Organic reactions vol 3 adams

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Organic Reactions VOLUME III EDITORIAL BOARD ROGER ADAMS, Editor-in-Chief WERNER E BACHMANN JOHN R JOHNSON LOUIS F FIESER H R SNYDER ASSOCIATE EDITORS MARVIN CARMACK PETER A S SMITH H E CARTER C M SUTER W E HANFORD EVERETT S WALLIS CHARLES C PRICE HANS WOLFF JOHN L WOOD NEW YORK JOHN WILEY & SONS, INC LONDON: CHAPMAN & HALL, LIMITED COPYRIGHT, 1946 BY ROQEE ADAMS All Rights Reserved This book or any part thereof must not be reproduced in any form without the written permission of the publisher THIRD PRINTING, AUGUST, 1947 PRINTED IN THE UNITED STATES OP AMERICA PREFACE TO THE SERIES In the course of nearly every program of research in organic chemistry the investigator finds it necessary to Use several of the better-known synthetic reactions To discover the optimum conditions for the application of even the most familiar one to a compound not previously subjected to the reaction often requires an extensive search of the literature; even then a series of experiments may be necessary When the results of the investigation are published, the synthesis, which may have required months of work, is usually described without comment The background of knowledge and experience gained in the literature search and experimentation is "thus lost to those who subsequently have occasion to apply the general method The student of preparative organic , chemistry faces similar difficulties The textbooks and laboratory manuals furnish numerous examples of the application of various syntheses, but only rarely they convey an accurate conception of the scope and usefulness of the processes For many years American organic chemists have discussed these problems The plan of compiling critical discussions of the more important reactions thus was evolved The volumes of Organic Reactions are collections of about twelve, chapters, each devoted to a single reaction, or a definite phase of a reaction, of wide applicability The authors have had experience with the processes surveyed The subjects are presented from the preparative viewpoint, and particular attention is given to limitations, interfering influences, effects of structure, and the selection of experimental techniques Each chapter includes several detailed procedures illustrating the significant modifications of the method Most of these procedures have been found satisfactory by the author or one of the editors, but unlike those in Organic Syntheses they have not been subjected to careful testing in two or more laboratories When all known examples of the reaction are not mentioned in the text, tables are given to list compounds which have been prepared by or subjected to the reaction Every effort has been made to include in the tables all such compounds and references; however, because of the very nature of the reactions discussed and their frequent use as one of the several steps of syntheses in which not all of the intermediates have been isolated, some instances may well