CN108774137B - 一种双核锰配合物催化合成仲胺化合物的方法 - Google Patents
一种双核锰配合物催化合成仲胺化合物的方法 Download PDFInfo
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 44
- 239000011572 manganese Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 secondary amine compound Chemical class 0.000 title claims abstract description 24
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 150000003138 primary alcohols Chemical class 0.000 claims abstract description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 9
- 239000002798 polar solvent Substances 0.000 claims abstract description 8
- 230000002829 reductive effect Effects 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 238000004440 column chromatography Methods 0.000 claims abstract description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 13
- 150000003141 primary amines Chemical class 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 claims description 7
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 6
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- GCWCHLULHAWMEH-UHFFFAOYSA-N hydrazine;methanol;hydrate Chemical compound O.OC.NN GCWCHLULHAWMEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
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- 150000003335 secondary amines Chemical class 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 6
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000543 intermediate Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 238000002451 electron ionisation mass spectrometry Methods 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000741 silica gel Substances 0.000 description 4
- 229910002027 silica gel Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 3
- MSHFRERJPWKJFX-UHFFFAOYSA-N 4-Methoxybenzyl alcohol Chemical compound COC1=CC=C(CO)C=C1 MSHFRERJPWKJFX-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052987 metal hydride Inorganic materials 0.000 description 2
- 150000004681 metal hydrides Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000007126 N-alkylation reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 238000010693 amine synthesis reaction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- BHAAPTBBJKJZER-UHFFFAOYSA-N p-anisidine Chemical compound COC1=CC=C(N)C=C1 BHAAPTBBJKJZER-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000006268 reductive amination reaction Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/18—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to carbon atoms of six-membered aromatic rings or from amines having nitrogen atoms bound to carbon atoms of six-membered aromatic rings
