Pub Date : 2015-03-11DOI: 10.1002/047084289X.RN00923.PUB2
Elena Herrero‐Gómez, A. Echavarren, E. Vinogradova
X-Phos[564483-18-7] C33H49P (MW 476.72) InChI = 1S/C33H49P/c1-23(2)26-21-30(24(3)4)33(31(22-26)25(5)6)29-19-13-14-20-32(29)34(27-15-9-7-10-16-27)28-17-11-8-12-18-28/h13-14,19-25,27-28H,7-12,15-18H2,1-6H3 InChIKey = UGOMMVLRQDMAQQ-UHFFFAOYSA-N (bulky, electron-rich monophosphine used as ligand in transition-metal catalyzed reactions, especially in the context of Pd chemistry) Alternate Names: 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl, X-Phos. Physical Data: mp 187–190°C. Solubility: soluble in most organic solvents. Form Supplied in: white solid; widely available. t-BuX-Phos [564483-19-8] C29H45P (MW 424.65) InChI = 1S/C29H45P/c1-19(2)22-17-24(20(3)4)27(25(18-22)21(5)6)23-15-13-14-16-26(23)30(28(7,8)9)29(10,11)12/h13-21H,1-12H3 InChIKey = SACNIGZYDTUHKB-UHFFFAOYSA-N (bulky, electron-rich monophosphine used as ligand in Pd-catalyzed reactions) Alternate Names: 2-di-tert-butylphosphino-2′,4′,6′-triisopropyl biphenyl, tert-BuX-Phos, di-tert-BuXPhos. Physical Data: mp 148–151 °C. Solubility: soluble in most organic solvents. Form Supplied in: white solid; widely available. Handling, Storage, and Precautions: the oxidation of these and related phosphines has been examined.1 The presence of three isopropyl groups on the 2′,4′, and 6′ positions of the nonphosphine-containing ring reduces their reactivity toward atmospheric oxygen to less than 3% at room temperature in toluene solution after 65 h. Under an atmosphere of O2 at 100 °C for 65 h only 28% and 13% phosphine oxide is formed from X-Phos and tert-BuX-Phos, respectively. Preparative Method: X-Phos can be prepared by reaction of 2-bromochlorobenzene with the Grignard reagent from 1-bromo-2,4,6-triisopropylbenzene in THF, followed by addition of catalytic CuCl and ClPCy2. A similar procedure using ClPtertBu2 was applied for the synthesis of tert-BuX-Phos.2
{"title":"Bis(1,1‐dimethylethyl)[2′,4′,6′‐tris‐(1‐methylethyl)[1,1′‐biphenyl]‐2‐yl]‐phosphine and Dicyclohexyl[2′,4′,6′‐tris(1‐methylethyl)[1,1′‐biphenyl]‐2‐yl]phosphine","authors":"Elena Herrero‐Gómez, A. Echavarren, E. Vinogradova","doi":"10.1002/047084289X.RN00923.PUB2","DOIUrl":"https://doi.org/10.1002/047084289X.RN00923.PUB2","url":null,"abstract":"X-Phos[564483-18-7] C33H49P (MW 476.72) \u0000 \u0000 \u0000 \u0000 \u0000 \u0000InChI = 1S/C33H49P/c1-23(2)26-21-30(24(3)4)33(31(22-26)25(5)6)29-19-13-14-20-32(29)34(27-15-9-7-10-16-27)28-17-11-8-12-18-28/h13-14,19-25,27-28H,7-12,15-18H2,1-6H3 \u0000 \u0000 \u0000 \u0000InChIKey = UGOMMVLRQDMAQQ-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000(bulky, electron-rich monophosphine used as ligand in transition-metal catalyzed reactions, especially in the context of Pd chemistry) \u0000 \u0000 \u0000 \u0000Alternate Names: 2-dicyclohexylphosphino-2′,4′,6′-triisopropyl biphenyl, X-Phos. \u0000 \u0000 \u0000 \u0000Physical Data: mp 187–190°C. \u0000 \u0000 \u0000 \u0000Solubility: soluble in most organic solvents. \u0000 \u0000 \u0000 \u0000Form Supplied in: white solid; widely available. \u0000 \u0000 \u0000 \u0000t-BuX-Phos \u0000 \u0000 \u0000 \u0000[564483-19-8] C29H45P (MW 424.65) \u0000 \u0000 \u0000 \u0000InChI = 1S/C29H45P/c1-19(2)22-17-24(20(3)4)27(25(18-22)21(5)6)23-15-13-14-16-26(23)30(28(7,8)9)29(10,11)12/h13-21H,1-12H3 \u0000 \u0000 \u0000 \u0000InChIKey = SACNIGZYDTUHKB-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000(bulky, electron-rich monophosphine used as ligand in Pd-catalyzed reactions) \u0000 \u0000 \u0000 \u0000Alternate Names: 2-di-tert-butylphosphino-2′,4′,6′-triisopropyl biphenyl, tert-BuX-Phos, di-tert-BuXPhos. \u0000 \u0000 \u0000 \u0000Physical Data: mp 148–151 °C. \u0000 \u0000 \u0000 \u0000Solubility: soluble in most organic solvents. \u0000 \u0000 \u0000 \u0000Form Supplied in: white solid; widely available. \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: the oxidation of these and related phosphines has been examined.1 The presence of three isopropyl groups on the 2′,4′, and 6′ positions of the nonphosphine-containing ring