Organic Reactions Volume 4 - Sciencemadness Dot Org

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410 ORGANIC REACTIONS Formula C24H36O5 C24H38O5 C24H30O7 C24H86O7 C24H34O8 025H88O8 C26H38O4 C26H38O6 C25H40O5 C26H36O7 TABLE II—Continued COMPOUNDS REDUCED BY THE WOLFF-KISHNER METHOD Compound 3(a)-Hydroxy-7,12-diketocholanic acid 3,7-Dihy droxy- 12-ketocholanic acid 3(a) ,ll-Dihydroxy-12-ketocholanic acid 3 (a), ll-Dihydroxy-12-ketocholanic acid 3 (a), 11 (a)-Dihydroxy-12-keto~ cholanic acid 3 (a), 11 (/3)-Dihydroxy-12-kotocholanic acid 3 (a), 12(«)-Dihydroxy-l 1-ketocholanic acid 3 (a), 12 (iS)-Dihy droxy-11-kotocholanic acid 3 (a), 12 (/3)-Dihy droxy-11-ketocholanic acid 7,12-Dihy droxy-3~ketocholanic acid Lobariol Hyodesoxybilianio acid Dcsoxybilianic acid Desoxybilianic acid /S-Desoxybilianic acid Bilianic acid Isobilianic acid Methyl 12-keto-9-cholenate Methyl 3(/3)~hydroxy-12~keto- 9-cholenate 3 (/8), 17 (a)-Diacetoxyallo-20pregnanone Methyl 3-keto-7(a), 12(a)dihydroxycholanate Methyl 3(a),12(a)-diacetoxy- 7-ketoetiocholanate Methyl 3 (a), 6-diacetoxy- 7~ketoetiocholanate Normal Normal Product 3(a)-Hydroxy-9-cholemc acid 3 (a), 11,12-Trihy droxycholanic acid Normal f 3(a), 1 l(«)-Dihydroxycholanic acidf 3 (a)~Hydroxy-A 1:l -cholemo acid t 3 (a)-Hydroxy-A 11 -cholenio acid X 3 (a)-Hydroxy-A 1:l -cholemc acid § Normal None Normal Normal Normal || Normal Normal Normal C25 and C26 A 9 ~Cholenic and A u -cholenic acids Normal 3(#>-Hydroxy-17a~methyl-Dhomo-17-androstene 7(a), 12 (a)-Dihy droxycholanic acid 3 (a), 12 (a)-Dihy droxyetiocholanio acid 3 (a), 6-Dihy droxyetiocholanic acid Method WD WS WD WD WH WH WH WH WD WD WH WH WS WS WS WS WS WD — WD K WD WD - Yield 91B (or.) 13A 28A 33B 20-30B — 27B — — — — 2OB 6OB 4OA 7B —• 100A (cr.) Reference* * References 86a-413 are listed on pp. 416-422. t Not isolated as such. {Isolated as the methyl ester. There were also formed 3(a), 11(a), 12(a)- and 3(a), 11 (a), 12(0)trihydroxycholanic acids. § There were also formed the two trihydroxycholanic acids mentioned before as well as some 3 (a), 11 (0) ,12(/S) -trihydroxycholanic acid. U The product consisted of both lithobilianic and allolithobilianic acids. — — 328 330 331 329 332 333 334 334 335 336 337 338 61 315 315 61 61 338a 323 303 3386 3096 3096
Formula C25H40O7 C26Hi6O C26H44O C26H50O C26H52O C26Hi6O2 C26Hs4O2 C26H42O3 C26H40O5 C26H3806 C26H9ON C26Hi6ON2 C27H42O C27H44O C27H46O THE WOLFF-KISHNER REDUCTION 411 TABLE II—Continued COMPOUNDS REDUCED BY THE WOLFF-KISHNER METHOD Compound Methyl 3(a),12(/8)-dihydroxy- 11-ketocholanate 9,9-Biphenylenophenanthrone A ketone from Diels' acid A pyroketone from coprostanol l-Phenyleicosanone-3 l-Phenyleicosanone-3 l-Phenyleicosanone-3 l-Cyclopentyl-4-heneicosanone 9-Hexacosanone Tetrabenzocyclodecan-1,6dione1,14-Diphenyltetradecadione-3,12 Acetylnorlithocholyl methyl ketone 3-Acetoxy-12-ketochoIanic acid Ethyl 12-hydroxy-3,7-diketocholanate 3,12-Diketo-7-acetoxycholanic acid 2,3-Benzo-4-azafiuorenone 4-(2'-Aminophenyl) 1,2,1',2'~ naphtho-3-azafluorenone 3-Keto-4,6-cholestadiene 7~Keto-3,5-cholestadiene Cholestenone Cholestenone Cholestenone A 2 -Cholesten-6-one A 5 -Cholesten~4-one Cholestanone t Product Normal Normal Normal Normal Normal Normal Normal Normal Tetrabenzonaphthalene Normal Norlithocholyl methyl carbinol Normal 12-Hydroxycholanic acid H 7-Hydroxycholanic acid Normal Normal C27 Inseparable mixture Normal Normal ** Normal f f Normal Normal Normal Xt §§ Method WD WHJ WS WS WD WD WD WD WD WHt WD WS WS WD WS WD| WD| WS WS WS WS WA WD ? WS - Yield — — _ § 65A* 67A 79A 51A — — __ — — Il Smoothly — Small 79B 4OB 64B 94A (cr.) _ — Reference* * References 86a-413 are listed on pp. 416-422, f There were isolated 3(a)-hydroxy-A 1:l -ch.olenic acid and three 3,11,12-trihydroxycholanic acids. $ No alkaline catalyst was used. § The yield was 32%, 78%, and 83% in triethanolamine, diethylene glycol, and octyl alcohol respectively. Il The yield was 5%, 47%, and 60% in triethanolamine, diethylene glycol, and triethylene glycol respectively. *f Not isolated as such. ** There were also formed some cholesterol and some /S-cholestanol. ft There were also formed lesser amounts of a-coprostanol, /3-cholestanol, cholesterol, and allocholesterol. Jt Not isolated as such. §§ By the Wolff reduction of the semicarbazone at 180° with either sodium ethoxide or sodium benzylate as catalyst there were formed only a- and /3-cholestanols. At 200° the semicarbazone, hydrazone or azine yielded 75% of cholestanols and 15% of cholestane. The semicarbazone on treatment with sodium ethoxide and hydrazine hydrate gave 75% of cholestane; the azine under the same conditions gave 98% of cholestane. 335 339 340 341 37 38 342 342 342 339 37 343 36 336 344 28 248 345 348 340 5 5 346 347 5
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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 365 and 366: SYNTHESIS OF BENZOQUINONES BY OXIDA
Page 367 and 368: 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 and 412: Formula Ci8H13ON Ci8H2IO3N Ci8Hi9O4
Page 413 and 414: Formula C2IH34O C21H30O2 C21H32O2 C
Page 415: Formula C23H32O7 C23Hi7ON C24H3603
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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