22749-43-5

Basic information

• Product Name: 6-Chlorobenzo[c][1,2]benzoxaphosphinine
• Synonyms: 6-Chlorodibenz[c,e][1,2]oxaphosphorin;6-chloro-6H-dibenzo[c,e][1,2]oxaphosphinine;6-CHLOROBENZO[C][1,2]BENZOXAPHOSPHININE;10-Chloro-9,10-Dihydro-9-oxa-10-phosphaphenanthrene;6-Chloro-6H-dibenz[c,e][1,2]oxaphosphorin;6H-Dibenz(C,E)(1,2)oxaphosphorin, 6-chloro-
• CAS NO: 22749-43-5
• Molecular Formula: C₁₂H₈ClOP
• Molecular Weight: 234.62
• Mol File: 22749-43-5.mol
• Article Data: 21

Chemical Properties

• Melting Point: 87 °C
• Boiling Point: 374.6 °C at 760 mmHg
• Flash Point: 180.3 °C
• Appearance: /
• Vapor Pressure: 1.78E-05mmHg at 25°C
• CAS DataBase Reference: 6-Chlorobenzo[c][1,2]benzoxaphosphinine(CAS DataBase Reference)
• NIST Chemistry Reference: 6-Chlorobenzo[c][1,2]benzoxaphosphinine(22749-43-5)
• EPA Substance Registry System: 6-Chlorobenzo[c][1,2]benzoxaphosphinine(22749-43-5)

Safety Data

• Hazardous Substances Data: 22749-43-5(Hazardous Substances Data)

Usage

General Description

6-Chlorobenzo[c][1,2]benzoxaphosphinine is a chemical compound with the molecular formula C13H8ClO2P. It is a phosphorous-containing heterocyclic compound that features a benzoxaphosphinine ring system. 6-Chlorobenzo[c][1,2]benzoxaphosphinine is primarily used as a building block in the synthesis of more complex organic and inorganic compounds. It has been studied for its potential applications in materials science and medicinal chemistry. Additionally, its unique structure and reactivity make it a valuable tool for researchers in the fields of organic chemistry and chemical biology.

InChI:InChI=1/C12H8ClOP/c13-15-12-8-4-2-6-10(12)9-5-1-3-7-11(9)14-15/h1-8H

Synthetic route

2-Phenylphen-1-oxydichlorphosphan (33771-47-0) → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
With zinc(II) chloride at 150℃; for 2h;	100%
With zinc(II) chloride at 194℃; for 1.25h;	79%
With aluminium trichloride In n-heptane
With zinc(II) chloride at 250℃; for 2h;
With zinc at 180℃; for 3h; Inert atmosphere;

2-Phenylphenol (90-43-7) → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
With zinc(II) chloride; phosphorus trichloride at 20 - 180℃; for 7h;	100%
With anhydrous phosphorus trichloride; phosphorus trichloride; Zinc chloride In 5,5-dimethyl-1,3-cyclohexadiene	95%
Stage #1: 2-Phenylphenol With phosphorus trichloride at 140℃; for 5h; Inert atmosphere; Neat (no solvent); Stage #2: With zinc(II) chloride at 210℃; for 3h; Inert atmosphere; Neat (no solvent);	90%

2-Phenylphenol (90-43-7) + diphenyl ether , 4-oxy-diphenyl → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
Multi-step reaction with 2 steps 1: phosphorus trichloride / 5 h / 148 °C 2: 79 percent / ZnCl2 / 1.25 h / 194 °C View Scheme

2-Phenylphenol (90-43-7) + phosphorus trichloride (7719-12-2, 52843-90-0) → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
Zinc chloride In toluene

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

Conditions	Yield
With phosphorus trichloride In chloroform for 3h; Inert atmosphere; Reflux;
With phosphorus trichloride In chloroform for 4h; Inert atmosphere; Reflux;

9,10-dihydro-9-oxa-10-phosphaphenanthrene (25072-46-2) → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
With phosphorus trichloride In chloroform for 3h; Inert atmosphere; Reflux;

tris(2-phenylphenyl)phosphite (2752-19-4) → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
With zinc(II) chloride; phosphorus trichloride at 200℃; for 4h; Temperature;	35 g

