5301-78-0

Basic information

• Product Name: 2,6,7-Trioxa-1-phosphabicyclo2.2.2octane-4-methanol, 1-oxide
• Synonyms: 2,6,7-Trioxa-1-phosphabicyclo2.2.2octane-4-methanol, 1-oxide;(1-oxo-2,6,7-trioxa-1$l^{5}-phosphabicyclo[2.2.2]oct-4-yl)methanol;4-Hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo(2.2.2)octane-1-oxide;pentaerythritol phosphate alcohol;pentaerythritol, cyclic phosphate;4-(Hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane;CN 1137;NH 1197
• CAS NO: 5301-78-0
• Molecular Formula: C₅H₉O₅P
• Molecular Weight: 180.1
• Mol File: 5301-78-0.mol
• Article Data: 11

Chemical Properties

• Melting Point: 209-212℃
• Boiling Point: 271℃
• Flash Point: 118℃
• Appearance: White/Powder
• Density: 1.53
• Vapor Pressure: 0.000872mmHg at 25°C
• Refractive Index: 1.502
• PKA: 13.70±0.10(Predicted)
• CAS DataBase Reference: 2,6,7-Trioxa-1-phosphabicyclo2.2.2octane-4-methanol, 1-oxide(CAS DataBase Reference)
• NIST Chemistry Reference: 2,6,7-Trioxa-1-phosphabicyclo2.2.2octane-4-methanol, 1-oxide(5301-78-0)
• EPA Substance Registry System: 2,6,7-Trioxa-1-phosphabicyclo2.2.2octane-4-methanol, 1-oxide(5301-78-0)

Safety Data

• RTECS: YK0690700
• Hazardous Substances Data: 5301-78-0(Hazardous Substances Data)

Usage

Uses

Different sources of media describe the Uses of 5301-78-0 differently. You can refer to the following data:
1. suzuki reaction
2. 4-(Hydroxymethyl)-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-Oxide is flame retardant; used in preparation method of green environmental protection polymer hard wall decoration material.

InChI:InChI=1/C5H9O5P/c6-1-5-2-8-11(7,9-3-5)10-4-5/h6H,1-4H2

Synthetic route

Pentaerythritol (115-77-5) → 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0)

Conditions	Yield
With trichlorophosphate	95%
With trichlorophosphate In 1,4-dioxane at 90℃; for 8h; Reflux;	94%
With trichlorophosphate In 1,4-dioxane at 80 - 100℃; Reflux;	88%

Pentaerythritol (115-77-5) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8) → 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0)

Conditions	Yield
In 1,4-dioxane at 20 - 95℃; Inert atmosphere; Reflux; Large scale;	85%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + benzene-1,3-dicarbonyl dichloride (99-63-8) → C18H20O12P2

Conditions	Yield
With triethylamine In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 6h;	95%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C20H32O20P4Si

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With tetrachlorosilane In 1,4-dioxane at 20 - 100℃; for 6h; Inert atmosphere; Industrial scale; Stage #2: With pyridine In 1,4-dioxane for 1h; Temperature; Solvent; Inert atmosphere; Heating; Industrial scale;	94.6%

bis(phenyl) carbonate (102-09-0) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → carbonic acid bis-(1-oxo-2,6,7-trioxa-1λ5-phospha-bicyclo[2.2.2]oct-4-ylmethyl) ester

Conditions	Yield
With 1H-imidazole In various solvent(s) at 180 - 210℃; under 10 - 50 Torr; transesterification;	94%

dimethyldimethoxysilan (1112-39-6) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C12H22O10P2Si

Conditions	Yield
In 1,4-dioxane at 100℃; for 8h; Solvent; Temperature; Inert atmosphere;	93.6%

Methyltrichlorosilane (75-79-6) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C16H27O15P3Si

Conditions	Yield
In 1,4-dioxane at 30 - 100℃; for 7h; Solvent; Temperature;	93.2%

Methyltrimethoxysilan (1185-55-3) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C16H27O15P3Si

