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{{chembox
{{chembox
| Watchedfields = changed
|Watchedfields = changed
| verifiedrevid = 470615759
|verifiedrevid = 470615759
| ImageFileL1 = Trimethylsilyl-cyanide-skeletal.png
|ImageFileL1 = Trimethylsilyl-cyanide-skeletal.png
| ImageSizeL1 = 120px
|ImageSizeL1 = 120px
| ImageFileR1 = Trimethylsilyl-cyanide-3D-vdW.png
|ImageFileR1 = Trimethylsilyl-cyanide-3D-vdW.png
| ImageSizeR1 = 120px
|ImageSizeR1 = 120px
|PIN = Trimethylsilanecarbonitrile
| IUPACName = trimethylsilylformonitrile
| OtherNames = Cyanotrimethylsilane; TMS cyanide; Trimethylsilylnitrile; Trimethylsilanecarbonitrile' Trimethylsilylcarbonitrile
|OtherNames = Cyanotrimethylsilane; TMS cyanide; Trimethylsilylnitrile; Trimethylsilylcarbonitrile; Trimethylsilylformonitrile
|Section1={{Chembox Identifiers
|Section1={{Chembox Identifiers
| Abbreviations = TMSCN
|Abbreviations = TMSCN
| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
|ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}}
| ChemSpiderID = 74110
|ChemSpiderID = 74110
| InChI = 1/C4H9NSi/c1-6(2,3)4-5/h1-3H3
|InChI = 1/C4H9NSi/c1-6(2,3)4-5/h1-3H3
| InChIKey = LEIMLDGFXIOXMT-UHFFFAOYAM
|InChIKey = LEIMLDGFXIOXMT-UHFFFAOYAM
| StdInChI_Ref = {{stdinchicite|correct|chemspider}}
|StdInChI_Ref = {{stdinchicite|correct|chemspider}}
| StdInChI = 1S/C4H9NSi/c1-6(2,3)4-5/h1-3H3
|StdInChI = 1S/C4H9NSi/c1-6(2,3)4-5/h1-3H3
| StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
|StdInChIKey_Ref = {{stdinchicite|correct|chemspider}}
| StdInChIKey = LEIMLDGFXIOXMT-UHFFFAOYSA-N
|StdInChIKey = LEIMLDGFXIOXMT-UHFFFAOYSA-N
| CASNo_Ref = {{cascite|correct|CAS}}
|CASNo_Ref = {{cascite|correct|CAS}}
| CASNo = 7677-24-9
|CASNo = 7677-24-9
|EC_number = 231-657-3
| EINECS =
| PubChem = 82115
|PubChem = 82115
| SMILES = C[Si](C)(C)C#N
|SMILES = C[Si](C)(C)C#N
⚫
|ChEBI_Ref = {{ebicite|correct|EBI}}
| RTECS =
⚫
|KEGG_Ref = {{keggcite|correct|kegg}}
| MeSHName =
⚫
}}
⚫
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI =
⚫
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG =
| ATCCode = }}
|Section2={{Chembox Properties
|Section2={{Chembox Properties
| C=4 | H=9 | Si=1 | N=1
|C=4 | H=9 | Si=1 | N=1
⚫
|Density = 0.793 g/mL at 20 °C
| Appearance =
⚫
|MeltingPtC = 8 to 11
⚫
| Density = 0.793 g/mL at 20 °C
⚫
|BoilingPtC = 114 to 117
⚫
| MeltingPtC = 8
⚫
|Solubility = hydrolyzes
| MeltingPtCH = 11
⚫
|SolubleOther = organic solvents
| Melting_notes =
⚫
|RefractIndex = 1.392
⚫
| BoilingPtC = 114
}}
| BoilingPtCH = 117
| Boiling_notes =
⚫
| Solubility = reacts with water
⚫
| SolubleOther = organic solvents
| Solvent =
| pKa =
| pKb =
| IsoelectricPt =
| SpecRotation =
⚫
| RefractIndex = 1.392
| Viscosity =
| Dipole = }}
|Section3={{Chembox Structure
| CrystalStruct =
| Coordination =
| MolShape =
| Dipole = }}
|Section7={{Chembox Hazards
|Section7={{Chembox Hazards
|GHSPictograms = {{GHS02}}{{GHS06}}{{GHS09}}
| ExternalMSDS =
|GHSSignalWord = Danger
| EUClass =
|HPhrases = {{H-phrases|225|300|310|330|410}}
| EUIndex =
|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}}
| MainHazards =
| NFPA-H =
|FlashPtC = 1
}}
| NFPA-F =
| NFPA-R =
| NFPA-O =
| RPhrases = {{R11}} {{R26/27/28}} {{R29}}
| SPhrases = {{S16}} {{S36/37/39}} {{S45}}
| RSPhrases =
| FlashPtC = 1
| AutoignitionPtC =
| ExploLimits =
| PEL = }}
|Section8={{Chembox Related
|Section8={{Chembox Related
| OtherAnions =
|OtherAnions = [[Trimethylsilyl chloride]]
}}
| OtherCations =
| OtherFunctn =
| Function =
| OtherCpds =
⚫
}}
}}
}}


