CN102531929B - Nitrogen and oxygen heteroatom-containing compound and preparation and application thereof - Google Patents
Nitrogen and oxygen heteroatom-containing compound and preparation and application thereof Download PDFInfo
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- CN102531929B CN102531929B CN201110419507.7A CN201110419507A CN102531929B CN 102531929 B CN102531929 B CN 102531929B CN 201110419507 A CN201110419507 A CN 201110419507A CN 102531929 B CN102531929 B CN 102531929B
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- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title 1
- -1 aluminum compound Chemical class 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- 150000002576 ketones Chemical class 0.000 claims description 5
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000001953 recrystallisation Methods 0.000 claims description 3
- OQOGEOLRYAOSKO-UHFFFAOYSA-N 1,1-dichloro-1-nitroethane Chemical compound CC(Cl)(Cl)[N+]([O-])=O OQOGEOLRYAOSKO-UHFFFAOYSA-N 0.000 claims description 2
- QQLIGMASAVJVON-UHFFFAOYSA-N 1-naphthalen-1-ylethanone Chemical compound C1=CC=C2C(C(=O)C)=CC=CC2=C1 QQLIGMASAVJVON-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 2
- IHLVCKWPAMTVTG-UHFFFAOYSA-N lithium;carbanide Chemical group [Li+].[CH3-] IHLVCKWPAMTVTG-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 238000007039 two-step reaction Methods 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 abstract description 7
- 125000001118 alkylidene group Chemical group 0.000 abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 abstract description 5
- 229910052725 zinc Inorganic materials 0.000 abstract description 5
- 239000011701 zinc Substances 0.000 abstract description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 125000004430 oxygen atom Chemical group O* 0.000 abstract 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical group O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 7
- 238000000605 extraction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- DZXAIYQRCQALGE-UHFFFAOYSA-N n,n,2,4-tetramethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1C DZXAIYQRCQALGE-UHFFFAOYSA-N 0.000 description 5
- 150000001414 amino alcohols Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- 229920001610 polycaprolactone Polymers 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 3
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical group CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 235000008397 ginger Nutrition 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GYVGXEWAOAAJEU-UHFFFAOYSA-N n,n,4-trimethylaniline Chemical compound CN(C)C1=CC=C(C)C=C1 GYVGXEWAOAAJEU-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012643 polycondensation polymerization Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
The invention relates to a compound containing nitrogen and oxygen atoms and a preparation method thereofPreparation and application; the general formula of the structure is shown as the following I, wherein R is alkylidene and Me is methyl abbreviation, the compound is used for preparing a zinc and aluminum compound, and the zinc and aluminum compound is used as a catalyst for epsilon-caprolactone ring-opening polymerization.
Description
Technical field
The present invention relates to a kind of nitrogenous, oxygen heteroatom compound and preparation and application, this compound is for the preparation of zinc, aluminum compound, and this type of zinc, aluminum compound are used as the catalyzer of 6-caprolactone ring-opening polymerization.
Background technology
Polyester fat lactone is the important thermoplastic plastic of a class, has important application in medical material.Particularly poly-epsilon-caprolactone and poly-gamma-butyrolactone, can also be doped among many other plastics, and it is carried out to modification (X.Zhang, U.P.Wyss, D.Pichora, M.F.A.Goosen, J.Macromol.Sci.Pure Appl.Chem.A30 (1993) 933; R.G.Sinclair, J.Macromol.Sci.Pure Appl.Chem.A33 (1996) 585; A.Duda, A.Kowalski, S.Penczek, H.Uyama, S.Kobayashi.Macromolecules 35 (2002) 4266).The poly-epsilon-caprolactone (PCL) that 6-caprolactone (ε-CL) ring-opening polymerization obtains is example, and it has high-crystallinity (can reach 69%) and good thermostability, and decomposition temperature is up to 350 ℃.Meanwhile, poly-epsilon-caprolactone is easy to again be decomposed by microorganism or enzyme under field conditions (factors), finally generates carbonic acid gas and water.Its good biodegradable and well biocompatibility, can with the material blend such as starch, make the macromolecular material of fully biodegradable.
Condensation polymerization method and ring-opening polymerization method are the main method of synthetic polylactone.But, the reaction of direct polycondensation method is a balanced reaction, a small amount of water of later stage of polycondensation is difficult to remove completely, often obtain oligopolymer, so less employing (Xie Deliang, ginger mark, Yang Changzheng. alcohol acid causes the research [J] of 6-caprolactone ring-opening polymerization. polymer journal, 2000 (5): 532-537).Ring-opening polymerization method can obtain the polymkeric substance of high molecular, low dispersiveness, so the synthetic research work of current most of polyester all concentrates in application lactone ring opening polymerization method.
