ORGANIC CHEMISTRY - A "CARBONYL EARLY" APPROACH Kirk McMichael Washington State University Washington State University Organic Chemistry - A "Carbonyl Early" Approach Kirk McMichael This text is disseminated via the Open Education Resource (OER) LibreTexts Project (https://LibreTexts.org) and like the hundreds of other texts available within this powerful platform, it freely available for reading, printing and "consuming." Most, but not all, pages in the library have licenses that may allow individuals to make changes, save, and print this book. Carefully consult the applicable license(s) before pursuing such effects. Instructors can adopt existing LibreTexts texts or Remix them to quickly build course-specific resources to meet the needs of their students. Unlike traditional textbooks, LibreTexts’ web based origins allow powerful integration of advanced features and new technologies to support learning. 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This text was compiled on 09/26/2021 TABLE OF CONTENTS This is the textbook for a one semester organic chemistry "survey" course . You will be learning and applying the principles which govern the structure of organic compound and relating your understanding of structure to the reactions--the changes in structure--which happen when specific portions of organic compounds interact with other chemical substances. We will spend the first several weeks of the semester looking at a group of organic compounds which share a common structural element--the ca 1: CHAPTERS 1.1: CARBONYL GROUP- NOTATION, STRUCTURE, BONDING 1.2: FUNCTIONAL GROUPS, HYBRIDIZATION, NAMING 1.3: ADDITIONS- ELECTROPHILIC AND NUCLEOPHILIC 1.4: ACETAL FORMATION, MECHANISM, RESONANCE 1.5: NITROGEN NUCLEOPHILES - IMINE FORMATION 1.6: ADDITION OF ORGANOMETALLICS - GRIGNARD 1.7: OXIDATION AND REDUCTION, ALPHA-C-H ACIDITY 1.8: ENOLATES, ALDOL CONDENSATION, SYNTHESIS 1.9: CARBOXYLIC ACID DERIVATIVES- INTERCONVERSION 1.10: CARBOXYLIC ACID DERIVATIVES - ALPHA CARBON REACTIONS 1.11: FATS, FATTY ACIDS, DETERGENTS 1.12: CARBOXYLIC ACIDS 1.13: ALCOHOLS 1.14: ETHERS, EPOXIDES, THIOLS 1.15: CHIRALITY, THREE DIMENSIONAL STRUCTURE 1.16: R/S NAMING, TWO OR MORE STEREOGENIC CENTERS 1.17: CARBOHYDRATES- MONOSACCHARIDES 1.18: GLYCOSIDES, DISACCHARIDES, POLYSACCHARIDES 1.19: AMINES- STRUCTURE AND SYNTHESIS 1.20: AMINES- REACTIONS 1.21: AMINO ACIDS AND PEPTIDES 1.22: PROTEINS 1.23: NUCLEIC ACIDS 1.24: NUCLEOPHILIC SUBSTITUTION, SN2, SN1 1.25: ELIMINATION - E2 AND E1 1.26: ALKENES AND ALKYNE STRUCTURE 1.27: ELECTROPHILIC ADDITIONS 1.28: POLYMERS 1.29: METABOLIC ORGANIC REACTIONS 1.30: AROMATIC COMPOUNDS 1.31: ELECTROPHILIC SUBSTITUTION 1.32: SIDE CHAIN OXIDATIONS, PHENOLS, ARYLAMINES 1.33: RADICAL REACTIONS BACK MATTER INDEX GLOSSARY 1 9/26/2021 CHAPTER OVERVIEW 1: CHAPTERS 1.1: CARBONYL GROUP- NOTATION, STRUCTURE, BONDING You will be learning and applying the principles which govern the structure of organic compound and relating your understanding of structure to the reactions--the changes in structure--which happen when specific portions of organic compounds interact with other chemical substances. We will spend the first several weeks of the semester looking at a group of organic compounds which share a common structural element--the carbonyl group. 1.2: FUNCTIONAL GROUPS, HYBRIDIZATION, NAMING First, let's look at the various structural representations you were asked to develop for the molecules given at the end of the last lecture. Here they are: 1.3: ADDITIONS- ELECTROPHILIC AND NUCLEOPHILIC Last time we listed three reasons to expect that the carbonyl (C=O) group would be a functional group, a reactive part of the molecule. All of these reasons were connected with the way electrons are distributed in the group. Functional groups are the places where changing the location of electrons can happen fairly easily, which means that the distribution of electrons in a functional group is a key to its reactivity. We need a specific example to make these ideas useful. 