Chapter 9 Oxidation – Reduction Reaction 氧化 — 还原反应
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Transcript of Chapter 9 Oxidation – Reduction Reaction 氧化 — 还原反应
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Chapter 9 Oxidation – Reducti
on Reaction 氧化 — 还原反应
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一、氧化 - 还原反应基本概念二、还原 — 催化氢化 — 电子 - 质子还原(液氨 / 金属) — 负氢还原(金属氢化物)三、氧化 — 醇 — 不饱和烃 — 醛酮
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一、氧化 - 还原反应基本概念
• 无机化学中的氧化还原表现为元素的原子价态的变化
• 在有机化学中,碳始终是四价,其氧化还原的特点是部分的电子得失
• 因此广义的说多数有机反应都是氧化还原反应,不过习惯上将加氧或脱氢的反应称为氧化,脱氧或加氢的反应称为还原
C H: C Cl:
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This is a reduction reaction, and it also can be called as an addition reaction.
This is an addition reaction, but in fact, it can be considered as an oxidation reaction.
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脱氧或加氢脱氧或加氢的反应的反应
称为还原称为还原
加氧或脱氢加氧或脱氢的反应的反应
称为氧化称为氧化
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Oxidation State (氧化态)
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二、还原反应 ( 一 ) 催化氢化
The reduction by addition of two hydrogen Ato
ms (通过加氢的还原) can be carried out in th
e presence of a metal catalyst, so it is called C
atalytic Hydrogenation ( 催化氢化 ).
• alkenes ( C=C ), alkynes ( C≡C )
• imines ( C=N ), nitriles ( C≡N )
• aldehydes or ketones ( C=O )
Yes
No But, RCOOH, RCOOR’, and RCONHR’
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1. 机理• 催化氢化的机理还没有完全研究清楚,通
常认为氢吸附在金属的表面,烯烃也通过p- 轨道与金属络合,然后烯烃与氢加成。
• 其立体化学特征是 —— Syn-addition
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2. Hydrogenation of C = C and C≡C bonds
—— 烷烃或顺式烯烃的合成
CH
CCH3 C CCH3
H
H3C
H
H2 / Pt, Pd, or Ni
H2 / Pt, Pd, or Ni
H2 / Lindlar's cat.
CH3CH2CH=CH2 CH3CH2CH2CH3
CH3CH2CH2C CH3CH2CH2CH2CH3
CH3C
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• 反应活性: —— 芳香烃的氢化还原难 —— 烯烃活性:乙烯 > 单取代烯烃 > 双取代烯烃 > 三
取代烯烃 > 四取代烯烃
Ïà ¶Ô·´ Ó¦»î ÐÔ
900 306 294 150 134 5 1.0
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CH3CH2CH2CH3
H2,Ni
200 °C
CH3CH2CH2CH2CH3H2,12%Pt/C
300 °C
CH3CH2CH3
H2,Ni
120 °C
反应活性:反应活性:
———— 小环易氢化开环小环易氢化开环
———— 催化剂活性:催化剂活性: Pt > Pd > NiPt > Pd > Ni
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CH3
H3CCH3
HH
CH3H3C
not
HH
CH3H3C
H3C
H2,PtO2,EtOH
~100MPa,25 C°
H3C
Cis-Syn-erythro
立体化学:立体化学:顺式加成,立体专一性反应顺式加成,立体专一性反应
trans-Syn-threo
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3. Hydrogenation of C=O, C=N and C≡N bonds —— 醇、醛、胺的制备
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酰卤的催化氢化在部分钝化的催化剂作用下可以停留在醛的阶段—— Rosenmund 还原
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4. 其它基团的还原 ① 苄基醚(或硫醚)的还原(去保护)
CH2-SCH2Ph
OCH2Ph
H2 , Raney Ni CH3
OH
CH3
CH(CH3)2
NO2 H2 , Raney Ni
CH3
CH(CH3)2
NH2
② ② 硝基化合物的还原(芳香胺的合成)硝基化合物的还原(芳香胺的合成)
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5. Relative reactivity of the Functional Groups by Catalytic Hydrogenation
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Ph-HC CH-CH
O1mol H2
Pd / C
Ph-HC CH-C-Ph
O1mol H2
Pd / C
Ph-H2C CH2-CH
O
Ph-HC CH-CH
O?
