35948-25-5

Usage

Uses

Different sources of media describe the Uses of 35948-25-5 differently. You can refer to the following data:
1. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-Oxide
2. 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-Oxide is an high effective componant of flame retardant epoxy resins.

Flammability and Explosibility

Nonflammable

InChI:InChI=1/C12H9O2P/c13-15-12-8-4-2-6-10(12)9-5-1-3-7-11(9)14-15/h1-8,15H

Synthetic route

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) → 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5)

Conditions	Yield
With water; hydrogenchloride at 80℃; for 1h; Product distribution / selectivity;	98%
With water In toluene for 4h; Heating / reflux;	95%
In ethanol
With water
With water	10.1 g

2-(2-hydroxyphenyl)-phenylphosphonous acid (35948-24-4) → 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5)

Conditions	Yield
With toluene-4-sulfonic acid In water; toluene for 4h; Reflux;	97.5%
at 160℃; under 30 Torr; for 2h; Activation energy; Cyclization;
at 160℃; under 30 Torr; for 2h; Dehydration;
at 180℃; under 3.75038 Torr; for 6h; Pressure; Temperature;

2-Phenylphen-1-oxydichlorphosphan (33771-47-0) → 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: AlCl3 / heptane 2: aq. ethanol View Scheme

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 2-Phenylphenol (90-43-7) → 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5)

Conditions	Yield
In toluene

1-propylammonium (2-hydroxy-biphenyl-2-yl)-phosphinate (1208129-37-6) → propylamine (107-10-8) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5)

Conditions	Yield
at 165℃; under 3.75038 Torr; for 2.25h;

2-Phenylphenol (90-43-7) → 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: trifluorormethanesulfonic acid; phosphorus trichloride / 4.5 h / 150 °C 2: water View Scheme
Multi-step reaction with 3 steps 1.1: phosphorus trichloride; zinc(II) chloride / 4 h / 80 - 180 °C 2.1: diatomaceous earth / toluene / 0.5 h / 20 °C 2.2: 4 h / Reflux 3.1: 6 h / 180 °C / 3.75 Torr View Scheme

9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 6-Chloro-6H-dibenz<1,2>oxaphosphorin (32186-92-8)

Conditions	Yield
With chlorine; sodium hydroxide In dichloromethane at 20℃; for 12.6h; Inert atmosphere; Large scale;	100%
With chlorine In dichloromethane at 40℃; for 5h; Appel Halogenation;	100%
With tetrachloromethane; triethylamine In chloroform at 5℃;

hexaepoxypropanoxycyclotriphosphazene + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → C90H84N3O24P9

Conditions	Yield
at 160℃; for 5h; Temperature; Time;	99.8%

dimethylvinylphosphonate (4645-32-3) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 2-(9,10-dihydro-9-oxo-10-phosphaphenanthrene-10-oxide-10-yl)dimethyl ethylphosphonate

Conditions	Yield
at 130℃; for 8h; Inert atmosphere;	99.38%
With trimethylphosphane In tetrahydrofuran at 0 - 25℃; for 20.5h; Schlenk technique;	90%

N,N-bis(2-((trimethylsilyl)oxy)ethyl)acrylamide (1367371-13-8) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 3-(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)-N,N-bis{2-[(trimethylsilyl)oxy]ethyl}propanamide (1367371-14-9)

Conditions	Yield
With triethylamine In toluene Michael addition; Inert atmosphere; Reflux;	99%

2,2-bis(3-allyl-4-hydroxyphenyl)propane (1745-89-7) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → DDBA

Conditions	Yield
With 2,2'-azobis(isobutyronitrile) In propan-1-ol at 75℃; for 24h; Temperature; Solvent;	98.8%

formaldehyd (50-00-0) + diethylamine (109-89-7) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → C17H22NO3P (1133910-18-5)

Conditions	Yield
In ethanol at 80℃; for 1.5h; Mannich condensation;	98%

salicylaldehyde (90-02-8) + 4-amino-benzoic acid (150-13-0) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → C26H20NO5P (1160307-73-2)

Conditions	Yield
In N,N-dimethyl-formamide at 20℃; for 12h;	98%

formaldehyd (50-00-0) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)methanol (35948-26-6)

Conditions	Yield
In benzene at 70℃; for 12h; Solvent; Temperature; Inert atmosphere;	98%
With sulfuric acid In diethylene glycol dimethyl ether at 50 - 120℃; for 6.5h; Temperature; Reagent/catalyst; Solvent; Inert atmosphere;	97%
at 100℃; for 4h;

phenylacetylene (536-74-3) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → E-10-(styr-2-yl)-9,10-dihydro-9-oxa-10-phosphaphenantrene-10-oxide (1586744-35-5)

Conditions	Yield
Stage #1: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide With copper acetylacetonate In tetrahydrofuran; N,N-dimethyl-formamide Inert atmosphere; Stage #2: phenylacetylene In tetrahydrofuran; N,N-dimethyl-formamide at 70℃; for 16h; Catalytic behavior; Reagent/catalyst; Inert atmosphere; diastereoselective reaction;	98%

