36198-87-5

Basic information

• Product Name: DIMETHYL TRIMETHYLSILYL PHOSPHITE
• Synonyms: Phosphorous acid, dimethyl trimethylsilyl ester;DIMETHYL TRIMETHYLSILYL PHOSPHITE;Dimethoxy[(trimethylsilyl)oxy]phosphine;Trimethylsiloxydimethoxyphosphine;Dimethyl trimethylsilyl phosphite,96%;Dimethyl(trimethylsilyl)phosphite, tech-95;O,O'-DIMETHYL(TRIMETHYLSILYL)PHOSPHITE, tech-95;O,O'-DIMETHYL(TRIMETHYLSILYL)PHOSPHITE
• CAS NO: 36198-87-5
• Molecular Formula: C₅H₁₅O₃PSi
• Molecular Weight: 182.23
• EINECS: 252-908-3
• Product Categories: Organic Building Blocks;Organic Phosphates/Phosphites;Phosphorus Compounds
• Mol File: 36198-87-5.mol
• Article Data: 10

Chemical Properties

• Boiling Point: 36-37 °C11 mm Hg(lit.)
• Flash Point: 102 °F
• Appearance: /
• Density: 0.954 g/mL at 25 °C(lit.)
• Vapor Pressure: 5.82mmHg at 25°C
• Refractive Index: n20/D 1.410(lit.)
• Storage Temp.: 2-8°C
• BRN: 1849308
• CAS DataBase Reference: DIMETHYL TRIMETHYLSILYL PHOSPHITE(CAS DataBase Reference)
• NIST Chemistry Reference: DIMETHYL TRIMETHYLSILYL PHOSPHITE(36198-87-5)
• EPA Substance Registry System: DIMETHYL TRIMETHYLSILYL PHOSPHITE(36198-87-5)

Safety Data

• Hazard Codes: C
• Statements: 10-34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 2920 8/PG 2
• WGK Germany: 3
• F: 10-13
• TSCA: No
• HazardClass: 3.2
• PackingGroup: III
• Hazardous Substances Data: 36198-87-5(Hazardous Substances Data)

Usage

Chemical Properties

clear colorless liquid

Uses

Dimethyl trimethylsilyl phosphite may be used in the preparation of:protected phosphoamino acid, Fmoc-Abu(PO3Me2)-OH, used in Fmoc/solid-phase peptide synthesis phosphoenolpyruvate (PEP) via trimethylsilylation, bromination and Perkow reaction sialyl phosphonate sulfonamide phosphonates

InChI:InChI=1/C5H15O3PSi/c1-6-9(7-2)8-10(3,4)5/h1-5H3

Synthetic route

Dimethyl phosphite (868-85-9) + 1,1,1,3,3,3-hexamethyl-disilazane (999-97-3) → dimethyl trimethylsilyl phosphite (36198-87-5)

Conditions	Yield
at 90℃; for 2h;	89%

chloro-trimethyl-silane (75-77-4) + Dimethyl phosphite (868-85-9) → dimethyl trimethylsilyl phosphite (36198-87-5)

Conditions	Yield
Stage #1: Dimethyl phosphite With triethylamine In dichloromethane at 0℃; Inert atmosphere; Stage #2: chloro-trimethyl-silane In dichloromethane at 0℃; for 0.5h; Inert atmosphere;	75%
With triethylamine In dichloromethane at 0℃; Inert atmosphere;

chloro-trimethyl-silane (75-77-4) + Dimethyl phosphite (868-85-9) → dimethyl trimethylsilyl phosphite (36198-87-5) + tetramethyl (1-(Benzylamino)-5-phenylpent-4-ene-1,3-diyl)(Z)-bis(phosphonate)

Conditions	Yield
With triethylamine In dichloromethane at 0℃; for 0.5h; Inert atmosphere;	A 75% B n/a

chloro-trimethyl-silane (75-77-4) + methyl phosphite (96-36-6, 868-85-9) → dimethyl trimethylsilyl phosphite (36198-87-5)

Conditions	Yield
With 1,1,1,3,3,3-hexamethyl-disilazane In hexane for 1h; Heating;	67%
With triethylamine In benzene
With sodium 1.) ether, 2.) ether, RT, 1.5 h; Yield given. Multistep reaction;
With triethylamine In dichloromethane at 0℃;
With triethylamine In dichloromethane at 0℃; for 1h;

O,O-dimethyl dithiophosphoric acid S-trimethylsilyl ester (18135-34-7) + phosphorous acid trimethyl ester (121-45-9) → dimethyl S-methyl phosphorodithioate (2953-29-9) + dimethyl trimethylsilyl phosphite (36198-87-5)

