清华大学有机化学李艳梅老师课件第4章
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1, Spiro cycloalkanes 螺环烃
1）选母体：根据成环的总碳原子数，称为“螺某烷”。
2）编号：从小环开始；从第一个非螺原子开始。 3）书写：先写词头“螺” 方括号内沿着编号方向写出每个环中除螺原子 1 2 3 4 10 9 1 5 8 6 7 外的每个环的碳原子数 数字之间用圆点隔开 最后写出包括螺原子在内碳原子数的烷烃名称
A.von.Baeyer put forward the strain theory
1883
1885
4.2.1 Baeyer’s strain theory
Assumption:
Bayer’s张力学说
1, carbon atoms in the ring are on the same plane;
2,7,7-trimethylbicyclo[2.2.1]heptane
2,7,7-三甲基二环[2.2.1]庚烷
bicyclo[1.1.0]butane
二环[1.2.0]丁烷
For polycyclic compound as following 多元环
Deciding the main ring 选“主环”：最大的环 Choosing the main bridged carbon 选“主桥头碳”：主环与非主环的最长桥共用的桥头碳
Tricyclic[3.2.2.12.7]decane
Fused ring
区别：母体！
naphthalene Endo/exa
Hydrogenated naphthalene
H OH endo H exa
OH
4.2 Structure of cycloalkanes
4.2.1 Baeyer’s strain theory
3-cyclohexylhexane 3-环己基己烷
3, When two rings are connected
两环相连时
Cyclopropylcyclohexane 环丙基环己烷
Cyclopropylcyclopropane 环丙基环丙烷
4, Cis and trans isomerism:
CH3 H
将桥（稠）环烃变为链状化合物时需要断裂的碳链 数。如需断裂两次，则为二环化合物，断裂三次则 为三环化合物。
Some interesting bridging compounds
Cubane 立方烷 篮烷
Primane 棱烷
Diamentane 金刚烷
4.1.2 Isomerism Constitutional isomers are derivated from the change of size of rings and length of side chains C5H10
多环
桥头碳
螺原子 Spiro rings 螺环 两环之间共用一个 碳原子
Fused ring 稠环 Bridged ring 桥环
两环之间共用一根共 价键（共用两个直接 相连的碳原子）
两环之间共用两个 不直接相连的碳原 子
几环？
To define the number of the rings: The number of cutting you need to get a chain molecule out of a poly ring compound
2）编号：从桥头碳开始；从最长桥开始。
3）书写：先写环数 方括号内沿着编号方向写出每个环中除桥头碳原子
外的每个环的碳原子数
8 7 6 5 1 2 3 4
数字之间用圆点隔开 最后写出包括桥头碳原子在内碳原子数的烷烃名称
bicyclo[3.2.1]octane
二环[3.2.1]辛烷
注意：有两个桥头碳可 供选择
成环的碳原子均在同一同面上，且呈正多边形 2, carbon atoms are sp3 carbon atoms; 碳原子采取sp3杂化形式，正常键角应为约109.5度 3, to meet some special angles in the ring, the bonds have to be bending; 为了满足平面正多边形的内角要求，成环的键必须向内或向
By the saturation CnH2n
CnH2n-2 CnH2n-4
按不饱和度
Cycloalkanes 环烷
Cyclo olefines 环烯 Cyclo alkynes 环炔
By the number of the rings
按环的数目
Monocyclic compounds 单环
Polyring compounds
4.2.2 Heat of combustion for cycloalkane
4.2.3 Current opinions
4.2.4 Conformations of cyclohexane
4.2.5 Configuration of decalin
Before 1880
Only penta rings and hexa rings were found. It was regarded that rings smaller than penta rings and bigger than hexa rings do not exist, or are not stable. W.H.Perkin synthesized C3, C4, and identified the relative reactivity: double bond > C3 > C4 ,while C5 and C6 rings are relatively more stable.
CH2
2 3 1
1 2
H H
扭转张力： 三组H－C－C 均处于全重叠式
HH
C C C
105.5o
C C C
角张力：
109.50-105.50=40
Bent Bond （弯曲键、香蕉键）
A nonplanar conformation
非平面构象
也存在弯曲键
111.50 部分交叉式
H H H H H H
Van de waals No No No No Great No
4.2.4 Conformations of cyclohexane
A history
Year 1883 1890 1915-1918 1920 1943 1950 O.Hassel D.Barton Name of scientist Baeyer H.Sachse W.M.Mohr Point of view Assumes that six carbon atoms are on the same plane Two conformations may exist Chair model and boat model Cyclohexane was proved to be nonplanar experimentally Chair model is most stable (electron diffraction method) Conformation analysis of cyclohexane
环的大小及侧链长短与位置变化
4.1.3 Nomenclature
命名
4.1.3.1 Monocyclic alkane 单环烷烃
1, When the side Hale Waihona Puke Baiduhain is not very complicate: 当支链不复杂时，以环烷烃为母体
1,2-dimethylcyclopentane
4.3 Physical properties & spectrum data
4.4 Chemical properties 4.5 Preparation (learn on your own)
4.1 Classification, Isomerization and nomenclature
4.1.1 Classification
Large ring
多于13个碳原子的环体系中，分子链一般呈皱折形
Strain energy in cycloalkanes
Name C3 C4 C5 C6 C7~C12 C12~
Angle strain Great Great Slight No Medium No
Twist strain Medium Medium Medium No Medium No
2 3
1 5
6 7 8
4 10 9
4-methylspiro[2.4]heptane 4-甲基[2.4]庚烷
6-methylspiro[4.5]decane 6-甲基[4.5]癸烷
2, Bridged-ring alkane and fused-ring alkane 桥环烃和稠环烃 1）选母体：根据成环的总碳原子数及环数，称为“n环某烷”。
Cycloalkanes
第四章 环烷烃
Organic Chemistry A (1) By Prof. Li Yan-Mei Tsinghua University
Content
4.1 Classification, Isomerization and nomenclature 4.2 Structure of cycloalkanes
methylcyclopentane 甲基环戊烷
1,2-二甲基环戊烷
1-ethyl-3-methylcyclopentane
2-ethyl-4-methyl-1propylcycloheptane
1-甲基-3-乙基环戊烷
4-甲基-3-乙基-1-丙基环己烷
2, When the side chain is complicate or difficult to name: 当支链较复杂或不易命名时，以环烷基为取代基
n
Heat of combustion per CH2 kJ/mol
697
686
664
659
662
658
Do not fit the strain theory!
影响环体系稳定性的主要因素： 角张力（Baeyer 张力） 扭转张力 范氏力
4.2.3 Current opinions
3
Decide the serial number
编号：从主桥头碳开始；从最长桥开始
7 4
Naming the compound 书写（注意与非主桥相连的桥需注明所连桥的编号）
5
3 1 6 2
Tricyclic[2.2.1.02.6]heptane
思考：
1 8 9 7 5 2
10
3
6
4 tricyclic[3.2.2.12.7]dacane
外“屈挠”， “屈挠”的程度越大，体系越不稳定。 More bending More angle strain Higher energy
Less stability
60o
90o
108o
120o
129o
Most stable?
可解释一些体系的稳定性特点，但还有一些体系无法解释。
4.2.2 Heat of combustion for cycloalkane
角张力：111.50－109.50 = 20
H
H H H
H
扭转张力较小
4
H
3
H
2
H
1
H H
4
H H
1 2
蝴蝶状 蝴蝶式
H2 C H2C
3
H
H
6.3kJ/mol higher
全重叠式
2.5kJ/mol
envelop structure
信封式
half-chair structure
半椅式
如果：
具有多组全重叠式
螺[4.5]癸烷
“小原则”：在不违背螺环烃命名的“大”原则基础上，在编号 时应尽可能令取代基的位号最小。
1 2 3 4
6
7 8
5
9
10
1-甲基螺[4.5]癸烷
思考！
2 3
1 5
6
7 8
4 10 9
螺[4.5]癸烷 spiro[5.5]undecane 螺[5.5]十一烷
spiro[4.5]decane
CH 3 H
CH3 H
H CH 3
CH 3
CH 3
CH 3
Cis-1,4-dimethylcyclohexane
CH 3
Trans-1,4-dimethylcyclohexane
CH3
CH 3
CH 3
How to name this compound ?
