CN1164568C - A kind of condensation method of salicylaldehyde and arylamine - Google Patents
A kind of condensation method of salicylaldehyde and arylamine Download PDFInfo
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- CN1164568C CN1164568C CNB011183144A CN01118314A CN1164568C CN 1164568 C CN1164568 C CN 1164568C CN B011183144 A CNB011183144 A CN B011183144A CN 01118314 A CN01118314 A CN 01118314A CN 1164568 C CN1164568 C CN 1164568C
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- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 11
- 150000004982 aromatic amines Chemical class 0.000 title abstract 6
- 238000009833 condensation Methods 0.000 title description 5
- 230000005494 condensation Effects 0.000 title description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 20
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000002304 perfume Substances 0.000 claims description 8
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 6
- ICSNLGPSRYBMBD-UHFFFAOYSA-N 2-aminopyridine Chemical compound NC1=CC=CC=N1 ICSNLGPSRYBMBD-UHFFFAOYSA-N 0.000 claims description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 6
- KSEPMOMKAQKOSM-UHFFFAOYSA-N 1-aminofluoren-9-one Chemical compound C12=CC=CC=C2C(=O)C2=C1C=CC=C2N KSEPMOMKAQKOSM-UHFFFAOYSA-N 0.000 claims description 3
- SOHDPICLICFSOP-UHFFFAOYSA-N 2-bromo-6-methylpyridine Chemical class CC1=CC=CC(Br)=N1 SOHDPICLICFSOP-UHFFFAOYSA-N 0.000 claims description 3
- CKQHAYFOPRIUOM-UHFFFAOYSA-N 3'-Aminoacetophenone Chemical compound CC(=O)C1=CC=CC(N)=C1 CKQHAYFOPRIUOM-UHFFFAOYSA-N 0.000 claims description 3
- NMCBWICNRJLKKM-UHFFFAOYSA-N 3-(benzyloxy)pyridin-2-amine Chemical compound NC1=NC=CC=C1OCC1=CC=CC=C1 NMCBWICNRJLKKM-UHFFFAOYSA-N 0.000 claims description 3
- ABBVSNXAPJUUJO-UHFFFAOYSA-N 3-butyl-1,2-oxazole Chemical compound CCCCC=1C=CON=1 ABBVSNXAPJUUJO-UHFFFAOYSA-N 0.000 claims description 3
- QSNSCYSYFYORTR-UHFFFAOYSA-N 4-chloroaniline Chemical compound NC1=CC=C(Cl)C=C1 QSNSCYSYFYORTR-UHFFFAOYSA-N 0.000 claims description 3
- SJWHILBZPGQBJE-UHFFFAOYSA-N 4-ethylpyridin-2-amine Chemical compound CCC1=CC=NC(N)=C1 SJWHILBZPGQBJE-UHFFFAOYSA-N 0.000 claims description 3
- GRIATXVEXOFBGO-UHFFFAOYSA-N 4-methyl-1,3-benzothiazol-2-amine Chemical compound CC1=CC=CC2=C1N=C(N)S2 GRIATXVEXOFBGO-UHFFFAOYSA-N 0.000 claims description 3
- ORLGLBZRQYOWNA-UHFFFAOYSA-N 4-methylpyridin-2-amine Chemical compound CC1=CC=NC(N)=C1 ORLGLBZRQYOWNA-UHFFFAOYSA-N 0.000 claims description 3
- WGOLHUGPTDEKCF-UHFFFAOYSA-N 5-bromopyridin-2-amine Chemical compound NC1=CC=C(Br)C=N1 WGOLHUGPTDEKCF-UHFFFAOYSA-N 0.000 claims description 3
- FKPXGNGUVSHWQQ-UHFFFAOYSA-N 5-methyl-1,2-oxazol-3-amine Chemical compound CC1=CC(N)=NO1 FKPXGNGUVSHWQQ-UHFFFAOYSA-N 0.000 claims description 3
- CMBSSVKZOPZBKW-UHFFFAOYSA-N 5-methylpyridin-2-amine Chemical compound CC1=CC=C(N)N=C1 CMBSSVKZOPZBKW-UHFFFAOYSA-N 0.000 claims description 3
- JXKAUUVMXZIJNZ-UHFFFAOYSA-N 6-ethylpyridin-2-amine Chemical compound CCC1=CC=CC(N)=N1 JXKAUUVMXZIJNZ-UHFFFAOYSA-N 0.000 claims description 3
- QUXLCYFNVNNRBE-UHFFFAOYSA-N 6-methylpyridin-2-amine Chemical compound CC1=CC=CC(N)=N1 QUXLCYFNVNNRBE-UHFFFAOYSA-N 0.000 claims description 3
- XJGFWWJLMVZSIG-UHFFFAOYSA-N 9-aminoacridine Chemical compound C1=CC=C2C(N)=C(C=CC=C3)C3=NC2=C1 XJGFWWJLMVZSIG-UHFFFAOYSA-N 0.000 claims description 3
- FLCUFRXOCPMLPF-UHFFFAOYSA-N NC1(C(=O)O)CC(C(=O)O)=CC(=C1)C Chemical group NC1(C(=O)O)CC(C(=O)O)=CC(=C1)C FLCUFRXOCPMLPF-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229960001441 aminoacridine Drugs 0.000 claims description 3
