940-71-6

Basic information

• Product Name: Phosphonitrilic chloride trimer
• Synonyms: PPZ;PHOSPHORUS NITRILE DICHLORIDE TRIMER;PHOSPHONITRILIC CHLORIDE TRIMER;PHOSPHONITRILIC CHLORIDE;OTAVA-BB BB7110952524;1,3,5,2,4,6-Triazatriphosphorine, hexachloro-;2,2,4,4,6,6-Hexachloro-2,2,4,4,6,6-hexahydro-1,3,5,2,4,6-triazatriphosphorine;2,2,4,4,6,6-Hexachloro-2λ5,4λ5,6λ5-cyclotriphosphaza-1,3,5-triene
• CAS NO: 940-71-6
• Molecular Formula: Cl6N3P3
• Molecular Weight: 347.66
• EINECS: 213-376-8
• Product Categories: API intermediates;organophosphorus compound
• Mol File: 940-71-6.mol
• Article Data: 19

Chemical Properties

• Melting Point: 112-115 °C(lit.)
• Boiling Point: 127 °C (13 mmHg)
• Appearance: white/crystal
• Density: 1.98 g/mL at 25 °C(lit.)
• Refractive Index: 1.789
• PKA: -12.98±0.10(Predicted)
• Water Solubility: Insoluble in water
• Sensitive: Moisture Sensitive
• CAS DataBase Reference: Phosphonitrilic chloride trimer(CAS DataBase Reference)
• NIST Chemistry Reference: Phosphonitrilic chloride trimer(940-71-6)
• EPA Substance Registry System: Phosphonitrilic chloride trimer(940-71-6)

Safety Data

• Hazard Codes: C
• Statements: 14-34-20/21/22
• Safety Statements: 26-36/37/39-45-7/8-41
• RIDADR: UN 3260 8/PG 2
• WGK Germany: 3
• F: 21
• TSCA: Yes
• HazardClass: 8
• PackingGroup: II
• Hazardous Substances Data: 940-71-6(Hazardous Substances Data)

Usage

Chemical Properties

white crystalline powder

Uses

Reagent for the synthesis of ″dandelion″ (spherical) dendrimers. Ring-opening polymerization, ligand and/or ligand precursor for transition metals, and the study of P-Cl bond substitution reactions are among the interesting uses for this product.

Preparation

Hexachlorocyclotriphosphazene (PNCl2)3 (mp114 ℃, bp 256℃), which is produced on an industrial scale as the starting material for the manufacture of organosubstituted polyphosphazenes. It forms an almost planar six-membered ring with equal P?N bond lengths.

Purification Methods

Purify it by zone melting, by crystallisation from pet.ether, n-hexane or *benzene, and by sublimation. [van der Huizen et al. J Chem Soc, Dalton Trans 1311 1986, Meirovitch et al. J Phys Chem 88 1522 1984, Alcock et al. J Am Chem Soc 106 5561 1984; Winter & van de Grampel J Chem Soc, Dalton Trans 1269 1986.] Phosphoric acid [7664 -38 -2] M 98.0, m 42.3o, pK 1 2.15, pK 2 7.21, pK 3 12.37. Pyrophosphate can be removed from phosphoric acid by diluting with distilled H2O and refluxing overnight. By cooling to 11o and seeding with crystals obtained by cooling a few millilitres in a Dry-ice/acetone bath, 85% orthophosphoric acid crystallises as H3PO4.H2O. The crystals are collected on a sintered glass filter. [Weber & King Inorg Synth I 101 1939.]

