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Trimethylsilyldiazomethane

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Trimethylsilyldiazomethane
Ball-and-stick model of the trimethylsilyldiazomethane molecule
Names
IUPAC name (Diazomethyl)trimethylsilane
Other names Trimethylsilyldiazomethane
Diazo(trimethylsilyl)methane
Identifiers
CAS Number
3D model (JSmol)
Beilstein Reference 1902903
ChemSpider
ECHA InfoCard 100.131.243 Edit this at Wikidata
EC Number
  • 605-915-4
MeSH Trimethylsilyldiazomethane
PubChem CID
UNII
CompTox Dashboard (EPA)
InChI
  • InChI=1S/C4H10N2Si/c1-7(2,3)4-6-5/h4H,1-3H3Key: ONDSBJMLAHVLMI-UHFFFAOYSA-N
  • InChI=1/C4H10N2Si/c1-7(2,3)4-6-5/h4H,1-3H3Key: ONDSBJMLAHVLMI-UHFFFAOYAN
SMILES
  • C(C)(C)#N
  • ==C(C)(C)C
Properties
Chemical formula C4H10N2Si
Molar mass 114.223 g·mol
Appearance greenish-yellow liquid
Boiling point 96.0 °C (204.8 °F; 369.1 K)
Hazards
GHS labelling:
Pictograms GHS02: FlammableGHS06: ToxicGHS08: Health hazardGHS09: Environmental hazard
Signal word Danger
Hazard statements H330, H350, H370
Precautionary statements P201, P202, P210, P233, P240, P241, P242, P243, P260, P261, P264, P270, P271, P273, P280, P281, P284, P302+P352, P303+P361+P353, P304+P340, P307+P311, P308+P313, P310, P311, P314, P320, P332+P313, P362, P370+P378, P391, P403+P233, P403+P235, P405, P501
Safety data sheet (SDS) External MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C , 100 kPa). checkY verify (what is  ?) Infobox references
Chemical compound

Trimethylsilyldiazomethane is the organosilicon compound with the formula (CH3)3SiCHN2. It is classified as a diazo compound. Trimethylsilyldiazomethane is commercially available as solutions in hexanes, DCM, and ether. It is a specialized reagent used in organic chemistry as a methylating agent for carboxylic acids. It is a safer replacement for diazomethane, which is a sensitive explosive gas, whereas trimethylsilyldiazomethane is a relatively stable liquid and thus easier to handle.

Preparation

Trimethylsilyldiazomethane can be prepared by treating (trimethylsilyl)methylmagnesium chloride with diphenyl phosphorazidate. An isotopically labelled variant, with C at the diazomethyl carbon, is also known.

Reactions

Trimethylsilyldiazomethane is useful for conversion of carboxylic acids to their methyl esters in high yield. The typical reaction conditions for this purpose use methanol as a cosolvent. Under these conditions, diazomethane itself is generated in situ as the active methylating agent, by an acid-catalyzed reaction between trimethylsilyldiazomethane and the alcohol with trimethylsilyldiazomethane as byproduct:

CH 3 OH   + TMSCHN 2 → acid CH 3 OTMS   + CH 2 N 2 {\displaystyle {\ce {CH3OH\ +TMSCHN2->CH3OTMS\ +CH2N2}}}

When the methanol is omitted, substantial amounts of trimethylsilyl ester and trimethylmethyl ester products are formed as well.

It also reacts with alcohols to give methyl ethers, whereas diazomethane may not.

The compound is a reagent in the Doyle–Kirmse reaction with allyl sulfides and allyl amines.

Trimethylsilyldiazomethane is deprotonated by butyllithium:

(CH3)3SiCHN2 + BuLi → (CH3)3SiCLiN2 + BuH

The lithio compound is versatile. From it can be prepared other trimethylsilyldiazoalkanes:

(CH3)3SiCLiN2 + RX → (CH3)3SiCRN2 + LiX

(CH3)3SiCLiN2 reacts with ketones and aldehydes to give, depending on the substituents, acetylenes.