'''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 | collvol = 7 | collvolpages = 517 | year = 1990 | prep = CV7P0517}}</ref>
'''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>
:LiCN + (CH<sub>3</sub>)<sub>3</sub>SiCl &rarr; (CH<sub>3</sub>)<sub>3</sub>SiCN + LiCl
:LiCN + (CH<sub>3</sub>)<sub>3</sub>SiCl → (CH<sub>3</sub>)<sub>3</sub>SiCN + LiCl


==Structure==
⚫
In its principal reaction, it adds across carbon-oxygen double bonds, for example in an [[aldehyde]]:
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>
⚫
:RCHO + (CH<sub>3</sub>)<sub>3</sub>SiCN &rarr; RCH(CN)OSi(CH<sub>3</sub>)<sub>3</sub>

⚫
The product is an O-silylated [[cyanohydrin]].
==Reactions==
⚫
Trimethylsilyl cyanide [[hydrolyzes]] to give [[hydrogen cyanide]] and [[trimethylsilanol]]:
⚫
:(CH<sub>3</sub>)<sub>3</sub>SiCN + H<sub>2</sub>O → (CH<sub>3</sub>)<sub>3</sub>SiOH + HCN

⚫
In its principal application, it adds across carbon-oxygen double bonds, for example in an [[aldehyde]], to form a new carbon-carbon bond:<ref name=eros/>
:{{color|#0a0|RCH{{=}}O}} + (CH<sub>3</sub>)<sub>3</sub>SiC≡N → N≡C&ndash;{{color|#0a0|CHR&ndash;O}}Si(CH<sub>3</sub>)<sub>3</sub>
⚫
The product is an ''O''-silylated [[cyanohydrin]].


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.

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>
<span style="float:right;padding-right:50px;padding-top:30px;">'''''(4)'''''</span>[[File:CNAddScope1.png|center]]


==Safety==
==Safety==
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>
⚫
Trimethylsilyl cyanide is treated with care since it hydrolyzes to give [[hydrogen cyanide]]:
:2 (CH<sub>3</sub>)<sub>3</sub>SiCN + H<sub>2</sub>O &rarr; (CH<sub>3</sub>)<sub>3</sub>SiOSi(CH<sub>3</sub>)<sub>3</sub> + 2 HCN


==References==
==References==
{{Reflist}}
<references/>

{{Cyanides}}


[[Category:Nitriles]]
[[Category:Nitriles]]
[[Category:Silanes]]
[[Category:Trimethylsilyl compounds]]

Latest revision as of 17:02, 5 July 2023

Trimethylsilyl cyanide
Names
Preferred IUPAC name
Trimethylsilanecarbonitrile
Other names
Cyanotrimethylsilane; TMS cyanide; Trimethylsilylnitrile; Trimethylsilylcarbonitrile; Trimethylsilylformonitrile
Identifiers
3D model (JSmol)
Abbreviations TMSCN
ChemSpider
ECHA InfoCard 100.028.780 Edit this at Wikidata
EC Number
  • 231-657-3
  • InChI=1S/C4H9NSi/c1-6(2,3)4-5/h1-3H3 checkY
    Key: LEIMLDGFXIOXMT-UHFFFAOYSA-N checkY
  • InChI=1/C4H9NSi/c1-6(2,3)4-5/h1-3H3
    Key: LEIMLDGFXIOXMT-UHFFFAOYAM
  • C[Si](C)(C)C#N
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
1.392
Hazards
GHS labelling:
GHS02: FlammableGHS06: ToxicGHS09: Environmental hazard
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
 Trimethylsilyl chloride
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)

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]
  1. ^ Livinghouse, T. (1981). "Trimethylsilyl Cyanide: Cyanosilation of p-Benzoquinone". Organic Syntheses. 60: 126. doi:10.15227/orgsyn.060.0126.
  2. ^ 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.
  3. ^ Booth, M. R.; Frankiss, S. G. (1968). "Trimethylsilyl isocyanide". Chem. Commun. (21): 1347–1348. doi:10.1039/C19680001347.
  4. ^ 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.
  5. ^ Nazarov, N. ; Zav'yalov, I. J. Gen. Chem. USSR (Engl. Transl.) 1954, 24, 475 [C.A., 49, 6139f (1955)].
  6. ^ MSDS of trimethylsilyl cyanide. (PDF). Gelest. [Jun 13, 2019]
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