InChI:InChI=1/Cl6N3P3/c1-10(2)7-11(3,4)9-12(5,6)8-10

Synthetic route

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonium chloride (12125-02-9) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
With pyridine; magnesium chloride In chlorobenzene at 80 - 132℃; Inert atmosphere;	71%
Stage #1: ammonium chloride With pyridine; magnesium chloride In 1,1,2,2-tetrachloroethane at 145℃; for 12h; Stage #2: phosphorus pentachloride In 1,1,2,2-tetrachloroethane at 145℃; Solvent; Temperature;	61.78%
In chlorobenzene at 120 - 130℃; Inert atmosphere; Reflux;	60.6%

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonium chloride (12125-02-9) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + (NPCl2)8 (14514-98-8) + octachlorocyclotetraphosphazene (2950-45-0) + Cl18N9P9 + pentakisphosphorus nitride dichloride (13596-41-3) + hexakisphosphorus nitride dichloride (2851-52-7) + heptakisphosphorus nitride dichloride (13827-30-0)

Conditions	Yield
In chlorobenzene Schlenk technique; Reflux;	A 64% B 6% C 5% D 2% E 16% F 16% G 13%

...Expand

tris(trimethylsilyl)amine (1586-73-8) + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
In dichloromethane inert atmosphere; dropwise addn. of 1 equiv. PCl5 to amine at 25°C, stirring for 12 h; not isolated, detd. by (31)P-NMR spectroscopy;	49%

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonium chloride → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
In chlorobenzene react. of PCl5 with NH4Cl (ratio 1:1.5) in C6H5Cl at 124-127 °C (20-50 h);;	40%
In chlorobenzene react. of PCl5 with NH4Cl (ratio 1:1.2) in C6H5Cl at 132-134 °C (20 h);;	20-22
In further solvent(s) in 1,1,2,2-tetrachloroethane; recrystn. from petroleum ether;

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonia (7664-41-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
In further solvent(s) passing gaseous NH3 in a soln. of PCl5 in (CHCl2)2;;	16%

tris(trimethylsilyl)amine (1586-73-8) + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + trichloro(trimethylsilyl)phosphoranimine (40678-60-2)

Conditions	Yield
In dichloromethane inert atmosphere; dropwise addn. of 0.5-1 equiv. PCl5 to amine at -78 or25°C, stirring for 30 min to 12 h; yields depending on educt rat io, reaction temp., time and rate of addn.; product mixt. not sepd., detd. by (31)P-NMR spectroscopy;	A 5% B 5%

thionyl chloride (7719-09-7) + tetrasulfur tetranitride (28950-34-7) + phosphorus trichloride (7719-12-2, 52843-90-0) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
In benzene addn. of PCl3 to a soln. of S4N4 in C6H6 containing SOCl2; formation of a brown main product and crystals of (PNCl2)3;;
In benzene addn. of PCl3 to a soln. of S4N4 in C6H6 containing SOCl2; formation of a brown main product and crystals of (PNCl2)3;;

mercury amidochloride (10124-48-8) + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + phosphorus chloride nitride + ammonium chloride + mercury dichloride

Conditions	Yield
In neat (no solvent) heating with HgNH2Cl; formation of a mixture of P3N3Cl6, (PNCl2)(n), HgCl2 and NH4Cl;;
In neat (no solvent) heating with HgNH2Cl; formation of a mixture of P3N3Cl6, (PNCl2)(n), HgCl2 and NH4Cl;;

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonia (7664-41-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + octachlorocyclotetraphosphazene (2950-45-0) + ammonium chloride

Conditions	Yield
In tetrachloromethane pptn. of NH4Cl from a soln. of 3 g PCl5 in 1000 ml CCl4 half-saturated with gaseous NH3 at -3 °C; soln. contains (PNCl2)3 and (PNCl2)4;; evapn. of the mother liquor, fractional crystn. from toluene;;
In tetrachloromethane pptn. of NH4Cl from a soln. of 3 g PCl5 in 1000 ml CCl4 half-saturated with gaseous NH3 at -3 °C; soln. contains (PNCl2)3 and (PNCl2)4;; evapn. of the mother liquor, fractional crystn. from toluene;;

ammonium chloride + chlorine (7782-50-5) + phosphorus trichloride (7719-12-2, 52843-90-0) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In further solvent(s) dissolving PCl3 distd. under N2 in benzyl chloride distd. under N2; addn. of NH4Cl dryed in vac. and passing in the corresponding amount of Cl2; heating in a stream of N2 at 130 °C; removal of formed HCl by a stream of N2;; filtration, distg. off the solvent at 40 °C and 0.5 Torr; recrystn. from petroleum ether; product contains small amounts of higher polymers;;

