756-79-6

Basic information

• Product Name: Dimethyl methylphosphonate
• Synonyms: Dimethoxymethylphosphine oxide;dimethoxymethylphosphineoxide;Dimethyl ester of methylphosphonic acid;dimethylmethanephosphate;Furan tf 2000;Fyrol dmmp;fyroldmmp;Metaran
• CAS NO: 756-79-6
• Molecular Formula: C₃H₉O₃P
• Molecular Weight: 124.08
• EINECS: 212-052-3
• Product Categories: Miscellaneous;Horner-Emmons Reaction;Synthetic Organic Chemistry;Wittig & Horner-Emmons Reaction;C-C Bond Formation;Horner-Wadsworth-Emmons Reagents;Olefination;organophosphorus compound
• Mol File: 756-79-6.mol
• Article Data: 87

Chemical Properties

• Melting Point: <50°
• Boiling Point: 181 °C(lit.)
• Flash Point: 156 °F
• Appearance: Clear colorless/Liquid
• Density: 1.145 g/mL at 25 °C(lit.)
• Vapor Pressure: <0.1 mm Hg ( 20 °C)
• Refractive Index: n20/D 1.413(lit.)
• PKA: pKa (20°) in water: 2.37
• Water Solubility: >=10 g/100 mL at 21 ºC
• Stability: Stability Combustible. Incompatible with strong oxidizing agents, strong bases. May soften some rubbers or plastics. Hydrolyzes
• Merck: 14,3391
• BRN: 878263
• CAS DataBase Reference: Dimethyl methylphosphonate(CAS DataBase Reference)
• NIST Chemistry Reference: Dimethyl methylphosphonate(756-79-6)
• EPA Substance Registry System: Dimethyl methylphosphonate(756-79-6)

Safety Data

• Hazard Codes: T,Xi
• Statements: 46-36-62
• Safety Statements: 53-26-45
• RIDADR: 2810
• WGK Germany: 2
• RTECS: SZ9120000
• TSCA: Yes
• Hazardous Substances Data: 756-79-6(Hazardous Substances Data)

Usage

Chemical Properties

colourless liquid

Uses

Different sources of media describe the Uses of 756-79-6 differently. You can refer to the following data:
1. NMR probe for cell volume. Flame retardant. Simulant for nerve agents.
2. As a flame retardant, a preignition additive for gasoline, an antifoam agent, a plasticizer and stabilizer, a textile conditioner, and an antistatic agent; used experimentally to mimic the physical and spectroscopic (but not biological) properties of anticholinesterase agents
3. Dimethyl methylphosphonate is used as a catalyst and a reagent in organic synthesis for the conversion of esters to ketophosphonates. It is an additive for the synthesis of unsaturated polyester resin which has flame retardant high phosphorous and UV-cured epoxy acrylate. It finds application as hydraulic fluids as well.

Synthesis Reference(s)

Synthetic Communications, 20, p. 239, 1990 DOI: 10.1080/00397919008052289

General Description

Clear colorless liquid with a pleasant odor.

Air & Water Reactions

Highly flammable. Water soluble. Hydrolyzes slowly upon contact with water.

Reactivity Profile

Dimethyl methylphosphonate is incompatible with strong oxidizing agents and strong bases. Dimethyl methylphosphonate reacts with organic halides at 302-392° F. When heated to temperatures greater than 302° F, Dimethyl methylphosphonate will act as an alkylating agent with basic nitrogen compounds and phenols. Dimethyl methylphosphonate reacts with enol lactones. Dimethyl methylphosphonate has plasticizing properties and may soften or deteriorate some plastics and elastomers (particularly vinyl-based resins, neoprene and natural rubbers) upon contact.

Health Hazard

Dimethyl methylphosphonate (DMMP) administered to male rats is a reproductive toxicant and carcinogen. Effects in humans are unknown.

Fire Hazard

Dimethyl methylphosphonate is combustible.

