Weygand/Hilgetag Preparative Organic Chemistry

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722 Formation of carbon-phosphorus bonds b. Replacement of halogen by phosphorus by means of tertiary phosphines Alkylation of tertiary phosphines to quaternary phosphonium salts by alkyl halides is usually a smooth reaction that gives high to quantitative yields. 222 For unsubstituted and higher alkyl halides (up to C3) it is best not to use a solvent. Secondary and tertiary alkyl halides give olefins on occasions, 223 and /9-unsaturated alkyl halides give products of allylic rearrangement. 224 #,
Replacement of halogen by phosphorus 723 (2) Use of the 2-cyanoethyl group, which is removed analogously by strong bases (sodium ethoxide). 229 (3) Cathodic reduction of phosphonium salts. The ease of removal decreases in the series C6H5CH2, HOCH2CH2, tert-C4U9 > iso-C3H7 > n-C4U9 > C2H5 > C6H5 > CH3. This selective fission makes the process of alternate quaternization and reduction generally applicable to the synthesis of asymmetric phosphines, and moreover the yield and purity of the products are both high. 230 Also, both the cathodic reduction and the quaternization proceed with retention of configuration, so that the process is valuable for preparation of optically active phosphines. 231 Arylation of tertiary phosphines cannot be achieved directly by means of aryl halides, but it can be effected photochemically 232 or under irradiation 233 or above 200° in the presence of aluminum chloride 234 or other anhydrous metal halides. Bis(tetraphenylphosphonium) tetrabromoniccolate: 235 Triphenylphosphine (10 g), nickel bromide (4 g), and bromobenzene (15 g) are heated in a sealed tube for 2 h at 250°. The resulting dark blue crystals are washed from the tube with bromobenzene. Extraction with hot bromobenzene removes unchanged starting material. The product (12 g, 63 %) melts at 273° after drying for 2 days in a vacuum at 130°. Another method of arylating tertiary phosphines is provided by the "cobalt salt method", in which the aryl halide reacts in the presence of cobalt(n) chloride and a Grignard reagent. The process has radical character and the alkyl group of the Grignard reagent does not become attached to the phosphorus. General directions for the preparation of quaternary arylphosphonium salts by the cobalt salt method: 236 Anhydrous cobaltous chloride (5 mmoles) is suspended in a solution of a tertiary phosphine (50 mmoles) and an aryl halide (100 mmoles) in ether (75 ml); into this is dropped a 2N-solution of phenylmagnesium bromide (50 mmoles) in ether under nitrogen. The mixture is stirred vigorously for 0.5 h, then boiled for 3 h, after which it is hydrolysed with 2N-hydrochloric acid (100 ml). Filtration removes at most a small precipitate — if present it is boiled out with water. Addition of sodium iodide to the aqueous phase precipitates the phosphonium iodide. After recrystallization from water or aqueous ethanol, yields are around 50%. Diaryliodonium salts can also be used for arylating tertiary phosphines. 237 The supposed arylation of tertiary phosphines by bromophenols 238 does 229 M. Grayson, P. T. Keough, and G. A. Johnson, /. Amer. Chem. Soc, 81, 4803 (1959). 230 L. Homer and A. Mentrup, Ann. Chem., 646, 65 (1961). 231 L. Horner and co-workers, Tetrahedron Lett., 1963, 965; 1964, 1421. 232 J. B. Plumb and C. E. Griffin, /. Org. Chem., 27, 4711 (1962). 233 H. Drawe and G. Caspari, Angew. Chem. Int. Ed., EngL, 5, 317 (1966). 234 J. Chatt and F. C. Mann, /. Chem. Soc, 1940, 1192. 235 F. A. Cotton, O. D. Faut, and D. M. L. Goodgame, /. Amer. Chem. Soc, 83, 344 (1961). 236 L. Horner and H. Hoffmann, Chem. Ber., 91, 50 (1958). 237 L. G. Makarowa and A. N. Nesmejanow, "Synthesen organischer Verbindungen", VEB Verlag Technik, Berlin, 1959, Vol. 1, p. 143. 238 R. N. McDonald and T. W. Campbell, /. Amer. Chem. Soc, 82, 4669 (1960).