Ph-HC CH-CH
O O1mol H2
Pd / C Ph-H2C CH2-CH
O OHCl
Ph-HC CH-CH2OH
Ph-H2C CH2-C-Ph
O
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( 二 ) 电子-质子还原
• Reduction by addition of an electron, a proton, an electron, a proton
—— Na (Li) in liquid ammonia, Na (Li) donates an electron to the compound and ammonia donates a proton.
—— is called as a dissolving metal reduction
—— 可被还原的化合物主要有炔烃、苯和酮
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1. 炔烃的还原
炔烃被还原成炔烃被还原成反式烯烃反式烯烃此条件下此条件下双键不被还原双键不被还原
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C CH3C CH3 + Na C CH3C CH3Na- H NH2
NH2-
C CH3CH
CH3 Na-
NaC CH3C
H
CH3
H NH2
NH2-
H
CH3
H3C
H
a radical anion
a vinylic radical a vinylic anion a trans alkene
反应机理
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Na or Li
NH3 ( liq ) , EtOH
Na or Li
NH3 ( liq ) , EtOH
CH3 CH3
Na or Li
NH3 ( liq ) , EtOH
Na or Li
NH3 ( liq ) , EtOH
2. Birch Reduction of Benzene
• 与苯环共轭的双键可以被还原,而不与苯环共轭的双键不能被还原
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三 伯奇还原 (Birch reduction)
定义:金属钠溶解在液氨中可得到一种蓝色的溶液, 它在醇的存在下,可将芳香化合物还原成 1 , 4- 环己二烯化合物,该还原反应称为伯奇还原。
Na NH3(l) C2H5OH
1 K 、 Li 能代替 Na ,乙胺能代替氨。
2 卤素、硝基、醛基、酮羰基等对反应有干扰。
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反应机理:
Na + NH3 Na+ + ( e-) NH3
(e-)NH3
H H
H H
CH3OH -CH3O-
(e-) NH3CH3OH
自由基负离子
金属钠溶解在液氨中可得到一种兰色的溶液,这是由钠与液氨作用生成的溶剂化电子引起的。
溶剂化电子
自由基
负离子
环上有给电子取代基时,反应速率减慢。
环上有吸电子取代基时,反应速率加快。
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伯奇还原的实例和说明
COOHCOOH
A A
CH3
*1 一取代苯还原时,可以有两种产物,
A 为给电子取代基时,主要得( 1 )。
A 为吸电子取代基时,主要得( 2 )。
*1 一取代苯还原时,可以有两种产物,
A 为给电子取代基时,主要得( 1 )。
A 为吸电子取代基时,主要得( 2 )。
( 1 )( 2 )
CH3
Na NH3(l) C2H5OH
Na NH3(l) C2H5OH
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OCH3 OCH3
OOH O
Li NH3(L) C2H5OH HCl, H2O
H+
*2 不与苯环共轭的双键不能在该条件下发生还原,与苯环共轭的 C=C 双键能在该条件下发生还原。而且反应首先在此处发生。
*2 不与苯环共轭的双键不能在该条件下发生还原,与苯环共轭的 C=C 双键能在该条件下发生还原。而且反应首先在此处发生。
*3 经伯奇还原,制备,不饱和酮。*3 经伯奇还原,制备,不饱和酮。