Conditions	Yield
In diethyl ether Yield given;

trimethylsilyl bromide (2857-97-8) + phosphorous acid trimethyl ester (121-45-9) → dimethyl trimethylsilyl phosphite (36198-87-5)

Conditions	Yield
In dichloromethane for 1.25h;

dimethyl trimethylsilyl phosphite (36198-87-5) + triethylamine (121-44-8) → triethylammonium dimethyl boranophosphate

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite With borane-THF In tetrahydrofuran Stage #2: triethylamine In methanol	100%

dimethyl trimethylsilyl phosphite (36198-87-5) + acetophenone (98-86-2) → (1-phenyl-1-trimethylsilanyloxy-ethyl)-phosphonic acid dimethyl ester (36190-36-0)

Conditions	Yield
With C4H9O(1-)*C13H27KO6(1+) In tetrahydrofuran at 0℃; for 0.25h; Inert atmosphere;	99%

pentanal (110-62-3) + dimethyl trimethylsilyl phosphite (36198-87-5) + N-Phenylhydroxylamine (100-65-2) → C16H30NO4PSi

Conditions	Yield
With diethyl ether; lithium perchlorate at 20℃; for 0.25h;	99%

1-(thiophen-3-yl)-ethanone (1468-83-3) + dimethyl trimethylsilyl phosphite (36198-87-5) → (1-thiophen-3-yl-1-trimethylsilanyloxy-ethyl)-phosphonic acid dimethyl ester (1172141-67-1)

Conditions	Yield
With C4H9O(1-)*C13H27KO6(1+) In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;	99%

dimethyl trimethylsilyl phosphite (36198-87-5) + 1-phenyl-propan-1-one (93-55-0) → (1-phenyl-1-trimethylsilanyloxy-propyl)-phosphonic acid dimethyl ester (1172141-66-0)

Conditions	Yield
With C4H9O(1-)*C13H27KO6(1+) In tetrahydrofuran at 0℃; for 1h; Inert atmosphere;	99%

dimethyl trimethylsilyl phosphite (36198-87-5) + 2-furaldehyde tosylimine (13707-47-6) → dimethyl (furan-2-yl)-(4-methylphenylsulfonamido)methylphosphonate (1154063-26-9)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; 2-furaldehyde tosylimine In tetrahydrofuran at 0 - 20℃; for 5h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	99%
With iodine In dichloromethane at 0 - 20℃; Inert atmosphere;	86%
With Amberlyst-15 In dichloromethane at 0℃; for 3h; Inert atmosphere;	86%

dimethyl trimethylsilyl phosphite (36198-87-5) + 4-methyl-N-(4-trifluoromethylbenzylidene)-benzenesulfonamide (198012-02-1) → dimethyl (((4-methylphenyl)sulfonamido)(4-(trifluoromethyl)phenyl)methyl)phosphonate (1396319-24-6)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; 4-methyl-N-(4-trifluoromethylbenzylidene)-benzenesulfonamide In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	99%

dimethyl trimethylsilyl phosphite (36198-87-5) + tert-butyl (2S)-2-[(tert-butoxycarbonyl)amino]-4-oxobutanoate (81323-59-3) → t-butyl (2S,4RS)-2-(t-butoxycarbonylamino)-4-(dimethylphosphono)-4-hydroxybutanoate (130568-04-6)

Conditions	Yield
In acetonitrile for 1.5h; Heating;	98%

dimethyl trimethylsilyl phosphite (36198-87-5) + N-tosyl-4-nitrobenzaldimine (13707-46-5) → dimethyl (((4-methylphenyl)sulfonamido)(4-nitrophenyl)methyl)phosphonate (1154063-22-5)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; N-tosyl-4-nitrobenzaldimine In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	98%
With iodine In dichloromethane at 0 - 20℃; Inert atmosphere;	91%
With Amberlyst-15 In dichloromethane at 0℃; for 3.5h; Inert atmosphere;	86%

dimethyl trimethylsilyl phosphite (36198-87-5) + 4-methyl-N-(3-nitrobenzylidene)benzenesulfonamide (73845-02-0) → dimethyl (4-methylphenylsulfonamido)(3-nitrophenyl)methylphosphonate (1373284-91-3)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; 4-methyl-N-(3-nitrobenzylidene)benzenesulfonamide In tetrahydrofuran at 0 - 20℃; for 4h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	98%

dimethyl trimethylsilyl phosphite (36198-87-5) + N-Phenylhydroxylamine (100-65-2) + isobutyraldehyde (78-84-2) → C15H28NO4PSi