Applications

It has also been employed widely in tandem with GC-MS for the analysis of various carboxylic compounds which are ubiquitous in nature. The fact that the reaction is rapid and occurs readily makes it attractive. However, it can form artifacts which complicate spectral interpretation. Such artifacts are usually the trimethylsilylmethyl esters, RCO2CH2SiMe3, formed when insufficient methanol is present. Acid-catalysed methanolysis is necessary to achieve near-quantitative yields of the desired methyl esters, RCO2Me.

Safety

Trimethylsilyldiazomethane is highly toxic. It has been implicated in the death of at least two chemists, a pharmaceutical worker in Windsor, Nova Scotia and one in New Jersey. Inhalation of diazomethane is known to cause pulmonary edema; trimethylsilyldiazomethane is suspected to behave similarly.

It is possible that upon contact with water on the surface of the lung, trimethylsilyldiazomethane converts to diazomethane.

Trimethylsilyldiazomethane is nonexplosive.

References

  1. ^ Seyferth, Dietmar.; Dow, Alan W.; Menzel, Horst.; Flood, Thomas C. (1968). "Trimethylsilyldiazomethane and trimethylsilylcarbene". J. Am. Chem. Soc. 90 (4): 1080–1082. doi:10.1021/ja01006a055.
  2. Seyferth, Dietmar; Menzel, Horst; Dow, Alan W.; Flood, Thomas C. (1972). "Trimethylsilyl-substituted diazoalkanes I. Trimethylsilyldiazomethane". J. Organomet. Chem. 44 (2): 279–290. doi:10.1016/S0022-328X(00)82916-2.
  3. "Trimethylsilyldiazomethane". pubchem.ncbi.nlm.nih.gov.
  4. Shioiri, Takayuki; Aoyama, Toyohiko; Snowden, Timothy (2001). "Trimethylsilyldiazomethane". e-EROS Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rt298.pub2. ISBN 0471936235.
  5. ^ Shioiri, Takayuki; Aoyama, Toyohiko; Mori, Shigehiro (1990). "Trimethylsilyldiazomethane". Organic Syntheses. 68: 1. doi:10.15227/orgsyn.068.0001.
  6. Nottingham, Chris; Lloyd-Jones, Guy C. (2018). "Trimethylsilyldiazo[C]methane: A Versatile C-Labelling Reagent". Organic Syntheses. 95: 374–402. doi:10.15227/orgsyn.095.0374. hdl:20.500.11820/c801073c-6b4b-4a85-be68-2c4313b6e53d.
  7. ^ Kühnel, E.; Laffan, D. D. P.; Lloyd-Jones, G. C.; Martínez del Campo, T.; Shepperson, I. R.; Slaughter, J. L. (2007). "Mechanism of Methyl Esterification of Carboxylic Acids by Trimethylsilyldiazomethane". Angew. Chem. Int. Ed. 46 (37): 7075–7078. doi:10.1002/anie.200702131. PMID 17691089.
  8. Presser, Armin; Hüfner, Antje (2004). "Diazo(trimethylsilyl)methane – A Mild and Efficient Reagent for the Methylation of Carboxylic Acids and Alcohols in Natural Products". Chemical Monthly. 135 (8). doi:10.1007/s00706-004-0188-4. S2CID 93420685.
  9. Moody, Christopher J.; Shioiri, Takayuki; Aoyama, Toyohiko (2011). "Diazo(trimethylsilyl)methyllithium". E-EROS Encyclopedia of Reagents for Organic Synthesis. pp. 1–7. doi:10.1002/047084289X.rd019.pub2. ISBN 978-0471936237.
  10. "Guilty plea in N.S. drug lab death".
  11. "N.S. probe into pharma worker's death finds vent hoods turned off in lab | SaltWire". www.saltwire.com. Retrieved 2022-05-03.
  12. "OSHA accident report regarding a trimethylsilyldiazomethane fatality". osha.gov. Retrieved 10 April 2020.
  13. ^ Murphy, N. G.; Varney, S. M.; Tallon, J. M.; Thompson, J. R.; Blanc, P. D. (2009). "Fatal Occupational Exposure to Trimethylsilyl-Diazomethane". Clin. Toxicol. 47 (7): 712. doi:10.1080/15563650903076924. S2CID 218859698.
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