822-39-9

Basic information

• Product Name: 2-Chloro-1,3,2-dioxaphospholane
• Synonyms: 1,3,2-Dioxaphospholane, 2-chloro-;1,3,2-Dioxaphosphorane.2-chloro-;2-dioxaphospholane,2-chloro-3;Ethylenephosphorochloridite;AURORA KA-1222;ETHYLENE CYCL-CHLOROPHOSPHITE;ETHYLENE CYCLO-CHLOROPHOSPHITE;ETHYLENE CHLOROPHOSPHITE
• CAS NO: 822-39-9
• Molecular Formula: C₂H₄ClO₂P
• Molecular Weight: 126.48
• EINECS: 212-499-4
• Product Categories: Biochemistry;Nucleosides, Nucleotides & Related Reagents;Phosphorylating and Phosphorothioating Agents;Phosphorylation;Protecting Agents, Phosphorylating Agents & Condensing Agents;Synthetic Organic Chemistry;Phosphorylating and Phosphitylating Agents
• Mol File: 822-39-9.mol
• Article Data: 22

Chemical Properties

• Melting Point: -28°C(lit.)
• Boiling Point: 62 °C20 mm Hg(lit.)
• Flash Point: 158 °F
• Appearance: clear colorless to slightly yellow liquid
• Density: 1.422 g/mL at 25 °C(lit.)
• Vapor Pressure: 20.8mmHg at 25°C
• Refractive Index: n20/D 1.489(lit.)
• Storage Temp.: 2-8°C
• Sensitive: Moisture Sensitive
• BRN: 506179
• CAS DataBase Reference: 2-Chloro-1,3,2-dioxaphospholane(CAS DataBase Reference)
• NIST Chemistry Reference: 2-Chloro-1,3,2-dioxaphospholane(822-39-9)
• EPA Substance Registry System: 2-Chloro-1,3,2-dioxaphospholane(822-39-9)

Safety Data

• Hazard Codes: C
• Statements: 14-34-37
• Safety Statements: 26-36/37/39-45-8-25
• RIDADR: UN 3264 8/PG 2
• WGK Germany: 3
• F: 1-10
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 822-39-9(Hazardous Substances Data)

Usage

Chemical Properties

Clear Colourless Oil

Uses

Ethylene chlorophosphite acts as a phosphitylating agent involved in the preparation of phosphocholine and spirophosphoranes. For example, it is used in the phosphorylation of p-tert-butyl(thia)calixarenes.

InChI:InChI=1/C2H4ClO2P/c3-6-4-1-2-5-6/h1-2H2

Synthetic route

ethylene glycol (107-21-1) → 2-chloro-1,3,2-dioxaphospholan (822-39-9)

Conditions	Yield
With phosphorus trichloride In dichloromethane at 0℃; for 14h;	92%
With phosphorus trichloride In dichloromethane at 20℃; for 0.5h; Inert atmosphere;	74.7%
With phosphorus trichloride In dichloromethane at 20℃; for 3h; Inert atmosphere;	67%

ethylene glycol (107-21-1) → 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphosphahexane (37445-80-0) + 2-chloro-1,3,2-dioxaphospholan (822-39-9)

Conditions	Yield
With triethylamine; phosphorus trichloride at 45℃; Reagent/catalyst;	A 51.7% B n/a
With phosphorus trichloride anfangs unter Luehlung,dann bei 60-70grad;

2-methyl-[1,3,2]dioxarsolane (18882-67-2) → 2-chloro-1,3,2-dioxaphospholan (822-39-9)

Conditions	Yield
With phosphorus trichloride In benzene

pyridine (110-86-1) + diethyl ether (60-29-7) + ethylene glycol (107-21-1) + phosphorus trichloride (7719-12-2, 52843-90-0) → 2-chloro-1,3,2-dioxaphospholan (822-39-9)

dichloromethane (75-09-2) + ethylene glycol (107-21-1) + phosphorus trichloride (7719-12-2, 52843-90-0) → 2-chloro-1,3,2-dioxaphospholan (822-39-9)

diethyl ether (60-29-7) + ethylene glycol (107-21-1) + N,N-dimethyl-aniline (121-69-7) + phosphorus trichloride (7719-12-2, 52843-90-0) → 2-chloro-1,3,2-dioxaphospholan (822-39-9)

ethylene glycol (107-21-1) + phosphorus trichloride (7719-12-2, 52843-90-0) → 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphosphahexane (37445-80-0) + 2-chloro-1,3,2-dioxaphospholan (822-39-9)

Conditions	Yield
anfangs unter Kuehlung, dann bei 60-70grad;

2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-azido-1,3,2-dioxaphospholane (85741-80-6)

Conditions	Yield
With trimethylsilylazide at 0 - 5℃; for 3h;	100%
With (C2H5)3N*NH3

N-methylbenzamide (88070-48-8) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → ethylene benzoylmethyphosphoramidite

Conditions	Yield
In diethyl ether Ambient temperature;	97%

2,3-Di(stearoyloxy)-1-propanthiol (127472-90-6) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(2,3-Distearoyloxypropyl)-1,3,2-dioxaphospholan-2-sulfid (134152-76-4)

