Organic Reactions Volume 4 - Sciencemadness Dot Org

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10 ORGANIC REACTIONS it likewise dissociates into its components. On the other hand, the adducts from cyclohexadiene and its derivatives are much more thermostable. Indeed, this difference in properties has been suggested as a means of differentiating between five- and six-carbon cyclic dienes m (compare Chapter 2). The reactions between maleic anhydride and a number of polycyclic hydrocarbons containing the anthracene nucleus are truly reversible. 123 Identical mixtures of hydrocarbon, maleic anhydride, and adduct were obtained by heating xylene solutions of either the pure adduct or the components in equimolecular proportion. The quantitative results of this investigation are discussed in a later section (p. 28). The course taken by dissociation of maleic anhydride adducts is in keeping with the thermal decomposition of other bicyclic compounds. It has been observed 124 ~ 126 that the bonds that undergo pyrolytic rupture are those once removed from unsaturation rather than those adjacent to unsaturation (the double bond rule). In a typical maleic anhydride a /3 aQ Il O adduct the ou-bonds are strong, whereas the /3-bonds are weak and subject to thermal cleavage. Stereochemical Selectivity of the Reaction. The Diels-Alder reaction exhibits pronounced stereochemical selectivity. The configuration of a given adduct conforms to the following general principles, 27, m commonly known as the Alder rules. 1. The addition of a dienophile to a diene is a purely cis addition. The relative positions of substituents in the dienophile are retained in the adduct. For example, maleic anhydride reacts with anthracene to yield the m-anhydride adduct IX, while fumaric acid yields the transdicarboxylic acid adduct X. 128a * 22 Alder and Rickert, Ann., 524, 180 (1936). 123 Bachmann and Kloetzel, J. Am. Chem. Soc, 60, 481 (1938). 124 Littmann, J. Am. Chem. Soc, 57, 586 (1935). 125 Norton, Chem. Revs., 31, 387, 469 (1942). 126 Allen and Van Allan, J. Am. Chem. Soc., 65, 1384 (1943). 127 Alder and Stein, Angew. Chem., 50, 510 (1937). 128 (a) Bachmann and Scott, J. Am. Chem. Soc, 70, 1458, 1462 (1948); (&) Bachmann and Chemerda, /, Am, Chem. Soc,t 70, 1468 (1948).
Maleic anhydride Fumaric anhydride DIENE SYNTHESIS I 11 H—C—C00H HOOC—C—H 2. In the reaction of maleic anhydride with a cyclic diene, such as cyclopentadiene, two modes of addition are theoretically possible, leading to the formation of an u endo" configuration (XI) or an "exo" configuration (XII) respectively. Actually, the endo configuration (XI) is produced exclusively. 127 ' 129 This "one-sided" addition indicates that immediately before combination the components must always be oriented in exactly the same manner with respect to each other; that is, of the two possible orientations, A and B, A is favored. The favored orientation (A) corresponds to the maximum accumulation of double bonds (the double bonds of the carbonyl groups are in- 129 Alder, Stein, Buddenbrock, Eckardt, Frercks, and Schneider, Ann., 514, 1 (1934). XII
Page 1 and 2: Organic Reactions VOLUME IV EDITORI
Page 3 and 4: PREFACE TO THE SERIES In the course
Page 5 and 6: CONTENTS CHAPTER PAGE 1. THE DIELS-
Page 7 and 8: CHAPTER 1 THE DIELS-ALDER REACTION
Page 9 and 10: 2. C6H5CH=CHA. DIENE SYNTHESIS I S
Page 11 and 12: DIENE SYNTHESIS I 5 ^Lehmann, Ber.,
Page 13 and 14: DIENE SYNTHESIS I 7 and IV for thes
Page 15: DIENE SYNTHESIS I 9 tion of the com
