有機(jī)化學(xué)Chap10aldehydesandketones20140414-7Y

1、Chapter 10 Aldehydes and Ketones HOUndecanal十一醛OO2-Heptanone2-庚酮trans-2-Hexenal反-2-庚醛Civetone香貓酮HOOVanillin香草醛(Vanilla flavor 香草味)Cinnamon flavor 肉桂醛(Cinnamaldehyde 桂皮味)(R)-Carvone R-香芹酮(Spearmint flavor 薄荷味)Benzaldehyde 苯甲醛(Almond flavor 杏仁味）HOH3COHOOHHOProgesterone 孕酮Testosterone 睪酮OHHOH3CCH3OHOHH

2、OHOHHH甲醛 丙酮Carbonyl group 羰基羰基Aldehyde 醛Ketone 酮ORRORHCommon names(普通命名法普通命名法) are normally used for the aldehydes containing four carbons or fewer. 1 Nomenclature1.1 分類分類芳香醛（酮）脂肪醛（酮）1.2 普通命名法普通命名法 CH3CH2CHOCH3CCH3OCHOCCH3O丙醛甲(基)乙(基)酮甲(基)環(huán)己(基)酮二苯(基) 酮苯乙醛CH3CH2CHOCH3CC2H5OCCH3OCH2CHOO1 NomenclatureFo

3、r systemic names(系統(tǒng)命名法系統(tǒng)命名法), the “e” of the parent alkanes name is dropped and the suffix “al” is added.In the priority system the aldehyde group is always number 1, and higher numbers are given to any substituents.1.3 系統(tǒng)命名法系統(tǒng)命名法 Aldehyde 醛醛 1 NomenclatureH C HOformaldehydeH COCH3acetaldehydeC HOCH

4、3CH2CH2CHCH32-methylpentanal2-甲基戊醛C HOClCH2CH23-chloropropanal3-氯丙醛(甲醛 mathanal )( 乙醛ethanal )5 4 3 2 13 2 11 NomenclatureClHOHCHOCH33-methylbenzaldehyde3-甲基苯(基)甲醛(Z)-3-chloro-3-phenyl-2-propenal(Z)- 3-苯基-3-氯-2-丙烯醛3 24 15 63 2 11 NomenclatureThe “e” of the parent alkane is dropped, and the suffix “o

5、ne” is appended. The number of the carbon atom bearing the carbon-oxygen double bond begins the name. Give the carbonyl group the smallest number as far as possible. Aromatic ketones are often named by treating the benzene ring as a phenyl group.Ketone 酮酮1 NomenclatureCOCH3CH3propanoneCOCH3CHCH2CH3C

6、H33-methyl-2-pentanone3-甲基-2-戊酮OOOOCH34-methoxycyclohexanone4-甲氧基環(huán)己酮1,4-cyclohexanedione1，4-環(huán)己二酮(acetone丙酮)1 2 3 4 51 42 36 52 31 NomenclatureCOCH3COmethyl phenyl ketone苯苯(基基) 甲甲(基基) 酮酮甲(基)苯(基) 酮cyclopropyl phenyl ketone 苯基環(huán)丙基酮( phenylethanone 苯乙酮 )OCH3CH3CH3( 2,2-dimethyl-1-phenylpropanone, 2,2-二甲基

7、-1-苯基-丙酮)t-butyl phenyl ketone (苯基叔丁基酮)1 Nomenclature1 232 Preparing Aldehydes and Ketones2.1 Oxidation of alcoholsRCHORCH2OHCrO3C5H5N2Collins reagent: CrO32C5H5NR C ROR CH ROHK2Cr2O7/H+KMnO4/H+or2. Ozonization of alkenesR COH +COR1R2CCHRR1R2O3O OCCORR1R2HZn/H2OOzonide臭氧化物臭氧化物2 Preparing Aldehydes a

8、nd KetonesShow the major product of the following reaction:Exercise:H3CO3Zn /H2OCOH3CCH2CH2CH2CHO3. Friedel-Crafts Acylation ReactionAcyl chlorides or acid anhydrides react with benzene under the influence of an equivalent (not a catalytic amount) AlCl3 to form aromatic ketones. R CO2)( R COOR COCl