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3. 酮的双分子还原 —— 片呐醇( pinacol )的合成及 Pinacol 重排
O2 C
OH
Ph
Ph
C
OH
Ph
PhNa
NH3( L)
C
O
H3C CH32Mg
±½C C
OH
CH3
CH3
CH3
H3C
OH
Ph2C
O
PhCPh
Na , NH3(liq)2
Na
CPh
O
PhNaNa
Ph
O
Ph
O
Ph
Ph2
H2OPh
OH
Ph
OH
Ph
Ph
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( 三 ) 负氢还原
• Reduction by Addition of a Hydride ion and a Proton
NaBH4 (硼氢化钠) LiAlH4 (氢化铝锂)
醛、酮 醇
酸、酯酰胺
醇、胺
NaBHNaBH
44
LiAlHLiAlH44NaBHNaBH44不反应
常用还原剂
Al-H bonds are more polar than B-H bonds, so Al-H bonds are more polar than B-H bonds, so LiAlHLiAlH4 4 is a stronger reducing reagent thanis a stronger reducing reagent than NaBHNaBH44
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• Mechanism:
H3Al H C O AlH3 C O+
H
C O
H
AlH3
C OC O
H
AlH
3
C O
H
Al
4
C O
2H2OC OH
H
+ AlO2
负氢对羰基亲核加成负氢对羰基亲核加成
C O
H
AlH2
2
C O
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选择性还原:
反应活性
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CH3CH2CH2COOCH3 CH3CH2CH2CH
O1.[(CH3)2CHCH2]2AlH,-78¡æ
2.H2O
CH3CH2CH2CH2COCl1.LiAl[OC(CH3)3]3H,-78¡æ
2.H2OCH3CH2CH2CH2CH
O
—— 使用体积大活性低的烷基氢化铝或烷氧基氢化铝锂,低温下还原酰卤或酯,可以将反应控制在生成醛的一步
醛的制备:
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• 环己酮还原的立体化学
OR
H3C
H3C
1,LiAlH4 or NaBH4
2,H2O
R
H3C
H3C
R
H3C
H3C
+
OH H
OHH
½ø¹¥Î» ×èС·´ Ó¦»î » ÄÜµÍ ²úÎï ½ÏÎȶ¨µ±R=Hʱ,bΪ Ö÷²úÎï ;
µ±R¡ÙHʱ,aΪ Ö÷²úÎï
a
b
a b
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( 四 ) 羰基还原成亚甲基的方法
• Clemmensen 还原
• Wolff-Kishner- 黄鸣龙还原
O
RCR RCH2RZn-Hg , HCl
O
RCR RCH2RNH2-NH2 , KOH
(HOCH2CH2)2O ,
适用于对碱 敏感的醛酮
适用于对酸 敏感的醛酮
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EtS SEt
O
H2 , Raney Ni
OH
AcO
OS
H2 , Raney Ni
AcO
O
• 缩硫酮的催化氢化还原
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小资料:关于小资料:关于 NaBHNaBH44 还原羧酸的发展还原羧酸的发展
因为因为 LiAlHLiAlH44 第一个氢活性最高,以后依次减少;第一个氢活性最高,以后依次减少;
而而 NaBHNaBH44 的第一个氢活性最低,以后依次增高;的第一个氢活性最低,以后依次增高;
辅助试剂的作用在于先除去辅助试剂的作用在于先除去 NaBHNaBH44 的第一个氢的第一个氢
NaBH4-BF3or NaBH4-H2SO4orNaBH4
-(CH3)3SiCl orNaBH4-I2
H2N H
COOH
R
H2N H
CH2OH
R
WhyWhy??