reduces their reactivity toward atmospheric oxygen to less than 3% at room temperature in toluene solution after 65 h. Under an atmosphere of O2 at 100 °C for 65 h only 28% and 13% phosphine oxide is formed from X-Phos and tert-BuX-Phos, respectively. \u0000 \u0000 \u0000 \u0000Preparative Method: X-Phos can be prepared by reaction of 2-bromochlorobenzene with the Grignard reagent from 1-bromo-2,4,6-triisopropylbenzene in THF, followed by addition of catalytic CuCl and ClPCy2. A similar procedure using ClPtertBu2 was applied for the synthesis of tert-BuX-Phos.2","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"148 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2015-03-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"77768893","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2012-09-14DOI: 10.1002/047084289X.RN01475
L. A. Adrio, K. K. Hii
(R)-4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane [364732-88-7] C40H34P2 (MW 576.65) InChI = 1S/C40H34P2/c1-5-13-35(14-6-1)41(36-15-7-2-8-16-36)39-29-31-21-25-33(39)27-23-32-22-26-34(28-24-31)40(30-32)42(37-17-9-3-10-18-37)38-19-11-4-12-20-38/h1-22,25-26,29-30H,23-24,27-28H2 InChIKey = GYZZZILPVUYAFJ-UHFFFAOYSA-N Physical Data: white solid, mp 222–226 °C. [α]d = −34 ± 4° (c 1, CHCl3). (S)-4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane [192463-40-4] InChI = 1S/C40H34P2/c1-5-13-35(14-6-1)41(36-15-7-2-8-16-36)39-29-31-21-25-33(39)27-23-32-22-26-34(28-24-31)40(30-32)42(37-17-9-3-10-18-37)38-19-11-4-12-20-38/h1-22,25-26,29-30H,23-24,27-28H2 InChIKey = GYZZZILPVUYAFJ-UHFFFAOYSA-N Physical Data: white solid, mp 222–226 °C. [α]22d = +34° (c 1, CHCl3) (used as a chiral diphosphine ligand in transition metal-catalyzed reactions and also as organocatalyst) Solubility: not reported. Form Supplied in: white solid. Commercially available. Handling, Storage, and Precautions: readily oxidized to the phosphine oxide in solution and should be handled under N2 or Ar. Solid samples can be handled in air. Avoid contact with strong oxidizing agents and halogens.
{"title":"PhanePhos and Related Derivatives","authors":"L. A. Adrio, K. K. Hii","doi":"10.1002/047084289X.RN01475","DOIUrl":"https://doi.org/10.1002/047084289X.RN01475","url":null,"abstract":"(R)-4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane [364732-88-7] C40H34P2 (MW 576.65) \u0000 \u0000InChI = 1S/C40H34P2/c1-5-13-35(14-6-1)41(36-15-7-2-8-16-36)39-29-31-21-25-33(39)27-23-32-22-26-34(28-24-31)40(30-32)42(37-17-9-3-10-18-37)38-19-11-4-12-20-38/h1-22,25-26,29-30H,23-24,27-28H2 \u0000 \u0000InChIKey = GYZZZILPVUYAFJ-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000 \u0000 \u0000Physical Data: white solid, mp 222–226 °C. [α]d = −34 ± 4° (c 1, CHCl3). \u0000 \u0000 \u0000 \u0000 \u0000 \u0000(S)-4,12-Bis(diphenylphosphino)-[2.2]-paracyclophane [192463-40-4] \u0000 \u0000InChI = 1S/C40H34P2/c1-5-13-35(14-6-1)41(36-15-7-2-8-16-36)39-29-31-21-25-33(39)27-23-32-22-26-34(28-24-31)40(30-32)42(37-17-9-3-10-18-37)38-19-11-4-12-20-38/h1-22,25-26,29-30H,23-24,27-28H2 \u0000 \u0000InChIKey = GYZZZILPVUYAFJ-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000 \u0000 \u0000Physical Data: white solid, mp 222–226 °C. [α]22d = +34° (c 1, CHCl3) \u0000 \u0000 \u0000 \u0000(used as a chiral diphosphine ligand in transition metal-catalyzed reactions and also as organocatalyst) \u0000 \u0000 \u0000 \u0000Solubility: not reported. \u0000 \u0000 \u0000 \u0000Form Supplied in: white solid. Commercially available. \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: readily oxidized to the phosphine oxide in solution and should be handled under N2 or Ar. Solid samples can be handled in air. Avoid contact with strong oxidizing agents and halogens.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"54 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2012-09-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"83153818","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2010-10-15DOI: 10.1002/047084289X.RN01145
Hongbo Li, Thomas J. Colacot
