有機(jī)化學(xué)上-習(xí)題課二68章

(

CH3CH2)3COH3-乙基-3-戊醇反-6-氯-4-己烯-2-醇ClCH2C

CHCH2CHCH3OHHCH3HO3-甲基-2-環(huán)戊烯-1-醇O

CH2CH3O四氫呋喃(THF)乙基環(huán)己基醚H3COHC

CHCH3甲基丙烯基醚15-冠-5OO

OO

O1S,2S-2-氯環(huán)己醇1R,2R-2-溴環(huán)丙醇4-甲氧基乙苯或：對乙苯基甲醚CH3IHC2H5BrH(2R，3S)-3-溴-2-碘戊烷二、完成下列各反應(yīng)式CHCH3OHClClCH

CH2投影式表示))(以(PhC

H3C

BrC2H5+

H2OPhCH3

CH3OH

HO

PhC2H5

C2H5ClNaICH3COCH3OH-H2O(H3C)2HCBrH3CCH3C2H5ONaC2H5OH3

2(H

C)

HCH3CCH3ClCH3C2H5OHCH(CH3)2C2H5ONa2

5C

H

ONaC2H5OHBrCH33

2ClHHCH3H(CH3)2CHClCH3H(CH

)

CH

ββHH,β,(CH3)2CH

CH3唯一產(chǎn)物CH3BrH3CCH3OH22

2

7CH3CHCH2CH3KCHNHCuaB2,rSrOO4/H

SO2

CCHH4

CCCHHCHCHCH333CCHH33C2CCHH2H3CCC3HCH2H2CCCHHHH3H332OONa

Br

O寫出2-丁醇與下列試劑作用的產(chǎn)物：（1）H2SO4

，加熱

（2）HBr

3）Na（4）Cu

，加熱

（5）

K2Cr2O7+H2SO4CH3CHCCH2CHCH3OH(

PCC

)CH3CHCCH2CCH3CH3CH3OHBrROORPCC：(pyridinium

chlorochromate)吡啶和CrO3在鹽酸溶液中的絡(luò)合物，橙紅晶體，溶于CH2Cl2。CH3CHCHCH2CCH3Br

CH3

OCH3CHCH2CH2COOHOH(

NaCHCH2CH2CHONaBH43CH

CHCH3CHCHCH2CH2CH2OHBrMgEt2O(1)HCHO(2)H3OCrO3NMgBrOHOHHO

CH3C6H5SOCl2乙醚(H3C)2CC(CH3)2OHOHH+ClHCH3C6H5構(gòu)型保持機(jī)理？C

O

S

OR'H23

ClC

ClHRR'RR'O-S

OC+ClH

24醇與氯化亞砜在乙醚溶劑體系中反應(yīng)——構(gòu)型保持RSO2氯代亞硫酸酯

構(gòu)型保持醇與氯化亞砜在吡啶或叔胺溶劑體系中反應(yīng)——構(gòu)型翻轉(zhuǎn)SOCl2Cl

+

HCl+SO2R

OH

R+

Cl-2+

SOCl+－HClNR'R

RR'C

OHHCl-O+

C

O

S

NH

25RC

ORR'HSON+

R'Cl

CH+SO2N構(gòu)型翻轉(zhuǎn)CHOCHOCHCH3CHCH3OHOH(

)2CH3MgBr(

)3H

+OO3/Zn,

H2OOCH2HNO3H2SO4(A)

?HI(B

+

C)?ClOHCH33Br

C

COBrCH+AlClCS23

（ClOH

BrO

CH3C

C

CH3NaC2H5OHClOOCH3CH3）H3C

CH

CH2OCH3OHH+CH3CHCH2OHOCH3OCH3CH3OHH3C

C

CH2CH3ONa(少量）OHBr過量Br,CH3OHH2C

CHCD2ClONaOCH3CH3OH?H2C

CHCD2ClO3CH

O-+Cl-CH3OCH2HC

CD2OOOHCH3CH3OH+S,S-R,R-第一步時(shí)雙鍵也被氧化下列路線是否能進(jìn)行，請給予解釋。OHK

Cr

O2

2

7H+CH2=CHCCH3O

HBrBrCH

CH

CCH32

2O[(CH3)2CHO]3Al

BrCH2CH2CHCH3OH1.

CH2=CHCHCH3異丙醇3+

CH

MgIH3O+Et2OOOHCH(CH3)2CH3(H3C)3CHOH下列化合物酸性強(qiáng)弱的順序是：三、基本概念題BCH3CH3bB.

a>c>d>bHC

CHcC.

d>c>b>aaA.

a>b>c>dD.

b>d>c>aCH+HHHC-HC+CH+C-HHC-ABCDEFA

E

F下列化合物中具有芳香性的是：d下列化合物與Br2水反應(yīng)，按活性大小排列成序。B>

A

>C下列4個(gè)化合物進(jìn)行SN1反應(yīng)的活性大?。?

>

2

>

1

>

4將下列化合物按SN1反應(yīng)活性大小排列成序。A

>

B

>

CCH3CH2CH2Br1CH3CHBrCH32CH2=CHCH2Br3CH2=CBrCH34下列各對化合物按SN2歷程反應(yīng),哪一個(gè)反應(yīng)速率較快?為什么？(CH3)2CHI

(CH3)3CCla.

(CH3)2CHIb.

(CH3)2CHClc.CH2ClCld.

CH3CHCH

2CH2BrCH3CH3CH2CHCH2BrCH3e.

CH3CH2CH2CH2ClCH3CH2CH=CHCl及

及及及及均前者快將下列化合物按SN1歷程反應(yīng)的活性由大到小排列，并說明理由。a.

