Trimethylsilyl cyanide: Difference between revisions
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|verifiedrevid = 470615759 |
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|ImageFileL1 = Trimethylsilyl-cyanide-skeletal.png |
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|ImageSizeL1 = 120px |
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|ImageFileR1 = Trimethylsilyl-cyanide-3D-vdW.png |
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|ImageSizeR1 = 120px |
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|PIN = Trimethylsilanecarbonitrile |
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| IUPACName = trimethylsilylformonitrile |
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|OtherNames = Cyanotrimethylsilane; TMS cyanide; Trimethylsilylnitrile; Trimethylsilylcarbonitrile; Trimethylsilylformonitrile |
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|Section1={{Chembox Identifiers |
|Section1={{Chembox Identifiers |
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|Abbreviations = TMSCN |
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|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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|ChemSpiderID = 74110 |
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|InChI = 1/C4H9NSi/c1-6(2,3)4-5/h1-3H3 |
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|InChIKey = LEIMLDGFXIOXMT-UHFFFAOYAM |
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|StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChI = 1S/C4H9NSi/c1-6(2,3)4-5/h1-3H3 |
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|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}} |
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|StdInChIKey = LEIMLDGFXIOXMT-UHFFFAOYSA-N |
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|CASNo_Ref = {{cascite|correct|CAS}} |
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|CASNo = 7677-24-9 |
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|EC_number = 231-657-3 |
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| EINECS = |
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|PubChem = 82115 |
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|SMILES = C[Si](C)(C)C#N |
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|Section2={{Chembox Properties |
|Section2={{Chembox Properties |
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|C=4 | H=9 | Si=1 | N=1 |
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| Appearance = |
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|MeltingPtC = 8 to 11 |
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|BoilingPtC = 114 to 117 |
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| BoilingPtC = 114 to 117 |
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|Section3={{Chembox Structure |
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| Dipole = }} |
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|Section7={{Chembox Hazards |
|Section7={{Chembox Hazards |
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|GHSPictograms = {{GHS02}}{{GHS06}}{{GHS09}} |
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| ExternalSDS = |
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|GHSSignalWord = Danger |
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|HPhrases = {{H-phrases|225|300|310|330|410}} |
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| MainHazards = |
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|PPhrases = {{P-phrases|210|233|240|241|242|243|260|262|264|270|271|273|280|284|301+310|302+350|303+361+353|304+340|310|320|321|322|330|361|363|370+378|391|403+233|403+235|405|501}} |
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|FlashPtC = 1 |
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| RPhrases = {{R11}} {{R26/27/28}} {{R29}} |
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| SPhrases = {{S16}} {{S36/37/39}} {{S45}} |
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| RSPhrases = |
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| FlashPtC = 1 |
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| PEL = }} |
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|Section8={{Chembox Related |
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|OtherAnions = [[Trimethylsilyl chloride]] |
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'''Trimethylsilyl cyanide''' is the [[chemical compound]] with the [[chemical formula|formula]] (CH<sub>3</sub>)<sub>3</sub>SiCN. |