ammonium chloride + chlorine (7782-50-5) + phosphorus trichloride (7719-12-2, 52843-90-0) → hydrogenchloride (7647-01-0) + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In further solvent(s) dissolving PCl3 distd. under N2 in (CHCl2)2 distd. under N2; addn. of NH4Cl dryed in vac. and passing in the corresponding amount of Cl2; heating in a stream of N2 at 130 °C; removal of formed HCl by a stream of N2;; filtration, distg. off the solvent at 40 °C and 0.5 Torr; recrystn. from petroleum ether; products (NPCl2)3, (NPCl2)4 and a small amount of oily polymers;;
In chlorobenzene dissolving PCl3 distd. under N2 in C6H5Cl distd. under N2; addn. of NH4Cl dryed in vac. and passing in the corresponding amount of Cl2; heating in a stream of N2 at 130 °C; removal of formed HCl by a stream of N2;; filtration, distg. off the solvent at 40 °C and 0.5 Torr; recrystn. from petroleum ether; product contains small amounts of higher polymers;;
In further solvent(s) dissolving PCl3 distd. under N2 in (CHCl2)2 distd. under N2; addn. of NH4Cl dryed in vac. and passing in the corresponding amount of Cl2; heating in a stream of N2 at 130 °C; removal of formed HCl by a stream of N2;; filtration, distg. off the solvent at 40 °C and 0.5 Torr; recrystn. from petroleum ether; yield 35-40 %, product contains small amounts of higher polymers;;	A n/a B 35-40 C n/a D n/a

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonium chloride → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In not given react. of 400 g PCl5 with 120 g NH4Cl in an inert solvent;; sucking off the formed mass, washing with ice-cold C6H6; fractional distn.; yield 50 % (NPCl2)3, 25 % (NPCl2)4 and 25 % higher polymers;;

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonium chloride → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In not given react. of 400 g PCl5 with 120 g NH4Cl in an inert solvent;; sucking off the formed mass, washing with ice-cold C6H6; fractional distn.; yield 75 g (NPCl2)3, 25 g (NPCl2)4;;
In not given react. of PCl5 with NH4Cl;; fractionation at 185-190 °C and 13 Torr; fraction contains 10 % (NPCl2)3;;
In not given react. of PCl5 with NH4Cl;; fractionation at 185-190 °C and 13 Torr; fraction contains 10 % (NPCl2)3;;
In further solvent(s) react. of finely divided NH4Cl and PCl5 in refluxing sym-tetrachloroethane; fractional crystn. from glacial acetic acid, cold benzene and conc. H2SO4;

phosphorus(V) nitride + chlorine (7782-50-5) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride + phosphorus pentachloride (10026-13-8, 874483-75-7) + nitrogen (7727-37-9)

Conditions	Yield
In neat (no solvent) formation of a mixt. of phosphorus nitride dichlorides with a large amount of (NPCl2)3 and a small amount of PCl5 by react. of P3N5 with Cl2 at 700 °C;;

sodium azide + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
In nitrobenzene small amount of azide; detected by NMR;

lithium azide (19597-69-4) + trichloro(o-phenylenedioxy)phosphorane (2007-97-8) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + hexaazido cyclotriphosphazene (22295-99-4) + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In nitrobenzene not isolated, detected by NMR;

2,4-dichloro-1,3-bis(dichlorophosphoryl)-2,4-dioxocyclodiphosph(V)azane (64373-45-1) + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + dichlorophosphinylphosphorimidic trichloride (13966-08-0) + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In trichlorophosphate byproducts: Cl2(O)P(NPCl2)5Cl; under reflux; treatment of the crude product with n-heptane, products identified in the sol. and in the insol. phase with NMR spectroscopy;

P4N6 + chlorine (7782-50-5) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride + phosphorus pentachloride (10026-13-8, 874483-75-7) + nitrogen (7727-37-9)

Conditions	Yield
In neat (no solvent) formation of a mixt. of phosphorus nitride dichlorides with a large amount of (NPCl2)3 and a small amount of PCl5 by react. of P4N6 with Cl2 at 700 °C;;

thionyl chloride (7719-09-7) + tetrasulfur tetranitride (28950-34-7) + phosphorus trichloride (7719-12-2, 52843-90-0) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride

Conditions	Yield
In benzene formation of phosphorus nitride dichlorides with a large amount of (NPCl2)3 as by-products by addn. of PCl3 to a soln. of S4N4 in C6H6 containing SOCl2;;
In benzene

phospham → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
With hydrogenchloride In further solvent(s) passing dry gaseous HCl into a suspension of phospham in 1.1.2.2-tetrachlorethane at 148°C for several h;;

phosphorus(V) chloride * 8 NH3 → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride

Conditions	Yield
In neat (no solvent) formation of phosphorus nitride dichlorides with a large amount of (NPCl2)3 on heating PCl5*8NH3 at 175-200 °C and 50 Torr;;

phosphorus(V) chloride * 8 NH3 → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + ammonia (7664-41-7)

Conditions	Yield
In neat (no solvent) sublimation of (PNCl2)3 at 175-200 °C and 50 Torr;;
In neat (no solvent) sublimation of (PNCl2)3 at 175-200 °C and 50 Torr;;

Mg2PN3 + chlorine (7782-50-5) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cyclic polyphosphorus nitride dichloride + nitrogen (7727-37-9) + magnesium chloride (7786-30-3)

Conditions	Yield
In neat (no solvent) formation of phosphorus nitride dichlorides with a large amount of (NPCl2)3 on heating PN3Mg2 in a stream of Cl2 at 700 °C;;

{Cl(Cl2PN)3PCl3}(1+)*{BCl4}(1-)={Cl(Cl2PN)3PCl3}{BCl4} (21246-65-1) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + {PCl4}(1+)*{BCl4}(1-)={PCl4}{BCl4} (18460-54-3)

Conditions	Yield
130°C;

phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + heptakisphosphorus nitride dichloride (13827-30-0)

Conditions	Yield
With quinoline In further solvent(s) heating a soln. of PCl5 in (CHCl2)2 with quinoline at 145 °C on refluxing;; distn. off solvent; formation of a mixt. of 40 % (NPCl2)3, 55-60 % (PNCl2)7 and 0-5 % impurities;;
With quinoline

phosphorus pentachloride (10026-13-8, 874483-75-7) + phosphoramide (25758-26-3, 13597-72-3) → hydrogenchloride (7647-01-0) + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + dichlorophosphinylphosphorimidic trichloride (13966-08-0) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8)

Conditions	Yield
In further solvent(s) react. of a soln. in tetrachlorethane with PCl5; immediate removal of HCl on passing thruogh a stream of air;;
In further solvent(s) react. of a soln. in tetrachlorethane with PCl5; immediate removal of HCl on passing thruogh a stream of air;;

tris(trimethylsilyl)amine (1586-73-8) + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + octachlorocyclotetraphosphazene (2950-45-0) + pentakisphosphorus nitride dichloride (13596-41-3) + hexakisphosphorus nitride dichloride (2851-52-7)

Conditions	Yield
In dichloromethane byproducts: high oligomers; inert atmosphere; dropwise addn. of 1 equiv. PCl5 to amine at reflux, refluxing for 8 h; distn.; product mixt. not sepd., detd. by (31)P-NMR spectroscopy;

phosphorus pentachloride (10026-13-8, 874483-75-7) + ammonia (7664-41-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + octachlorocyclotetraphosphazene (2950-45-0)

Conditions	Yield
In tetrachloromethane incomplete satn. of a soln. of PCl5 in CCl4 with gaseous NH3;;
In tetrachloromethane

lithium azide (19597-69-4) + phosphorus pentachloride (10026-13-8, 874483-75-7) → 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6)

Conditions	Yield
In nitrobenzene small amount of azide; detected by NMR;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + hydrogen fluoride (7664-39-3) → hydrogenchloride (7647-01-0) + ammonium hexafluorophosphate

Conditions	Yield
In not given react. with HF;;	A n/a B 100%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + sodium fluoride → hexafluorophosphazene (15599-91-4)

