15599-91-4

Basic information

• Product Name: HEXAFLUOROCYCLOTRIPHOSPHAZENE
• Synonyms: 1,3,5,2,4,6-Triazatriphosphorine, hexafluoro-;Phosphonitrilefluoridetrimer;tris(phosphorusnitridedifluoride);PHOSPHONITRILIC FLUORIDE TRIMER;1,3,5-TRIAZA-2,4,6-TRIPHOSPHORIN-2,2,4,4,6,6-HEXAFLUORIDE;HEXAFLUOROCYCLOTRIPHOSPHAZENE;AURORA KA-1097;1,3,5-Triaza-2,4,6-triphosphorin-2,2,4,4,6,6-hexafluoride, Hexafluorocyclotriphosphazene
• CAS NO: 15599-91-4
• Molecular Formula: F₆N₃P₃
• Molecular Weight: 248.93
• Mol File: 15599-91-4.mol
• Article Data: 16

Chemical Properties

• Melting Point: 25-30 °C(lit.)
• Boiling Point: 50.9 °C(lit.)
• Flash Point: °C
• Appearance: /
• Density: 2.237 g/cm3 (20 ºC )
• Refractive Index: 1.3183 (589.3 nm 32℃)
• Storage Temp.: 2-8°C
• Solubility: soluble in Toluene
• PKA: -27.34±0.27(Predicted)
• CAS DataBase Reference: HEXAFLUOROCYCLOTRIPHOSPHAZENE(CAS DataBase Reference)
• NIST Chemistry Reference: HEXAFLUOROCYCLOTRIPHOSPHAZENE(15599-91-4)
• EPA Substance Registry System: HEXAFLUOROCYCLOTRIPHOSPHAZENE(15599-91-4)

Safety Data

• Hazard Codes: C
• Statements: 34
• Safety Statements: 26-36/37/39-45
• RIDADR: UN 3260 8/PG 2
• WGK Germany: 3
• F: 10-21
• HazardClass: 8
• PackingGroup: III
• Hazardous Substances Data: 15599-91-4(Hazardous Substances Data)

Usage

General Description

HEXAFLUOROCYCLOTRIPHOSPHAZENE is a chemical compound with the molecular formula (PNF2)3. It consists of a six-membered ring with alternating phosphorus and nitrogen atoms, each of which is surrounded by two fluorine atoms. It is commonly used as a flame retardant and a high-temperature resistant material due to its high thermal stability and low reactivity. HEXAFLUOROCYCLOTRIPHOSPHAZENE has also been studied for its potential application in various fields, including as a solvent and as a precursor for the synthesis of other phosphazene compounds. Its unique structure and properties make it a valuable and versatile compound with potential applications in a wide range of industries.

InChI:InChI=1/F6N3P3/c1-10(2)7-11(3,4)9-12(5,6)8-10

Synthetic route

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;

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) → 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) + sodium hexafluorosilicate → hexafluorophosphazene (15599-91-4)

Conditions	Yield
In neat (no solvent) react. at 280-350 °C; complete react. after 2 1/2 h; passing through N2 at the end of the react.;; distn. off the product or removal of product with N2;;	84.5%
In neat (no solvent) react. at 280-350 °C; complete react. after 2 1/2 h; passing through N2 at the end of the react.;; distn. off the product or removal of product with N2;;	84.5%

potassium fluoride + 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + sulfur dioxide (7446-09-5) → hexafluorophosphazene (15599-91-4)

