有机化学第五版第十章课后答案李景宁编.docx
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有机化学第五版第十章课后答案李景宁编
第十章醇酚n
1.解:
ch3ch2ch2ch2ch2oh
*
ch3chzchzchch3
I
OH
CHjCHzCHCH^Hj
I
OH
CH3CHCH£CH2OH
I
ch3
*
ch3ch,chch£oh
I
ch3
*
CH3CH—CHCHs
II1
ch3oh
OH
I
H3C—C—€H2CHs
I
ch3
ch3
I
HaC—C—CH2OH
I
ch3
2.解:
⑴3-甲氧基-£-戊醇
C3)2-对氯苯基乙醇
〔5)2-甲基-1-乙氧基丙烷
(7)对漠苯乙讎
(9)1,2,3-三甲氧基丙烷
题斩
1-戊醇
2-戊醇(一对对映体)
・.
3-戊醇
3-甲基一1-丁醇
2—甲基-1一丁醇(一对对映体)
3-甲基-2-丁醇(一对对映体)
2—甲基—2—~J~醇
2,2-二甲基丙醇
(2)(E)—4—己烯—2—醇
(4)(1S,2R)-2—甲基-1一乙基环己醇
(6)5-硝基—3-氯一—苯二酚
(8)4-异丙基-2,6-二滉苯酚
(10)1,2-环氧丁烷
3.解:
H3Ck/H
(1)O-C
h/\:
h2oh
ch2och3
(2)h2c=chch2cxdh2ch2ch2cii3
(5)CHsCH—CHCH3IIOCII3OCH3
CH3
(7)珂c—C—CH2OHICHS
(8)
(9)H3CIICHCH2CH3
Ndz
(10)
4・解:
ch3ch3
(1)CH3CH2CHCH2CHCH2OH
,OH
(2)CH2—CHCH2chch3
ch3
(4)'Y
jToh
(5)HjC—C-—0_
(6)CHt—CH2
1hJ
no2
ch3
OCH3OCHj
OH
ONa
1
5.解:
(1)
CH3CHCH3
Na1
>CH3CHCH5
[(CH3)2CHO]3A1
OH
(2)3CH3CHCH3+A1—
OH
I冷
(3)CHjCHCHs+H2SO4(浓)►CH3CHOS()2OH
CHS
Oil
(4)CH3CHCH3
竺4吧CH3CHYH2
OH
(5)CH3CHCH3
H2Sg_V14°",(CH3)2CHOCH(CH3)2
(6)
OH
1
CH3CHCH3
+NaBr+H2SO4—>
Br
I
CH3CHCH3
(7)
OH
I
CH3CHCH3+I2
I
ch3chch3
(8)
OH
I
CH3CHCH3
+SOCI2
Cl
I
CH3CHCH3+SO2+HC1
OH
(9)
CH3CHCH3
SO2C1
SO2OCH(CH3)2
(10)(CU3)2CHONa+C2H5Br—>(CH3)2CHOCH2CH3
(11)(CH,)2CHONa+(CH,)3CC1—>H?
CY(CHJ?