Conditions	Yield
With 1-butyl-3-methylimidazolium Tetrafluoroborate In N,N-dimethyl-formamide at 50℃; for 5h; Reagent/catalyst; Solvent; Temperature;	99.8%
With H2O or HF In nitrobenzene dissolving (NPCl2)3 in freshly distd. C6H5NO2; addn. of an excess of NaF or a small amount of H2O or HF under exclusion of H2O (drying tube with P2O5); heating on refluxing;; fractionation;;
In gas byproducts: NaCl; (NPCl2)3 gas was passed over heated NaF at 550°C; monitoring by IR spectroscopy;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + potassium thioacyanate (333-20-0) → hexaisothiocyanatocyclotriphosphazene (1858-42-0) + potassium chloride

Conditions	Yield
In acetone	A n/a B 99%
In acetone	A n/a B 99%

potassium fluoride + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → hexafluorophosphazene (15599-91-4)

Conditions	Yield
With 4-n-butyl-4-methylmorpholinium hydroxide In acetonitrile at 30℃; for 2h; Temperature; Solvent; Reagent/catalyst; Ionic liquid;	98.7%
Reflux;	90%
With catalyst: 18-crown-6 In tetrahydrofuran refluxing KF with catalytic amt. of crown for 20 min, dropwise addn. of 0.1 equiv. of N3P3Cl6, refluxing (1 h); fractional distn.;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 4-bromo-phenol (106-41-2) → hexakis(4-bromophenoxy)cyclotriphosphazene (4376-72-1)

Conditions	Yield
With potassium carbonate In acetone for 18h; Inert atmosphere; Reflux;	98%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → hexafluorophosphazene (15599-91-4)

Conditions	Yield
With potassium fluoride; Triethylene glycol dimethyl ether; ethanol In hexane at 0 - 30℃; for 2h; Solvent; Reagent/catalyst; Temperature;	97.2%
With sodium fluoride In diethylene glycol dimethyl ether at 100℃; for 2h; Temperature; Solvent; Inert atmosphere;	86%
In not given (N2); as in: (Schmutzler, R. Inorg Synth. 1967, 9, 75); fractional distn.;
With sodium fluoride In ethyl acetate at 10℃; for 3h; Solvent; Temperature; Reflux;	130 g

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + isobutylamine (78-81-9) → hexakis(iso-butylamino) cyclotriphosphazene (101201-65-4)

Conditions	Yield
In toluene for 24h; Reflux;	97%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 2,2'-dihydroxybiphenyl (1806-29-7) → 2,2-dichloro-4,4,6,6-bis[spiro(2',2''-dioxy-1'',1''-biphenyl)]cyclotriphosphazene (128175-80-4)

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 65℃; for 12h; Inert atmosphere;	95.4%
With potassium carbonate In acetone at 0 - 20℃; for 24h; Inert atmosphere;	92%
With potassium carbonate In acetone at 0 - 20℃; for 24h; Inert atmosphere;	92%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + phenol (108-95-2) → 2,2,4,4,6,6-hexaphenoxycyclotriphosphazene (1184-10-7)

Conditions	Yield
Stage #1: phenol With tetrabutylammomium bromide; chlorobenzene; potassium hydroxide at 50℃; for 0.5h; Stage #2: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine at 90℃; for 9h; Reagent/catalyst; Temperature;	95.04%
Stage #1: phenol With sodium hydride In tetrahydrofuran Inert atmosphere; Stage #2: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In tetrahydrofuran at 70℃; Inert atmosphere;	85%
With potassium carbonate In tetrahydrofuran at 50℃; for 24h;	85.6%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + ammonia (7664-41-7) → 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazene (10535-05-4)

Conditions	Yield
In diethyl ether at 0℃; for 1.5h;	95%
In diethyl ether; ammonia NH3 (liquid); molar ratio P3N3Cl2:NH3 1:4;
In diethyl ether Schlenk technique;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 4-hydroxy-benzaldehyde (123-08-0) → hexakis(4-formylphenoxy)cyclotriphosphazene (77958-57-7)