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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Abstract
双核锰配合物催化合成仲胺化合物的方法，氮气保护下，将双核锰配合物催化剂和叔丁醇钾在室温下溶解于极性溶剂中，然后加入伯醇和伯胺，于100‑130℃温度下反应12‑48h，减压除去极性溶剂，所得混合物通过柱色谱法分离得纯品，即为所述仲胺化合物。优点是：1）锰催化剂制备简单、产率高；2）催化剂只含锰金属，地壳丰度高，价格低廉；3）催化过程选择性好，绿色环保。
Description
技术领域
本发明涉及仲胺类化合物的金属催化合成方法领域，尤其涉及一种双核锰配合物催化合成仲胺化合物的方法。
背景技术
仲胺类化合物是化学研究和工业中最普遍、最重要的有机合成原料及中间体，胺的合成也是学术界及业界最重要的研究课题之一。伯胺的N-烷基化是化学合成和中间体合成的常见方法，合成路线和方法也比较多，合成产物不仅是橡胶、石油等的填加剂，也是药物合成中最常用的中间体
传统上，仲胺主要通过伯胺与卤代烃的亲核取代反应以及醛酮与胺的还原胺化反应制备。而如何确保这类反应的选择性，以及避免烷基化试剂的高毒性是仲胺合成的研究趋势。以‘借氢（或氢自转移）’反应为代表的新型胺合成反应具有非常高的原子经济性，因此成为当前绿色化学的重要研究方向之一。
借氢仲胺合成反应是指用金属催化剂将相对惰性的有机分子（如伯醇或胺）催化脱氢，并形成高活性的金属氢化物催化剂中间体，其后脱氢产物与胺偶联形成中间体，随后金属氢化物催化剂再利用前面释放的氢分子将中间体还原成仲胺的反应。比如，胺与醇的借氢反应生成仲胺和一分子水，伯胺与胺的借氢反应生成仲胺和一分子氨气。该方法既简洁高效，又绿色环保。以钌和铱为代表的贵金属催化剂近年来相继被报道。虽然这些催化剂具有广泛的底物适用性，但因为这些金属价格高昂且有毒性，发展廉价而低毒的金属催化剂（如锰, 铁, 钴 等）是当前绿色化学的重大挑战之一。
近年来，据文献报道，几种基于铁, 钴，锰作为非贵金属的配合物催化剂已经应用到伯胺与醇的借氢反应而合成仲胺。但是所有已知的催化剂都利用了含磷配体，而其较低的空气、湿度稳定性以及昂贵的价格繁琐的合成过程极大地限制了它们在实际工业中的应用。本发明报道了一种利用结构新颖、原料简单易得、价格便宜且空气稳定的双核锰催化剂通过催化胺-醇借氢战略合成仲胺的反应。相比于已知的催化方法，该发明具有以下优点：1）锰催化剂制备简单、产率高； 2）催化剂只含锰金属，地壳丰度高，价格低廉；3）催化过程选择性好，绿色环保。
发明内容
本发明目的是提供一种双核锰配合物催化合成仲胺化合物的方法。
一种仲胺化合物, 其通式（I）为：
其中R1 代表碳原子数为２-８的链烷基、碳原子数为５-８的环烷基、苯基、取代苯基。R2 代表取代苯基、碳原子数为２-８的链烷基。
制备方法包括以下步骤：
（II）
如上述通式（II）所述，氮气保护下，将双核锰配合物催化剂和叔丁醇钾在室温下溶解于非极性溶剂中，然后加入伯醇和伯胺，于100-130℃温度下反应 12-48h，减压除去非极性溶剂，所得混合物通过柱色谱法分离得纯品，即为所述仲胺化合物。
伯醇与双核锰配合物催化剂的投料摩尔比为10:0.2，伯醇在反应体系中的浓度为0.5mol/L。
伯醇与叔丁醇钾的投料摩尔比为10:1。
伯醇和伯胺的投料摩尔比为10:12。
所述极性溶剂为甲苯、乙苯、四氢呋喃中的任意一种。
反应温度为120℃，反应时间为24h。
所述双核锰配合物催化剂的合成方法为：
室温条件下，将2-吡啶醛或2-乙酰基吡啶溶于甲醇,搅拌状态下逐滴加入水合肼甲醇溶液后，室温搅拌12h后过滤，所得黄色沉淀用甲醇洗涤后真空干燥，然后将所得黄色沉淀溶解于乙醚中，再加入五羰基溴锰固体粉末，氮气保护下室温搅拌24h后，过滤，所得混合沉淀用乙醚洗涤三次，然后真空干燥得淡橘色固体粉末，即制得所述双核锰配合物催化剂。
2-吡啶醛或2-乙酰基吡啶与水合肼、五羰基溴锰的投料摩尔比为2:1:0.4。
本发明的优点是: 利用廉价、简单的锰配合物作为催化剂, 选择性合成仲胺衍生物,操作方便、成本低、收率高，可进行大批量合成，适合工业生产应用。该反应效率高、化学选择性优异、副产物无污染、且放大反应效果稳定，适宜大批量工业应用。反应底物简单易得，可作为合成仲胺以及衍生产品的优良途径。其结构单元中的R1和R2 取代基团范围广，可适用于脂肪链、环烷烃、芳香烃。因此应用广泛，可用于制备多种药物中间体的原材料。
具体实施方式
一种双核锰配合物催化合成仲胺化合物的方法,包括：氮气保护下，将双核锰配合物催化剂在室温溶解于极性溶剂中，然后加入伯醇和伯胺，其后100-130℃反应 12-48 h，去除溶剂，所得混合物通过柱色谱法分离得纯品，即为仲胺化合物。其中：伯醇原料和催化剂的投料摩尔比是10 : 0.2，伯醇和叔丁醇钾的投料摩尔比是10 : 1，伯醇和胺的投料摩尔比是10 : 12，伯醇在反应体系中的浓度为0.5mol/L。