Conditions	Yield
In neat (no solvent) condensation of 80 ml liquid SO2 on a mixt. of 200 g (NPCl2)3 and 300 g KF; heating at 98-100 °C for 22 days;; removal of an excess of SO2; fractionation, transition temp. 49-49.8 °C at 747 Torr; yield 115.3 (NPCl2)3;;	80%
In neat (no solvent) heating (NPCl2)3 with KF and SO2;;
In neat (no solvent) heating (NPCl2)3 with a 50 % excess of KF and less than the stoichiometric amount of SO2 at 100 °C in an autoclave for a few days on stirring;;
In neat (no solvent) heating (NPCl2)3 with a 50 % excess of KF and less than the stoichiometric amount of SO2 at 100 °C in an autoclave for a few days on stirring;;
In neat (no solvent) heating (NPCl2)3 with KF and SO2;;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + potassium fluorosulphinate (14986-57-3) → hexafluorophosphazene (15599-91-4) + sulfur dioxide (7446-09-5)

Conditions	Yield
In nitrobenzene heating a soln. of (NPCl2)3 in C6H5NO2 with solid 90 % KSO2F on refluxing; react. starting at 100. degree.C under evolution of gas;; condensation of (NPCl2)3 and formed SO2 on cooling with dry ice; isolation on distg. at 0 °C;;	A 64.5% B n/a
In nitrobenzene heating a soln. of (NPCl2)3 in C6H5NO2 with solid 90 % KSO2F on refluxing; react. starting at 100. degree.C under evolution of gas;; condensation of (NPCl2)3 and formed SO2 on cooling with dry ice; isolation on distg. at 0 °C;;	A 64.5% B n/a

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

nitrogen trifluoride (7783-54-2) + phosphorus(V) nitride → octafluorophosphazene (14700-00-6) + hexafluorophosphazene (15599-91-4)

Conditions	Yield
In neat (no solvent) react. of P3N5 with NF3 at 710 °C;; fractional vac. distn.;;
In neat (no solvent) react. of P3N5 with NF3 at 710 °C;; fractional vac. distn.;;

phosphorus(V) nitride + CF3SF5 (373-80-8) → Hexafluoroethane (76-16-4) + sulfur tetrafluoride (7783-60-0) + octafluorophosphazene (14700-00-6) + hexafluorophosphazene (15599-91-4) + trifluorophosphane (7783-55-3)

Conditions	Yield
In neat (no solvent) heating P3N5 at 710 °C on passing in gaseous CF3SF5; flushing with N2 before and after react.; cooling the receivers with dry ice-actone;; fractional vac. distn.;;
In neat (no solvent) heating P3N5 at 710 °C on passing in gaseous CF3SF5; flushing with N2 before and after react.; cooling the receivers with dry ice-actone;; fractional vac. distn.;;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + potassium fluorosulphinate (14986-57-3) → hexafluorophosphazene (15599-91-4) + potassium chloride + sulfur dioxide (7446-09-5)

Conditions	Yield
In neat (no solvent) react. of (NPCl2)3 with KSO2F at 120-125 °C;;
In neat (no solvent) react. of (NPCl2)3 with KSO2F at 120-125 °C;;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + (C2H5)3N*0.6HF → hexafluorophosphazene (15599-91-4) + hexafluorophosphate anion

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In tetrahydrofuran; benzene room temp., Cl/F ratio 1-2/1, 1 h;

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

Conditions	Yield
With water In not given no formation in presence of H2O;;	0%
With H2O In not given no formation in presence of H2O;;	0%

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + lead(II) fluoride → 2,2-difluoro-4,4,6,6-tetrachlorocyclotriphosphazene (21846-67-3) + 2,2-dichloro-4,4,6,6-tetrafluorocyclotriphosphazene (21846-69-5) + N4P4F6Cl2 + octafluorophosphazene (14700-00-6) + hexafluorophosphazene (15599-91-4)

Conditions	Yield
In not given byproducts: N4P4F4Cl4; react. of (NPCl2)3 with PbF2;; freezing out, dissolving in petroleum ether; fractionation, at 50 °C (NPF2)3, at 70-95 °C (NPF2)4;;
In not given byproducts: N4P4F4Cl4; react. of (NPCl2)3 with PbF2;; freezing out, dissolving in petroleum ether; fractionation, at 50 °C (NPF2)3, at 70-95 °C (NPF2)4;;

nitrogen trifluoride (7783-54-2) + phosphorus nitride → octafluorophosphazene (14700-00-6) + hexafluorophosphazene (15599-91-4)

