有机化学英文讲义Chapter14
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有机化学第十四章
COOC2H5 CH3COCH2COOC2H5 + C2H5OH COCH2COOC2H5
两种产物在性质上有较大差别， 两种产物在性质上有较大差别，可分离
分子内Claisen 酯缩合（Dieckmann狄克曼缩合） 酯缩合（ 狄克曼缩合） 分子内 狄克曼缩合
CH2CH2COOC2H5 CH2CH2COOC2H5 O
C2H5C O + CH2COOC2H5 CN CH3
乙酸铵－乙酸
C6H6
CH3 C2H5
C C COOC2H5 CN 85%
CHO
+
CH2(COOH)2
哌啶,95~100℃ ℃ -H2O
CH C(COOH)2
- CO2
CH CHCOOH (80%~95%)
五、Michael加成 加成
O + CH2(COOC2H5)2 C2H5ONa C2H5OH CH(COOC2H5)2 90% (C2H5)3N,叔丁醇 叔 O
三、丙二酸二乙酯的合成及应用
1、制备 、
CH2COONa Cl
NaCN
CH2COONa CNOC H 2 5
腈化反应
水解、 水解、成酯反应
2、应用 、 （1）制备取代乙酸（一取代或二取代）： ）制备取代乙酸（一取代或二取代）： 脱H+,生成钠盐 生成钠盐
步2
制备甲基酮或烷基取代酸： 制备甲基酮或烷基取代酸：
①稀OH -,②H+,③∆ 酮式分 解 ①40%OH-,②H+,③∆ 酸式分解
CH3 CH3COCCOOC2H5 CH2CH2CH3
CH3 CH3COCHCH2CH2CH3
CH3 CH3CH2CH2CHCOOH
有机化学英文课件
+ C H 3 C H 2 -O -H + C H 3 C H 2 -O -H
SN 2
+ C H 3 C H 2 -O -C H 2 C H 3 + O -H
H
H
H
A new oxonium ion
11-11
Preparation of Ethers
Step 3: proton transfer to solvent completes the reaction
+
CH 3 CH 2 -O -CH 2 C H 3 + O -H
H
H
proton tran sf er
+ CH 3 CH 2 -O -CH 2 C H 3 + H O -H
H
11-12ቤተ መጻሕፍቲ ባይዱ
Preparation of Ethers
Acid-catalyzed addition of alcohols to alkenes
Acid-catalyzed dehydration of alcohols
• diethyl ether and several other ethers are made on an industrial scale this way
• a specific example of an SN2 reaction in which a poor leaving group (OH-) is converted to a better one (H2O)
CH 3 CH3C=CH2 + H
+ O CH3
H
CH3 C H 3 C+C H 3 +
(完整版)Chapter14,15
十四章土壤及其应用Soil and land are not the same. Land is the part of the world not covered by the oceans. Soil is a thin covering over the land consisting of a mixture of minerals, organic material, living organisms, air, and water that together support the growth of plant life.土壤和陆地是不同的。
陆地是地球上未被海洋覆盖的部分。
土壤是陆地上一层薄的覆盖层，由矿物质、有机质、活的生物体、空气和水组成的混合物，这些物质一起支持植物的生长。
A combination of physical, chemical, and biological events acting over time is responsible for the formation of soil.土壤的形成涉及一系列物理、化学和生物过程。
The organic material resulting from the decay of plant and animal remains is known as humus.植物和动物残骸分解产生的有机物质称为腐殖质。
Soil properties include soil texture, structure, atmosphere, moisture, biotic content and chemical composition. Soil texture is determined by the size of the mineral particles within the soil.土壤的性质包括土壤的质地、结构、含气量、水分、生物和化学组分等。
Chapter 14 Ethers, Epoxides, and Sulfides 有机化学英文版教学课件(美国达拉斯社区学院) 《Organic Ch
formed.
Chapter 14
=> 18
Phenyl Ether Cleavage
• Phenol cannot react further to become halide.
• Example:
OC H 2C H 3 H B r
O H +C H 3C H 2 B r
=>
Chapter 14
19
=>
Chapter 14
13
Phenyl Ethers
• Phenoxide ions are easily produced for use in the Williamson synthesis.
• Phenyl halides or tosylates cannot be used in this synthesis method.
• These are the same products that were formed in acid.
• Different products are formed in acid and base if epoxide is unsymmetrical. =>
Chapter 14
28
Orientation of Epoxide Opening
• Precautions:
➢Do not distill to dryness.
➢Store in full bottles with tight caps. =>
Chapter 14
20
Sulfides (Thioethers)
• R-S-R, analog of ether
• Name like ethers, replacing “sulfide” for “ether” in common name, or “alkylthio” for “alkoxy” in IUPAC system.
IG补课用Chapter 14 organic chemistry(完整版课件)
5.aliphatic（脂肪族的，无环的） alcohols and ketones (are named in a similar way to alkene)
CH3CH2CH2OH
propan-1-ol
H OH H H CCC H
H HH
propan-2-ol
CH3CH2COCH2CH3 pentan-3-one
Carboxylic acid 羧酸
ester 酯
benzene
-X,where X=F、Cl、 Br、I
chloromethane
-OH
methanol
ethanal
propanone
ethanoic
ethyl ethanoate
amine胺 nitrile腈
-NH2
methylamine
YCIC AS Organic Chemistry
2. π bond
① π bonds are formed by sideways overlap of p orbitals.原子轨道“肩 并肩”重叠。
② π bonds are not symmetrical about a line jointing the nuclei of the atoms forming the bond.
e.g ethane molecular formula: C2H6 Exercise： 1.propane 2.ethanoic acid
3.butanol
C3H8
C2H4O2
C4H10O
YCIC AS Organic Chemistry
3.Structural formula(结构式）
Denefition: the formula that tell us about the atoms bonded to each carbon atom in an
14第十四章 醇、酚、醚
ONO2
CH2 ONO2
CH ONO2
CH2 ONO2
+ 3H2O
4、山梨醇和甘露醇
山梨醇和甘露醇都是六元醇， 二者是异构体。它们都是白 色结晶粉末，味甜，广泛存 在于植物中，如许多水果及 蔬菜中均含有。山梨醇和甘 露醇均易溶于水。它们的 20%或25%的溶液，在临床 上用作渗透性利尿药，能将 周围组织及脑组织的水分吸 入血中随尿排出，从而降低 颅内压，消除水肿，对治疗 脑水肿与循环衰竭有效。
⑵ 分子间脱水——单醚的合成
CH3CH2OH + HO CH2CH3
H2SO4 170℃
H2SO4 140℃
CH2
CH3CH2OCH2CH3 + H2O
比较：
CH3CH2OH
CH2 + H2O
反应条件决定反应产物； 醇的分之间脱水用于制备简单醚（简称单醚），但 不适合制备混合醚。 比较：Williamson混合醚合成法
R OH + H
O CH3OH + HO S O OH
ONO2
RONO2 + H2O
硝酸酯
－H2O CH3O O S O OH CH3OH CH3O O S O OCH3 + H2O
硫酸氢甲酯
CH2 OH
CH OH
CH2 OH
+ 3HONO2
CH2 ONO2
硫酸二甲酯：有机合成 中重要的甲基化试剂， 但有剧毒！ CH CH2 + 3H2O ONO2 ONO2
① 状态：大多数为无色固体，但易被空气中的氧气氧化而产 生有色杂质； ② 溶解性：可部分溶于水（为什么？），羟基越多，水溶性 越好，易溶于有机溶剂。
三、酚的化学性质chemical properties
有机化学 Chapter 14 organometal
§14.3 Preparation of organometallic compounds
A, Organolithium compounds
B, Organomagnesium compounds (Grignard reagent)
Aryl and vinyl chlorides don’t form Grignard reagents in diethyl ether. However, when THF is used as the solvent, they are okay.
2. Alkane synthesis
Primary alkyl halides, especially iodides, are the best substrates
Secondary and tertiary halides encounter elimination side reaction
§14.4 Organolithium & organomagnesium compounds as Brønsted bases
Organolithium and organomagnesium compounds are stable species They are strongly basic, and react instantly with proton donors even alcohol and water
Example:
环丙基锂
二乙基镁
When the metal bears a substituent other than carbon, the substituent is treated as if it were an anion and named separately:
有机化学(英文影印版)-chapter+4+Teaching+Contest
Include in brackets beginning with the largest bridge and proceed to the shortest identifying the number of carbons in
each bridge and include in brackets.
• Nomenclature of straight chain alkanes
• Nomenclature of alkyl groups • Nomenclature of branched alkanes • Nomenclatures of simple cycloalkanes
3
Definition of Alkanes and Cycloalkanes • Alkanes:
• Characteristics of Alkanes
– Hybridization of Carbons = SP3 – Geometrical Molecular Shape = Tetrahedral – Bond Angles = 109º – Polarity = Non-Polar
2
• Definition of alkanes and cycloalkanes
CH3 CH2CH3 CH3 C CH3 CH CH2 CH2
(3-ethyl-4,4-dimethy)pentyl
9
Nomenclature of Branched Alkyl Groups
• -CH(CH3)2 • -CH(CH3)CH2CH3 1-methylethyl (isopropyl) 1-methylpropyl (sec-Butyl)
Chapter 4
each bridge and include in brackets.