have been missed v vi PEEFACE TO THE SERIES Nevertheless, the investigator will be able to use the tables and their accompanying bibliographies in place of most or all of the literature search so often required Because of the systematic arrangement of the material in the chapters and the entries in the tables, users of the books will be able to find information desired by reference to the table of contents of the appropriate chapter In the interest of economy the entries in the indices have been kept to a minimum, and, in particular, the compounds listed in the tables are not repeated in the indices The success of this publication, which will appear periodically in volumes of about twelve chapters, depends upon the cooperation of organic chemists and their willingness to devote time and effort to the preparation of the chapters They have manifested their interest already by the almost unanimous acceptance of invitations to contribute to the work The editors will welcome their continued interest' and their suggestions for improvements in Organic Reactions CONTENTS CHAPTER PAGE T H E ALKYLATION OF AROMATIC COMPOUNDS BY THE FBIEDEL-CRAFTS M E T H O D — C h a r l e s C Price T H E W I L L G E R O D T R E A C T I O N — M a r v i n Carmack a n d M A Spielman P R E P A R A T I O N O F K E T E N E S AND K E T E N E D I M E R S — W E Hanford a n d John C Sauer DIRECT SULFONATION OF AROMATIC HYDROCARBONS AND THEIR HALOGEN , DERIVATIVES—C M Suter and Arthur W Western AZLACTONES—H E Carter 83 108 141 198 SUBSTITUTION AND ADDITION REACTIONS OF THIOCTANOGEN—John L Wood 240 THE HOFMANN REACTION—Everett S Wallis and John F Lane 267 THE SCHMIDT REACTION—Hans Wolff 307 THE CURTIUS REACTION—Peter A S Smith 337 INDEX 451 vu SUBJECTS OF PREVIOUS VOLUMES VOLUME AcETOACETIC ESTEE CONDENSATION AND RELATED REACTIONS I ALIPHATIC FLUORINE COMPOUNDS II AMINATION OF HETEROCYCLIC BASES I ARNDT-EISTERT REACTION I AROMATIC ARSONIC AND ARSINIC ACIDS II BlAETLS II BUCHERER REACTION , I CANNIZZARO REACTION II CHLOROMETHYLATION OF AROMATIC COMPOUNDS CLAISBN REARRANGEMENT I , CLEMMENSEN REDUCTION CYCLIC KETONES II I II ELBS REACTION I FRIES REACTION I JACOBSEN REACTION I MANNICH REACTION ' I PERIODIC ACID OXIDATION PERKIN REACTION AND RELATED REACTIONS REDUCTION WITH ALUMINUM ALKOXIDBS REFORMATSKY REACTION II I II I REPLACEMENT OF AROMATIC PRIMARY AMINO GROUP BY HYDROGEN II RESOLUTION OF ALCOHOLS II CHAPTER THE ALKYLATION OF AROMATIC COMPOUNDS BY THE FRIEDEL-CRAFTS METHOD CHARLES C PRICE University of Illinois CONTENTS PAGE INTBODUCTION SCOPE AND LIMITATIONS Activity of Catalysts Alkylating Agents Aromatic Compounds Rearrangements of Alkyl Groups Orientation in Alkylation Identification Related Reactions Limitations Other Methods of Alkylation 2 10 12 13 14 ; EXPERIMENTAL DIRECTIONS 16 ' Selection of Experimental Conditions Triethylbenzene Simons and Bassler, J Am Chem Soc., 63,88(5 (1941) 18 446 ORGANIC REACTIONS REFERENCES FOR TABLE 868 Curtius and Hofmann, J prakt Chem., 53, 513 (1896) Stolle, J prakt Chem., 69, 145 (1904) 