作为优选：
所述的伯醇和伯胺为具有通式（II）所示结构的化合物，两种皆可作为市售商业品购得：
其中，其中R1代表碳原子数为２-８的链烷基、碳原子数为５-８的环烷基、苯基、取代苯基。R2 代表取代苯基、碳原子数为２-８的链烷基。
所述的极性溶剂可为甲苯、乙苯、四氢呋喃等，优选为甲苯。
本发明所述的伯醇和伯胺都可采用市售工业品。但更高纯度的底物有利于提高产率和选择性。
本发明所述反应温度优选为100-130℃，更优选为120℃。
本发明所述反应过程需要氮气或氩气保护。
本发明所述反应过程需要的反应时间为12-48小时，优选为24小时。
本发明所述的催化剂载入量优选为2mol%，降低投料量至1mol% 仍可得到较高收率的纯产品，反应时间应延长。所述的伯醇和双核锰配合物催化剂的投料摩尔比优选为10:0.2。
本发明所述的伯醇和胺原料可根据化学反应计量比加入或过量加入，为了降低原料消耗、节约成本以及保持较高反应产率和选择性，伯醇和胺的投料摩尔比优选为1:1.2。并且伯醇在反应体系中的浓度优选为0.2mol/L-1.0mol/L, 更优选为0.5mol/L。
所述双核锰配合物催化剂的合成方法为：
室温条件下，将2-吡啶醛或2-乙酰基吡啶溶于甲醇,搅拌状态下逐滴加入水合肼甲醇溶液后，室温搅拌12h后过滤，所得黄色沉淀用甲醇洗涤后真空干燥，然后将所得黄色沉淀溶解于乙醚中，再加入五羰基溴锰固体粉末，氮气保护下室温搅拌24h后，过滤，所得混合沉淀用乙醚洗涤三次，然后真空干燥得淡橘色固体粉末，即制得所述双核锰配合物催化剂。
2-吡啶醛或2-乙酰基吡啶与水合肼、五羰基溴锰的投料摩尔比为2:1:0.4。
下面结合具体实施例对本发明作进一步说明。
本发明实施例中的反应的通式如下：
其中R1代表碳原子数为２-８的链烷基、碳原子数为５-８的环烷基、苯基、取代苯基。R2代表取代苯基、碳原子数为２-８的链烷基。
实施例一：
N2保护下，在100 毫升硬质玻璃管中加入双核锰配合物催化剂 (0.02 mmol, 2mol%) 以及叔丁醇钾（11.2 mg, 0.10 mmol, 10 mol%），然后加入2毫升甲苯，磁子搅拌。其后分别加入苯甲醇 (108.0 mg, 1.0 mmol)和苯胺(111.6 mg, 1.2 mmol)。将玻璃管密封后于油浴中加热至120℃， 搅拌过夜。反应24小时后冷却至室温，将溶剂减压蒸馏，粗产品通过硅胶柱分离（洗脱剂：乙酸乙酯/己烷：1 ：5）。产率：164 毫克 （90%）。表征数据：1H NMR(400 MHz, Chloroform-d) δ 7.41 – 7.31 (m, 4H), 7.31 – 7.25 (m, 1H), 7.22 –7.12 (m, 2H), 6.72 (td, J = 7.3, 1.2 Hz, 1H), 6.69 – 6.60 (m, 2H), 4.33 (s,2H), 4.02 (s, br, 1H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 148.30 , 148.30 ,139.58 , 129.40 , 128.77 , 127.64 , 127.36 , 117.70 , 112.98 , 48.47 ppm. EI-MS (m/z): 183 (calc. 183)。
实施例二：
N2保护下，在100 毫升硬质玻璃管中加入双核锰配合物催化剂 (0.02 mmol, 2mol%) 以及叔丁醇钾（11.2 mg, 0.10 mmol, 10 mol%），然后加入2毫升甲苯，磁子搅拌。其后分别加入苯甲醇 (108.0 mg, 1.0 mmol)和4-甲氧基苯胺 (147.6 mg, 1.2 mmol)。将玻璃管密封后于油浴中加热至120℃，搅拌过夜。反应24小时后冷却至室温，将溶剂减压蒸馏，粗产品通过硅胶柱分离（洗脱剂：乙酸乙酯/己烷：1：5）。产率：198毫克 （93%）。表征数据：1HNMR (400 MHz, Chloroform-d) δ 7.42 – 7.30 (m, 4H), 7.30– 7.20 (m, 1H), 6.82 –6.73 (m, 2H), 6.65 – 6.50 (m, 2H), 4.28 (s, 2H), 3.76 (s, br, 1 H,overlapping), 3.73 (s, 3H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 152.42,142.69, 128.80, 127.75, 127.37, 115.15, 114.32, 56.03, 49.47 ppm. EI-MS (m/z): 213 (calc. 213).
实施例三：
N2保护下，在100 毫升硬质玻璃管中加入双核锰配合物催化剂 (0.02 mmol, 2mol%) 以及叔丁醇钾（11.2 mg, 0.10 mmol, 10 mol%），然后加入2毫升甲苯，磁子搅拌。其后分别加入4-甲氧基苯甲醇(138.0 mg, 1.0 mmol)和苯胺(111.6 mg, 1.2 mmol)。将玻璃管密封后于油浴中加热至120℃，搅拌过夜。反应24小时后冷却至室温，将溶剂减压蒸馏，粗产品通过硅胶柱分离（洗脱剂：乙酸乙酯/己烷：1：5）。产率：180毫克 （85%）。表征数据：1HNMR (400 MHz, Chloroform-d) δ 7.28 (d, J = 8.3 Hz, 2H), 7.17 (td, J = 7.2,1.7 Hz, 2H), 6.90 – 6.83 (m, 2H), 6.70 (t, J = 7.4 Hz, 1H), 6.66 – 6.60 (m,2H), 4.24 (s, 2H), 3.93 (s, br, 1H), 3.79 (s, 3H) ppm. 13C NMR (101 MHz,Chloroform-d) δ 159.08, 148.42, 131.63, 129.45, 129.01, 117.71, 114.24,113.05, 55.51, 48.02 ppm. EI-MS (m/z): 213 (calc. 213)。