• Nomenclature of straight chain alkanes
• Nomenclature of alkyl groups • Nomenclature of branched alkanes • Nomenclatures of simple cycloalkanes
3
Definition of Alkanes and Cycloalkanes • Alkanes:
• Characteristics of Alkanes
– Hybridization of Carbons = SP3 – Geometrical Molecular Shape = Tetrahedral – Bond Angles = 109º – Polarity = Non-Polar
2
• Definition of alkanes and cycloalkanes
CH3 CH2CH3 CH3 C CH3 CH CH2 CH2
(3-ethyl-4,4-dimethy)pentyl
9
Nomenclature of Branched Alkyl Groups
• -CH(CH3)2 • -CH(CH3)CH2CH3 1-methylethyl (isopropyl) 1-methylpropyl (sec-Butyl)
Chapter 4
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R R
C=O
HSH-CHH+2O2CH2SHcycRlRicCthiSSoacet-RaHlaSnCeyHN2Ci(HH22S) H
R R
CH2
The reduction of C=O groups of aldehydes and ketones into
CH2 group: Clemmensen reduction: Zn(Hg)/HCl, △ Wolff-Kishner reduction: NH2NH2/NaOH/(HOCH2CH2)2O, △ Reduction of aryl alkylketone: H2/Pd (neutral condition) Reduction of thioacetals: Raney Ni(H2)
9
d. Addition of ammonia and its derivatives (H2NX)
NH2NH2
H2NNH
O2N H2NNH
O2N
hydrazine phenylhydrazine 2,6-dinitrophenylhydrazine
肼
苯肼
2,6-二硝基苯肼
O
O
H2NCNH 2
H2NNHCNH 2
central C of an acyl group will benefit the nucleophilic addition. 2) Steric hindrance—The less steric hindrance of the central C will increase the reaction rate of nucleophilic addition.
+H2O R
+
C OR'
H
R'OH R'OH
R H
C
+
H OR'
OR'
H+
+
+H3O
R C
OR'
H OR'
ac etal缩醛
stable in basic solution
HO R'
R C=O +
R
CH CH
HO R'
H2SO4(conc.) H3O+
RO C
RO
R' R'
cyclic ketals 环缩酮
+
CCH3 CH3
-
H3O HOCH2CH2OH
O
O" CCH3Biblioteka CH3MgClOH
C-CH3 CH3
8
c. Addition of thiols (mercaptan RSH)
R C=O
R
H+ 2RSH -H2O
R SR Raney Ni(H2)
C R SR
- 2RSH
thioacetal
R R CH2
R' OH
R or R’ = H hemiacetal
半缩醛
HOCH2CH2CH2CH2C
O H
C O+
O H
H
C O
OH H
6
R C
OH
H OR'
hemiac etal
HCl(gas)
or H2SO 4(conc.)
H+
R H
C
+
H O.. H
O. . R'
R + .. H2O H C O..R'
hydrocyanic acid sodium bisulfite
OH
R C=O + H2O
H
R OH C
H OH
gem-diol hydrate
Cl3CCH OH
chloral hydrate
水合三氯乙醛
hypnotic
The study on the mechanism of this reaction:
carbamide(urea) semicarbazide
尿素
氨基尿素
O
H2NNHCNHNH 2
carbazide
卡巴肼
H2NOH
RR'C=NR"
C=C NRR'
R'
Nu
C=O
R
Nu
C R'
R
O+
R' RCO
Nu
H+
Nu
R'
R' C OH + R C OH
R
Nu
1
b. Weak nucleophiles with acidic catalysts (acidic conditions)
R'
H+
CO
R
-H+
R'
C R
+ HNu OH
Nu R'
R' C OH+ R
Chapter 14 Addition to the Carbonyl Group
14.2 General mechanism of nucleophilic addition to the carbonyl groups of aldehydes and ketones
a. Strong nucleophiles without catalysts (basic conditions)
Ph C=O
H5C2
H3C
Ph
H3C C O
A
H3C C O
NO2 B
H3C C O
CH3 C
H3C CH3 C
O D
4
14.4 14.5 14.9 14.10 The addition of H20, ROH, RSH, H2NX, HCN, NaHSO3
a. Addition of water
3
The general order of the reaction rate of the nucleophilic addition of carbonyls is as follows:
H C=O >
H3C C=O >
Ph
H3C C=O > C=O >
O>
H
H
H
H3C
H5C2 C=O >
Ph C=O >
+
NuH
R'
R' C OH + R
R
C OH
C OH NuH
+
R
Nu
HNu = H2O, HOR, NH3, HNR2
2
c. Reactivity of aldehydes and ketones towards nucleophilic addition
Two factors: 1) Electronic effect—The more electron-deficient
O16 C-C-C
H2O18
16O +
C-C-O18H2
C
16OH 18
C-C-OH C
-H2O16 H2O16
O18 C-C-C
5
b. Addition of alcohols
R
C=O + HOR" R'
H R C O+ R" R' O
R,R’ = alkyl
hemiketal
R OR"
半缩酮
C
7
To make the following synthesis:
from O
O COC2H5 to O
O
O COC2H5
+
H
HOCH2CH2OH
O O
OH C-CH3 CH3
O COC2H5
CH3MgCl
"O O
OMgCl " COC2H5
H5C2OMgCl "
CH3
O O
" O O
OMgCl "