Conditions	Yield
In neat (no solvent) react. at 710°C;;

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

Conditions	Yield
In acetonitrile at 0℃; for 2h;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + cesium fluoride (13400-13-0) → hexafluorophosphazene (15599-91-4)

Conditions	Yield
In acetonitrile at 0℃; for 2h;

2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine (940-71-6) + hydrogen fluoride (7664-39-3) → hexafluorophosphazene (15599-91-4)

Conditions	Yield
With α,α,α-trifluorotoluene; antimonypentachloride at 20 - 30℃; for 10h; Reagent/catalyst; Temperature; Flow reactor; Cooling;	75 g

hexafluorophosphazene (15599-91-4) + tris(dimethylamino)sulfonium trimethylsilyldifluoride (150746-76-2) → 2S(N(CH3)2)3(1+)*P3N3F5NPF2NPF2NPF5(2-) = [S(N(CH3)2)3]2[P3N3F5NPF2NPF2NPF5]

Conditions	Yield
In acetonitrile 235 K, then slight warming;	99%

hexafluorophosphazene (15599-91-4) + sodium trimethylsilanolate (18027-10-6) → C3H9F5N3OP3Si

Conditions	Yield
In Petroleum ether at 10 - 20℃; for 10h; Solvent;	97%

hexafluorophosphazene (15599-91-4) + lithium trimethylsilanolate (2004-14-0) → C3H9F5N3OP3Si

Conditions	Yield
In benzonitrile at 10 - 20℃; for 10h; Solvent;	97%

hexafluorophosphazene (15599-91-4) + potassium trimethylsilonate (10519-96-7) → C3H9F5N3OP3Si

Conditions	Yield
In hexane at 40℃; for 10h; Solvent; Temperature;	96%

hexafluorophosphazene (15599-91-4) + ammonia (7664-41-7) → 2,4,4,6,6-pentafluoro-2λ5,4λ5,6λ5-cyclotriphosphazen-2-ylamine (21475-58-1)

Conditions	Yield
In diethyl ether High Pressure; (N2); Schlenk techniques; P3N3F6, liq. NH3 (1:8) in Et2O sealed into a tube; kept at 20°C for 24 h; detn. by GC/MS;	95%

n-butyllithium (109-72-8, 29786-93-4) + ferroceneacetylene (1271-47-2) + hexafluorophosphazene (15599-91-4) → (ethynylferrocenyl)pentafluorocyclotriphosphazene (1231713-57-7)

Conditions	Yield
In tetrahydrofuran (N2); using Schlenk techniques; cooling of soln. of HCCC5H4FeC5H5 in THFto -78°C, addn. of soln. of n-BuLi, stirring at room temp. for 3 h, cooling to -78°C, addn. to cooled to -78°C soln. of N3 P3F6, stirring at room temp. for 24 h; evapn. of solvent, chromy. over silica gel, elution with ethyl acetate/hexane (2%), slow evapn., crystn.; elem. anal.;	80%

n-butyllithium (109-72-8, 29786-93-4) + bromoferrocene (1273-73-0) + hexafluorophosphazene (15599-91-4) → ferrocene (102-54-5) + N3P3F5(η-C5H4)Fe(η-C5H5) + N3P3F4{(C5H4)Fe(C5H5)}2 (84462-68-0)

Conditions

Yield

In diethyl ether reaction of C4H9Li (1.2 equiv.) and Br(C5H4)Fe(C5H5) to Li(C5H4)Fe(C5H5) in diethyl ether, warmed up to room temp., stirred 45min, recooled to -78°C, dropwise addn. of (NPF2)3 in diethyl ether, stirred, 6h, room temp., solvent removed, under N2; chromy. (hexane (Fe(C5H5)2) - dichloromethane/hexane(1:5) (N3P3F5(C5H4)Fe(C5H5)), elem. anal. - dichloromethane/hexane(1:1) (N3P3F4((C5H4)Fe(C5H5))2));