+(CH>CHOH
(12)(CH,)3CHOCH(CH3)24-HKidfi)—2(CH3)2CHI
6.解:
两个反应的反应式分别为:
CH$CH:
(1)
(2)
H3C-4—ONa+CH3CH:
Br一>H,C——OCZHS+NaBr
CH,•CH;
CH,
HjC—j—Br十GHsONa—CH,=-C(CH3)t+C,H5OHCH3
(1)式是CH3CH2Br与(CHJsCONa发生的亲核取代反应,生成醸;
(2)式是(CH3)3CBr在CH3CH2ONa作用下发生的消除反应,产物为牙丙烯。
7.解:
该反应过程中经过CH3CH2CDCH3的產排反应,反应式为
OH
OH
CH3CH2CDCH3
CH3CH2CDCH3
二ch3ch2cdch3
氢遠排+Br"
CH3CHCHDCH3>CH3CHCHDCH3
I
Br
Br~
CH3CH2CDCH3
CH2ONO2
CH2ONO2
&解:
(1)
(4)
(5)
(6)
(CH3CH2)2CHI+CH3I
(7)
(8)
CH3CHCH2OH
(9)
CH3CHCH2OCH3
(10)
OH
9.解:
)
Hs
OH
H
(2)
—ch3
OHOHOH
10.解:
OH
CH3CHCH(CH3)2
OH
Br"
解:
(1)
CHsCH—CH—CH-
CH,CH—CH—CH—
Br
CH3CHCH
CHaCHC
(2)-H2O
C^CHiCCCH,):
CH3CHCH(CH3)2
H贡排
+
CH3CH2C(CH3):
Br
CH3
OSO
ch3
(CH3)3CONa
最后一步反应为E2反式消除
OH
,不能得3-甲基环己烯
解^
(1)
H2CH2MgCl
(1)CH3CHO
(2)H3O+
O
H
CH3
"a
C—CH3
(CH3)2CHMgBr
H3O+
OH
(1)HCHO
CH2CH2CH:
OH
(2)
CHCH3
(1)CHaMgBr
⑵HsO+
(1)(CH3)2CHCHO
CHSCH—CH—CH(CH3):
CH3OH
(2)H3O+
HH*
H3-A'解:
(1)ch3ch2ch2ch2oh-a2Cr2O7+HtSO<
CH3MgBr
CH3CH2CH2CH2OHCH3CH2CH—CH2
ch3ch2ch2cooh
竺咚'ch3ch2chch2
BrBr
CH3CH2CH2CH2OH—CH3CH2CH—CH2
HOC1
CH3CH2CHCH2
II
OHC1
(1)
(2)
11.
(2)
(3)
12.
(2)
(3)
(4)
(5)
13.
(1)CH3COCH3
(2)H3O+>(3)Na
(3)HaC^CHCH$拧CH3CH?
CH?
Br-CH】H2CCH?
MgBr
H2O2
CH3
I
CH3CH2CH2C—ONa
I
ch3
H3CHC—€H2
Cb,高温
C1H2CHC—ch2
ch3
I
H20-CHCH2oc—ch2ch2ch3
ch3
ch3
I.
CH3CH2CH2C—ONa+C1H2CHC=CH2
I
ch3
Br
(4)H2C—CHCHs
业ch3chch3
(CHs)2CH—'
磺化碱熔-厂0—ONaCH3CHCH3
/=\CH3CH—CH:
H*
CH,
CHS
(1)Cb•高温
(2)oftho
(3)Na
(CHj),CH—0-^2^—CH(CH,)2
CHsCHzCHzCl
*Na
(5)5CH4+3O2—>HC=CH+3CO+6H2+3H2O
Cu"NH代H?
cYHCKH&OHS沁
2HC三CH
o
II
h2c=c—cch3
5…尹
(6)
H
OH
OH
O
MgBr
MgBr
(7)
H2/Pd-BaSO4
HC三CHNaN%HC三CNa讯叫HC三CCH3h2c—chch3CH3CHCH3HC^CNa>(CH3)2CHC^CH
Br
沁(CH3)2CHCH2CH2MgBr"(CH3)2CHCH2CH2C-CH3
ch3
:
5.解:
(1)加入适量Na后除去乙醇,或加入无水CaCL后滤去结晶醇。
(2)加入干燥的CaO后除去水。
(3)加入NaOH溶液,分层后分出上层环己醇。
16.解:
a的可能结构为〔丁。
14或Ct°h(反应式略)。
OHOH
7
11
c—ch3
CH3CH3
h3c—c=c—ch3
II
CH3CH3
冷KMnO4
(A)
OH
I
H3C—C—CH—CH3
II
CH3CH3
(C)
(B)
巴丄2CH3COCH3
18.解:
结构式为
乩653.6H3C\ff
CH—CHCHs^l.1愍/in
82.6
19.
解:
A的结构式为
HI
OH
(B)
h3
H2SO4
OHC(CH2)4CCH3
(2)Zn/H2O
20.
为主
E2,CH3CH=CHCH3
E2,CH3C=CH
CzHsONa
H
H
H
(5)
CH3CH2Br―
CH3CH2OCH2CH3(Sn2)
NaNH2
ch2
C2HsOK
CH2(E2)
(6)
CH3(CH2)15CH2CH2Br一
CH3(CH2))5CH?
CH2OGHs空JQK,CH3(CH2)15CH=-CH2(E2)
(Sn2)
CzHsONa
CHOH,25・CCHsfCH?
(E2)
(CH3)3CBr—
CH3
C2H5OH
(CHs^COGHs(SN1)
CHsCHzCHzBr「CaHsOH'
(CH3)2CHCH2Br
C2H5OH1
C2H5OCH2CH2CH】(Sn2)
(CHJ2C—CH?