Safety Profile

Moderately toxic by intravenous route. Experimental reproductive effects. Questionable carcinogen with experimental carcinogenic data. Mutation data reported. An experimental nerve gas stimulant. A flame retardant. When heated to decomposition it emits toxic fumes of POx

InChI:InChI=1/C3H9O3P/c1-5-7(3,4)6-2/h1-3H3

Synthetic route

phosphorous acid trimethyl ester (121-45-9) + methyl iodide (74-88-4) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
In neat (no solvent) at 100℃; for 0.138833h; Solvent; Arbuzov Reaction; Flow reactor;	99%
for 1h; Irradiation;	95%
for 0.0833333h; Michaelis-Arbuzov reaction; microwave irradiation;	95%

phosphorous acid trimethyl ester (121-45-9) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With iodine for 24h; Heating;	99%
With trimethylsilyl trifluoromethanesulfonate In chloroform at 60℃; for 18h; Michaelis-Arbuzov rearrangement;	98%
With trimethylsilyl iodide at 50℃; for 6h; Michaelis-Arbuzov rearrangement;	95%

1,1,1-tri(hydroxymethyl)propane (77-99-6) + phosphorous acid trimethyl ester (121-45-9) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
Stage #1: 1,1,1-tri(hydroxymethyl)propane; phosphorous acid trimethyl ester at 80 - 120℃; for 4h; Stage #2: With methyl p-toluene sulfonate at 170 - 180℃; for 2h; Reagent/catalyst; Temperature;	96%

methylphosphonic acid dichloroanhydride (676-97-1) + methanol (67-56-1) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With aluminum oxide at 20℃;	95%
With triethylamine	80%

benzyl bromide (100-39-0) + phosphorous acid trimethyl ester (121-45-9) → dimethyl benzylphosphonate (773-47-7) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
at 120℃; for 9h;	A 95% B 144 g

phosphorous acid trimethyl ester (121-45-9) + 1-Bromo-2-bromomethyl-benzene (3433-80-5) → dimethyl (2-bromobenzyl)phosphonate (103474-07-3) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
	A 93% B n/a

ethyl 4-(acetoxymethyl)-2-(bromomethyl)-5-tert-butylfuran-3-carboxylate + phosphorous acid trimethyl ester (121-45-9) → dimethyl methane phosphonate (756-79-6) + ethyl 4-(acetoxymethyl)-5-tert-butyl-2-(dimethoxyphosphorylmethyl)furan-3-carboxylate

Conditions	Yield
at 100 - 140℃; for 0.2h; Arbuzov reaction;	A n/a B 90%

methanol (67-56-1) + methylphosphonic acid (993-13-5) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With tetrachlorosilane at 0℃;	89%
With p-TsOH-Celite at 20℃;	87%
Stage #1: methylphosphonic acid With 1H-imidazole; iodine In dichloromethane at 45 - 50℃; for 0.5h; Gareg-Samuelsson reaction; Stage #2: methanol In dichloromethane at 45 - 50℃; for 0.666667h; Gareg-Samuelsson reaction;	85%

1,2,2,2-tetrachloro-1-isocyanato-ethane (15145-29-6) + phosphorous acid trimethyl ester (121-45-9) → 2,2-dichloro-1-(dimethoxyphosphinyl)vinyl isocyanate (85978-66-1) + 2,2,2-trichloro-1-(dimethoxyphosphinyl)ethyl isocyanate (85978-65-0) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
at 100℃; for 1h;	A 7% B n/a C 81%

phosphorous acid trimethyl ester (121-45-9) + Benzyl bromoacetate (5437-45-6) → benzyl 2-(dimethoxyphosphoryl)acetate (57443-18-2) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
at 85℃; for 60h;	A 81% B n/a

iodobenzene (591-50-4) + Dimethyl phosphite (868-85-9) → dimethyl phenylphosphonate (2240-41-7) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With N-benzyl-N,N,N-triethylammonium chloride; potassium carbonate; palladium diacetate; triphenylphosphine In acetonitrile at 70℃; for 4h; Title compound not separated from byproducts;	A 80% B n/a

