18755-43-6

Basic information

• Product Name: dimethyl propylphosphonate
• Synonyms: DiMethyl prpylphosphonate;Dimethyl-1-propylphosphonate;dimethyl propylphosphonate;Einecs 242-555-3;Phosphonic acid, p-propyl-, dimethyl ester;Phosphonic acid, propyl-, dimethyl ester
• CAS NO: 18755-43-6
• Molecular Formula: C₅H₁₃O₃P
• Molecular Weight: 152.128681
• EINECS: 242-555-3
• Product Categories: Aliphatics, Phosphorylating and Phosphitylating Agents;Aliphatics;Phosphorylating and Phosphitylating Agents
• Mol File: 18755-43-6.mol
• Article Data: 8

Chemical Properties

• Boiling Point: 185°Cat760mmHg
• Flash Point: 80°C
• Appearance: /
• Density: 1.028g/cm³
• Vapor Pressure: 0.975mmHg at 25°C
• Refractive Index: 1.396
• Storage Temp.: Hygroscopic, Refrigerator, under inert atmosphere
• Solubility: Chloroform (Sparingly), Methanol (Slightly)
• CAS DataBase Reference: dimethyl propylphosphonate(CAS DataBase Reference)
• NIST Chemistry Reference: dimethyl propylphosphonate(18755-43-6)
• EPA Substance Registry System: dimethyl propylphosphonate(18755-43-6)

Safety Data

• Hazardous Substances Data: 18755-43-6(Hazardous Substances Data)

Usage

Uses

Dimethyl propylphosphonate as a fireproofing agent for isocyanate-based plastics.

InChI:InChI=1/C5H13O3P/c1-4-5-9(6,7-2)8-3/h4-5H2,1-3H3

Synthetic route

methanol (67-56-1) + propylphosphonic dichloride (4708-04-7) → propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
With aluminum oxide at 20℃;	92%

methanol (67-56-1) + propylphosphonic acid (4672-38-2) → propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
With tetrachlorosilane at 0℃;	89%
Stage #1: propylphosphonic 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;	87%
With p-TsOH-Celite at 20℃;	86%

(Z)-2-benzoyloxy-1-dimethoxyphosphoryl-1-propene → (R)-2-benzoyloxy-1-dimethoxyphosphorylpropane (1104662-10-3) + propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
With BF4(1-)*C8H12*C42H46O3P2*Rh(1+); hydrogen In dichloromethane at 25℃; under 3040.2 Torr; for 24h; Inert atmosphere; optical yield given as %ee; enantioselective reaction;	A 88% B n/a
With BF4(1-)*C50H59IrO3P2(1+); hydrogen In dichloromethane at 25℃; under 3040.2 Torr; for 24h; optical yield given as %ee; enantioselective reaction;

propyl bromide (106-94-5) + Dimethyl phosphite (868-85-9) → propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
Stage #1: Dimethyl phosphite With sodium hydride In tetrahydrofuran; mineral oil at 30 - 40℃; Stage #2: propyl bromide In tetrahydrofuran for 96h; Inert atmosphere; Reflux;	46%
With sodium methylate

dipropyl propylphosphonate (1789-95-3) + methyl p-toluene sulfonate (80-48-8) → propanephosphonic acid dimethyl ester (18755-43-6) + Methyl propyl propylphosphonate (18755-44-7) + propyl tosylate (599-91-7)

Conditions	Yield
at 130 - 140℃; for 3.5h;

(Z)-2-benzoyloxy-1-dimethoxyphosphoryl-1-propene → (S)-2-benzoyloxy-1-dimethoxyphosphorylpropane (1104662-26-1) + (R)-2-benzoyloxy-1-dimethoxyphosphorylpropane (1104662-10-3) + propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
With BF4(1-)*C8H12*C32H50O3P2*Rh(1+); hydrogen In dichloromethane at 25℃; under 3040.2 Torr; for 24h; Inert atmosphere; optical yield given as %ee;

dimethyl (2-oxopropyl)phosphonate (4202-14-6) → (R)-2-benzoyloxy-1-dimethoxyphosphorylpropane (1104662-10-3) + propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium hydride / tetrahydrofuran; mineral oil / 0.5 h / Inert atmosphere 1.2: 16 h / Inert atmosphere 2.1: BF4(1-)*C50H59IrO3P2(1+); hydrogen / dichloromethane / 24 h / 25 °C / 3040.2 Torr View Scheme

dimethyl (2-oxopropyl)phosphonate (4202-14-6) → (S)-2-benzoyloxy-1-dimethoxyphosphorylpropane (1104662-26-1) + propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
Multi-step reaction with 2 steps 1.1: sodium hydride / tetrahydrofuran; mineral oil / 0.5 h / Inert atmosphere 1.2: 16 h / Inert atmosphere 2.1: BF4(1-)*C40H62IrO3P2(1+); hydrogen / dichloromethane / 24 h / 25 °C / 3040.2 Torr View Scheme