In 1979, the people such as Gschwend H W under study for action, at N, N, N ', under the existence of N '-Tetramethyl Ethylene Diamine, 4, N, N-trimethylaniline reacts with n-Butyl Lithium, pulls out the benzene ring hydrogen at amino ortho position, then reacts with benzophenone, finally be hydrolyzed and the separated amino alcohol part that obtains, but the kind of such amino alcohol part is less.And before the present invention, also, not with 2,4, N, N-tetramethyl-aniline is amino alcohol part prepared by starting raw material.
Summary of the invention
The object of the present invention is to provide a kind of nitrogenous, oxygen heteroatom compound and preparation and application.
Described nitrogenous, oxygen heteroatom compound of the present invention, shown in the following I of its general structure:
In general formula I, R is alkylidene group, and in formula, Me is methyl abbreviation;
In described general formula I shown in the following II of the general formula of alkylidene group R:
In general formula I I, R
1and R
2be respectively hydrogen or alkyl or phenyl or substituted-phenyl or naphthyl or fused ring aryl;
Or in described general formula I shown in the following III of general formula of alkylidene group R:
In general formula III, n is 0 or 1 or 2 or 3 or 4.
In order to contribute to more clearly understand the structure of above-claimed cpd, illustrate below, what need emphasize is the compound that the present invention does not limit following these structures, in formula, Ph is phenyl abbreviation:
Synthetic method nitrogenous, oxygen heteroatom compound of the present invention is as follows, by two-step reaction, formed: under (1) nitrogen protection, between-78 ℃ to 80 ℃, in N, N, N ', under N '-Tetramethyl Ethylene Diamine exists, compound V reacts 10 minutes to 8 hours with lithium alkylide or phenyl lithium, obtains compound IV, without separation, is directly used in next step reaction; (2) between-78 ℃ to 80 ℃, in organic solvent, not separated compound IV obtained in the previous step was reacted 20 minutes after 6 hours with aldehydes or ketones, reaction solution is poured in excessive formic acid or acetic acid or hydrochloric acid and is hydrolyzed, and through separation and Extraction, obtained Novel Ligands I.
Reaction formula is as follows:
LiR
3for lithium methide or lithium ethide or n-Butyl Lithium or tert-butyl lithium or phenyl lithium;
TMEDA is N,N,N′,N′ tetramethylethylene diamine;
R is alkylidene group as previously mentioned;
Described organic solvent is normal hexane or tetrahydrofuran (THF) or ether or benzene;
Described compound V and the mol ratio of N,N,N′,N′ tetramethylethylene diamine are 1: 1.5;
Described compound V and the mol ratio of lithium alkylide or phenyl lithium are 1: 1 to 1: 1.5;
Described compound IV and the mol ratio of aldehydes or ketones are 1: 1 to 1: 1.1;
The separation and Extraction of the second step in the synthetic method of described compound of Formula I specifically comprises following two steps: (1) is poured reaction solution in excessive formic acid or acetic acid or hydrochloric acid into and is hydrolyzed, add hydrochloric acid to pH value to be less than 2, add again ether or ethyl acetate or methylene dichloride or trichloromethane, separate water; (2) water hydro-oxidation sodium water solution to pH value is greater than 8, then adds ether or ethyl acetate or methylene dichloride or trichloromethane, separates organic phase, dry, filters, and after desolventizing, with ethyl acetate or normal hexane recrystallization, obtains compound of Formula I.
The purposes of compound of Formula I of the present invention is synthetic a series of zinc, aluminum compound.
Invention effect
For the preparation of series of new amino alcohol part provides synthetic method.
Embodiment
Embodiment 1:
Part HL
1synthetic
Under nitrogen protection, room temperature is to adding N, N, 2,4-tetramethyl-aniline (7.47g, 50.0mmol) and N, N, N ', N '-Tetramethyl Ethylene Diamine (8.81g, in 200mlSchlenk bottle 76.0mmol), splash into the hexane solution (30.4ml, 76.0mmol, 2.84M) of n-Butyl Lithium, have immediately a large amount of Bubble formations, it is muddy and from the colourless light red that becomes that solution becomes; React after 4 hours, add wherein anhydrous diethyl ether (40ml) solution of benzophenone (13.8g, 75.0mmol), reaction is stirred and is spent the night, and solution becomes yellow.Then reaction solution is slowly poured into ether (30ml) solution of acetic acid (12g, 200mmol) under vigorous stirring, then used the hydrochloric acid extraction 4 times of 50ml water and 5%, merge water; Water is adjusted to pH value with 10% sodium hydroxide solution and is greater than 8, and it is muddy that solution becomes, and adds methylene dichloride separatory, separates organic phase, dry, filters, and after desolventizing, with ethyl acetate and normal hexane mixed solvent crystallization, obtains white crystal 6.68g, and yield is 40%.Fusing point: 126-128 ℃.