Dimethyl phosphite (868-85-9) + methyl iodide (74-88-4) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
Stage #1: Dimethyl phosphite With sodium hydroxide for 0.25h; Michaelis-Becker reaction; Ionic liquid; Stage #2: methyl iodide for 12h; Michaelis-Becker reaction; Ionic liquid;	80%
Stage #1: Dimethyl phosphite With sodium In dichloromethane for 40h; Heating; Stage #2: methyl iodide In dichloromethane for 10h; Michaelis-Becker reaction; Heating;

trimethyl phosphonoformate (31142-23-1) → trimethyl phosphite (512-56-1) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
at 295℃; for 6h;	A 18% B 75%

dichloromethane (75-09-2) + Dimethyl phosphite (868-85-9) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With tetraethylammonium bromide; cyclohexene at 20℃; electrolysis, Pt electrodes;	75%

methanol (67-56-1) + methyl hydrogen methylphosphonate (1066-53-1) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With polymer supported sulfonated magnetic resin In toluene at 20 - 70℃; for 0.75h;	74%

phosphorous acid trimethyl ester (121-45-9) → trimethyl phosphite (512-56-1) + O,O,O-trimethylthiophosphate (152-18-1) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With sulfur trioxide In dichloromethane at -95℃;	A 25% B 4% C 71%

carbonic acid bromomethyl ester 1-ethoxy-ethyl ester + phosphorous acid trimethyl ester (121-45-9) → 1-ethoxyethyl O,O-dimethylphosphorylethanoate (749887-15-8) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
at 50 - 60℃; for 2.5h; Arbuzov reaction;	A 71% B 25.9%

methanol (67-56-1) → trimethyl phosphite (512-56-1) + Dimethyl phosphite (868-85-9) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With phosphorous; tetraethylammonium iodide In acetonitrile at 18℃; electrolysis;	A 70% B 11% C 3%
With phosphorous; tetraethylammonium iodide In acetonitrile at 18℃; Mechanism; Product distribution; electrolysis; var. nucleophiles; var. temperatures;	A 70% B 11% C 3%
With phosphorous In acetonitrile at 18℃; Electrolysis;	A 70% B 11% C 3%

methyl phosphite (96-36-6, 868-85-9) + methyl iodide (74-88-4) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With potassium carbonate at 25℃; for 4h;	70%
With potassium carbonate at 25℃; for 4h; other phosphonates;	70%

carbonic acid 1-ethoxy-ethyl ester iodomethyl ester + phosphorous acid trimethyl ester (121-45-9) → 1-ethoxyethyl O,O-dimethylphosphorylethanoate (749887-15-8) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
at 40 - 50℃; for 2h; Arbuzov reaction;	A 67.2% B 27.4%

dimethyl (1-methylethyl) phosphite (52956-34-0) + methyl iodide (74-88-4) → isopropyl methyl methylphosphonate (690-64-2) + diisopropyl methyl phosphonate + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
for 2h; Arbusov rearrangement; Heating;	A 66% B 7 % Chromat. C 3 % Chromat.

Dimethyl phosphite (868-85-9) + MeX (X = Br or I) → dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With tetraethylammonium bromide In acetonitrile at 20℃; on a platinum electrode;	65%

phosphorous acid trimethyl ester (121-45-9) → trimethyl phosphite (512-56-1) + O,O,O-trimethylthiophosphate (152-18-1) + dimethyl sulfate (77-78-1) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With sulfur trioxide In dichloromethane at -78℃; Product distribution; other trialkyl phosphite,trialkyl phosphine, trialkyl arsines, trialkoxyarsines, var. molar ratio and temperatures;	A 22% B 4% C 55% D 19%
With sulfur trioxide In dichloromethane at -78℃;	A 48% B 16% C 3% D 9%

methanol (67-56-1) → trimethyl phosphite (512-56-1) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With phosphorous; tetraethylammonium iodide In acetonitrile at 50℃; electrolysis;	A 51% B 28%
With phosphorous In acetonitrile at 50℃; Electrolysis;	A 51% B 28%

