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Catalogue Zirconocene-E.Pdf Technical Data Cl Zr Cl NICHIA CORPORATION Ever Researching for a Brighter World CONTENTS １． General Features ２． Product Guide ３． Solubility in Various Solvents ４． Solubility in Water and ｐH ５． Stability ６． Applications (Examples) ７． Application in Organic Synthesis ◆ Schwartz Reagent ◆ Hydrozirconation ◆ Cross Coupling Reaction ◆ Cp2ZrCl2-Catalyzed Carbometalation ◆ Cp2ZrCl2-Catalyzed Hydrometalation ◆ Negishi Reagent ◆ Zirconocene-Ethylene Complex ◆ Intramolecular Bicyclization Reactions of Enynes Using “Cp2Zr” ◆ Preparation and Reactions of Allylic Zirconium Species ◆ Synthesis of Benzene Derivatives Using Zirconacyclopentadienes ８． Storage and Safety Handling etc． １．General Features （１）Technologies involved were developed by Nichia’soriginalideas. （２）Consistently high/uniform quality was realized by the strict manufacturing process/quality control. ex ; Schwartz Reagent, Negishi Reagent We have strong customer-service engineering team in our V-plant listed on the last page. Please feel free to contact us at the nearest Nichia sales office if you are interested in Cp2ZrCl2 or other Zirconocene derivatives. Ever Researching for a Brighter World ２．Product Guide ２－１． Physical and Chemical Properties Chemical Name ： Bis-Ｃyclopentadienyl Ｚirconium Ｄichloride Zirconocene Dichloride Molecular Formula ： （Ｃ５Ｈ５）２ＺｒＣｌ２ Molecular Weight ： ２９２．３２ Appearance ： White Needle Crystal Melting Point ： ２４２～２４５ ℃ Sublimation Point ： １５０～１８０ ℃ （２９．１ ｋＰａ) Solubility ： Soluble in halogenated Hydrocarbon, Aromatic Hydrocarbon and Protic Solvents. Slightly soluble in Aliphatic Hydrocarbon. Decomposability ： Zirconocene Dichloride gradually decomposes by the moisture and the Oxygen in air if left in the open air. （ Zirconocene Dichloride forms Hydrochloride and [ZrCl(C5H5)2]2O ） ２－２． Assay and Impurities Specifications Typical Data Theoretical Value Purity ： ≧ ９９．００％ ９９．８３％ Zirconium (Ｚｒ) ： ≧ ３０．９０％ ３１．１６％ ３１．２１％ Chlorine ( Cl ) ： ≧ ２４．００％ ２４．２０％ ２４．２６％ Iron (Fe ) ： ≦ ０．０５％ ０．