4648-54-8

Basic information

• Product Name: Azidotrimethylsilane
• Synonyms: TRIMETHYLSILYL AZIDE;(CH3)3SiN3;azidotrimethyl-silan;Silane, azidotrimethyl-;Silane,azidotrimethyl-;AZIDOTRIMETHYLSILANE;Trimethylsilylazide,95%;Trimethylsilylazide,typically95%
• CAS NO: 4648-54-8
• Molecular Formula: C₃H₉N₃Si
• Molecular Weight: 115.21
• EINECS: 225-078-5
• Product Categories: Si (Classes of Silicon Compounds);Silicon Compounds (for Synthesis);Si-N Compounds;Synthetic Organic Chemistry;Trimethylsilylazide, etc.
• Mol File: 4648-54-8.mol

Chemical Properties

• Melting Point: -95°C
• Boiling Point: 92-95 °C(lit.)
• Flash Point: 74 °F
• Appearance: Clear colorless to slightly yellow/Liquid
• Density: 0.876 g/mL at 20 °C(lit.)
• Refractive Index: n20/D 1.415(lit.)
• Storage Temp.: Refrigerator
• Solubility: Miscible with toluene, dichloromethane, diethyl ether and most o
• Water Solubility: decomposes
• Sensitive: Moisture Sensitive
• BRN: 1903730
• CAS DataBase Reference: Azidotrimethylsilane(CAS DataBase Reference)
• NIST Chemistry Reference: Azidotrimethylsilane(4648-54-8)
• EPA Substance Registry System: Azidotrimethylsilane(4648-54-8)

Safety Data

• Hazard Codes: F,T,N
• Statements: 11-23/24/25-50/53-29
• Safety Statements: 16-36/37/39-45-8-57-36/37-29
• RIDADR: UN 1992 3/PG 2
• WGK Germany: 3
• F: 10-33
• TSCA: Yes
• HazardClass: 3
• PackingGroup: II
• Hazardous Substances Data: 4648-54-8(Hazardous Substances Data)

Usage

Uses

1. Used in Organic Synthesis:
Azidotrimethylsilane is used as a substitution reagent for converting benzyl, allyl, and substituted alkyl halides into the corresponding azides with yields ranging from 60-100% under neutral conditions in a nonaqueous solvent. With the use of tin(IV) chloride as a catalyst, secondary and tertiary cyclic and polycyclic halides can also be transformed into azides with yields between 50-92%.
2. Used as an Azidonation Reagent:
Azidotrimethylsilane is employed as an azidonation reagent for amines, amides, aldehydes, and ketones. It plays a crucial role in the preparation of αand β-siloxy azides from carbonyl compounds and epoxides, as well as in the synthesis of heterocyclic compounds. Additionally, it serves as an effective substitute for hydrazoic acid.
3. Used in the Total Synthesis of Oseltamivir:
Azidotrimethylsilane is utilized in the total synthesis of Oseltamivir, an antiviral medication used to treat and prevent influenza A and B.
4. Used in the Preparation of Heterocyclic Compounds:
Azidotrimethylsilane is also used in the preparation of various heterocyclic compounds, contributing to the development of new pharmaceuticals and chemical compounds with potential applications in different industries.

Preparation

several methods for the synthesis of this azide have been reported.The procedure involving aluminum chloride is not recommended, since an explosive product is formed.Azidotrimethylsilane is now commercially available, and a representative synthetic procedure is as follows. A mixture of sodium azide and chlorotrimethylsilane is refluxed in di-n-butyl ether for 2 days and the azide is safely distilled directly from the reaction vessel. Purer compound (99% content) is obtained by redistillation of the product. Several improved conditions have been reported for the preparation of this azide.In these procedures, trimethylsilyl chloride is reacted with sodium azide either neat or in a high boiling point solvent, such as a mixture of silicone oil and polyethylene glycol. Distillation of the crude product usually provides trimethylsilyl azide (TMSA) in high purity (97.9%) and yield (97%).

Purification Methods

Distil the azide through a Vigreux column (p 11) in a N2 atmosphere maintaining the oil bath temperature thermostat at 135-140o . Check the purity by 1H NMR [CHCl3, : single peak at 13cps from Me4Si]. Likely impurities are siloxane hydrolysis products. The azide is thermally stable even at 200o when it decomposes slowly without explosive violence. All the same, it is advisable to carry out the distillation behind a thick safety screen in a fumehood because unforseen EXPLOSIVE azides may be formed on long standing. [Birkofer & Wagner Org Synth Coll Vol VI 1030 1988.]