benzophenone (119-61-9) + dimethyl α-trimethylsilylmethylphosphonate (13433-42-6) → 1,1-Diphenylethylene (530-48-3) + dimethyl (2,2-diphenylvinyl)phosphonate (71265-07-1) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With cesium fluoride	A 20% B 30% C 50%
With cesium fluoride In tetrahydrofuran for 24h; Heating;	A 20% B 30% C 50%

propargyl bromide (106-96-7) + phosphorous acid trimethyl ester (121-45-9) → Dimethyl propargylphosphonate (4885-44-3) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
for 5h; Heating;	A 45% B n/a

phosphorous acid trimethyl ester (121-45-9) → Dimethyl propargylphosphonate (4885-44-3) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
With propargyl bromide for 5h; Heating;	A 45% B n/a

methyl trifluoromethanesulfonate (333-27-7) + phosphorous acid trimethyl ester (121-45-9) → methyltrimethoxyphosphonium triflate (64294-66-2) + dimethyl methane phosphonate (756-79-6)

Conditions	Yield
In chloroform-d1 at 0 - 20℃; for 1h; Time; Inert atmosphere; Schlenk technique;	A 45% B 27 %Spectr.

benzaldehyde (100-52-7) + dimethyl methane phosphonate (756-79-6) → dimethyl (2-hydroxy-2-phenyl)ethylphosphonate

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.0833333h; Metallation; Stage #2: benzaldehyde In tetrahydrofuran; hexane at -78℃; for 0.0833333h; Addition;	100%
With n-butyllithium 1.) THF, hexane, -78 deg C, 15 min, 2.) THF, hexane, -78 -> -20 deg C; Yield given. Multistep reaction;
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran at -70℃; Inert atmosphere; Stage #2: benzaldehyde In tetrahydrofuran Inert atmosphere;

(S)-3-(4-Methoxy-benzyl)-2,2-dimethyl-oxazolidine-4-carboxylic acid methyl ester (231291-83-1) + dimethyl methane phosphonate (756-79-6) → {2-[(S)-3-(4-Methoxy-benzyl)-2,2-dimethyl-oxazolidin-4-yl]-2-oxo-ethyl}-phosphonic acid dimethyl ester (231291-85-3)

Conditions	Yield
With n-butyllithium In tetrahydrofuran at -78℃;	100%

N-carbobenzoxy-L-phenylalanine methyl ester (35909-92-3) + dimethyl methane phosphonate (756-79-6) → dimethyl [(3S)-4-phenyl-3-[(benzyloxycarbonyl)amino]-2-oxobutyl]phosphonate (347851-53-0)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: N-carbobenzoxy-L-phenylalanine methyl ester In tetrahydrofuran; hexane Further stages.;	100%
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexanes at -78℃; under 760.051 Torr; for 0.333333h; Stage #2: N-carbobenzoxy-L-phenylalanine methyl ester In tetrahydrofuran; hexanes at -78 - 20℃; under 760.051 Torr; for 1.25h; Stage #3: With water; acetic acid In tetrahydrofuran; hexanes at 0℃; under 760.051 Torr;	100%

2-methyl-3-oxocyclohex-1-en-1-yl trifluoromethanesulfonate (150765-78-9) + dimethyl methane phosphonate (756-79-6) → 1-(dimethylphosphonato)-2-oxo-6-octyne (475467-02-8)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Stage #2: 2-methyl-3-oxocyclohex-1-en-1-yl trifluoromethanesulfonate In tetrahydrofuran; hexane at -78 - 60℃; for 1.33333h; Inert atmosphere;	100%
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Inert atmosphere; Stage #2: 2-methyl-3-oxocyclohex-1-en-1-yl trifluoromethanesulfonate In tetrahydrofuran; hexane at -78 - 60℃; Inert atmosphere; Stage #3: With water; ammonium chloride In tetrahydrofuran; diethyl ether; hexane Inert atmosphere;	97%
Stage #1: dimethyl methane phosphonate With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Stage #2: 2-methyl-3-oxocyclohex-1-en-1-yl trifluoromethanesulfonate In tetrahydrofuran at -78 - 60℃; for 1.33333h; Claisen condensation;	21%
Stage #1: dimethyl methane phosphonate With lithium hexamethyldisilazane In tetrahydrofuran at -78℃; for 0.5h; Stage #2: 2-methyl-3-oxocyclohex-1-en-1-yl trifluoromethanesulfonate In tetrahydrofuran at -78 - 60℃; Claisen condensation;	21%