- 229950011175 aminopicoline Drugs 0.000 claims description 3
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical compound C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 claims description 3
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-Lutidine Substances CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 2
- VMPITZXILSNTON-UHFFFAOYSA-N o-anisidine Chemical compound COC1=CC=CC=C1N VMPITZXILSNTON-UHFFFAOYSA-N 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- -1 schiff base compound Chemical class 0.000 abstract description 23
- 230000035484 reaction time Effects 0.000 abstract description 4
- 239000002262 Schiff base Substances 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 description 33
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 32
- 239000002585 base Substances 0.000 description 31
- 238000005160 1H NMR spectroscopy Methods 0.000 description 26
- 238000005481 NMR spectroscopy Methods 0.000 description 20
- 238000004458 analytical method Methods 0.000 description 18
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 17
- 239000003513 alkali Substances 0.000 description 9
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 5
- 150000004705 aldimines Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- IDQNBVFPZMCDDN-UHFFFAOYSA-N 2-Amino-4,6-dimethylpyrimidine Chemical compound CC1=CC(C)=NC(N)=N1 IDQNBVFPZMCDDN-UHFFFAOYSA-N 0.000 description 2
- PMZBHPUNQNKBOA-UHFFFAOYSA-N 5-methylbenzene-1,3-dicarboxylic acid Chemical compound CC1=CC(C(O)=O)=CC(C(O)=O)=C1 PMZBHPUNQNKBOA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000005982 diphenylmethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical group CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 1
- ZHBHWSJJEQNEFB-UHFFFAOYSA-N 2-methoxyaniline Chemical group COC1=CC=CC=C1N.COC1=CC=CC=C1N ZHBHWSJJEQNEFB-UHFFFAOYSA-N 0.000 description 1
- BRBUBVKGJRPRRD-UHFFFAOYSA-N 4,6-dimethylpyridin-2-amine Chemical compound CC1=CC(C)=NC(N)=C1 BRBUBVKGJRPRRD-UHFFFAOYSA-N 0.000 description 1
- 241001657948 Midea Species 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FHHZOYXKOICLGH-UHFFFAOYSA-N dichloromethane;ethanol Chemical compound CCO.ClCCl FHHZOYXKOICLGH-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000009897 systematic effect Effects 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Pyridine Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The present invention discloses a process for condensing salicyladehyde and aryl amine, which is carried out according to the following steps: adding the salicylaldehyde and the aryl amine to a reaction vessel; putting the salicylaldehyde and the aryl amine in a microwave device of 600 to 800 W; cooling the salicylaldehyde and the aryl amine after reacting for 2 seconds to 6 minutes; crystallizing the salicylaldehyde and the aryl amine. In the present invention, a method in which a microwave is used to promote chemical reaction is adopted to ensure that the reaction of condensing and synthesizing aldehydeamine into schiff bases can efficiently occur under the condition of no solvent, short reaction time and high yield; therefore, the present invention has the advantage of little environmental pollution, and is suitable for producing a schiff base compound and derivants thereof in small amount, multiple kinds and no nuisance.
Description
The present invention relates to the synthetic method of a series of salicylic alidehyde imine compounds, particularly a kind of method of producing the salicylic alidehyde imine compound by salicylic aldehyde and aromatic perfume amine condensation.
