Organic Reactions Volume 4 - Sciencemadness Dot Org

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406 ORGANIC REACTIONS Formula C20Hi6O C20H20O C20H22O C20H28O C20H30O C20H32O C20H40O C20HiSO2 C20H32O2 C20H22O4 C20H2eO4 C20H3o04 C20HS0O5 C20HHON C20H25O3N C2IHi2O C2IHi6O TABLE II—Continued COMPOUNDS REDUCED BY THE WOLFF-KISHNER METHOD Compound 7, y-Diphenyl-a-hydrindone 3-Acetylretene 2-Acetyldmydroretene Dohydroabietinal Dehydroabietinal Abietinal Phenyl n-tridooyl ketone p-Tolyl n-dodecyl ketone 3-Eicosanone 2,1 l-Diketo-9,18-dimcthyl- 1,2,9,10,11,18-hoxahydrochryseno-a 2, ll-Diketo-9,18-diraethyl- 1,2,9,10,11,18-hexahydrochrysone-b Kotomanoyloxido 1,4-Di-p-anisoyibutane Methyl bisdehydromarrianolate aldehyde 7-rncthyl ether Methyl marrianolate aldehyde 7-methyl ether Mothyl lumimarrianolate aldehyde 7-methyl other Diketocassanic aeid 3 (a), 12-Dihydroxy-l 1-kotoetioeholanio acid l,2(ll2)-Naphtho-3-assafluoro- 6-(4-Benzyloxy-3~methoxyphenyl)»2,2-dimethyl-4-piperidone 1,2,6,7~Dibenzofiuoronone 1,2,7,8-Dibenzofluorenone 2,3,5,6-Dibenzofluorenone 2,3,6,7-Dibenzofluorenone 2,3,6,7-Dibenzofluorcnone 3,4,5,6-Dibenzofluorenone 3,4-Benzopyrene-5-aldehyde 2-Phenylacetylfluorene l-Propionyl-3,4-benzophenanthrene2-Propionyl-3,4-benzophenanthrene Normal Normal Normal Normal Normal Normal Normal Normal Normal Normal Normal Product Normal Normal Bisdehydrodoisynolic acid t Doiaynolic acid 7-methyl other Lumidoisynolic acid Normal 3(a),ll,12-Trihydroxyetiocholanic acid Normal None C21 Normal Normal Normal and some of the difluorene Normal Normal § Normal Normal Normal Normal Normal Method WH1WS WS WS WS WS WS ' WD WD WD WH WH WS K WD WD WS WH WD WDJ WD WD WDJ WD WDJ WD WDt WH WD, WS WS WS Yield Good 5OB Poor 7OB 82A 81B 40-50A „ 40A 66A 55A 83B 82A 5OA 50A —- 82A — 10OA O 9OA _ __ __ 39A __ 7OB _ — * References 86a-413 are listed on pp. 416-422. t The crude product was treated with hydrochloric acid to remove the methoxyl group. t No alkaline catalyst was used. § Some of the azine and some 2,2',3,3',6,6',7,7'-tetrabenzo-9,9'-bifluorenyl were also formed. Reference* 293 294 53 270 294a 295 43 129 38 265 265 296 56 297 297 297 298 298a 28 222 299 300 300a 300 299 300 301 299 279 279
Formula C2IH34O C21H30O2 C21H32O2 C2IH34O2 C21H30O3 C21H32O3 C2IH84O3 C21H3G03 C2IH22O4 C2IH28O4 C21H3204 C21H32O5 C21Hi5ON C22H160 C22H20O C22H220 THE WOLFF-KISHNER REDUCTION 407 TABLE II—Continued COMPOUNDS REDUCED BY THE WOLFF-KISHNER METHOD Compound Allopregnan-3-one 17a-Methyl-D-homo-3-androstanoneO-Methyl-7-isopropylpodocarpinal 6-MethoxydehydroabietinaI Methylhinokione 17a-Methyl-D-homoandrostan- 3,17-dione 17a-Methyl-D-etiochola-3,17dione Diketodiginane Pregnan-3 («)-ol-20-one Dehydroandrosterone acetate Dehydroisoandrosterone acetate Dihydrodehydrodesoxodiginigenin Dihydr odesoxo diginigenin Methyl 3-ketoctioaIlocholanate 3(/3),17a-D]hydroxy-17amethyl-D-homo-17-androstanone Pregnanol-20(a)-on-3 acetate Half methyl ester of bisdehydromarrianolic half aldehyde methyl ether Diginigenm Methyl 3-keto-12(a)-hydroxyetiocholanato Methyl 3(a),7(o:)-dihydroxy- 12-ketoetiocholanic acid 3-Benzoyl-2-phcnylpyrrocoline 6MXeto^5~dimethylene-r,2',~ S'^'-tetrahydro-S^-benzopyreneDi-o-tolylphenylmethane-ocarboxaldehyde l'-Keto-l'^'.S'^'-tetrahydro- 3,4-benzoretene Normal Normal Ferruginol f Product Ferruginol f Normal (not isolated) Normal Normal Normal Normal Unknown compound -t Normal None Etioallocholanic acid § C2IH34O Pregnanodiol-3 (a) ,20 (a) Normal || Desoxodiginigenin H 12(a)»Hydroxyetiocholanic acid 3 (a) ,7 (aO-Dihy droxyctiocholanic acid Normal ** None Normal Normal C22 Method WH WD WS WS ? WH WD WD WS WS WS WD WS WD WD WS WD WS WD WD WD Yield 98B — — — _ 3OB 100A 45A 85B 89B (or.) — 84A — 48A 85B 24B — — 26A Reference* 302 303 270 270 304 35 305 306 307 308 308a * References 86a-413 are listed on pp. 416-422. t This is the normal product in which the methoxyl group has undergone cleavage. $ A mixture of etiocholan~3(a)~ol, A 5 -androsten-303)-ol, and androstan~3(/3)-ol was formed. § There was also formed a small amount of a second acid, probably the 17-iso acid. Il After methylation of the crude product. If Aside from the normal product (one carbonyl group reduced) there was formed dihydroxyketodiginene, C21H32O3, and a compound C21H34O2 (not isolated) presumably formed by the reduction of two carbonyl groups and the reductive cleavage of an ether link. ** 2-Phenylpyrrocoline was also formed to the extent of 49%. ? WD WS - 83A 71B 306 306 309 303 79 309a 306 3096 309& 249 312 313 314