Benzyloxymethyl-oxiran (2930-05-4) + dimethyl methane phosphonate (756-79-6) → dimethyl 4-(benzyloxy)-3-hydroxybutanephosphonate (476310-16-4)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.25h; Stage #2: Benzyloxymethyl-oxiran With boron trifluoride diethyl etherate In tetrahydrofuran; hexane at -70℃; for 2h;	100%
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran at -78℃; for 0.25h; Stage #2: Benzyloxymethyl-oxiran With boron trifluoride diethyl etherate In tetrahydrofuran at -70℃; for 2h;	100%

methyl 3-(adamantan-1-yl)propanoate (29542-59-4) + dimethyl methane phosphonate (756-79-6) → dimethyl 2-oxo-4-(1-adamantyl)butylphosphonate (53273-30-6)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane; water	100%

methyl 2-((tert-butyl(diphenyl)silyl)oxy)acetate (154698-92-7) + dimethyl methane phosphonate (756-79-6) → dimethyl 3-(tert-butyldiphenylsilyl)oxy-2-oxopropylphosphonate (1075244-38-0)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: methyl 2-((tert-butyl(diphenyl)silyl)oxy)acetate In tetrahydrofuran; hexane for 0.5h; Inert atmosphere; Stage #3: With ammonium chloride In tetrahydrofuran; hexane; water	100%

1-(tert-butyl) 2-methyl (R)-pyrrolidine-1,2-dicarboxylate (73323-65-6) + dimethyl methane phosphonate (756-79-6) → (R)-1-tert-butyl 2-(2-(dimethoxyphosphoryl)acetyl)pyrrolidine-1-carboxylate (1140496-59-8)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexanes at -78℃; for 0.5h; Stage #2: 1-(tert-butyl) 2-methyl (R)-pyrrolidine-1,2-dicarboxylate In tetrahydrofuran; hexanes at -78℃; for 3h; Stage #3: With water; ammonium chloride In tetrahydrofuran; hexanes	100%

dimethyl (2S)-N-(triphenylmethyl)aspartate (116393-72-7) + dimethyl methane phosphonate (756-79-6) → methyl (2S)-2-(tritylamino)-4-oxo-5-(dimethoxyphosphoryl)pentanoate (1197335-24-2)

Conditions	Yield
With n-butyllithium In tetrahydrofuran at -78℃; Inert atmosphere; regioselective reaction;	100%
With n-butyllithium In tetrahydrofuran at -78℃; for 2h; Inert atmosphere;	92%
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: dimethyl (2S)-N-(triphenylmethyl)aspartate In tetrahydrofuran at -78℃; for 2h; Inert atmosphere;	92%

ethyl 4-methoxy-5-(4-((4-methoxybenzyl)oxy)phenyl)-2-oxo-1,2-dihydropyridine-3-carboxylate (1309567-74-5) + dimethyl methane phosphonate (756-79-6) → dimethyl (2-(4-methoxy-5-(4-((4-methoxybenzyl)oxy)phenyl)-2-oxo-1,2-dihydropyridin-3-yl)-2-oxoethyl)phosphonate (1309567-75-6)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78 - -20℃; for 0.25h; Inert atmosphere; Stage #2: ethyl 4-methoxy-5-(4-((4-methoxybenzyl)oxy)phenyl)-2-oxo-1,2-dihydropyridine-3-carboxylate In tetrahydrofuran; hexane at -78 - 0℃; for 0.166667h; Inert atmosphere;	100%