2,2'-dihydroxybiphenyl (1806-29-7) → p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5)

Conditions	Yield
With phosphorus trichloride In toluene at 140℃; for 8h; Cooling with ice;

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 2,4,6-triamino-s-triazine (108-78-1) → 2,4,6-tris(9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-ylamino)-1,3,5-triazine

Conditions	Yield
With 1-methyl-1H-imidazole at 100℃; for 16h; Inert atmosphere;	100%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + C20H17O3P → 6H-dibenz[c,e][1,2]oxaphosphorin,6'6-(1,2-phenethyl)bis-,6'6-dioxide (1631149-46-6)

Conditions	Yield
Stage #1: p-chlorodibenzo[c.e][1,2]oxaphosphorine; C20H17O3P With triethylamine at 10℃; for 2h; Stage #2: With Methyl benzenesulfonate at 100 - 150℃; for 5h;	99.3%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + recorcinol (108-46-3) → 6,6'-(1,3-phenylenebis(oxy))bis(6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide)

Conditions	Yield
Stage #1: p-chlorodibenzo[c.e][1,2]oxaphosphorine; recorcinol In toluene at 20 - 120℃; for 6h; Heating / reflux; Stage #2: With ammonia In toluene at 20℃; for 0.0833333h; Stage #3: With water; ozone more than 3 stages;	98.9%

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

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + (-)-menthol (2216-51-5) → 6-(1R,2S,5R)-(-)-menthyl-dibenzo[c.e][5,6]oxaphosphorine

Conditions	Yield
With triethylamine In toluene at 26℃; for 3h;	97%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) → 6-chloro-6H-dibenzo[c,e]-[1,2]oxaphosphinine 6-sulfide (30343-12-5)

Conditions	Yield
With sulfur at 130 - 160℃; for 5h; Inert atmosphere;	95%
With sulfur
Multi-step reaction with 2 steps 1: hydrogen sulfide; sodium hydroxide / water; toluene / 20 °C 2: chloroform; triethylamine / tetrachloromethane / 0 °C View Scheme
Multi-step reaction with 3 steps 1: water 2: tetraphosphorus decasulfide / toluene / 17 h / 40 - 55 °C / Inert atmosphere 3: chloroform; triethylamine / tetrachloromethane / 0 °C View Scheme
With sulfur; triethylamine In toluene at 20℃; for 6h; Inert atmosphere; Reflux;

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + (S)-1-phenyl-ethylamine (2627-86-3) → 6-(S)-(-)-α-methyl-benzylamino-dibenzo[c.e][5,6]oxaphosphorine

Conditions	Yield
With triethylamine In toluene at 26℃; for 3h;	95%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + chloro-trimethyl-silane (75-77-4) + 2-bromoanisole (578-57-4) → 2'-[di-o-anisylphosphanyl]-2-(trimethylsilyloxy)-1,1'-biphenyl (1268251-51-9)

Conditions	Yield
Stage #1: 2-bromoanisole With tert.-butyl lithium In diethyl ether; pentane at 20℃; for 2h; Inert atmosphere; Stage #2: p-chlorodibenzo[c.e][1,2]oxaphosphorine In tetrahydrofuran; diethyl ether; pentane at -90 - 20℃; Inert atmosphere; Stage #3: chloro-trimethyl-silane In tetrahydrofuran; diethyl ether; pentane at 20℃; for 2h; Inert atmosphere;	95%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + phenol (108-95-2) → 6-phenoxy-6H-dibenz<1,2>oxaphosphorin

Conditions	Yield
With triethylamine at 210℃; for 4h;	94%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + diethylamine (109-89-7) → 2-diethlylaminodibenzo[c.e][1,2]oxaphosphorine

Conditions	Yield
In toluene at 26℃; for 3h;	94%
In toluene at 26℃; for 3h;
In toluene at 26℃; for 4h; Inert atmosphere;
In toluene at 20℃; for 3h; Inert atmosphere;