9、acyl acyl chloride acid anhydride ?；?酰氯 酸酐2 Preparing Aldehydes and KetonesR C ClO/AlCl3C RO(RCO)2O/AlCl3C RO2 Preparing Aldehydes and KetonesH3CO(CH3CO)2O /AlCl3H3COCOCH33. Structure and Physical PropertiesFIGURE. Structure of acetaldehyde乙醛乙醛3.1 羰基的結(jié)構(gòu)羰基的結(jié)構(gòu)CCHOHHHAlkene Carbonyl group烯烴烯烴 羰基羰基3. St

10、ructure and Physical PropertiesEthylene Formaldehyde乙烯 甲醛C H3C H2C H C H2C H3C H2C H OC H3C H2C H2O H1-Butene Propanal1-丁烯 丙醛Dipole moment: 0.3D 2.5D沸點(diǎn)：水溶性：(g/100 mL)不溶性 20 任意比混合3. Structure and Physical Properties-6 49 97CH3CH2CHCH2CH3CH2CHOCH3CH2CH2OH1-Butene Propanal 1-Propanol3.2 物理性質(zhì)物理性質(zhì)4. Chem

11、ical Properties燃燒熱：燃燒熱： (Heat of Combustion)FormaldehydeORHORRButanal 2-Butanone2475kJ/mol 2442kJ/molCH3CH2CH2CHOCH3CH2CCH3O電效應(yīng)電效應(yīng)(Electronic effects) Recall that alkyl groups are electron donating. 空間位阻效應(yīng)空間位阻效應(yīng)(Steric effects) 4. Chemical PropertiesKetone酮酮has two electron-donating alkyl groups tha

12、t stabilize the partial positive chargehas only one electron-donating alkyl groups that stabilizes the partial positive chargeAldehyde醛醛CO(H)RCH 親核加成反應(yīng)親核加成反應(yīng)(Nucleophilic Addition) 碳及碳及 氫的反應(yīng)氫的反應(yīng)(Reactions at the -position)氧化和還原反應(yīng)氧化和還原反應(yīng)(Oxidation and Reduction)4. Chemical Propertieso + + - -4.1 親核加成

13、反應(yīng)親核加成反應(yīng)(Nucleophilic Addition)4. Chemical Propertiessp2 sp3Lewis basesLewis acidsArrhenius concept of acids and basesBrnsted-Lowry concept of acids and basesLewis concept of acids and bases4. Chemical PropertiesAcid-base conceptAcid-base concept4.1.1 與氫氰酸加成與氫氰酸加成(Addition of Hydrocyanic Acid)Cyanoh

14、ydrin氰醇(-羥基腈)Alcohol Acid-羥基酸4. Chemical PropertiesAldehyde HydrogencyanideR COCH3HCNC CH3OHCNR+HR C CH3OHCOOHketoneR-COHHCNC HOHCNR-+HR-C HOHCOOH All aldehydes include aliphatic and aromatic aldehydes.COHR-Aliphatic methyl ketones.R COCH3 Cyclic ketones which the rings contain eight or less carbon

15、atoms.(CH2)nOn8反應(yīng)物的結(jié)構(gòu)要求：反應(yīng)物的結(jié)構(gòu)要求：CyclohexanoneHCNOOHCN+HOHCOOH4. Chemical Properties4.1.1Addition of Hydrocyanic AcidCyanohydrin Derivatives in NatureAmygdalin苦杏仁苷Mandelonitrile苯乙醇酰(扁桃腈)Benzaldehyde苯甲醛COHNHOHCN+ToxicOOOOHHOHOOHHOOOHOHCNcyanohydrinalcohol acid氰醇， -羥基腈醇酸(Ar) RCOHHCN(Ar) RCOHHCN(Ar) RC

16、OHHCOOHH2O / H+ H (Ar) RCOHHCH2NH2-hydroxy amine-羥基胺4.1.1 與氫氰酸加成與氫氰酸加成(Addition of Hydrocyanic Acid)4. Chemical Properties4.1.2 與亞硫酸氫鈉的加成與亞硫酸氫鈉的加成(Addition of sodium bisulfite)-H2O/OH+H2O/HorR-COHWhite Crystal4. Chemical PropertiesR-COHC HSO3HONaR-R-C HOHSO3NaNaHSO3-H2O/OH+H2O/HorCOCH3RNaHSO3C CH3ON

