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quick208

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注册: 2007-12-27

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N-(Cycloheptyl)butylamine 3b. The reaction was conducted
and worked up as described for 3a, except that butylamine was
used  instead of triethylamine. The following quantities were
used: cycloheptanone (5.61 g, 5.90 cm3, 50 mmol), butylamine
(1 1 .O g, 14.8 cm3, 150 mmol), Mg (5.47 g, 225 mmol) and AcOH
(9.0 g, 8.6 cm3, 150 mmol), followed by additional amount of
AcOH (15.0 g, 14.3 cm3, 250 mmol). The monooxalate salt wasobtained with anh. oxalic acid (5.40 g, 60 mmol) in 72% yield
(9.32 g).
N-(Cyclohexyl)isobutylamine  3s. The same equipment was
used as for 3a. Isobutyraldehyde (3.60 g, 4.55 cm3, 50 mmol),
cyclohexylamine (4.46 g, 5.15 cm3, 45 mmol), Et3N (15.18 g,
20.9 cm3, 150 mmol), Mg (5.47 g, 225 mmol) and MeOH (60
cm3) were combined. The mixture was stirred and cooled (water
bath), while AcOH (12.0 g, 1 1.45 cm3, 200 mmol) was added
with a pipette below the surface of the liquid. The mixture was
stirred vigorously, at 20-25  "C for 3 h, after which AcOH (12.0
g,  11.45 cm3, 200 mmol) was added, portionwise, from the
dropping funnel, over a 2 h period. After being further stirred
for 12 h (overnight) at 20-25  OC, the mixture was worked up as
described above to afford the monooxalate salt (7.98 g, 72%).
N-Methyl-l,5-diphenylpentan-3-ylamine 3c. Into a 250 cm3,
single-necked flask, were combined  1,5-diphenylpentan-3-0ne
(7.15 g, 30 mmol), a solution of MeNH,  in MeOH (5.4 mol
dm-3, 44.5 cm3, 240 mmol), and Mg (3.28 g, 135 mmol). AcOH
(14.4 g, 13.75 cm3, 240 mmol) was added as above, and the flask
capped  with  a  mercury-filled  bubbler,  to  reduce  escape  of
MeNH,. The mixture was stirred vigorously, at 20-25  "C, for
12 h. If the reaction was incomplete (TLC), additional Mg (0.73
g, 30 mmol), MeNH, solution (1 1.1 cm3, 60 mmol) and AcOH
(3.6 g, 3.4 cm3, 60 mmol) were added and the stirring continued
until completion (3-6  h). Work-up afforded the monooxalate
salt (6.72 g, 65%).
1-Methyl-3-phenylpropylamine 30.  In  a  250  cm3, single-
necked flask were combined 4-phenylbutan-2-one (7.41 g, 50
mmol), AcONH,  (38.54 g, 500 mmol), Mg (6.08 g, 250 mmol)
and 70% aqueous MeOH (100 cm3). The flask was capped with
a mercury-filled bubbler, to reduce escape of NH,,  and the
mixture was stirred at 20-25  OC, for 12 h. If the reaction was not
complete (TLC), additional AcOH (6.0 g, 5.70 cm3, 100 mmol)
and  Mg  (2.43  g,  100 mmol)  were  added  and  the  stirring
continued for an additional 12 h. The mixture was poured into
water (600 cm3) to which NaHCO, (50 g) was then added; the
whole was then internally steam distilled until 500 cm3 of the
distillate collected. It was made alkaline (pH > 12) with 50%
aq. NaOH, and extracted with  CH,Cl,  (3 x 50 cm3). The
combined extracts were dried (K,CO,),  filtered and evaporated
on a rotatory evaporator. The residue was dissolved in MeOH
(20 cm3) and added slowly, with stirring, to a solution of anh.
oxalic acid (5.40 g, 60 mmol) in MeOH. Complete precipitation
was effected by  adding Et,O  (50 cm3) to the mixture and
cooling it to -20  "C. The yield of the mixed monooxalate salt
was 8.63 g. An analytical sample of the free amine was obtained
as for 3a: purity (GC): 90% of the primary amine and 10% of the
secondary amine. The pure primary  amine was obtained by
vacuum fractional distillation: bp 90-95 OCjlO Torr; yield 3.71
g (50%).
