99208-50-1

Usage

Flammability and Explosibility

Notclassified

Synthetic route

p-benzoquinone (106-51-4) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1)

Conditions	Yield
In 2-ethoxy-ethanol at 125℃; for 4h; Inert atmosphere;	93%
In toluene at 110℃; for 3.5h; Temperature; Inert atmosphere;	92%
In toluene at 120℃; for 5h; Inert atmosphere;	91.2%

2,5-dihydroxy-1-iodobenzene (23030-43-5) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium acetate In 1,4-dioxane at 100℃; for 12h; Inert atmosphere;	65%

2-bromobenzene-1,4-diol (583-69-7) + 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (35948-25-5) → 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1)

Conditions	Yield
With tetrakis(triphenylphosphine) palladium(0); sodium acetate In 1,4-dioxane at 100℃; for 24h; Inert atmosphere;	25%

Diisopropyl chlorophosphate (2574-25-6) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenedi(diisopropyl phosphate)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 8h; Reflux;	93%

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) + dibutyl chlorophosphate (819-43-2) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenedi(di(n-butyl) phosphate)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 8h; Reflux;	89.2%

diethyl chlorophosphate (814-49-3) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenedi(diethyl phosphate)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 8h; Reflux;	82.6%

dipropyl chlorophosphate (2510-89-6) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenedi(di(n-propyl) phosphate)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 8h; Reflux;	80.5%

Dimethyl chlorophosphate (813-77-4) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenedi(dimethyl phosphate)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 8h; Reflux;	78%

di(sec-butyl) phosphoryl chloride (54757-38-9) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 2-(6-oxido-6H-dibenz(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenedi(di(sec-butyl) phosphate)

Conditions	Yield
With potassium carbonate In acetonitrile at 20℃; for 8h; Reflux;	76.2%

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) + cyanogen chloride (506-77-4) → C20H11N2O4P (1018986-69-0)

Conditions	Yield
With triethylamine In acetone at -9 - -6℃; for 2.75h;	75%

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 2-(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinine-6-yl)cyclohexa-2,5-diene-1,4-dione (1384457-22-0)

Conditions	Yield
With manganese(IV) oxide In acetone at 20℃; for 1h;	68.8%

4-Fluoronitrobenzene (350-46-9) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → C30H19N2O8P

Conditions	Yield
With potassium carbonate In N,N-dimethyl acetamide at 160℃; for 12h; Inert atmosphere;	67%
With cesium fluoride In N,N-dimethyl acetamide at 160℃; for 10h;	55.55%

4-Vinylbenzyl chloride (1592-20-7) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → C36H29O4P

Conditions	Yield
Stage #1: 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide With sodium hydroxide In toluene at 70℃; for 0.5h; Stage #2: 4-Vinylbenzyl chloride With tetrabutylammomium bromide In toluene at 70℃; for 10h;	65%
Stage #1: 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide With sodium hydroxide In toluene at 70℃; for 0.5h; Stage #2: 4-Vinylbenzyl chloride With tetrabutylammomium bromide In toluene for 10h;	65%

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) + 4-[4-(2-methylbutoxy)phenyl] benzoic acid → C54H49O8P

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran	58%

4'-octyloxy(1,1'-biphenyl)-4-carboxylic acid (59748-18-4) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → C60H61O8P

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran for 6h;	28%

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) + 4-{4-[2-(2-methoxyethoxy)ethoxy]phenyl} benzoic acid (823222-06-6) → C54H49O12P

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran	27%

epichlorohydrin (106-89-8) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 9,10-dihydro-10-(2',5'-diglycidyloxyphenyl)-9-oxa-10-phosphaphenanthrene-10-oxide

Conditions	Yield
With sodium methylate Etherification;
With N-benzyl-N,N,N-triethylammonium chloride at 95℃; for 4h; Reagent/catalyst; Temperature; Inert atmosphere;

4'-n-hexyloxybiphenyl-4-carboxylic acid (59748-16-2) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → C56H53O8P

Conditions	Yield
With dmap; dicyclohexyl-carbodiimide In tetrahydrofuran

Reaxys ID: 11458169 + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → Reaxys ID: 13061976

formaldehyd (50-00-0) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) + 3,4-difluoroaniline (3863-11-4) → C34H23F4N2O4P (1151509-52-2)

Conditions	Yield
at 90℃;

formaldehyd (50-00-0) + Reaxys ID: 19448680 + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → Reaxys ID: 19448679

Conditions	Yield
Heating;

4-Fluoronitrobenzene (350-46-9) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → C30H19N2O8P + 1,4'-bis(4-nitrophenoxy)benzene (20638-32-8) + C30H20N2O9P(1-)*K(1+)

Conditions	Yield
With potassium carbonate In N,N-dimethyl acetamide at 160℃; for 12h; Inert atmosphere;

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 6-(2-(diphenylphosphoryl)-3,6-dihydroxyphenyl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide (1384457-24-2)

Conditions	Yield
Multi-step reaction with 2 steps 1: manganese(IV) oxide / acetone / 1 h / 20 °C 2: toluene / 3 h / Inert atmosphere; Reflux View Scheme