实施例四：
N2保护下，在100 毫升硬质玻璃管中加入双核锰配合物催化剂 (0.02 mmol, 2mol%) 以及叔丁醇钾（11.2 mg, 0.10 mmol, 10 mol%），然后加入2毫升甲苯，磁子搅拌。其后分别加入正己醇 (102.0 mg, 1.0 mmol)和苯胺(111.6 mg, 1.2 mmol)。将玻璃管密封后于油浴中加热至120℃，搅拌过夜。反应24小时后冷却至室温，将溶剂减压蒸馏，粗产品通过硅胶柱分离（洗脱剂：乙酸乙酯/己烷：1：5）。产率：152毫克 （86%）。表征数据：1H NMR(400 MHz, Chloroform-d) δ 7.16 (dd, J = 8.5, 7.2 Hz, 2H), 6.68 (t, J = 7.3Hz, 1H), 6.59 (d, J = 8.0 Hz, 2H), 3.57 (s, br, 1H), 3.09 (t, J = 7.1 Hz,2H), 1.61 (p, J = 7.2 Hz, 2H), 1.36 (ddd, J = 28.7, 7.6, 4.7 Hz, 6H), 0.95 –0.85 (m, 3H) ppm. 13C NMR (101 MHz, Chloroform-d) δ 129.41, 117.27, 112.89,44.22, 31.87, 29.78, 27.08, 22.84, 14.25 ppm. EI-MS (m/z): 177 (calc. 177)。
所述双核锰配合物催化剂的通式为:
其中配体中取代基R代表氢原子或者甲基取代基，所得催化剂效果相当。
下述为双核锰配合物催化剂的合成：
室温条件下，在100毫升圆底烧瓶中将2-吡啶醛或者2-乙酰基吡啶（20 mmol）溶于甲醇(20 mL), 磁子搅拌下逐滴加入水合肼(10 mmol)甲醇溶液(5 mL)。室温搅拌12小时后过滤，所得黄色沉淀用少量冷却甲醇洗涤后真空干燥。其后将所得黄色固体（2 mmol）溶解于乙醚（20 mL）中，加入五羰基溴锰（4 mmol）固体粉末，氮气保护下室温搅拌24小时后，过滤，用乙醚洗涤三次。真空干燥得淡橘色固体纯品。总收率90%。将淡橘色固体溶解于四氢呋喃中，加入等量乙醚，于零下30℃放置3天得橘色单晶。通过X-射线衍射表征分析得结构式如上图III所示。
Claims (8)
1.一种双核锰配合物催化合成仲胺化合物的方法，其特征在于包括以下步骤：
氮气保护下，将双核锰配合物催化剂和叔丁醇钾在室温下溶解于极性溶剂中，然后加入伯醇和伯胺，于100-130℃温度下反应 12-48h，减压除去极性溶剂，所得混合物通过柱色谱法分离得纯品，即为所述仲胺化合物; 所述双核锰配合物催化剂的通式为:
其中配体中取代基R代表氢原子或者甲基取代基;
所述仲胺化合物, 其通式为：
其中R1 代表碳原子数为２-８的链烷基、碳原子数为５-８的环烷基、苯基,R2 代表苯基、碳原子数为２-８的链烷基;
所述伯醇和伯胺为:
2.根据权利要求1所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于伯醇与双核锰配合物催化剂的投料摩尔比为10:0.2，伯醇在反应体系中的浓度为0.5mol/L。
3.根据权利要求2所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于伯醇与叔丁醇钾的投料摩尔比为10:1。
4.根据权利要求3所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于伯醇和伯胺的投料摩尔比为10:12。
5.根据权利要求1所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于所述极性溶剂为甲苯、乙苯、四氢呋喃中的任意一种。
6.根据权利要求1所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于反应温度为120℃，反应时间为24h。
7.根据权利要求1所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于所述双核锰配合物催化剂的合成方法为：
室温条件下，将2-吡啶甲醛或2-乙酰基吡啶溶于甲醇,搅拌状态下逐滴加入水合肼甲醇溶液后，室温搅拌12h后过滤，所得黄色沉淀用甲醇洗涤后真空干燥，然后将所得黄色沉淀溶解于乙醚中，再加入五羰基溴锰固体粉末，氮气保护下室温搅拌24h后，过滤，所得混合沉淀用乙醚洗涤三次，然后真空干燥得淡橘色固体粉末，即制得所述双核锰配合物催化剂。
8.根据权利要求7所述的一种双核锰配合物催化合成仲胺化合物的方法，其特征在于2-吡啶甲醛或2-乙酰基吡啶与水合肼、五羰基溴锰的投料摩尔比为2:1:0.4。
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