4.1.3.2 Polyring alkane 多环烷烃
4.1.2 Isomerism
4.1.3 Nomenclature
4.1.1 Classification
By the size of the ring
Small rings Medium rings
按环的大小
Common rings C5~C7
C3~C4
C8~C12
Large rings
C13~
1）选母体：根据成环的总碳原子数，称为“螺某烷”。
2）编号：从小环开始；从第一个非螺原子开始。 3）书写：先写词头“螺” 方括号内沿着编号方向写出每个环中除螺原子 1 2 3 4 10 9 1 5 8 6 7 外的每个环的碳原子数 数字之间用圆点隔开 最后写出包括螺原子在内碳原子数的烷烃名称
A.von.Baeyer put forward the strain theory
1883
1885
4.2.1 Baeyer’s strain theory
Assumption:
Bayer’s张力学说
1, carbon atoms in the ring are on the same plane;
2,7,7-trimethylbicyclo[2.2.1]heptane
2,7,7-三甲基二环[2.2.1]庚烷
bicyclo[1.1.0]butane
二环[1.2.0]丁烷
For polycyclic compound as following 多元环
Deciding the main ring 选“主环”：最大的环 Choosing the main bridged carbon 选“主桥头碳”：主环与非主环的最长桥共用的桥头碳
Tricyclic[3.2.2.12.7]decane
Fused ring
区别：母体！
naphthalene Endo/exa
Hydrogenated naphthalene
H OH endo H exa
OH
4.2 Structure of cycloalkanes
4.2.1 Baeyer’s strain theory
3-cyclohexylhexane 3-环己基己烷
3, When two rings are connected
两环相连时
Cyclopropylcyclohexane 环丙基环己烷
Cyclopropylcyclopropane 环丙基环丙烷
4, Cis and trans isomerism:
CH3 H
将桥（稠）环烃变为链状化合物时需要断裂的碳链 数。如需断裂两次，则为二环化合物，断裂三次则 为三环化合物。
Some interesting bridging compounds
Cubane 立方烷 篮烷
Primane 棱烷
Diamentane 金刚烷
4.1.2 Isomerism Constitutional isomers are derivated from the change of size of rings and length of side chains C5H10
多环
桥头碳
螺原子 Spiro rings 螺环 两环之间共用一个 碳原子
Fused ring 稠环 Bridged ring 桥环
两环之间共用一根共 价键（共用两个直接 相连的碳原子）
两环之间共用两个 不直接相连的碳原 子
几环？
To define the number of the rings: The number of cutting you need to get a chain molecule out of a poly ring compound
2）编号：从桥头碳开始；从最长桥开始。
3）书写：先写环数 方括号内沿着编号方向写出每个环中除桥头碳原子
外的每个环的碳原子数
8 7 6 5 1 2 3 4
数字之间用圆点隔开 最后写出包括桥头碳原子在内碳原子数的烷烃名称
bicyclo[3.2.1]octane
二环[3.2.1]辛烷
注意：有两个桥头碳可 供选择
成环的碳原子均在同一同面上，且呈正多边形 2, carbon atoms are sp3 carbon atoms; 碳原子采取sp3杂化形式，正常键角应为约109.5度 3, to meet some special angles in the ring, the bonds have to be bending; 为了满足平面正多边形的内角要求，成环的键必须向内或向
By the saturation CnH2n
CnH2n-2 CnH2n-4
按不饱和度
Cycloalkanes 环烷
Cyclo olefines 环烯 Cyclo alkynes 环炔
By the number of the rings
按环的数目
Monocyclic compounds 单环
Polyring compounds
4.2.2 Heat of combustion for cycloalkane
4.2.3 Current opinions
4.2.4 Conformations of cyclohexane
4.2.5 Configuration of decalin
Before 1880
Only penta rings and hexa rings were found. It was regarded that rings smaller than penta rings and bigger than hexa rings do not exist, or are not stable. W.H.Perkin synthesized C3, C4, and identified the relative reactivity: double bond > C3 > C4 ,while C5 and C6 rings are relatively more stable.