[12289-94-0] C16H26Ru (MW 319.5) InChI = 1S/C8H12.2C4H7.Ru/c1-2-4-6-8-7-5-3-1;2*1-4(2)3;/h1-2,7-8H,3-6H2;2*1-2H2,3H3;/b2-1-,8-7-;;; InChIKey = GRYFGFSAXGLJLN-PHFPKPIQSA-N (asymmetric hydrogenation, transfer hydrogenation, alkyne addition) Physical Date: white solid (typically off-white). Solubility: soluble in THF, toluene, pentane; insoluble in alcohols. From Supplied in: white solid; Johnson Matthey (trade name Ru-124) for commercial quantities, Alfa Aesar for catalog quantities. Preparative method: the original milligram to gram synthesis is reported in the literature with modest to moderate yield.1 A very large excess of Grignard reagent was used in the synthesis.1 Analysis of Reagent Purity: this compound can be characterized by mp (80–85 °C), elemental assay, and 1H NMR and 13C NMR spectroscopy.2 1H NMR (300 MHz, C6D6, 20 °C): d 0.20 (s, 2H, anti-H of Me-allyl), 1.08-1.26 (m, 2H, CH of COD), 1.45-1.70 (m, 4H, CH2 of COD), 1.56 (s, 2H, syn-H of Me-allyl), 1.70 (s, 6H, CH3 of Me-allyl), 2.64–3.00 (m, 4H, CH2 of COD), 2.88 (s, 2H, anti-H of Me-allyl), 3.52 (d, 2H, J = 2 Hz, syn-H of Me-allyl), 3.98 (dd, 2H, J = 5, 9 Hz, CH- of COD).13C{1H} NMR (C6D6, 20 °C): d 24.74 (CH3 of Me-allyl), 26.26 and 38.34 (CH3C(CH2)2), 51.22 and 51.68 (CH2 of COD), 70.63 and 88.22 (CH- of COD), 111.49 (CH3C(CH2)2). Handling, Storage, and Precantions: sensitive to temperature and possibly to light.
{"title":"(1,5‐Cyclooctadiene)bis(2‐Me‐allyl)ruthenium(II)","authors":"Hongbo Li, Thomas J. Colacot","doi":"10.1002/047084289X.RN01145","DOIUrl":"https://doi.org/10.1002/047084289X.RN01145","url":null,"abstract":"[12289-94-0] C16H26Ru (MW 319.5) \u0000 \u0000InChI = 1S/C8H12.2C4H7.Ru/c1-2-4-6-8-7-5-3-1;2*1-4(2)3;/h1-2,7-8H,3-6H2;2*1-2H2,3H3;/b2-1-,8-7-;;; \u0000 \u0000InChIKey = GRYFGFSAXGLJLN-PHFPKPIQSA-N \u0000 \u0000 \u0000 \u0000 \u0000 \u0000(asymmetric hydrogenation, transfer hydrogenation, alkyne addition) \u0000 \u0000 \u0000 \u0000Physical Date: white solid (typically off-white). \u0000 \u0000 \u0000 \u0000Solubility: soluble in THF, toluene, pentane; insoluble in alcohols. \u0000 \u0000 \u0000 \u0000From Supplied in: white solid; Johnson Matthey (trade name Ru-124) for commercial quantities, Alfa Aesar for catalog quantities. \u0000 \u0000 \u0000 \u0000Preparative method: the original milligram to gram synthesis is reported in the literature with modest to moderate yield.1 A very large excess of Grignard reagent was used in the synthesis.1 \u0000 \u0000 \u0000 \u0000Analysis of Reagent Purity: this compound can be characterized by mp (80–85 °C), elemental assay, and 1H NMR and 13C NMR spectroscopy.2 1H NMR (300 MHz, C6D6, 20 °C): d 0.20 (s, 2H, anti-H of Me-allyl), 1.08-1.26 (m, 2H, CH of COD), 1.45-1.70 (m, 4H, CH2 of COD), 1.56 (s, 2H, syn-H of Me-allyl), 1.70 (s, 6H, CH3 of Me-allyl), 2.64–3.00 (m, 4H, CH2 of COD), 2.88 (s, 2H, anti-H of Me-allyl), 3.52 (d, 2H, J = 2 Hz, syn-H of Me-allyl), 3.98 (dd, 2H, J = 5, 9 Hz, CH- of COD).13C{1H} NMR (C6D6, 20 °C): d 24.74 (CH3 of Me-allyl), 26.26 and 38.34 (CH3C(CH2)2), 51.22 and 51.68 (CH2 of COD), 70.63 and 88.22 (CH- of COD), 111.49 (CH3C(CH2)2). \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precantions: sensitive to temperature and possibly to light.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"26 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2010-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"80965265","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2010-10-15DOI: 10.1002/047084289X.RN01221
V. Zgonnik, M. Mazières, J. Plaquevent
(1; X = BF4) [109705-14-8] C8H11BF5N (MW 226.98) InChI = 1S/C8H11FN.BF4/c1-6-4-7(2)10(9)8(3)5-6;2-1(3,4)5/h4-5H,1-3H3;/q+1;-1 InChIKey = RRNLYYDDEUOXBB-UHFFFAOYSA-N (2; X = OTf) [107264-00-6] C9H11F4NO3S (MW 289.25) InChI = 1S/C8H11FN.CHF3O3S/c1-6-4-7(2)10(9)8(3)5-6;2-1(3,4)8(5,6)7/h4-5H,1-3H3;(H,5,6,7)/q+1;/p-1 InChIKey = PRIGFEJKMMRJSF-UHFFFAOYSA-M (reactive and easy-to-handle electrophilic fluorinating reagent for preparing various organofluorine compounds) Alternate Name: 1-fluoro-sym-collidinium tetrafluoroborate. Physical Data: (1) mp 215–217° C; (2) mp 168–170° C.1 Solubility: soluble in CH3CN, CH2Cl2, THF, Et2O. Form Supplied in: beige powder. Analysis of Reagent Purity: NMR 19F (CD3CN): −17.3 (1F, s, NF); 149.6 (4F, s, BF4).2 Preparative Method: a solution of the 2,4,6-trimethylpyridine with NaBF4 in CH3CN at −40° C is treated with fluorine (10%) in nitrogen.1 Purification: recrystallization from CH3CN–Et2O.1 Handling, Storage, and Precautions: avoid contact with skin and eyes. Avoid formation of dust and aerosols. Provide appropriate exhaust ventilation at places where dust is formed. Normal measures for preventive fire protection. Store in cool place. Keep container tightly closed in a dry and well-ventilated place.
