ClaydenJ.etal.-Organicchemistry-教育文档类资源-CSDN下载

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14 Nucleophilic substitution at C=0 with loss of carbonyl oxygen15 Review of spectroscopic methods16 Stereochemistry17 Nucleophilic substitution at saturated carbor18 Conformational analysis19 Elimination reactions20 Electrophilic addition to alkenes21 Formation and reactions of enols and enolates22 Electrophilic aromatic substitution23 Electrophilic alkenes24 Chemoselectivity: selective reactions and protection25 Synthesis in action26 Alkylation of enolates27 Reactions of enolates with aldehydes and ketones: the aldol reaction28 Acylation at carbon29 Conjugate addition of enolates30 Retrosynthetic analysis31 Controlling the geometry of double bonds32 Determination of stereochemistry by spectroscopic methods33 Stereoselective reactions of cyclic compounds34 Diastereoselectivity35 Pericyclic reactions 1: cycloadditions36 Pericyclic reactions 2: sigmatropic and electrocyclic reactions37 Rearrangements38 Fragmentationl100339 Radical reactions40 Synthesis and reactions of carbenes41 Determining reaction mechanisms42 Saturated heterocycles and stereoelectronics43 Aromatic heterocycles 1: structures and reactions44 Aromatic heterocycles 2: synthesis45 Asymmetric synthesis46 Organo-main-group chemistry l: sulfur47 Organo-main-group chemistry II: boron, silicon, and tin48 Organometallic chemistry49 The chemistry of life50 Mechanisms in biological chemistry51 Natural products52 Polymerization53 Organic chemistry todayIndexWhat is organic chemistry?Organic chemistry and youYou arc alrcady a highly skilled organic chemist. As you rcad thesc words, your cycs are using anorganic compound (retinal)to convert visible light into ncrve impulses. When you picked up thisbook, your muscles were doing chemical rcactions on sugars to give you the cncrgy you needed. Asyou undcrstand, gaps bctwcen your brain cclls arc bcing bridged by simplc organic molccules(ncurotransmitter amincs) so that ncrve impulses can be passcd around your brain. and you did all that11-cis-retinalwithout consciously thinking about it. you do not yct undcrstand thesc proccsscs in your mind asabsorbs light when we seewell as you can carry them out in your brain and body. You arc not alone thcre. No organic chemist,however brilliant, understands the detailed chemical working of the human mind or body very well. HoWe, the authors, include ourselves in this generalization, but we are going to show you in thisbook what cnormous strides have bcen taken in thc understanding of organic chemistry sincc thescicncc camc into bcing in the carly ycars of the ninctccnth century. Organic chemistry began as atentative attempt to understand the chemistry of life. It has grown into the confident basis of vastserotoninmultinational industries that feed, clothe, and cure millions of people without their even beinghuman neurotransmitteraware of the role of chemistry in thcir lives. Chemists coopcrate with physicists and mathematicians to understand how molecules behave and with biologists to understand how molecules Ddetermine life processes. The development of these ideas is already a revelation at the beginning of We are going to give youthe twenty-first century, but is far from complete. We aim not to give you the measurements of the structures of organic compoundsskeleton of a dcad science but to equip you to understand the conflicting demands of anin this chapter--otherwise itadolescent onewould be rather dull. If you do notunderstand the diagrams, do notLike all sciences, chemistry has a unique place in our pattern of understanding of the universe. It worry Explanation is on its wayis the science of molecules. But organic chemistry is something more. It literally creates itself as itgrows. Of course we need to study the molecules of nature both because they are interesting in theirown right and because their functions are important to our lives. Organic chemistry often studies lifeby making new molecules that give information not available from the molecules actually present inliving thingsThis creation of new molecules has given us new materials such as plastics, new dyes to colour ourclothes, new perfumes to wear new drugs to cure diseases. Some people think that these activities areunnatural and their products dangerous or unwholesome. But these new molecules are built byhumans from other molecules found on earth using the skills inherent in our natural brains. birdbuild nests; man makes