Conditions	Yield
With diethyl ether; lithium perchlorate at 20℃; for 0.25h;	97%

dimethyl trimethylsilyl phosphite (36198-87-5) + propionaldehyde (123-38-6) + 1,1-dimethylhydrazine (57-14-7) → [1-(N',N'-dimethyl-hydrazino)-propyl]-phosphonic acid dimethyl ester

Conditions	Yield
Stage #1: propionaldehyde; N,N-Dimethylhydrazine With lithium perchlorate In diethyl ether at 20℃; for 0.0833333h; Stage #2: dimethyl trimethylsilyl phosphite In diethyl ether at 20℃; for 0.25h;	97%

dimethyl trimethylsilyl phosphite (36198-87-5) + β-naphthaldehyde (66-99-9) → (S)-dimethyl (hydroxy(naphthalen-2-yl)methyl)phosphonate

Conditions	Yield
With 3,3’-bis[3,5-bis(trifluoromethyl)phenyl]-1,1’-binaphthalene-2,2’-sulfonimide In diethyl ether at -78℃; for 96h; Abramov Phosphorylation; enantioselective reaction;	97%

dimethyl trimethylsilyl phosphite (36198-87-5) + C14H17N → dimethyl ((2E,4E)-1-(isopropylamino)-5-phenylpenta-2,4-dien-1-yl)phosphonate

Conditions	Yield
With sulfuric acid In dichloromethane for 0.25h; Inert atmosphere; Reflux; regioselective reaction;	97%

dimethyl trimethylsilyl phosphite (36198-87-5) + cyclohexanethione (2720-41-4) → (1-Trimethylsilanylsulfanyl-cyclohexyl)-phosphonic acid dimethyl ester (79967-05-8)

Conditions	Yield
at 5 - 20℃;	96%

dimethyl trimethylsilyl phosphite (36198-87-5) + 1,1-dimethylhydrazine (57-14-7) + cyclohexanecarbaldehyde (2043-61-0) → [cyclohexyl-(N',N'-dimethyl-hydrazino)-methyl]-phosphonic acid dimethyl ester

Conditions	Yield
Stage #1: N,N-Dimethylhydrazine; cyclohexanecarbaldehyde With lithium perchlorate In diethyl ether at 20℃; for 0.0833333h; Stage #2: dimethyl trimethylsilyl phosphite In diethyl ether at 20℃; for 0.25h;	96%

1,10-Phenanthroline (66-71-7) + dimethyl trimethylsilyl phosphite (36198-87-5) → dimethyl [4-(dimethoxyphosphoryl)-1,2,3,4-tetrahydro-1,10-phenantrolin-2-yl]phosphonate

Conditions	Yield
With sulfuric acid In dichloromethane at 45℃; Inert atmosphere; Microwave irradiation; Sealed tube;	96%

thiophosphoric acid O,O'-dimethyl ester-O''-trimethylsilanyl ester (18135-15-4) + dimethyl trimethylsilyl phosphite (36198-87-5) → tetramethyl symmetrical monothiopyrophosphate (71861-22-8)

Conditions	Yield
With sulfuryl dichloride In dichloromethane -10 deg C then -40 deg C to R.T.;	95%

dimethyl trimethylsilyl phosphite (36198-87-5) → tetramethyl symmetrical monothiopyrophosphate (71861-22-8)

Conditions	Yield
With sulfur dichloride 1.) from -50 deg C to r.t.; 2.) r.t., 15 min;	95%
With sulfur dichloride In dichloromethane at -50℃;

dimethyl trimethylsilyl phosphite (36198-87-5) + butyraldehyde (123-72-8) + N-Phenylhydroxylamine (100-65-2) → C15H28NO4PSi

Conditions	Yield
With diethyl ether; lithium perchlorate at 20℃; for 0.25h;	95%

(E)-3-phenylpropenal (14371-10-9) + dimethyl trimethylsilyl phosphite (36198-87-5) + N-Phenylhydroxylamine (100-65-2) → C20H28NO4PSi

Conditions	Yield
With diethyl ether; lithium perchlorate at 20℃; for 0.25h;	95%

dimethyl trimethylsilyl phosphite (36198-87-5) + butyraldehyde (123-72-8) + 1,1-dimethylhydrazine (57-14-7) → [1-(N',N'-dimethyl-hydrazino)-butyl]-phosphonic acid dimethyl ester