作业:请尝试查出上述方法的文献出处,并看是否有其他方法。作业:请尝试查出上述方法的文献出处,并看是否有其他方法。
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CO2Et
CO2Et
H2NOH
R
HO
HN
HN
OHR RO O
SOCl2
OH- OO
R R
R'R'
Cl
HN
HN
ClR RO O
R' R'
O
N N
O
R R
NO
N N
O
R R
O
N N
O
OO
MeMe
RR
O
N
O
N
R2
R2
R1
R1
N
O
N
O
R
RFe
PPh2
PPh2
O
N
N
O
R
R
手性双噁唑啉的
常用合成方法
部分已合成手性
双噁唑啉
小资料:小资料:
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手性双噁唑啉催化环丙化反应
(a) Nishiyama H, Sakaguchi H, Nakamura T, Horihata M, Kondo M, Itoh K. Organometallics, 1989, 8:846; (b) Nishiyama H, Yamaguchi S, Kondo M, Itoh K. J. Org.Chem., 1992, 57: 4306; (c) Nishiyama H, Yamaguchi S, Park S-B, Itoh K. Tetrahedron: Asymmetry, 1993, 4: 143; (d) Nishiyama H, Park S-B, Itoh K. Tetrahedron: Asymmetry, 1992, 3:1029
H
Ph
CO2Et
H HH
Ph CO2EtPh
NO
N N
O
RuCl
Cl
N2 COOEt +
(1R, 2S) (1R, 2R)catalyst (2mol%)
92%-93%ee Trans/Cis>98:2
小资料:小资料:
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手性双噁唑啉催化硅氢化还原反应
(a) Nishiyama H, Sakaguchi H, Nakamura T, Horihata M, Kondo M, Itoh K. Organometallics, 1989, 8:846; (b) Nishiyama H, Yamaguchi S, Kondo M, Itoh K. J. Org.Chem., 1992, 57: 4306; (c) Nishiyama H, Yamaguchi S, Park S-B, Itoh K. Tetrahedron: Asymmetry, 1993, 4: 143; (d) Nishiyama H, Park S-B, Itoh K. Tetrahedron: Asymmetry, 1992, 3:1029
NO
N N
O
X
Me
O
Me
HHO
Ru
Cl
ClCl
Pybox-RuCl3 (1mol%)
AgBF4, Ph2SiH2 H3O+
Catalyst ee%
X=H 94X=Cl 83X=OMe 89X=NME2 92
小资料:小资料:
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三、氧化反应1. Oxidation of Alcohols
RCH2OH RCHO RCOOH
RR'CHOH RR'C=O
RR'R''OH ²»·´ Ó¦
[O] [O]
[O]
[O]
氧化醇的氧化剂主要有铬酸、高锰酸钾和硝酸等
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2200 alcohol alcohol (醇)氧化成 (醇)氧化成 ketoneketone (酮)(酮)
CH3CH2CHCH3 CH3CH2CCH3
OH OCrO3
H2SO4
OH ONa2Cr2O7
H2SO4
CHCH2CH3 CCH2CH3
H2CrO4
OH O
1) 最常用的氧化剂是铬酸( H2CrO4 ) —— 三氧化铬溶于水或重铬酸纳溶于酸性水溶液
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• Primary alcohols :
CH3CH2CH2CH2OHH2CrO4
CH3CH2CH2CHO
further
oxidationCH3CH2CH2COOH
但是在 PCC ( CrO3ClH-Py )或 Sarrett L H 试剂 (CrO3 – Py) 作用下可以停留在醛的阶段
CH3CH2CH2CH2OH CH3CH2CH2CHOPCC
CH2Cl2,25¡æ
CH3(CH2)4C CCH2OH CH3(CH2)4C CCHOSarrett ÊÔ¼Á
CH2Cl2,25¡æ
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• Mechanism
• —— first forming a chromate ester
• —— then E2 elimination
HO Cr
O
O
OHH+
-H+HO Cr
O
O
OH2
RCH2OH:
:
HO Cr
O
O
OHRH2C
H2O
O Cr
O
O
OHRHC
H
H+ -H+
H2O
::
RCH=O + H2CrO3 + H2O
Note—— 因为在这个过程中包含了连氧碳上的氢的消去,叔醇的连氧碳上没有氢,所以通常不氧化
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2 ) Jones reagent ( 选择性氧化方法 ):
—— CrO3-diluted H2SO4-acetone
HO O
Jones reagent
—— —— Unsaturated secondary alcohols can be oUnsaturated secondary alcohols can be oxidized to ketones while carbon-carbon xidized to ketones while carbon-carbon doubldouble bonds remain unchangede bonds remain unchanged..