C42H43N6O16P + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → C90H79N6O24P5

Conditions	Yield
at 160℃; for 3h;	98%

1-p-toluenesulfonyl-4-ethynyl-1,4-dihydro-2H-benzo[d][1,3]-azahexan-2-one + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 6-((1-tosyl-1H-indol-2-yl)methyl)dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
Stage #1: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide With copper(l) iodide; N-ethyl-N,N-diisopropylamine; 2,6-bis(4,5-dihydrooxazol-2-yl)pyridine In 1,2-dichloro-ethane at 20℃; for 0.166667h; Inert atmosphere; Schlenk technique; Stage #2: 1-p-toluenesulfonyl-4-ethynyl-1,4-dihydro-2H-benzo[d][1,3]-azahexan-2-one In 1,2-dichloro-ethane at 20℃; for 1h; Inert atmosphere; Schlenk technique;	98%

acrylonitrile (107-13-1) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 6H-dibenz[c,e][1,2]oxaphosphorin-6-propanenitrile 6-oxide

Conditions	Yield
	97%
at 130℃; for 1h; microwave irradiation;	89%

2-Isocyanatoethyl methacrylate (30674-80-7) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → C19H18NO5P

Conditions	Yield
With triethylamine In dichloromethane at 30℃; for 10h;	97%

Upstream product

• 22749-43-5 p-chlorodibenzo[c.e][1,2]oxaphosphorine 
• 35948-24-4 2-(2-hydroxyphenyl)-phenylphosphonous acid 
• 90-43-7 2-Phenylphenol 
• 1208129-37-6 1-propylammonium (2-hydroxy-biphenyl-2-yl)-phosphinate 
• 33771-47-0 2-Phenylphen-1-oxydichlorphosphan 

Downstream Products

• 1141556-59-3 2-(cyclohexan-3-on-1-yl)-dibenzo[c,e][1,2]oxaphosphorin 2-oxide 
• 1141556-62-8 3-(dibenzo[c,e][1,2]oxaphosphorinoxido)-4-chloro-5-methyl-1-phenyl-1,2,3,6-tetrahydrophosphinine 1-oxide 
• 443769-57-1 6-((2-hydroxyphenyl)(phenylamino)methyl)-6H-dibenzo[c,e][1,2]oxaphosphinine6-oxide 
• 1166187-86-5 P-DDM-HB 
• 1166187-88-7 P-DDS-HB 
• 1166187-87-6 P-BAPP-HB 
• 1166187-91-2 C₄₀H₃₄N₂O₆P₂ 
• 1166187-93-4 C₄₂H₃₈N₂O₆P₂ 
• 1166187-94-5 C₄₄H₄₂N₂O₆P₂ 
• 1166187-98-9 C₄₆H₄₆N₂O₆P₂ 
• 1398408-97-3 3-(6-oxido-6H-dibenz[c,e][1,2]oxaphosphorin-6-yl)phenol 
• 99208-50-1 10?(2,5?dihydroxyphenyl)?10H-9?oxa?10?phosphaphenanthrene?10?oxide 
• 1224321-66-7 C₂₈H₂₅O₄P 
• 22749-43-5 p-chlorodibenzo[c.e][1,2]oxaphosphorine 

Relevant academic research and scientific papers

Thermogravimetric analysis study of a cyclic organo-phosphorus compound

Four methods were used to study the thermal cyclisation of 2-(2-hydroxyphenyl)-phenylphosphonous acid 3, and the results were compared with the thermal decomposition of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO). The decomposition of DOPO was found to be a simple process composed of at least one stage for which apparent activation energies can be calculated. These investigated methods were those of van Krevelen, Horowitz-Metzger, Coats-Redfern, and MacCallum-Tanner. These methodologies evaluated the similar apparent activation energies Ea for cyclisation of 3 and for decomposition of DOPO. Moreover, these apparent activation energies for decomposition of DOPO were compared with that calculated by the isothermal method.

Preparation method of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and intermediate of DOPO

The invention relates to a preparation method of DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) and an intermediate of DOPO and belongs to the field of chemistry. Aiming at solving the technical problems, the invention provides the preparation method of the DOPO intermediate CDOP; the method comprises the following steps: raising the temperature of a mixture of o-phenylphenol, zinc chloride and phosphorus trichloride to 60 DEG C to 140 DEG C and carrying out esterification reaction; continually raising the temperature to 160 DEG C to 220 DEG C and reacting to obtain the product. Byadopting the preparation method provided by the invention, the phosphorus trichloride can be added in one step in a material feeding process and the excessive phosphorus trichloride and reaction byproducts do not need to be removed by decompressing and distilling after the reaction is finished, so that the production operation is greatly simplified; compared with an existing technology, the preparation method has remarkable advantages.