270 Stolle and Zinsser, J prakt Chem., 69, 486 (1904) 271 Curtius, Sieber, Nadenheim, Hambsoh, and Bitter, J prakt Chem., 125, 152 (1930) 272 Stolle and Gutmann, / prakt Chem., 69, 497 (1904) S t o l l e and Hille, J prakt Chem., 69, 481 (1904) 274 Spiegel and Spiegel, Ber., 40, 1733 (1907) 276 Curtius and Schwan, J prakt Chem., 51, 353 (1895) 276 Blaise and Luttringer, BuU soc Mm., [3] 33, 1095 (1905) 277 Blaise and Luttringer, Compt rend., 140, 790 (1905) 278 Darapsky, Berger, and Neuhaus, J prakt Chem., 147, 145 (1936) 279 Blaise and Luttringer, BuU soc chim., [3] 33, 816 (1905) 280 van Marie, Rec trav chim., 39, 549 (1920) 281 Kiliani, Ber., 55, 2817 (1922); 58, 2361 (1925) 282 Curtius and Levy, J prakt Chem., 70, 89 (1904) 283 Curtius, Ber., 35, 3226 (1902) 284 Curtius, Ber., 27, 778 (1894) 286 Curtius, Hallaway, and Heil, J prakt Chem., 89, 481 (1914) 286 Billow and Weidlich, Ber., 39, 3372 (1906) 287 Blanksma and Bakels, Rec trav chim., 58, 497 (1939) 288 Blanksma and de Graf, Rec trav chim., 57, (1938); thesis, Leiden, 1930 [C A., 24, 5723 (1930)] 23 Turner and Hartman, J Am Chem Soc, 47, 2044 (1925) 290 Curtius and Casar, / prakt Chem., 94, 299 (1916) 281 Curtius and Rechnitz, J prakt Chem., 94, 309 (1916) 292 Billow and Bozenhardt, Ber., 42, 4801 (1909) 293 ' Fischer and Brauns, Ber., 47, 3181 (1914) 294 Traube and Lehmann, Ber., 34, 1975 (1901) 296 Resting, Ber., 57, 1321 (1924) 296 Franzen and Sohmitt, Ber., 58, 222 (1925) 297 Franzen and Ostertag, Z physiol Chem., 119, 150 (1922) 298 Curtius and Burkhardt, J prakt Chem., 58, 205 (1898) 299 K e r p a n d Unger, Ber., , 585 (1897) 800 S a h a n d H a n , Science Repts Natl Tsing Hua Univ., A , 469 (1936) [C A , , 3825 (1937)] 301 C u r t i u s a n d Raschig, J prakt Chem., 125, 466 (1930) 302 Dickey and Straley, U S pat., 2,360,210 (to Eastman Kodak Company); [C A., 39, 946 (1945)] 303 Curtius, von Brilning, and Derlon, J prakt Chem., 125, 63 (1930) 304 Curtius and Clemm, Ber., 29, 1166 (1896) 306 Curtius and Steller, J prakt Chem., 62, 212 (1900) 306 Ruzicka and Stoll, Helv Chim Ada, 10, 691 (1927) 307 Frankland and Slator, J Chem Soc., 83, 1363 (1903) 308 Nagel and Mertens, Ber., 72, 985 (1939) 309 Curtius and Hoffmann, J prakt Chem., 96, 202 (1918) 31 " ° Curtius and Hechtenberg, J prakt Chem., 105, 319 (1923) 811 Curtius and Hartmann, Ber., 45, 1050 (1912) 112 Curtius and Hesse, J prakt Chem., 62, 232 (1900) 313 Curtius and Thiemann, J prakt Chem., 94, 364 (1916) 314 Muckerman, J prakt Chem., 83, 513 (1911) 815 Ruhemann, Ber., 27, 1661 (1894) 316 Oskerko, Mem Inst Ukrain Acad Sci., 3, 577 (1936) [C A., 31, 7844 (1937)] »« Vogelesang, Rec trav chim., 62, (1943) [C A., 39, 1393 (1945)] 269 THE CURTIUS REACTION 818 447 Stollf, Nieland, and Merkle, J prakt Chem., 117, 185 (1927) Hurd and Spenee, J Am Chem Soc., 49, 266 (1927) 820 Stolle, Ber., 43, 2468 (1910) 321 Stolle and Krauch, Ber., 47, 728 (1914) 322 Stolle and Merkle, J prakt Chem., 119, 275 (1928) 823 Buchman, Keims, Skei, and Schlatter, / Am Chem Soc., 64, 2696 (1942) 824 Diels, Blom, and Koll, Ann., 443, 246, 257 (1925) 326 Skita and Rossler, Ber., 72, 461 (1939) 326 Alder, Stein, Rolland, and Schulze, Ann., 514, 211 (1934) 327 Alder and Wuidemuth, Ber., 71, 1956 (1938) 328 Vanghelovici, Bui Soc Chim Romdnia, 19A, 35 (1937) [C A., 33, 639 (1939)] 829 Bondi and Miiller, Z physiol Chem., 47, 499 (1906) "^Windaus, Schramme, and Jensen, Ber., 57, 1875 (1924) 331 Windaus and Eiokel, Ber., 57, 1871 (1924) 332 Cook, Graham, Cohen, Lapaley, and Lawrencq, / Chem Soc., 1944, 322 333 Aggarwal, Khera, and Ray, J Chem Soc., 1930, 2354 334 C u r t i u s a n d J o r d a n , J prakt Chem., , 297 (1901) 336 San a n d K a o , Science Repts Natl Tsing Hua Univ., A , 525 (1936) [C A , , 3889 (1937)] 836 Darapsky, J prakt Chem., 96, 321 (1917) 337 Sah and Tseu, J Chinese Chem Soc., 5, 134 (1937)! 338 Jansen, Rec trav chim., 50, 291 (1931) 339 Barger and Ewins, J Chem Soc., 97, 2253 (1910) 340 Manske and Holmes, J Am Chem Soc., 67, 95 (1945) 341 Bernstein and Whitmore, J Am Chem Soc., , 1324 (1939) 342 Jones and Wallis, / , Am Chem Soc., 48, 169 (1926) 343 Wallis, J Am Chem Soc, 51, 2982 (1929) 844 Mayer and Schnecko, Ber., 56, 1408 (1923) 346 Stuart and Mosettig, J Am Chem Soc, 62, 1110 (1940) 346 van de Kamp, Burger, and Mosettig, J Am Chem Soc, 60, 1321 (1938) 347 Curtius and Marangolo, J prakt Chem., 94, 331 (1916) 348 Curtius and Kenngott, J prakt Chem., 107, 99 (1924) -34» Stoermer, Ann., 313, 86 (1900) 350 Wedel, Ber., 33, 766 (1900) 351 Curtius and Miiller, Ber., 34, 2794 (1901) 382 Schroeter, Frdl., 10, 1309 (1910-12) 363 Darapsky and Berger, J prakt Chem., 147, 161 (1936) 364 Borsche and Hahn, Ann., 537, 236 (1939) ' " Kindlmann, Oesterr Chem Ztg., 42, 15 (1939) [C A., 33, 6275 (1939)] 366 Stolle and Stevens, / prakt Chem., 69, 366 (1904) 367 Darapsky and Gaudian, J prakt Chem., 147, 43 (1936) 358 Stoermer, Ber., 42, 3133 (1909) 869 Schiemann and Baumgarten, Ber., 70, 1416 (1937) 360 Curtius and Foerster, J prakt Chem., 64, 324 (1901) 361 Sah and Wu, Science Repts Natl Tsing Hua Univ., A3, 443 (1936) [C A., 30, 8148 (1936)] 382 Sah'and Wu, / Chinese Chem Soc, 4, 513 (1936) [C A., 31, 3891 (1937)] 363 Kao, Fang, and Sah, J Chinese Chem Soc, 3, 137 (1935) [C A., 29, 6172 (1935)] 364 Kao, Science Repts Natl Tsing Hua Univ., A3, 555 (1936) [C A., 31, 3825 (1937)] 386 Chen and Sah, / Chinese Chem Soc.,-i, 62 (1936); Kao, Tao, Kao, and Sah, ibid., 4, 69 (1936) [C A., 30, 8074 (1936)] 366 Sah and Chang, Rec trav chim., 58, (1939) 367 Wang, Kao, Kao, and Sah, Science Repts Nail Tsing Hua Univ., A3, 279 (19351 [C A., 30, 2875 (1936)] 388 Sah, Kao, and Wang, J Chinese Chem Soc, 4, 193 (1936) 889 Sah and Hsu, Rec trav, chim., 59, 349 (1940) 319 448 ORGANIC REACTIONS *"> Sah and Young, Rec trav chim., 59, 357, 364 (1940) [C A., 35, 4363 (1941)] 871 Sah, Rec trav chim., 59, 231, 248 (1940) 872 Sah and Woo, Rec trav chim., 58, 1013 (1939) " ' C h e n , J Chinese Chem Soc, 3, 251 (1935) 874 Sah and Chiao, Rec trav chim., 58, 595 (1939) "• Sah, Rec trav chim., 58, 582 (1939) 878 Vaailevsku, Bloshtein, and Kustrya, J Gen Chem (U.S.S.R.), 5, 1652 (1935) [C A., 30, 3416 (1936)] 877 Stolle and Bambach, J prakt Chem., 74, 13 (1906) 878 Sah and Chang, Ber., 69, 2762 (1936) ""Brunner and Wohrl, Monatsh., 63, 374 (1933) 880 Seka and Fuchs, Monatsh., 57, 63 (1931) ^ P e p e , J prakt Chem., 126, 241 (1930) 882 Wegscheider and Rusnov, Monatsh., 24, 378 (1903) S88 Bondi, Z, physM Chem., 52, 170 (1907) 884 Teppema, Rec trav chim., 42, 30 (1923) 886 Heller, Ber., 48, 1183 (1915) "•Heller, Goring, Kloss, and Kohler, J prakt Chem., I l l , 36 (1925) ^ K r a t z , / prakt Chem., 53, 210 (1896) ^Labriola and Felitte, Anales asoc quim argentina, 32, 57 (1944) [C A., 39, 1405 (1945)] 889 Hsing and Adams, J Am Chem Soc, 58, 587 (1936) 890 Sah, J Chinese Chem Soc, 5, 100 (1937) [C A., 31, 4655 (1937)] """Franzen and Eichler, J prakt Chem., 78, 164 (1908) 892 Burger and Mosettig, J Am Chem Soc, 56, 1745 (1934) ^ ' K n o r r and Horlein, Ber., 40, 2040 (1907) 894 von Braun, Manz, and Kratz, Ann., 496, 170 (1932) 895 Curtius and Dorr, J prakt Chem., 125, 425 (1930) 896 Blioke, Warzynski, Faust, and Gearien, J Am Chem Soc, 66, 1675 (1944) ""Blicke, Faust, Warzynski, and Gearien, J Am Chem Soc, 67, 205 (1945) 898 Blicke, Gearien, Warzynski, and Faust, J Am Chem Soc, 67, 240 (1945) 399 Metzger and Fischer, Ann., 527, (1937) 4°° Fischer and Plieninger, Z physiol Chem., 274, 231 (1942) [C A., 38, 1231 (1944)] 401 Fiaoher and Dietl, Ann., 547, 86 (1941) 402 Menon and Robinson, J Chem Soc, 1931, 773 408 Menon, Perkin, and Robinson, J Chem Soc, 1930, 830 ^Siddiqui, Proc Indian Acad Sci., 11A, 268 (1940) [C A., 34, 6295 (1940)] 406 Seka, Ber., 57, 1527 (1924) ôằ Leuchs and Gladkorn, Ber., 56, 1780 (1923) " •"Hofmann, J\ Am Chem Soc, 66, 157 (1944) 408 Archer and Pratt, J Am Chem Soc, 66, 1656 (1944) ^Freundler, Bull soc chim., [3] 17, 419 (1897) 410 Marquis, Ann chim., [8] 4, 196, 283 (1905) 411 Stork, / Am Chem Soc, 67, 884 (1945) 412 Darapsky and Stauber, J prakt Chem., 146, 209 (1936) 418 Stoermer and Konig, Ber., 39, 492 (1906) 414 Stoermer and Calov, Ber., 34, 770 (1901) 415 Mayer and Krieger, Ber., 55, 1659 (1922) 4Ua Knorr, Ber., 37, 3520 (1904) 4U Seka and Preissecker, Monatsh., 57, 71 (1931) 417 Balaban, J Chem Soc., 1930, 268 *" Freri, Oast chim Hal., 62, 459 (1932) [C A., 26, 5952 (1932)] 4Ute Jensen and Hanson, Dansk Tids Farm., 17, 189 (1943) [C A., 39, 2058 (1945)] 4U Curtius and Klavehn, / prakt Chem., 125, 498 (1930) 410 Meyer and Mally, Monatsh., 33, 393 (1912) 411 Curtius and Mohr, Ber., 31, 2494 (1898) THE CURTIUS REACTION 422 449 Fox and Field, J Bid Chem., 147, 651 (1943) Mohr, Ber., 33, 1114 (1900) Thielepape, Ber,, 55, 127 (1922) 426 Byd6wna, Roczniki Chem., 12, 89 (1932) [C A., 27, 298 (1933)] 426 Borsche, Doeller, and Wagner-Roemmich, Ber., 76, 1099 (1943) [C A., 38, 4947 (1944)] 427 John and Grossmann, Ber., 68, 2799 (1925) 428 Robinson and Tomlinson, / Chem Soc, 1934, 1524 429 John, Grossmann, and Fisohl, Ber., 59, 1447 (1926) 430 John and Ottawa, J prakt