'''Trimethylsilyl cyanide''' is the [[chemical compound]] with the [[chemical formula|formula]] (CH<sub>3</sub>)<sub>3</sub>SiCN. This volatile liquid consists of a [[cyanide]] group, that is CN, attached to a [[trimethylsilyl]] group. The molecule is used in [[organic synthesis]] as the equivalent of [[hydrogen cyanide]]. It is prepared by the reaction of [[lithium cyanide]] and trimethylsilyl chloride:<ref>{{OrgSynth | author = Livinghouse, T. | title = Trimethylsilyl Cyanide: Cyanosilation of p-Benzoquinone | volume = 60 | pages = 126 | year = 1981 | doi = 10.15227/orgsyn.060.0126}}</ref><ref name=eros>{{cite book |doi=10.1002/047084289X.rc276.pub2 |chapter=Cyanotrimethylsilane |title=Encyclopedia of Reagents for Organic Synthesis |year=2011 |last1=Groutas |first1=William C. |last2=Jin |first2=Zhendong |last3=Zhang |first3=Heng |isbn=978-0471936237 }}</ref> |
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:LiCN |
:LiCN + (CH<sub>3</sub>)<sub>3</sub>SiCl → (CH<sub>3</sub>)<sub>3</sub>SiCN + LiCl |
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==Structure== |
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The molecule exhibits the structure of a nitrile-like compound. The compound exists in a rapid equilibrium with a small amount of the [[isomer]]ic [[isocyanide]] (CH<sub>3</sub>)<sub>3</sub>SiNC.<ref>{{cite journal|first1 = M. R.|last1 = Booth|first2 = S. G.|last2 = Frankiss|title = Trimethylsilyl isocyanide|journal = [[Chem. Commun.]]|issue = 21|year = 1968|pages = 1347–1348|doi = 10.1039/C19680001347}}</ref> By contrast, the nearly isostructural [[Pivalonitrile|''tert''-butyl nitrile]] does not readily isomerize to [[Tert-Butyl isocyanide|''tert''-butyl isocyanide]]. The isocyanide isomer can be stabilized by [[complexation]] to metals.<ref>{{cite journal |doi=10.1039/C8NJ00246K |title=Synthesis and Characterization of Cyano and Isocyano Complexes of Bis(dithiolato) Molybdenum Using Me<sub>3</sub>SiCN: A Route to a Cyanide-Bridged Multimer to a Monomer |year=2018 |last1=Bose |first1=Moumita |last2=Moula |first2=Golam |last3=Begum |first3=Ameerunisha |last4=Sarkar |first4=Sabyasachi |journal=New Journal of Chemistry |volume=42 |issue=7 |pages=5580–5592 }}</ref> |
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==Reactions== |
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:{{color|#0a0|RCH{{=}}O}} + (CH<sub>3</sub>)<sub>3</sub>SiC≡N → N≡C–{{color|#0a0|CHR–O}}Si(CH<sub>3</sub>)<sub>3</sub> |
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One use of this reagent is to convert [[pyridine]]-''N''-[[oxide]]s into 2-cyanopyridine. This transformation is best done in [[dichloromethane]] solution using dimethyl[[carbamoyl chloride]] as the activating [[electrophile]]. It is possible to use [[benzoyl chloride]] but the yields and [[regioselectivity]] of the addition of the cyano group are lower. |
One use of this reagent is to convert [[pyridine]]-''N''-[[oxide]]s into 2-cyanopyridine. This transformation is best done in [[dichloromethane]] solution using dimethyl[[carbamoyl chloride]] as the activating [[electrophile]]. It is possible to use [[benzoyl chloride]] but the yields and [[regioselectivity]] of the addition of the cyano group are lower. |
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Acetone cyanohydrin can be used to reversibly generate the cyanide anion.<ref>Nazarov, N. ; Zav'yalov, I. ''J. Gen. Chem. USSR (Engl. Transl.)'' '''1954''', ''24'', 475 [C.A., 49, 6139f (1955)].</ref> |
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<span style="float:right;padding-right:50px;padding-top:30px;">'''''(4)'''''</span>[[File:CNAddScope1.png|center]] |
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==Safety== |
==Safety== |
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Trimethylsilyl cyanide behaves equivalently to [[hydrogen cyanide]], a potent poison.<ref name=eros/> The compound can be disposed of by using a mixture of alkali hydroxide and bleach.<ref>[https://www.gelest.com/wp-content/uploads/product_msds/SIT8585.1-msds.pdf MSDS of trimethylsilyl cyanide. (PDF)]. Gelest. [Jun 13, 2019]</ref> |
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:2 (CH<sub>3</sub>)<sub>3</sub>SiCN + H<sub>2</sub>O → (CH<sub>3</sub>)<sub>3</sub>SiOSi(CH<sub>3</sub>)<sub>3</sub> + 2 HCN |
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==References== |
==References== |
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{{Reflist}} |
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<references/> |
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{{Cyanides}} |