Conditions	Yield
In 1,4-dioxane at 100℃; for 7h; Solvent; Temperature; Inert atmosphere;	92.7%

tetraethoxy orthosilicate (78-10-4) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C20H32O20P4Si

Conditions	Yield
In 1,4-dioxane at 100℃; Solvent; Inert atmosphere;	92.4%

triphenyl phosphite (101-02-0) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → (1-oxo-2,6,7-trioxa-1λ5-phospha-bicyclo[2.2.2]oct-4-ylmethyl)-phosphonic acid bis-(1-oxo-2,6,7-trioxa-1λ5-phospha-bicyclo[2.2.2]oct-4-ylmethyl) ester

Conditions	Yield
With sodium In various solvent(s) at 180 - 210℃; under 10 - 50 Torr; transesterification;	92%

chloro-trimethyl-silane (75-77-4) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C8H17O5PSi

Conditions	Yield
In 1,4-dioxane at 50 - 100℃; for 8h; Solvent; Temperature;	91.6%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8) → C15H24O16P4

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane; trichlorophosphate With aluminum (III) chloride In acetonitrile at 80 - 85℃; Inert atmosphere; Autoclave; Stage #2: With hydrogenchloride In water; acetonitrile	90%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + p-toluenesulfonyl chloride (98-59-9) → (1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-yl)methyl 4-methylbenzenesulfonate (104501-54-4)

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With triethylamine In acetone at 25℃; for 0.333333h; Inert atmosphere; Stage #2: p-toluenesulfonyl chloride In acetone at 25℃; for 8h; Inert atmosphere;	88%
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With triethylamine In acetone at 20℃; for 0.25h; Inert atmosphere; Stage #2: p-toluenesulfonyl chloride In acetone at 80℃; Inert atmosphere;	80.6%

Tetraisopropoxysilan (1992-48-9) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C20H32O20P4Si

Conditions	Yield
In 5,5-dimethyl-1,3-cyclohexadiene at 120℃; Solvent; Inert atmosphere;	87.5%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + methanesulfonyl chloride (124-63-0) → (1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-yl)methyl methanesulfonate

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With pyridine In tetrahydrofuran at 50℃; for 0.166667h; Inert atmosphere; Stage #2: methanesulfonyl chloride In tetrahydrofuran at 50℃; for 10h; Inert atmosphere;	86%
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With triethylamine In dichloromethane at 20℃; for 0.25h; Stage #2: methanesulfonyl chloride In dichloromethane at 20℃;	82.5%

tetrapropoxysilane (682-01-9) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C20H32O20P4Si

Conditions	Yield
In diethylene glycol dimethyl ether at 140℃; Solvent; Inert atmosphere;	85.7%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + 2-(4-fluorophenoxy)acetyl chloride (405-78-7) → C13H14FO7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	84%

perfluoro-1-butanesulfonyl fluoride (2386-60-9) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C9H17O7PS

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With triethylamine In dichloromethane at 35℃; for 0.166667h; Inert atmosphere; Stage #2: perfluoro-1-butanesulfonyl fluoride In dichloromethane at 35℃; for 8h; Inert atmosphere;	83%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 6-((1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-yl)methoxy)dibenzo[c,e][1,2]oxaphosphinine-6-oxide

Conditions	Yield
With 1-methyl-1H-imidazole In tetrachloromethane; dichloromethane at 15 - 20℃; for 7h; Reflux;	82%
With tetrachloromethane In dichloromethane at 15 - 45℃; for 4h; Inert atmosphere; Large scale;	76%
With 1-methyl-1H-imidazole; tetrachloromethane In dichloromethane at 45℃; for 7h; Inert atmosphere; Cooling with ice;	70%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + 1-<2-(trichlorosilyl)ethyl>adamantane (37843-11-1) → C27H43O15P3Si