００２％ Analytical Data of Zirconocene Dichloride Cl/Zr Suppliers Zr(%) Cl(%) Notes (Molar Ratio) Nichia 31.16 24.20 2.00 White Needle Crystal Reagent A 31.19 24.22 2.00 Reagent B 31.09 24.24 2.01 Colored Crystal Reagent C 31.18 24.20 2.00 Reagent D 31.20 24.21 2.00 Theoretical 31.21 24.26 2.00 Value Zr and Cl contents were determined in Nichia. Ever Researching for a Brighter World ３． Solubility in Various Solvents N,N-Dimethylformamide Chloroform, Toluene Tetrahydrofuran, 1,2-Dimethoxyethane Cyclohexane, n-Hexane, n-Heptane 800 200 10 180 Tetrahydrofuran Solubility（ｇ/ｌ） Solubility （g/l） Solubility Solubility（ｇ/ｌ） 700 Chloroform 160 8 600 140 Cyclohexane 120 6 500 100 1,2-Dimethoxyethane 400 80 4 n-Heptane 60 300 40 2 200 Toluene n-Hexane 20 100 0 0 0 102030405060708090100 0 102030405060708090100 0 1020304050607080 Temperature(℃） Temperature（℃） Temperature（℃） ４． Solubility in Water and ｐH 500 400 Solubility （g/l) Solubility 300 Cｏｎｓｐｉｃｕｏｕｓ Solubility Hｙｄｒｏｌｙｓｉｓ 200 100 Temperature(℃) 0 0 1020304050 ０．５-100 １．０-200 pH Cｏｎｓｐｉｃｕｏｕｓ p Ｈ １．５-300 Hｙｄｒｏｌｙｓｉｓ ２．０-400 ２．５-500 Ever Researching for a Brighter World ５． Stability （１） Zirconocene Dichloride is stable in nitrogen atomosphere under 50℃ and its purity will not deteriorate. Ａｉｒ （Temperature:２５℃、humidity:５０％） 100 Purity(%) 98 96 94 92 90 0 5 10 15 20 25 30 35 40 （day） （２） In open air its quality will deteriorate due to hydrolysis and influence of oxygen. Nitrogen 100 Purity(%) 98 ５０℃ 96 １００℃ 94 92 １５０℃ 90 0 5 10 15 20 25 30 35 40 （day） （３） It’s quality will deteriorate under the influence of ultraviolet rays. Ultraviolet rays (Temperature ３０℃） 100 Purity(%) 98 96 94 92 90 0 5 10 15 20 25 30 35 40 （day） Ever Researching for a Brighter World ６. Applications ( Examples ) Ｃｐ２ＺｒＣｌ２ Polymerization Catalysts Olefin Polymerization 1)～10） Ethylene-α-Olefin Copolymerization 11)～13) Organic Synthesis Catalysts Ｄｅｒｉｖａｔｉｖｅｓ Coupling Reactions 14）、15） Addition Reactions 16） Carbometallation 17）、18） Cyclization 19） Oligomerization 20) Electronic Materials Optical Recording Materials 21～23） Stabilizers Dicarboxylic Acid Anhydrides 24） Halohydrocarbons 25） References of Applications １） Ｉｎｏｒｇａｎｉｃａ Ｃｈｉｍｉｃａ Ａｃｔａ．， ２７０， ２０ （１９９５） ２） Ａｃｔａ Ｐｏｌｙｔｅｃｈ． Ｓｃａｎｄ． Ｃｈｅｍ． Ｔｅｃｈｎｏｌ． Ｓｅｒ．， ２２７， １－５０ （１９９５） ３） Ｊ． Ｐｏｌｙｍ． Ｓｃｉ．， ｐａｒｔ Ａ ：Ｐｏｌｙｍ．Ｃｈｅｍ．， ２６，（１１）， ３０８９ （１９８８） ４） ＪＰＨ １１－０３５６１７ Ａ ５） ＪＰＨ １１－００１５１１Ａ ６） ＪＰＨ ５－３３１２１９Ａ ７） ＪＰＨ ９－３０２０１７Ａ ８） ＪＰＨ １０－３１６６９５Ａ ９） ＪＰＨ １０－１３０３１６Ａ １０） ＪＰＨ ９－３２８５０８Ａ １１） ＪＰＨ １０－１８２７４９Ａ １２） ＪＰＨ ９－２４１３２６Ａ １３） ＪＰＨ １０－２５４０９４Ａ １４） Ｊ． Ａｍ． Ｃｈｅｍ． Ｓｏｃ．， １０９， ２３９３ （１９８７） １５） Ｊ． Ａｍ． Ｃｈｅｍ． Ｓｏｃ．， １０８， ７４１１ （１９８６） １６） Ｊ． Ａｍ． Ｃｈｅｍ． Ｓｏｃ．