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 1-(6-oxidodibenzo[c,e][1,2]oxaphosphinin-6-yl)ethan-1-aminium chloride → 6-(1-(bis(6H-dibenzo[c,e][1,2]oxaphosphinin-6-yl)amino)ethyl)dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
at 40℃; for 18h; Inert atmosphere;	94%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + methanol (67-56-1) → 10-methoxy-10H-9-oxa-10-phosphaphenanthrene (37632-28-3)

Conditions	Yield
With triethylamine In toluene at 50℃; for 2h;	92%
With pyridine In diethyl ether; benzene

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 2-methyl-but-3-yn-2-ol (115-19-5) → 6-(3-methylbuta-1,2-dien-1-yl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃; for 8h;	92%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 1-Ethynyl-1-cyclohexanol (78-27-3) → 6-(2-cyclohexylidenevinyl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃;	91%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + phenylmagnesium bromide → 2'-hydroxy-2-diphenylphosphinobiphenyl (155566-51-1)

Conditions	Yield
In tetrahydrofuran at 26℃; for 20h;	90%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + acetophenone (98-86-2) → 6H-dibenz[c,e][1,2]oxaphosphorin,6'6-(1,2-phenethyl)bis-,6'6-dioxide (1631149-46-6)

Conditions	Yield
With phosphoric acid In 5,5-dimethyl-1,3-cyclohexadiene; water at 160℃; for 4.5h; Concentration; Temperature; Reagent/catalyst; Inert atmosphere;	90%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) → 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-sulfide (1259405-60-1)

Conditions	Yield
With hydrogen sulfide; sodium hydroxide In water; toluene at 20℃;	89%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 3-ethyl-1-pentyn-3-ol (6285-06-9) → 6-(3-ethylpenta-1,2-dien-1-yl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃;	89%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + triethylamine (121-44-8) → triethylammonium 6H-dibenzo[c,e][1,2]oxaphosphinine-6-thiolate 6-sulfide (1259405-65-6)

Conditions	Yield
With sulfur In toluene at 20℃; for 8h; Inert atmosphere; Reflux;	87%

1,4-dihydroxybut-2-yne (110-65-6) + p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) → C28H20O4P2

Conditions	Yield
With N-ethylmorpholine; In dichloromethane at 0 - 20℃;	86%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + meparfynol (77-75-8) → 6-(3-methylpenta-1,2-dien-1-yl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃; diastereoselective reaction;	86%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 2-Phenyl-3-butyn-2-ol (127-66-2) → 6-(3-phenylbuta-1,2-dien-1-yl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃;	86%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 1-ethynylcyclopentanol (17356-19-3) → 6-(2-cyclopentylidenevinyl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃;	85%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 3,5-dimethyl-1-hexyn-3-ol (107-54-0) → 6-(3,5-dimethylhexa-1,2-dien-1-yl)-6H-dibenzo[c,e][1,2]oxaphosphinine 6-oxide

Conditions	Yield
With pyridine In diethyl ether at 0 - 28℃; diastereoselective reaction;	84%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) → C36H24N3O3P3

Conditions	Yield
With trimethylsilylazide In toluene at 50℃; for 24h; Inert atmosphere;	83.4%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + (2,4,6-triisopropylphenyl)magnesium bromide (108894-99-1) → 10-(2,4,6-triisopropyl-phenyl)-10H-9-oxa-10-phospha-phenanthrene (843615-07-6)

Conditions	Yield
In tetrahydrofuran at 26℃;	82%
In tetrahydrofuran at 0 - 26℃;

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + ethylmagnesium bromide (925-90-6) → (2'-hydroxy-biphenyl-2-yl)-diethylphosphane (1093348-90-3)

Conditions	Yield
In tetrahydrofuran at 20 - 65℃; Inert atmosphere;	82%

p-chlorodibenzo[c.e][1,2]oxaphosphorine (22749-43-5) + 2-(pyridine-2-yl)propan-2-ol (37988-38-8) → 2-ethyl(1'-methyl-1'-hydroxy)pyridine-6H-dibenz[c,e][1,2]oxaphosphorin (605666-57-7)

Conditions	Yield
Stage #1: 2-(pyridine-2-yl)propan-2-ol With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: p-chlorodibenzo[c.e][1,2]oxaphosphorine In tetrahydrofuran; hexane at 20℃; for 12h; Further stages.;	80%