1H?NMR(600MHz，293K，CDCl
3)：δ(ppm)3.70(s，2H，ArCH
2C)，2.04(s，3H，ArCH
3)，2.74(s，6H，NMe
2)，6.92-7.42(m，13H，ArH)，8.61(s，1H，OH)。ESl-MS?m/z(％)：332.4(100)[M+H]
+。IR(KBr，cm
-1)：3053.5(br，s)，2831.2(s)，1473.1(s)，699.9(m)。
Embodiment 2:
Part HL
2synthetic
Under nitrogen protection, room temperature is to adding N, N, 2,4-tetramethyl-aniline (9.95g, 66.0mmol) and N, N, N ', N '-Tetramethyl Ethylene Diamine (9.68g, in 200mlSchlenk bottle 84.0mmol), splash into the hexane solution (33.6ml, 84.0mmol, 2.5M) of n-Butyl Lithium, have immediately a large amount of Bubble formations, it is muddy and from the colourless light red that becomes that solution becomes; React after 4 hours, splash into wherein the solution of the anhydrous diethyl ether (40ml) of methyl phenyl ketone (10.1g, 84.0mmol), reaction is stirred and is spent the night, and solution becomes yellow.Then reaction solution is slowly poured into ether (30ml) solution of acetic acid (12g, 200mmol) under vigorous stirring, then used the hydrochloric acid extraction 4 times of 50ml water and 5%, merge water; Water is greater than 8 by 10% sodium hydroxide solution key to pH value, and it is muddy that solution becomes, and adds methylene dichloride, separates organic phase, dry, filters, and after desolventizing, by re-crystallizing in ethyl acetate, obtains white crystal 3.72g, and yield is 30%.Fusing point: 84-85 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)3.08(d，
2J
H-H＝14.1Hz，1H，ArCH
2C)，3.22(d，
2J
H-H＝14.1Hz，1H，ArCH
2C)，2.20(s，3H，ArCH
3)，1.46(s，3H，CCH
3)，2.69(s，6H，NMe
2)，6.72-7.51(m，8H，ArH)，7.94(s，1H，OH)。ESI-MS?m/z(％)：270.4(100)[M+H]
+。IR(KBr，cm
-1)：3183.3(br，s)，2966.6(s)，1509.9(s)，705.8(m)。
Embodiment 3:
Part HL
3synthetic
Under nitrogen protection, room temperature is to adding N, N, 2,4-tetramethyl-aniline (14.92g, 100mmol) and N,N,N′,N′ tetramethylethylene diamine (14.53g, 1.2 * 10
2mmol), in 200mlSchlenk bottle, splash into hexane solution (50.0ml, 1.2 * 10 of n-Butyl Lithium
2mmol, 2.5M), there are immediately a large amount of Bubble formations, it is muddy and from the colourless light red that becomes that solution becomes; React after 4 hours, splash into wherein α-acetonaphthone (21.3g, 1.2 * 10
2mmol) solution of anhydrous diethyl ether (40ml), reaction is stirred and is spent the night, and solution becomes yellow.Then reaction solution is slowly poured into ether (30ml) solution of acetic acid (12g, 200mmol) under vigorous stirring, then used the hydrochloric acid extraction 4 times of 50ml water and 5%, merge water; Water is adjusted to pH value with 10% sodium hydroxide solution and is greater than 8, and it is muddy that solution becomes, and adds methylene dichloride, separates organic phase, dry, filters, and after desolventizing, with obtaining white crystal 5.72g with normal hexane recrystallization, yield is 31%.Fusing point: 113-115 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)3.40(d，
2J
H-H＝14.3Hz，1H，ArCH
2C)，3.74(d，
2J
H-H＝14.3Hz，1H，ArCH
2C)，2.13(s，3H，ArCH
3)，1.72(s，3H，CCH
3)，2.72(s，6H，NMe
2)，6.74-7.88(m，10H，ArH)，8.11(s，1H，OH)。ESI-MS?m/z(％)：320.4(100)[M+H]
+。IR(KBr，cm
-1)：3201.2(br，s)，2978.0(s)，1506.0(s)，1115.3(s)，782.2(m)。
Embodiment 4:
Part HL
4synthetic
Under nitrogen protection, room temperature is to adding N, N, 2,4-tetramethyl-aniline (14.92g, 100mmol) and N,N,N′,N′ tetramethylethylene diamine (14.53g, 1.2 * 10
2mmol), in 200mlSchlenk bottle, splash into hexane solution (50.0ml, 1.2 * 10 of n-Butyl Lithium