Chem., 133, 13 (1932) 431 Htlbner, Ber., 39, 982 (1906) 432 J o h n , / prakt Chem., , 314 (1931) 433 John and Ottawa, / prakt Chem., 131, 301 (1931) 434 John and Sohmit, J prakt Chem., 132, 15 (1932) 435 Feist and Kuklinski, Arch Pharm., 274, 244 (1936) [C A., 30, 4863 (1936)] 436 John and Andraschko, J prakt Chem., 128, 180 (1930) 437 G Farbenindustrie, Ger pat., 492,250 [Frdl 16, 2682 (1931)] 438 I G Farbenindustrie, Swiss pat., 148,955 {Chem Zentr., 1932 I, 2239] 438 John and Lukas, / prakt Chem., 130, 314 (1931) 440 John and Andraschko, J prakt Chem., 128, 201 (1930) 441 John and Lukas, J prakt Chem., 130, 304 (1931) 442 Diels and Thiele, Ann., 543, 79 (1939) 443 E i s l e b , Med u Chem Abhandl med.-chem Forschungsstatten I G Farbenind., , (1936) [C A , , 5804 (1937)] 444 J o h n a n d S c h m i t , J prakt Chem., 3 , (1932) 446 Barnum and Hamilton, J Am Chem Soc, 64, 540 (1942) 449 Sandoz Ltd., Belg pat., 445,225 (1942) [C A., 39, 532 (1945)] 447 John and Andraschko, J prakt Chem., 128, 223 (1930) 448 Darapsky and Heinrichs, J prakt Chem., 146, 307 (1936) 449 Todd, Bergel, Fraenkel-Conrat, and Jacob, J Chem Soc., 1936, 1601 4M Borsche and Doeller, Ann., 537, 44 (1939) 461 Piutti and Marini, Gazz chim Hal., 66,'"270 (1936) 462 Holdsworth and Lions, / Proc Roy Soc N S Wales, 70, 431 (1937) [C A., 31, 6653 (1937)] 463 Mohunta and Ray, J Chem Soc., 1934, 1263 464 Bergmann and Fruton, J Biol Chem., 117, 189 (1937) 466 Newman, J Am Chem Soc, 57, 732 (1935) 423 424 INDEX Numbers in bold-face type refer to experimental procedures Acetamide, reaction with bromine and alkali, 268 Acetamido-3-naphthoyl hydrazide, 355 Acetaminocinnamic acid, 205 Acetic anhydride, as an azlactonizing agent, 202-212 commercial preparation of, 110 Acetoacetic acid and derivatives, preparation from diketene, 127 Acetoacetic ester condensation, Vol I Acetoacetic esters, reaction with thiocyanogen, 248 in Schmidt reaction, 316 Acetone, conversion to ketene, 109-114, 132 mechanism of, 110 in Schmidt reaction, 330, 331 • Acetone quinide, 351 Acetophenone in Willgerodt reaction, Acyl glycines in Erlenmeyer azlactone synthesis, 208 Adamantane-l,3-dicarboxylic ester, 341 |8-Alanine, preparation by Curtius reaction, 347 Alanine ethyl ester hydrochloride, preparation of, 346 Alcohols, in Friedel-Crafts reaction, 1-82 in Willgerodt reaction, 91 Aldehydes, aromatic, alkylation of, 72 preparation of, by Curtius reaction, 343, 345, 350, 356, 384 by Hofmann reaction, 269, 275, 276, 280, 282, 285 reaction with hydrazoic acid, 308, 314, 315, 318 in Willgerodt reaction, 91 Aldoketenes, 108-140 Alkylation, by free radicals, 15 95,97 by Friedel-Crafts reaction, 1-82 alkylating agents, 4-5 Z-Acetylasparagine, 275 Acetylenes, reaction with thiocyanogen, relative reactivity of, aromatic compounds alkylated, 246-248 catalyst assistants, table, 263 catalysts, relative activity of, in Willgerodt reaction, 86, 88 dealkylation, 14, 16 Acetylenic amides in Hofmann reaction, destructive alkylation, 276 experimental conditions, 16 2-Acetylnaphthalene