， １０２， １３３３ （１９８０） １７） Ｊ． Ａｍ． Ｃｈｅｍ． Ｓｏｃ．， １０８， ６６３９ （１９８５） １８） Ｊ． Ｏｒｇａｎｏｍｅｔａｌ． Ｃｈｅｍ．， ３０４， １７ （１９８６） １９） Ｔｅｔｒａｈｅｄｒｏｎ Ｌｅｔｔ ．， ２８， ９１７ （１９８７） ２０） Ｉｎｏｒｇａｎｉｃａ Ｃｈｉｍｉｃａ Ａｃｔａ．， ２７０， ２０， （１９９８） ２１） ＪＰＳ ６３－１６５１８１Ａ ２２） ＪＰＳ ６３－１６５１８２Ａ ２３） ＪＰＳ ６３－１６８３９３Ａ ２４） ＪＰＳ ４８－０２８４０５Ａ ２５） ＪＰＨ ５－１５６０６２Ａ Ever Researching for a Brighter World ７．Application７．Application inin OrganicOrganic SynthesisSynthesis Schwartz Reagent H H LiAlH4 Cp2ZrCl2 Cp2Zr + Cp2Zr THF Cl H Schwartz Reagent CH2Cl2 Wash Tetrahedron Lett., 28, 3895 (1987) J.Org.Chem., 56, 2590 (1991) Tetrahedron Lett., 31, 7257 (1990) Hydrozirconation ZrCp2 Cl H Cp2Zr + Cl Schwartz Reagent ZrCp2 Cl R H R H ZrCp2 Cl Angew.Chem.Int.Ed.Eng., 15, 333 (1976) Cross Coupling Reaction R H ArX , Ni or Pd cat. H Ar X H , Pd cat. H R' R H H H R H H R' H ZrCp2 Cl X- -R' , Pd cat. R H H R' X , Pd cat. R H H Yukigoseikagaku Kyokaishi, 47, 2 (1989) J.Am.Chem.Soc., 109, 2393 (1987) Tetrahedron Lett., 30, 4299 (1989) Ever Researching for a Brighter World Cp2ZrCl2-Catalyzed Carbometalation H H Me3Al-cat.Cp2ZrCl2 (10 mol%) Ph Ph PhC CH + (CH2Cl)2 Me AlMe2 Me2Al Me 96 : 4 J.Am.Chem.Soc., 108, 6639 (1985) Me Catalytic Mechanism Aldrichim. Acta, 18, 31 (1985) Me Cl Synthesis, 1 (1988) Me3Al + Cl2ZrCp2 Me2Al ZrCp2 Me2Al ZrCp2 Cl Cl Cl RC CH RH RC CH Me ZrCp2 Cl AlMe2Cl Me ZrCp2 Cl Cl AlMe2 RHRH + Cl2ZrCp2 Me AlMe Me AlMe2 Me Cl ZrCp2Cl OCH2Ph OCH2Ph Me3Al-Cp2ZrCl2 ,(CH2Cl)2 OH 2) n-BuLi 3) O Zoapatanol J.Chem.Soc., Perakin Trans., Ⅰ, 1589 (1985) Cp2ZrCl2-Catalyzed Hydrometalation i-Bu Al-cat.Cp ZrCl 3 2 2 i-Bu2Al Tetrahedron. Lett., 21, 1501 (1985) Pure. Appl. Chem., 53, 2333 (1981) Catalytic Cycle i-Bu2Al(C8H17) i-Bu3Al Cp2ZrCl2 Cl Cl i-Bu2AlCl Cp2Zr Cp2Zr C8H17 i-Bu Cl Cp2Zr 1-octene H Ever Researching for a Brighter World ～～ OrganicOrganic SynthesisSynthesis UsingUsing Zirconocene(Ⅱ)Zirconocene(Ⅱ) ComplexesComplexes ～～ Negishi Reagent CH Et 2 n-BuLi 2 C Et Cp2ZrCl2 Cp ZrBu ＝ " Cp Zr " 2 2 Cp Zr H 2 -78℃ ~ r.t 2 Cp2Zr Bu Tetrahedron Lett., 27, 2829 (1986) ○ C-C Bond Formation Reactions Using “Cp2Zr” R PMe3 RCH=CHR' Cp2Zr(PMe3)2 PMe3 Cp2Zr R Me P RC≡CR R 3 R' Cp2Zr " Cp2Zr " R R R 1) CO R R R 2) H+ Cp2Zr Cp Zr O RC≡CR' 2 Me P PMe R R 3 R' 3 Yukigoseikagaku Kyokaishi, 47, 2 (1989) Synthesis., 1 (1988) Aldrichim. Acta, 18, 31 (1985) Chem.Rev.,88, 1047 (1989) Zirconocene-Ethylene Complex CH2 2 EtMgBr CH2 Cp ZrCl Cp