A n/a B 77% C n/a

lithiumferrocene (1271-15-4) + hexafluorophosphazene (15599-91-4) → N3P3F5(η-C5H4)Fe(η-C5H5)

Conditions	Yield
In diethyl ether Fe-complex and ligand were reacted in Et2O at -78°C for 6 h, warmed to 25°C; solvent was removed, chromd. on silica gel with hexane-CH2Cl2;	77%

hexafluorophosphazene (15599-91-4) + dimethyl amine (124-40-3) + cyclopentene (142-29-0) → fluorocyclopentane (1481-36-3) + Dimethylaminopentafluorocyclotriphosphonitril (23208-17-5)

Conditions	Yield
In acetonitrile at -10 - 0℃; for 1h; Inert atmosphere;	A n/a B 77%

hexafluorophosphazene (15599-91-4) + dimethyl amine (124-40-3) → Dimethylaminopentafluorocyclotriphosphonitril (23208-17-5)

Conditions	Yield
With Trimethylmethoxysilane at -10 - 0℃; for 2h; Reagent/catalyst; Inert atmosphere;	75%
In 1-methyl-pyrrolidin-2-one at -10 - 0℃; for 1h; Solvent; Temperature;	49%

ethanol (64-17-5) + hexafluorophosphazene (15599-91-4) → 1-ethoxy-1,3,3,5,5-pentafluorocyclotriphosphazene (33027-66-6)

Conditions	Yield
With ammonia In benzene at 10℃; for 2h; Solvent; Temperature;	69.6%

n-butyllithium (109-72-8, 29786-93-4) + ferroceneacetylene (1271-47-2) + hexafluorophosphazene (15599-91-4) → gem-ethynylferrocenyltetrafluorocyclotriphosphazene (1231713-65-7)

Conditions	Yield
In tetrahydrofuran (N2); using Schlenk techniques; cooling of soln. of HCCC5H4FeC5H5 (2 equiv) in THF to -78°C, addn. of soln. of BuLi, stirring at room temp. for 3h, cooling to -78°C, addn. to soln. of N3P3Cl6 at -78°C, stirring at room temp. for 24h; evapn. of solvent, chromy. over silica gel, elution with ethyl acetate/hexane (2%), slow evapn., crystn.; elem. anal.;	68%

hydroxyferrocene + hexafluorophosphazene (15599-91-4) → [Fe(C5H5)(C5H4O)P3N3F5] (198129-12-3)

Conditions	Yield
With NEt3 In tetrahydrofuran byproducts: NEt3*HF; Ar atm.; equimolar ratio, cooling (-78°C), stirring (overnight, room temp.); concn. (vac.);	60%

dilithium ferrocene dithiolate * 2 tetrahydrofuran + hexafluorophosphazene (15599-91-4) → [Fe(C5H4S)2P3N3F4] (198129-17-8)

Conditions	Yield
With NEt3 In tetrahydrofuran byproducts: LiF; Ar atm.; molar ratio Fe complex:phosphazene:NEt3 1:1:2, cooling (-78°C), stirring (overnight, room temp.); filtn., concn. (vac.), chromatography (SiO2/CH2Cl2);	59%

(C5H5)Fe(C5H4)CH2P(S)(CH2OSi(CH3)3)2 (301155-77-1) + hexafluorophosphazene (15599-91-4) → [(ferrocenyl)CH2P(S)(CH2O)2PN](F2PN)2 (301155-79-3)

Conditions	Yield
cesium fluoride In tetrahydrofuran (N2); Schlenk glassware; N3P3F6 was sublimed into oven-dried, evacuatedflask; CsF added; Fe complex in dry THF added into flask by syringe; stirred at 60°C for 12 h; solvent removed in vac.; chromd. (ethyl acetate/hexane); elem. anal.;	52%