Upstream product

• 25072-46-2 9,10-dihydro-9-oxa-10-phosphaphenanthrene 
• 90-43-7 2-Phenylphenol 
• 7719-12-2 phosphorus trichloride 
• 33771-47-0 2-Phenylphen-1-oxydichlorphosphan 
• 35948-25-5 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 
• 1806-29-7 2,2'-dihydroxybiphenyl 
• 2752-19-4 tris(2-phenylphenyl)phosphite 

Downstream Products

• 83937-47-7 10-(2,6-Dimethyl-phenoxy)-10H-9-oxa-10-phospha-phenanthrene 
• 155566-51-1 2'-hydroxy-2-diphenylphosphinobiphenyl 
• 185543-56-0 2-[bis-(4-N,N-diisopropylaminomethylphenyl)phosphino]-2'-hydroxybiphenyl 
• 185543-54-8 2-[bis-(4-N,N-dimethylaminophenyl)phosphino]-2'-hydroxybiphenyl 
• 73662-43-8 6-(N,N-Di-cyclohexyl-amino)-dibenz[c,e][1,2]oxaphosphorine 
• 35948-25-5 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 
• 139995-03-2 6-Phenyl-6H-dibenzo[c,e][1,2]oxaphosphorine 
• 1631149-46-6 6H-dibenz[c,e][1,2]oxaphosphorin,6'6-(1,2-phenethyl)bis-,6'6-dioxide 

Relevant articles and documents

Cleavage of Aromatic C-O Bonds via Intramolecular SNAr Reaction and Preparation of P, C, Axial-Stereogenic Menthyl Phosphine Derivatives

Phosphine ligands with up to six chiral sites were prepared, starting from 2-phenylphenol, via O- and P-alkylation, cyclization, and coupling. The chirality was transferred from (L)-menthyl to phosphorus, α-carbon, and axis, to achieve excellent diastereoselectivities. During an intramolecular SNAr reaction with alkoxyl as the leaving groups, the C-O bond was converted to a C-C bond. Both phosphine boranes and oxides could be used for the conversions, affording a series of cyclic phosphines.

Practical synthesis of 6-chloro-dibenzo[c.e][1,2]oxaphosphorine

The title P-heterocycle 3, a versatile intermediate in synthesis, was prepared by two independent methods. The first involves an environmentally friendly version of an old protocol starting from 2-phenylphenol (1) and phosphorus trichloride. Their interaction could be accomplished at 50C under solventless conditions. Cyclization of the intermediate (2) so obtained could be realized best under microwave conditions at 150C in the presence of ZnCl2. This method offers advantages over the traditional ones. According to another approach, the chloro-dibenzooxaphosphorine (3) was obtained by the novel reaction of 6H-dibenzo[c.e][1,2]oxaphosphorine-6-oxide (4) with phosphorus trichloride in boiling chloroform. Efficiency of the syntheses was demonstrated by converting the crude product 3 to a more stable phosphonic amide (6) that was stable enough to be isolated.

One-pot synthesis of new 6-(alkylamine)dibenzo[c,e][1,2]oxaphosphinine-6-oxides

Several new 6-(alkylamine)-6H-dibenz[c,e][1,2]oxaphosphinine-6-oxides were prepared through a one-pot reaction, starting with 2-phenylphenol, phosphorus trichloride, and a Zn catalyst, to form 6-chloro-6H-dibenz[c,e][1,2]oxaphosphine. The alkylamine derivatives were subsequently prepared through a nucleophilic substitution reaction involving aliphatic amines and H2O2oxidation under soft conditions. This method has the advantages that it is a one-pot synthesis, does not require an inert atmosphere, and involves in situ catalyst formation.

HALOGEN-FREE ACTIVE ESTER CURING AGENT COMPOUND FOR EPOXY RESINS, FLAME RETARDANT COMPOSITION COMPRISING SAME, ARTICLES MADE THEREFROM AND METHOD OF MAKING SAID COMPOUND

There is provided herein a curing agent compound for curing thermosetting resins, e.g., epoxy resins, a composition comprising a thermoplastic and/or thermosetting resin, e.g., an epoxy resin and the curing agent, an article comprising the curing agent, and a method of making the curing agent.