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 6-(2-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)-3,6-dihydroxyphenyl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide (1384457-25-3)

Conditions	Yield
Multi-step reaction with 2 steps 1: manganese(IV) oxide / acetone / 1 h / 20 °C 2: toluene / 3 h / Inert atmosphere; Reflux View Scheme

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 6-(4-hydroxy-3-(6-oxido-6H-dibenzo[c,e][1,2]-oxaphosphinine-6-yl)phenoxy)-6H-dibenzo[c,e][1,2]-oxaphosphinine 6-oxide (1384457-27-5)

Conditions	Yield
Multi-step reaction with 3 steps 1: manganese(IV) oxide / acetone / 1 h / 20 °C 2: toluene / 3 h / Inert atmosphere; Reflux 3: triethylamine / toluene / 120 h / Reflux View Scheme

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 6,6'-(3,6-dihydroxy-1,2-phenylene)bis(6H-dibenzo[c,e][1,2]oxaphosphinine-6-oxide)

Conditions	Yield
Multi-step reaction with 2 steps 1: manganese(IV) oxide / acetone / 1 h / 20 °C 2: toluene / 3 h / Inert atmosphere; Reflux View Scheme

10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → diphenyl (3,6-dihydroxy-2-(6-oxido-6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)phenyl)phosphonate

Conditions	Yield
Multi-step reaction with 2 steps 1: manganese(IV) oxide / acetone / 1 h / 20 °C 2: toluene / 3 h / Inert atmosphere; Reflux View Scheme

teroxirone (2451-62-9) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → C42H43N6O16P

Conditions	Yield
at 150℃; for 5h;

Allyl ether (557-40-4) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → 9,10-dihydro-10-(2',5'-diglycidyloxyphenyl)-9-oxa-10-phosphaphenanthrene-10-oxide

Conditions	Yield
With magnesium sulfate; 3-chloro-benzenecarboperoxoic acid In chloroform at 25℃; for 8h; Inert atmosphere;

α-Naphthol Orange (523-44-4) + 1,4-bis[4-(carbonochloridoyl)phenyl] benzene-1,4-dicarboxylate (82684-68-2) + 10‑(2,5‑dihydroxyphenyl)‑10H-9‑oxa‑10‑phosphaphenanthrene‑10‑oxide (99208-50-1) → Reaxys ID: 30918465

Upstream product

• 23030-43-5 2,5-dihydroxy-1-iodobenzene 
• 35948-25-5 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 
• 583-69-7 2-bromobenzene-1,4-diol 
• 106-51-4 p-benzoquinone 

Downstream Products

• 1018986-69-0 C₂₀H₁₁N₂O₄P 
• 20638-32-8 1,4'-bis(4-nitrophenoxy)benzene 

Relevant academic research and scientific papers

Single-crystal structure analysis of a novel aryl phosphinate diglycidyl ether

The crystal structure of 10-[2,5-bis(2,3-epoxy-1-propoxy)phenyl]-9-oxa-10-phosphaphenanthren-10-one has been studied by single-crystal X-ray diffraction. The unit cell of C24H21O6P, Mr = 436.4, is triclinic, P1, with a = 8.507 (3), b = 10.613 (4), c = 12.457 (3) A, α = 80.05 (3), β = 71.38 (2), γ = 76.69 (3)°, V = 1031.1 (6) A3, Z = 2, Dx = 1.406 Mg m-3 and μ(Mo Kα) = 0.17 mm-1. The final R (wR) is 0.063 (0.057) {w = 1/[σ2(F) + 0.0004F2]} for 3619 unique reflections measured at 295 K. The aryl phosphinate group bonded to the central phenyl ring comes close to one of the two glycidyl ether groups, the epoxide ring of which is ordered. The epoxide ring far from the aryl phosphinate group is disordered. The NMR chemical shifts of the protons of the glycidyl ether group close to the aryl phosphinate group are reduced by the 'ring-current effect'.

Preparation method of high-purity DOPO-HQ

The invention relates to a preparation method of high-purity 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide(DOPO-HQ). the preparation method comprises the following steps that activated carbon and atlapulgite are added into a 1,4-para benzoquinone solvent organic solvent, a decoloration reaction is conducted at 60-130 DEG C, and thus a treated 1,4-para benzoquinone solution is obtained; under the protective atmosphere, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide is dissolved in the organic solvent, then the treated 1,4-para benzoquinone solution is added intothe organic solvent dropwise, reaction is conducted at 60-130 DEG C, and after complete reaction, a crude product is obtained; and the crude product is dissolved in the organic solvent, the activatedcarbon and the atlapulgite are added into the organic solvent, the crude product is subjected to a decoloration reaction at 60-130 DEG C, after complete reaction, the activated carbon and the atlapulgite are removed, cooling crystallization is conducted, and after a crystal is dried, the 10-(2,5-dihydroxyphenyl)-10-hydrogen-9-oxa-10-phosphaphenanthrene-10-oxide is obtained. As for the DOPO-HQ prepared through the preparation method, the purity is 99.9% or above (HPLC), and the whiteness is 95 or above.