(E2)
CH3CH2CH2CH2OH(Sn2)
CH3CH2CH=CH2(E2)
KOHhIo-(9)CH3CH2CH2CH2Br一
KOH
C2H5OH
23.解(略)
24.解(略)
25.解:
(1)(£)一5-径基一1一氯一2-己烯
(2)3-甲基-2-环戊烯-1-醇
(3)2,2—二氯乙醯
(5)2-甲基-4-乙烯基苯酚
(4)聚乙二醇
CH3
CH3
(7)
HCH
(8
(10)ch2=chch2sch2ch—ch:
(12)
(14)H
H2CHCOO-
NH3+
OH
26•解:
(8)
CH3CH—CHCH3;CH3CH=CHCH2Cl;CH3CH=>CHCH2Ph
(13)(CH3)2CBrC(CH3)s;(CH3)2CDC(CH3)3
ch3
27.解:
(1)反应经CH3CH2CHCH2CH,重排成CHjCHjCHCHCH:
和CH3CH2CCH2CH3•再
CH)
CH
发生取代和消除反应得产物。
(2)先生成铎盐,然后生成碳正离子,再发生频哪醉重排。
(3)反应经<5重排成,p-消除反应得产物。
/XX./Ok
(4)在(CH3)3COK的作用下,先生成(CH6C——CHCH2和CH)C——CHCHS,再生成
O~O'
(CH3)2C—CH=CH2和IIsC—C—CH—CHj,接受H“得产物。
CH2
OHH
/O\
(5)经HaC—C—CHH2和(CHS)2C—^CHCH^Br中间体,再脱H十得产物。
I、B/ch3
OH
(6)先生成,再扩环•脱H+得产物。
(7)反应按加成-消除历程进行芳环上的亲核取代反应。
C无光学活性,是内消旋体
(2)
CH(CHs)2
(5)
A:
D:
HO
OH
(6)
(7)
(8)
29.
(2)
CHa
A:
(CH3)2CCH2CH3o—chch=ch2心
H3(\・/CHs
A:
C—C
*、H
或
反应式略
OH
B:
(9)
H2CH=CHCH3
•ZHo=c
、CHj
C:
CH3CH2CHCH3IOH
解.⑴氯甲基化.Mg,无水乙醸
HjO+
OH
ch3
(3)
H3C—C—CH2
TM
HCHOFT—砖™
OH・
(2)Mg•无水乙熬
OH
(4)CH,CHO
CH2=CHCH2MgBrH*无水乙NH?
O
H2O-CHCH2CHCH3
CHiCH2CH2CHCH3—S°^TM
(I)BzHe
⑵HQ,OH-
OHOH
⑸o警
(1)ClHsMgBr
~C2)H3O7
(6)
30.
c-
解:
(1)
△
3出Bri»Av
Ni,A•压力•*
Ag20,02
ch3
6
7°
V)
97^H2SO4
130~140r
TM
无水AlCh
H:
OKMnO<
CH3
Fe+HClNaNO?
+HCI
TM
31.
解:
(1)
CHiCHtCOCi
AlCb
FeCh
C0+HC1“_c
AlCl^Cu^TH,c_vl/CH01
o
HjC—CHO+
H3PO4
HCHO4-HC1
H:
MgCl
王為rCXMgC1
CHyCHOH3O+HBr
—无水THF
Mg
HCHO
磺化破熔
TT混酸H►
OH+O2N
NO2
/NO2
■^3-oh塑Q-oh
HCHO.HCI"hTpoT"
NaOH
O~CH2C1
TM
32.解
(1)2H2C——t
ch2
ch3ch2o-
CII3CH2OCH?
CH?
och2CH2OH
tjc
(2)H2C^—^CH2-j^-HOCHiCHzOH
0OHSOC12
H+
°—OH
n-BuOH/NaOH-H2O
TM
(4)
(5)
CHwCH+CHsMgCl
CHwCMgCl
—2ch=cch2ch?
oh
OCH2CH2CH3
h2o
Hg+HSO.™
H3C—C—CHzHgOAc
NaBH<
TM
CHS
CH3
Br
(CHahCHCI
A1C13_
H(CH3)2Cl.FeCh
NBS
引发剂
c(ch3)2
9
Cl