Conditions	Yield
With caesium carbonate In tetrahydrofuran at 20℃; for 48.5h; Reagent/catalyst; Cooling with ice;	94%
Stage #1: 4-hydroxy-benzaldehyde With triethylamine In acetone at 0℃; for 0.5h; Stage #2: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In acetone at 0 - 20℃;	94.19%
With potassium carbonate In tetrahydrofuran for 24h; Reflux;	92.8%
In tetrahydrofuran for 48h; Reflux;	82%
With sodium hydride In tetrahydrofuran at 65℃; for 48h; Inert atmosphere;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + methyl 4-hydroxylbenzoate (99-76-3) → hexa(4-carbomethoxyphenoxy)cyclotriphosphazene

Conditions	Yield
With potassium carbonate In acetone at 80℃;	93.6%
With caesium carbonate In tetrahydrofuran for 16h; Reflux; Schlenk technique; Inert atmosphere;	79%

hydrogenchloride (7647-01-0) + gallium(III) trichloride + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → Cl6N3P3*Cl4Ga(1-)*H(1+)

Conditions	Yield
In chloroform at 20℃; Glovebox; Darkness;	92%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene

Conditions	Yield
With ammonia at 20℃; for 1.5h;	92%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 1-amino-2-propene (107-11-9) → hexakis(allylamino)cyclotriphosphazene (986-11-8)

Conditions	Yield
With triethylamine In tetrahydrofuran for 4h; Inert atmosphere; Reflux;	92%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 4-Vinylphenol (2628-17-3) → 2,2,4,4,6,6-hexakis-(4-vinyl-phenoxy)-2λ5,4λ5,6λ5-[1,3,5,2,4,6]triazatriphosphinine

Conditions	Yield
With potassium carbonate In tetrahydrofuran at 20 - 60℃; for 23h;	91%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + ammonia (7664-41-7) → 2,2-diamino-4,4,6,6-tetrachlorocyclotriphosphazene (10535-05-4) + 2,2,4,4-tetraamino-6,6-dichlorocyclotriphosphazene

Conditions	Yield
In acetonitrile at 20℃; for 1.5h; Solvent;	A 1% B 91%
In diethyl ether at 20℃; for 1.5h; Solvent;	A 80% B 3%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + Boc-Tyr-OMe → C90H120N9O30P3

Conditions	Yield
With caesium carbonate In tetrahydrofuran at 20℃; for 16h; Schlenk technique; Inert atmosphere;	91%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 2,2'-diaminodiethyl ether (2752-17-2) → 1,9,11,11,13,21,23,23-Octachloro-5,17-dioxa-2,8,10,12,14,20,22,24,25,26-decaaza-1λ5,9λ5,11λ5,13λ5,21λ5,23λ5-hexaphospha-tricyclo[19.3.1.19,13]hexacosa-1(25),9,11,13(26),21,23-hexaene (129577-49-7)

Conditions	Yield
In diethyl ether; water Ambient temperature;	90%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 3,6-dioxa-1,8-diaminooctane (929-59-9) → 1,12,14,14,16,27,29,29-Octachloro-5,8,20,23-tetraoxa-2,11,13,15,17,26,28,30,31,32-decaaza-1λ5,12λ5,14λ5,16λ5,27λ5,29λ5-hexaphospha-tricyclo[25.3.1.112,16]dotriaconta-1(31),12,14,16(32),27,29-hexaene (129577-50-0)

Conditions	Yield
In diethyl ether; water Ambient temperature;	90%

aluminium trichloride (7446-70-0) + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → (PCl2N)3AlCl3

Conditions	Yield
In dichloromethane (under vac.); AlCl3 reacted with (PCl2N)3 in CH2Cl2;	90%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + tetraethylene glycol monomethyl ether (23783-42-8) → 2,2,4,4,6,6-hexakis-(2-(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)ethoxy)cyclotriphosphazene (1289636-24-3)