A novel diol precursor for preparing flame-retardant polyurethane

The present invention relates to a novel diol precursor for manufacturing flame retardant polyurethane. The polyurethane manufactured by using the diol precursor for manufacturing the flame-retardant polyurethane of the present invention has excellent flame retardancy. In addition, after the thermoplastic flame retardant polyurethane is formed, a crosslinking reaction occurs by a double bond, resulting in thermosetting flame retardant polyurethane. As a result of cross-liked after processing, the thermosetting flame retardant polyurethane is excellent in durability as well as thermal stability.(AA) Step 1: crosslinkable flame retardant diol(BB) Step 2: flame-retardant polyurethane with double bonds(CC) Step 3: high durability flame-retardant polyurethane after crosslinking(DD) Durability(EE) Flame resistance(FF) All(GG) Phosphorus based flame retardant material(HH) Double bond(II) Urethane bindingCOPYRIGHT KIPO 2018

XANTHENE-CONTAINING OR THIOXANTHENE-CONTAINING PHOSPHINATED COMPOUNDS AND PREPARATION METHODS THEREOF

Xanthene-containing or thioxanthene-containing phosphinated compounds and preparation methods thereof are disclosed. The method includes reacting compounds (i) with compounds (ii) and compounds (iii) in the presence of an acid catalyst to synthesize compounds having the structure of formula (I).

DOPS-1,4 phenol and preparation method thereof

The invention discloses DOPS-1,4 phenol. The DOPS-1,4 phenol is characterized in that the formula is shown in the description. The DOPS-1,4 phenol is brown powdery solid, and the melting point ranges from 123 DEG C to 125 DEG C. A preparation operation method is simple, the yield is in the middle level, raw materials are wide in source, no severe pollution is produced, the repeatability is good, and mass production is easy.

Synthesis of flame-retardant phosphaphenanthrene derivatives with high phosphorus contents

Two novel types of phosphate derivatives of phosphaphenanthrene with a high phosphorus content were prepared by phosphorylation reaction between either 2-(6-oxido-6H-dibenzc,e1,2oxaphosphorin-6-yl)-methanol (ODOPM) or 2-(6-oxido-6H-dibenzc,e1,2.oxaphosphorin-6-yl)-1,4-benzenediol (ODOPB) and dialkyl phosphoryl chloride. The structures of all compounds were characterised by 1H NMR, 13C NMR, 31P NMR, Fourier transform infrared spectroscopy, and high-resolution mass spectrometry. The thermal stability of representative compounds was determined by thermal gravimetric analysis and differential scanning calorimetry. The results showed that the compounds have excellent resistance to oxidation, high thermal stability with an onset decomposition temperature above 200°C, and a high char yield over 25 %, owing to the high P content. The representative compound was added to conventional electrolytes of lithium-ion batteries as flame retardant additive, and the self-extinguishing time and ionic conductivity were measured. The result showed that the compounds have effective flame retardant properties.

Solubilities of (2,5-dihydroxyphenyl)diphenyl phosphine oxide in selected solvents

A phosphorus-containing flame retardant (2,5-dihydroxyphenyl)diphenyl phosphine oxide (HPO) was characterized by a differential scanning calorimeter (DSC), thermogravimetric analysis (TGA), elemental analysis, and nuclear magnetic resonance (1H NMR and 31P NMR). Using a static analytical method, the solubilities of HPO were measured in 12 solvents and correlated with an empirical equation. The estimated uncertainty of all of the solubility values on error analysis and repeated observations was within 2.0 %.

Flame retardancy and thermal degradation mechanism of epoxy resin composites based on a DOPO substituted organophosphorus oligomer

A series of flame-retardant epoxy resins (EP) with different content of poly(DOPO substituted dihydroxyl phenyl pentaerythritol diphosphonate) (PFR) were prepared. The PFR was synthesized via the polycondensation between 10-(2,5-dihydroxyl phenyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-BQ) and pentaerythritol diphosphonate dichloride (SPDPC). The structure of PFR was confirmed by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance (1H NMR). The flame retardancy and the thermal stability of the EP/PFR hybrids were investigated by limiting oxygen index (LOI) test and thermogravimetric analysis (TGA) in air. The results showed that the incorporation of PFR into EP can improve the thermal stability dramatically. The mechanical results demonstrated that PFR enhanced failure strain slightly accompanied by a decrease in tensile strength. The thermal oxidative degradation mechanisms of the EP/PFR hybrids were investigated by real time Fourier transform infrared spectra (RTFTIR) and direct pyrolysis/mass (DP-MS) analysis. X-ray photoelectron spectroscopy (XPS) was used to explore chemical components of the residual char of EP and EP/PFR hybrid. DP-MS analysis showed that the degradation process of EP/PFR hybrid was divided into two characteristic temperature regions, attributed to the decomposition of phosphate and aromatic structure.

Palladium-catalyzed arylation of 9,10-Dihydro-9-oxa-10-phosphaphenanthrene- 10-oxide (DOPO) with halogen-substituted phenols

Phenol functionalized 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) derivatives are synthesized via palladium-catalyzed arylation of DOPO with halogen-substituted phenols. 2-,3-, and 4-Substituted halogen phenols are successfully applied to th