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3 ) KMnO4 or MnO2
• 冷、稀、中性高锰酸钾不能氧化醇,但在较强烈的条件下(如酸、碱、加热)醇可被氧化。
—— 10 醇 羧酸 —— 20 醇 酮 —— 30 醇 — 碱性条件不反应;酸性条件下脱水成烯
后再氧化断裂。• KMnO4 在不同条件下的活性:酸性 > 碱性 > 中性 加热有利于反应• 新制 MnO2 可以氧化烯丙位的羟基,而不氧化双键
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4) Other reagents
—— Swern oxidation: DMSO-(COCl)2-Et3N
CH3CH2CH2CH2OH CH3CH2CH2CHO
CH3CH2CHCH3 CH3CH2CCH3
OH O
1. DMSO, (COCl)2, -600
2. Et3N
1. DMSO, (COCl)2, -600
2. Et3N
由伯醇、仲醇制备醛、酮的常用方法
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5) Other reagents
—— HIO4 (邻二醇的氧化断裂)
C
CH3
H3C
OH
CH
OH
C
CH3
OH
CH2
OH
C OH3C
H3C+
HC
O
OH+
COH
O
H3C+ CH2OHIO4
OHOH
OH
OH OH
OH
trans(e,e) trans(a,a) cis(e,a)A B C
C
CH3
CH3
OH
CHCH3
OH
C
CH3
CH3 CHCH3
O OI
O OOH
C OH3C
H3C+ O C
CH3
H
HIO4
-H2O-HIO3
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2. Oxidation of Alkenes, Alkynes
1) Oxidation with KMnO4 and OsO4
—— OsO4 氧化烯烃生成邻二醇 —— syn-addition
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—— KMnO4 在温和条件下,生成邻二醇 —— syn-addition
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2 ) Oxidative cleavage of alkenes with KMnO4
—— KMnO4 在较强烈的反应条件如酸性、碱性、中性加热下, 会发生烯烃的氧化断裂,生成酮、酸或酮酸混合物
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C CR
H
R
R
OOO
3) Oxidative cleavage of Alkenes — ozonolysis—— ozone (O3)
C CR
HR
R
OOO
molozonide
C CR
H
R
ROO
ozonide
O
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Example
4) Oxidative cleavage of Alkenes — ozonolysis
用途:可用于测定未知烯烃的结构
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5) Oxidation with peroxyacids ( 过酸 ) —— Epoxidation ( 环氧化 ) —— 环氧化物的合成
C C
OO
O H
R
C C
OHO
R
O
RCO3H
one eq.?
这是亲电加成反应,烯烃上的电子云密度越大,环氧化速率就越快
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—— 立体专一性
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烯烃的氧化反应总
结
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3. Oxidation of aldehydes and ketones
1) Oxidation with peroxyacids—— Baeyer-Villiger oxidation
CH3CH2CH2CH
ORCO3H
CH3CH2CH2COH
O
CH3CH2CCH2CH3
ORCO3H
CH3CH2COCH2CH3
O
CCH3
ORCO3H
COCH3
O
+ OCCH3
O
? ?
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R C
O
R' + CH3CO-OH
O
::
:
:
R CO-
R'
HO OCCH3
O
-H+
H+
R CO-
R'
O OCCH3
O
RO C
O
R' + CH3COH
O
:
:
—— Baeyer-Villiger oxidation 机理
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relative migration tendencies:
H > tert-alkyl > sec-alkyl = phenyl
> primary alkyl > methyl
CCH3
ORCO3H
COCH3
O
+ OCCH3
O
? ?√
Baeyer-Villiger oxidationBaeyer-Villiger oxidation
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2) 铬酸氧化
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3) Tollens test
—— Tollens’ reagent: Ag2O/NH3
—— 银镜反应
—— 醛的鉴定方法