Conditions	Yield
Stage #1: tetraethylene glycol monomethyl ether With sodium hydride In 1,4-dioxane at 50℃; for 24h; Inert atmosphere; Stage #2: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,4-dioxane at 60℃; for 48h; Inert atmosphere;	90%

hydrogenchloride (7647-01-0) + aluminum (III) chloride (7446-70-0, 7784-13-6) + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → Cl6N3P3*AlCl4(1-)*H(1+)

Conditions	Yield
In chloroform at 21.84℃; Schlenk technique; Glovebox;	90%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 2-[tricarbonyl(η(6)-phenoxy)chromium]ethanol (134177-52-9) + sodium hydride (7646-69-7) → N3P3{(η6-OCH2CH2OC6H5)Cr(CO)3}6 (134208-38-1)

Conditions	Yield
In tetrahydrofuran (N2), added at 0. degree.C, warmed to 25°C and stirred for 5 h, added dropwise N3P3Cl6, stirred at 40-45°C for 12 h; removed solvent in vac., column chromy.; elem. anal., IR, mass. spectra,NMR;	89%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + (Z)-oct-5-en-1-ol (64275-73-6) → 2,2,4,4,6,6-hexakis-(cis-5-octenyl-1-oxy)cyclotriphosphazene (1289636-29-8)

Conditions	Yield
Stage #1: (Z)-oct-5-en-1-ol With sodium hydride In 1,4-dioxane at 50℃; for 24h; Inert atmosphere; Stage #2: 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine In 1,4-dioxane at 60℃; for 48h; Inert atmosphere;	89%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 2-Allylphenol (1745-81-9) → C54H54N3O6P3

Conditions	Yield
With sodium hydroxide In tetrahydrofuran at 20 - 60℃; for 13.5h;	89%

5,5-difluoro-10-(4-hydroxyphenyl)-5H-dipyrrolo[1,2-c :2’,1’-f][1,3,2]diazaborinin-4-ium-5-uide + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → hexakis[4,4-difluoroboryl-8-(p-phenoxy)-4-bora-3a,4a-diaza-s-indacene]cyclotriphosphazene

Conditions	Yield
With Cs2CO3 In tetrahydrofuran hydroxyphenyl and Cs2CO3 was added to hexachlorotriphosphazene in THF at0°C, stirred for 6 h at 50°C; concd. in vac., column chromy. (silica, CH2Cl2), evapd. in vac.;	88%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + 2,2'-dihydroxybiphenyl (1806-29-7) → 4',4',6',6'-tetrachloro-4'λ5,6λ5,6'λ5-spiro[dibenzo[d,f][1–3]-dioxaphosphepine-6,2'-[1–6]triazatriphosphinine] (128175-79-1)

Conditions	Yield
In acetone at 20℃; for 0.25h;	87%
With caesium carbonate In tetrahydrofuran at 20℃; for 10h;
With potassium carbonate

C16H20NPO4 (918636-17-6) + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) → C96H114N9O24P9

Conditions	Yield
With caesium carbonate In acetonitrile at 20℃; for 24h;	87%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + aluminium bromide (7727-15-3) → (PCl2N)3AlBr3

Conditions	Yield
In dichloromethane (under vac.); AlBr3 reacted with (PCl2N)3 in CH2Cl2;	87%

Upstream product

• 7719-09-7 thionyl chloride 
• 28950-34-7 tetrasulfur tetranitride 
• 7719-12-2 phosphorus trichloride 
• 10026-13-8 phosphorus pentachloride 
• 7664-41-7 ammonia 
• 7782-50-5 chlorine 
• 19597-69-4 lithium azide 
• 2007-97-8 trichloro(o-phenylenedioxy)phosphorane 
• 25758-26-3 phosphoramide 
• 1586-73-8 tris(trimethylsilyl)amine 
• 10124-48-8 mercury amidochloride 
• 10025-87-3 trichlorophosphate 
• 12125-02-9 ammonium chloride 
• 7646-85-7 zinc(II) chloride 

