22737-36-6

Basic information

• Product Name: O-(TRIMETHYLSILYL)HYDROXYLAMINE
• Synonyms: AMINOXYTRIMETHYLSILANE;AKOS MSC-0140;O-(TRIMETHYLSILYL)HYDROXYLAMINE;O-(TRIMETHYLSILYL)HYDROXYLAMINE, TECH., 90%;0-Trimethylsilylhydroxylamine;O-(TRIMETHYLSILYL)HYDROXYLAMINE,PRACT;O-(Trimethylsilyl)hydroxylamine,97%;O-TriMethylsilyl hydroxylaMine Min 97%
• CAS NO: 22737-36-6
• Molecular Formula: C₃H₁₁NOSi
• Molecular Weight: 105.21
• Product Categories: Hydroxylamines;Hydroxylamines (O-Substituted);Si (Classes of Silicon Compounds);Silanols;Si-O Compounds
• Mol File: 22737-36-6.mol
• Article Data: 6

Chemical Properties

• Boiling Point: 98-100 °C(lit.)
• Flash Point: 48 °F
• Appearance: Clear colorless/Liquid
• Density: 0.86 g/mL at 25 °C(lit.)
• Vapor Pressure: 39mmHg at 25°C
• Refractive Index: n20/D 1.405(lit.)
• Storage Temp.: 2-8°C
• PKA: 3.28±0.70(Predicted)
• BRN: 2035893
• CAS DataBase Reference: O-(TRIMETHYLSILYL)HYDROXYLAMINE(CAS DataBase Reference)
• NIST Chemistry Reference: O-(TRIMETHYLSILYL)HYDROXYLAMINE(22737-36-6)
• EPA Substance Registry System: O-(TRIMETHYLSILYL)HYDROXYLAMINE(22737-36-6)

Safety Data

• Hazard Codes: F,C
• Statements: 11-34
• Safety Statements: 16-26-36/37/39-45
• RIDADR: UN 2733 3/PG 2
• WGK Germany: 3
• F: 10-21
• TSCA: No
• HazardClass: 3.1
• PackingGroup: II
• Hazardous Substances Data: 22737-36-6(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

Uses

O-(Trimethylsilyl)hydroxylamine may be used for the preparation of O-trimethylsilyl oxime ethers.

General Description

O-(Trimethylsilyl)hydroxylamine is an O-substituted hydroxylamine. It is formed as an intermediate during the trimethylsilyl chloride catalyzed synthesis of α-branched amines.

InChI:InChI=1/C3H11NOSi/c1-6(2,3)5-4/h4H2,1-3H3

Synthetic route

trimethylsilyl N-[(chloromethyl)dimethylsilyl]-N-(trimethylsiloxy)carbamate → Hexamethyldisiloxane (107-46-0) + O-Trimethylsilylhydroxylamine (22737-36-6) + 1,3-Bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane (2362-10-9)

Conditions	Yield
In water; acetone at 60℃;	A n/a B 91% C n/a

chloro-trimethyl-silane (75-77-4) → O-Trimethylsilylhydroxylamine (22737-36-6)

Conditions	Yield
With hydroxylamine hydrochloride In dichloromethane; ethylenediamine for 24h;	80%
With hydroxylamine hydrochloride; ethylenediamine 1.) CH2Cl2, RT, 6 h, 2.) CH2Cl2, RT, 24 h; Yield given. Multistep reaction;
With pyridine; hydroxylamine hydrochloride at 20℃;

trimethylsilyl amine (7379-79-5) → O-Trimethylsilylhydroxylamine (22737-36-6)

Conditions	Yield
With hydroxylamine hydrochloride In diethyl ether; ammonia

1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) → O-Trimethylsilylhydroxylamine (22737-36-6)

Conditions	Yield
With hydroxylamine hydrochloride; triethylamine In pentane
With tri-n-propylamine; hydroxylamine hydrochloride

1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) → Hexamethyldisiloxane (107-46-0) + O-Trimethylsilylhydroxylamine (22737-36-6)

Conditions	Yield
With tri-n-propylamine; hydroxylamine hydrochloride for 24h; Ambient temperature; Yield given;

oxalyl dichloride (79-37-8) + 2-[(3,4-dimethoxyphenyl)sulfonyl]-6-phenylhexanoic acid + O-Trimethylsilylhydroxylamine (22737-36-6) → N-hydroxy-2-[(3,4-dimethoxyphenyl)sulfonyl]-6-phenylhexanamide

