680-31-9

Usage

Uses

Used in Chemical Industry:
Hexamethylphosphoramide is used as an efficient anti-corrosion agent for PVC and other chlorine-containing resin products and coatings, enhancing their durability and resistance to environmental factors.
Used in Polymer Synthesis:
Hexamethylphosphoramide is used as a solvent in the synthesis of polymers, particularly polyphenylene sulfide and aromatic polyamide, due to its special effect on the polymerization process.
Used in Plastics and Films:
Hexamethylphosphoramide is used as a weathering solvent for polyvinyl chloride, improving the low-temperature resistance and aging resistance of agricultural films, and as a multi-functional high-boiling polar solvent.
Used in Propylene Polymerization:
Hexamethylphosphoramide is used as a co-catalyst in propylene polymerization catalysts, enhancing the missile and oil resistance of ethylene propylene rubber.
Used in Gas Chromatography:
Hexamethylphosphoramide is used as a fixative in gas chromatography, with the highest usage temperature being 35°C when methanol is used as the solvent.
Used in Organic Synthesis:
Hexamethylphosphoramide is used as an aprotic solvent in organic synthesis, facilitating various chemical reactions and separation processes.
Used in Insect Pest Control:
Hexamethylphosphoramide is used as a chemosterilant for a number of insect pests, providing an effective method for pest control.
Used in Chemical Mutagenesis:
Hexamethylphosphoramide is used as a chemical mutagen, playing a role in genetic research and development.
Used in De-icing Jet Fuels:
Hexamethylphosphoramide is used as a de-icing additive for jet fuels, improving the performance and safety of aircraft operations in cold weather conditions.
Used in Polymer Stabilization:
Hexamethylphosphoramide is used as a stabilizer against thermal degradation in polystyrene and as a UV stabilizer in polyvinyl and polyolefin resins, protecting them from UV light degradation.
Used in Dipolar Co-solvent:
Hexamethylphosphoramide is used as a dipolar co-solvent and an effective additive in reactions such as reduction of halides, deoxygenation of sulfones, halide olefin couplings, and cleavage of carbon-sulfur bonds, enhancing the efficiency and selectivity of these reactions.

Harmful effects and symptoms of poisoning

To animals: Hexamethylphosphoramide (HMPA) is known to have various kinds of toxic effects on experimental animals. HMPA-induced acute poisoning in rats is characterized with nephropathy, severe bronchiectasis and bronchial pneumonia. Application of HMPA repetitively to rabbit skin can lead to weight loss, changes in gastric function and apparent neurological disorders. Rats subjecting to oral administration of HMPA can exhibit testicular atrophy and semen deficiencies. Small chickens subjecting to oral administration of HMPA can also get highly inhibited growth in its testis. HMPA has been known to induce mutagenesis in Drosophila. However, the effects of HMPA on sex chromosomes in mice showed that the frequency of chromosome aberration induced by HMPA was not significant compared with the control group. Preliminary results of the toxicity study upon inhaling HMPA revealed that nasal tumors will appear in rats after 8 months after being exposed to 400 to 4000 ppb HMPA. In some diseased mice, cancer initiated from the epithelium connecting the nasal bone can fill the nasal cavity and penetrates into the brain. Rats exposed to 50 ppb HMPA didn’t develop nasal cancer compared with the control group. To humans: the role of HMPA on human toxicity has not been reported.

Protective measures

The traditional measure is that the operator should wear protective clothing, wearing protective glasses and gloves, to avoid direct contact with the product with the production site should be well ventilated.

Production method

It can be obtained through the reaction between dimethylamine and alkali chlorophosphorus. Put the dimethylamine and phosphorus oxychloride for reaction in triethylene glycol as the solvent; control the temperature at 40-60 °C; upon reaction, add ammonia as acid-binding agent with interaction with the generated hydrogen chloride to become ammonium chloride precipitation. After completion of the reaction, filtration was performed. Recycle the trichlorethylene from the filtration and then perform alkali treatment, and then conduct distillation, collecting the fraction of 113-118 °C (2.0kPa) fractions to derive Hexamethylphosphoramide (HMPA). Tsinghua Unisplendour Group Corporation has cooperated with the production plant to develop a new solvent-free process that can achieve a product purity of 99.2% or more. The industrial hexamethylphosphoramide appears as colorless or light yellow transparent liquid. Catalyst grade content ≥ 99.5%; first-class grade ≥ 99.0%; second-class products ≥ 98.0%. Fixed consumption amount of raw materials: dimethylamine 2410kg/t, phosphorus oxychloride: 1610kg/t, liquid ammonia 430kg/t.