The organic chemistry develop rapidly benefits from the foundation (1874 of carbon tetravalence theory, Holland chemist Jacobus Hendricus van ' t Hoff), and the aldimine condensation reaction western Buddhist alkali of formation (Schiff-base) launches (Ann.Chem.1869 before the theoretical proposition of carbon tetravalence, 150 volumes, 193 pages), be the earliest one of Chemical Problem in the organic chemistry research, thereby with investigator's naming.Although to aldimine condensation reaction having carried out systematic research, yet because the critical role of carbon-to-nitrogen double bon in the heteroato mic organic compound, still be widely used in the synthesizing of medicine, agricultural chemicals and organic chemical industry's product.Thermal chemical reaction is generally adopted in this class reaction, needs solvent to make medium, and environment is being produced certain pollution; Simultaneously, react length often consuming time (several hours to a couple of days), the productive rate height does not wait.In order to improve reaction efficiency and to make full use of the natural resources, realize the synthetic of some unknown compounds, enrich western Buddhist alkali cpd family, enlarge using value and the Application Areas of western Buddhist alkali in people's daily life and industrial and agricultural production, need to inquire into new western Buddhist alkali synthetic method.
The objective of the invention is to overcome in the thermal response of the synthetic western Buddhist alkali of traditional aldimine condensation, need solvent, reaction times is longer, aftertreatment is trouble, the productive rate instability has the shortcoming of pollution to environment, and a kind of method that adopts microwave to promote chemical reaction is provided, make that being reflected at of the synthetic western Buddhist alkali of aldimine condensation is solvent-free, the reaction times short and high yield under efficiently carry out, environmental pollution is little.Be applicable to short run, many kinds, nuisanceless western Buddhist alkali cpd and the derivative thereof produced.
Microwave of the present invention promotes the reaction expression of the synthetic western Buddhist alkali of aldehyde ketone condensation reaction to be:
Western Buddhist alkali general structure of the present invention is:
Ar is respectively: 5-methyl isophthalic acid H-pyrazole-3-yl, 2-anisole-1-base, pyridine-2-base, 6-picoline-2-base; 2,6-dimethyl benzene-1-base, 2; 3-dimethyl benzene-1-base, 4,6-lutidine-2-base; 5-methyl-isoxazole-3-base, 5-picoline-2-base, 4-picoline-2-base; 3-benzyloxy pyridine-2-base, 3-chloro-5-5-flumethiazine-2-base, 5-Shu butyl isoxazole-3-base; 6-ethylpyridine-2-base, 4,6-dimethyl pyrimidine-2-base; 3,5-two bromo-6-picoline-2-bases, 4-ethylpyridine-2-base; 3-acetylbenzene-1-base, different quinone quinoline-1-base, 3; 5-dibromo pyridine-2-base, 5-bromopyridine-2-base, 5-ethylmercapto group-1; 3,4-thiadiazoles-2-base, 4-chloro-2-Benzoylbenzene-1-base; 9-Fluorenone-1-base, different quinone quinoline-5-base, diphenyl-methyl; 5-ethyl-1,3,4-thiadiazoles-2-base; acridine-9-base, 2-hydroxybenzene-1-base, 2; 6-diisopropyl benzene-1-base, 4-methylbenzothiazole-2-base, 2-carboxyl benzene-1-base.
Microwave of the present invention promotes the novel method of salicylic aldehyde and aromatic perfume amine condensation, and raw material comprises salicylic aldehyde,
3-amino-5-methyl isophthalic acid H-pyrazoles, 2-anisidine, 2-aminopyridine, 2-amino-6-picoline; 2,6-xylidine, 2; the 3-xylidine, 2-amino-4,6-lutidine; 3-amino-5-methyl-isoxazole, 2-amino-5-picoline, 2-amino-4-picoline; 2-amino-3-benzyloxy pyridine, 2-amino-3-chloro-5-5-flumethiazine, 3-amino-5-Shu butyl isoxazole; 2-amino-6-ethylpyridine, 2-amino-4,6-dimethyl pyrimidine; 2-amino-3,5-two bromo-6-picolines, 2-amino-4-ethylpyridine; the 3-aminoacetophenone, the amino different quinone quinoline of 1-, 2-amino-3; the 5-dibromo pyridine, 2-amino-5-bromopyridine, 2-amino-5-ethylmercapto group-1; 3,4-thiadiazoles, 2-amino-5-chlorobenzene formacyl benzene; 1-amino-9-Fluorenone, the amino different quinone quinoline of 5-, benzhydrylamine; 2-amino-5-ethyl-1,3, the 4-thiadiazoles; 9-amino-acridine, 2-amino phenol, 2; the 6-diisopropyl aniline, 2-amino-4-methylbenzothiazole, 2-benzaminic acid.