Pub Date : 2010-10-15DOI: 10.1002/047084289X.RN01164
A. Phillips
[920-66-1] C3H2F6O (MW 168.04) InChI = 1S/C3H2F6O/c4-2(5,6)1(10)3(7,8)9/h1,10H InChIKey = BYEAHWXPCBROCE-UHFFFAOYSA-N (highly polar, thermally stable, UV transparent solvent that is miscible with water and many polar organic solvents; additive for catalysis applications)1 Alternative Names: 1,1,1,3,3,3-hexafluoro-2-hydroxypropane; 1,1,1,3,3,3-hexafluoro-2-propanol; 1,1,1,3,3,3-hexafluoroisopropanol; 1,1,1,3,3,3-hexafluoroisopropyl alcohol; 2,2,2-trifluoro-1-(trifluoromethyl)ethanol; bis(trifluoromethyl)methanol; hexafluoroisopropanol; hexafluoroisopropyl alcohol; HFIP, HFIPA, HFP. Physical Data: bp 58.2 °C/760 mmHg; mp −3.3 °C; d 1.6047 g cm−3; pKa = 9.3.2 Analysis of Reagent Purity: generally used as supplied (>99% technical or >99.97 specialty grade). Form Supplied in: water-white liquid; commercially available. Handling, Storage, and Precautions: corrosive to eyes on contact and a strong skin and respiratory irritant. May contain traces of 1,1,1,3,3,3-hexafluoroacetone, a potential reproductive hazard. Appropriate precautions should be taken to minimize exposure. Solubility: miscible with water and most organic solvents, with the exception of long-chain hydrocarbon solvents.
{"title":"1,1,1,3,3,3‐Hexafluoro‐2‐propanol","authors":"A. Phillips","doi":"10.1002/047084289X.RN01164","DOIUrl":"https://doi.org/10.1002/047084289X.RN01164","url":null,"abstract":"[920-66-1] C3H2F6O (MW 168.04) \u0000 \u0000InChI = 1S/C3H2F6O/c4-2(5,6)1(10)3(7,8)9/h1,10H \u0000 \u0000InChIKey = BYEAHWXPCBROCE-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000 \u0000 \u0000(highly polar, thermally stable, UV transparent solvent that is miscible with water and many polar organic solvents; additive for catalysis applications)1 \u0000 \u0000 \u0000 \u0000Alternative Names: 1,1,1,3,3,3-hexafluoro-2-hydroxypropane; 1,1,1,3,3,3-hexafluoro-2-propanol; 1,1,1,3,3,3-hexafluoroisopropanol; 1,1,1,3,3,3-hexafluoroisopropyl alcohol; 2,2,2-trifluoro-1-(trifluoromethyl)ethanol; bis(trifluoromethyl)methanol; hexafluoroisopropanol; hexafluoroisopropyl alcohol; HFIP, HFIPA, HFP. \u0000 \u0000 \u0000 \u0000Physical Data: bp 58.2 °C/760 mmHg; mp −3.3 °C; d 1.6047 g cm−3; pKa = 9.3.2 \u0000 \u0000 \u0000 \u0000Analysis of Reagent Purity: generally used as supplied (>99% technical or >99.97 specialty grade). \u0000 \u0000 \u0000 \u0000Form Supplied in: water-white liquid; commercially available. \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: corrosive to eyes on contact and a strong skin and respiratory irritant. May contain traces of 1,1,1,3,3,3-hexafluoroacetone, a potential reproductive hazard. Appropriate precautions should be taken to minimize exposure. \u0000 \u0000 \u0000 \u0000Solubility: miscible with water and most organic solvents, with the exception of long-chain hydrocarbon solvents.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"1 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2010-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"89917741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2007-09-17DOI: 10.1002/047084289X.RN00752
Katsunori Tanaka, K. Fukase