Air & Water Reactions

Water soluble.

Reactivity Profile

Hexamethylphosphoramide may react with strong oxidizing agents and strong acids . Susceptible to formation of highly toxic and flammable phosphine gas in the presence of strong reducing agents such as hydrides. Partial oxidation by oxidizing agents may result in the release of toxic phosphorus oxides.

Hazard

Possible carcinogen. Toxic by skin contact. Combustible.

Health Hazard

The acute toxicity of hexamethylphosphoramide is low. HMPA can cause irritation upon contact with the skin and eyes. Hexamethylphosphoramide has been found to cause cancer in laboratory animals exposed by inhalation and meets the criteria for classification as an OSHA "select carcinogen." Chronic exposure to HMPA can cause damage to the lungs and kidneys. Reproductive effects in male animals treated with hexamethylphosphoramide have been observed. HMPA should be regarded as a substance with poor warning properties.

Fire Hazard

Combustible liquid. Its decomposition at high temperatures or in a fire can produce phosphine, phosphorus oxides, and oxides of nitrogen, which are extremely toxic. Carbon dioxide or dry chemical extinguishers should be used for HMPA fires.

Fire Hazard

Hexamethylphosphoramide is combustible.

Flammability and Explosibility

Combustible liquid. Its decomposition at high temperatures or in a fire can produce phosphine, phosphorus oxides, and oxides of nitrogen, which are extremely toxic. Carbon dioxide or dry chemical extinguishers should be used for HMPA fires.

Potential Exposure

Hexamethylphosphoric triamide is a material possessing unique properties and is widely used as a solvent in small quantities, in organic and organometallic reactions in laboratories. This is the major source of occu pational exposure to HMPA in the United States. It is also used as a processing solvent in the manufacture of aramid fibers. HMPA has been evaluated for use as an ultraviolet light absorber or inhibitor in polyvinylchloride formulations; as an additive for antistatic effects; as a flame retardant; and as a deicing additive for jet fuels. Hexamethylphosphoric triamide has also been extensively investigated as an insect chemosterilant.

Carcinogenicity

Hexamethylphosphoramide is reasonably anticipated to be a human carcinogen based on sufficient evidence of carcinogenicity from studies in experimental animals.

storage

Hexamethylphosphoramide should be handled only in a fume hood, using appropriate impermeable gloves and splash goggles to prevent skin and eye contact. Containers of this substance should be stored in secondary containers.

Shipping

UN3082 Environmentally hazardous substances, liquid, n.o.s., Hazard class: 9; Labels: 9-Miscellaneous haz ardous material, Technical Name Required

Purification Methods

The industrial synthesis is usually by treatment of POCl3 with excess of dimethylamine in isopropyl ether. Impurities are water, dimethylamine and its hydrochloride. It is purified by refluxing over BaO or CaO at about 4mm pressure in an atmosphere of nitrogen for several hours, then distilled from sodium at the same pressure. The middle fraction (b ca 90o) is collected, refluxed over sodium under reduced pressure under nitrogen and distilled. It is kept in the dark under nitrogen, and stored in solid CO2. It can also be stored over 4A molecular sieves. Alternatively, it is distilled under vacuum from CaH2 at 60o and is crystallised twice in a cold room at 0o, seeding the liquid with crystals obtained by cooling in liquid nitrogen. After about two-thirds are frozen, the remaining liquid is drained off [Fujinaga et al. Pure Appl Chem 44 117 1975]. For tests of purity see Fujinaga et al. in Purification of Solvents, Coetzee Ed., Pergamon Press, Oxford, 1982. For efficiency of desiccants in drying HMPA see Burfield and Smithers [J Org Chem 43 3966 1978, Sammes et al. J Chem Soc, Faraday Trans 1 281 1986]. [Beilstein 4 IV 284.] CARCINOGEN.

Incompatibilities

Incompatible (possibly violent reaction; fire and explosions) with oxidizers (chlorates, nitrates,peroxides, permanganates, perchlorates, chlorine, bromine, fluorine, etc.). Keep away from alkaline materials, chemi cally active metals, strong acids, strong bases.