The method of condensing of a kind of salicylic aldehyde of the present invention and aromatic perfume amine, carry out according to the following steps:
Salicylic aldehyde and aromatic perfume amine are added reaction vessel, be placed in 600-800 watt the microwave device, react 2 seconds to 6 minutes postcooling, products obtained therefrom employing ordinary method is as with ethanol or ethanol-methylene dichloride recrystallization.Productive rate 65%～98%, known compound structure warp
1H NMR confirms, the unknown compound structure is through IR,
1H NMR,
13C NMR and ultimate analysis data confirm.
Product preparation method of the present invention is simple, and purifying is easy, the productive rate height, and compound stability is better, and production cost is lower, is convenient to produce in enormous quantities.
Below in conjunction with embodiment the present invention is done further detailed description.
Embodiment 1:
2-[[(5-methyl isophthalic acid H-pyrazole-3-yl) imido grpup] methyl]-preparation of phenol: adding waits the salicylic aldehyde and the 3-amino-5-methyl isophthalic acid H-pyrazoles of amount of substance (3mmol) in the 25ml Erlenmeyer flask, put into " beautiful " (Midea PJ21B-A, the 800W type, 21 liters of volumes) in the microwave oven, " middle high fire " (616W) 30 seconds of shelves reaction, get solid after the cooling, use ethyl alcohol recrystallization, productive rate 96%.FT-IR(KBr)：3430.6，3204.7，1614.4，1576.6，1499.3，1470.2。
1H?NMR(CDCl
3，200MHz，TMS)δ：2.33(s，3H)，6.12(s，1H)，6.91-7.39(m，4H)，8.82(s，1H)，11.90(s，1H)，13.00(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：11.3，95.2，117.0，118.6，118.9，132.2，133.0，141.7，156.4，160.8，162.5ppm。Ultimate analysis measured value (in the bracket is calculated value, down together), C:66.65% (65.66%), H:5.49% (5.51%), N:20.86% (20.88%).
Experimental technique is identical with embodiment 1 among the embodiment 2 to embodiment 30, and institute's column data is in proper order: reaction raw materials, and the reaction times, productive rate, fusing point, the FT-IR data,
1H NMR data,
13C NMR data, the ultimate analysis data.Known compound is only listed
1H NMR data.
Embodiment 2
2-[[(2-anisole-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and adjacent aminoanisole (2-anisidine) reaction, 3 minutes, 98%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 3.89 (s, 3H), 6.91-7.40 (m, 8H), 8.70 (s, 1H), 13.89 (s, 1H) ppm.
Embodiment 3
2-[(pyridine-2-imido grpup) methyl]-preparation of phenol: salicylic aldehyde and 2-aminopyridine, 2 minutes, 93%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 6.96-7.87 (m, 7H), 8.50 (d, 1H), 9.44 (s, 1H), 13.47 (s, 1H) ppm.
Embodiment 4
2-[[(6-picoline-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-6-picoline, 2 minutes, 95%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.57 (s, 3H), 6.92-7.90 (m, 7H), 9.42 (s, 1H), 13.48 (s, 1H) ppm.
Embodiment 5
2-[[(2,6-dimethyl benzene-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2, the 6-xylidine, 3 minutes, 97%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.30 (s, 3H), 2.33 (s, 3H), 6.92-7.40 (m, 7H), 8.50 (s, 1H), 13.44 (s, 1H) ppm.
Embodiment 6
2-[[(2,3-dimethyl benzene-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 23 dimethyl aniline, 1 minute, 98%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.31 (s, 3H), 2.34 (s, 3H), 6.94-7.42 (m, 7H), 8.53 (s, 1H), 13.43 (s, 1H) ppm.
