Org. Synth. 1965, 45, 102
DOI: 10.15227/orgsyn.045.0102
TETRAMETHYLBIPHOSPHINE DISULFIDE
[Diphosphine, tetramethyl-, disulfide]
Submitted by G. W. Parshall
1
Checked by W. S. Wadsworth and William D. Emmons.
1. Procedure
Caution! See the discussion in Org. Synth. 1990, Coll. Vol. 7, 533 with regard to potential hazards associated with the title compound.
A 3-l. round-bottomed flask equipped with mechanical stirrer, condenser (surmounted by a drying tube), thermometer, and addition funnel is charged with 800 ml. of 3M methylmagnesium bromide solution (2.4 moles) (Note 1) and 600 ml. of anhydrous ether. The solution is stirred and cooled to 0–5° while a solution of 135 g. (83 ml., 0.80 mole) of thiophosphoryl chloride (Note 2) in 85 ml. of ether is added over a period of 3 hours. A thick white precipitate forms during the course of the addition. After completion of the addition, the reaction mixture is poured onto 500 g. of ice in a 4-l. beaker. Sulfuric acid (900 ml. of 10% solution) is added over a period of 20 minutes with gentle stirring. The mixture is filtered, and the white solid product is washed with 4 l. of water and recrystallized from 2 l. of ethanol. The product is dried over phosphorus pentoxide in a vacuum desiccator to give 50–55 g. (67–74%) of white crystalline tetramethylbiphosphine disulfide, m.p. 223–227° (Note 3). Evaporation of the mother liquor to a volume of 900 ml. gives an additional 3 g. of tetramethylbiphosphine disulfide, m.p. 222–225°.
2. Notes
1.
A suitable 3
M solution of
methylmagnesium bromide in
diethyl ether can be purchased from Arapahoe Chemical Co., Boulder, Colorado.
2.
Although
practical grade thiophosphoryl chloride obtained from Eastman Organic Chemicals will serve in this reaction, a much cleaner product is obtained if the
thiophosphoryl chloride is redistilled (b.p.
122–123°).
3.
Tetramethylbiphosphine disulfide melts sharply at
227° when pure, but the material obtained as described above is satisfactory for most reactions.
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The paragraphs above were added in September, 2014. The statements above do not supersede any specific hazard caution notes and safety instructions included in the procedure.
3. Discussion
Tetramethylbiphosphine disulfide has been prepared by reaction of methylmagnesium halides with
thiophosphoryl chloride.
2,3,4
4. Merits of the Preparation
Tetramethylbiphosphine disulfide is an extremely versatile intermediate for the preparation of compounds containing two methyl groups on
phosphorus, for example,
dimethylphosphine.
5 Most other methods for the preparation of such compounds give large amounts of mono- and trimethylated by-products.
Tetramethylbiphosphine disulfide has been converted in high yields to
dimethylphosphinic acid,
3,4 dimethylphosphinyl chloride,
4,6 dimethylchlorophosphine,
7 and
dimethylthiophosphinic bromide.
8 Other tetraalkylbiphosphine disulfides have been converted to tetraalkylbiphosphines, dialkylthiophosphoryl bromides, and dialkylphosphinic anhydrides.
9 Addition of
tetramethylbiphosphine disulfide to
ethylene followed by desulfurization gives
tetramethylethylenediphosphine, a powerful chelating agent.
10 Other alkyl Grignard reagents also react with
thiophosphoryl chloride under the conditions of the present procedure to give the corresponding tetraalkylbiphosphine disulfides in high yield.
5,11
This preparation is referenced from:
Appendix
Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)
Tetramethylbiphosphine disulfide
Diphosphine, tetramethyl-, disulfide
ethanol (64-17-5)
sulfuric acid (7664-93-9)
ether,
diethyl ether (60-29-7)
PHOSPHORUS (7723-14-0)
ethylene (9002-88-4)
methylmagnesium bromide (75-16-1)
thiophosphoryl chloride (3982-91-0)
dimethylphosphine (676-59-5)
dimethylphosphinic acid (3283-12-3)
dimethylphosphinyl chloride (1111-92-8)
dimethylchlorophosphine (811-62-1)
dimethylthiophosphinic bromide (6839-93-6)
tetramethylethylenediphosphine
phosphorus pentoxide (1314-56-3)
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