Organic Reactions Volume 4 - Sciencemadness Dot Org

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92 ORGANIC REACTIONS the main fraction is collected at 135-145°, both at 0.1 mm. The distillate solidifies in the receiver to a waxy, camphorlike solid; weight 4 g. The product, after thorough pressing on a clay plate, melts at 141-142°. The residue remaining in the distillation flask is crystallized from ethyl acetate. The crystalline product, m.p. 218°, is the result of the addition of two moles of cyclopentadiene to one of A 2 -dihydrothiophenedioxide. Dehydro-norbornyl Acetate (XLVI, R = H)—Addition of Vinyl Acetate to Cyclopentadiene. 89 One hundred grams of freshly distilled cyclopentadiene is heated in an autoclave with 150 g. (50% excess) of vinyl acetate at 185-190° for ten hours. From the oily reaction mixture 72 g. of vinyl acetate is recovered by distillation and the remaining oil is fractionated in vacuum. The fraction boiling at 73-77°/14 mm. is dehydro-norbornyl acetate; yield 100 g. (79%). A fraction boiling at 140-145°/14 mm. is the result of the addition of a second mole of cyclopentadiene to the primary adduct. Diethyl 3,6~Diphenyl-A M -dihydrophthalate—Addition of Ethyl Acetylenedicarboxylate to ^ran5-^ran5-l,4-Diphenylbutadiene. 63 A mixture of 4.4 g. of 2rans~£raws~l,4~diphenylbutadiene and 3.7 g. of ethyl acetylenedicarboxylate is heated at 140-150° for five hours. The reaction mixture solidifies to a mass of glistening prisms; m.p. 88°, yield 90%. Dimethyl 9,10-Dihydroanthracene»9,10-endo»a,iS»maleate (LIII)— Addition of Methyl Acetylenedicarboxylate to Anthracene, 60 A mixture of 5 g. of anthracene and 5 ml. of methyl acetylenedicarboxylate is heated cautiously until a lively reaction sets in. In a short time, the reaction is complete. When the mixture is cooled it sets to a solid mass. To remove small traces of oily material the solid is pressed on a clay plate and then crystallized from acetonitrile and finally from methanol, m.p. 160-161°; yield, quantitative. From ethyl malonate the adduct crystallizes in stout crystals. ABBREVIATIONS USED IN TABLES I-XI A -= acid chloride. B = methyl ester. C « * ethyl ester. D « - the salicylate. Quant. — = quantitative yield. Reflux = - reflux temperature, t. as subscript indicates that the reaction is carried out in a sealed tube or autoclave.
Acetylenic Dienophile Ethyl acetylenedicarboxylate Methyl acetylenedicarboxylate Acetylenediearbonitrile Propiolic acid TABLE I YIELDS OF ADDUCTS FROM ACETYLENIC AND ETHYLENIC DIENOPHILES Diene Isosafrole Tetraphenyleyclopentadienone 1,4-Diphenylbutadiene Anthracene Cyclohexadiene 9,10-Dibromoanthracene 2,5-Dimethylfuran Tetraphenyleyclopentadienone Cyclopentadiene Cyclopentadiene * References 69-116 are listed on pp. 172-173. Temperature, 0 C 100 300 140 20 0 — 100 200
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Organic Reactions VOLUME IV EDITORI
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PREFACE TO THE SERIES In the course
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CONTENTS CHAPTER PAGE 1. THE DIELS-
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CHAPTER 1 THE DIELS-ALDER REACTION
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2. C6H5CH=CHA. DIENE SYNTHESIS I S
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DIENE SYNTHESIS I 5 ^Lehmann, Ber.,
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DIENE SYNTHESIS I 7 and IV for thes
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DIENE SYNTHESIS I 9 tion of the com
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Maleic anhydride Fumaric anhydride
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DIENE SYNTHESIS I 13 jugated system
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DIENE SYNTHESIS I 15 Mesaconic (met
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DIENE SYNTHESIS I 17 An interesting
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DIENE SYNTHESIS I 19 CH2 CH3 O Il I
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CH C2H5 I CH2 XXX DIENE SYNTHESIS I
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DIENE SYNTHESIS I cyclic dienes fre
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DIENE SYNTHESIS I 25 Although l,2,3
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DIENE SYNTHESIS I 27 Certain types
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DIENE SYNTHESIS I 29 Hydrocarbons c
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DIENE SYNTHESIS I 31 Diels-Alder re
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DIENE SYNTHESIS I 33 give LXXX. If
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DIENE SYNTHESIS I 35 Numerous other