C17H28O4 + dimethyl methane phosphonate (756-79-6) → C19H33O6P

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: C17H28O4 In tetrahydrofuran; hexane at -78℃; for 2h; Stage #3: With ammonium chloride In tetrahydrofuran; hexane; water at -78℃;	100%

methyl 5-methylpyridine-2-carboxylate (29681-38-7) + dimethyl methane phosphonate (756-79-6) → C10H14NO4P (1369491-73-5)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Inert atmosphere; Stage #2: methyl 5-methylpyridine-2-carboxylate In tetrahydrofuran; hexane at -78℃; for 0.333333h; Inert atmosphere; Stage #3: With ammonium chloride In tetrahydrofuran; hexane; water	100%

methyl 2,3-O-isopropylidene-α-D-mannopyranoside-4,6-cyclic sulfate (139978-82-8) + dimethyl methane phosphonate (756-79-6) → [2-((2R,3S,4S,5S,6S)-3,4,5-Trihydroxy-6-methoxy-tetrahydro-pyran-2-yl)-ethyl]-phosphonic acid dimethyl ester (454183-61-0)

Conditions	Yield
Stage #1: methyl-2,3-O-isopropylidene-4,6-cyclic sulfate-α-D-mannopyranoside; dimethyl methane phosphonate With 1,1-Diphenylethylene; N,N,N,N,N,N-hexamethylphosphoric triamide; n-butyllithium In tetrahydrofuran at -78℃; Stage #2: In tetrahydrofuran; methanol regioselective reaction;	100%

dimethyl methane phosphonate (756-79-6) + ethyl 4-iodopent-4-enoate → dimethyl (5-iodo-2-oxohex-5-en-1-yl)phosphonate (1569075-94-0)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.333333h; Inert atmosphere; Stage #2: ethyl 4-iodopent-4-enoate In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere;	100%

methyl 2-(((tert-butoxycarbonyl)oxy)methyl)benzofuran-5-carboxylate + dimethyl methane phosphonate (756-79-6) → tert-butyl ((5-(2-(dimethoxyphosphoryl)acetyl)-1-benzofuran-2-yl)methyl) carbonate

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Stage #2: methyl 2-(((tert-butoxycarbonyl)oxy)methyl)benzofuran-5-carboxylate In tetrahydrofuran; hexane at -78℃; for 2h;	100%

dimethyl methane phosphonate (756-79-6) → methylphosphonic acid dichloroanhydride (676-97-1) + methylene chloride (74-87-3)

Conditions	Yield
With thionyl chloride; N-Formylpiperidine for 19h; Heating; various conditions and cactalasts investigated;	A 99.2% B n/a

3-[2-(tert-Butyl-dimethyl-silanyloxy)-4-(trityl-amino)-phenyl]-propionic acid methyl ester (117625-50-0) + dimethyl methane phosphonate (756-79-6) → {4-[2-(tert-Butyl-dimethyl-silanyloxy)-4-(trityl-amino)-phenyl]-2-oxo-butyl}-phosphonic acid dimethyl ester (110828-45-0)

Conditions	Yield
With n-butyllithium	99%
With n-butyllithium Yield given;

methyl (4Z)-6,6,9-trimethyl-10-(tetrahydropyranyloxy)dec-6-en-2-ynoate (260970-23-8) + dimethyl methane phosphonate (756-79-6) → (7Z)-1-dimethoxyphosphiryl-7,10,10-trimethyl-11-(tetrahydropyranyloxy)undec-7-en-3-yn-2-one (260970-36-3)

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; Substitution;	99%

Dodecanal (112-54-9) + dimethyl methane phosphonate (756-79-6) → dimethyl 2-hydroxytridecylphosphonate (88708-59-2)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.0833333h; Metallation; Stage #2: Dodecanal In tetrahydrofuran; hexane at -78℃; for 0.0833333h; Addition;	99%