Downstream Products

• 7803-51-2 phosphan 
• 15599-91-4 hexafluorophosphazene 
• 74-90-8 hydrogen cyanide 
• 22295-99-4 hexaazido cyclotriphosphazene 
• 7647-14-5 sodium chloride 
• 7647-01-0 hydrogenchloride 
• 14097-18-8 trimetaphosphimic acid 
• 21846-69-5 2,2-dichloro-4,4,6,6-tetrafluorocyclotriphosphazene 
• 29871-62-3 (NPFCl)2(NPF₂) 
• 25251-04-1 tetrachlorodifluorocyclotriphosphazene 
• 13778-06-8 pentachlorofluorocyclotriphosphazene 
• 1858-42-0 hexaisothiocyanatocyclotriphosphazene 
• 22722-08-3 phosphorus(V) nitride imide 
• 7382-17-4 2,4-diamino-4,4,6,6-pentachoro-2λ5,4λ5,6λ5-cyclotriphosphaza-1,3,5-triene 

Relevant articles and documents

Purification method of hexaphenoxy cyclotriphosphazene

The invention discloses a purification method of hexaphenoxy cyclotriphosphazene. The method comprises the following steps: firstly, adding a 5-10% sodium hydroxide solution into a hexaphenoxy cyclotriphosphazene synthesis liquid, stirring for 10 to 30 minutes at room temperature, standing, separating out a water phase, adding water, stirring at room temperature for 10-30 minutes, standing, separating out the water phase, adding a 5-10% hydrochloric acid solution, stirring at room temperature for 10-30 minutes, standing, separating out the water phase, adding water, stirring at room temperature for 10-30 minutes, standing, and separating out the water phase; finally steaming out chlorobenzene in the washed oil phase to obtain a hexaphenoxy cyclotriphosphazene crude product; and heating anddissolving the crude product with absolute ethyl alcohol, cooling to -10-0 DEG C, crystallizing for 4 to 8 hours, filtering, washing a filter cake with absolute ethyl alcohol twice, and drying at 90to 100 DEG C until the weight is constant so as to obtain the hexaphenoxy cyclotriphosphazene. According to the purification method disclosed by the invention, the yield of the hexaphenoxy cyclotriphosphazene is remarkably improved.

ALLYL-PHENOXY-CYCLOPHOSPHAZENE COMPOUND, AND PRODUCTION METHOD THEREFOR

An object of the present invention is to provide a mixture of cyclophosphazenes suitably substituted with phenoxy having a polymerizable functional group, such as allyl, on the phenyl ring and a production method for the mixture. The invention relates to a mixture of cyclophosphazene compounds that each contain a plurality of constituent units linked to each other, each constituent unit being represented by formula (I): wherein R1 and R2 are identical or different and represent C1-4 alkyl or the like, the mixture containing cyclophosphazene compounds in which 3, 4, and 5 constituent units represented by formula (I) are linked, wherein the cyclophosphazene compound containing 3 linked constituent units is cyclophosphazene compound (I-A) with a specific structure, compound (I-A) includes cyclophosphazene compounds (I-A2) and (I-A3) having a specific structure, and compounds (I-A2) and (I-A3) are present in an amount of 80 wt % or more in total in cyclophosphazene compound (I-A).

Preparation method of hexaphenoxycyclotriphosphazene

The invention discloses a preparation method of hexaphenoxycyclotriphosphazene. The preparation method comprises the following steps: (1) adding ammonium chloride, an inert solvent and a catalyst into a synthesis kettle, heating to 100-145 DEG C, uniformly putting phosphorus pentachloride into the synthesis kettle within 5-40 hours, and after the reaction is ended, carrying out filtrate concentration and cooling crystallization to obtain phosphonitrilic chloride trimer; (2) adding the inert solvent, phenol, alkali metal hydroxide and water into the synthesis kettle, heating to 100-145 DEG C, dropwise adding an inert solvent solution of phosphonitrilic chloride trimer after azeotropic separation of water, insulating and carrying out reflux reaction; and (3) adding a chloride-ion removing agent, continuously reacting for 3-6 hours at the temperature of 100-135 DEG C, then carrying out alkali washing, acid washing, water washing and steam distillation, and drying to obtain granular hexaphenoxycyclotriphosphazene with low chloride content. The preparation method disclosed by the invention has the advantages that the process is simple, the obtained product is low in chloride content and the stability is good in the use process.