Conditions	Yield
In dichloromethane; ethyl acetate	100%

Allyl glycidyl ether (106-92-3) + O-Trimethylsilylhydroxylamine (22737-36-6) → C9H21NO3Si

Conditions	Yield
With lithium perchlorate In diethyl ether at 20℃; for 0.5h;	98%

O-Trimethylsilylhydroxylamine (22737-36-6) + acetyl chloride (75-36-5) → N-acetoxyacetamide (7340-09-2)

Conditions	Yield
In pentane at 20℃; for 12h;	96%

O-Trimethylsilylhydroxylamine (22737-36-6) + Phenyl glycidyl ether (122-60-1) → C12H21NO3Si

Conditions	Yield
With lithium perchlorate In diethyl ether at 20℃; for 0.5h;	96%

indole (120-72-9) + O-Trimethylsilylhydroxylamine (22737-36-6) + pivalaldehyde (630-19-3) → C16H26N2OSi

Conditions	Yield
With chloro-trimethyl-silane; lithium perchlorate In diethyl ether at 20℃; for 2h; Friedel-Crafts reaction;	96%

indole (120-72-9) + O-Trimethylsilylhydroxylamine (22737-36-6) + hexanal (66-25-1) → C17H28N2OSi

Conditions	Yield
With chloro-trimethyl-silane; lithium perchlorate In diethyl ether at 20℃; for 2h; Friedel-Crafts reaction;	95%

indole (120-72-9) + O-Trimethylsilylhydroxylamine (22737-36-6) + isobutyraldehyde (78-84-2) → C15H24N2OSi

Conditions	Yield
With chloro-trimethyl-silane; lithium perchlorate In diethyl ether at 20℃; for 2h; Friedel-Crafts reaction;	95%

oxalyl dichloride (79-37-8) + (-)-2-(2-Benzenesulfonyl-ethyl)-3-(3,4-dimethoxy-phenylsulfanyl)-7-phenyl-heptanoic acid (193549-76-7) + O-Trimethylsilylhydroxylamine (22737-36-6) → (-)-N-hydroxy-2-(2-benzenesulfonylethyl)-3-(3,4-dimethoxyphenylsulfanyl)-7-phenylheptanamide

Conditions	Yield
In dichloromethane; N,N-dimethyl-formamide	95%

carbon monoxide (201230-82-2) + O-Trimethylsilylhydroxylamine (22737-36-6) + 17-iodo-androsta-16-ene (26313-26-8) → 17-(N-(trimethylsilyloxy)carbamoyl)androst-16-ene

Conditions	Yield
With triethylamine; triphenylphosphine; palladium diacetate at 60℃; Carbonylation;	94%

indole (120-72-9) + O-Trimethylsilylhydroxylamine (22737-36-6) + butyraldehyde (123-72-8) → C15H24N2OSi

Conditions	Yield
With chloro-trimethyl-silane; lithium perchlorate In diethyl ether at 20℃; for 2h; Friedel-Crafts reaction;	94%

indole (120-72-9) + pentanal (110-62-3) + O-Trimethylsilylhydroxylamine (22737-36-6) → C16H26N2OSi

Conditions	Yield
With chloro-trimethyl-silane; lithium perchlorate In diethyl ether at 20℃; for 2h; Friedel-Crafts reaction;	93%

2-methyl-1,2-epoxypropane (558-30-5) + O-Trimethylsilylhydroxylamine (22737-36-6) → C7H19NO2Si

Conditions	Yield
With lithium perchlorate In diethyl ether at 20℃; for 0.5h;	92%

carbon monoxide (201230-82-2) + O-Trimethylsilylhydroxylamine (22737-36-6) + 17-iodo-4-aza-4-methyl-androst-16-en-3-one (204317-14-6) → 17-(N-(trimethylsilyloxy)carbamoyl)-4-aza-4-methylandrost-16-en-3-one

Conditions	Yield
With triethylamine; triphenylphosphine; palladium diacetate at 60℃; Carbonylation;	91%

indole (120-72-9) + O-Trimethylsilylhydroxylamine (22737-36-6) + cyclohexanecarbaldehyde (2043-61-0) → C18H28N2OSi

Conditions	Yield
With chloro-trimethyl-silane; lithium perchlorate In diethyl ether at 20℃; for 2h; Friedel-Crafts reaction;	90%

di-tert-butyl dicarbonate (24424-99-5) + O-Trimethylsilylhydroxylamine (22737-36-6) → N-trimethylsiloxy O-tert-butyl carbamate