houses. Which is unnatural? To the organic chemist this is a meaningless distinction. There are toxic compounds and nutritious ones, stable compounds and reactive ones butthere is only one type of chemistry: it goes on both inside our brains and bodies and also in our flasksand reactors, born from the ideas in our minds and the skill in our hands. We are not going to seourselves up as moral judges in any way. We believe it is right to try and understand the world aboutus as best we can and to use that understanding creatively. This is what we want to share withOrganic compoundsOrganic chemistry started as the chemistry of life, when that was thought to be different from thehemistry in the laboratory. Then it became the chemistry of carbon compounds, especially thosefound in coal. Now it is both. It is the chemistry of the compounds of carbon along with other elements such as are found in living things and elsewhere1. What is organic chemistry?The organic compounds available to us today arc those prcscnt in living things and those formedYou will be able to read towards theovcr millions of ycars from dcad things In carlicr times, the organic compounds known from naturcend of the book( Chapters 49-51)were thosc in the cssential oils that could be distilled from plants and the alkaloids that could beabout the extraordinary chemistry thatallows life to exist but this is knownextracted from crushed plants with acid. Menthol is a famous cxamplc of a flavouring compoundonly from a modern cooperationbetween chemists and biologistsfrom the essential oil of spearmint and cis-jasmone an cxamplc of a perfume distilled from jasmineowersCISJasmonementholquinineEven in the sixteenth century one alkaloid was famous-quinine was extracted from the bark ofthe South american cinchona trcc and uscd to trcat fevers, especially malaria. The jesuits who didthis work(the remedy was known as Jesuit\'s bark) did not of course know what the structure ofquinine was, but now we doThe main reservoir of chemicals available to the nineteenth century chemists was coal. distillation of coal to give gas for lighting and hcating(mainly hydrogen and carbon monoxide) alsogave a brown tar rich in aromatic compounds such as benzene, pyridine, phenol, aniline, andthiophenebenzenepyridineanilinethiophenePhenol was used by lister as an antiseptic in surgery and aniline became the basis for the dyestuffsindustry. It was this that really started the search for new organic compounds made by chemistsrather than by nature. a dyestuff of this kind -still available -is Bismarck Brown, which should tellyou that much of this early work was done in germanyBismarck Brown yIn the twentieth century oil overtook coal as the main source of bulk organic compounds so thatsimple hydrocarbons like methane( CH, natural gas) and propane(CH, CH, CH,, calor gas)You can read about polymers andbecame available for fuel. At the same time chemists began the search for new molecules from newplastics in Chapter 52 and about finesources such as fungi, corals, and bacteria and two organic chemical industries developed in paralchemicals throughout the book.lel-bulk\' and\'fine\' chemicals. Bulk chemicals like paints and plastics are usually based on simpleCH3-(CH2)n-CH3molecules produced in multitone quantities while fine chemicals such as drugs, perfumes, andflavouring materials are produced in smaller quantities but much more profitablyn= an enormous numberlength of molecule is n+ 2At the time of writing there were about 16 million organic compounds known How many morecarbon atomsare possible? There is no limit(except the number of atoms in the universe). Imagine you\' ve justCH3-(CH2)n-CHz-CH3made the longest hydrocarbon ever made--you just have to add another carbon atom and you\'ven= an enormous numbermade another This process can go on with any type of compound ad infinitum.length of molecule is n+3But these millions of compounds are not just a long list of linear hydrocarbons; they embrace allcarbon atomskinds of molecules with amazingly varied properties. In this chapter we offer a selectionOrganic compoundsWhat do they look like? Thcy may be crystallinc solids, oilswaxes, plastics, clastics, mobilc or volatile liquids, or gasesFamiliar oncs include white crystallinc sugar, a cheap naturalcompound isolated from plants as hard white crystals when purcand petrol, a mixture of colourless, volatile, flammable hydrocarCH3 CH3bons. Isooctane is a typical cxamplc and gives its namc to theoctane rating of petrolThe compounds nccd not lack colour. Indccd we can soondrcam up a rainbow of organic compounds covering the whespectrum, not to mention black and brown. In this table we havesucrose- ordinary sugarisooctane(2, 3. 