1.4: ACETAL FORMATION, MECHANISM, RESONANCE Last time I left you with a problem, "what is the mechanism for the base catalyzed addition of water to a carbonyl group?" Let's go through that and see how it goes. 1.5: NITROGEN NUCLEOPHILES - IMINE FORMATION In many of the biological reactions of carbonyl groups the nucleophile is a nitrogen atom. The eventual outcome is different, so let's take a look at the details. The specific molecule as an example of a nitrogen nucleophile is methylamine. What happens if Nu = CH3NH2? Here's the complete mechanism. 1.6: ADDITION OF ORGANOMETALLICS - GRIGNARD Last time we looked at a reaction in which a new carbon-carbon bond was made. Today, we'll look at another such reaction, one which is generally quite useful for synthesis, the assembly of larger carbon structures from smaller molecules. 1.7: OXIDATION AND REDUCTION, ALPHA-C-H ACIDITY Last time we saw how a nucleophilic addition of a carbon atom to the carbonyl carbon could be carried out through the use of a Grignard reagent. This time we'll look at oxidations and reductions of carbonyl groups and at the acidity of the alpha hydrogen atom 1.8: ENOLATES, ALDOL CONDENSATION, SYNTHESIS Last time we worked through the reagents which oxidize aldehydes to carboxylic acids and the reagents which reduce aldehydes to primary alcohols and ketones to secondary alcohols. We also learned how enolate ions can be formed by the removal of an alpha hydrogen atom and how these enolate ions can act as nucleophiles toward bromine. 1.9: CARBOXYLIC ACID DERIVATIVES- INTERCONVERSION Today we'll look at carboxylic acid derivatives. This group of compounds also contains a carbonyl group, but now there is an electronegative atom (oxygen, nitrogen, or a halogen) attached to the carbonyl carbon. This difference in structure leads to a major change in reactivity. Here we find that the reactions of this group of compounds typically involve substitution of the electronegative atom by a nucleophile. 1.10: CARBOXYLIC ACID DERIVATIVES - ALPHA CARBON REACTIONS Last time we looked at several reactions of carboxylic acid derivatives and learned how to make esters and amides. Today we'll look at some further reactions of esters, including some which make new carbon-carbon bonds. 1.11: FATS, FATTY ACIDS, DETERGENTS Last time we looked at several reactions of carboxylic acid derivatives and learned how to make esters and amides. Today we'll look at some further reactions of esters. We'll also examine the chemistry of the ester functional group in fats. 1.12: CARBOXYLIC ACIDS Last time we looked the reactions of esters with lithium aluminum hydride and with Grignard reagents. We followed that with the chemistry of enolates formed from esters and then looked at fats and soaps. Today we'll look at the parent functional group of carboxylic acid derivatives, the carboxylic acid group itself. We'll see how we can make carboxylic acids and ask why they are acids. 1 9/26/2021 1.13: ALCOHOLS Today, we'll examine the chemistry of alcohols. First, we'll review the reactions we've already seen which make alcohols. Then we'll look at the reactions of the alcohol functional group. 1.14: ETHERS, EPOXIDES, THIOLS Today, we'll go on to look at the acidity of alcohols and the uses of their conjugate bases as nucleophiles. That will take us to the chemistry of ethers. We'll finish with a look at thiols, close relatives of alcohols in which a sulfur atom has replaced the oxygen. 1.15: CHIRALITY, THREE DIMENSIONAL STRUCTURE Today we'll take a look at structure. We'll find that we have to begin to think in three dimensions to understand some structural differences between very similar compounds. 1.16: R/S NAMING, TWO OR MORE STEREOGENIC CENTERS Today, we'll look at naming compounds with stereocenters, and then we'll examine the complications which arise when a molecule has more than one stereocenter in it. 1.17: CARBOHYDRATES- MONOSACCHARIDES Last time we learned how a chiral compound's absolute configuration can be described by the R/S naming system. We also considered the situations which can arise when a compound has two (or more) stereogenic carbons. Our examples for that were in fact sugars; monosaccharide aldotetroses.