N-(Phenethyl)heptan-3-ylamine  3k.  The procedure  adopted
was the same as that for 3a except that stoichiometric amounts
of the reactants were used: heptan-3-one (50 mmol, 5.71 g, 7.0
cm3) and phenethylamine (50 mmol, 6.06 g, 6.30 cm')). After
completion of the reduction (6 h), ethyl fonnate (20 mmol, 1.48
g, 1.62 cm3) was added to the mixture and heating discontinued.
After  1.5 h of stirring, the mixture was worked up as for 3a;
yield of the monooxalate salt: 6.95 g (45%).
N,N'-Di(butan-2-yl)hexane-1,6-diamine  31. The  procedure
adopted  was  the  same  as  that  for  3a with  the  following
reactants: ethyl methyl ketone (10.82 g, 13.4 cm3, 150 mmol),
hexane-1,6-diamine (5.81 g, 50 mmol), Et,N (30.36 g, 41.8 cm3,
300 mmol), Mg (10.94 g, 450 mmol), AcOH (24 g, 22.9 cm3, 400
mmol) followed by portionwise addition of AcOH (24 g, 22.9
cm3, 400 mmol). The product was precipitated as the dioxalate
salt: 15.81 g (77%).
5-Methyl-N-(phenethyI)-2-pyrrolidone  3q.  The  procedure
adopted  was  the  same  as  that  for  3a with  the  following
reactants: methyl levulinate (8.46 g, 8.3 cm3, 65 mmol) and
phenethylamine (6.06 g, 6.3 cm3, 50 mmol). In the work-up, the
ether  extract  was  washed  with  5% aqueous oxalic  acid  to
remove basic components, dried  (MgSO,),  and evaporated.
Vacuum distillation gave a pale yellow oil, bp 130-1 35 'C/O. 1
Torr; yield 7.95 g (78%).

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liuyan001

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N - （对环己烷）丁胺第3 B 。除丁胺是用三乙胺代替外,其它反应如3 A所述的进行，使用数量如下： cycloheptanone （ 5.61克，5.90立方厘米， 50mmol ），丁胺（ 1 1 . o克， 14.8立方厘米， 150 mmol ），镁（5.47克， 225 mmol ）和醋酸（ 9.0克，8.6立方厘米， 150 mmol ），如下是额外数量