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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
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DIENE SYNTHESIS I 41 anhydride. In
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DIENE SYNTHESIS I 43 tetrahydronaph
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DIENE SYNTHESIS I 45 TABLE III—Co
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DIENE SYNTHESIS I 47 TABLE IV ADDtr
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Cycloheptatriene DIENE SYNTHESIS I
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BIENE SYNTHESIS I 51 TABLE V—Cont
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DIENE SYNTHESIS I 53 TABLE VI ADDTJ
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BIENE SYNTHESIS I 55 TABLE VII—Co
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DIENE SYNTHESIS I 57 REFERENCES TO
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DIENE SYNTHESIS I 59 422 Diels and
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DIENE SYNTHESIS II 61 PAGE TABLKs O
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DIENE SYNTHESIS II 63 The configura
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DIENE SYNTHESIS II 65 Aromatic comp
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DIENE SYNTHESIS II 67 55%). 13 Cycl
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H8Cr H8C JCO2H XSV iOCH, DIENE SYNT
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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,
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DIENE SYNTHESIS II 79 (XLVII) that
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~r (PH.)* + CO2H CO5 :H CO2CH3 CO2C
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DIENE SYNTHESIS II 83 covered as th
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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
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DIENE SYNTHESIS II 91 liquid separa
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Acetylenic Dienophile Ethyl acetyle
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DIENE SYNTHESIS II 95 TABLE IV YIEL
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1-Diethylaminobutadiene 1,1-Dimeth
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1-Methylbutadiene (piperylene) l-Me
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1,5,5,6-Tetramethylcyclohexadiene (
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1-Methyl-l-phenylbtrfcadiene l-Met
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Benzalacetophenone Bicyclohexenyl r
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f$-Benzoylacrylic acid, 2, b-dimeth
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Bicyelohexenyl c r 2,3-Dimethylbuta
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Isoprene Cinnamic acid,2,6~ dimetho
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Isoprene Cinnamic acid,omeihoxy- (t
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Coumann Butadiene 2,3-Dimethylbutad
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1,3-Dimethylbutadiene 1,4-Dimethyl
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1,1,3-Trimethylbutadiene 1,1,4-Tri
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2,3-Dimethylbutadiene Croio7toladon
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2,3-Dimethylbutadiene2,3-Diphenylbu
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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
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Ethyl ethytidenemalonate Butadiene
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1,4-Diphenylbutadiene2,3-Diphenylbu
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6 The product gradually decomposes
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Cyclohexadiene Cyclopentadiene 2,3-
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p-Nitrostyrenej 3,4-cfomethoxy- 2,3
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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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Page 361 and 362: SYNTHESIS OF BENZOQUINONES BY OXIDA
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: Formula Ci8H13ON Ci8H2IO3N Ci8Hi9O4
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
Page 423 and 424: THE WOLFF-KISHNER REDUCTION 417 133
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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