17、aSO3HRR C CH3SO3NaOHCOCH3RWhite Crystal-H2O/OH+H2O/HorONaHSO3SO3HONaOHSO3NaOThe product of bisulfite(亞硫酸氫鹽) addition is often a nice isolable solid. So it is also a distinguish reaction. But more important, via this reaction we can purify aldehydes and some ketones. 4. Chemical Properties4.1.2Additi

18、on of sodium bisulfite All aldehydes include aliphatic and aromatic aldehydes.COHR- Aliphatic methyl ketones.R COCH3 Cyclic ketones which the rings contain eight or less carbon atoms.(CH2)nOn8反應(yīng)物的結(jié)構(gòu)要求：反應(yīng)物的結(jié)構(gòu)要求：4. Chemical Properties4.1.2Addition of sodium bisulfiteExample ：Point out which compounds

19、of the following molecules can react with sodium bisulfite:COCH3(1)COCH3CH2(2)(3)COHCH3CH2CH2CH2CH3O(4)CH3CH2C CH2CH3O(5)Exercise:4.1.2Addition of sodium bisulfite4.1.3 與水的加成與水的加成(Addition of water)R C H(R)OH2OR C H(R)OHOHGeminal Diol偕二醇4. Chemical PropertiesH2OC H(R)OCl3CC H(R)OHOHCl3CChloral Hydra

20、te, Ataractic水合三氯乙醛，鎮(zhèn)靜劑Chloral三氯乙醛H+CORH + ROHHemiacetal半縮醛Acetal 縮醛4. Chemical Properties4.1.4 與醇的加成與醇的加成(Addition of Alcohols)AldehydeROHCORHdry HClCRHOHORdry HClROHCRHORORAcetals(縮醛) or ketals(縮酮) are stable to base, oxidants and reducer. So carbonyl compounds can be protected by converting them

21、into their acetal or ketal forms, and then regenerating as needed.OOOCH2CH2HOCH2CH2OH/H+4. Chemical Properties4.1.4 Addition of AlcoholsKetals縮酮縮酮Acetals as ProdrugsProdrug(前藥前藥)pharmacologically inactive compounds that are converted by the body into active compounds.Fluocinolone Acetonide Acetate醋酸

22、氟輕松OHHOFFHOHOOOHO+OActive drugOHHOFFHOOOOOExercise:OOHOHOOOHHOO10-12 根據(jù)下列環(huán)狀半縮醛或縮醛的結(jié)構(gòu)，推測其原來的開鏈羥基醛或羥基酮的結(jié)構(gòu)(2)(1)Exercise:H3COOCH3H3CHOHOCH3OHOHOCH3H3CO(3)H C HORMgXH C HROMgXH+RCH2OH4.1.5. 與格氏試劑的加成與格氏試劑的加成(Addition of Grignard Reagents)4. Chemical PropertiesRMgXH+CHORCHROMgXRRCHROHRMgXH+CORR1CROMgXRR1R

23、CR1ROH伯醇仲醇叔醇甲醛醛酮4.1.6 與氨衍生物的加成與氨衍生物的加成(Addition of derivatives of ammonia)Carbinolamine醇胺ImineN-取代亞胺Schiff s base 希夫堿4. Chemical PropertiesCORR1CRR1OHNH YR C N-YR1H2N YH2O-Primary amine 伯胺4. Chemical PropertiesOxime肟 (w)Hydroxy amine羥胺Hydrazine 肼Hydrazone腙4.1.6 Addition of derivatives of ammoniaCORR

24、1R CR1N OHH2N OHH2N NH2R CR1N NH2CORR1Phenyl hydrazine苯肼Phenyl hydrazoneH2N NHCORR1R CR1N NH2,4-dinitrophenyl hydrazone2,4-二硝基苯腙Yellow precipitationFormation of 2,4-dinitrophenyl hydrazone can diagnose the presence of a carbonyl group.4. Chemical Properties4.1.6 Addition of derivatives of ammoniaCOR

25、R1H2N NHNO2NO2R CR1N NHNO2NO22,4-dinitrophenyl hydrazine2,4-二硝基苯肼Imines as ProdrugsH2NOHONOOHHHhydrolysisH2NOHOProgabideOHFNClNH2O-氨基丁酸羸羸 贏贏在“ ”中找到“ ”哈雷望遠(yuǎn)鏡級別哈雷望遠(yuǎn)鏡級別羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸

26、羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸贏羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸贏羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸羸-carotene-胡蘿卜素胡蘿卜素OHvitamin A (retinol)視黃醇視黃醇(維生素維生素A)OHOOHOHhH2NproteinNHproteinNHproteinOH+H2N-proteinH2Oretinal 視黃醛視黃醛 11-cis-r

27、etinalrhodopsin視紫紅質(zhì)視紫紅質(zhì)vitamin A (retinol)視黃醇視黃醇(維生素維生素A)4.2 碳及碳及 氫的反應(yīng)氫的反應(yīng)(Reactions at the -position)4. Chemical PropertiesCOCH+-. . - 共軛效應(yīng)共軛效應(yīng)4.2.1 醇醛縮合醇醛縮合(Aldol Condensation)COHRCH22dilute OH-COHCHCHRCH2ROHAldol 醇醛4. Chemical Properties -hydroxyaldehyde(-羥醛羥醛) , -unsaturated aldehyde( , -不飽和羥醛不飽

28、和羥醛)COHCRCH2CHRMechanism of aldol condensation :COHRCH2 OH-R CH CHOR CH CHOCOHRCH2+COHRCH2COHCHCHRCH2RO-COHCHCHRCH2ROHH2OCarbanion碳負(fù)離子IntermediateAldol4. Chemical Properties4.2.1 Aldol CondensationCCH2CH3CHOCH3CH2CH2CHLike most intermolecular reaction(分子間反應(yīng)), the aldol condensation has an intramolec

29、ular version. Particularly favorable are intramolecular condensation that form the relatively strain-free five- and six-membered rings.NaOH,H2OCH3CH2CH2CHO4. Chemical Properties4.2.1 Aldol CondensationNaOH,H2OCOCH3CH2CH2CH2CH2COCH3CH3CCH3OCH3OHOCH3COHCHCCH3交叉醇醛縮合(Crossed Aldol Condensation)4. Chemic

30、al Properties4.2.1 Aldol CondensationCOHCHCHCH3OH+COHCH3CH2NaOH,H2OCHO克萊森克萊森-斯密特反應(yīng)斯密特反應(yīng)(Claisen-Schmidt)4.2.2 鹵代反應(yīng)鹵代反應(yīng)(Haloform Reactions)4. Chemical PropertiesCORCH2H(R)X2, H+COH(R)RCHXCORCH2H(R) OH-X2,COH(R)CRXXCOR(H)CH3X2,NaOHCOR(H)OH + CHX3Haloform鹵仿X2+ NaOHNaOXCOR(H)CH3COR(H)CX3NaOXNaOHCHX3+COR

31、(H)OH4. Chemical Properties4.2.2 Haloform Reactions鹵仿反應(yīng)鹵仿反應(yīng)NaOHCOCH3I2,COOH + CHI3IodoformYellow solidCHI3CH3CH R(H)OHI2,NaOHR(H)COOH +NaOICOCH3R(H)4. Chemical Properties4.2.2 Haloform ReactionsYellow solidCuprous OxideBrick red colorFehlings reagent: A + B A: CuSO4 (Copper Sulfate), B: the solution

32、 of potassium sodium tartrate(酒石酸鉀酒石酸鉀) and sodium hydroxide(氫氫氧化鈉氧化鈉).R CHOR COOHFehlings reagentCu2O+COOHR-H+KMnO4/CHOR-Silver mirror reaction銀鏡反應(yīng)銀鏡反應(yīng)Tollens reagentAg+Ag(NH3)2OHCOOHR-CHOR-4. Chemical Properties4.3 氧化和還原反應(yīng)氧化和還原反應(yīng)(Oxidation and Reduction)4.3.1 OxidationTollens reagent can react wit

33、h all aldehydes (aliphatic and aromatic), but Fehlings reagent only can react with aliphatic aldehydes. You can use Fehlings reagent to distinguish aliphatic aldehydes and aromatic aldehydes.4. Chemical Properties4.3.1 OxidationAldehydes 醛Ketones 酮Tollens reagentFehlings reagentAliphatic aldehydesAr

