18107-18-1

Basic information

• Product Name: (TRIMETHYLSILYL)DIAZOMETHANE
• Synonyms: (trimethylsilyl)diazomethanesolution;(DIAZOMETHYL)TRIMETHYLSILANE;TMS-DIAZOMETHANE;(TRIMETHYLSILYL)DIAZOMETHANE;(TRIMETHYLSILYL)DIAZOMETHANE, 2.0 M IN D;(TRIMETHYLSILYL)DIAZOMETHANE, 2.0M SOLUT ION IN HEXANES;(TRIMETHYLSILYL)DIAZOMETHANE SOLUTION, ~2 M IN HEXANE;Trimethylsilyldiazomethane2.0MINdiethylester
• CAS NO: 18107-18-1
• Molecular Formula: C₄H₁₀N₂Si
• Molecular Weight: 114.22
• Product Categories: Analytical Chemistry;Diazomethane Precursors & Equivalents (GC Derivatizing Reagents);Esterification & Alkylation (GC Derivatizing Reagents);GC Derivatizing Reagents;Si (Classes of Silicon Compounds);Si-(C)4 Compounds;Silicon Compounds (for Synthesis);Synthetic Organic Chemistry
• Mol File: 18107-18-1.mol
• Article Data: 12

Chemical Properties

• Boiling Point: 96 °C
• Flash Point: −31 °F
• Appearance: White/Solution
• Density: 0.773 g/mL at 25 °C
• Refractive Index: 1.4362
• Storage Temp.: Refrigerator
• Solubility: Sol most organic solvents; insol H2O.
• Water Solubility: Immiscible with water. Miscible with organic solvents.
• Sensitive: Moisture & Light Sensitive
• Stability: Shock Sensitive
• BRN: 1902903
• CAS DataBase Reference: (TRIMETHYLSILYL)DIAZOMETHANE(CAS DataBase Reference)
• NIST Chemistry Reference: (TRIMETHYLSILYL)DIAZOMETHANE(18107-18-1)
• EPA Substance Registry System: (TRIMETHYLSILYL)DIAZOMETHANE(18107-18-1)

Safety Data

• Hazard Codes: F+,Xn,N,F,T,T+
• Statements: 12-19-22-66-67-65-62-51/53-48/20-38-11-23-39/26-26-45
• Safety Statements: 9-16-29-33-36/37-61-62-45-28-53
• RIDADR: UN 1208 3/PG 2
• WGK Germany: 3
• F: 10
• TSCA: Yes
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 18107-18-1(Hazardous Substances Data)

Usage

Chemical Properties

clear yellow solution

Physical properties

bp 96 °C/775 mmHg; nD/25 1.4362.2

Uses

Different sources of media describe the Uses of 18107-18-1 differently. You can refer to the following data:
1. Reactant for preparation of: &bull Macrolactam analogs of the natural product macrolide (-)-A26771B with improved metabolic stability and antibacterial activity &bull Aigialomycin D analogues as protein kinase inhibitors for cancer treatment &bull Unnatural α-amino acid derivatives containing gem-bisphosphonates via Michael addition reaction &bull Capped 4-methylumbelliferyl hyaluronan disaccharides and tetrasaccharides as potential hyaluronidase substrates &bull Stictamides A-C as matrix metallopeptidase 12 (MMP12) inhibitors with antitumor invasion activity &bull Endothelin converting enzyme (ECE) Inhibitors WS 75624A and WS 75624B via a cross-metathesis approach &bull Ent-kaurene derivatives as anti-inflammatory agents &bull Desmosdumotin C analogs as potent antitumor agents acting via activation of spindle assembly checkpoint &bull Imidazolo[2,1-b]benzothiazole derivatives as potential p53 inhibitors
2. Trimethylsilyldiazomethane is used as one-carbon homologation reagent; stable, safe substitute for diazomethane;participating in the synthesis reactions of insertion reactions;ketenylation reactions;preparation of homoallylic sulfides;pericyclic reactions;[C-N-N] 1,3-dipole for the preparation of azoles.
3. (Trimethylsilyl)diazomethane is used as an analyte in the determination of some phenolic organohalogens in human serum by GC-MS.

Preparation

Trimethylsilyldiazomethane is prepared by the diazo-transfer reaction of trimethylsilylmethylmagnesium chloride with diphenyl phosphorazidate (DPPA) (eq 1).

General Description

(Trimethylsilyl)diazomethane is considered as a non-explosive substitute to diazomethane for the homologation of carbonyl derivatives, mainly ketones, via reactions such as Tiffeneau-Demjanov rearrangement.

