CN1058488C - 1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法 - Google Patents
1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法 Download PDFInfo
- Publication number
- CN1058488C CN1058488C CN95100483A CN95100483A CN1058488C CN 1058488 C CN1058488 C CN 1058488C CN 95100483 A CN95100483 A CN 95100483A CN 95100483 A CN95100483 A CN 95100483A CN 1058488 C CN1058488 C CN 1058488C
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- ketone
- azepines
- reaction
- formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 150000001538 azepines Chemical class 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 19
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- 150000001875 compounds Chemical class 0.000 abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 6
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 abstract description 3
- 239000001569 carbon dioxide Substances 0.000 abstract description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 3
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 24
- 238000000034 method Methods 0.000 description 15
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 238000009835 boiling Methods 0.000 description 8
- 238000005481 NMR spectroscopy Methods 0.000 description 7
- LRFHTDKOTJCGSF-UHFFFAOYSA-N CN(C)C.NCCNCCN Chemical compound CN(C)C.NCCNCCN LRFHTDKOTJCGSF-UHFFFAOYSA-N 0.000 description 6
- 238000004821 distillation Methods 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 5
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 5
- 150000003973 alkyl amines Chemical class 0.000 description 5
- 238000005576 amination reaction Methods 0.000 description 5
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 5
- 239000012965 benzophenone Substances 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- -1 n-pro-pyl Chemical group 0.000 description 4
- CFQPVBJOKYSPKG-UHFFFAOYSA-N 1,3-dimethylimidazol-2-one Chemical compound CN1C=CN(C)C1=O CFQPVBJOKYSPKG-UHFFFAOYSA-N 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- VMHYWKBKHMYRNF-UHFFFAOYSA-N (2-chlorophenyl)-phenylmethanone Chemical class ClC1=CC=CC=C1C(=O)C1=CC=CC=C1 VMHYWKBKHMYRNF-UHFFFAOYSA-N 0.000 description 1
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- 208000031404 Chromosome Aberrations Diseases 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WZELXJBMMZFDDU-UHFFFAOYSA-N Imidazol-2-one Chemical compound O=C1N=CC=N1 WZELXJBMMZFDDU-UHFFFAOYSA-N 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 231100000005 chromosome aberration Toxicity 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- XTUSEBKMEQERQV-UHFFFAOYSA-N propan-2-ol;hydrate Chemical compound O.CC(C)O XTUSEBKMEQERQV-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/02—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers
- H01L27/04—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body
- H01L27/10—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components specially adapted for rectifying, oscillating, amplifying or switching and having potential barriers; including integrated passive circuit elements having potential barriers the substrate being a semiconductor body including a plurality of individual components in a repetitive configuration
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D255/00—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00
- C07D255/02—Heterocyclic compounds containing rings having three nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D249/00 - C07D253/00 not condensed with other rings
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Dram (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明涉及式(1)代表的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法,其制备方法包括使式(2)代表的N,N′,N″-三烷基二亚乙基三胺与脲、光气或二氧化碳反应;式(1)和式(2)如下式中R是C1-C8烷基。
Description
1,3-二甲基-2-咪唑啉酮和N-甲基-2-吡咯烷酮是公知的常规疏质子极性化合物。
这些化合物是有用的溶剂,尤其是聚酰胺、聚氯乙烯、聚乙烯醇、聚苯乙烯、聚氨酯、酚醛树脂和其它高聚物的极好的溶剂。而且,这些化合物也可用作许多有机反应的溶剂。然而,公知的疏质子极性化合物存在许多问题。例如1,3-二甲基-2-咪唑啉酮在高温下抗氧化性差,N-甲基-2-吡咯烷酮会引起染色体畸变。
本发明的目的是提供溶剂效应极佳的新的疏质子极性化合物。
为了开发出新的疏质子极性溶剂,本发明人进行了深入的研究,结果成功地制备了具有与1,3-二甲基-2-咪唑啉酮类似的环状脲结构的并预期是强极性的1,3,6-三烷六氢-1,3,6-三氮杂辛因-2-酮,并且发现,该新化合物作为疏质子极性物质能够产生极佳的溶剂效应。从而完成了本发明。
也就是说,本发明的一个方面是式(1)代表的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮:式中R是C1-C8烷基。
本发明的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮表现出比常规疏质子极性溶剂优异的溶剂效应。
因此,本发明能够提供溶剂效应极佳的新的疏质子物质,从而具有重要的意义。
图1是1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮的IR光谱图;
图2是1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的IR光谱图;
图3是1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的IR光谱图。
在式(1)中,R是具有1-8个碳原子的烷基。所述烷基的例子包括甲基、乙基、正丙基、异丙基、正丁基、异丁基、仲丁基、叔丁基、正戊基、异戊基、2-戊基、3-戊基、新戊基、正己基、异己基、正庚基、异庚基、正辛基和异辛基。
必要时,也可通过在相应的烷基胺的共存下使N,N′-二烷基亚乙基二胺与1,2-二卤代乙烷反应来制备所述三元胺。将这样得到的N,N′,N″-三烷基二亚乙基三胺与脲、光气或二氧化碳反应,经环化作用得1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮。
在优选的制备中间体N,N′,N″-三烷基二亚乙基三胺的方法中,烷基胺与1,2-二卤代乙烷的摩尔比优选4-6。当烷基胺的摩尔比率太高时,中间体副产物N,N′-二烷基亚乙基二胺的量容易增加。
对于1,2-二卤代乙烷胺化的反应温度没有特别限制,只要温度在能给出适当反应速率的范围内就行。优选的温度范围是80-150℃。
胺化反应可根据反应温度而在加压下进行。在实践中,当使用沸点高于正丁胺沸点(沸点:78℃)的胺时,反应可在大气压力下进行。然而,当使用沸点低于正丁胺沸点的胺时,反应必须在加压下进行。
已知的常规溶剂均可用于胺化反应,不存在任何问题。然而,胺化反应通常在无溶剂情况下进行,即仅在烷基胺和1,2-二囟代己烷的存在下进行。
这样生成的N,N′,N″-三烷基二亚乙基三胺可通过用氢氧化钠或其它适当的碱中和胺化反应混合物并蒸除未反应的烷基胺的方法来分离。进一步蒸馏残余物可获得纯产物。