2mmol, 2.5M), there are immediately a large amount of Bubble formations, it is muddy and from the colourless light red that becomes that solution becomes; React after 4 hours, splash into wherein the solution of the anhydrous diethyl ether (40ml) of pimelinketone (12.3g, 1.2 * 102mmol), reaction is stirred and is spent the night, and solution becomes yellow.Then under vigorous stirring, slowly pour reaction solution into solution that acetic acid (12g, 200mmol) is dissolved in 30ml ether, then use the hydrochloric acid extraction 4 times of 50ml water and 5%, merge water; Water is adjusted to pH value with 10% sodium hydroxide solution and is greater than 8, and it is muddy that solution becomes, and adds methylene dichloride, separates organic phase, dry, filters, and after desolventizing, by re-crystallizing in ethyl acetate, obtains white crystal 3.73g, and yield is 35%.Fusing point: 71-72 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)2.87(q，2H，ArCH
2C)，2.28(s，3H，ArCH
3)，2.66(s，6H，NMe
2)，1.46(m，10H，-(CH
2)
5-)，6.88-7.01(m，3H，ArH)，6.88(s，1H，OH)。ESI-MS?m/z(％)：248.4(100)[M+H]
+。IR(KBr，cm
-1)：3159.2(br，s)，2933.9(s)，1500.4(m)，817.3(m)。
Claims (2)
1. the synthetic method of nitrogenous, an oxygen heteroatom compound, it is characterized in that: by two-step reaction, formed: under (1) nitrogen protection, at room temperature, in N, N, N ', under N '-Tetramethyl Ethylene Diamine exists, compound V reacts 10 minutes to 8 hours with lithium alkylide or phenyl lithium, and the compound IV obtaining is directly used in to next step reaction, wherein compound V and N without separation, N, N ', the mol ratio of N '-Tetramethyl Ethylene Diamine is 1:1.5, the mol ratio of compound V and lithium alkylide or phenyl lithium is 1:1 to 1:1.5;
(2) between-78 ℃ to 80 ℃, in organic solvent, by not separated compound IV obtained in the previous step and reactive ketone 20 minutes after 6 hours; Reaction solution is poured in excessive formic acid, acetic acid or hydrochloric acid and is hydrolyzed, add hydrochloric acid to pH value to be less than 2, then add ether, ethyl acetate, methylene dichloride or trichloromethane, separate water; Water hydro-oxidation sodium water solution to pH value is greater than 8, then adds ether, ethyl acetate, methylene dichloride or trichloromethane, separates organic phase, dry, filters, and after desolventizing, with ethyl acetate or normal hexane recrystallization, obtains formula I part; Wherein the mol ratio of compound IV and ketone is 1:1 to 1:1.1;
Described organic solvent is normal hexane, tetrahydrofuran (THF), ether or benzene;
Described nitrogenous, oxygen heteroatom compound is:
Described ketone is benzophenone, methyl phenyl ketone, α-acetonaphthone or pimelinketone;
Formula IV is:
formula V is:
2. the synthetic method of nitrogenous, oxygen heteroatom compound as claimed in claim 1, is characterized in that: described lithium alkylide is lithium methide or lithium ethide or n-Butyl Lithium or tert-butyl lithium.
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Non-Patent Citations (4)
| Title |
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| Ortho functionalization of aromatic amines: ortho lithiation of N-pivaloylanilines;Walter Fuhrer et al;《J. Org. Chem.》;19791231;第44卷(第7期);1133–1136 * |
| Walter Fuhrer et al.Ortho functionalization of aromatic amines: ortho lithiation of N-pivaloylanilines.《J. Org. Chem.》.1979,第44卷(第7期),1133–1136. |
| 硅桥联有机锂化合物的合成及结构测定.硅桥联有机锂化合物的合成及结构测定.《山西大学学报(自然科学版)》.2010,第33卷(第4期),565-567. |
| 硅桥联有机锂化合物的合成及结构测定;硅桥联有机锂化合物的合成及结构测定;《山西大学学报(自然科学版)》;20101231;第33卷(第4期);565-567 * |
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