InChI:InChI=1/C4H10N2Si/c1-7(2,3)4-6-5/h4H,1-3H3

Synthetic route

(N-nitroso-N-trimethylsilylmethyl)acetamide (59546-83-7) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With phenethylamine under 8 - 10 Torr;	95%
With phenethylamine at 40℃; under 14 Torr;

diphenyl phosphoryl azide (26386-88-9) + Chloromethyltrimethylsilane (2344-80-1) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
Stage #1: Chloromethyltrimethylsilane With magnesium; ethylene dibromide In diethyl ether at 40℃; for 1h; Stage #2: diphenyl phosphoryl azide In diethyl ether at 0℃; for 2h;	79%

diphenyl phosphoryl azide (26386-88-9) + (trimethylsilyl)methylmagnesium chloride (13170-43-9) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
In diethyl ether for 16h; cooling;	78%

diazomethane (186581-53-3, 908094-01-9) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In diethyl ether 1.) -78 deg C, 2.) 0 deg C;	74%

Chloromethyltrimethylsilane (2344-80-1) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
Stage #1: Chloromethyltrimethylsilane With lithium In diethyl ether at -23 - 20℃; for 2h; Inert atmosphere; Stage #2: With 4-toluenesulfonyl azide In diethyl ether at 0 - 20℃; for 22h; Inert atmosphere;	40%
With diphenyl phosphoryl azide; magnesium 1) diethyl ether, room temp., 2) diethyl ether or dibutyl ether, 0 deg C to room temp.; Multistep reaction;

N-nitroso-N-trimethylsilylmethylurea (39482-21-8) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With potassium hydroxide In benzene	28.2%
With potassium hydroxide In benzene
With potassium hydroxide
With potassium hydroxide In pentane at 0℃; for 1.5h;

Methyl-nitroso-(trimethylsilylmethyl)carbamat (26205-77-6) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With sodium hydroxide

[N-(trimethylsilyl)methyl]urea (5663-03-6) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With hydroxide; cis-nitrous acid Multistep reaction;

diazomethane (186581-53-3, 908094-01-9) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) → Hexamethyldisiloxane (107-46-0) + diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In diethyl ether at -78℃; for 2h;

diphenyl phosphoryl azide (26386-88-9) + Chloromethyltrimethylsilane (2344-80-1) → Hexamethyldisiloxane (107-46-0) + diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With magnesium In diethyl ether 2h, 0 deg C -> 3h, r.t.;	A n/a B 8.2 g

N-trimethylsilylmethylamine (18166-02-4) → diazomethyl-trimethyl-silane (18107-18-1)

Conditions	Yield
With 4-nitro-phenol; propane-1,3-diyl dinitrite In 2-methyltetrahydrofuran at 80℃; for 0.333333h; Solvent; Reagent/catalyst; Temperature; Reflux;

Upstream product

• 186581-53-3 diazomethane 
• 27607-77-8 trimethylsilyl trifluoromethanesulfonate 
• 18166-02-4 N-trimethylsilylmethylamine 
• 26386-88-9 diphenyl phosphoryl azide 
• 13170-43-9 (trimethylsilyl)methylmagnesium chloride 
• 2344-80-1 Chloromethyltrimethylsilane 
• 5663-03-6 [N-(trimethylsilyl)methyl]urea 
• 59546-83-7 (N-nitroso-N-trimethylsilylmethyl)acetamide 
• 39482-21-8 N-trimethylsilylmethyl-N-nitrosourea 
• 26205-77-6 Methyl-nitroso-(trimethylsilylmethyl)carbamat 

Downstream Products

• 18178-59-1 (E)-1,2-bis(trimethylsilyl)ethene 
• 1473-61-6 (Z)-1,2-bis(trimethylsilyl)ethylene 
• 55395-25-0 1,1,2-trimethylsilene 
• 82518-20-5 trans-2-phenyl-1-(trimethylsilyl)cyclopropane 
• 82518-20-5 Trimethyl-((1R,2R)-2-phenyl-cyclopropyl)-silane 
• 2550-26-7 4-Phenyl-2-butanone 
• 84655-22-1 2-phenacyl-5-trimethylsilyltetrazole 
• 1083-30-3 dihydrochalcone 
• 58416-23-2 benzyl thiophene-2-acetate 
• 121876-51-5 5-Benzhydryl-1-(4-bromo-phenyl)-4-trimethylsilanyl-1H-[1,2,3]triazole 
• 112-12-9 methyl nonyl ketone 
• 122053-65-0 ((2R,3R)-2,3-Diphenyl-cyclopropyl)-trimethyl-silane 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 606-27-9 methyl 2-nitrobenzoate 

Relevant articles and documents

METALLORGANISCHE DIAZOALKANE XVI. SYNTHESE VON SILYLDIAZOALKANEN Me3Si(LnM)CN2

Silyldiazoalkanes Me3Si(LnM)CN2 (LnM = Me3Ge, Me3Sn, Me3Pb; Me2As, Me2Sb, Me2Bi) have been synthesized by three different routes: (a) reactions of Me3SiCHN2 with metal amides LnMNR1R2 of Group IVB and VB elements, using Me3SnCl as ca

Catalytic trimerization of bis-silylated diazomethane

(Me3Si)2CNN isomerizes upon addition of traces of [Me3Si]+ ions to give (Me3Si)2NNC, which then undergoes an unusual trimerization reaction to give exclusively 4-diazenyl-3-hydrazinylpyrazo

Trimethylsilyldiazomethane - A mild and efficient reagent for the methylation of carboxylic acids and alcohols in natural products

Esterification of various naturally occurring carboxylic acids with trimethylsilyldiazo-methane proceeds nearly quantitatively under very mild conditions. Furthermore, highly sterically hindered alcohols can be converted directly to the corresponding methyl ethers. Improved methods for the preparation and quantification of this reagent are described. Springer-Verlag 2004.