in Kindler-Willexperimental procedures, 16-19 gerodt reaction, 97 isomerization of alkyl groups, N-Acetylnaphthimidazolone, 355 limitations, 13 1-Acetylpyrene in Willgerodt reaction, 96 mechanism, Acid halides, dehydrohalogenation of, migration of halogen atoms, 14 124-126, 138, 139, 140 orientation, 8-M) tables, 126 in Schmidt reaction, 314 rearrangement of alkyl groups, 6-8 Acids, aromatic, alkylation of, 72 related processes, 12, 14 conversion to amines, 267-449 tables, 21-82 Active methylene compounds in Will- Alkylbenzenes, alkylation of, 48-51 gerodt reaction, 90 sulfonation of, 150-153, 156, 168-179 Acylamino acids, azlactonization of, Alkyl halides, in Friedel-Crafts reaction, 1-82 202-205 451 452 INDEX Alkyl halides, relative reactivity of, Alkylhalobenzen.es, sulfonation of, 154155, 171-179 Alkylthiocarbonic acids, preparation of amides of, 250 Allyl alcohol in Friedel-Crafts alleviations, Allyl chloride in Friedel-Crafts alkylations, Aluminum alkoxides, reduction with, Vol II Aluminum chloride, 1-82 procedure for use of, in Friedel-Crafts reaction, 16 reaction with benzene, 21 Amides, Hofmann reaction of, 267-306 , optically active, in Hofmann reaction, 270-271 preparation of, 83-107, 377 reaction with hydrazoic acid, 322 Amidoximes, reaction with hydrazoic acid, 322 Amidrazones, 362 A ruination of heterocyclic bases by alkali amides, Vol I Amines, aliphatic, reaction with thiocyanogen, 247 aromatic, alkylation of, 73-75 reaction with thiocyanogen, 243-245 -tables, 258-261 preparation of, by Curtius reaction, 337-149 by Hofmann reaction, 267-306 by Schmidt reaction, 307-336 tertiary, as dehydrohalogenating agents, 124-126 Amino acids, preparation of, 218-220, 275, 284, 312, 316, 318, 346, 359, 384, 385 acyl derivatives, 354 deacylation of, by hydrazine, 355 racemization of, 203, 214 amides, from azlactones, 215 azlactonization of, 202, 204, 205, 211, 212 in Curtius reaction, 353 esters, from azlactones, 215 TO-Aminoazobenzene, 387 Aminobenzothiazoles, formation of, 244, 267 l-Amino-2-butanone, 345 4-Aminocamphane, 274 l-Amino-2-cycloheptene, 276 Aminodihydrocampholytic acids, 272 • 2-Amino-4,6-dimethylbenzothiazole, 256 2-Amino-6-ethoxybenzothiazole, 267 Amino group, primary aromatic, replacement by hydrogen, Vol II 16-Aminohexadecanoic acid, lactam of, 330 Aminomethylcyclohexanes, 274 o-Aminophenol, 277 o-Aminophthalhydrazide, 348 Aminopyridines, 279 Aminoquinolines, 279 Aminoveratrole, 277 Ammonium polysulfide, 84, 91, 96, 96 Ammonium sulfide, 92 Ammonium thiooyanate, reaction with azlactones, 213 • Anhydrides, cyclic, reaction with hydrazine, 347 in Schmidt reaction, 314 Aniline, alkylation of, 73 reaction with thiocyanogen, 266 Anisole, alkylation of, 14 Anthracene, sulfonation of, 149, 158159, 188 Anthranilic acid, 277 derivatives, 278 Anthranils, reaction with hydrazine, 369 Anthranilyl hydrazide, 353 Anthraquinone, sulfonation of, 145 Antimony compounds, reaction with thiocyanogen, 241 Z-Arabinosamide, 276
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