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[[Category:Nitriles]] |
[[Category:Nitriles]] |
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[[Category: |
[[Category:Trimethylsilyl compounds]] |
Latest revision as of 17:02, 5 July 2023
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Names | |||
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Preferred IUPAC name
Trimethylsilanecarbonitrile | |||
Other names
Cyanotrimethylsilane; TMS cyanide; Trimethylsilylnitrile; Trimethylsilylcarbonitrile; Trimethylsilylformonitrile
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Identifiers | |||
3D model (JSmol)
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Abbreviations | TMSCN | ||
ChemSpider | |||
ECHA InfoCard | 100.028.780 | ||
EC Number |
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PubChem CID
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CompTox Dashboard (EPA)
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Properties | |||
C4H9NSi | |||
Molar mass | 99.208 g·mol−1 | ||
Density | 0.793 g/mL at 20 °C | ||
Melting point | 8 to 11 °C (46 to 52 °F; 281 to 284 K) | ||
Boiling point | 114 to 117 °C (237 to 243 °F; 387 to 390 K) | ||
hydrolyzes | |||
Solubility | organic solvents | ||
Refractive index (nD)
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1.392 | ||
Hazards | |||
GHS labelling: | |||
Danger | |||
H225, H300, H310, H330, H410 | |||
P210, P233, P240, P241, P242, P243, P260, P262, P264, P270, P271, P273, P280, P284, P301+P310, P302+P350, P303+P361+P353, P304+P340, P310, P320, P321, P322, P330, P361, P363, P370+P378, P391, P403+P233, P403+P235, P405, P501 | |||
Flash point | 1 °C (34 °F; 274 K) | ||
Related compounds | |||
Other anions
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Trimethylsilyl chloride | ||
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
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Trimethylsilyl cyanide is the chemical compound with the formula (CH3)3SiCN. This volatile liquid consists of a cyanide group, that is CN, attached to a trimethylsilyl group. The molecule is used in organic synthesis as the equivalent of hydrogen cyanide. It is prepared by the reaction of lithium cyanide and trimethylsilyl chloride:[1][2]
- LiCN + (CH3)3SiCl → (CH3)3SiCN + LiCl
Structure
[edit]The molecule exhibits the structure of a nitrile-like compound. The compound exists in a rapid equilibrium with a small amount of the isomeric isocyanide (CH3)3SiNC.[3] By contrast, the nearly isostructural tert-butyl nitrile does not readily isomerize to tert-butyl isocyanide. The isocyanide isomer can be stabilized by complexation to metals.[4]
Reactions
[edit]Trimethylsilyl cyanide hydrolyzes to give hydrogen cyanide and trimethylsilanol:
- (CH3)3SiCN + H2O → (CH3)3SiOH + HCN
In its principal application, it adds across carbon-oxygen double bonds, for example in an aldehyde, to form a new carbon-carbon bond:[2]
- RCH=O + (CH3)3SiC≡N → N≡C–CHR–OSi(CH3)3
The product is an O-silylated cyanohydrin.
One use of this reagent is to convert pyridine-N-oxides into 2-cyanopyridine. This transformation is best done in dichloromethane solution using dimethylcarbamoyl chloride as the activating electrophile. It is possible to use benzoyl chloride but the yields and regioselectivity of the addition of the cyano group are lower.
Acetone cyanohydrin can be used to reversibly generate the cyanide anion.[5]
(4)
Safety
[edit]Trimethylsilyl cyanide behaves equivalently to hydrogen cyanide, a potent poison.[2] The compound can be disposed of by using a mixture of alkali hydroxide and bleach.[6]
References
[edit]- ^ Livinghouse, T. (1981). "Trimethylsilyl Cyanide: Cyanosilation of p-Benzoquinone". Organic Syntheses. 60: 126. doi:10.15227/orgsyn.060.0126.
- ^ a b c Groutas, William C.; Jin, Zhendong; Zhang, Heng (2011). "Cyanotrimethylsilane". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rc276.pub2. ISBN 978-0471936237.
- ^ Booth, M. R.; Frankiss, S. G. (1968). "Trimethylsilyl isocyanide". Chem. Commun. (21): 1347–1348. doi:10.1039/C19680001347.
- ^ Bose, Moumita; Moula, Golam; Begum, Ameerunisha; Sarkar, Sabyasachi (2018). "Synthesis and Characterization of Cyano and Isocyano Complexes of Bis(dithiolato) Molybdenum Using Me3SiCN: A Route to a Cyanide-Bridged Multimer to a Monomer". New Journal of Chemistry. 42 (7): 5580–5592. doi:10.1039/C8NJ00246K.
- ^ Nazarov, N. ; Zav'yalov, I. J. Gen. Chem. USSR (Engl. Transl.) 1954, 24, 475 [C.A., 49, 6139f (1955)].
- ^ MSDS of trimethylsilyl cyanide. (PDF). Gelest. [Jun 13, 2019]