(Z)-2-benzoyloxy-1-dimethoxyphosphoryl-1-propene → (S)-2-benzoyloxy-1-dimethoxyphosphorylpropane (1104662-26-1) + propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
With BF4(1-)*C40H62IrO3P2(1+); hydrogen In dichloromethane at 25℃; under 3040.2 Torr; for 24h; optical yield given as %ee; enantioselective reaction;

methanol (67-56-1) + methyl hydrogen propylphosphonate → propanephosphonic acid dimethyl ester (18755-43-6)

Conditions	Yield
With thionyl chloride at 65℃; for 2h;

propanephosphonic acid dimethyl ester (18755-43-6) → 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide (68957-94-8)

Conditions	Yield
With acetic anhydride; 1-ethyl-3-methylimidazolium tetrafluoroborate at 45℃; for 4.5h; Temperature; Reflux;	95.14%

propanephosphonic acid dimethyl ester (18755-43-6) → C4H12N(1+)*C4H10O3P(1-)

Conditions	Yield
With /BRN= 956566/ In acetone at 100℃; Rate constant;

propanephosphonic acid dimethyl ester (18755-43-6) + (5R)-2-(1-Chloro-1-methylethyl)-5-methylcyclohexanone (66448-75-7, 125225-97-0, 125226-00-8) → ((R)-1-Ethyl-4,8-dimethyl-2-oxo-non-7-enyl)-phosphonic acid dimethyl ester (145235-33-2)

Conditions	Yield
With n-butyllithium 1.) THF, hexane, -72 deg C, 1.5 h, 2.) -72 to 0 deg C; Yield given. Multistep reaction;

propanephosphonic acid dimethyl ester (18755-43-6) → methylene chloride (74-87-3) + methyl propylphosphono chloridate (28829-99-4) + Triphenylphosphine oxide (791-28-6)

Conditions	Yield
With chloro(triphenyl)phosphonium chloride In chloroform Ambient temperature;

Upstream product

• 67-56-1 methanol 
• 4672-38-2 propylphosphonic acid 
• 53621-95-7 methyl hydrogen propylphosphonate 
• 4708-04-7 propylphosphonic dichloride 
• 1789-95-3 dipropyl propylphosphonate 
• 80-48-8 methyl p-toluene sulfonate 
• 106-94-5 propyl bromide 
• 868-85-9 Dimethyl phosphite 
• 4202-14-6 dimethyl (2-oxopropyl)phosphonate 

Downstream Products

• 68957-94-8 2,4,6-tripropyl-1,3,5,2,4,6-trioxatriphosphinane-2,4,6-trioxide 
• 74-87-3 methylene chloride 
• 28829-99-4 methyl propylphosphono chloridate 
• 791-28-6 Triphenylphosphine oxide 

Relevant articles and documents

Fragmentation-Related Phosphonylation of Nucleophiles Utilizing P-Alkyl 2,3-oxaphosphabicyclo[2.2.2]octene 3-oxide Precursors

New P-alkyl 2,3-oxaphosphabicyclo-[2.2.2]octene 3-oxides were synthesized by the Bayer-Villiger oxidation of the corresponding 7-phosphanorbornene 7-oxides and were used as precursors for reactive alkylmetaphosphonates useful in the phosphonylation of alcohols. This is the first case that the reactivity of the two regioisomers formed by O-insertion was differentiated and that the fragmentation-related phosphonylation leading to phosphonic acid-esters was achieved under microwave-assisted conditions.

Mild and efficient esterification of alkylphosphonic acids using polymer-bound triphenylphosphine

Mild and efficient esterification of alkylphosphonic acids using primary alcohols, iodine, imidazole and polymer-bound triphenylphosphine is developed.

Highly enantioselective hydrogenation of enol ester phosphonates: A versatile procedure for the preparation of chiral β-hydroxyphosphonates

A study was conducted to demonstrate a procedure for the preparation of chiral β-hydroxyphosphonates. The reaction sequence was investigated and the validity of the approach was demonstrated. The study also reported an olefin hydrogenation reaction, which gives access to a wide variety of chiral β-hydroxyphosphonates 2, with excellent levels of asymmetric induction, which can be converted into the corresponding alcohols. The application of phosphane-phosphite ligands 4 and 5 were investigated in diverse hydrogenation reactions. Unsaturated phosphonates 1 were chosen as substrates, in an effort to broaden the scope of these catalysts. Investigations were also initiated by the development of a convenient procedure for the synthesis of a set of olefins 1.