在本发明方法的第一步中,先使N,N′,N″-三烷基二亚乙基三胺与脲反应生成脲中间体。反应温度优选在100-155℃、更优选在120-145℃的范围内。反应温度高于155℃将导致脲的分解。另一方面,当反应温度低于100℃时,则反应速率太低。在该起始反应中,脲中间体的生成定量地进行,反应的终点可通过测定随反应进行而释放出的氨气来检测。
脲中间体的分解反应是通过随后将反应温度升至180℃或高、优选200-260℃、更优选210-240℃进行的。这样便可高收率地得到1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮。当温度低于180℃时,分解反应太慢。另一方面,300℃左右的温度会使加热设备产生问题。
在本发明方法中,对于1mol脲,N,N′,N″-三甲基二亚乙基三胺的用量为0.8-2.5mol,优选1.0-2.0mol,更优选1.2-1.7mol。当N,N′,N″-三甲基二亚乙基三胺的用量少于0.8mol时,副产物的生成加剧。另一方面,用量超过2.5mol将导致工业中的不利因素,例如,体积效率降低。
本发明方法中可用的溶剂包括例如乙醇、甲基·异丁基酮、N-甲基-2-吡咯烷酮、1,3-二甲基-2-咪唑啉酮、二甘醇二甲醚和三甘醇二甲醚。然而,本发明方法也可在无溶剂条件下实施。也就是说,即使在仅有N,N′,N″-三烷基二亚乙基三胺和脲存在下进行反应得到1,3,6-三烷基六氢-1,3,6-三氢杂辛因-2-酮的收率也等于或高于有溶剂存在下所得的收率。因此,从免除复杂程序如蒸除溶剂的观点来看,最好使反应在无溶剂条件下进行。而且,当使用高沸点溶剂时,反应可在大气压力下进行。然而,当使用低沸点溶剂时,则需要在加压下进行反应,从生产设施的角度来看,这在工业上是不利的。然而,在N,N′,N″-三烷基二亚乙基三胺中,N,N′,N″-三甲基二亚乙基三胺的沸点最低,但仍可达201℃。因而,不需要加压,从而优选在无溶剂条件下进行反应。
这样生成的1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮可通过蒸馏提纯。未反应的N,N′,N″-三烷基二亚乙基三胺作为1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮的初馏物被回收并可再次使用。
下面通过实施例和对比例来详细说明本发明。
实施例1
向5.0升装有温度计和搅拌器的高压釜中投入1286.5g(13mol)1,2-二氯乙烷和2018.9g(65mol)甲胺。搅拌加热至100℃,保持该温度,继续胺化反应2小时。
随后,将反应混合物冷却至室温,通过将反应器减压来回收过量的甲胺。用气相色谱分析此阶段的反应物料。1,2-二氯乙烷全部转化。随后,投入1072.2g 97%的片状氢氧化钠以中和反应物料,然后蒸馏回收未反应的甲胺。蒸馏后,滤除反应物料中沉淀的氯化钠,将滤液蒸馏,分离出229.4g N,N′,N″-三甲基二亚乙基三胺。
向0.5升装有回流冷凝器、温度计和搅拌器的烧瓶中投入217.9g(1.5mol)N,N′,N″-三甲基二亚乙基三胺和60.1g(1.0mol)脲,于125-140℃搅拌反应4小时。
随后,将温度升至215-225℃,在该温度下进行脲中间体的分解反应2小时。反应完毕后,用气相色谱测定1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮。基于脲计,收率为80.3%。蒸馏反应混合物,回收63.2g在第一步中未反应的N,N′,N″-三甲基二亚乙基三胺,然后得127.1g 1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮。产物的沸点为258℃,纯度为99.0%。
用′H NMR、13C NMR、IR和MS m/z:171(M+)鉴定1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮的结构。○ 1H NMR,δ(CDCl3,400MHz)
2.42(s,3H,④),2.66(m,4H,③),
2.78(s,6H,①),3.33(m,4H,②),○ 13C NMR,δ(CDCl3,100MHz)
36.8(q,①),46.6(q,④),
53.8(t,②),54.7(t,③),
图1是1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮的IR图。
实施例2
用与实施例1相同的方法进行反应和分析,只是要用正丙胺来代替甲胺。结果,1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的收率为66.5%(基于脲计算)。1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的结构用′HNMR、13C NMR、IR和MS m/z:297(M+)鉴定:
○ 1H NMR,δ(CDCl3,400MHz)
0.89(t,9H,①和⑧),
1.50(m,2H,⑦),1.56(m,4H,②),
2.47(t,2H,⑥),2.70(m,4H,④),
3.09(t,4H,③),3.35(t,4H,⑤),
○ 13C NMR,δ(CDCl3,100MHz)
11.5(q,①),11.7(q,⑧),
20.4(t,⑦),21.0(t,②),
51.5(t,③),51.8(t,⑤),
53.3(t,④),60.3(t,⑥),
163.5(s,C=0,⑨),
其中(①-⑧)代表下式中的位置;
图2是1,3,6-三正丙基六氢-1,3,6-三氮杂辛因-2-酮的IR图。
实施例3
用与实施例1相同的方法进行反应和分析,只是要用正丁胺来代替甲胺,并且N,N′,N″-三正丁基二亚乙基三胺的合成在大气压力下进行。结果,1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的收率为51.5%(基于脲计算)。1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的结构用′HNMR、13C NMR、IR和MS m/z:256(M+)鉴定。○1H NMR,δ(CDCl3,400MHz)
