RO RO V O RO Technical data NICHIA CORPORATION Ever Researching for a Brighter World Vanadiumoxytriisopropoxide (Commercial product) ① Physical and Chemical Properties Chemical Name: Vanadiumoxytriisopropoxide CAS#. 5588-84-1 Structural Formula: O C3H7 i i O V O C3H7 O i C3H7 Molecular Formula: C9H21O4V Molecular Weight: 244.20 Appearance: Pale yellow liquid. Boiling Point: 80～82 ℃/2 mmHg Solubility: Freely soluble in almost organic solvents. Stability: Air and moisture-sensitive. Slowly decompose at high temperature. ② Quality Specification Typical data V5+ : ≧ 20.50% 20.83% V3+, V4+ : ≦ 0.50% 0.21% Fe : ≦ 0.01% 0.001% Theoretical value 20.86% Ever Researching for a Brighter World Vanadiumoxyalkoxide (Trial product) Compositional Formula Chemical name CAS No Physical State VO(OC 2 H 5 ) 3 Vanadium oxytriethoxide 1686-22-2 Orange-Yellow Liquid Vapour Pressure：72 ℃(400 Pa) VO(OC 2 H 5 )Cl 2 Vanadium oxyethoxide dichloride 1801-77-0 Pale Yellow Liquid Vapour Pressure：63 ℃(600 Pa) VO(OC 2 H 5 ) 2 Cl Vanadium oxydiethoxide chloride - Orange-Yellow Liquid Vapour Pressure：68 ℃(400 Pa) VO(O n C 3 H 7 ) 3 Vanadium oxytri-n-propoxide 1686-23-3 Yellow Liquid Vapour Pressure：72 ℃(20 Pa) VO(O n C 4 H 9 ) 3 Vanadium oxytri-n-butoxide 1801-76-9 Yellow Liquid Vapour Pressure：115 ℃(133 Pa) VO(Oi C 4 H 9 ) 3 Vanadium oxytri-i-butoxide 19120-62-8 Yellow Liquid Vapour Pressure：80 ℃(40 Pa) VO(O s C 4 H 9 ) 3 Vanadium oxytri-sec-butoxide - Yellow Liquid Vapour Pressure：80 ℃(50 Pa) Ever Researching for a Brighter World 1. Applications ( Examples ) Polymerization Catalysts 1) ～ 3) Vanadiumoxyalkoxide VO(OR)3 VO(OR)nClｍ Electronics Materials SOL-GEL Process V2O5 Thin Films 4) ～ 9) Organics Synthesis Isomerization, Epoxidation, Oxydation catalyst 10) ～ 17) Ｒｅｆｅｒｅｎｃｅｓ ｏｆ Ａｐｐｌｉｃａｔｉｏｎｓ 1) J. Polym. Sci., Macromol., (A) 3, 2047-2054 (1965) 2) J. Polym. Sci., Macromol. Rev., 10, 1 (1975) 3) Macromolecules, 4, 482 (1971) 4) Chemical Physics Letters, 445, 293 (2007) 5) Chem, Mater., 21, 1618 (2009) 6) J. Mater. Chem., 4, (10), 1581 (1994) 7) J. Mater. Chem., 6, (1), 49 (1996) 8) Chem, Mater., 5, (11), 1591 (1993) 9) J. Non-Crystalline Solids, 121, 68 (1990) 10) Tetrahedron, 57, 5073 (2001) 11) Chemistry Letters, 357 (1982) 12) JP S 51-48608 13) JP S 52-131506 14) USP 6566564 B1 15) J.Am.Chem.Soc.,95, 6136 (1973) 16) J.Am.Chem.Soc.,122, 10452 (2000) 17) JP S 61-236737 Ever Researching for a Brighter World 2. Application in Organic Synthesis Isomerization R3 R3 + R2 [H ] R4 R4 R2 R1 OH R5 R1 R5 OH Tetrahedron, 33, 14, 1775 (1977) H OH H OH H OH cat. VO(OnBu)3 : 54x10-3 mol% 200 oC , 2.5 hr Conversion : 38% Chemistry Letters, 357 (1982) Epoxidation Ph 1 mol% VO(Oi-Pr)3 Ph O OH OH R O O R= Ph, Me R O N N t-Bu OH 1.5 mol% 95% ee (R=Ph, Me) t-BuOOH, toluene J. Am. Chem. Soc., 130, 5410 (2000) J. Am. Chem. Soc., 122, 10452 (2000) Ever Researching for a Brighter World Oxidative transformation reaction of carbonyl compound Dehydrogenation-oxidation O OEt 2 eq.VO(OEt)Cl2, O2 o Me Me EtOH, 80 C, 0.5 h Me Me Yield: 91% J. Org. Chem., 55, 358 (1990) Oxidative cleavage O O 2 eq.VO(OEt)Cl2, CBrCl3 Br OEt EtOH, r.t., 13 h Yield: 60% J. Org. Chem., 56, 2264 (1991) O OH OH 1 mol% VO(OEt)Cl2, O2 EtO2C CO2Et EtOH, r.t., 15 min OH Yield: 74% J. Chem. Soc., Perkin Trans. 1, 7 (1998) Ever Researching for a Brighter World Oxidative coupling reaction R R Li 3 eq.VO(OEt)Cl2 Et2O, r.t., 1 h 2 Yield: 90% (R=H) 90% (R=o-OMe) 91% (R=p-OMe) 80% (R=o-Ph) Organometallics, 17, 5713 (1998) Oxidative transformation reaction of organometallic compound Formation of C-C bond O OSiMe3 Me 3 eq.VO(OEt)Cl2 SiMe3 + Me CH2Cl2, -75 ℃, 2 h Yield: 65% Tetrahedron, 50, 10207 (1994) Synthesis of 1,4-diketone O OSiMe3 Ph OSiMe3 + 3 eq.VO(OEt)Cl2 CH2Cl2 Ph O Yield: 65% Tetrahedron Lett., 33, 5823 (1992) Synthesis of conjugated “Enyne” C6H13 i-Bu2AlH C6H13 hexane Ph Li Et2O 3 eq.VO(OEt)Cl2 Et2O, -78 ℃, 3 h Yield: 76% Ph J. Am. Chem. Soc., 120, 5124 (1998) Vicinal dialkylation reaction O O R2R'ZnLi THF n R 2 eq.VO(OEt)Cl2 THF, 0 ℃ ～ r.t., 20 h n R' Yield: 72% (n=2, R=Me, R'=Me) 51% (n=2, R=Me, R'=Bu) 38% (n=1, R=Bu, R'=Bu) Org. Lett., 2, 3659 (2000) Ever Researching for a Brighter World ■ The contents of this brochure are updated as of March, 2010. ■ Reference （The manufacturer & engineering department） NICHIA CORPORATION TOKUSHIMA PLANT (V-PLANT) 224 Hiraishi Ebisuno, Kawauchi-Cho, Tokushima-Shi, TOKUSHIMA 771-0132, JAPAN TEL: +81-88-665-2311 FAX: +81-88-665-5292 （Sales） NICHIA CORPORATION TOKYO SALES OFFICE 13F Tamachi Center Building 34-7, Shiba 5-Chome, Minato-Ku, TOKYO 108-0014, JAPAN TEL: +81-3-3456-3784 FAX: +81-3-3453-2369 http://www.nichia.co.jp Ever Researching for a Brighter World