(S)-methyl 2-palmitamido-3-(4-((4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methoxy)phenyl)propanoate (935548-14-4) + dimethyl methane phosphonate (756-79-6) → (S)-dimethyl 2-oxo-3-palmitamido-4-(4-((4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methoxy)phenyl)butylphosphonate (935548-32-6)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran at -78℃; for 0.25h; Inert atmosphere; Stage #2: (S)-methyl 2-palmitamido-3-(4-((4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methoxy)phenyl)propanoate In tetrahydrofuran at -78℃; for 0.333333h; Inert atmosphere;	99%
Stage #1: dimethyl methane phosphonate With n-butyllithium Stage #2: (S)-methyl 2-palmitamido-3-(4-((4-(2,2,2-trifluoroethoxy)pyridin-2-yl)methoxy)phenyl)propanoate at -78℃; for 3h;

C36H54N2O5Si + dimethyl methane phosphonate (756-79-6) → C37H56NO7PSi

Conditions	Yield
With n-butyllithium In tetrahydrofuran at -78℃;	99%

dihydro isoquinoline-1-methyl formate + dimethyl methane phosphonate (756-79-6) → dimethyl 2-(1-isoquinolinyl)-2-oxoethyl phosphonate

Conditions	Yield
With n-butyllithium In tetrahydrofuran; hexane at -60 - 20℃; for 2h;	99%

butyryl chloride (141-75-3) + dimethyl methane phosphonate (756-79-6) → dimethyl (2-oxopentyl)phosphonate (65921-74-6)

Conditions	Yield
	99%

ziconium(IV) oxychloride octahydrate (13520-92-8) + dimethyl methane phosphonate (756-79-6) → zirconium bis(methylphosphonate)

Conditions	Yield
With aq. HCl In water reflux (24 h or 112 h); aq. HBr or H2O alone may also be used; filtration, washing (H2O; acetone), drying (40°C, 18 h, then 200°C, 24 h); elem. anal.;	99%

methyl 3-pyridinecarboxylate (93-60-7) + dimethyl methane phosphonate (756-79-6) → lithio dimethyl (2-oxo-2-pyridin-3-ylethyl)phosphonate

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran Barbier reaction; Cooling with ice; Inert atmosphere;	99%

methyl 4-iodobenzoate (619-44-3) + dimethyl methane phosphonate (756-79-6) → lithio dimethyl [2-(4-iodophenyl)-2-oxoethyl]phosphonate

Conditions	Yield
With lithium hexamethyldisilazane In tetrahydrofuran Barbier reaction; Cooling with ice; Inert atmosphere;	99%

N-Ethylimidazole (7098-07-9) + dimethyl methane phosphonate (756-79-6) → [EMIM] methyl methylphosphonate (1059603-87-0)

Conditions	Yield
at 100℃; for 24h; Neat (no solvent);	99%

methyl-2-[N-(2,4,6-trimethylbenzenesulfonyl)amino]-3-phenyl-propionate (1439462-50-6) + dimethyl methane phosphonate (756-79-6) → dimethyl-{3-[N-(2,4,6-trimethylbenzenesulfonyl)amino]-2-oxo-4-phenyl-butyl}phosphonate (1439462-62-0)

Conditions	Yield
Stage #1: dimethyl methane phosphonate With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.5h; Inert atmosphere; Stage #2: methyl-2-[N-(2,4,6-trimethylbenzenesulfonyl)amino]-3-phenyl-propionate In tetrahydrofuran; hexane at -78 - 0℃; for 5h; Inert atmosphere;	99%

Upstream product

• 676-97-1 methylphosphonic acid dichloroanhydride 
• 124-41-4 sodium methylate 
• 96-36-6 methyl phosphite 
• 77-78-1 dimethyl sulfate 
• 121-45-9 phosphorous acid trimethyl ester 
• 186581-53-3 diazomethane 
• 67-56-1 methanol 
• 60705-73-9 Bis (4-methoxyphenyl) methylphosphonate 
• 138869-16-6 Bis (3-methoxyphenyl) methylphosphonate 
• 88847-59-0 Bis (2-methoxyphenyl) methylphosphonate 
• 993-13-5 methylphosphonic acid 
• 119-61-9 benzophenone 
• 13433-42-6 dimethyl α-trimethylsilylmethylphosphonate 
• 2487-90-3 trimethoxysilane 