5-trimethylpentane)isolated from sugar canetiuent of petrolavoided dyestuffs and have chosen compounds as varied in strucor sugar beetvolatile inf ammable liquidture as possiblewhite crystalline solids ColourDescriptionCompoundStructuredark red hexagonal plates3-methoxybenzocycloheptatriene.2 -oneamber needlesdichloro dicyano quinone(DDQ)toxic yellow explosive gasdiazomethanegreen prisms with ag-nitroso julolidinesteel-blue lustredeep blue liquid with aazurepeppery smelpurple deep blue gas condensingnitroso trifluoromethaneto a purple solidColour is not the only characteristic by which we recognize compounds. All too often it is theirodour that lets us know they are around. There are some quite foul organic compounds too; thesmell of the skunk is a mixture of two thiols-sulfur compounds containing SH groupsskunk spray contains1. What is organic chemistry?1. But perhaps the worst aroma was that which causcd the cvacuation of thc city of Frciburg in 1889ttempts to make thioacetone by the cracking of trithioacctonc gave risc to an offensive smell whichspread rapidly over a grcat arca of thc town causing fainting, vomiting and a panic evacuationothcthioacetonelaboratory work was abandonedIt was perhaps foolhardy for workers at an Esso rescarch station to repeat the expcriment of cracking trithioacctonc south of Oxford in 1967. Lct them take up the story. \' Rccentlyowc found ourselveswith an odour problem beyond our worst expectations. During early experiments, a stopper jumpedfrom a bottle of residues, and, although replaced at once, resulted in an immediate complaint of nausca and sickness from collcagucs working in a building two hundred yards away. Two of ourchemists who had donc no more than investigate the cracking of minute amounts of trithioacc-toneofound themselves the object of hostile stares in a restaurant and suffered the humiliation ofhaving a waitress spray the area around them with a deodorant. The odours defied the expectedtrithioacetonecffects of dilution since workers in the laboratory did not find the odours intolerable.. and genu-Freiburg was evacuatedinely denied responsibility since they were working in closed systems. To convince them otherwisebecause of a smell fromthe distillation this compound they were dispersed with other observers around the laboratory, at distances up to a quarter of amile, and one drop of either acetone gem-dithiol or the mother liquors from crude trithioacetonecrystallisations wcre placed on a watch glass in a fumc cupboard. The odour was detected downwindIn seconds 3HS SHThere are two candidates for this dreadful smell- propane dithiol (called acetone gem-dithiolabove)or 4-methyl-4-sulfanylpentan-2-one. It is unlikely that anyone else will be brave enough toresolve the controversy4-methyl-4-propanesulfanylpentanNasty smells have their uses. The natural gas piped to our homes contains small amounts of deliadithiol2-oneerately added sulfur compounds such as tert-butyl thiol(CH3 )3CSH. When we say small, we meanvery small humans can detect one part in 50000 000000 parts of natural gastwo candidates forthe worst smell in the worldOther compounds have delightful odours. To redeem the honour of sulfur compounds we mustcite the truffle which pigs can smell through a metre of soil and whose taste and smell is so delightfulno one wants to find the winner.that truffles cost more than their weight in gold. damascenones are responsible for the smell of rosesIf you smell one drop you will be disappointed, as it smells rather like turpentine or camphor, butnext morning you and the clothes you were wearing will smell powerfully of roses. Just like the comthe divine smellpounds from trithioacetone, this smell develops on dilutionof the black truffleHumans are not the only creatures with a sense of smell. We can find mates using our eyes alonecomes from this compoundthough smell does play a part)but insects cannot do this. They are small in a crowded world andthey find others of their own species and the opposite sex by smell. Most insects produce volaticompounds that can be picked up by a potential mate in incredibly weak concentrations Only 1.5mg of serricornin, the sex pheromone of the cigarette beetle, could be isolated from 65 000 femalebeetles--so there isnt much in each beetle. Nevertheless, the