Waste Disposal

Excess hexamethylphosphoramide and waste material containing this substance should be placed in an appropriate container, clearly labeled, and handled according to your institution's waste disposal guidelines.

InChI:InChI=1/C6H18N3OP/c1-7(2)11(10,8(3)4)9(5)6/h1-6H3

Synthetic route

dimethyl amine (124-40-3) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + C11H30N6P(1+) + 1,1,1,3,3,3-hexakis(dimethylamino)-1λ5,3λ5-diphosphazenium fluoride (137334-99-7)

Conditions	Yield
Multistep reaction;	A n/a B n/a C 93%
Yield given. Multistep reaction;

triphenylphosphine (603-35-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9)

Conditions	Yield
With Oxone In tetrahydrofuran; methanol Ambient temperature;	93%

Hexamethylphosphorous triamide (1608-26-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9)

Conditions	Yield
With benzenesulfonyl chloride In diethyl ether	92%
With substituted 3-hydroperoxy-1,2-benzisothiazole 1,1-dioxide In dichloromethane at 0℃; for 0.75h;	98 % Spectr.
With oxygen; fullerene-C60 In 1,2-dichloro-benzene at 20℃;

carbon dioxide (124-38-9) + iminotris(dimethylamino)phosphorane (49778-01-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + N,N,N',N',N'',N''-hexamethylphosphorimidic triamide cyanate

Conditions	Yield
In benzene for 48h;	A 91% B 89%

iminotris(dimethylamino)phosphorane (49778-01-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + N,N,N',N',N'',N''-hexamethylphosphorimidic triamide cyanate

Conditions	Yield
With carbon dioxide In benzene for 48h;	A 91% B 89%

CaCl2*3(N(CH3)2)3PO → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + CaCl2*2(N(CH3)2)3PO

Conditions	Yield
In neat (no solvent) heated (vac., 200°C); residue dissolved in C6H6; hexane added; vac. (100°C); elem.anal.;	A n/a B 89.1%

Hexamethylphosphorous triamide (1608-26-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + tris(dimethylamino)methylphosphonium tetraphenylborate (61904-00-5)

Conditions	Yield
With dimethylselenuranylidene derivative of 1,3-indandione In dichloromethane for 12h; Product distribution; Ambient temperature; other reagent, other time;	A n/a B 89%

1,1'-azodicarbonyl-dipiperidine + Hexamethylphosphorous triamide (1608-26-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 2,5-di(piperidin-1-yl)-1,3,4-oxadiazole (1355083-83-8)

Conditions	Yield
at 20℃; for 0.25h;	A n/a B 85%

pyridine N-oxide (694-59-7) + bromo-tris-dimethylamino-phosphonium hexafluorophosphate + cyclohexylamine (108-91-8) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + N-cyclohexylpyridin-2-amine (15513-16-3)

Conditions	Yield
With N-ethyl-N,N-diisopropylamine In dichloromethane at 25℃;	A n/a B 83%

N,N,N',N'-Tetramethylphosphorodiamidic chloride (1605-65-8) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + dimefox (115-26-4) + N,N-dimethylphosphoramidic difluoride (354-43-8)

Conditions	Yield
With sodium hexaflorophosphate In various solvent(s) at 200℃; for 0.25h;	A 2% B 77% C 15%

dimethyl amine (124-40-3) + trichlorophosphate (10025-87-3, 12599-09-6, 63736-95-8) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9)

Conditions	Yield
In tetrahydrofuran; dichloromethane at 0℃; Inert atmosphere; Schlenk technique;	70%

4-nitrobenzaldehdye (555-16-8) + tris(dimethylamino)<(ethoxycarbonyl)methylene>phosphorane (76486-69-6) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + ethyl 4-nitrocinnamate (953-26-4)

Conditions	Yield
In ethanol at 80℃; for 4h;	A n/a B 63.7%

C14H22N5OP → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 2-[(furan-2-yl)methyl]propanedinitrile (4846-25-7)

Conditions	Yield
With water In benzene	A n/a B 62.3%

C14H22N5OP → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 2-[(furan-2-yl)methyl]propanedinitrile (4846-25-7)

Conditions	Yield
With water In benzene	A n/a B 62.3%

benzaldehyde (100-52-7) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + amarine