N-Ethylmethylamine (624-78-2) + hexafluorophosphazene (15599-91-4) → C3H8F5N4P3

Conditions	Yield
at 10 - 20℃; for 0.5h;	48%

hexafluorophosphazene (15599-91-4) + diethylamine (109-89-7) → Diethyl-(2,4,4,6,6-pentafluoro-2λ5,4λ5,6λ5-[1,3,5,2,4,6]triazatriphosphinin-2-yl)-amine (38668-23-4)

Conditions	Yield
In 1-methyl-pyrrolidin-2-one at 0 - 10℃; for 0.5h; Temperature; Solvent;	47%

dilithium ferrocene diselenolato * 2 tetrahydrofuran + hexafluorophosphazene (15599-91-4) → [Fe(C5H4Se)2P3N3F4] (198129-18-9)

Conditions	Yield
With NEt3 In tetrahydrofuran byproducts: LiF; Ar atm.; molar ratio Fe complex:phosphazene:NEt3 1:1:2, cooling (-78°C), stirring (overnight, room temp.); filtn., concn. (vac.), chromatography (SiO2/CH2Cl2);	46%

n-butyllithium (109-72-8, 29786-93-4) + (ferrocenyl)CH2P(S)(CH2OH)2 (180794-53-0) + hexafluorophosphazene (15599-91-4) → exo-FcCH2P(S)(CH2O)2[P(F)N]2(F2PN) + endo-FcCH2P(S)(CH2O)2[P(F)N]2(F2PN)

Conditions

Yield

In tetrahydrofuran byproducts: LiF; (N2); Schlenk glassware; various product yields for various conditions;compd. FcCH2P(S)(CH2OH)2 was treated with N-BuLi in THF at -80°C; stirred for 4 h; soln. of N3P3F6 in THF added at -80°C; stirredat room temp. for 12 h; solvent removed in vac.; residue dissolved in toluene; filtered; analyzed by TLC; chromd. (SiO2, ethyl acetate/hexane); recrystd. (ethyl acetate/hexane); elem. anal.;

A 18.9% B 44.5%

hexafluorophosphazene (15599-91-4) → ammonia*phosphorus pentafluoride (1/1) (84724-54-9)

Conditions	Yield
With HF In acetonitrile warmed from -15°C to room temp.; KF added, filtration, filtrate extd. (ether), elem. anal.;	41%

ferrocene (102-54-5) + hexafluorophosphazene (15599-91-4) + tert.-butyl lithium (594-19-4) → N3P3F4(η-C5H4)Fe

Conditions	Yield
In diethyl ether byproducts: butane; prepn. of Li2(C5H5)2Fe by addn. of C4H9Li to soln. of (C5H5)Fe(C5H5), 0°C, stirring, 4h, 0°C, soln. added to soln. of (NPF2)3 in diethyl ether, -78°C, warmed up to room temp., stirred 17h, solvent removed, under N2; chromy. ((hexane) (Fe(C5H5)2) - dichloromethane-hexane(1:9));;	40%

1,1′-ferrocenediol + hexafluorophosphazene (15599-91-4) → [Fe(C5H4O)2P3N3F4] (198129-15-6)

Conditions	Yield
With NEt3 In tetrahydrofuran byproducts: NEt3*HF; Ar atm.; molar ratio Fe(C5H4OH)2:phosphazene:NEt3 1:1:2, cooling (-78°C), stirring (overnight, room temp.); filtn., concn. (vac.), chromatography (SiO2/CH2Cl2);	39%

1,4-bis(ferrocenyl)butadiyne + hexafluorophosphazene (15599-91-4) → FcC≡C-C≡CP3N3F5 + [(FcC≡C-C≡C)2PN](F2PN)2