Embodiment 7
2-[[(4,6-lutidine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-4, the 6-lutidine, 4 minutes, 98%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.34 (s, 3H), 2.53 (s, 3H), 6.91-7.51 (m, 7H), 9.41 (s, 1H), 13.61 (s, 1H) ppm.
Embodiment 8
2-[[(5-methyl-isoxazole-3-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 3-amino-5-methyl-isoxazole, 4 minutes, 98%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.46 (s, 3H), 6.12 (s, 1H), 6.96-7.43 (m, 4H), 8.84 (s, 1H), 12.44 (s, 1H) ppm.
Embodiment 9
2-[[(5-picoline-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-5-picoline, 30 seconds, 94%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.36 (s, 3H), 6.94-7.56 (m, 6H), 8.30 (d, 1H), 9.41 (s, 1H), 13.53 (s, 1H) ppm.
Embodiment 10
2-[[(4-picoline-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-4-picoline, 1 minute, 95%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.40 (s, 3H), 6.94-7.50 (m, 6H), 8.36 (d, 1H), 9.43 (s, 1H), 13.51 (s, 1H) ppm.
Embodiment 11
2-[[(3-benzyloxy pyridine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-3-benzyloxy pyridine, 4 minutes, 88%, 106-107 ℃, FT-IR (KBr): 3436.8,1605.3,1580.3,1555.6,1453.9,1021.8;
1H NMR (CDCl
3, 200MHz, TMS) δ: 5.21 (s, 2H), 6.79-7.48 (m, 11H), 8.10 (d, 1H), 9.44 (s, 1H), 14.17 (s, 1H) ppm;
13C NMR (CDCl
3, 300MHz, TMS) δ: 70.3,117.4,118.3,118.7,119.1,121.1,126.7,127.9,128.5,133.0,133.6,135.9,139.9,147.4,148.5,162.4,162.9ppm.Ultimate analysis data: C:74.97% (74.98%), H:5.33% (5.30%), N:9.17% (9.20%).
Embodiment 12
2-[[(3-chloro-5-(trifluoromethyl) pyridine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-3-chloro-5-5-flumethiazine, 4 minutes, 76%, 146.5-148 ℃, FT-IR (KBr): 3447.9,1614.7,1599.1,1559.8,1451.9.
1H NMR (CDCl
3, 200MHz, TMS) δ: 6.99-7.58 (m, 4H), 8.05 (s, 1H), 8.64 (s, 1H), 9.51 (s, 1H), 13.31 (s, 1H) ppm;
13C NMR (CDCl
3, 300MHz, TMS) δ: 117.6,118.6,119.5,120.8,124.4,127.5,134.1,135.3,135.9,143.7,156.5,162.5,167.3ppm; Ultimate analysis data: C:51.91% (51.93%), H:2.65% (2.68%), N:9.28% (9.32%).
Embodiment 13
2-[[(5-Shu butyl isoxazole-3-base) imido grpup] methyl]-preparation of phenol:, salicylic aldehyde and 3-amino-5-Shu butyl isoxazole, 4 minutes, 96%, 69.5-71 ℃, FT-IR (KBr): 3445.4,1620.6,1598.8,1577.1,1457.3;
1H NMR (CDCl
3, 200MHz, TMS) δ: 1.38 (s, 9H), 6.08 (s, 1H), 6.94-7.42 (m, 4H), 8.88 (s, 1H), 12.45 (s, 1H) ppm;
13C NMR (CDCl
3, 300MHz, TMS) δ: 28.6,33.0,93.2,117.4,118.3,119.3,133.2,134.5,61.5,166.9,167.4,182.9ppm.Ultimate analysis data: C:68.80% (68.83%), H:6.61% (6.60%), N:11.47% (11.47%).
Embodiment 14
2-[[(6-ethylpyridine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-6-ethylpyridine, 2 minutes, 87%, 38.5-40 ℃, FT-IR (KBr): 3436.9,1612.8,1554.8,1496.5,1458.8.
1H?NMR(CDCl
3，200MHz，TMS)δ：1.31-1.38(t，3H)，2.79-2.90(q，2H)，6.86-7.71(m，7H)，9.46(s，1H)，13.62(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：13.6，31.1，117.0，117.3，118.9，120.8，133.2，133.4，138.4，156.6，161.7，163.0，164.1，172.2ppm。Ultimate analysis data: C:74.36% (74.31%), H:6.22% (6.24%), N:12.34% (12.38%).
