Weygand/Hilgetag Preparative Organic Chemistry

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178 Formation of carbon-halogen bonds the product affords 55% (FeCls) or 69%(I2) of dimethyl 2,5-dichloroadipates, b.p. 122-128° 0.6 mm. On cooling and seeding of the distillate 43 % of these esters crystallize and these products are hydrolysed when boiled with concentrated HC1 to complete dissolution (1 h). The resulting acids can be separated by recrystallization from water into the difficultly soluble w^o-2,5-dichloroadipic acid, m.p. 186°, and the readily soluble racemic isomer, m.p. 145°. 3,4-Dichloroadipic acid: Under the preceding conditions but with UV-irradation and exclusion of the polarizing catalyst, 61 % of dimethyl dichloroadipates, b.p. 108-112°/0.6 mm, are obtained which on hydrolysis gives acids consisting to 94% of 3,4-dichloroadipic acid, m.p. 126°. In contrast to the two 2,5-dichloro acids, this is soluble in benzene; it is the main product of chlorination in the dark by SO2C12 and dibenzoyl peroxide (4 g per mole of dichloride). 569 For the chlorination of glutaric acid see Treibs and Michaelis. 570 Chlorination of nitriles RCH2CN gives mainly #, [CH2C1—C=NH] + Cl" > AH [CC13—C=NH] + Cl- • CCI3CN + HC1 It is therefore advantageous to pass in HC1 (ca. 1 part per 10 parts of nitrile) below 36° and then to chlorinate at not too high a temperature (35-42°). 571 Monochloroacetonitrile is obtained from monochloroacetamide and P4O10 in 5 72 trimethyl benzene. Glutarodinitrile, 573 and also adipodinitrile, heptanedinitrile, and octanedinitrile, 574 are converted into the
Replacement of hydrogen by halogen or thiocyanate 179 just boils, very good yields of substituted bromomalonic acids are obtained whose hydrolysis has afforded a large number of #-bromo aliphatic acids and their aryl derivatives. /COOHI /COOH RHC( • RBrC( X COOH XCOOH •> RCHBrCOOH + CO2 This method is exemplified in <strong>Organic</strong> Syntheses 519 by the synthesis of 2-bromo-3-phenylpropionic acid which is important for preparation of DL-phenylalanine. 5 8 ° Higher dicarboxylic acids are brominated by the Hell-Volhard-Zelinsky procedure or as the crude dichlorides formed by SOC12. It is advantageous to hydrolyse
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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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694 Formation of carbon-phosphorus
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CHAPTER 10 Formation of Metal-Carbo
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750 Formation of metal-carbon bonds
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7 52 Formation of metal-carbon bond
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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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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 carbon monoxide 1025 It
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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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Hydrolytic cleavage 1049 Ethyl acet
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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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Rearrangement of halogen compounds
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Migration from oxygen to carbon 106
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Migration from oxygen to carbon 107
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Migration from carbon to nitrogen 1
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Wagner-Meerwein rearrangement and r
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Wagner-Meerwein rearrangement and r
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Cope rearrangement; valence isomeri
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Cope rearrangement; valence isomeri
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Rearrangement on decomposition of d
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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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Aldehyde nitrates, 423 Aldehydes, a
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Amidic acids, 485 Amidines, 472 —
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Aporphine, 970 D-Arabinose, 1029
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Methane, diphenyltolyl-, 949 —, n
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Oxazole, 5-ethoxy-2-phenyl-, 858 Ox
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Phenyl azide, 584 — isocyanate, 4
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Propane, l,2,3-trichloro-2-methyl-,
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Silane, trichloro(chloromethyl)-, 7
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Sulfoxides, 630, 667, 668 —, redu
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Thiouronium salts, 692 , S-cyclohex
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Valence isomerization, 1088 Valeral
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