InChI:InChI=1/C3H9Si.N3/c1-4(2)3;1-3-2/h1-3H3;/q+1;-1

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 10497-05-9 Tris(trimethylsilyl) phosphate 
• 52764-24-6 tetrakis(trimethylsilyl)tetrazene 
• 79345-35-0 Lithium-tris(trimethylsilyl)tetrazenid 
• 108148-45-4 1-(Di-tert-butylmethylsilyl)-5,5-dimethyl-4-(trimethylsilyl)-1,2,3,4-tetraaza-5-sila-2-cyclopenten 
• 67-64-1 acetone 
• 108148-46-5 5,5-Dimethyl-1-(tri-tert-butylsilyl)-4-(trimethylsilyl)-1,2,3,4-tetraaza-5-sila-2-cyclopenten 
• 2845-62-7 benzenesulphonyl isocyanate 
• 75465-62-2 1,4-Bis(trimethylsilyl)tetrazen 
• 35331-49-8 Tris(trimethylsilyl)tetrazen 
• 75465-64-4 1,1-Bis(trimethylsilyl)tetrazen 

Downstream Products

• 55848-60-7 2-azido-1-phenyl-1-(trimethylsilyloxy)ethane 
• 34314-64-2 trimethylsilyl o-isocyanatobenzoate 
• 34314-65-3 N-(trimethylsilyl)isatoic anhydride 
• 63803-32-7 5-(tri-O-benzyl-α-D-ribofuranosyl)-1H-[1,2,3]triazole-4-carboxylic acid methyl ester 
• 65501-08-8 (1-Azido-2-phenyl-propoxy)-trimethyl-silane 
• 67154-89-6 trans-N,N-Bis(trimethylsilyl)aminostyrol 
• 54124-00-4 1,3-Bis--propan 
• 69249-08-7 Diphenyltrifluorvinylphosphantrimethylsilylimin 
• 61717-86-0 C₂₁H₃₄N₂P₂Si 
• 6063-72-5 trimethylsilyltrimethylphosphanimine 
• 13892-06-3 N-trimethylsilyl(triphenylphosphoranylidene)amine 
• 66055-17-2 1,4-bis(diphenyl(trimethylsilylimino)phosphoranyl)butane 
• 38458-18-3 N-Trimethylsilyl-phenyl-dimethylphosphinimin 
• 51649-11-7 Me₃SiNPPh₂CH₃ 

Relevant articles and documents

Trimethylsilyl Pseudohalide Adducts of GaCl3 and B(C6F5)3

Me3Si?X (X=CN, N3, OCN, and SCN) was treated with the Lewis acids GaCl3 and B(C6F5)3 in toluene yielding the desired adducts Me3Si?X→GaCl3 and Me3Si?X→B(C6F5)3. All synthesized adducts were isolated and completely characterized including single crystal structure elucidations. The different structures, thermodynamics of formation and charge transfer effects are discussed on the basis of experimental and theoretical data.

Borane Adducts of Hydrazoic Acid and Organic Azides: Intermediates for the Formation of Aminoboranes

The reaction of HN3 with the strong Lewis acid B(C6F5)3 led to the formation of a very labile HN3?B(C6F5)3 adduct, which decomposed to an aminoborane, H(C6F5)NB(C6F5)2, above ?20 °C with release of molecular nitrogen and simultaneous migration of a C6F5 group from boron to the nitrogen atom. The intermediary formation of azide–borane adducts with B(C6F5)3 was also demonstrated for a series of organic azides, RN3 (R=Me3Si, Ph, 3,5-(CF3)2C6H3), which also underwent Staudinger-like decomposition along with C6F5 group migration. In accord with experiment, computations revealed rather small barriers towards nitrogen release for these highly labile azide adducts for all organic substituents except R=Me3Si (m.p. 120 °C, Tdec=189 °C). Hydrolysis of the aminoboranes provided C6F5-substituted amines, HN(R)(C6F5), in good yields.