Embodiment 15
2-[[(4,6-dimethyl pyrimidine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-4,6-dimethyl pyrimidine, 4 minutes, 67%, 75-78 ℃, FT-IR (KBr): 3423.6,1627.5,1598.5,1570.0,1466.4.
1H?NMR(CDCl
3，200MHz，TMS)δ：2.29(s，3H)，6.37(s，1H)，6.97-7.58(m，4H)，9.90(s，1H)，11.05(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：23.7，110.5，117.6，119.8，121.1，133.7，136.9，161.6，162.8，167.7，196.5ppm。Ultimate analysis data: C:68.62% (68.70%), H:5.79% (5.77%), N:18.54% (18.49%).
Embodiment 16
2-[[(3,5-two bromo-6-picoline-2-yls) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-3,5-two bromo-6-picolines, 4 minutes, 88%, 149-150.5 ℃, FT-IR (KBr): 3442.8,1607.1,1574.8,1533.7,1448.9;
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.63 (s, 3H), 6.93-7.56 (m, 4H), 8.09 (s, 1H), 9.43 (s, 1H), 13.43 (s, 1H) ppm;
13C NMR (CDCl
3, 300MHz, TMS) δ: 24.3,114.8,117.5,118.7,118.9,119.2,133.7,134.4,144.1,152.5,155.5,162.1,165.2ppm.Ultimate analysis data: C:42.17% (42.20%), H:2.72% (2.72%), N:7.55% (7.57%).
Embodiment 17
2-[[(4-ethylpyridine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-4-ethylpyridine, 2 minutes, 89%, 46-48 ℃, FT-IR (KBr): 3433.1,1601.9,1575.9,1545.9,1455.6.
1H?NMR(CDCl
3，200MHz，TMS)δ：1.25-1.32(t，3H)，2.64-2.72(q，2H)，6.93-7.51(m，6H)，8.37-8.39(d，1H)，9.43(s，1H)，13.52(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：14.1，28.0，117.4，119.0，119.8，121.9，122.3，133.2，133.5，148.5，155.7，157.5，161.7，164.3ppm。Ultimate analysis data: C:74.35% (74.31%), H:6.21% (6.24%), N:12.39% (12.38%).
Embodiment 18
2-[[(3-acetylbenzene-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 3-aminoacetophenone, 3.5 minutes, 97%, 90-92 ℃, FT-IR (KBr):
3436.4，1676.4，1618.0，1572.4，1498.9。
1H?NMR(CDCl
3，200MHz，TMS)δ：2.65(s，3H)，6.90-7.85(m，8H)，8.66(s，1H)，13.01(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：26.6，117.1，118.8，119.1，120.2，126.0，126.5，129.5，132.4，133.4，138.1，148.7，160.9，163.6，197.5ppm。Ultimate analysis data: C:75.31% (75.30%), H:5.42% (5.48%), N:5.83% (5.85%).
Embodiment 19
The different quinone quinoline of 2-[[(-1-yl) imido grpup] methyl]-preparation of phenol: the amino different quinone quinoline of salicylic aldehyde and 1-, 4 minutes, 90%, 117-118.5 ℃, FT-IR (KBr):
3451.9，1614.0，1579.2，1551.4，1494.7。
1H?NMR(CDCl
3，200MHz，TMS)δ：6.87-8.84(m，10H)，9.51(s，1H)，13.64(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：117.1，119.0，119.2，120.3，123.7，124.8，126.3，127.6，130.5，133.6，134.1，137.6?141.3，156.0，161.9，165.8ppm。Ultimate analysis data: C:77.35% (77.40%), H:4.84% (4.87%), N:11.25% (11.27%).
Embodiment 20
2-[[(3,5-dibromo pyridine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-3, the 5-dibromo pyridine, 3 minutes, 92%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 6.96-7.55 (m, 4H), 8.15 (s, 1H), 8.48 (s, 1H), 9.43 (s, 1H), 13.33 (s, 1H) ppm.
Embodiment 21
2-[[(5-bromopyridine-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-5-bromopyridine, 4 minutes, 92%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 6.86-7.95 (m, 6H), 8.45 (s, 1H), 9.38 (s, 1H), 13.20 (s, 1H) ppm.