(CH3)2CHBr

b.

(CH3)3CI

c.(CH3)3CBrb>c>

a下列化合物中哪一個(gè)具有最小的Pka值？為什么？OHOHCH3OHClOHOCH3OHNO2(a)(b)(c)(d)(e)將下列化合物按堿性強(qiáng)弱次序排列，并說明理由。(a)CH3CH2ONa(c)

CF3CH2ONa(b)

CCl3CH2ONa(a)

>

(b

)

>

(c)比較下列化合物在水中的溶解度：(a)

HOCH2CH2CH2CH2OH(b)

CH3CH2OCH2CH3(a)>

(b)>

(c)(c)

CH3CH2CH2CH2CH3解釋下列問題：1、為什么鄰二甲苯的沸點(diǎn)比間二甲苯、對二甲苯的高？2、為什么對二甲苯的

比鄰二甲苯、間二甲苯的高？1、鄰二甲苯分子間接觸面積較大，分子間作用力較大，所以其沸點(diǎn)較高。2、對二甲苯對稱性好，分子排列整齊、緊密，所以其比鄰和間二甲苯的高。比較下列各組反應(yīng)中反應(yīng)速率常數(shù)的大?。?、乙苯的間位硝化、溴苯的鄰位硝化2、苯甲醚的對位硝化、苯的硝化3、苯甲腈的硝化、間苯二甲腈的硝化4、N,N-二甲基苯胺的硝化、甲苯的硝化均前者大于后者。用簡單的化學(xué)方法鑒別以下各組化合物。1)

1,3-環(huán)己二烯、苯和1-己炔四、鑒別、分離題2）(A)(B)(C)(D)Br2CCl4AgNO3醇AgNO3醇BrCH3CH2BrBrBrClClCl3)a.b.c.CH2=CHCH2CHCH2CH3

d.Cl鑒別a、b、d：AgNO3

/EtOHc：Br2如何鑒別對甲苯酚、苯甲醇和苯甲醚？OHCH3CH2OHOCH3FeCl3(aq)Lucas用1H

NMR譜的方法鑒別以下各組化合物。1)

A.B.CH2CH2CH3CHCH3CH3從有幾組吸收峰判別。2) A.

BrCH2CH2BrA.

單峰B.

CH3CHBr2B.

低場四重峰高場二重峰CH3CH3DBr2FeMgD2OCH3H2SO4H2O，P干醚T.

M.五、題以甲苯、乙烯為原料(無機(jī)試劑任選)CH3Cl2hvCH2Cl(A)CH2

CH2HBrCH3CH2BrLiCH3CH2LiCuI(CH3CH2)2CuLi(A)Ph

CH2CH2CH3Ph CH

CH

CH2

2

3Br2hvPh CHCH

CH2

3BrNaOHalcoholPh

CH

CHCH3Cl2500℃2Ph

CH CHCH

ClPh

CH

CHCH2ClBr

BrBr2CCl4OHCHCH2ClClOHCHCH2ClCH3CH2Cl無水AlCl3CH2CH3Cl2FeCH2CH3ClCl2光CHClCH3ClNaOH乙醇，ClHCCH2Cl2-H2O由苯及兩個(gè)碳的有機(jī)原料：ClClDClMgClMgEt2OOH2.

H2OMgBrD2OPBr3MgD1.CH3CH2CHOCl2FeClHNO3H2SO4ClNO2NO2NaOHOHNO2H2ONO2NO2CH3CH2BrCH3CH2MgBrOEt2OH3O+CH3CH2CH2CH2OH2CH

CH2HBrMgEt2O2CH

CH2O2,

AgOCH2

CH2CH3CH2CH2CH2OH以≤C3有機(jī)物及苯(CH3)2C=CHCH2C6H5C

CHCH2C6H5CH3CH3OHCH3CH3CH3CH

CHCH2C6H5消除得共軛烯烴CH3C

CH2CH2C6H5OH①②①OCH3CCH2CH2C6H5②CH3MgXH3CH3CC

OC6H5CH2CH2MgX不可取不可取分析：路線：BrMgBrCH2CH2OHC6H5CH2CH2MgBrCH3CH3CCH2CH2C6H5OHC

CHCH2C6H5CH3CH3Br2FeMgEt2OO①②

H3OPBr3Mg2Et

OCH3CCH3O①②H3OH3PO4以≤C4的烴

乙基叔

醚。CH3CH2O

C(CH3)3CH3CH2Br(

CH3

)3CONaCH3CH2ONa(

CH3

)3CBrCH2CH2HBrCH3CH2Br3

2(CH

)

C

CH2H2SO4H2O3

3(CH

)

COHNa3

3(CH

)

CONaOCH21.

ROHOOROH六、寫出下列反應(yīng)可能的機(jī)理OH+OHOROHOROHOROH+2.OHH2OHOHH+OH2H2OH+(CH3)2CIC(CH3)2OHAg+3

2OH(CH

)

C

C

CH3CH3CH3CH3C

C

CH3CH3

OHCH3CH3C

C

CH3CH3

OH+重排(CH3)2CIC(CH3)2OHCH3CCH3CH3

OCCH3Ag3-苯基-1-丁烯在稀硫酸存在下與水加成，主要得到2-苯基-2-丁醇，而不是3-苯基-2-丁醇，請解釋。CH3CHPh2C

CHHH+CH33CH

CH

CHPhCH3

C

CHPhH2OCH3CHCHCH3PhOHH+H2OH+CH3CCH2CH3PhOH化合物A(C7H12)在中與KMnO4堿性水溶液反應(yīng)生成化合物B(C7H14O2)，A在CHCl3

中與C6H5CO3H反應(yīng)生成化合物

C(C