Downstream Products

• 676-97-1 methylphosphonic acid dichloroanhydride 
• 36892-73-6 C₂₉H₃₁P₃ 
• 18279-83-9 methylphosphonic acid bis(trimethylsilyl) ester 
• 13433-42-6 dimethyl α-trimethylsilylmethylphosphonate 
• 2404-73-1 dibutyl methylphosphonate 
• 683-32-9 methyl n-butyl methylphosphonate 
• 63578-31-4 1,1,7,7-tetra(dimethylamino)-4-methyl-1,4,7-phospha-heptane 
• 95868-81-8 Didodecyl-methylphosphonat 
• 55761-51-8 dimethyl 4-cyclohexyl-2-oxo-butylphosphonate 
• 41691-13-8 dimethyl-[2-(4'-methyl-cyclohexyl)-2-oxo-ethyl]-phosphonate 
• 51360-32-8 1-Phenyl-1-phenylethylene 
• 55761-50-7 dimethyl 3-cyclohexyl-2-oxobutylphosphonate 
• 1066-52-0 methyl methylphosphonochloridate 
• 103225-46-3 4-((dimethoxyphosphinyl)methyl)-2,6-diphenyl-4-hydroxy-4H-thiopyran 1,1-dioxide 

Relevant articles and documents

Carboranyl Oligonucleotides. 1. Synthesis of Thymidine(3',5')thymidine (o-Carboran-1-ylmethyl)phosphonate

Using methyl (o-carboran-1-ylmethyl)phosphonate 6 as a novel and versatile borophosphonylating agent, 5'-O-(monomethoxytrityl)thymidine 3'-O- (8) and thymidine(3',5')thymidine (o-carboran-1-ylmethyl)phosphonate (12) were synthesized.The internucleotide (o-carboran-1-ylmethyl)phosphonate linkage was resistant to cleavage by phosphorodiesterases.The dinucleotide 12 represents a new class of modified lipophilic oligonucleotide-bearing carboranyl residue, designed as a carrier for boron neutron capture therapy and for potential use in antisense oligonucleotide technology.

Molecular interactions of monosulfonate tetraphenylporphyrin (TPPS1) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) with dimethyl methylphosphonate (DMMP)

The molecular interactions of monosulfonate tetraphenylporphyrin (TPPS1) and meso-tetra(4-sulfonatophenyl)porphyrin (TPPS) with dimethyl methylphosphonate (DMMP) have been investigated by UV-vis and fluorescence spectroscopies. The association

Challenging synthesis of bisphosphonate derivatives with reduced steric hindrance

An alternative approach is reported for the synthesis of methyl ester protected bisphosphonate building blocks, such as methylene bisphosphonate, vinylidenebisphosphonate and aryl substituted prochiral vinylidenebisphosphonates, that cannot be obtained directly from dimethyl phosphite and dichloromethane.

Preparation method of cyclic phosphonate flame retardant

The invention discloses a preparation method of a cyclic phosphonate flame retardant, which relates to the technical field of organic phosphorus flame retardant synthesis. The method comprises the following steps of taking trimethylolpropane and trimethyl phosphite as raw materials with the feed mole ratio of 1: 2-4, selecting methyl benzenesulfonate or methyl p-toluenesulfonate as a catalyst, controlling proper process parameters such as catalyst quantity, temperature, time and the like, and carrying out transesterification and rearrangement reaction to obtain the phosphonate flame retardantwith a cyclic structure and the byproduct dimethyl methylphosphonate flame retardant. The method provided by the invention has the advantages of few raw material varieties, easy source, low cost, rapid reaction, high efficiency, environment-friendly process, energy conservation and consumption reduction; the product prepared by the method is the same as the product prepared by the existing method,but the production period is shortened by 2/3-3/4, the production capacity is greatly improved, and the method is suitable for industrial production.