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All posts Subject: Preparation of Trimethyloxonium Fluoborate Please login to post

zealot
(Мастер)
10-27-03 17:27
No 467040
User Picture Preparation of Trimethyloxonium Fluoborate
(Rated as: excellent)

Trimethyloxonium Fluoborate
Organic Syntheses, Coll. Vol. 5, p. 1096 (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p1096)
Submitted by H. Meerwein¹

1. Procedure

Freshly prepared triethyloxonium fluoborate² (170 g., 0,90 mole) is dissolved in 500 ml. of anhydrous methylene chloride in a 1 L three-necked flask equipped with a stirrer, gas-inlet tube, and drying tube (Note 1). The reaction flask is immersed in an ice bath, the stirrer is started, and 138 g (3.00 moles) of dry dimethyl ether is passed into the solution from a tared cylinder over a period of about 2 hours. The reaction mixture is allowed to stand overnight at room temperature. An hour after the addition of dimethyl ether is complete, trimethyloxonium fluoborate begins to separate. The initially liquid product solidifies slowly.

The stirrer is replaced by a filter stick, and the supernatant methylene chloride is withdrawn from the crystalline mass of trimethyloxonium fluoborate; nitrogen is admitted through a bubbler during this operation to prevent atmospheric moisture from entering the flask. The crystals are washed with three 100-ml. portions of anhydrous methylene chloride. The flask is transferred to a dry box, and trimethyloxonium fluoborate is collected on a sintered-glass filter, dried for 2 hours in a vacuum desiccator at 25°C (1 mmHg), and bottled in a stream of dry nitrogen (Note 2). The fluoborate is colorless; mp 141-143°C with darkening and slight decomposition; yield 114-124g (86-94%).

2. Notes

1. In order to obtain maximum yields, all operations must be carried out under rigorously dry conditions. The apparatus should be dried in an oven at 110°C, assembled while hot, and dried in a stream of dry nitrogen. The checkers dried the methylene chloride over PA 100 silica gel (12-28 mesh) obtained from Davison Chemical Co., Baltimore, Maryland.
2. Trimethyloxonium fluoborate is less hygroscopic and keeps better than triethyloxonium fluoborate, but it should be stored at 0-5°C in a tightly closed screw-cap bottle.² So stored, it can be kept at least a few weeks.

3. Methods of Preparation

The procedure used is essentially that described by Meerwein and co-workers.³ The salt has also been prepared from the same reagents in a sealed tube.⁴
Curphey has described a convenient synthesis from boron trifluoride diethyl etherate, dimethyl ether, and epichlorohydrin.⁵

4. Merits of the Preparation

This facile preparation is suitable for preparation of larger amounts of salt. Like triethyloxonium fluoborate,² trimethyloxonium fluoborate is a potent alkylating agent. In comparison with trimethyloxonium 2,4,6-trinitrobenzenesulfonate,⁶ trimethyloxonium fiuoborate is easier to make but does not keep quite as well on storage.

5. References

1. Deceased October 24, 1965; formerly at University of Marburg, Marburg, Germany.
2. H. Meerwein, Org. Syntheses, this volume, p. 1080. (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p1080)
3. H. Meerwein, P. Borner, 0. Fuchs, H. J. Sasse, H. Schrodt, and J. Spille, Ber., 89, 2071 (1956).
4. H. Meerwein, E. Battenberg, H. Gold, E. Pfeil, and G. Willfang, J. Prakt. Chem., [2] 164, 143 (1939).
5. T. J. Curphey, Org. Syntheses, 51, 142 (1971) (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv6p1019)
6. G. K. Helmkamp and D. J. Pettitt, Org. Syntheses, this volume, p. 1099. (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p1099)

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	All posts		Subject: Preparation of Trimethyloxonium Fluoborate		Please login to post


		zealot (Мастер) 10-27-03 17:27 No 467040				Preparation of Trimethyloxonium Fluoborate (Rated as: excellent)
						Trimethyloxonium Fluoborate Organic Syntheses, Coll. Vol. 5, p. 1096 (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p1096) Submitted by H. Meerwein¹ 1. Procedure Freshly prepared triethyloxonium fluoborate² (170 g., 0,90 mole) is dissolved in 500 ml. of anhydrous methylene chloride in a 1 L three-necked flask equipped with a stirrer, gas-inlet tube, and drying tube (Note 1). The reaction flask is immersed in an ice bath, the stirrer is started, and 138 g (3.00 moles) of dry dimethyl ether is passed into the solution from a tared cylinder over a period of about 2 hours. The reaction mixture is allowed to stand overnight at room temperature. An hour after the addition of dimethyl ether is complete, trimethyloxonium fluoborate begins to separate. The initially liquid product solidifies slowly. The stirrer is replaced by a filter stick, and the supernatant methylene chloride is withdrawn from the crystalline mass of trimethyloxonium fluoborate; nitrogen is admitted through a bubbler during this operation to prevent atmospheric moisture from entering the flask. The crystals are washed with three 100-ml. portions of anhydrous methylene chloride. The flask is transferred to a dry box, and trimethyloxonium fluoborate is collected on a sintered-glass filter, dried for 2 hours in a vacuum desiccator at 25°C (1 mmHg), and bottled in a stream of dry nitrogen (Note 2). The fluoborate is colorless; mp 141-143°C with darkening and slight decomposition; yield 114-124g (86-94%). 2. Notes 1. In order to obtain maximum yields, all operations must be carried out under rigorously dry conditions. The apparatus should be dried in an oven at 110°C, assembled while hot, and dried in a stream of dry nitrogen. The checkers dried the methylene chloride over PA 100 silica gel (12-28 mesh) obtained from Davison Chemical Co., Baltimore, Maryland. 2. Trimethyloxonium fluoborate is less hygroscopic and keeps better than triethyloxonium fluoborate, but it should be stored at 0-5°C in a tightly closed screw-cap bottle.² So stored, it can be kept at least a few weeks. 3. Methods of Preparation The procedure used is essentially that described by Meerwein and co-workers.³ The salt has also been prepared from the same reagents in a sealed tube.⁴ Curphey has described a convenient synthesis from boron trifluoride diethyl etherate, dimethyl ether, and epichlorohydrin.⁵ 4. Merits of the Preparation This facile preparation is suitable for preparation of larger amounts of salt. Like triethyloxonium fluoborate,² trimethyloxonium fluoborate is a potent alkylating agent. In comparison with trimethyloxonium 2,4,6-trinitrobenzenesulfonate,⁶ trimethyloxonium fiuoborate is easier to make but does not keep quite as well on storage. 5. References 1. Deceased October 24, 1965; formerly at University of Marburg, Marburg, Germany. 2. H. Meerwein, Org. Syntheses, this volume, p. 1080. (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p1080) 3. H. Meerwein, P. Borner, 0. Fuchs, H. J. Sasse, H. Schrodt, and J. Spille, Ber., 89, 2071 (1956). 4. H. Meerwein, E. Battenberg, H. Gold, E. Pfeil, and G. Willfang, J. Prakt. Chem., [2] 164, 143 (1939). 5. T. J. Curphey, Org. Syntheses, 51, 142 (1971) (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv6p1019) 6. G. K. Helmkamp and D. J. Pettitt, Org. Syntheses, this volume, p. 1099. (http://www.orgsyn.org/orgsyn/prep.asp?prep=cv5p1099)

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