Conditions	Yield
With triethylamine In benzene for 3h; Ambient temperature;	96%

lithium 2-(diphenylphosphanyl)pyrrolide + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-diphenylphosphino-1-(1,3,2-dioxaphospholane)pyrrole

Conditions	Yield
In diethyl ether at 23℃; for 25h; Glovebox; Inert atmosphere;	96%

methanol (67-56-1) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → methoxy-2 dioxaphospholane-1,3,2 (3741-36-4)

Conditions	Yield
Stage #1: methanol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	95%
With pyridine
With 2,3-Dimethylaniline
With triethylamine

ethanol (64-17-5) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-Ethoxy-1,3,2-dioxaphospholan (695-11-4)

Conditions	Yield
Stage #1: ethanol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	95%
With triethylamine

2,2,2-trichloro-1-(2-oxo-1-aza-1-cyclopentyl)ethanol (7042-60-6) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → ethylene 2,2,2-trichloro-1-(2-oxo-1-aza-1-cyclopentyl)ethyl phosphite

Conditions	Yield
With triethylamine In benzene at 0℃;	95%

2-chloro-1,3,2-dioxaphospholan (822-39-9) + 1-butyn-4-ol (927-74-2) → 2-(3-butynyloxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: 3-Butyn-1-ol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	95%

1,1,1-trifluoro-2,4-pentanediol (400-32-8) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → C9H15F3O6P2

Conditions	Yield
In dichloromethane at 0 - 20℃; for 8h;	95%

2-chloro-1,3,2-dioxaphospholan (822-39-9) + (R)-oxiranemethanol (57044-25-4) → (R)-2-(oxiran-2-ylmethoxy)-1,3,2-dioxaphospholane

Conditions	Yield
With triethylamine In diethyl ether at 0 - 20℃; for 3h; Reagent/catalyst; Solvent;	94.8%

2-chloro-1,3,2-dioxaphospholan (822-39-9) + allyl alcohol (107-18-6) → 2-allyloxy-1,3,2-dioxaphospholane (53969-10-1)

Conditions	Yield
Stage #1: allyl alcohol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%
With pyridine; diethyl ether
With triethylamine

2-chloro-1,3,2-dioxaphospholan (822-39-9) + phenol (108-95-2) → 2-phenoxy-[1,3,2]dioxaphospholane (1077-05-0)

Conditions	Yield
Stage #1: phenol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 13.5h;	94%
With triethylamine
With triethylamine In hexane

α-naphthol (90-15-3) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(1-naphthalenoxy)-1,3,2-dioxaphospholane (110232-62-7)

Conditions	Yield
Stage #1: α-naphthol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%
With triethylamine In benzene

2-chloro-1,3,2-dioxaphospholan (822-39-9) + diisopropylamine (108-18-9) → 2-Diisopropylamino-1,3,2-dioxaphospholane (28623-31-6)

Conditions	Yield
In dichloromethane Cooling with ice; Inert atmosphere;	94%
In dichloromethane at 20℃; for 16h; Amination;	93%
In diethyl ether at 0℃;

2-(N-benzylidenamino)ethanol (770-37-6) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(benzylideneamino)ethyl ethylene phosphite

Conditions	Yield
With triethylamine In diethyl ether at 20℃;	94%

4-cyanophenol (767-00-0) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(4-cyanophenoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: 4-cyanophenol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%

homoalylic alcohol (627-27-0) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(but-3-en-1-yloxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: homoalylic alcohol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%

pentafluoroethyl alcohol (7057-80-9) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(1,1,2,2,2-pentafluoroethoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: pentafluoroethyl alcohol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%

1,1,1,3',3',3'-hexafluoro-propanol (920-66-1) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-((1,1,1,3,3,3-hexafluoropropan-2-yl)oxy)-1,3,2-dioxaphospholane (85762-88-5)

Conditions	Yield
Stage #1: 1,1,1,3',3',3'-hexafluoro-propanol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%

2-chloro-1,3,2-dioxaphospholan (822-39-9) + β-naphthol (135-19-3) → 2-(2-naphthalenoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: β-naphthol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	94%

2-methyl-1.3-propanediol (2163-42-0) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → C8H16O6P2

Conditions	Yield
In dichloromethane at 0 - 20℃; for 12h;	94%

2,4-dimethylpentane-2,4-diol (24892-49-7, 139687-48-2) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → C11H22O6P2

Conditions	Yield
In dichloromethane at 0 - 20℃; for 12h;	94%

propylene glycol (57-55-6) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2,2'-(1-methyl-ethane-1,2-diyldioxy)-bis-[1,3,2]dioxaphospholane (92304-17-1)

Conditions	Yield
In dichloromethane at 0 - 20℃; for 12h;	93%
With triethylamine

2-chloro-1,3,2-dioxaphospholan (822-39-9) + trimethyleneglycol (504-63-2) → 2,2'-propane-1,3-diyldioxy-bis-[1,3,2]dioxaphospholane (92304-16-0)