slightest whiff of it causes the males togather and attempt frenzied copulationdamascenone- the smell of roses The sex pheromone of the Japanese beetle, also given off by the females, has been made bychemists. As little as 5 ug(micrograms, note! )was more effective than four virgin females in attracting the males.serricorninjaponilurethe sex pheromone of the cigarette beetlthe sex pheromone of the Japanese beetleLasioderma serricornePapilla japonicaThe pheromone of the gypsy moth, disparlure, was identified from a few ug isolated from themoths and only 10 ug of synthetic material. As little as 2x 10g is active as a lure for the males infield tests. The three pheromones we have mentioned are available commercially for the specifictrapping of these destructive insect pestsOrganic compoundsDont supposc that the females always do all the work; bothmale and female olive flics produce pheromones that attract theothcr scx. The remarkable thing is that one mirror image ofdisparlurethe molcculc attracts the males whilc the other attracts thcthe sex pheromone of the Gypsy mothfemalesPortheria disparoleanthis mirror image isomer thiIs mirror image isomersex pheromone of the olive flyattracts the malesattracts the femalesBactrocera oleaeWhat about taste? Take the grapefruit. The main flavour comes from another sulfur compoundand human beings can detect 2 x 10 parts per billion of this compound. This is an almost unimaginably small amount cqual to 10 mg per tonne or a drop, not in a bucket, but in a good-sizcd lakeWhy evolution should have left us abnormally sensitive to grapefruit, we leave you to imagineFor a nasty taste, we should mention bittering agents, put into dangerous household substanceslike toilet cleaner to stop children eating them by accident. Notice that this complex organic com-flavouring principle of grapefruitpound is actually a salt--it has positively charged nitrogen and negatively charged oxygen atoms-and this makes it soluble in waterch en he ride of h cep enw end uder fe rimchly ewwrminh and then和hming preducts or bleachbitrexwien if irritationsd, wash with deon waierdenatonium benzoatebenzyldiethyl[(2, 6-xylyIcarbamoyl)methylammonium benzoateOther organic compounds have strange effects on humans. Various drugs suchComMEas alcohol and cocaine are taken in various ways to make people temporarily happyThey have their dangers. Too much alcohol leads to a lot of misery and any cocainealcohol(ethanol)at all may make you a slave for lifeAgain, let\'s not forget other creatures. Cats seem to be able to go to sleep at anycocainetime and recently a compound was isolated from the cerebrospinal fluid of cats that makes them,oran addictive alkaloidrats, or humans go off to sleep quickly. It is a surprisingly simple compounda sleep-inducing fatty acid derivativecis-9, 10-octadecenoamideThis compound and disparlure are both derivatives of fattyacids, molecules that feature in many of the food problems peopleare so interested in now(and rightly so). Fatty acids in the diet area popular preoccupation and the good and bad qualities of satu-rates, monounsaturates, and polyunsaturates are continually inthe news. This too is organic chemistry One of the latest molecules to be recognized as an anticancer agent in our diet is claCLA (Conjugated Linoleic Acid(conjugated linoleic acid) in dairy productscis-9-trans- 11 conjugated linoleic aciddietary anticancer agent1. What is organic chemistry?Anothcr fashionable molcculc is rcsvcratrolc, which maybe responsible for the beneficial cffects of red winc in prc-venting hcart discasc. It is a quite diffcrent organic compound with two benzene rings and you can rcad about it inChaptcr 51For our third edible molecule we choose vitamin c. this isVitamin C (ascorbic acid)is aan essential factor in our diets-indeed, that is why it is called resveratrole from the skins of grapesis this the compound in red winevitamin for primates, guinea-piga vitamin. The discasc scurvy a degeneration of soft tissot which helps to prevent heart disease?and fruit bats, but other mammals particularly in the mouth, from which sailors on long voyagescan make it for themselveslike thosc of Columbus suffcrcd, results if we dont have vitamin C. It also is a universal antioxidant,scavenging for rogue free radicals and so protecting us against cancer. Some people think an extralarge intake protects us against the common cold, but this is not yet provedOrganic chemistry and industrVitamin C is manufactured on a huge scale by