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3,5-Bis(trimethylsilyl)-4-chloropyridine

Industrial Research Ltd., P.O.Box 31 310, Lower Hutt, New Zealand
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Author to whom correspondence should be addressed.
Molecules 2001, 6(12), M241; https://doi.org/10.3390/M241
Submission received: 8 June 2001 / Accepted: 14 December 2001 / Published: 20 December 2001
(This article belongs to the Section Molbank Section of Molecules, 1997-2001)
Molecules 06 m241 i001
In connection with our studies of the nonlinear optical properties of pyridinylidene compounds we required some pyridine derivatives bearing bulky substituents at the 3- and 5-positions in addition to having an efficient leaving group at the 4-position. To this end we synthesised 3,5-bis(trimethylsilyl)-4- chloropyridine using a bromine-magnesium exchange method recently described [1].
To a stirred solution of 3,5-dibromo-4-chloropyridine [2] (5.27 g, 19.4 mmol) in anhydrous thf (20 mL) under a N2 atmosphere and at room temperature was added dropwise a solution of isopropyl magnesium chloride in thf (10.2 mL, 1.91 M, 19.5 mmol). After 1 h, chlorotrimethylsilane (2.12 g, 2.47 mL, 19.5 mmol) was added and the mixture stirred overnight at room temperature. A further portion of isopropyl magnesium chloride (19.5 mmol) was then added, followed by a second addition of chlorotrimethylsilane (19.5 mmol) 1 h later. The mixture was stirred overnight, poured into water (50 mL) and extracted with dichloromethane (3 x 50 mL). The combined organic extracts were washed with water (50 mL), dried (MgSO4) and concentrated under vacuum to a brown oil. This was subjected to flash chromatography (hexanes elution) to give 3,5-bis(trimethylsilyl)-4-chloropyridine as a white solid (3.47 g, 70 %).
Recrystallisation (benzene) gave colourless crystals.
M.p. 68-70 °C.
MS: Found: MH+ m/z 258.08984 C11H20ClNSi2 requires 258.08956 D = 0.8 p.p.m.
1H NMR (300 MHz, CDCl3): d 0.20, s, 18 H; 8.33, s, 2H.
13C NMR (75 MHz, CDCl3): d 0.0 (CH3), 134.5 (CQ), 156.9 (CH), 158.9 (CQ).
IR (nujol): 1535, 1404, 1250, 1055.

References

  1. Trecourt, F.; Breton, G.; Bonnet, V.; Mongin, F.; Marsais, F.; Queguiner, G. Tetrahedron 2000, 56, 1349. [CrossRef]
  2. den Hertog, H. J.; Hoogzand, C. Recl. Trav. Chim Pays-Bas 1957, 76, 261. [CrossRef]
Sample Availability: Available from the authors and from MDPI.

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MDPI and ACS Style

Kay, A.J.; Woolhouse, A.D. 3,5-Bis(trimethylsilyl)-4-chloropyridine. Molecules 2001, 6, M241. https://doi.org/10.3390/M241

AMA Style

Kay AJ, Woolhouse AD. 3,5-Bis(trimethylsilyl)-4-chloropyridine. Molecules. 2001; 6(12):M241. https://doi.org/10.3390/M241

Chicago/Turabian Style

Kay, A.J., and A.D. Woolhouse. 2001. "3,5-Bis(trimethylsilyl)-4-chloropyridine" Molecules 6, no. 12: M241. https://doi.org/10.3390/M241

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