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DIENE SYNTHESIS I 37 Maleic anhydri
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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
Page 73 and 74: 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
Page 79 and 80: DIENE SYNTHESIS II , 73 been report
Page 81 and 82: DIENE SYNTHESIS II 75 drogenation u
Page 83 and 84: DIENE SYNTHESIS II 77 Allyl, Vinyl,
Page 85 and 86: DIENE SYNTHESIS II 79 (XLVII) that
Page 87 and 88: ~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
Page 93 and 94: DIENE SYNTHESIS II 87 or even preve
Page 95 and 96: DIENE SYNTHESIS II 89 SELECTION OF
Page 97: DIENE SYNTHESIS II 91 liquid separa
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
Page 125 and 126: 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
Page 133 and 134: Z}4rDihydro-5-bromo- 1\8-dimethoxy-
Page 135 and 136: Z^Dihydro-l-ftieihoxy-2-naphthoic a
Page 137 and 138: Ethyl ethytidenemalonate Butadiene
Page 139 and 140: 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
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Piperylcyclone Tetraphenyleyelopent
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AUyI iodide Cyclopentadiene AUyI is
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Tetraphenylcyclopentadienone Pheney
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Indene a,a , -Diphenyl-/3,j3'isoben
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1,5,5-Trimethyleyclopentadiene Tri
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Addends Acetylene Tetraphenylcyelop
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Trimethylcyclopentadiene? (Damsky)
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Cyclopentadiene 9,10-Dibromoaiithra
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Propargyl aldehyde 2,3-Dimethylbuta
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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
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1,3-Dimethylbutadiene 1,1,3-Trimet
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DIENE SYNTHESIS II 110 Diels and Al
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PREPARATION OF AMINES BY REDUCTIVE
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CH3CH=CHCHO CH3(CHS)2CH=C(CH2CH3)CH
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(CHs)2C=CHCOCH3 (CH3)2C=CH(CH2)2COC
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CH3COCH3 CH3COCH3 CH3COCH2CH3 CH3CO
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H2N (CH2) 2NH2 H2N(CH2)2NH2 H2N{CH2
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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
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P-HOC6H4NH2 P-HOC6H4NH2 - P-HOC6H4N
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CeHgNHs C6H5NH2 C6HgNH2 C6H5NH2 P-C
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HN=C(CH3)CO2H CH2 SehifPs Base / \
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CH3CH2N=CHC6H5J CH3(CH2)2N=CHCH3f C
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C6HuN=CH(CH2)2CH3t C6Hi1N=CH(CH2)2C
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p-C6H5(CH2)2N=CHC6H40H f p-C6H5(CH2
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C6H5N-=CHCH2CH(CH3)2f C6H5N=CH(CHOH
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2,4'-CH3C6H4N=CHC6H4CIf 2,4 / -CH3C
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0-CH3OC6H4N=CH(CHOH)4CH2OH m-CH3OC6
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Amine Used CH3CH2NH2 Amine Used CH3
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Nitro Compound Used ^HOC6H4NO2 P-H2
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C6H5CHOHCH2CH(CH3)- NHCH3 C6H5CHOHC
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Amine Used (CHs)2NH (CHs)2NH (CH3)2
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C6H5NH(CHs)2CH3 C6H5NH(CHs)3CH3 C6H
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THE ACYLOINS 257 euphony and to avo
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THE ACYLOINS 259 A mechanism simila
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THE ACYLOINS 261 There is a strikin
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TSE ACYLOINS 263 upon the rigid exc
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THE ACYLOINS 265 carbonate. This pr
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THE ACYLOINS 267 is thought that py
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CHAPTER 6 THE SYNTHESIS OF BENZOINS
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THE SYNTHESIS OF BENZOINS 271 are i
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THE SYNTHESIS OF BENZOINS 273 metri