Conditions	Yield
With N,N,N,N,N,N-hexamethylphosphoric triamide at 140℃; for 1h;	A 55% B 12%

acetophenone (98-86-2) + N,N,N',N',N'',N''-hexamethylphosphorohydrazonic triamide (13754-82-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + hexamethyl-N'''-(α-methylbenzylidene)phosphorohydrazonic triamide

Conditions	Yield
With barium(II) oxide In benzene for 1h;	A 32% B 52%

2-thiocyanatoethyl phosphorodichloridite (140476-47-7) + dimethyl amine (124-40-3) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + S-(2-chloroethyl) tetramethylphosphorodiamidothioate (140476-50-2)

Conditions	Yield
In diethyl ether for 2h; Ambient temperature;	A 14% B 49%

tetra(dimethylamido)phosphonium bromide → methanol (67-56-1) + N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + dimethyl amine (124-40-3) + hydrochloride of heptamethylphosphorimidic triamide

Conditions	Yield
With sodium hydroxide at 230℃; under 9 Torr; Product distribution; Mechanism;	A n/a B 40% C n/a D 45%

Hexamethylphosphorous triamide (1608-26-0) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + tris(dimethylamino)phosphorus sulfide (3732-82-9)

Conditions	Yield
With sulfur dioxide at 0℃; for 1h;	A 5% B 20%
With sulfur dioxide at -78℃; Mechanism; var. in presence of o-dibromobenzene;
With sulfur dioxide at -78℃; Yield given;

dimethyl amine (124-40-3) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9)

Conditions	Yield
With trichlorophosphate
With toluene; trichlorophosphate
With tetrachloromethane; trichlorophosphate

4-Cyanochlorobenzene (623-03-0) + C4H12O4P(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Trifluoro-methanesulfonate(4-chloro-phenylmethylidyne)-methyl-ammonium;

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

diphenyl sulfide (139-66-2) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + methyldiphenylsulfonium trifluoromethanesulfonate (105229-70-7)

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

1,1'-sulfinylbisbenzene (945-51-7) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Diphenylmethylsulfoxonium triflate

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

2,4-dimethoxybenzonitrile (4107-65-7) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Trifluoro-methanesulfonate(2,4-dimethoxy-phenylmethylidyne)-methyl-ammonium;

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

4-fluorobenzonitrile (1194-02-1) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Trifluoro-methanesulfonate(4-fluoro-phenylmethylidyne)-methyl-ammonium;

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

4-bromobenzenecarbonitrile (623-00-7) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Trifluoro-methanesulfonate(4-bromo-phenylmethylidyne)-methyl-ammonium;

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

bis(4-nitrophenyl)sulfide (1223-31-0) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Trifluoro-methanesulfonatemethyl-bis-(4-nitro-phenyl)-sulfonium;

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

para-methylbenzonitrile (104-85-8) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + (N-methyl)(4-methyl-phenyl)carbonitrilium trifluoromethylsulfonate (136139-18-9)

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

4-methoxybenzonitrile (874-90-8) + C7H21N3OP(1+)*CF3O3S(1-) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Trifluoro-methanesulfonate(4-methoxy-phenylmethylidyne)-methyl-ammonium;

Conditions	Yield
In sulfolane at 30℃; Equilibrium constant;

C7H21N3OP(1+)*CF3O3S(1-) + methyl trifluoromethanesulfonate (333-27-7) → N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Dimethylsulfat

Conditions	Yield
With /BRN= 506008/ In sulfolane at 30℃; Equilibrium constant; further compounds;

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) + triphenylbismuthane (603-33-8) → diphenylbismuth triflate - (hexamethylphosphoric triamide)2 complex

Conditions	Yield
In methanol; N,N,N,N,N,N-hexamethylphosphoric triamide; dichloromethane Ar-atmosphere; mixing BiAr3, 2 equivs. of HMPA and 1 equiv. of Me3SiOTf at 0°C, stirring for 0.5-2 h at room temp.; evapn.; elem. anal.;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) + tri-o-tolylbismuth (10050-08-5) → bis(2-methylphenyl)bismuth triflate - (hexamethylphosphoric triamide)2 complex

Conditions	Yield
In methanol; N,N,N,N,N,N-hexamethylphosphoric triamide; dichloromethane Ar-atmosphere; mixing BiAr3, 2 equivs. of HMPA and 1 equiv. of Me3SiOTf at 0°C, stirring for 0.5-2 h at room temp.; evapn.; elem. anal.;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) + tri(p-tolyl)bismuth (5142-75-6) → bis(4-methylphenyl)bismuth triflate - (hexamethylphosphoric triamide)2 complex