[2797-28-6] C24BF20Li (MW 685.98) InChI = 1S/C24BF20.Li/c26-5-1(6(27)14(35)21(42)13(5)34)25(2-7(28)15(36)22(43)16(37)8(2)29,3-9(30)17(38)23(44)18(39)10(3)31)4-11(32)19(40)24(45)20(41)12(4)33;/q-1;+1 InChIKey = WTTFKRRTEAPVBI-UHFFFAOYSA-N (reagent especially used for generating “free” acid catalysts with a noncoordinating (C6F5)4B− ligand) Alternative Name: lithium tetrakis(pentafluorophenyl)borate. Physical Data: mp 120–124 °C (measured for diethylether complex, LiB(C6F5)4·2.5(Et2O)). Solubility: soluble in diethyl ether, MeOH, and H2O. Form Supplied in: commercially available as a diethyl ether complex (white powder). Analysis of Reagent Purity: IR, elemental analysis. Preparative Methods and Purification: LiB(C6F5)4 1 is prepared by the reaction of tris(pentafluorophenyl)borane [B(C6F5)3] with lithium pentafluorobenzene (LiC6F5) in pentane at −78 °C.1, 2 Filtration of the white precipitate provides the salt 1 (white powder) sufficiently pure for elemental analysis. LiC6F5 is prepared from bromopentafluorobenzene (BrC6F5) and n-BuLi in pentane. Handling, Storage, and Precautions: should be stored in a dry, dark, and cold place. Not to be exposed to oxidants, acids, and bases.
{"title":"Lithium Tetra(pentafluorophenyl)borate","authors":"Katsunori Tanaka, K. Fukase","doi":"10.1002/047084289X.RN00752","DOIUrl":"https://doi.org/10.1002/047084289X.RN00752","url":null,"abstract":"[2797-28-6] C24BF20Li (MW 685.98) \u0000 \u0000 \u0000 \u0000 \u0000 \u0000InChI = 1S/C24BF20.Li/c26-5-1(6(27)14(35)21(42)13(5)34)25(2-7(28)15(36)22(43)16(37)8(2)29,3-9(30)17(38)23(44)18(39)10(3)31)4-11(32)19(40)24(45)20(41)12(4)33;/q-1;+1 \u0000 \u0000 \u0000 \u0000InChIKey = WTTFKRRTEAPVBI-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000(reagent especially used for generating “free” acid catalysts with a noncoordinating (C6F5)4B− ligand) \u0000 \u0000 \u0000 \u0000Alternative Name: lithium tetrakis(pentafluorophenyl)borate. \u0000 \u0000 \u0000 \u0000Physical Data: mp 120–124 °C (measured for diethylether complex, LiB(C6F5)4·2.5(Et2O)). \u0000 \u0000 \u0000 \u0000Solubility: soluble in diethyl ether, MeOH, and H2O. \u0000 \u0000 \u0000 \u0000Form Supplied in: commercially available as a diethyl ether complex (white powder). \u0000 \u0000 \u0000 \u0000Analysis of Reagent Purity: IR, elemental analysis. \u0000 \u0000 \u0000 \u0000Preparative Methods and Purification: LiB(C6F5)4 1 is prepared by the reaction of tris(pentafluorophenyl)borane [B(C6F5)3] with lithium pentafluorobenzene (LiC6F5) in pentane at −78 °C.1, 2 Filtration of the white precipitate provides the salt 1 (white powder) sufficiently pure for elemental analysis. LiC6F5 is prepared from bromopentafluorobenzene (BrC6F5) and n-BuLi in pentane. \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: should be stored in a dry, dark, and cold place. Not to be exposed to oxidants, acids, and bases.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"40 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2007-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"90119801","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2007-03-15DOI: 10.1002/9780470842898.RN00699
B. Ashfeld, A. Judd
[12092-47-6] C16H24Cl2Rh2 (MW 493.08) InChI = 1S/2C8H12.2ClH.2Rh/c2*1-2-4-6-8-7-5-3-1;;;;/h2*1-2,7-8H,3-6H2;2*1H;;/q;;;;2*+1/p-2/b2*2-1-,8-7-;;;; InChIKey = QSUDXYGZLAJAQU-MIXQCLKLSA-L (catalyst precursor for reactions involving heteroatom nucleophiles, aryl boronic acids, alkenes, alkynes, and a variety of organometallic reagents; most notably cross-couplings, asymmetric hydrogenations, Pauson–Khand annulations, carbonyl 1,2- and 1,4-additions, cycloisomerizations, and various tandem processes) Alternate Names: 1,5-cyclooctadienerhodium(I) chloride dimer and rhodium(I) chloride 1,5-cyclooctadiene complex dimer. Physical Data: mp 243 °C. It exists as hygroscopic yellow to orange crystals. Solubility: soluble in dichloromethane; moderately soluble in chloroform, acetic acid, and acetone; slightly soluble in ether, methanol, ethanol and benzene; insoluble in water. Analysis of Reagent Purity: strong infrared bands at 819, 964 and 998 cm−1 (Nujol mull). 