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THE SYNTHESIS OF BENZOINS 275 Symme
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THE SYNTHESIS OF BENZOINS 277 cent
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THE SYNTHESIS OF BENZOINS 279 Since
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Benzoin Reaction 1 * 54 Benzoin Ben
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LESS STABLE V C6H5COCHOHC6H4OCH3^ V
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THE SYNTHESIS OF BENZOINS 285 66-86
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THE SYNTHESIS OF BENZOINS 287 Aliph
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THE SYNTHESIS OF BENZOINS 289 the i
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THE SYNTHESIS OF BENZOINS 291 The e
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THE SYNTHESIS OF BENZOINS 293 effec
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THE SYNTHESIS OF BENZOINS 295 The e
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THE SYNTHESIS OF BENZOINS 297 ethox
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THE SYNTHESIS OF BENZOINS 299 C6HBC
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Formula CI5HHO2 CI6HHO3 CI6HHO3 CI5
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Formula C19H22O2 C20H1GO2 C20H24O2
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CHAPTER 6 SYNTHESIS OF BENZOQUINONE
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SYNTHESIS OF BENZOQUINONES BY OXIDA
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SYNTHESIS OF BENZOQUINpNES BY OXIDA
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Quinone 5,6-Dimethoxy-2hydi oxyquin
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Quinone 3-Hydroxythymoqui- J none |
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Quinone 2-Methoxy-6-tridecylquinone
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ROSENMUND REDUCTION 363 For accompl
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ROSENMUND REDUCTION 365 acid in alm
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ROSENMUND REDUCTION 367 The Hydroge
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ROSENMUND REDUCTION 369 solution of
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ROSENMUND REDUCTION 371 TABLE I ALI
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Acid Chloride Benzoyl chloride p-Ca
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Acid Chloride 3-Furoic- 4~Carbometh
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ROSENMUND REDUCTION 377 106 Shoesmi
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THE WOLFF-KISHNER REDUCTION 379 INT
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THE W0LFF-KISHNER REDUCTION 381 mol
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THE WOLFF-KISHNER REDUCTION 383 dan
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THE WOLFF-KISHNER REDUCTION 385 Sod
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THE WOLFF-KISHNER REDUCTION 387 TAB
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THE WOLFF-KISHNER REDUCTION 389 Red
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THE WOLFF-KISHNER REDUCTION 391 Dir
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C7Hi2O C7H14O C7H0O2 C7H8O2 C7H6O4
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C9Hi0O C9Hi2O C9Hi4O Formula C9Hi6O
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Formula Ci0Hi6O CioHisO Ci0H6O2 Ci0
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Formula CnH16O CnHi8O CnHi6O2 CnHi8
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Formula Ci3H22O C13H10O3 Ci3Hi8O3 C
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Formula CI6HHO2 CI6HHO3 CI6H24O3 C1
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Formula Ci8H13ON Ci8H2IO3N Ci8Hi9O4
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Formula C2IH34O C21H30O2 C21H32O2 C
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Formula C23H32O7 C23Hi7ON C24H3603
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Formula C25H40O7 C26Hi6O C26H44O C2
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Formula C29H46O C29H46O2 C29H48O3 C
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Formula C32H52O3 C32H46O4 C32H50O4
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THE WOLFF-KISHNER REDUCTION 417 133
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DEX Numbers in bold-face type r :ef
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Dialkylaminoquinonedisulfonates, 35
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3-Methylpyrene, preparation by Wolf
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