Organic Reactions Volume 4 - Sciencemadness Dot Org

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CHAPTER 7 THE ROSENMUND REDUCTION OF ACID CHLORIDES TO ALDEHYDES ERICH MOSETTIG National Institute of Health, U. S, Public Health Service AND RALPH MOZINGO Merck and Company, Inc. CONTENTS PAGE INTRODUCTION 362 SCOPE AND LIMITATIONS OF THE REACTION 363 EXPERIMENTAL CONDITIONS AND REAGENTS 366 Preparation of the Acid Chloride 366 The Hydrogen 367 The Solvent 367 The Catalyst 367 The Regulator 367 General Precautions , 368 EXPERIMENTAL PROCEDURES 368 Preparation of the Regulator (Quinoline-Sulfur) 368 Preparation of Palladium-Barium Sulfate 368 Preparation of 1-Accnaphthaldehyde 369 Preparation of 3-Phenanthraldehyde 369 2- and 9-Phenanthraldehydes 370 TABLES OF ACID CHLORIDES REDUCED BY THE ROSENMUND METHOD . . . . 370 I Aliphatic, Hydroaromatic, and Aliphatic-Aromatic Aldehydes . . . . 371 II Aromatic Aldehydes 373 III Heterocyclic Aldehydes 375 INTRODUCTION In the synthesis of complex molecules, particularly in connection with natural products, it is occasionally desirable to prepare an aldehyde when the readily available starting material is the corresponding acid. 362
ROSENMUND REDUCTION 363 For accomplishing this transformation, RCO2H —> RCHO, the Rosenmund reduction x is probably the most useful method for Application to a large number of aldehydes of varied types. The Rosenmund reduction consists in the selective hydrogenation of an acid chloride in the presence of a suitable catalyst, usually supported palladium, to the corresponding aldehyde. The reduction RCOCl + H2 Pd-BaSO4 ^ RCHO + HCi is carried out by bubbling hydrogen through a hot solution of the acid chloride in which the catalyst is suspended. SCOPE AND LIMITATIONS OF THE REACTION The success of the method is dependent upon the resistance of the aldehyde to reduction under the conditions which permit its formation from the acid chloride. Since the reduction is effected by hydrogen in the presence of a catalyst, the aldehyde so formed may be reduced further to the corresponding alcohol and hydrocarbon. RCHO + H2 ° atalyst > RCH2OH RCH2OH + H2 ° atalyst > RCH3 + H2O The reduction of the aldehyde can be prevented by the use of an appropriate catalyst "poison" or "regulator" which inactivates the catalyst towards reduction of aldehyde but not of acid chloride. The addition of a regulator was the result of an early observation of Rosenmund and Zetzsche. 2 These authors obtained nearly quantitative yields of benzaldehyde in their first experiments on the reduction of benzoyl chloride but later experienced difficulty in repeating the preparation. It has been supposed that the success of the early experiments was due to the presence of impurities, either in the solvents or in the acid chloride, which acted as the poison. Consequently much attention has been paid to the development of such regulators. 3-10 They usually contain sulfur !Rosenmund, Ber., 51, 585 (1918). 2 Rosenmund and Zetzsche, Ber., 54, 425 (1921). 3 Rosenmund, Zetzsche, and Heise, Ber., 54, 638 (1921). 4 Rosenmund, Zetzsche, and Heise, Ber., 54, 2038 (1921). 5 Abel, Ber , 54, 1407 (1921). 6 Rosenmund and Zetzsche, Ber., 54, 2885 (1921). 7 Abel, Ber., 55, 322 (1922). 8 Rosenmund and Zetzsche, Ber., 55, 2774 (1922). 9 Weygand and Meusel, Ber., 76, 503 (1943). 10 Weygand and Mejsel, Ber., 76, 498 (1943).
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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 BENZOQUINONES BY OXIDA
Page 317 and 318: SYNTHESIS OF BENZOQUINONES BY OXIDA
Page 339 and 340: SYNTHESIS OF BENZOQUINpNES BY OXIDA
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 367: SYNTHESIS OF BENZOQUINONES BY OXIDA
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
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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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