Embodiment 22
2-[[(5-ethylmercapto group-1,3,4-thiadiazoles-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-5-ethylmercapto group-1,3, the 4-thiadiazoles, 4 minutes, 84%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 1.42-1.58 (t, 3H), 3.44-3.58 (q, 2H), 6.90-7.28 (m, 4H), 8.98 (s, 1H), 11.80 (s, 1H) ppm.
Embodiment 23
2-[[(5-chloro-Benzoylbenzene-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-5-chlorobenzene formacyl benzene, 3 minutes, 89%, 141-143 ℃, FT-IR (KBr): 3439.5,1666.4,1614.1,1579.4,1453.2.
1H?NMR(CDCl
3，200MHz，TMS)δ：6.81-7.82(m，12H)，8.49(s，1H)，11.61(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：117.1，118.6，119.0，120.0，128.2，128.6，128.7，129.8，131.3，132.2，132.5，133.7，135.6，136.4，145.5，160.6，164.0，195.3ppm。Ultimate analysis data: C:71.56% (71.54%), H:4.11% (4.20%), N:4.00% (4.17%).
Embodiment 24
2-[[(9-Fluorenone-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 1-amino-9-Fluorenone, 4 minutes, 77%, 89.5-92 ℃, FT-IR (KBr): 3435.1,1682.2,1620.2,1489.0,1457.5.
1H?NMR(CDCl
3，200MHz，TMS)δ：6.80-7.62(m，11H)，8.78(s，1H)，13.24(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：109.5，117.1，117.6，118.1，118.8，119.6，120.2，123.0，124.1，127.4，129.2，132.5，133.3，133.7，134.2，135.3，136.0，161.5，164.2，186.3ppm。Ultimate analysis data: C:80.17% (80.25%), H:4.35% (4.38%), N:4.85% (4.68%).
Embodiment 25
The different quinone quinoline of 2-[[(-5-yl) imido grpup] methyl]-preparation of phenol: the amino different quinone quinoline of salicylic aldehyde and 5-, 2 minutes, 65%, 88-89 ℃, FT-IR (KBr): 3436.9,1616.0,1577.3,1485.7,1459.56.
1H?NMR(CDCl
3，200MHz，TMS)δ：6.98-8.01(m，8H)，8.57-8.60(d，1H)，8.68(s，1H)，9.27(s，1H)，13.10(s，1H)ppm；
13CNMR(CDCl
3，300MHz，TMS)δ：116.0，117.4，117.9，119.2，119.4，126.2，127.4，129.0，131.0，132.6，133.9，143.7，145.1，152.3，161.2，164.5ppm。Ultimate analysis data: C:77.1 7% (77.40%), H:4.94% (4.94%), N:11.40% (11.28%).
Embodiment 26
2-[(diphenyl-methyl imido grpup) methyl]-preparation of phenol: salicylic aldehyde and benzhydrylamine, 2 seconds, 98%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 5.60 (s, 1H), 6.82-7.40 (m, 14H), 8.42 (s, 1H), 13.45 (s, 1H) ppm.
Embodiment 27
2-[[(5-ethyl-1,3,4-thiadiazoles-2-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino-5-ethyl-1,3, the 4-thiadiazoles, 2 minutes, 71%,
1H NMR (CDCl
3, 200Hz, TMS) δ: 1.41-1.48 (t, 3H), 3.09-3.18 (q, 2H), 6.97-7.49 (m, 4H), 9.09 (s, 1H), 11.93 (s, 1H) ppm.
Embodiment 28
2-[[(acridine-9-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 9-aminoacridine, 4 minutes, 68%, 231-233 ℃, FT-IR (KBr): 3442.7,1622.3,1554.0,1516.6,1462.1.
1HNMR(CDCl
3，200MHz，TMS)δ：7.05-8.26(m，12H)，8.64(s，1H)，12.43(s，1H)ppm；
13C?NMR(CDCl
3，300MHz，TMS)δ：116.4，116.7，117.2，118.4，122.2，124.5，128.3，129.2，131.9，133.4，148.0，150.4，160.0，167.9ppm。Ultimate analysis data: C:80.46% (80.52%), H:4.69% (4.73%), N:9.42% (9.39%).