Conditions	Yield
In methanol; N,N,N,N,N,N-hexamethylphosphoric triamide; dichloromethane Ar-atmosphere; mixing BiAr3, 2 equivs. of HMPA and 1 equiv. of Me3SiOTf at 0°C, stirring for 0.5-2 h at room temp.; evapn.; elem. anal.;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + (4-chlorophenyl)bis(2-methylphenyl)bismuthane (88756-72-3) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) → (4-chlorophenyl)(2-methylphenyl)bismuth triflate - (hexamethylphosphoric triamide)2 complex

Conditions	Yield
In methanol; N,N,N,N,N,N-hexamethylphosphoric triamide; dichloromethane Ar-atmosphere; mixing BiAr3, 2 equivs. of HMPA and 1 equiv. of Me3SiOTf at 0°C, stirring for 0.5-2 h at room temp.; evapn.; elem. anal.;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + (4-chlorophenyl)bis(2-methoxyphenyl)bismuthane (176704-27-1) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) → (4-chlorophenyl)(2-methoxyphenyl)bismuth triflate - (hexamethylphosphoric triamide)2 complex

Conditions	Yield
In methanol; N,N,N,N,N,N-hexamethylphosphoric triamide; dichloromethane Ar-atmosphere; mixing BiAr3, 2 equivs. of HMPA and 1 equiv. of Me3SiOTf at 0°C, stirring for 0.5-2 h at room temp.; evapn.; elem. anal.;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + trimethylsilyl trifluoromethanesulfonate (27607-77-8) + tris(2-methoxyphenyl)bismuthine (83724-41-8) → bis(2-methoxyphenyl)bismuth triflate - (hexamethylphosphoric triamide)2 complex

Conditions	Yield
In methanol; N,N,N,N,N,N-hexamethylphosphoric triamide; dichloromethane Ar-atmosphere; mixing BiAr3, 2 equivs. of HMPA and 1 equiv. of Me3SiOTf at 0°C, stirring for 0.5-2 h at room temp.; evapn.; elem. anal.;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + lanthanum (7439-91-0) + 1,3,5,7-cycloocatetraene → (C8H8)La(OP(N(CH3)2)3)4(1+)*La(C8H8)2(1-)=[(C8H8)La(OP(N(CH3)2)3)4][La(C8H8)2] (209743-19-1)

Conditions	Yield
iodine In tetrahydrofuran Ar-atmosphere; stirring (50°C, 10 d); crystn. on concg. (-20°C);	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + trifluorormethanesulfonic acid (1493-13-6) → tris(dimethylamino)(hydroxy)phosphonium trifluoromethanesulfonate

Conditions	Yield
In dichloromethane at 20℃; for 3h;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + bis(trifluoromethanesulfonyl)amide (82113-65-3) → tris(dimethylamino)(hydroxy)phosphonium bis(trifluoromethanesulfonyl)azanide

Conditions	Yield
In dichloromethane at 20℃; for 3h;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 2-chloro-6-(trifluoromethyl)nicotinonitrile (386704-06-9) → 2-dimethylamino-6-(trifluoromethyl)pyridine-3-carbonitrile (935518-01-7)

Conditions	Yield
at 150℃; for 48h;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + trimethylsilyl iodide (16029-98-4) → C9H27N3OPSi(1+)*I(1-)

Conditions	Yield
In toluene for 0.166667h; Inert atmosphere; Schlenk technique; Glovebox;	100%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + triphenyltin(IV) azide (1158-51-6) → azido(hexamethylphosphoramide)triphenyltin(IV)

Conditions	Yield
In toluene components dissoln. (heating or stirring), crystn. on soln. leaving overnight at room temp.;	99%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + (C8H8)U(N(C2H5)3)(SP(C6H5)2CC(C6H5)CHC(C6H5)C(P(C6H5)2S)PCH3)(1+)*B(C6H5)4(1-)=((C8H8)U(N(C2H5)3)(C42H34S2P3))B(C6H5)4 (1050381-21-9) → (C8H8)U(OP(N(CH3)2)3)(SP(C6H5)2CC(C6H5)CHC(C6H5)C(P(C6H5)2S)PCH3)(1+)*B(C6H5)4(1-)=C80H80BN3OP4S2U (1050381-32-2)