0.90(t,3H,⑩),0.91(t,6H,①),
1.30(m,6H,②and⑨)
1.42(m,2H,⑧),1.52(m,4H,③),
2.48(t,2H,⑦),2.67(m,4H,⑤),
3.11(t,4H,④),3.34(m,4H,⑥),○ 13C NMR,δ(CDCl3,100MHz)
13.8(q,①),13.9(q,⑩),
20.1(t,②),20.3(t,⑨),
29.4(t,⑧),29.6(t,③),
49.5(t,④),51.8(t,⑥),
53.2(t,⑤),58.0(t,⑦),
163.4(s,C=0,)其中(①-⑩)代表下式中的位置;
图3是1,3,6-三正丁基六氢-1,3,6-三氮杂辛因-2-酮的IR图。
对比例1
向0.3升装有搅拌器和温度计的反应器中投入25.1g(0.1mol)4,4′-二氯二苯酮、24.0g(0.22mol)间氨基苯酚、12.9g(0.22mol)96%的氢氧化钾和150g用作溶剂的得自实施例1的1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮,于150-160℃反应8小时。
反应完成后,将反应物料冷却至室温,滤除生成的无机盐。从滤液中减压蒸除溶剂。将残余物与20.8g 35%的盐酸和100g水混合,加热溶解。随后向所得溶液中加入11.7g氯化钠,在搅拌下冷却至20-25℃以沉淀盐酸盐。滤出盐酸盐,用10%氯化钠水溶液重结晶,然后在50%异丙醇水溶液中,用氨水溶液中和。过滤沉淀的晶体,水洗、干燥,得25.6g(收率:88.3%)4,4′-二(3-氨基苯氧基)二苯酮白色晶体。用高效液相色谱测得纯度为99.5%。
对比例2
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为1,3,6-三正丙基六氢-1,3,6-三氮杂辛-2-酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为88.0%。
对比例3
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为1,3,6-三正丁基六氢-1,3,6-三氮杂辛-2-酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为87.5%。
对比例4
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为1,3-二甲基-2-咪唑啉酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为87.0%。
对比例5
采用与对比例1相同的方法,只是要将反应溶剂1,3,6-三甲基六氢-1,3,6-三氮杂辛因-2-酮变为N-甲基-2-吡咯烷酮。
得到4,4′-二(3-氨基苯氧基)二苯酮,收率为76.5%。
Claims (5)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP031174/1994 | 1994-03-01 | ||
JP031174/94 | 1994-03-01 | ||
JP3117494 | 1994-03-01 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1111624A CN1111624A (zh) | 1995-11-15 |
CN1058488C true CN1058488C (zh) | 2000-11-15 |
Family
ID=12324085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN95100483A Expired - Fee Related CN1058488C (zh) | 1994-03-01 | 1995-02-28 | 1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法 |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0670316B1 (zh) |
KR (2) | KR950026865A (zh) |
CN (1) | CN1058488C (zh) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE102012019149A1 (de) | 2012-09-27 | 2014-03-27 | Epg (Engineered Nanoproducts Germany) Ag | Robustes, von der Einwirkung katalytisch aktiver Substanzen unabhängiges Bindemittel zur Anwendung in der Öl und Gas fördernden Industrie |
DE102012019150A1 (de) | 2012-09-27 | 2014-03-27 | Epg (Engineered Nanoproducts Germany) Ag | Bindemittel für die Verfestigung von Formationen bei der Erdöl- und Erdgasproduktion |