Method for synthesizing 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide

The invention discloses a method for synthesizing 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide. The method includes adding phosphorus trichloride into excessive o-phenylphenol drop by drop and carrying out esterification reaction to obtain phosphorous acid tri-orthophthalic phenyl ester; adding ZnCl2 catalysts into the phosphorous acid tri-orthophthalic phenyl ester, adding phosphorus trichloride into the phosphorous acid tri-orthophthalic phenyl ester drop by drop and carrying out acylation reaction to obtain 6-chlorine-(6 hydrogen)-dibenzo-(c, e)-oxygen phosphorus heterocyclic hexa-rings; sequentially carrying out hydrolysis reaction and cyclization reaction on the 6-chlorine-(6 hydrogen)-dibenzo-(c, e)-oxygen phosphorus heterocyclic hexa-rings to obtain the 9, 10-dihydro-9-oxygen-10-phosphaphenanthrene-10-oxide. The method has the advantages that the o-phenylphenol can be prevented from being volatilized or oxidized at high temperatures, the method is high in reaction speed and suitable for industrial production, and target products are high in yield and purity.

Superacid-catalyzed Friedel–Crafts phosphination of 2-hydroxybiphenyls with phosphorus trichloride

Cyclic phosphorus compounds, 6H-dibenz[c,e][1,2]oxaphosphorin-6-oxide derivatives, were efficiently synthesized by the Friedel–Crafts reaction of 2-hydroxybiphenyls with phosphorus trichloride in the presence of superacids, especially trifluoromethanesulfonic acid (TfOH) as a catalyst. TfOH was investigated for the first time as an effective catalyst for the aromatic phosphination of 2-hydroxybiphenyls.

METHOD FOR SYNTHESIZING 9,10-DIHYDRO-9-OXA-10-PHOSPHAPHENANTHRENE-10-OXIDE AND DERIVATIVES THEREOF

A method for synthesizing 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivatives has a step of introducing 6-chloro-6H-dibenz[c,e][1,2]oxaphosphorin or its derivative, an acid compound and water into a reacting chamber to form an organic layer having 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivative and an aqueous layer. Because the acid compound is from an external source and has a catalyzing effect, employing the method can prevent side reaction from occurring and increase yield of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide or its derivative. Furthermore, the method is a one-pot operation of hydrolysis, dehydration and cyclization, so the method does not require purification of intermediates. Therefore, the method is time-and cost-saving and requires less organic solvent, resulting in less pollution to the environment.

Synthesis and reactivity of 6H-dibenzo[c,e][1,2]oxaphosphinine 6-sulfide, a novel thiophosphacyclic molecule

The new 6H-dibenzo[c,e][1,2]oxaphosphinine 6-sulfide (1) was synthesized and characterized by 1H-, 13C-, 31P-NMR, IR spectroscopy as well as X-ray diffraction and HR-MS. The reactivity of (1) was investigated with a series of test reactions, including Michael-type additions and the Atherton-Todd-reaction and finally compared to that of the parent 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

METHOD FOR THE PRODUCTION OF DIBENZ[C,E] [1,2]-OXAPHOSPHORIN DERIVATIVES, AMINO-DIBENZ[C,E] [1,2]-OXAPHOSPHORIN AND ALSO USE THEREOF

The invention relates to general syntheses of (6H)-dibenz[c,e] [1,2]-oxaphosphorins which are substituted with nitrogen compounds on the phosphorus atom and comprising commercially available 6H-dibenz[c,e] [1,2]-oxaphosphorin-6-oxides. These nitrogen-containing (6H)-dibenz[c,e] [1,2]-oxaphosphorins can be used as reactive starting substances for further syntheses or as flameproofing agents or as stabilisers.

Bisbiphenylacylphosphine oxide and preparation method therefore

A bisbiphenylacylphosphine oxide of formula (I) and its preparation method are provided. The formula of —Ar— is First, 10-chloro-9,10-dihydro-9-oxa-10-phosphaphenanthrene (CDOP) is prepared by using 2-phenylphenol, and then is esterified to synthesize 6-methoxy-(6H)-dibenz[c,e][1,2]oxa-phosphorin (MDOP). Next, acid chloride compounds are added for performing the Arbuzov reaction to synthesize bisbiphenylacylphosphine oxide. CDOP is hydrolyzed to be derived into 9,10-dihydro-9-oxa-10-phosphaphen-anthrene-10-oxide (DOPO), and then DOPO reacts with arylaldehyde to form secondary alcohol. Therefore, bisbiphenylacylphosphine oxide is prepared by using secondary alcohol under oxidation. Also, under a coupling reaction, DOPO reacts with the acid chloride compounds by using a Lewis acid as a catalyst to prepare bisbiphenylacylphosphine oxide.

Organophosphorous composition, method of producing organophosphorous compound, polyester composition and method of producing the same

A polyester having a good color tone can be obtained by using, as an ester-forming component, a compound derived from an organophosphorous composition comprising an organophosphorous compound represented by the general formula (1): wherein R1and R2represent an organic group or a halogen atom, and m and n represent an integer of 0 to 4, provided that R1and R2may be the same or different when m or n is an integer of 2 to 4, and a divalent metallic compound in an amount more than 30 ppm and not more than 2300 ppm in terms of a divalent metal based on the organophosphorous compound.