Conditions	Yield
Stage #1: butyraldehyde; N,N-Dimethylhydrazine With lithium perchlorate In diethyl ether at 20℃; for 0.0833333h; Stage #2: dimethyl trimethylsilyl phosphite In diethyl ether at 20℃; for 0.25h;	95%

dimethyl trimethylsilyl phosphite (36198-87-5) + N-(4-methylbenzylidene)-p-toluenesulfonamide (75159-10-3) → dimethyl (4-methylphenyl)(4-methylphenylsulfonamido)methylphosphonate (1154063-25-8)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; N-(4-methylbenzylidene)-p-toluenesulfonamide In tetrahydrofuran at 0 - 20℃; for 5h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	95%
With iodine In dichloromethane at 0 - 20℃; Inert atmosphere;	92%
With Amberlyst-15 In dichloromethane at 0℃; for 2.5h; Inert atmosphere;	91%

dimethyl trimethylsilyl phosphite (36198-87-5) + 4-nitro-N-(phenylmethylene)benzenesulfonamide (63160-16-7) → dimethyl [{[(4-nitrophenyl)sulfonyl]amino}(phenyl)methyl]phosphonate (1373284-94-6)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; 4-nitro-N-(phenylmethylene)benzenesulfonamide In tetrahydrofuran at 0 - 20℃; for 3h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	95%

dimethyl trimethylsilyl phosphite (36198-87-5) + N-(cyclohexylmethylene)-4-methylbenzenesulfonamide (175355-34-7) → dimethyl cyclohexyl(4-methylphenylsulfonamido)methylphosphonate (1373284-93-5)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; N-(cyclohexylmethylene)-4-methylbenzenesulfonamide In tetrahydrofuran at 0 - 20℃; for 5h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	95%

pentanal (110-62-3) + dimethyl trimethylsilyl phosphite (36198-87-5) + 1,1-dimethylhydrazine (57-14-7) → [1-(N',N'-dimethyl-hydrazino)-pentyl]-phosphonic acid dimethyl ester

Conditions	Yield
Stage #1: pentanal; N,N-Dimethylhydrazine With lithium perchlorate In diethyl ether at 20℃; for 0.0833333h; Stage #2: dimethyl trimethylsilyl phosphite In diethyl ether at 20℃; for 0.25h;	94%

dimethyl trimethylsilyl phosphite (36198-87-5) + 1,1-dimethylhydrazine (57-14-7) + isobutyraldehyde (78-84-2) → [1-(N',N'-dimethyl-hydrazino)-2-methyl-propyl]-phosphonic acid dimethyl ester

Conditions	Yield
Stage #1: N,N-Dimethylhydrazine; isobutyraldehyde With lithium perchlorate In diethyl ether at 20℃; for 0.0833333h; Stage #2: dimethyl trimethylsilyl phosphite In diethyl ether at 20℃; for 0.25h;	94%

4-(4-methylthiophenyl)thiobutyric chloride + dimethyl trimethylsilyl phosphite (36198-87-5) → tetramethyl 4-(4-methylthiophenyl)thio-1-trimethylsiloxybutylidene-1,1-diphosphonate (151426-18-5)

Conditions	Yield
With phosphorous acid trimethyl ester In tetrahydrofuran	94%

dimethyl trimethylsilyl phosphite (36198-87-5) + benzaldehyde N-boc imine (150884-50-7) → carbamic acid N-[(dimethoxyphosphinyl)phenylmethyl] 1,1-dimethylethyl ester (71864-40-9)

Conditions	Yield
Stage #1: dimethyl trimethylsilyl phosphite; benzaldehyde N-boc imine In tetrahydrofuran at 0 - 20℃; for 5h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	94%
With C4H9O(1-)*C13H27KO6(1+) In tetrahydrofuran at -40℃; for 3h; Inert atmosphere;	83%

dimethyl trimethylsilyl phosphite (36198-87-5) + N-(benzylidene)-p-methylbenzenesulfonamide (51608-60-7) → dimethyl (((4-methylphenyl)sulfonamido)(phenyl)methyl)phosphonate (59191-36-5)

Conditions	Yield
With Amberlyst-15 In dichloromethane at 0℃; for 2h; Inert atmosphere;	94%
With iodine In dichloromethane at 0 - 20℃; Inert atmosphere;	93%
Stage #1: dimethyl trimethylsilyl phosphite; N-(benzylidene)-p-methylbenzenesulfonamide In tetrahydrofuran at 0 - 20℃; for 24h; Inert atmosphere; Stage #2: With water In tetrahydrofuran for 0.5h; Inert atmosphere;	93%