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With aluminum (III) chloride; triethylamine In N,N-dimethyl-formamide at 75℃; Inert atmosphere; Stage #2: 1-<2-(trichlorosilyl)ethyl>adamantane In N,N-dimethyl-formamide for 23h; Solvent; Reagent/catalyst; Reflux;	81.2%

octane-1-sulfonyl chloride (7795-95-1) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C13H25O7PS

Conditions	Yield
Stage #1: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With C9H14N2O4P(1+)*CH3O3S(1-) In dichloromethane at 25℃; for 0.166667h; Inert atmosphere; Stage #2: octane-1-sulfonyl chloride at 28℃; for 6h;	81%

4,4-bis(4-hydroxyphenyl)valeric acid (126-00-1) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C22H25O8P

Conditions	Yield
With toluene-4-sulfonic acid In acetonitrile at 70℃; for 24h; Inert atmosphere;	80.2%
With toluene-4-sulfonic acid In acetonitrile for 24h; Inert atmosphere; Reflux;	55%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + 2-(2,4-dichlorophenoxy)acetyl chloride (774-74-3) → C13H13Cl2O7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	78%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + 2-(2-chloro-4-fluorophenoxy)acetyl chloride (826990-46-9) → C13H13ClFO7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	78%

6-Chloro-6H-dibenz<1,2>oxaphosphorin (32186-92-8) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → 6-((1-oxido-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octan-4-yl)methoxy)dibenzo[c,e][1,2]oxaphosphinine-6-oxide

Conditions	Yield
With triethylamine In dichloromethane at 20℃; for 8h; Inert atmosphere; Large scale;	76%
In dichloromethane at 0 - 20℃; Inert atmosphere;	60%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + <2-Fluor-phenoxy>-acetylchlorid (2965-17-5) → C13H14FO7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	73%

2-(4-methylphenoxy)acetyl chloride (15516-47-9) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C14H17O7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	71%

2-methyl-4-chlorophenoxyacetyl chloride (6597-79-1) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → C14H16ClO7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	71%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) → DOPS-PEPA

Conditions	Yield
Stage #1: p-chlorodibenzo[c.e][1,2]oxaphosphorine With sulfur In toluene for 5h; Reflux; Stage #2: 4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane With 1-methyl-1H-imidazole In toluene at 15 - 20℃; for 3h; Reflux;	70%

4-(hydroxymethyl)-1-oxido-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (5301-78-0) + Phenoxyacetyl chloride (701-99-5) → C13H15O7P

Conditions	Yield
With triethylamine In acetonitrile at 0 - 20℃; for 1h;	69%

Upstream product

• 115-77-5 Pentaerythritol 
• 10025-87-3 trichlorophosphate 

Downstream Products

• 93289-09-9 Benzoic acid 1-oxo-2,6,7-trioxa-1λ⁵-phospha-bicyclo[2.2.2]oct-4-ylmethyl ester 

Relevant articles and documents

Study of thermal properties of intumescent additive : Pentaerythritol phosphate alcohol

Bicyclic compounds containing phosphorus on their skeleton such as 2,4,6-trioxa-1-phosphabicyclo[2,2,2]octane-4-methanol phosphate (PEPA) having three active ingredients required for intumescence have been synthesized. The structural characterization of PEPA was carried out by FT-IR, 1H and 13C NMR. The thermal behaviour of the material was studied using TGA, TGA-MS and pyrolysis GC-MS. Thermogravimetric analysis reveals that PEPA undergoes several stages of degradation with a char of about 12% at 800 °C. The TGA-MS studies indicate that the material degrades with the liberation of water, formaldehyde, alkene and alcohols as the major degradation products. Pyrolysis GC-MS results reveal that PEPA isomerizes in the acidic medium. PEPA and/or isomers of PEPA react with formaldehyde, one of the degradation products, to form cross-linked structure and cyclic products with the elimination of water molecule. The thermal degradation mechanisms for PEPA are presented and discussed.

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Preparation method and application of novel adamantane-ring-containing phosphorus-silicon flame retardant

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