34、omatic aldehydes(1) A B CABCI2 / NaOH不產(chǎn)生黃色沉淀不產(chǎn)生黃色沉淀BCAAg(NH3)2NO3產(chǎn)生銀鏡產(chǎn)生銀鏡B不產(chǎn)生銀鏡不產(chǎn)生銀鏡C產(chǎn)生黃色沉淀產(chǎn)生黃色沉淀P14610-14 試用簡便的化學(xué)方法化學(xué)方法鑒別下列各組化合物OHCHO CH3CHOExercise:CH3(CH2)4CHOCHOCH2OHCOCH3 A B C DABCD托倫試劑托倫試劑不產(chǎn)生銀鏡不產(chǎn)生銀鏡ABCD斐林試劑斐林試劑產(chǎn)生磚紅色沉淀產(chǎn)生磚紅色沉淀A不產(chǎn)生磚紅色沉淀不產(chǎn)生磚紅色沉淀B產(chǎn)生銀鏡產(chǎn)生銀鏡I2 / NaOH不產(chǎn)生黃色沉淀不產(chǎn)生黃色沉淀C產(chǎn)生黃色沉淀產(chǎn)生黃色沉淀DExerci

35、se:(3)R-CHOR-H2,PtCH2OHR-COH2,PtR-R-CHOHR-CH2OHR-CHOR-LiAlH4Lithium aluminium hydrideCH2OHR-CHOR-NaBH4Sodium borohydride4. Chemical Properties4.3.2 Reduction:Metal hydrides can reduce aldehydes and ketones to give alcohols. 伯醇仲醇醛酮Compare with hydrogenation reaction, application of metal hydrides is

36、more selective. Metal hydrides only reduce the carbonyl group but not carbon-carbon double bond.H2,PtNaBH4CH2CH CH2CH2CHOCH3CH2CH2CH2CH2OHCH2CH CH2CH2CH2OH4. Chemical Properties4.3.2 Reduction:COHR-R-( )R-Zn-Hg/HClCH2H R-( )Zn-Hg/HCl:鋅汞齊鋅汞齊(zinc amalgam)克萊門森反應(yīng)克萊門森反應(yīng)(Clemmensen Reaction)COHR-R-( )R-C

37、H2H R-( )85%H2NNH2H2O/NaOHDEG or TEGDEG: Diethylene glycol, 二聚乙二醇二聚乙二醇(HOCH2CH2)2 OTEG: Triethylene glycol, 三聚乙二醇三聚乙二醇(HOCH2CH2OCH2)2O烏爾夫?yàn)鯛柗?Wolff)-凱惜納凱惜納(Kishner)-黃鳴龍黃鳴龍 Reduction4. Chemical PropertiesMethylene亞甲基4.3.2 Reduction: If the start material contains acid sensitive groups, Wolff-Kishner-黃

38、鳴龍黃鳴龍 Reduction is applied to reduce the carbonyl group. Clemmensen Reaction is used to those carbonyl compounds which contain base sensitive groups.4. Chemical Properties4.3.2 Reduction:OHCOCH3Zn-Hg/HClOHCH2CH3康尼查羅反應(yīng)康尼查羅反應(yīng)(Cannizzaro Reaction)HCHOconc.NaOHHCOOH + CH3OHCHOconc.NaOHCOOH+CH2OHWhen a n

39、o -hydrogen aldehyde react with concentrated sodium hydroxide solution, some of the aldehyde has been oxidized to carboxylic acid and some reduced to alcohol. This is the Cannizzaro Reaction.4. Chemical Properties4.3.2 Reduction:HCHOHCOOHCHOconc.NaOH+CH2OH+The reductive ability of formaldehyde is st

40、ronger than most other aldehydes. When excessive formaldehyde react with another no -hydrogen aldehyde in concentrated sodium hydroxide solution, formaldehyde will become formic acid and the another aldehyde will become alcohol. This is the crossed Cannizzaro Reaction.4. Chemical Properties交叉康尼查羅反應(yīng)交叉康尼查羅反應(yīng)(crossed Cannizzaro Reaction)4.3.2 Reduction:5. 重要的醛酮與醌類重要的醛酮與醌類5.1 甲醛甲醛(Formaldehyde)Formaldehyde has antiseptic properties and can be employed in the treatment of urinary tract infections(尿路感染尿路感染) due to its ability to react with nucleophiles present in urine. However, for