KR101974388B1 (ko) | 2017-06-23 | 2019-05-02 | (주)에니켐텍 | 알킬 디에틸렌 트리아민 유도체 및 이의 제조방법 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2952125A1 (de) * | 1979-12-22 | 1981-06-25 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von 3,5-bis-carbalkoximethyl-1,3,5-triaza-2,4,6-trioxocycloheptanen |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1184766B (de) * | 1962-06-15 | 1965-01-07 | Bayer Ag | Verfahren zur Herstellung von cyclischen Harnstoffen |
-
1995
- 1995-02-23 KR KR1019950003539A patent/KR950026865A/ko not_active Application Discontinuation
- 1995-02-24 KR KR1019950003663A patent/KR100330996B1/ko not_active IP Right Cessation
- 1995-02-27 EP EP95102787A patent/EP0670316B1/en not_active Expired - Lifetime
- 1995-02-28 CN CN95100483A patent/CN1058488C/zh not_active Expired - Fee Related
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2952125A1 (de) * | 1979-12-22 | 1981-06-25 | Hoechst Ag, 6230 Frankfurt | Verfahren zur herstellung von 3,5-bis-carbalkoximethyl-1,3,5-triaza-2,4,6-trioxocycloheptanen |
Also Published As
Publication number | Publication date |
---|---|
KR950034774A (ko) | 1995-12-28 |
EP0670316B1 (en) | 1997-09-03 |
KR950026865A (ko) | 1995-10-16 |
EP0670316A1 (en) | 1995-09-06 |
KR100330996B1 (ko) | 2002-08-14 |
CN1111624A (zh) | 1995-11-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
HU230546B1 (hu) | Kvaterner ammónium-bikarbonátok és kvaterner ammónium-karbonátok előállítására szolgáló in situ eljárás | |
US6175027B1 (en) | Synthesis of bis (alkyl cyclopentadienyl) metallocenes | |
CN108191674A (zh) | 一种联苯胺化合物的合成方法 | |
CN1058488C (zh) | 1,3,6-三烷基六氢-1,3,6-三氮杂辛因-2-酮及其制备方法 | |
JP2012508237A (ja) | アリールアミン化合物の製造方法 | |
WO2021129359A1 (zh) | 一种双端胺基硅氧烷的纯化方法 | |
JPH07145122A (ja) | N−アルキル−α,β−不飽和カルボン酸アミドの製造方法 | |
JPH08253486A (ja) | ペンタフルオロフエニル化合物を製造するための方法 | |
CN111205216A (zh) | 一种制备沙格列汀的方法 | |
CN110615767B (zh) | 一种合成5-氟胞嘧啶的方法 | |
CN1056138C (zh) | 双脲化合物的制备方法 | |
CN114805345A (zh) | 一种他达拉非中间体顺式四氢咔啉盐酸盐的制备方法 | |
CN100591652C (zh) | 生产2-(4-氟-苄基)-苯基-乙酸的方法 | |
CN1158235C (zh) | 三、四乙二醇甲醚的制备方法 | |
CN115197085B (zh) | 2-氨基-5-氯-n,3-二甲基苯甲酰胺的制备方法 | |
CN114560764B (zh) | 一种亚油酸直接马来酰化制备c22三元羧酸的方法 | |
RU2245872C2 (ru) | Способ получения простых азоиминоэфиров и эфиров азокарбоновых кислот и новые смешанные эфиры азокарбоновых кислот | |
CN1172905C (zh) | 生产氰基苄胺盐的方法 | |
CN1599644A (zh) | 烯丙基醇的异构化方法 | |
CN106478423A (zh) | 合成n,n‑二异丙基乙胺的方法 | |
CN1038452A (zh) | 吡咯嗪衍生物的制备方法 | |
CN102093301A (zh) | 沙坦联苯四唑的溶剂热合成法 | |
CN117903194A (zh) | 一种精草铵膦前体及精草铵膦酸盐的制备方法 | |
CN114805094A (zh) | 一种双(3-氨基-4-羟基苯基)六氟丙烷的制备方法 | |
CN114478611A (zh) | 四乙烯硅烷的合成方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C06 | Publication | ||
PB01 | Publication | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |