-
1
、
About
216
–
224 g.
(1.62
–
1.68 moles) of
powdered anhydrous aluminum
chloride is
added to a 1Lthree-necked flask.
在
1L
的三口烧瓶中加入大约
216-224g(1.
62
–
1.68
moles)
的无水三氯化铝。
While the free-flowing catalyst is
stirred (Note 3), 81 g. (0.67 mole) of
acetophenone is added from the dropping
funnel in a slow stream over a period
of 20
–
30 minutes.
自由流动的催化剂边搅拌边用
滴液漏斗缓慢滴加
81g
苯乙酰。
Considerable heat is
evolved, and, if the drops of ketone
are not dispersed, darkening or
charring occurs.
放热反应，假如滴加的酮不能被分散，
就会变黑或是碳化。
When about one-third of
the acetophenone has been added, the
mixture becomes a viscous ball-like
mass that is difficult to stir.
当三分之一的乙酰
苯
被滴加，
反应混合物变成一个很难搅拌的粘性的球状团块。<
/p>
Turning of the stirrer by
hand or
more rapid addition of ketone
is necessary at this point.
在这时，改用手动搅拌或
快速
滴加酮是非常必要的。
The addition of
ketone, however, should not be so rapid as to
produce a temperature above
180°
.
然而，速度不能太快，当反应温度超过
180
℃时。
Near the end of
the addition, the mass becomes molten and can be
stirred easily
without being either
heated or cooled. The molten mass, in which the
acetophenone
is complexed with aluminum
chloride, ranges in color from tan to brown.
当快滴加完
时，团块开始融化，表明苯乙酰已经和三氯化铝混合完全，颜色也
逐渐从黄褐色变为棕色。
Bromine (128 g.,
0.80 mole) is added dropwise to the well-stirred
mixture over
a period of 40 minutes
(Note 4).
在
40
分钟内在
搅拌下把溴缓慢滴加到混合物中。
After all
the
bromine has been added, the molten mixture is
stirred at 80
–
85°
on a steam
bath for 1 hour.
溴
滴加完后，
熔融混合物在
80-85
℃
蒸气浴下搅拌
1
小时。
The complex is
added in
portions to a well-stirred mixture of 1.3 l. of
cracked ice and 100 ml. of
concentrated
hydrochloric acid in a 2-l. beaker (Note 6).
反应物加入到
1.3L
碎冰和
100ml
浓盐酸的混合物中在
2L
的烧杯中混合均匀。
Part of the cold aqueous layer
is added
to the reaction flask to
decompose whatever part of the reaction mixture
remains
there, and the resulting
mixture is added to the beaker.
把部分的冰水层加
入到烧瓶中
洗涤残留物，然后合并到烧杯中。
The dark oil that settles out is
extracted from the
mixture with four
150-ml. portions of ether
分四次把深色的油从混合物中
用
150ml
萃取
出来。
The extracts are combined, washed
consecutively with 100 ml. of water and
100 ml. of 5% aqueous sodium
bicarbonate solution, dried with anhydrous sodium
sulfate, and transferred to a short-
necked distillation flask.
合并萃取液，用
100ml
水和
100ml 5%
的小苏打洗涤，
用无水硫酸钠干燥。
The
ether is removed by distillation at
atmospheric pressure, and crude
3-bromoacetophenone is stripped from a few
grams of heavy dark residue by
distillation at reduced pressure.
乙醚在常压
下蒸馏，
微量的溴苯乙酮通过减压蒸馏的方法从大量深色残渣中被分离出来。
The colorless distillate is
carefully fractionated to obtain
94
–
100
g.
通过分馏，得到无色的流出液
94-100g
2
、
反应式：
3
、
2-M
ethyl-4-ethoxalylcyclopentane-1,3,5-trione. A
solution of sodium ethoxide
is prepared
in a 2-l. three-necked, round-bottomed flask
fitted with a
mercury-sealed stirrer, a
reflux condenser carrying a drying tube, and a
stopper by
the addition of 69.0 g. (3
moles) of sodium to 950 ml. of absolute ethanol. 6
9.0g
（
3mol
）
钠和
950ml
无水乙醇在配有干燥回流冷凝管和汞封
搅拌器的
2L
三口圆底烧瓶中制备
乙醇
钠。
The solution is cooled to
0
–
5°
in an ice
bath and stirred.
溶液在
0-5
℃下冰浴
搅拌。
The
stopper is replaced by a dropping funnel, and a
cold mixture
(5
–
15°
) of
108 g. (1.50 moles) of freshly
distilled 2-butanone and 482 g. (3.30 moles) of
diethyl oxalate (Note 1) is added
gradually over a period of 30 minutes.
