有机化学Chap 13 Nitrogenous Compounds and Alkaloids (2013)1

N R'
tertiary amine
2
R R1
N R'
R2X
R2 + R N R' X R1
季铵盐
AgOH
R2 + R N R' OH R1
季铵碱
tertiary amine
quaternary ammonium salt
quaternary ammonium hydrate
Quaternary ammonium hydrates are strong base. The basicity of quaternary ammonium hydrates are similar to sodium hydroxide.
O + CH3 C OCH2CH2N(CH3)3OH
Acetylcholine
（乙酰胆碱）
30
HO HO
CH2CH2NH2
Dopamine (DA，多巴胺), the decrease of DA will cause parkinsonism（帕金森氏症）.
31
瑞典阿尔维德· 卡尔松 (Arvid Carlsson )
3
氨：氨水、氨气或有机基团 ( ammonia，amino ) 胺：有机非离子型 (amine ) 铵：离子型 (ammonium ion )
4
aliphatic amines:
aromatic amines:
CH3CH2NHCH3
NHCH3
5
The systematic nomenclature names amines analogously to alcohol.
12
Sequence of the basicity of amines
+ -
R4N OH > R2NH > RNH2 > R3N > NH3 > ArNH2 >
NH3 > ArNH2 > Ar2NH > Ar3N
13
H2N
O C OCH2CH2N(C2H5)2
Procaine （普鲁卡因）
HCl
ammonium ion
A strongly basic amine is a good competitor for H+ and its ammonium ion is a relatively weak acid (more stable); a weakly basic amine is less effective competitor for H+, and its ammonium ion is a relatively strong acid.
36
(S)和(R)-西布曲明
37
HO HO
CHCH2NHCH3 OH
epinephrine （肾上腺素）
HO HO
CHCH2NH2 OH
norepinephrine (去甲肾上腺素）

So it is easy to distinguish primary, secondary and tertiary amine by reacting with nitrous acid.
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Something More:
Nitrosoamines（亚硝胺） are important because many are known to be potent carcinogens （致癌物） . This finding has led to a controversy over the use of sodium nitrite (NaNO2) as a preservative（防腐剂） in foods because it might be a nitrosating （ 亚 硝 基 化 的 ） agent under physiological conditions, or under the conditions in which food is prepared. The classic example is the frying of bacon, which generates nitrosoamines. However, the evidence is not definitive on this point. Many foods (spinach), even our own bodies, produce nitrites.
6
CH3NH2
methylamine
(CH3CH2)2NH
diethylamine
(CH3CH2)3N
triethylamine
PhCH2 CH3
CH3
N CH2CH3
N CH3
N,N-dimethylaniline
Benzylethylmethylamine 甲乙苄胺
7
CH3 CH CH2CH2NH2 CH3
20
Using Hinsberg Reaction can distinguish primary, secondary and tertiary amines.

The products of primary amines react with benzene sulfonyl chloride is weak acid, so can dissolve in sodium hydroxide solution. The products of secondary amines are crystal, and can not dissolve in sodium hydroxide solution.
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(2) Secondary amines
R2NH
HNO2
R2N-NO
HNO2
亚硝胺
NHCH3
NO N-CH3
nitrosoamines (yellow oil)
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(3) Tertiary amines
R3N
HNO2
R3N HNO2
Aliphatic tertiary amines do not react with nitrous acid to give an isolable product.
H2N
H2N
+ O H C OCH2CH2N(C2H5)2 Cl
O C OCH2CH2N(C2H5)2 HCl
procaine hydrochloride, local anesthesia
14
Cl H2N Cl CHCH2NHC(CH3)3 OH HCl H2N
Cl CHCH2NHC(CH3)3 HCl OH Cl
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O H3CO N H CH2CH2NH C CH3
Melatonin (MLT)
褪黑素 (又称松果体素或脑白金)
34
Are you prozac today?
F3C
O CHCH2CH2NHCH3
Fluoxetine (氟西汀 )
Prozac (百忧解)
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NH F O O O
Paroxetine，Seroxat（帕罗西汀，赛乐特）
美国保罗· 格林加德 (Paul Greengard )
奥地利埃里克· 坎德尔 (Eric Kandel )
The Nobel Prize in Physiology or Medicine 2000
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HO N H
CH2CH2NH2
5-Hydroxytryptamine (5-羟色胺)
Serotonine (血清胺 )
R2NH
(R'CO)2O
O R2N C R'
R3N
R'COCl or (R'CO)2O
×
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O NH C CH3
Acetanilide
Acetanilide had been used as antifebric, but its toxicity is too high.
C2H5O
O NH C CH3
Another method names amines as substituted alkanes.
The names of aromatic amines are base on the parent compound, called benzenamine（苯胺） by the official world and aniline (or aminobenzene) by everyone else. Amines bearing different R are named by ordering the groups alphabetically.
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Hinsberg Reaction（兴斯堡反应 ）
weak acid -I effect
※
SO2Cl + RNH2
SO2 NHR
benzene sulfonamide （苯磺酰胺）
SO2 N-+R Na
※
-
SO2Cl + R2NH
SO2 NR2
crystal （结晶）
※
SO2Cl + R3N
×
Clenbuterol hydrochloride, Spiropent
盐酸双氯醇胺、盐酸克仑特罗
瘦肉精
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2. Acylation（酰化反应）
R-NH2
R'COCl
O R-NH C R'
O R-NH C R'
Amide（酰胺）
R-NH2
(R'CO)2O
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