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PREPARATIVE ORGANIC CHEMISTRY
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WEYGAND/HILGETAG PREPARATIVE ORGANI
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Foreword to the 4 th Edition The fi
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Summary of Contents Introduction: O
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X Contents II. Addition of hydrogen
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x ii Contents II. Replacement of ha
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xiv Contents II. Esters 368 1. Repl
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xvi Contents 1. Replacement of nitr
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xviii Contents 5. Cleavage of the S
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xx Contents Chapter 11. Formation o
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xxii Contents 1.3. Formation of new
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xxiv Contents IV. Rearrangement of
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Introduction: Organization of the M
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PART A Reactions on the Intact Carb
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6 Formation of carbon-hydrogen bond
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8 Formation of carbon-hydrogen bond
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10 Formation of carbon-hydrogen bon
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86 Formation of carbon-deuterium bo
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100 Formation of carbon-deuterium b
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CHAPTER 3 Formation of Carbon-Halog
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104 Formation of carbon-halogen bon
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240 Formation of c arbon-halogen bo
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274 Formation of carbon-oxygen bond
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392 Cleavage of carbon-oxygen bonds
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CHAPTER 6 Formation of Carbon-Nitro
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406 Formation of carbon-nitrogen bo
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48 8 Formation of carbon-nitrogen b
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550 Alteration of nitrogen groups i
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CHAPTER 8 Formation of Carbon-Sulfu
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602 Formation of carbon-sulfur bond
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Page 698 and 699: 672 Formation of carbon-sulfur bond
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Page 774 and 775: CHAPTER 10 Formation of Metal-Carbo
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772 Formation of metal-carbon bonds
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814 Formation of carbon-carbon mult
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PARTB Formation of new carbon-carbo
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Addition to C=C bonds 847 Under the
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Addition to C= C bonds 849 A radica
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Addition to C=C bonds 851 ful catal
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formation (b) that is necessary for
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Addition to C —C bonds 855 Nitril
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Addition to C —C bonds 857 3,6-ep
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Addition to C—C bonds 8 59 Stereo
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Addition to C=C bonds 861 6. Additi
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Addition to C=C bonds 863 In this c
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Addition to C=C bonds 865 are added
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Addition to C=C bonds 867 amount of
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Addition to the C=O bond 869 Such a
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Addition to the C=O bond 871 Such c
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Addition to the C=O bond 873 3. For
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Addition to the C=O bond 875 In hyd
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Addition to the C=O bond 877 Finely
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Addition to the C=O bond 879 the te
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Addition to the C=O bond 881 A Grig
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Addition to the C=O bond 883 c. Tre
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Addition to the C= O bond 885 The d
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Addition to C-N multiple bonds 887
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C-C linkage by removal of hydrogen
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C~C linkage by removal of hydrogen
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C-C linkage by replacement of halog
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esters: 634 ' 640 ' 641 C-C linkage
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C-C linkage by replacement of hydro
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C-C linkage by replacement of OR by
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C-C linkage by replacement of O-acy
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C-C linkage by replacement of nitro
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tions (see also page 957): C-C link
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Removal of halogen with formation o
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Formation of a new C=C bond by remo
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Removal of sulfur with formation of
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Removal of phosphorus with formatio
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Removal of phosphorus with formatio
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PART C Cleavage of Carbon-Carbon Bo
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Removal of carbon dioxide 1005 Only
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Removal of carbon dioxide 1007 resp
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Removal of carbon dioxide 1009 e. N
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Removal of carbon dioxide 1011 Hydr
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Removal of carbon d ioxide 1013 Thi
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Removal of carbon d ioxide 1015 as
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Removal of carbon dioxide 1017 char
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Removal of carbon dioxide 1019 Conv
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Removal of carbon monoxide 1021 Thi
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Removal of carbon monoxide 1023 lab
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Removal of other fragments 1027 1.
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Removal of other fragments 1029 sol
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Removal of other fragments 1031 The
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Oxidative cleavage of C-C bonds in
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Oxidative degradation of olefins 10
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Oxidative cleavage of carbon-carbon
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Hydrolytic cleavage 1047 Cleavage b
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PART D Rearrangements of Carbon Com
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Migration of a multiple bond 1055 i
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Migration of a multiple bond 1057 A
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2 hours at 250-270°, thus: 54 Rear
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Migration from oxygen to carbon 106
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Rearrangement on decomposition of d
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Appendix I Purification and drying
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Purification and drying of organic
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Preparation and purification of gas
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Preparation and purification of gas
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Preparative organic work with small
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SUBJECT INDEX This index deals prim
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Acetophenone, co-amino-, 451 —, b
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Amidic acids, 485 Amidines, 472 —
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Valence isomerization, 1088 Valeral
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