瓶
塞用分液
漏斗取代，
108g
（
1.5mol
）的丁二酮和
482g
（
3.3mol
）的乙二酸二乙酯在
5-15
℃下低温混
合，在
30
分钟内逐步滴加到溶液中。
After the addition is complete, the
thick,
orange-red mixture is allowed to
warm with continued stirring to room temperature,
heated under reflux for 30 minutes, and
cooled again to 0°
in an ice bath.
完全加入
后，橘红色的粘稠物继续搅拌至室温，加热回流
30
分钟后在冰浴中冷却至
0
℃。
The mixture
is decomposed
by stirring with 165 ml. of sulfuric acid (1:1 by
volume) added in
portions.
将<
/p>
165ml
浓硫酸（体积比
1:1
）在搅拌加入，分解混合物。
The
sodium sulfate
formed is filtered by
suction and washed with ethanol
(150
–
200 ml.) (Note 2).
硫
酸钠抽滤后用乙醇（
150
< br>–
200 ml
）洗涤。
The
washings and filtrate are combined and
concentrated by evaporation
.
合并滤液和洗涤液后蒸发浓缩。
The yellowish
brown
product which accumulates by slow
crystallization is collected by filtration, washed
with small quantities of ice-cold
water, and dried in air.
过滤缓慢析出的棕黄色产品用<
/p>
小剂量的冰水洗涤后在空气中干燥。
The crude product weighs
140
–
150 g.
粗产品
140-150g
。
Further evaporative concentration of
the mother liquor followed by
cooling
furnishes an additional
40
–
50 g. of the keto ester,
此外将母液用冷冻蒸发浓缩
后又得到
4
0-50g
的酮酯。
bringing the total
yield to 180
–
200 g. (53
–
59%)
产品总共
18
0-200g
（产率
53-59%
）<
/p>
(Note 2). This crude
material (m.p.
120
–
130°
) is used
in
the next step.
粗品（熔点
120
–
130
℃）用于下
一步中
A pure sample can be
obtained by
crystallization from ethyl
acetate after treatment with Norit activated
carbon, m.p.
160
–
162°
.
纯品是经过活性炭处理后在乙酸乙酯中结晶得到，熔
点
160
–
162
℃。
The
procedure for 2- pyrrolealdehyde
2-
吡咯甲醛
In a 3-l.
three-necked round-bottomed flask,
fitted with
a sealed stirrer, a
dropping funnel,
and a reflux
condenser, is placed 80 g. (1.1 moles) of
dimethylformamide (Note 1).
在配有封闭搅
拌器、
滴液漏斗和冷凝回流装置的三口圆底烧瓶中放入
80g
（
1.1mol
）
的二甲基甲酰胺。
The
flask is immersed in an ice bath, and
the internal temperature is maintained at
10
–
20°
, while 169
g.
(1.1 moles) of phosphorus
oxychloride is added through the dropping funnel
over a period of 15
minutes.
烧瓶浸入冰浴中，内部温度保持在
10-20
℃，
169g
（
1.1mol
）的磷酰氯通过滴液漏
斗在
15
分钟内
滴加。
An
exothermic
reaction
occurs
with
the
formation
of
the
phosphorus
oxychloride -
dimethylformamide complex.
放热反应生成磷酰氯二甲基甲酰胺化合物。
The ice
bath is removed, and the mixture is
stirred for 15 minutes (Note 2).
移去冰浴，在
搅拌
15
分钟。
The ice bath is replaced, and 250 ml.
of ethylene dichloride is added to the mixture.
重新再
冰浴下加入
250ml
的二氯乙烯。
When the internal
temperature has been lowered to 5°
, a
solution
of 67 g. (1.0 mole) of freshly
distilled pyrrole in 250 ml. of ethylene
dichloride is added through a
clean
dropping funnel to the stirred, cooled mixture
over a period of 1 hour.
当内部温度降到
5
度
时，把
67g
（
1.0mol
）新蒸馏的吡咯加入到
250
二氯乙烯中，通过滴液漏斗在
1
小时内低温下
边搅拌边滴加。
After the
addition is complete, the ice bath is replaced
with a heating mantle, and
the mixture
is stirred at the reflux temperature for 15
minutes, during which time there is copious
evolution
of
hydrogen
chloride.
滴加完后，用加热装置取代冰浴，搅拌回流
15
分钟，
直到有
大量氯化氢产生。
The mixture is then cooled to
25
–
30°
, and to it
is added through the dropping funnel a solution of
750 g. (5.5 moles) of sodium acetate
trihydrate (Note 3) in about of water, cautiously
at first, then
as rapidly as possible.
当混合物降温到
25-30
℃后，通过
滴液漏斗加入
750g
（
5.5mol
）的三水
醋酸钠溶液，开始要小心，然后要尽可能地快。
The reaction mixture is again refluxed for
15
minutes, vigorous stirring being
maintained all the while (Note 4).
反应物在
充分搅拌下重新回
流
15
分钟。