Conditions	Yield
Stage #1: 1,4-bis(ferrocenyl)butadiyne With n-butyllithium In tetrahydrofuran; hexane at -78 - 20℃; for 3.25h; Schlenk technique; Inert atmosphere; Stage #2: hexafluorophosphazene In tetrahydrofuran; hexane at -78℃; for 12h; Schlenk technique; Inert atmosphere;	A 36% B 32%

lithiated bis(η(6)-benzene)chromium (125594-39-0) + hexafluorophosphazene (15599-91-4) → N3P3F4(C6H5)2Cr (104213-56-1)

Conditions	Yield
In cyclohexane byproducts: LiF; dry N2 atmosphere, 25°C, 4 h; washing (2-propanol), filtration, crystn. (-10°C); elem. anal.;	35%

Upstream product

• 940-71-6 2,2,4,4,6,6-hexachloro-1,3,5-triaza-2,4,6-triphosphorine 
• 11113-87-4 silver fluoride 
• 7783-54-2 nitrogen trifluoride 
• 373-80-8 CF₃SF₅ 
• 7789-23-3 potassium fluoride 
• 7446-09-5 sulfur dioxide 
• 7681-49-4 sodium fluoride 
• 14986-57-3 potassium fluorosulphinate 
• 23588-89-8 (C₂H₅)3N*0.6HF 
• 7789-24-4 lithium fluoride 
• 13400-13-0 cesium fluoride 
• 7664-39-3 hydrogen fluoride 

Downstream Products

• 33027-66-6 ethoxy(pentafluoro)cyclotriphosphazene 
• 1481-36-3 fluorocyclopentane 
• 23208-17-5 Dimethylaminopentafluorocyclotriphosphonitril 
• 38117-54-3 di(cyclopentadienideiron dicarbonyl) 
• 70538-16-8 1,1-[μ-carbonyl-bis(carbonylcyclopentadienyliron)(Fe-Fe)]-3,3,5,5-tetrafluorocyclotriphosphazene 
• 84303-21-9 (1,3,3,5,5-pentafluorocyclotriphos(P(V))azen-1-yl)dicarbonylcyclopentadienyliron 
• 38117-54-3 cyclopentadienyl iron(II) dicarbonyl dimer 
• 75896-11-6 1,1-bis(dicarbonylcyclopentadienyliron)-3,3,5,5-tetrafluorocyclotriphosphazene 
• 102-54-5 ferrocene 
• 84462-68-0 N₃P₃F₄{(C₅H₄)Fe(C₅H₅)}2 

Relevant articles and documents

Preparation of the First Examples of Ansa-Spiro Substituted Fluorophosphazenes and Their Structural Studies: Analysis of C-H···F-P Weak Interactions in Substituted Fluorophosphazenes

The reactions of fluorophosphazenes, endo ansa FcCH2P(S)(CH 2O)2[P(F)N]2(F2PN) (1) (Fc = ferrocenyl) and spiro [RCH2P(S)(CH2O) 2PN](F2PN)2 (R = Fc (2), C6H 5 (3)], with dilithiated diols have been explored. The study resulted in the formation of the first examples of ansa-spiro substituted fluorinated cyclophosphazenes as well as a bisansa substituted fluorophosphazene. The bisansa compound {1,3-[FcCH2P(S)(CH 2O)2]}{1,5-[CH2(CH2O) 2]}N3P3F2 (4) was found to be nongeminaly substituted with both the ansa rings in cis configuration, which is in stark contrast to the observations on cyclic chlorophosphazenes where geminal bisansa formation has been observed. The ansa-spiro compounds (5-7) underwent the ansa to spiro transformation leading to dispiro compounds in the presence of catalytic amounts of CsF at room temperature. Two of the ansa-spiro compounds, endo-{3,5-[FcCH2P(S)-(CH2O) 2]}{1,1-[CH2(CH2O)2]}N 3P3F2 (5) and endo-{3,5-[FcCH 2P(S)(CH2O)2]}{1,1-[FcCH 2P(S)(CH2O)2]}N3P3F 2 (6), were structurally characterized, and the crystal structures indicate boat-chair conformation as well as crown conformation for the eight-membered ansa rings. Weak C-H···F-P interactions observed in the crystal structures of the ansa-spiro substituted fluorophosphazene derivatives have been analyzed and compared with C-H···F-P interactions of other fluorinated phosphazenes and thionyl phosphazenes.