Conditions	Yield
In tetrahydrofuran under Ar; OP(NMe2)3 added to U complex in THF; evapd. to dryness; elem. anal.;	99%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + cyclopentadienyl iron(II) dicarbonyl dimer (38117-54-3) + Reaxys ID: 28905417 → YbFp2(HMPA)4

Conditions	Yield
Stage #1: N,N,N,N,N,N-hexamethylphosphoric triamide In tetrahydrofuran at 20℃; for 0.166667h; Stage #2: cyclopentadienyl iron(II) dicarbonyl dimer In tetrahydrofuran at 20℃; for 16h;	99%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + methy(oxo)bis(η(2)-peroxo)rhenium(VII) (152385-10-9) → (hexamethylphosphoramide)methyl(oxo)-bis(η(2)-peroxo)rhenium(VII) (182506-55-4)

Conditions	Yield
In diethyl ether N2-atmosphere; dropwise addn. of 1 equiv. HMPA to Re-complex at 0°C (pptn.); collection (filtration), washing (Et2O, pentane), drying (vac.); elem. anal.;	98%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + methyl 2-nitrobenzoate (606-27-9) → C13H22N6O2P(1+)*F6P(1-)

Conditions	Yield
Stage #1: N,N,N,N,N,N-hexamethylphosphoric triamide With trichloroisocyanuric acid In tetrahydrofuran at 0℃; for 2h; Stage #2: methyl 2-nitrobenzoate With guanidine hydrochloride; N-ethyl-N,N-diisopropylamine In tetrahydrofuran Reflux; Stage #3: With potassium hexafluorophosphate In tetrahydrofuran Reagent/catalyst; Solvent; Heating;	97.3%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + pentapropylphosphorodiamidimidic bromide (73954-61-7) → tris(dimethylamino)phosphonium bromide

Conditions	Yield
at 20℃; for 24h;	97%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) → bis(hexamethylphosphorotriamide)hydrogen tribromide

Conditions	Yield
With hydrogen bromide; bromine	97%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + chloro-trimethyl-silane (75-77-4) + calcium cyanamide (156-62-7) → CaCl2*2(N(CH3)2)3PO + bis(trimethylsilyl)carbodi-imide (1000-70-0)

Conditions	Yield
In N,N,N,N,N,N-hexamethylphosphoric triamide HMPTA added to suspn. of CaCN2 in Me3SiCl (stirring); heated to 60°C; heated gradually (120°C, 3 h); cooled; hexane added; ppt. filtered off; dried (vac., 90°C); liquid phase fractionated; elem.anal.;	A 97% B n/a

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + Benzylidenemalononitrile (2700-22-3) → N-(3,3-dicyano-2-phenylpropyl)-N,N,N,N,N-pentamethylphosphoric triamide

Conditions	Yield
With eosin y In dichloromethane at 20℃; for 16h; Catalytic behavior; Solvent; Reagent/catalyst; Inert atmosphere; Irradiation;	97%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 2-(3-cyanobenzylidene)malononitrile (60595-33-7) → N-(3,3-dicyano-2-(3-cyanophenyl)propyl)-N,N,N,N,N-pentamethylphosphoric triamide

Conditions	Yield
With eosin y In dichloromethane at 20℃; for 16h; Inert atmosphere; Irradiation;	97%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + (2-Phenyl-1-cyanethen)-phosphonsaeurediethylester (18896-73-6) → diethyl (1-cyano-3-(methyl(tetramethylphosphono)amino)-2-phenylpropyl)phosphonate

Conditions	Yield
With eosin y In dichloromethane at 20℃; for 16h; Inert atmosphere; Irradiation;	97%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) → chloro-N,N,N',N',N'',N''-hexamethyltriamidophosphonium dichlorophosphate

Conditions	Yield
With trichlorophosphate for 24h;	96%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + CrCl3*2N(CH3)3 → CrCl3(((CH3)2N)3PO)3 (32715-16-5, 76124-04-4, 76124-05-5)

Conditions	Yield
In benzene (N2), CrCl3*2NMe3 and organic compound in benzene reacted; elem. anal.;	96%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 2-neopentylidenemalononitrile (22123-53-1) → N-(2-(dicyanomethyl)-3,3-dimethylbutyl)-N,N,N,N,N-pentamethylphosphoric triamide