Upstream product

• 75-77-4 chloro-trimethyl-silane 
• 868-85-9 Dimethyl phosphite 
• 2857-97-8 trimethylsilyl bromide 
• 121-45-9 phosphorous acid trimethyl ester 
• 999-97-3 1,1,1,3,3,3-hexamethyl-disilazane 
• 18135-34-7 O,O-dimethyl dithiophosphoric acid S-trimethylsilyl ester 
• 96-36-6 methyl phosphite 

Downstream Products

• 67217-10-1 Dimethyl 1-(trimethylsilyloxy)-1-methylhexylphosphonat 
• 67217-11-2 dimethyl 1-(trimethylsiloxy)-1-cyclohexylphosphonate 
• 36190-35-9 Dimethyl trimethylsilyloxybenzylphosphonate 
• 36190-36-0 (1-phenyl-1-trimethylsilanyloxy-ethyl)-phosphonic acid dimethyl ester 
• 57451-27-1 Dimethylphenyl-(trimethylsilyl)-phosphoramidat 
• 1627-98-1 1,1,3,3-tetramethyl-1,3-disiletane 
• 75-77-4 chloro-trimethyl-silane 
• 67-66-3 chloroform 
• 29238-81-1 dimethyl trichloromethylphosphonate 
• 813-77-4 Dimethyl chlorophosphate 
• 146399-38-4 Phosphorsaeure-dimethyl-(2-trimethylsiloxy-3,4,5,6-tetrachlorphenyl)ester 
• 79967-05-8 (1-Trimethylsilanylsulfanyl-cyclohexyl)-phosphonic acid dimethyl ester 
• 132103-75-4 (1R*,2R*)-(+/-)-dimethyl-<2-benzyloxy-1-(trimethylsiloxy)propyl>phosphonate 
• 132103-74-3 (1R*,2S*)-(+/-)-dimethyl-<2-benzyloxy-1-(trimethylsiloxy)propyl>phosphonate 

Relevant articles and documents

Diphosphonylation of aromatic diazaheterocycles and theoretical rationalization of product yields

Diphosphonylated diazaheterocyclic compounds were synthesized in a one-step reaction by using dimethyl trimethylsilyl phosphite (DMPTMS) under acidic conditions. The reaction of DMPTMS with 1,5-naphthyridine yielded the corresponding diphosphonylated product through a tandem 1,4-1,2 addition under microwave conditions. This tandem 1,4-1,2 addition was also evaluated for other substrates, namely, 1,10-phenanthroline, 1,7-phenanthroline and 4,7-phenanthroline. Reactions under reflux and microwave conditions were compared. 1,5-Naphthyridine and the phenanthroline derived substrates are less reactive than previously investigated quinolines. The experimental trends in reactivity were rationalized by means of theoretical calculations. The intrinsic properties, such as aromaticity and proton affinities, showed distinct differences for the various substrates. Furthermore, the calculated free energies of activation for the rate-determining step of the tandem addition reaction enabled us to rationalize the differences in product yields. Both the theoretical and the experimental results show the substantial influence of the position of the nitrogen atoms in the (poly)aromatic compounds on the reaction outcome. Diphosphonylated diazaheterocyclic compounds are synthesized in a one-step reaction from naphthyridines and phenanthrolines by using dimethyl trimethylsilyl phosphite (DMPTMS). The substrate has a profound influence on the product yields for the tandem 1,4-1,2-addition. The product yields are theoretically rationalized by evaluating proton affinities, aromaticities and free energies of activation. Copyright

One-pot tandem 1,4-1,2-addition of phosphites to quinolines

Trialkyl and silylated dialkyl phosphites were evaluated as phosphorus nucleophiles for the addition to quinolines in a strong acidic medium allowing consecutive 1,4- and 1,2-addition breaking up the aromatic stabilisation, thereby leading to 2,4-diphosphono-1,2,3,4-tetrahydroquinolines in one single reaction step in moderate to good yields (2-84%).

Application of bromotrimethylsilane and trialkyl phosphites for convenient and effective synthesis of aminophosphonic acids and corresponding monoalkyl and dialkyl esters

Application of bromotrimethylsilane (Br-TMS) in a mixture with trialkyl phosphite for synthesis of various aminophosphonic acids and esters was investigated. It was found, that appropriate mixtures of Br-TMS and trimethyl phosphite or triethyl phosphite were effective reagents for phosphorylation of various aldimines, obtained from aromatic and heteroaromatic aldehydes. Products of these reactions were corresponding aminophosphonic acids, or corresponding dialkyl or monoalkyl esters, respectively.