roche, a Swiss company all over the world there arevitamin C(ascorbic acid) chemistry-based companies making organic molecules on scales varying from a few kilograms tothousands of tonnes per year. This is good news for students of organic chemistry; there are lots ofjobs around and it is an international job market. The scale of some of these operations of organicchemistry is almost incredible. The petrochemicals industry processes(and we use the productsover 10 million litres of crude oil every day. Much of this is just burnt in vehicles as petrol or diesel,but some of it is purified or converted into organic compounds for use in the rest of the chemicalindustry. Multinational companies with thousands of employees such as Esso(Exxon) and Shelldominate this sectorSome simple compounds are made both from oil and from plants. The ethanol used as a startingmaterial to make other compounds in industry is largely made by the catalytic hydration of ethylenefrom oil. But ethanol is also used as a fuel, particularly in Brazil where it is made by fermentation ofsugar cane wastes. This fuel uses a waste product, saves on oil imports, and has improved the qualityof the air in the very large brazilian cities, rio de janeiro and Sao pauloPlastics and polymers take much of the production of the petromonomers for polymerchemical industry in the form of monomers such as styrene,acrymanufacturelates, and vinyl chloride. The products of this enormous industry areeverything made of plastic including solid plastics for householdgoods and furniture, fibres for clothes (24 million tonnes perannum), elastic polymers for car tyres, light bubble-filled polymersstyrenefor packing, and so on. Companies such as BASF, dupont, amocoMonsanto, Laporte, Hoechst, and ICi are leaders here. Worldwideolymer production approaches 100 million tonnes per annum andPVC manufacture alone employs over 50 000 people to make over 20acrylatesvinyl chloridemillion tonnes per annumThe washing-up bowl is plastic too but the detergent you put in it belongs to another branch ofthe chemical industry-companies like Unilever(Britain)or Procter and Gamble(USa)whichproduce soap, detergent, cleaners, bleachesIngredientspolishes, and all the many essentials for theaqua, palmitic acidmodern home. These products may be lemontriethanolamine,and lavender scented but they too mostly comeglycereth-26, isopentanefrom the oil industry. Nowadays, most prooleamide-DEA, oleth-2stearic acid. isobutaneducts of this kind tell us, after a fashion what is inPEG-14M, parfumthem. Try this example-a well known brand ofallantoinshaving gel along with the list of contents on thehydroxyethyl-cellulosecontainerhydroxypropyl-cellulosePEG-150 distearateDoes any of this make any sense?42053.Cl47005Organic chemistry and industryIt doesnt all make sense to us, but here is a possible interpretation. We certainly hope the bookwill set you on the path of understanding the sense(and the nonsense! )of this sort of thingIngredientChemical meaningPurposewatersolventpalmitic acidCH3(CH2)14CO2Hacid. emuls ifiertriethanolamineN(CH,CH,OH)ycereth-26glyceryl(OCH, CH )sOHsurfactantisopentane(CH3 2 CHCH2CHpropellantoleamide-DEACH(CH2)7 CH=CH(CH,), ConEt,oleth-2Oleyl(OCH2CH2)2OHsurfactantstearic acidCH3(CH2)16CO2Hacid. emulsifierisobutane(CH3I2CHCHpropellantPEG-14Mpolyoxyethylene glycol estersurfactantallantoinpromotes healing inyourself while shPlantainhydroxyethyl-cellulose cellulose fibre from wood pulpgives bodywith -OCH, CH, OH groups addedhydroxypropyl-cellulose cellulose fibre from wood pulpgives bodywith -oCH2 CH(OH)CH3 groups addedPEG-150 distearatepolyoxyethylene glycol diestersurfactantC42053Fast Green FCF (see boxgreen dyeC47005Quinoline Yellow(see boxellow dyeThe structures of two dyesFast Green FCF and Quinoline Yellow are colours permitted to be used in foods and cosmetics and have the structuresshown here. Quinoline yellow is a mixture of isomeric sulfonic acids in the two rings shownHoOpSs020HFast green fceQuinoline YellowThe particular acids, bases, surfactants, and so on are chosen to blend together in a smooth emul-sion when propelled from the can. The result should feel, smell, and look attractive and a greenishcolour is considered clean and antiseptic by the customer. what the can actually says is thisSuperior lubricants within the gel prepare the skin for an exceptionally close, comfortable and effec-tive shave. It contains added moisturisers to help protect the skin from razor burn. Lightlyfragranced ...展开详情