醋酸（15.0克， 14.3立方厘米， 250 mmol ）。单乙二酸酯盐是从草酸（5.40克60 mmol ）中获得的,产量为72 ％（9.32克）。 N - （对环己烷）一丁胺 3S。同样的设备用于3 A 。异丁醛（ 3.60克，4.55立方厘米， 50 mmol ），环己胺（ 4.46克，5.15立方厘米， 45 mmol ）， Et3n （15.18克， 20.9立方厘米， 150mmol ）， Mg （5.47克， 225 mmol ）和甲醇（ 60 立方厘米）的总和。混合搅拌和冷却（水浴），而醋酸（ 12.0克， 1 1.45立方厘米， 200 mmol ）用移液器加到液体的下表面。大力搅拌该混合物，在20至25摄氏度保存 3小时后，醋酸（ 12.0 克，11.45立方厘米， 200 mmol ）加入后，沿着漏斗分离2小时以上。进一步震荡在20至25摄氏度静置12小时（过夜），如上文所述,该混合物提供单乙二酸酯盐盐（ 7.98克， 72 ％）。N -甲基1,5 二苯基 - 3 - 乙胺3C放入一个250立方厘米单颈瓶内，合并1,5 -二苯基 - 3 - 乙胺（ 7.15克， 30 mmol ）,氨基醇溶液，甲醇（ 5.4 mol cm- 3 ， 44.5立方厘米， 240 mmol ），和Mg （ 3.28克，135mmol ）。醋酸（14.4克，13.75立方厘米， 240 mmol ），加到上述溶液中，瓶子用水银填充的球盖上,以减少胺基醇的挥发。剧烈震荡混合，在20至25摄氏度保存12小时,如果反应不完全（薄层色谱法），再加入镁（ 0.73 克， 30 mmol ），胺基醇，溶液（ 1 1.1立方厘米， 60 mmol ）和醋酸（ 3.6克， 3.4立方厘米， 60 mmol ）并继续搅拌直到反应完全（ 3-6 h ）。提供单乙二酸酯盐（ 6.72克， 65 ％）,1 -甲基- 3 -苯丙胺30 ,放入一个250立方厘米单颈瓶内，合并1,5 -二苯基 - 3 - 乙胺（ 7.15克， 30 mmol 4 - phenylbutan - 2 - 1 （ 7.41克， 50mmol ），胺基乙醚（ 38.54克， 500 mmol ）， Mg （6.08克， 250 mmol ）和70 ％的甲醇水溶液，（100立方厘米）。瓶子用水银填充的球盖上减少胺的流失，混合物在20-25摄氏度旋转混合12小时.如果反应不完全（薄层色谱法），再加入醋酸（6.0克，5.70立方厘米， 100 mmol ）和Mg （ 2.43克， 100 mmol ）并搅拌混合12小时.混合物被注入
到600ml水中，然后加入 50克碳酸氢钠，然后进行蒸汽蒸馏直到500立方厘米的
馏分被收集。用50 ％氢氧化钠溶液配制成碱性（ pH值> 12 ），并用甲烷，氯提取。混合提取物过滤，旋转蒸发器蒸发至干。残留物中慢慢加入甲醇（20立方厘米）溶解，搅拌。加入到用甲醇配制的草酸溶液（5.40克， 60 mmol ）中。完成降水被加入的内皮素，氧（五零立方厘米）的混合物并冷却到-20摄氏度所影响.混合物单乙二酸酯盐的产量是8.63 g.自由胺的分析样本的获得如3 A 所述：纯度（ GC ）： 90 ％的伯胺和10 ％的二级胺。纯伯胺通过真空分馏获得：产量3.71克（ 50%）。 N - （对苯） heptan - 3 - ylamine的3 K 。采用的程序与3 A是一样的，除了该反应所用的： heptan - 3 - 1 （ 50 mmol ，5.71克， 7.0 立方厘米）和苯胺（50mmol ，6.06克，6.30厘米' ）化学计量的数额不同）。在反应完成后 6小时，乙基-fonnate （ 20 mmol ， 1.48克，1.62立方厘米）被加到混合物中并加热。搅拌1.5 h后，混合物如3 A所述进行 ; 单乙二酸酯盐的产量： 6.95克（ 45 ％）。N， N' -二（丁- 2 -基）己烷-1,6二胺31 。采用的程序与3 A是一样的，符合下列反应：甲基乙基酮（ 10.82克，13.4立方厘米， 150 mmol ），己烷-1,6 -二胺（5.81克， 5 0m mol），内皮素， N （30.36克，41.8立方厘米，300mmol ）， Mg （10.94克， 450 mmol ），醋酸（24克，22.9立方厘米， 400mmol ），其次是加入醋酸（ 24克， 22.9立方厘米， 400 mmol ）。该产品是二乙二酸酯
盐的沉淀：15.81克（ 77 ％）。5 -甲基-N - （ p henethyi） - 2 -吡咯烷酮 3q。程序和3 A所述是一样的，符合下列反应：甲基levulinate （ 8.46克，8.3立方厘米， 65 mmol ）苯乙胺（6.06克， 6.3立方厘米， 50 mmol ）。反应中，醚提取物被5 ％草酸水溶液冲洗来除去基本组成部分，烘干（ mgso4 ），蒸发。真空蒸馏得到淡黄色的石油，气压130-1 35 ' ;产量7.95克（ 78 ％）。