1H NMR: 4.3 ppm and 2.6–1.7 ppm (CDCl3). Preparative Method: prepared by refluxing RhCl3·3H2O and excess cis,cis-1,5-cyclooctadiene in ethanol for 3–18 h. The solution is then cooled, the orange solid filtered, washed with ethanol and dried. Recrystallization from dichloromethane/diethyl ether or acetic acid gives orange prisms.1-3 Note that if the RhCl3·3H2O is particularly acidic, Na2CO3 can be added to the solution of rhodium complex in refluxing ethanol to obtain satisfactory results. Handling, Storage and Precautions: although the catalyst is quite air-stable, it should be handled under an inert atmosphere, and stored at reduced temperature (2–8 °C), to ensure optimal catalytic activity. The complex is susceptible to slow oxidation upon exposure to air, and appropriate precautions should be taken to maintain its catalytic efficacy. Reproducible results are best obtained when the catalyst is prepared fresh and used immediately. Standard good laboratory practices should be used when working with this reagent.
{"title":"Chloro(1,5‐Cyclooctadiene)Rhodium(I) Dimer","authors":"B. Ashfeld, A. Judd","doi":"10.1002/9780470842898.RN00699","DOIUrl":"https://doi.org/10.1002/9780470842898.RN00699","url":null,"abstract":"[12092-47-6] C16H24Cl2Rh2 (MW 493.08) \u0000 \u0000 \u0000 \u0000 \u0000 \u0000InChI = 1S/2C8H12.2ClH.2Rh/c2*1-2-4-6-8-7-5-3-1;;;;/h2*1-2,7-8H,3-6H2;2*1H;;/q;;;;2*+1/p-2/b2*2-1-,8-7-;;;; \u0000 \u0000 \u0000 \u0000InChIKey = QSUDXYGZLAJAQU-MIXQCLKLSA-L \u0000 \u0000 \u0000 \u0000(catalyst precursor for reactions involving heteroatom nucleophiles, aryl boronic acids, alkenes, alkynes, and a variety of organometallic reagents; most notably cross-couplings, asymmetric hydrogenations, Pauson–Khand annulations, carbonyl 1,2- and 1,4-additions, cycloisomerizations, and various tandem processes) \u0000 \u0000 \u0000 \u0000Alternate Names: 1,5-cyclooctadienerhodium(I) chloride dimer and rhodium(I) chloride 1,5-cyclooctadiene complex dimer. \u0000 \u0000 \u0000 \u0000Physical Data: mp 243 °C. It exists as hygroscopic yellow to orange crystals. \u0000 \u0000 \u0000 \u0000Solubility: soluble in dichloromethane; moderately soluble in chloroform, acetic acid, and acetone; slightly soluble in ether, methanol, ethanol and benzene; insoluble in water. \u0000 \u0000 \u0000 \u0000Analysis of Reagent Purity: strong infrared bands at 819, 964 and 998 cm−1 (Nujol mull). 1H NMR: 4.3 ppm and 2.6–1.7 ppm (CDCl3). \u0000 \u0000 \u0000 \u0000Preparative Method: prepared by refluxing RhCl3·3H2O and excess cis,cis-1,5-cyclooctadiene in ethanol for 3–18 h. The solution is then cooled, the orange solid filtered, washed with ethanol and dried. Recrystallization from dichloromethane/diethyl ether or acetic acid gives orange prisms.1-3 Note that if the RhCl3·3H2O is particularly acidic, Na2CO3 can be added to the solution of rhodium complex in refluxing ethanol to obtain satisfactory results. \u0000 \u0000 \u0000 \u0000Handling, Storage and Precautions: although the catalyst is quite air-stable, it should be handled under an inert atmosphere, and stored at reduced temperature (2–8 °C), to ensure optimal catalytic activity. The complex is susceptible to slow oxidation upon exposure to air, and appropriate precautions should be taken to maintain its catalytic efficacy. Reproducible results are best obtained when the catalyst is prepared fresh and used immediately. Standard good laboratory practices should be used when working with this reagent.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"213 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2007-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76195470","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2006-04-15DOI: 10.1002/047084289X.RC041.PUB2
L. Paquette, G. Sabitha, J. Yadav
[7790-86-5] (·7H2O) CeCl3 (MW 246.47) InChI = 1S/Ce.3ClH/h;3*1H/q+3;;;/p-3 InChIKey = VYLVYHXQOHJDJL-UHFFFAOYSA-K [18618-55-8] H14CeCl3O7 (MW 372.59) InChI = 1S/Ce.3ClH.7H2O/h;3*1H;7*1H2/q+3;;;;;;;;;;/p-3 InChIKey = KPZSTOVTJYRDIO-UHFFFAOYSA-K (mild Lewis acid capable of selective acetalization;2 organocerium reagents have increased oxo-3 and azaphilicity4 and greatly reduced basicity;5 in combination with NaBH4 is a selective 1,2-reducing agent6; commercially available lanthanide reagent which is a mild Lewis acid, water tolerant, nontoxic, easy to handle, inexpensive7; in combination with NaI its activity is increased