Page 19 and 20: DIENE SYNTHESIS I 13 jugated system
Page 21 and 22: DIENE SYNTHESIS I 15 Mesaconic (met
Page 23 and 24: DIENE SYNTHESIS I 17 An interesting
Page 25 and 26: DIENE SYNTHESIS I 19 CH2 CH3 O Il I
Page 27 and 28: CH C2H5 I CH2 XXX DIENE SYNTHESIS I
Page 29 and 30: DIENE SYNTHESIS I cyclic dienes fre
Page 31 and 32: DIENE SYNTHESIS I 25 Although l,2,3
Page 33 and 34: DIENE SYNTHESIS I 27 Certain types
Page 35 and 36: DIENE SYNTHESIS I 29 Hydrocarbons c
Page 37 and 38: DIENE SYNTHESIS I 31 Diels-Alder re
Page 39 and 40: DIENE SYNTHESIS I 33 give LXXX. If
Page 41 and 42: DIENE SYNTHESIS I 35 Numerous other
Page 43 and 44: DIENE SYNTHESIS I 37 Maleic anhydri
Page 45 and 46: DIENE SYNTHESIS I 39 Indole derivat
Page 47 and 48: DIENE SYNTHESIS I 41 anhydride. In
Page 49 and 50: DIENE SYNTHESIS I 43 tetrahydronaph
Page 51 and 52: DIENE SYNTHESIS I 45 TABLE III—Co
Page 53 and 54: DIENE SYNTHESIS I 47 TABLE IV ADDtr
Page 55 and 56: Cycloheptatriene DIENE SYNTHESIS I
Page 57 and 58: BIENE SYNTHESIS I 51 TABLE V—Cont
Page 59 and 60: DIENE SYNTHESIS I 53 TABLE VI ADDTJ
Page 61 and 62: BIENE SYNTHESIS I 55 TABLE VII—Co
Page 63 and 64: DIENE SYNTHESIS I 57 REFERENCES TO
Page 65 and 66: DIENE SYNTHESIS I 59 422 Diels and
Page 67 and 68:
DIENE SYNTHESIS II 61 PAGE TABLKs O
Page 69 and 70:
DIENE SYNTHESIS II 63 The configura
Page 71 and 72:
DIENE SYNTHESIS II 65 Aromatic comp
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DIENE SYNTHESIS II 67 55%). 13 Cycl
Page 75 and 76:
H8Cr H8C JCO2H XSV iOCH, DIENE SYNT
Page 77 and 78:
DIENE SYNTHESIS II 71 additions wit
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DIENE SYNTHESIS II , 73 been report
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DIENE SYNTHESIS II 75 drogenation u
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DIENE SYNTHESIS II 77 Allyl, Vinyl,
Page 85 and 86:
DIENE SYNTHESIS II 79 (XLVII) that
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~r (PH.)* + CO2H CO5 :H CO2CH3 CO2C
Page 89 and 90:
DIENE SYNTHESIS II 83 covered as th
Page 91 and 92:
DIENE SYNTHESIS II 85 anhydride fro
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DIENE SYNTHESIS II 87 or even preve
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DIENE SYNTHESIS II 89 SELECTION OF
Page 97 and 98:
DIENE SYNTHESIS II 91 liquid separa
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Acetylenic Dienophile Ethyl acetyle
Page 101 and 102:
DIENE SYNTHESIS II 95 TABLE IV YIEL
Page 103 and 104:
1-Diethylaminobutadiene 1,1-Dimeth
Page 105 and 106:
1-Methylbutadiene (piperylene) l-Me
Page 107 and 108:
1,5,5,6-Tetramethylcyclohexadiene (
Page 109 and 110:
1-Methyl-l-phenylbtrfcadiene l-Met
Page 111 and 112:
Benzalacetophenone Bicyclohexenyl r
Page 113 and 114:
f$-Benzoylacrylic acid, 2, b-dimeth
Page 115 and 116:
Bicyelohexenyl c r 2,3-Dimethylbuta
Page 117 and 118:
Isoprene Cinnamic acid,2,6~ dimetho
Page 119 and 120:
Isoprene Cinnamic acid,omeihoxy- (t
Page 121 and 122:
Coumann Butadiene 2,3-Dimethylbutad
Page 123 and 124:
1,3-Dimethylbutadiene 1,4-Dimethyl
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1,1,3-Trimethylbutadiene 1,1,4-Tri
Page 127 and 128:
2,3-Dimethylbutadiene Croio7toladon
Page 129 and 130:
2,3-Dimethylbutadiene2,3-Diphenylbu
Page 131 and 132:
Cyclopentadiene 2,3-Dimethylbutadie
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Z}4rDihydro-5-bromo- 1\8-dimethoxy-
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Z^Dihydro-l-ftieihoxy-2-naphthoic a
Page 137 and 138:
Ethyl ethytidenemalonate Butadiene
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1,4-Diphenylbutadiene2,3-Diphenylbu
Page 141 and 142:
6 The product gradually decomposes
Page 143 and 144:
Cyclohexadiene Cyclopentadiene 2,3-
Page 145 and 146:
p-Nitrostyrenej 3,4-cfomethoxy- 2,3
Page 147 and 148:
Dihydrothiophene-1 - dioxide Butadi
Page 149 and 150:
Piperylcyclone Tetraphenyleyelopent
Page 151 and 152:
AUyI iodide Cyclopentadiene AUyI is
Page 153 and 154:
Tetraphenylcyclopentadienone Pheney
Page 155 and 156:
Indene a,a , -Diphenyl-/3,j3'isoben
Page 157 and 158:
1,5,5-Trimethyleyclopentadiene Tri
Page 159 and 160:
Addends Acetylene Tetraphenylcyelop
Page 161 and 162:
Trimethylcyclopentadiene? (Damsky)
Page 163 and 164:
Cyclopentadiene 9,10-Dibromoaiithra
Page 165 and 166:
Propargyl aldehyde 2,3-Dimethylbuta
Page 167 and 168:
Addends Acetylenedicarboxylic acid
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I-* SO N-ce-Dimethylindole 3,5-Dim
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Oi N-Methylindole a-Methylpyrrole N
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OS Quinaldine Quinoline CX | JCH. j
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2,3,4-Trimethylpyrrole H3Cp CCO2CH3
Page 177 and 178:
1,3-Dimethylbutadiene 1,1,3-Trimet
Page 179 and 180:
DIENE SYNTHESIS II 110 Diels and Al
Page 181 and 182:
PREPARATION OF AMINES BY REDUCTIVE
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Page 185 and 186:
Page 187 and 188:
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Page 191 and 192:
Page 193 and 194:
Page 195 and 196:
Page 197 and 198:
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Page 205 and 206:
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Page 215 and 216:
CH3CH=CHCHO CH3(CHS)2CH=C(CH2CH3)CH
Page 217 and 218:
(CHs)2C=CHCOCH3 (CH3)2C=CH(CH2)2COC
Page 219 and 220:
CH3COCH3 CH3COCH3 CH3COCH2CH3 CH3CO
Page 221 and 222:
H2N (CH2) 2NH2 H2N(CH2)2NH2 H2N{CH2
Page 223 and 224:
P-HOC6H4CH2CH(CH3)NH2 CH2O P-CH3OC6
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CH3NH2 CH3NH2 CH3NH2 CH3NH2 CH3NH2
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HO(CH2)2NH2 HO(CHa)2NH2 HO(CH2)2NH2
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(GHg)2COHCH2NH2 (CHs)2COHCH2NH2 CH3
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Amine, Nitro, Nitroso, or Azo Compo
Page 233 and 234:
P-HOC6H4NH2 P-HOC6H4NH2 - P-HOC6H4N
Page 235 and 236:
CeHgNHs C6H5NH2 C6HgNH2 C6H5NH2 P-C
Page 237 and 238:
HN=C(CH3)CO2H CH2 SehifPs Base / \
Page 239 and 240:
CH3CH2N=CHC6H5J CH3(CH2)2N=CHCH3f C
Page 241 and 242:
C6HuN=CH(CH2)2CH3t C6Hi1N=CH(CH2)2C
Page 243 and 244:
p-C6H5(CH2)2N=CHC6H40H f p-C6H5(CH2
Page 245 and 246:
C6H5N-=CHCH2CH(CH3)2f C6H5N=CH(CHOH
Page 247 and 248:
2,4'-CH3C6H4N=CHC6H4CIf 2,4 / -CH3C
Page 249 and 250:
0-CH3OC6H4N=CH(CHOH)4CH2OH m-CH3OC6
Page 251 and 252:
Amine Used CH3CH2NH2 Amine Used CH3
Page 253 and 254:
Nitro Compound Used ^HOC6H4NO2 P-H2
Page 255 and 256:
C6H5CHOHCH2CH(CH3)- NHCH3 C6H5CHOHC
Page 257 and 258:
Amine Used (CHs)2NH (CHs)2NH (CH3)2
Page 259 and 260:
C6H5NH(CHs)2CH3 C6H5NH(CHs)3CH3 C6H
Page 261 and 262:
Page 263 and 264:
THE ACYLOINS 257 euphony and to avo
Page 265 and 266:
THE ACYLOINS 259 A mechanism simila
Page 267 and 268:
THE ACYLOINS 261 There is a strikin
Page 269 and 270:
TSE ACYLOINS 263 upon the rigid exc
Page 271 and 272:
THE ACYLOINS 265 carbonate. This pr
Page 273 and 274:
THE ACYLOINS 267 is thought that py
Page 275 and 276:
CHAPTER 6 THE SYNTHESIS OF BENZOINS
Page 277 and 278:
THE SYNTHESIS OF BENZOINS 271 are i
Page 279 and 280:
THE SYNTHESIS OF BENZOINS 273 metri
Page 281 and 282:
THE SYNTHESIS OF BENZOINS 275 Symme
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THE SYNTHESIS OF BENZOINS 277 cent
Page 285 and 286:
THE SYNTHESIS OF BENZOINS 279 Since
Page 287 and 288:
Benzoin Reaction 1 * 54 Benzoin Ben
Page 289 and 290:
LESS STABLE V C6H5COCHOHC6H4OCH3^ V
Page 291 and 292:
THE SYNTHESIS OF BENZOINS 285 66-86
Page 293 and 294:
THE SYNTHESIS OF BENZOINS 287 Aliph
Page 295 and 296:
THE SYNTHESIS OF BENZOINS 289 the i
Page 297 and 298:
THE SYNTHESIS OF BENZOINS 291 The e
Page 299 and 300:
THE SYNTHESIS OF BENZOINS 293 effec
Page 301 and 302:
THE SYNTHESIS OF BENZOINS 295 The e
Page 303 and 304:
THE SYNTHESIS OF BENZOINS 297 ethox
Page 305 and 306:
THE SYNTHESIS OF BENZOINS 299 C6HBC
Page 307 and 308:
Formula CI5HHO2 CI6HHO3 CI6HHO3 CI5
Page 309 and 310:
Formula C19H22O2 C20H1GO2 C20H24O2
Page 311 and 312:
CHAPTER 6 SYNTHESIS OF BENZOQUINONE
Page 313 and 314:
SYNTHESIS OF BENZOQUINONES BY OXIDA
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Page 321 and 322:
Page 323 and 324:
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Page 327 and 328:
Page 329 and 330:
Page 331 and 332:
Page 333 and 334:
Page 335 and 336:
Page 337 and 338:
Page 339 and 340:
SYNTHESIS OF BENZOQUINpNES BY OXIDA
Page 341 and 342:
Page 343 and 344:
Page 345 and 346:
Page 347 and 348:
Page 349 and 350:
Page 351 and 352:
Quinone 5,6-Dimethoxy-2hydi oxyquin
Page 353 and 354:
Quinone 3-Hydroxythymoqui- J none |
Page 355 and 356:
Quinone 2-Methoxy-6-tridecylquinone
Page 357 and 358:
Page 359 and 360:
Page 361 and 362:
Page 363 and 364:
Page 365 and 366:
Page 367 and 368:
Page 369 and 370:
ROSENMUND REDUCTION 363 For accompl
Page 371 and 372:
ROSENMUND REDUCTION 365 acid in alm
Page 373 and 374:
ROSENMUND REDUCTION 367 The Hydroge
Page 375 and 376:
ROSENMUND REDUCTION 369 solution of
Page 377 and 378:
ROSENMUND REDUCTION 371 TABLE I ALI
Page 379 and 380:
Acid Chloride Benzoyl chloride p-Ca
Page 381 and 382:
Acid Chloride 3-Furoic- 4~Carbometh
Page 383 and 384:
ROSENMUND REDUCTION 377 106 Shoesmi
Page 385 and 386:
THE WOLFF-KISHNER REDUCTION 379 INT
Page 387 and 388:
THE W0LFF-KISHNER REDUCTION 381 mol
Page 389 and 390:
THE WOLFF-KISHNER REDUCTION 383 dan
Page 391 and 392:
THE WOLFF-KISHNER REDUCTION 385 Sod
Page 393 and 394:
THE WOLFF-KISHNER REDUCTION 387 TAB
Page 395 and 396:
THE WOLFF-KISHNER REDUCTION 389 Red
Page 397 and 398:
THE WOLFF-KISHNER REDUCTION 391 Dir
Page 399 and 400:
C7Hi2O C7H14O C7H0O2 C7H8O2 C7H6O4
Page 401 and 402:
C9Hi0O C9Hi2O C9Hi4O Formula C9Hi6O
Page 403 and 404:
Formula Ci0Hi6O CioHisO Ci0H6O2 Ci0
Page 405 and 406:
Formula CnH16O CnHi8O CnHi6O2 CnHi8
Page 407 and 408:
Formula Ci3H22O C13H10O3 Ci3Hi8O3 C
Page 409 and 410:
Formula CI6HHO2 CI6HHO3 CI6H24O3 C1
Page 411 and 412:
Formula Ci8H13ON Ci8H2IO3N Ci8Hi9O4
Page 413 and 414:
Formula C2IH34O C21H30O2 C21H32O2 C
Page 415 and 416:
Formula C23H32O7 C23Hi7ON C24H3603
Page 417 and 418:
Formula C25H40O7 C26Hi6O C26H44O C2
Page 419 and 420:
Formula C29H46O C29H46O2 C29H48O3 C
Page 421 and 422:
Formula C32H52O3 C32H46O4 C32H50O4
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THE WOLFF-KISHNER REDUCTION 417 133
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Page 429 and 430:
DEX Numbers in bold-face type r :ef
Page 431 and 432:
Dialkylaminoquinonedisulfonates, 35
Page 433 and 434:
3-Methylpyrene, preparation by Wolf
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