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The reactivity order of dihalomethanes is in accordance with that of the radical halogen abstraction from these compounds
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(3 ) The reactivity order of dihalomethanes is in accordance with that of the radical halogen abstraction from these compounds.
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Among other byproducts identified by GC/MS: 2,2,4,4tetramethylpentane (CAS 1070-87-7), 2,2,6,6-tetramethyl4-methyleneheptane (CAS 141-70-8), 2-tert-butyltetrahydrofuran (CAS 38624-45-2), 2,2-dimethyldecane (CAS 17302-37-3), 2,2,8-trimethyldecane (CAS 62238-01-1), 2,2dimethylundecane (CAS 17312-64-0), tert-butyl bromide (CAS 507-19-7), 1-bromo-2,2-dimethylpropane (CAS 63017-1), 2-bromotetrahydrofuran (CAS 59253-21-3), 3bromo-2,2,4,4- tetramethylpentane (CAS 107713-49-5)
-
Among other byproducts identified by GC/MS: 2,2,4,4tetramethylpentane (CAS 1070-87-7), 2,2,6,6-tetramethyl4-methyleneheptane (CAS 141-70-8), 2-tert-butyltetrahydrofuran (CAS 38624-45-2), 2,2-dimethyldecane (CAS 17302-37-3), 2,2,8-trimethyldecane (CAS 62238-01-1), 2,2dimethylundecane (CAS 17312-64-0), tert-butyl bromide (CAS 507-19-7), 1-bromo-2,2-dimethylpropane (CAS 63017-1), 2-bromotetrahydrofuran (CAS 59253-21-3), 3bromo-2,2,4,4- tetramethylpentane (CAS 107713-49-5).
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2 (3 equiv)/t-BuMgCl (4 equiv) (GC conversion to the corresponding cyclopropanes after 18 h in brackets): (E)-hex-2-enol (35%), (Z)-hex-2-enol (65%), nonadienol (50%), geraniol (50%), nerol (10%), oct-1-en-3ol (50%), linalool (40%), and nerolidol (50%)
-
2 (3 equiv)/t-BuMgCl (4 equiv) (GC conversion to the corresponding cyclopropanes after 18 h in brackets): (E)-hex-2-enol (35%), (Z)-hex-2-enol (65%), nonadienol (50%), geraniol (50%), nerol (10%), oct-1-en-3ol (50%), linalool (40%), and nerolidol (50%).
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(b) 1b: Schröder, F. WO 2006,066,436, 2005;
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2-Hexylcyclopent-2-enone = isojasmone B11. Commercial available from Oxford Chemicals
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2-Hexylcyclopent-2-enone = isojasmone B11. Commercial available from Oxford Chemicals.
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2I converted lb similarly into 2b but without remote cyclopropanation to 2a. Evidence for exchange reactions between lithium alkoxides and Grignard reagents
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2I converted lb similarly into 2b but without remote cyclopropanation to 2a. Evidence for exchange reactions between lithium alkoxides and Grignard reagents: Micha-Screttas, M.; Constantinos, G.; Steele, B. R.; Heropoulos, G. A. Tetrahedron Lett. 2002,43, 4871.
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72049110129
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A possible explanation for this rate enhancement is the more covalent character of the Mg-O bond of the MgX- alcoholates versus the lithium alcoholate ion pair. For mechanistic details see ref. 1
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A possible explanation for this rate enhancement is the more covalent character of the Mg-O bond of the MgX- alcoholates versus the lithium alcoholate ion pair. For mechanistic details see ref. 1.
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GC-analysis on a 5% phenyl-95% dimethylpolysiloxane column
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GC-analysis on a 5% phenyl-95% dimethylpolysiloxane column.
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