《有机化学》课程PPT教学课件（Organic Chemistry with Biological Applications, 3th Edition, John McMurry, 2016）Chapter 14 Aldehydes and Ketones - Nucleophilic Additions Reactions

CNGNGE JOHN MCMURRY CHAPTER 14 Aldehydes and Ketones: Nucleophilic Additions Reactions Organic Chemistry with Biological Applications

CHAPTER 14 Aldehydes and Ketones: Nucleophilic Additions Reactions

Aldehydes and Ketones Aldehydes(RCHO)and Ketones(R2CO)are among the most widely occurring of all compounds Required by living organisms Pyridoxal phosphate(PLP)is common coenzyme Hydrocortisone is steroid hormone secreted by adrenal glands CH2OH 2-03P0 H CH3 =0 HO C=0 -OH CH3 +N H OH H H CH3 Pyridoxal Hydrocortisone phosphate(PLP)

Aldehydes (RCHO) and Ketones (R2CO) are among the most widely occurring of all compounds ▪ Required by living organisms ▪ Pyridoxal phosphate (PLP) is common coenzyme ▪ Hydrocortisone is steroid hormone secreted by adrenal glands Aldehydes and Ketones

Aldehydes and Ketones Solvents and starting materials in chemical industry 1.9 million tons of formaldehyde,H2C=O,produced each year for insulation materials and resins 1.5 million tons of acetone,((CHa)2C=O),produced each year for use as industrial solvent OH OH Catalyst ZnO H C-H Heat H HgC-C-H 380℃ H3C CH3 H H3C Methanol Formaldehyde Propan-2-ol Acetone

▪ Solvents and starting materials in chemical industry ▪ 1.9 million tons of formaldehyde, H2C=O, produced each year for insulation materials and resins ▪ 1.5 million tons of acetone, ((CH3 )2C=O), produced each year for use as industrial solvent Aldehydes and Ketones

14-1 Naming Aldehydes and Ketones Aldehydes named by replacing terminal-e of corresponding alkane name with-al Parent chain must contain the -CHO group See Appendix A and Table A.2 for naming polyfunctional organic compounds containing an aldehyde -CHO carbon is numbered as C1 9 0 CH3 0 2 CH3CH CH3CH2CH CH3CHCH2CHCH 5°43 1 CH2CH3 Ethanal Propanal 2-Ethyl-4-methylpentanal (acetaldehyde) (propionaldehyde)

Aldehydes named by replacing terminal –e of corresponding alkane name with –al ▪ Parent chain must contain the –CHO group ▪ See Appendix A and Table A.2 for naming polyfunctional organic compounds containing an aldehyde ▪ – CHO carbon is numbered as C1 14-1 Naming Aldehydes and Ketones

Naming Aldehydes and Ketones Carbaldehyde suffix is used for cyclic aldehydes CHO CHO Cyclohexanecarbaldehyde Naphthalene-2-carbaldehyde

Carbaldehyde suffix is used for cyclic aldehydes Naming Aldehydes and Ketones

Naming Aldehydes and Ketones TABLE 14.1 Common Names of Some Simple Aldehydes Formula Common name Systematic name HCHO Formaldehyde Methanal CH3CHO Acetaldehyde Ethanal H2C-CHCHO Acrolein Propenal CH3CH-CHCHO Crotonaldehyde But-2-enal CHO Benzaldehyde Benzenecarbaldehyde Cengage Learing.All Rights Reserved

Naming Aldehydes and Ketones

Naming Aldehydes and Ketones Ketones named by replacing terminal -e of corresponding alkane name with -one Parent chain is longest chain containing ketone group Numbering begins at end of chain nearer the carbonyl carbon O= CH3CH2CCH2CH2CH3 CH3CH=CHCH2CCH3 CH3CH2CCH2CCH3 1°2341 5 6 6°54321 6°54321 Hexan-3-one Hex-4-en-2-one Hexane-2,4-dione (Old:3-Hexanone) (Old:4-Hexen-2-one) (Old:2,4-Hexanedione)

Ketones named by replacing terminal –e of corresponding alkane name with –one ▪ Parent chain is longest chain containing ketone group ▪ Numbering begins at end of chain nearer the carbonyl carbon Naming Aldehydes and Ketones

Naming Aldehydes and Ketones Some common names accepted by IUPAC 0 C CH3CCH3 CH3 Acetone Acetophenone Benzophenone

Some common names accepted by IUPAC Naming Aldehydes and Ketones

Naming Aldehydes and Ketones If R-C=O is a substituent the name acyl(a-sil)group is used and name ending-yl is attached R H3C An acyl group Acetyl Formyl Benzoyl The prefix oxo-is used if ketone is not highest priority functional group and the carbonyl is considered a substituent on the parent chain See Appendix A and Table A.2 for naming polyfunctional organic compounds containing a ketone 00 CH3CH2CH2CCH2COCH3 Methyl 3-oxohexanoate 654-32-1

If R-C=O is a substituent the name acyl (a-sil) group is used and name ending –yl is attached The prefix oxo- is used if ketone is not highest priority functional group and the carbonyl is considered a substituent on the parent chain ▪ See Appendix A and Table A.2 for naming polyfunctional organic compounds containing a ketone Naming Aldehydes and Ketones

14-2 Preparing Aldehydes and Ketones Preparing Aldehydes Aldehydes from oxidation of primary alcohols using the Dess- Martin periodinane reagent AcO OAc OAc CH2OH CH2Cl2 人 Geraniol Geranial(84%)

Preparing Aldehydes Aldehydes from oxidation of primary alcohols using the Dess￾Martin periodinane reagent 14-2 Preparing Aldehydes and Ketones