Synthesis, DNA-binding abilities and anticancer activities of triazole-pyrrolo[2,1-c][1,4]benzodiazepines hybrid scaffolds

We synthesized a new series of PBD-hybrid derivatives having tethered triazoles and investigated for their cytotoxicity. The studies indicated that cis-olefin compounds induce higher cytotoxicity with increase in the G1 cell cycle phase compared with the trans-compounds. Quantitative RT-PCR assay indicated that compounds (16a-d) induced G1 phase arrest through down-regulation of cyclin D1 and up-regulation of p21, p27, and p53 mRNA expressions. Compounds 16a-d induced A375 early apoptosis as detected by flow cytometry after double-staining with annexin V and propidium iodide. Moreover, the Western blot analysis showed that A375 treated by compounds (16a-d) resulted in decreased levels of Bcl-2 and Bcl-xL, increased levels of Bax and Bad, and caspase/PARP degradation to identify apoptotic cells.

METHOD FOR PRODUCING TRIMETHYLSILYL AZIDE

The present invention relate to a method for producing a trimethylsilyl azide represented by the formula (3): ????????(CH3)3SiN3?????(3) which comprises reacting a trimethylsilyl chloride represented by the formula (1): ????????(CH3)3SiCl?????(1) with an inorganic salt of hydrogen azide represented by the formula (2): ????????M(N3)n?????(2) wherein M represents an alkali metal or an alkaline earth metal, and n represents 1 or 2, in the presence of a phase-transfer catalyst and an organic solvent having a high boiling point.

Process for preparation of penam derivatives

The invention relates to novel processes for preparing penam derivatives, such as Tazobactam and derivatives thereof. The processes according to the invention encompass procedures for the protection and deprotection of the carboxylic group as well as for the oxidation of the sulphur moiety of penam derivatives. Additionally, the present invention relates to new intermediates for the production of penam derivatives, allowing the desired penam-derivatives to be formulated with high purity and in good yields.

Process for preparation of penam derivatives

The invention relates to novel processes for preparing penam derivatives, such as Tazobactam and derivatives thereof. The processes according to the invention encompass procedures for the protection and deprotection of the carboxylic group as well as for the oxidation of the sulfur moiety of penam derivatives. Additionally, the present invention relates to new intermediates for the production of penam derivatives, allowing the desired penam-derivatives to be formulated with high purity and in good yields.

The chemistry of N,N-bis(siloxy)enamines. Part 8. A general method for the preparation of α-azido oximes from aliphatic nitro compounds

A new strategy for the synthesis of α-azido oximes from aliphatic nitro compounds via interaction of N,N-bis(silyloxy)enamines with trimethylsilylazide was realized to give the target products with good yields.

A study on the haterogeneous reaction of trialkylsilyl chlorides with inorganic salts and monocarboxylates catalysed by PEG400

The important and useful trialkylsilyl pseudohalides R3SiX, where X=NCS, NCO, N3 or CN and R=methyl or ethyl, and trimethylsilyl monocarboxylates, where X=RCOO, were readily prepared in high yields by nucleophilic substitution of R3SiCl with X ions provided by NaX or KX at room temperature catalysed by PEG400 and zinc iodide. The reactions of trimethylsilyl chloride with some metal oxysalts were also studied for the first time.

An ESR study on structures of a series of silylnitrenes

Structures of a series of silylnitrenes formed from silyl azides were investigated by means of ESR. γ-Irradiation and photo-illumination of all the silyl azides resulted in the formation of triplet states even for those having two or three Si-N3 groups in a molecule. ESR spectra of the silylnitrenes exhibited a part of the fine structure at around 820 mT. All the silyl azides studied gave nearly identical D-values (ca. 1.5cm-1) and much larger than those in phenylnitrenes. The results suggested that electron spins are localized in the nitrogen p-orbitals to a large extent and was interpreted in terms of a mono-silane linkage of nitrene, -Si-N:, i.e., interrupting spin delocalization.

Herbicidal 1-aryl-4-substituted-1,4-dihydro-5H-tetrazol-5-ones and sulfur analogs thereof

Herbicidal aryltetrazolinones and thiones of the formula STR1 in which W is oxygen or sulfur; R is alkyl, fluoroalkyl, alkenyl, haloalkenyl, cyanoalkyl, alkylthioalkyl, haloalkoxyalkyl, trifluoromethylthio or alkoxyalkyl; one of X1 and X2 is fluorine, chlorine, or bromine and the other is fluorine, chlorine, bromine, alkyl, nitro or haloalkyl; and Z is a group selected from a variety of substituents including 2-propynyloxy as disclosed and exemplified.