ZrEt 2 2 2 2 H Cp Zr -78℃ ~ r.t Cp2Zr 2 Et ○ C-C Bond Formation Reactions Using Zirconocene-Ethylene Complex R R EtMgBr ,Cat.Cp2ZrCl2 ,THF Et MgBr J. Am. Chem. Soc. 113, 6266 (1991) Cp ZrCl Catalytic Cycle 2 2 2 EtMgBr EtH R Cp2Zr R MgBr Cp2Zr Cp2Zr R Et R MgBr EtMgBr Ever Researching for a Brighter World ～～ OrganicOrganic SynthesisSynthesis UsingUsing Zirconocene(Ⅱ)Zirconocene(Ⅱ) ComplexesComplexes ～～ Intramolecular Bicyclization Reactions of Enynes Using “Cp2Zr” Z 1) CO 1atm 2) 3N-HCl O (CH2)n Z Z - Cp2ZrCl2 n-BuLi Z (CH ) (CH ) 2 n Cp2Zr 2 n H O+ THF 3 H (CH2)n Z - = C,Si,Ge, or Sn Group Tetrahedron Lett., 27, 2829 (1986) J.Am.Chem.Soc., 107, 2568 (1985) Yukigoseikagaku Kyokaishi, 47, 2 (1989) SiMe3 Cp ZrCl SiMe 2 2 3 n-BuLi C6H5CH2 N H3C C6H5CH2 N ZrCp2 THF CH3 95% SiMe3 SiMe3 Cp2ZrCl2 C6H5CH2 N n-BuLi C6H5CH2 N ZrCp2 THF CH3 H CH3 92% SiMe3 Cp ZrCl SiMe 2 2 3 n-BuLi C6H5CH2 N CH3 C6H5CH2 N ZrCp2 THF H CH 86% 3 Tetrahedron Lett., 27, 2829 (1986) Yukigoseikagaku Kyokaishi, 47, 2 (1989) Ever Researching for a Brighter World ～～ OrganicOrganic SynthesisSynthesis UsingUsing Zirconocene(Ⅱ)Zirconocene(Ⅱ) ComplexesComplexes ～～ Preparation and Reactions of Allylic Zirconium Species 2 2 R 2 R " Cp2Zr " ZrCp2 R 1 3 THF 1 3 1 3 R OR R OR R ZrCp2OR OH R4CHO R4 1 R R2 anti selective Entry R1 R2 R3 R4 Yield (%) anti : syn 1 Ph H Me Ph 79 10 : 1 2 Ph H Bn Ph 89 15 : 1 3 Ph H TBDMS Ph 96 23 : 1 4 Ph H TBDMS iPr 96 49 : 1 5 Me H TBDMS Ph 41 CHO OH OEt " Cp2Zr " OEt OEt OEt ZrCp2OEt without BF3・ OEt2, 59%, anti/syn=14/86 with BF3・ OEt2, 85%, anti/syn=77/23 CHO OTBDMS OH Ph " Cp2Zr " Ph Ph ・ H ZrCp2OR 73%, anti/syn=22/1 Yakugaku Zasshi., 123, 933 (2003) Ever Researching for a Brighter World ～～ OrganicOrganic SynthesisSynthesis UsingUsing Zirconocene(Ⅱ)Zirconocene(Ⅱ) ComplexesComplexes ～～ Synthesis of Benzene Derivatives Using Zirconacyclopentadienes R1 R1 R1 R3 R1 Cp2ZrEt2 R2 R2 R3 R2 R3 R3 R2 R1 R1 R1 R1 Cp2ZrEt2 Cp2Zr Cp2Zr R1 R1 R R R1 R R R 2 2 3 3 R3 1 Cp2Zr NiBr2(PPh3)2 R R R2 3 2 R2 R2 J.Am.Chem.Soc., 121, 11093 (1999) ○ Synthesis of 1,2,3,5-Tetrasubstituted Benzene Derivatives R R R R R RR R Cp2ZrEt2 Et2Zn, CH2I2 1) CO Cp2Zr Cp2Zr 2)H+ RR R R R R R R J.Am.Chem.Soc., 124, 388 (2002) ○ Synthesis of Benzene Derivatives Mediated by Copper(Ⅰ) Salts R R R R Br 2eq.
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