dramatically, cerium(III) chloride/NaI supported on silica gel has been developed by Bartoli and marcantoni,8 to improve its utility in organic synthesis) Alternate Name: cerous chloride; cerium trichloride. Physical Data: mp 848 °C; bp 1727 °C; d 3.92 g cm−3. Solubility: insol cold H2O; sol alcohol and acetone; slightly sol THF. Form Supplied in: white solid; widely available. Drying: for some applications the cerium trichloride must be strictly anhydrous. The following procedure has proven most efficacious: a one-necked base-washed flask containing the heptahydrate and a magnetic stirring bar was evacuated to 0.1 Torr and heated slowly to 140 °C over a 2 h period. At 70 and 100 °C, considerable amounts of water are given off, and these critical temperature zones should not be passed through too quickly. The magnetically stirred white solid is heated overnight at 140 °C, cooled, blanketed with nitrogen, treated with dry THF (10 mL g−1), and agitated at rt for 3 h. To guarantee the complete removal of water, t-butyllithium is added dropwise until an orange color persists. Handling, Storage, and Precautions: anhydrous CeCl3 should be used as prepared for best results. Cerium is reputed to be of low toxicity.
{"title":"Cerium(III) Chloride","authors":"L. Paquette, G. Sabitha, J. Yadav","doi":"10.1002/047084289X.RC041.PUB2","DOIUrl":"https://doi.org/10.1002/047084289X.RC041.PUB2","url":null,"abstract":"[7790-86-5] (·7H2O) CeCl3 (MW 246.47) \u0000 \u0000InChI = 1S/Ce.3ClH/h;3*1H/q+3;;;/p-3 \u0000 \u0000InChIKey = VYLVYHXQOHJDJL-UHFFFAOYSA-K \u0000 \u0000 \u0000[18618-55-8] H14CeCl3O7 (MW 372.59) \u0000 \u0000InChI = 1S/Ce.3ClH.7H2O/h;3*1H;7*1H2/q+3;;;;;;;;;;/p-3 \u0000 \u0000InChIKey = KPZSTOVTJYRDIO-UHFFFAOYSA-K \u0000 \u0000 \u0000 \u0000 \u0000 \u0000 \u0000 \u0000(mild Lewis acid capable of selective acetalization;2 organocerium reagents have increased oxo-3 and azaphilicity4 and greatly reduced basicity;5 in combination with NaBH4 is a selective 1,2-reducing agent6; commercially available lanthanide reagent which is a mild Lewis acid, water tolerant, nontoxic, easy to handle, inexpensive7; in combination with NaI its activity is increased dramatically, cerium(III) chloride/NaI supported on silica gel has been developed by Bartoli and marcantoni,8 to improve its utility in organic synthesis) \u0000 \u0000 \u0000 \u0000Alternate Name: cerous chloride; cerium trichloride. \u0000 \u0000 \u0000 \u0000Physical Data: mp 848 °C; bp 1727 °C; d 3.92 g cm−3. \u0000 \u0000 \u0000 \u0000Solubility: insol cold H2O; sol alcohol and acetone; slightly sol THF. \u0000 \u0000 \u0000 \u0000Form Supplied in: white solid; widely available. \u0000 \u0000 \u0000 \u0000Drying: for some applications the cerium trichloride must be strictly anhydrous. The following procedure has proven most efficacious: a one-necked base-washed flask containing the heptahydrate and a magnetic stirring bar was evacuated to 0.1 Torr and heated slowly to 140 °C over a 2 h period. At 70 and 100 °C, considerable amounts of water are given off, and these critical temperature zones should not be passed through too quickly. The magnetically stirred white solid is heated overnight at 140 °C, cooled, blanketed with nitrogen, treated with dry THF (10 mL g−1), and agitated at rt for 3 h. To guarantee the complete removal of water, t-butyllithium is added dropwise until an orange color persists. \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: anhydrous CeCl3 should be used as prepared for best results. Cerium is reputed to be of low toxicity.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"37 2 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2006-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"84838253","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2003-04-28DOI: 10.1002/9780470842898.RT420.PUB2
B. Giese, J. Dickhaut, C. Chatgilialoglu