CH2
2 3 1
1 2
H H
扭转张力： 三组H－C－C 均处于全重叠式
HH
C C C
105.5o
C C C
角张力：
109.50-105.50=40
Bent Bond （弯曲键、香蕉键）
A nonplanar conformation
非平面构象
也存在弯曲键
111.50 部分交叉式
H H H H H H
Van de waals No No No No Great No
4.2.4 Conformations of cyclohexane
A history
Year 1883 1890 1915-1918 1920 1943 1950 O.Hassel D.Barton Name of scientist Baeyer H.Sachse W.M.Mohr Point of view Assumes that six carbon atoms are on the same plane Two conformations may exist Chair model and boat model Cyclohexane was proved to be nonplanar experimentally Chair model is most stable (electron diffraction method) Conformation analysis of cyclohexane
环的大小及侧链长短与位置变化
4.1.3 Nomenclature
命名
4.1.3.1 Monocyclic alkane 单环烷烃
1, When the side Hale Waihona Puke Baiduhain is not very complicate: 当支链不复杂时，以环烷烃为母体
1,2-dimethylcyclopentane
4.3 Physical properties & spectrum data
4.4 Chemical properties 4.5 Preparation (learn on your own)
4.1 Classification, Isomerization and nomenclature
4.1.1 Classification
Large ring
多于13个碳原子的环体系中，分子链一般呈皱折形
Strain energy in cycloalkanes
Name C3 C4 C5 C6 C7~C12 C12~
Angle strain Great Great Slight No Medium No
Twist strain Medium Medium Medium No Medium No
2 3
1 5
6 7 8
4 10 9
4-methylspiro[2.4]heptane 4-甲基[2.4]庚烷
6-methylspiro[4.5]decane 6-甲基[4.5]癸烷
2, Bridged-ring alkane and fused-ring alkane 桥环烃和稠环烃 1）选母体：根据成环的总碳原子数及环数，称为“n环某烷”。
Cycloalkanes
第四章 环烷烃
Organic Chemistry A (1) By Prof. Li Yan-Mei Tsinghua University
Content
4.1 Classification, Isomerization and nomenclature 4.2 Structure of cycloalkanes
methylcyclopentane 甲基环戊烷
1,2-二甲基环戊烷
1-ethyl-3-methylcyclopentane
2-ethyl-4-methyl-1propylcycloheptane
1-甲基-3-乙基环戊烷
4-甲基-3-乙基-1-丙基环己烷
2, When the side chain is complicate or difficult to name: 当支链较复杂或不易命名时，以环烷基为取代基
n
Heat of combustion per CH2 kJ/mol
697
686
664
659
662
658
Do not fit the strain theory!
影响环体系稳定性的主要因素： 角张力（Baeyer 张力） 扭转张力 范氏力
4.2.3 Current opinions
3
Decide the serial number
编号：从主桥头碳开始；从最长桥开始
7 4
Naming the compound 书写（注意与非主桥相连的桥需注明所连桥的编号）
5
3 1 6 2
Tricyclic[2.2.1.02.6]heptane
思考：
1 8 9 7 5 2
10
3
6
4 tricyclic[3.2.2.12.7]dacane
外“屈挠”， “屈挠”的程度越大，体系越不稳定。 More bending More angle strain Higher energy
Less stability
60o
90o
108o
120o
129o
Most stable?
可解释一些体系的稳定性特点，但还有一些体系无法解释。
4.2.2 Heat of combustion for cycloalkane
角张力：111.50－109.50 = 20
H
H H H
H
扭转张力较小
4
H
3
H
2
H
1
H H
4
H H
1 2
蝴蝶状 蝴蝶式
H2 C H2C
3
H
H
6.3kJ/mol higher
全重叠式
2.5kJ/mol
envelop structure
信封式
half-chair structure
半椅式
如果：
具有多组全重叠式
螺[4.5]癸烷
“小原则”：在不违背螺环烃命名的“大”原则基础上，在编号 时应尽可能令取代基的位号最小。
1 2 3 4
6
7 8
5
9
10
1-甲基螺[4.5]癸烷
思考！
2 3
1 5
6
7 8
4 10 9
螺[4.5]癸烷 spiro[5.5]undecane 螺[5.5]十一烷
spiro[4.5]decane
CH 3 H
CH3 H
H CH 3
CH 3
CH 3
CH 3
Cis-1,4-dimethylcyclohexane
CH 3
Trans-1,4-dimethylcyclohexane
CH3
CH 3
CH 3
How to name this compound ?
4.1.3.2 Polyring alkane 多环烷烃
4.1.2 Isomerism
4.1.3 Nomenclature
4.1.1 Classification
By the size of the ring
Small rings Medium rings
按环的大小
Common rings C5~C7
C3~C4
C8~C12
Large rings
C13~