Conditions	Yield
In dichloromethane at 0 - 20℃; for 12h;	93%
With triethylamine

2-chloro-1,3,2-dioxaphospholan (822-39-9) + dimethylglyoxal (431-03-8) → 2-(β-Chloroaethoxi)-2-oxo-4,5-dimethyl-1,3,2λ5-dioxaphospholen (76266-23-4)

Conditions	Yield
Mechanism;	93%
In neat (no solvent) at 80℃;	93%

p-cresol (106-44-5) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(4-methylphenoxy)-1,3,2-dioxaphospholane (857367-49-8)

Conditions	Yield
Stage #1: p-cresol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	93%
With pyridine In chloroform-d1

2-fluorophenol (367-12-4) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(2-fluorophenoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: 2-fluorophenol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	93%

4-Fluorophenol (371-41-5) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(4-fluorophenoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: 4-Fluorophenol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	93%

3-fluorophenol (372-20-3) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(3-fluorophenoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: 3-fluorophenol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	93%

2-(trifluoromethyl)phenol (444-30-4) + 2-chloro-1,3,2-dioxaphospholan (822-39-9) → 2-(2-trifluoromethylphenoxy)-1,3,2-dioxaphospholane

Conditions	Yield
Stage #1: 2-(trifluoromethyl)phenol In dichloromethane at 20℃; for 0.5h; Stage #2: 2-chloro-1,3,2-dioxaphospholan In dichloromethane at 0 - 20℃; for 12h;	93%

Upstream product

• 107-21-1 ethylene glycol 
• 7719-12-2 phosphorus trichloride 
• 60-29-7 diethyl ether 
• 121-69-7 N,N-dimethyl-aniline 
• 75-09-2 dichloromethane 
• 110-86-1 pyridine 
• 18882-67-2 2-methyl-[1,3,2]dioxarsolane 

Downstream Products

• 66441-98-3 2-(Cyclohex-1-enyloxy)-[1,3,2]dioxaphospholane 
• 1455-05-6 2-chloroethyl phosphorodichloridate 
• 41262-40-2 2-Menthoxy-1,3,2-dioxaphospholan 
• 81246-73-3 2-<(α-methoxybenzylidene)amino>-1,3,2-dioxaphospholane 
• 1003-11-8 2-oxo-1,3,2-dioxaphospholane 
• 100-47-0 benzonitrile 
• 81246-72-2 2-<(α-ethoxybenzylidene)amino>-1,3,2-dioxaphospholane 
• 108881-14-7 2-(Biphenyl-2-yloxy)-[1,3,2]dioxaphospholane 
• 28623-31-6 2-Diisopropylamino-1,3,2-dioxaphospholane 

Relevant articles and documents

Five-membered ring phosphite compound, and preparation method and application thereof

The invention belongs to the technical field of batteries, and especially relates to a five-membered ring phosphite compound. The structural general formula of the five-membered ring phosphite compound is represented by formula 1 shown in the description; and in the formula, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R, R and R are independently selected from hydrogen, an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an alkynyloxy group, an enyloxy group, a silyl group, a siloxane group, aryl silicon, an arylsilyl group, an arylsiloxy group, a halogenated alkyl group, a phenyl group, a biphenyl group, a naphthyl group, a pyridyl group, a thienyl group, a halogenated phenyl group, a halogenated biphenyl group, a phenolic group, an alkyl-containing phenolic group, an alkenyl-containing phenolic group, an alkynyl-containing phenolic group, a nitrile-containing phenolic group, a monohalogenated phenolic group and a polyhalogenated phenolic group. The five-membered ring phosphite compound provided by the invention has excellent flame retardant property, can effectively prevent electrolytes from being oxidized when being applied to the field of batteries, reduces oxygenolysis of the electrolytes on positive electrodes, and remarkably improves the comprehensive properties such as high temperature, circulation, storage and the like of the batteries.

Phosphine ligand compound and preparation method thereof, catalyst composition and application thereof, and vinyl acetate hydroformylation method

The invention relates to the field of vinyl acetate hydroformylation, and discloses a phosphine ligand compound and a preparation method thereof, a catalyst composition and application thereof, and avinyl acetate hydroformylation method. The phosphine ligand compound has a structure shown as a formula (1); wherein A is selected from substituted or unsubstituted biphenyl; B1 and B2 are each independently selected from substituted or unsubstituted C1-C20 alkylene groups; substituent groups optionally existing in A, B1 and B2 are respectively and independently selected from at least one of C1-C20 alkyl, halogen, C1-C10 alkoxyl, hydroxyl, carboxyl and aldehyde group; and the provided phosphine ligand compound can effectively improve the conversion rate of vinyl acetate and the selectivity of2-acetoxy propionaldehyde.

Method of Preparing 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphoshexane

A method for manufacturing 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphoshexane according to the present invention is the method for manufacturing 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphoshexane represented by chemical formula 2 by phosphorylation of an ethylene glycol compound represented by chemical formula 1 in the presence of an organic base. The method has effects of having an easy manufacturing process, being able to mass produce, obtaining 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphoshexane in a high yield, and manufacturing 1,1,6,6-tetrachloro-2,5-dioxa-1,6-diphoshexane with the high yield and a high purity.COPYRIGHT KIPO 2019