Conditions	Yield
With thioglycoluril In ethanol at 30 - 40℃; for 0.166667h; chemoselective reaction;	90%
With lithium perchlorate In dichloromethane at 20℃; for 5h;	76%

oxalyl dichloride (79-37-8) + O-Trimethylsilylhydroxylamine (22737-36-6) + (+/-)-3-(4-Methoxyphenylsulfanyl)-2-methyl-7-phenylheptanoic acid (193550-75-3) → (+/-)-3-(4-methoxyphenylsulfanyl)-2-methyl-7-phenylheptanoic acid hydroxyamide (193547-71-6)

Conditions	Yield
In dichloromethane	90%

O-Trimethylsilylhydroxylamine (22737-36-6) + Diisopropyl chlorophosphate (2574-25-6) → C9H24NO4PSi

Conditions	Yield
With triethylamine In hexane for 24h; Ambient temperature;	89%

O-Trimethylsilylhydroxylamine (22737-36-6) + 4-chlorobenzaldehyde (104-88-1) → C10H16ClNOSi

Conditions	Yield
With chloro-trimethyl-silane; zirconium borohydride-piperazine; lithium perchlorate In dichloromethane for 3h;	89%

O-Trimethylsilylhydroxylamine (22737-36-6) + 4-bromobenzyl mercaptan (19552-10-4) + 3-(chloromethyl)-1H-1,2,4-triazol-5(4H)-one (252742-72-6) → 5-({[(4-bromophenyl)methyl]thio}methyl)-2,4-dihydro-3H-1,2,4-triazol-3-one (935760-75-1)

Conditions	Yield
With potassium carbonate In tetrahydrofuran; N,N-dimethyl-formamide at 20℃; for 12h;	88%

O-Trimethylsilylhydroxylamine (22737-36-6) + dipropyl chlorophosphate (2510-89-6) → C9H24NO4PSi

Conditions	Yield
With triethylamine In hexane for 24h; Ambient temperature;	87%

O-Trimethylsilylhydroxylamine (22737-36-6) + diethyl chlorophosphate (814-49-3) → N-(diethoxyphosphoroyl)-O-trimethylsilylhydroxylamine (151452-12-9)

Conditions	Yield
With triethylamine In hexane for 24h; Ambient temperature;	86%

O-Trimethylsilylhydroxylamine (22737-36-6) + 4-(4-methoxyphenyl)-2-methyl-2-(methylsulfonyl)butanoic acid (1354546-78-3) → N-hydroxy-4-(4-methoxyphenyl)-2-methyl-2-(methylsulfonyl)butanamide (1289622-76-9)

Conditions	Yield
Stage #1: 4-(4-methoxyphenyl)-2-methyl-2-(methylsulfonyl)butanoic acid With oxalyl dichloride In dichloromethane for 1h; Stage #2: O-Trimethylsilylhydroxylamine In dichloromethane for 1h;	85%

oxalyl dichloride (79-37-8) + (+/-)-(2R*,3R*)-3-(4-methoxybenzenesulfonyl)-7-phenyl-2-(2-phenoxyethyl)heptanoic acid + O-Trimethylsilylhydroxylamine (22737-36-6) + acetonitrile (75-05-8) → (+/-)-(2R*,3R*)-3-(4-Methoxybenzenesulfonyl)-7-phenyl-2-(2-phenoxyethyl)heptanoic acid hydroxyamide

Conditions	Yield
In dichloromethane; water; trifluoroacetic acid	69%

O-Trimethylsilylhydroxylamine (22737-36-6) + 1-methyl-1-<4-(benzyloxy)phenyl>ethanol (94571-13-8) → N-<1-methyl-1-<4-(benzyloxy)phenyl>ethyl>hydroxylamine (118684-95-0)

Conditions	Yield
With trifluoroacetic acid In dichloromethane at 0℃; for 1h;	68%

O-Trimethylsilylhydroxylamine (22737-36-6) + di(4-isocyanatophenyl)methane (101-68-8) → (isocyanatooxy)trimethylsilane (86672-45-9)

Conditions	Yield
at 200℃;	67%

(3R)-6-cyclohexyl-3-(3-{[(3-pyridinylsulfonyl)amino]methyl}-1,2,4-oxadiazol-5-yl)hexanoic acid (438629-24-4) + O-Trimethylsilylhydroxylamine (22737-36-6) + 4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran (96042-30-7) → (3R)-6-cyclohexyl-N-hydroxy-3-(3-{[(3-pyridinylsulfonyl)amino]methyl}-1,2,4-oxadiazol-5-yl)hexanamide