New results in the ammonolysis of hexafluoro-cyclo-triphosphazene: Crystal structure of P3N3F5-NH-P3 N3F4NH2

The reaction of hexafluoro-cyclo-triphosphazene P3N3F6 with ammonia in acetonitrile has been studied. New compounds, (2-imino-2,4,4,6,6-pentafluoro-2λ5,4λ 5,6λ5-cyclo-triphosphaza-1,3,5-tri

Synthesis method of hexafluorocyclotriphosphazene

The invention discloses a synthesis method of hexafluorocyclotriphosphazene, which comprises the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinatingagent and a catalyst, carrying out fluorination reaction, and rectifying to obtain the target product hexafluorocyclotriphosphazene. The synthesis method of hexafluorocyclotriphosphazene has the advantages of mild reaction temperature, simple and easy-to-operate process, high yield, short time consumption, high purity, greenness, economy and convenience in industrial production.

Preparation method for hexafluorocyclotriphosphazene

The invention discloses a preparation method for hexafluorocyclotriphosphazene. In a nonpolar solvent, under the effect of catalysts, hexachlorocyclotriphosphazene and a fluridizer generate fluorination reaction to produce hexafluorocyclotriphosphazene, and the nonpolar solvent is any one or a mixture of more of normal hexane, cyclohexane, toluene, chlorobenzene and xylene; the mass ratio of the nonpolar solvent to hexachlorocyclotriphosphazene is (2:1) to (4:1); the catalysts comprise a main catalyst and an auxiliary catalyst, wherein the main catalyst is a glycol dimethyl ether homologue, and the dosage of the main catalyst is 0.1 to 20 percent of the mass of hexachlorocyclotriphosphazene; the auxiliary catalyst is alcohols or phenols, and the dosage of the auxiliary catalyst is 0.1 to 20 percent of the mass of hexachlorocyclotriphosphazene; and the mass ratio of the dosages of hexachlorocyclotriphosphazene and the fluridizer is 1:1. The invention has the advantages that the reactiontemperature is not high, byproducts are less, reaction is thorough, the conversion rate is high, and after the reaction is completed, reaction liquid can directly react with other derivatives.

Preparation method of pentafluoro aromatic oxyl cyclotriphosphazene

The invention discloses a preparation method of pentafluoro aromatic oxyl cyclotriphosphazene. The preparation method comprises: (1) adding hexachlorocyclotriphosphazene, a fluorinating agent and an organic solvent to a reaction container, and carrying out a reaction at a temperature of -30-80 DEG C to obtain a hexachlorocyclotriphosphazene-containing reaction liquid; (2) carrying out water washing on the reaction liquid obtained in the step (1), carrying out standing liquid layering to obtain a hexachlorocyclotriphosphazene-containing ogranic phase, and distilling the organic phase to obtainhexachlorocyclotriphosphazene; (3) adding an organic solvent, a phenol, an acid binder and the hexafluorocyclotriphosphazene obtained in the step (2) to another reaction container, and carrying out areaction at a temperature of -30-80 DEG C to obtain a reaction liquid containing pentafluoro aromatic oxyl cyclotriphosphazene; and (4) carrying out rectification on the reaction liquid obtained in the step (3) to obtain the pentafluoro aromatic oxyl cyclotriphosphazene. The preparation method of the present invention has advantages of less side reactions and high yield, and is suitable for industrial large-scale production, wherein the yield is not less than 60%.