, L. 2000. Sodium and Sodium Alloys. Ullmann's Encyclopedia of Industrial Chemistry. (Online)).

Sodium borohydride decomposes slowly in methanol or ethanol, evolving hydrogen gas (Sullivan, E. and Wade, R. 1980. Hydrides. Kirk-Othmer Encyclopedia of Chemical Technology, 3rd ed. John Wiley & Sons, Inc.).

Dialkylzinc compounds can react explosively with methanol above -60C (Methoden der Organischen Chemie; Muller, E. (Ed.); Stuttgart, Thieme, 1973, Vol. 13.2a, p. 855).

Barium acetylide ignites on contact with ethanol in air (Masdupay, E. et al., Compt. Rend., 1951, 232, 1837-1839).

ETHERS:

Butyllithium reacts with ethers to produce flammable low molecular weight hydrocarbon gases and water soluble lithium alkoxides (Kamienski, C.W. et al. 2001. Lithium and Lithium Compounds. In Kirk-Othmer Encyclopedia of Chemical Technology. John Wiley & Sons, Inc. (Online)).

Solutions of borane in THF build up pressure over time above 0 C, possibly due to the formation of H2 gas from interaction with NaBH4 stabilizer (Gaines, D.F. et al. 1963. Inorganic Chemistry 2:526).

Mixture of THF and CaH2 may explode if heated (Halonbrenner, R. et al. 1978. Chemical and Engineering News 56(6):3).

Distillation of dioxane and LiAlH4 may result in explosion and fire (Urben, P.G. 1995. Bretherick's Handbook of Reactive Chemical Hazards, 5th Edition. Oxford: Butterworth-Heinemann. pp. 47).

THF can react explosively with NaAlH4 if the solution is not properly stirred (Del Giudia, F.P. et al. 1961. Chemical and Engineering News E9(40):57).

Lithium aluminum hydride may ignite on contact with 1,2-dimethoxyethane (MCA Case History No. 1182, Case Histories of Accidents in the Chemical Industry, Washington, MCA).

Dimethyl ether reacts violently with hydrides (Lewis, R.J., Sr. 1992. Sax's Dangerous Properties of Industrial Materials, 8th Edition. New York: Van Nostrand Reinhold. pp. 2317).

Dioxane forms solids with triethynyl aluminum that are explosive when dry (Chini, P. et al. 1962. Chim. e Ind. (Milan) 44:1220).

Diethyl ether reacts vigorously with both triethynyl aluminum and trimethyl aluminum (Methoden der Organischen Chemie; Muller, E. (Ed.); Stuttgart, Thieme, 1970, Vol. 13.4, p. 159; Lewis, R.J., Sr. 1992. Sax's Dangerous Properties of Industrial Materials, 8th Edition. New York: Van Nostrand Reinhold. pp. 1614).

Lithium alkyls react exothermically with ethyl ether to give saturated and unsaturated hydrocarbons and lithium alkoxide (Dickinson, F. 1961. Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry. Vol. 2, Supplement 2, p. 91. Longmans, Green and Co Ltd.; MCA Safety Data Sheet 91, MCA, Washington, 1966).

The mixture of trimethylthallium and diethyl ether explodes at 0C (Leleu, J., Cahiers de Notes Documentaires, 1977, (88), 371).

Triphenylchromium tetrahydrofuranate (Ph3Cr * 3C4H8O) reacts with diethylether to form a black pyrophoric material (Bailar, J. C., Emeleus, H. J., Nyholm, R. S., Trotman-Dickenson, A. F., (Eds.). 1973. Comprehensive Inorganic Chemistry. Oxford, Pergamon. Vol. 4, 974).

Ethylmagnesium iodide reacts violently with ethoxyacetylene if the reaction mixture is not adequately diluted (Jordan, C. F., Chem. Eng. News, 1966, 44(8), 40).

3-Trifluoromethylphenylmagnesium bromide in diethylether decomposes violently if heated above 75C ('Benzotrifluorides Catalog 6/15' West Chester (Pa)., Marshallton Res. Labs., 1971).

Potential Gas Byproducts

• Hydrogen (H2)
• Hydrocarbons