Conditions	Yield
With CDI In methanol; ethyl acetate	67%

O-Trimethylsilylhydroxylamine (22737-36-6) + allyltributylstanane (24850-33-7) + 4-nitrobenzaldehdye (555-16-8) → N-tributyltin-N-trimethylsilyloxy-1-(4-nitrophenyl)but-3-en-1-amine (937737-41-2)

Conditions	Yield
With lithium perchlorate In diethyl ether amine was added to soln. of LiClO4 in Et2O at room temp.; stirred for 10min; Sn compd. was added; stirred at room temp. for 4-5 h; TLC monitoring; quenched with cooled brine; extd. (CH2Cl2); org. extracts dried (MgSO4); concd.; chromd. (silica gel, hexane/EtOAc, 2/1 to 3/1);elem. anal.;	67%

3-pyridinecarboxaldehyde (500-22-1) + O-Trimethylsilylhydroxylamine (22737-36-6) + allyltributylstanane (24850-33-7) → N-tributyltin-N-trimethylsilyloxy-1-(3-pyridinyl)but-3-en-1-amine (937737-40-1)

Conditions	Yield
With lithium perchlorate In diethyl ether amine was added to soln. of LiClO4 in Et2O at room temp.; stirred for 10min; Sn compd. was added; stirred at room temp. for 4-5 h; TLC monitoring; quenched with cooled brine; extd. (CH2Cl2); org. extracts dried (MgSO4); concd.; chromd. (silica gel, hexane/EtOAc, 2/1 to 3/1);elem. anal.;	64%

Upstream product

• 999-97-3 1,1,1,3,3,3-hexamethyl-disilazane 
• 75-77-4 chloro-trimethyl-silane 
• 7379-79-5 trimethylsilyl amine 

Downstream Products

• 41816-36-8 C₁₁H₂₁NOSi₂ 
• 220010-66-2 5-(S)-acetamidomethyl-3-[4'-(N-hydroxyamidino)-3'-fluorophenyl]oxazolidine-2-one 
• 193549-05-2 7-phenyl-3-phenylsulfanylheptanoic acid hydroxyamide 
• 193547-71-6 (+/-)-3-(4-methoxyphenylsulfanyl)-2-methyl-7-phenylheptanoic acid hydroxyamide 
• 193549-14-3 N-hydroxy-3-(4-methoxyphenylsulfanyl)-4-phenylbutyramide 
• 74203-36-4 O-Trimethylsilyl-p-nitrobenzaldoxim 
• 17922-31-5 benzophenone oxime O-trimethylsilyl ether 
• 54389-77-4 C₁₇H₂₉NOSi 

Relevant articles and documents

CRYSTAL FORMS OF 4-[4-(4-FLUOROPHENOXY)BENZENESULFONYLAMINO]-TETRAHYDROPYRAN-4-CARBOXYLIC ACID HYDROXYAMIDE

The present invention relates to a new crystal form of the compound 4-[4-(4-fluorophenoxy)benzenesulfonylamino]-tetrahydropyran-4-carboxylic acid hydroxyamide, combinations of forms of that compound, compositions containing one or more forms of the compound, processes for preparing forms of the compound and compositions containing one or more of them, and the use of one or more forms of the compound and compositions containing one or more of them in treating medical disorders. The invention also provides a new form of the compound 4-[4-(4-fluorophenoxy)benzenesulfonyl amino]-tetrahydropyran-4- carboxylic acid hydroxyamide which is referred to as Form B.

Synthesis of N-(dialkoxyphosphoroyl)-O-(p-nitrophenylsulfonyl)-hydroxylamines - Potential reagents for electrophilic amination

Synthesis of the title compounds by phosphorylation of O-trimethylsilylhydroxylamine followed by methanolysis and O-nosylation of the 'in situ' formed N-phosphoroylhydroxylamines has been described.

EXPEDIENT SYNTHESIS OF MONO-TRIMETHYLSILYL HYDROXYLAMINE AND BIS-TRIMETHYLSILYL HYDROXYLAMINE

Mono and Bis-trimethylsilylhydroxylamine are conveniently prepared by similar procedures on an arbitrarily large scale, without risk or undue effort on the part of the experimenter.