Conditions	Yield
With eosin y In dichloromethane at 20℃; for 16h; Inert atmosphere; Irradiation;	96%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + tert-butyl 2-nitrobenzoate (55666-41-6) → C13H22N6O2P(1+)*F6P(1-)

Conditions	Yield
Stage #1: N,N,N,N,N,N-hexamethylphosphoric triamide With trichloroisocyanuric acid In toluene at 0℃; for 2h; Stage #2: tert-butyl 2-nitrobenzoate With guanidine hydrochloride; N-ethyl-N,N-diisopropylamine In toluene Reflux; Stage #3: With potassium hexafluorophosphate In toluene Heating;	95.3%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 4-chloro-3-nitropyridine (13091-23-1) → 3-nitro-4-(N,N-dimethylamino)pyridine (5028-26-2)

Conditions	Yield
With sodium sulfide at 155℃; for 4h;	95%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + diphenylmethyl 3-(2-oxoazetidin-4-yl)-oxy-4-(4-toluenesulfonyl)oxy-butyrate → diphenylmethyl 3-(2-oxoazetidin-4-yl)-oxy-4-bromo-butyrate

Conditions	Yield
With lithium bromide	95%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + iron(III) chloride (7705-08-0) → Fe(NO3)2(Cl)(hexamethylphosphoric triamide)2

Conditions	Yield
With AgNO3 In acetonitrile byproducts: AgCl; dropwise addn. of AgNO3 in CH3CN to a soln. of anhydrous FeCl3 and HMPA in CH3CN, pptn. of AgCl, stirring of suspension for 1 h and let standing overnight; filtration, evapn. to dryness, washing with pentane and diethyl ether, drying under vac.;	95%

N,N,N,N,N,N-hexamethylphosphoric triamide (680-31-9) + 6,6-dimethyl-1,2,6-oxathiastanninan-2,2-dioxide monohydrate → (CH3)2Sn(OP((CH3)2N)3)OSO2(CH2)3

Conditions	Yield
In chloroform to a soln. of heterocyclus is added soln. of HMPT; warming the mixt. for 1 h at 50°C; removing all volatile parts in vac., crystn. by addn. of hexane to oil residue, recrystn. from CH2Cl2/hexane; elem. anal.;	95%

Upstream product

• 124-40-3 dimethyl amine 
• 623-03-0 4-Cyanochlorobenzene 
• 139-66-2 diphenyl sulfide 
• 945-51-7 1,1'-sulfinylbisbenzene 
• 874-90-8 4-methoxybenzonitrile 
• 333-27-7 methyl trifluoromethanesulfonate 
• 74783-16-7 C₁₃H₂₈N₃O₅P 
• 71423-78-4 tris(dimethylamino)iodophosphonium triiodide 
• 49778-01-0 iminotris(dimethylamino)phosphorane 
• 828-51-3 1-Adamantanecarboxylic acid 
• 56602-33-6 (benzotriazo-1-yloxy)tris(dimethylamino)phosphonium hexafluorophosphate 
• 3479-47-8 Z-Asp(OBzl)-OH 
• 6095-82-5 2,4,6-trimethylphenyl isothiocyanate 
• 103-72-0 phenyl isothiocyanate 

Downstream Products

• 68-12-2 N,N-dimethyl-formamide 
• 152-16-9 schradan 
• 1605-65-8 N,N,N',N'-Tetramethylphosphorodiamidic chloride 
• 127-19-5 N,N-dimethyl acetamide 
• 7334-51-2 N,N,N',N'-tetramethylsuccinamide 
• 2511-17-3 pentamethylphosphonic diamide 
• 14655-69-7 ethyl bis(dimethylamino)phosphonamide 
• 25419-06-1 N-methylpentylamine 
• 36764-08-6 <2-Oxo-cyclohexyl>-essigsaeure-dimethylamid 
• 36764-06-4 N,N,3-trimethyl-4-oxopentanamide 
• 13158-31-1 N¹,N¹,N⁴,N⁴-tetramethylterephthalamide 
• 2018-71-5 N,N-dimethyl-2-nitrobenzamide 
• 10278-71-4 N,N-dimethyl-N'-o-methylphenylformamidine 
• 5370-28-5 N,N-dimethylisovaleramide 

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An yttrium-based system to evaluate Lewis base coordination to an lectropositive metal in a metallocene environment

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