[1873-77-4] C9H28Si4 (MW 248.73) InChI = 1S/C9H28Si4/c1-11(2,3)10(12(4,5)6)13(7,8)9/h10H,1-9H3 InChIKey = SQMFULTZZQBFBM-UHFFFAOYSA-N (mediator of radical reactions;1, 2 nontoxic substitute for tri-n-butylstannane in radical reactions; slower hydrogen donor than tri-n-butylstannane3) Alternatives names: TTmss(Tms)3SiH Physical Data: bp 82–84 °C/12 mmHg; d 0.806 g cm−3; n20D 1.489. Solubility: sol pentane, ether, toluene, THF; modestly sol acetone, acetonitrile; insol H2O; decomposes rapidly in methanol and other alcohols. Form Supplied in: colorless liquid; commercially available. Preparative Method: easy to synthesize.4 Handling, Storage, and Precautions: is slightly sensitive to oxygen and should be stored under nitrogen.5 It showed no toxicity in several biological test systems.6
{"title":"Tris(trimethylsilyl)silane","authors":"B. Giese, J. Dickhaut, C. Chatgilialoglu","doi":"10.1002/9780470842898.RT420.PUB2","DOIUrl":"https://doi.org/10.1002/9780470842898.RT420.PUB2","url":null,"abstract":"[1873-77-4] C9H28Si4 (MW 248.73) \u0000 \u0000 \u0000 \u0000 \u0000 \u0000InChI = 1S/C9H28Si4/c1-11(2,3)10(12(4,5)6)13(7,8)9/h10H,1-9H3 \u0000 \u0000 \u0000 \u0000InChIKey = SQMFULTZZQBFBM-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000(mediator of radical reactions;1, 2 nontoxic substitute for tri-n-butylstannane in radical reactions; slower hydrogen donor than tri-n-butylstannane3) \u0000 \u0000 \u0000 \u0000Alternatives names: TTmss(Tms)3SiH \u0000 \u0000 \u0000 \u0000Physical Data: bp 82–84 °C/12 mmHg; d 0.806 g cm−3; n20D 1.489. \u0000 \u0000 \u0000 \u0000Solubility: sol pentane, ether, toluene, THF; modestly sol acetone, acetonitrile; insol H2O; decomposes rapidly in methanol and other alcohols. \u0000 \u0000 \u0000 \u0000Form Supplied in: colorless liquid; commercially available. \u0000 \u0000 \u0000 \u0000Preparative Method: easy to synthesize.4 \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: is slightly sensitive to oxygen and should be stored under nitrogen.5 It showed no toxicity in several biological test systems.6","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"56 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2003-04-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"75003966","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2001-04-15DOI: 10.1002/047084289X.RD398
Judi A. McKinney
[528-76-7] C6H3ClN2O4S (MW 234.63) InChI = 1S/C6H3ClN2O4S/c7-14-6-2-1-4(8(10)11)3-5(6)9(12)13/h1-3H InChIKey = GPXDNWQSQHFKRB-UHFFFAOYSA-N (sulfenylation agent used in electrophilic additions,1, 2 diene synthesis,12 protection of nucleosides,13 and preparation of propargyl alcohol synthons for use in cycloaddition chemistry15) Alternate Name: 2,4-dinitrophenylsulfenyl chloride. Physical Data: mp 94–97 °C. Solubility: sol most common organic solvents. Form Supplied in: commercially available as a solid (96% pure). Handling, Storage, and Precautions: corrosive; lachrymator. This reagent should be handled in a fume hood.
{"title":"2,4‐Dinitrobenzenesulfenyl Chloride","authors":"Judi A. McKinney","doi":"10.1002/047084289X.RD398","DOIUrl":"https://doi.org/10.1002/047084289X.RD398","url":null,"abstract":"[528-76-7] C6H3ClN2O4S (MW 234.63) \u0000 \u0000 \u0000 \u0000 \u0000 \u0000InChI = 1S/C6H3ClN2O4S/c7-14-6-2-1-4(8(10)11)3-5(6)9(12)13/h1-3H \u0000 \u0000 \u0000 \u0000InChIKey = GPXDNWQSQHFKRB-UHFFFAOYSA-N \u0000 \u0000 \u0000 \u0000(sulfenylation agent used in electrophilic additions,1, 2 diene synthesis,12 protection of nucleosides,13 and preparation of propargyl alcohol synthons for use in cycloaddition chemistry15) \u0000 \u0000 \u0000 \u0000Alternate Name: 2,4-dinitrophenylsulfenyl chloride. \u0000 \u0000 \u0000 \u0000Physical Data: mp 94–97 °C. \u0000 \u0000 \u0000 \u0000Solubility: sol most common organic solvents. \u0000 \u0000 \u0000 \u0000Form Supplied in: commercially available as a solid (96% pure). \u0000 \u0000 \u0000 \u0000Handling, Storage, and Precautions: corrosive; lachrymator. This reagent should be handled in a fume hood.","PeriodicalId":11669,"journal":{"name":"Encyclopedia of Reagents for Organic Synthesis","volume":"65 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2001-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"76877506","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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