Embodiment 29
2-[[(2-hydroxybenzene-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2-amino phenol, 4 minutes, 94%,
1H NMR (d
6-DMSO, 200MHz, TMS) δ: 6.88-7.59 (m, 8H), 8.95 (s, 1H), 9.72 (s, 1H), 13.80 (s, 1H) ppm.
Embodiment 30
2-[[(2,6-diisopropyl benzene-1-yl) imido grpup] methyl]-preparation of phenol: salicylic aldehyde and 2, the 6-diisopropyl aniline, 2 minutes, 93%,
1H NMR (CDCl
3, 200MHz, TMS) δ: 1.02-1.38 (d, 12H), 2.82-3.04 (q, 2H), 6.83-7.40 (m, 7H), 8.24 (s, 1H), 13.10 (s, 1H) ppm.
Embodiment 31
2-[[(4-methyl-benzothiazole-2-yl) imido grpup] methyl]-preparation of phenol: adding waits the salicylic aldehyde and the 2-amino-4-methylbenzothiazole of amount of substance (3mmol) in the 25ml Erlenmeyer flask, put into microwave oven, in " high fire " (800W) shelves reaction 6 minutes, get solid after the cooling, use ethyl alcohol recrystallization, productive rate 82%.Fusing point 99.5-102 ℃, FT-IR (KBr): 3440.2,1617.5,1597.9,1566.5,1473.1,752.2;
1H NMR (CDCl
3, 200MHz, TMS) δ: 2.75 (s, 3H), 7.04-7.70 (m, 7H), 9.27 (s, 1H), 12.29 (s, 1H) ppm;
13C NMR (CDCl
3, 300 MHz, TMS) δ: 18.4,117.6,118.3,119.0,119.6,125.1,127.1,133.2,133.9,134.4,135.1,150.8,161.8,167.1,167.7ppm.Ultimate analysis data: C:67.16% (67.14%), H:4.50% (4.51%), N:10.39% (10.44%).
Embodiment 32
2-[[(2-carboxyl benzene-1-yl) imido grpup] methyl]-preparation of phenol: method is with embodiment 31.Salicylic aldehyde and 2-benzaminic acid, 4 minutes, 77%, 199.5-201.5 ℃, FT-IR (KBr): 3439.7,3070.6,1683.3,1620.0,1488.6,1457.5.
1H?NMR(d
6-DMSO，200MHz，TMS)δ：6.41-7.68(m，8H)，8.84(s，1H)，10.25(s，1H)，10.70(s，1H)ppm；
13C?NMR(d
6-DMSO，300MHz，TMS)δ：116.5，119.3，119.7，122.5，129.4，129.5，130.7，131.4，134.0，136.7，151.7，160.8，169.8，191.9ppm。Ultimate analysis data: C:69.62% (69.70%), H:4.67% (4.60%), N:5.80% (5.81%).
Claims (1)
1. the method for condensing of salicylic aldehyde and aromatic perfume amine, carry out according to the following steps:
Salicylic aldehyde and aromatic perfume amine are added reaction vessel, be placed in 600-800 watt the microwave device, react 2 seconds to 6 minutes postcooling, crystallization;
Described aromatic perfume amine is 3-amino-5-methyl isophthalic acid H-pyrazoles; the 2-anisidine; the 2-aminopyridine; 2-amino-6-picoline; 2; the 6-xylidine; 2; the 3-xylidine; 2-amino-4; the 6-lutidine; 3-amino-5-methyl-isoxazole; 2-amino-5-picoline; 2-amino-4-picoline; 2-amino-3-benzyloxy pyridine; 2-amino-3-chloro-5-5-flumethiazine; 3-amino-5-Shu butyl isoxazole; 2-amino-6-ethylpyridine; 2-amino-4; the 6-dimethyl pyrimidine; 2-amino-3; 5-two bromo-6-picolines; 2-amino-4-ethylpyridine; the 3-aminoacetophenone; the amino different quinone quinoline of 1-; 2-amino-3; the 5-dibromo pyridine; 2-amino-5-bromopyridine; 2-amino-5-ethylmercapto group-1; 3; the 4-thiadiazoles; 2-amino-5-chlorobenzene formacyl benzene; 1-amino-9-Fluorenone; the amino different quinone quinoline of 5-; benzhydrylamine; 2-amino-5-ethyl-1; 3; the 4-thiadiazoles; 9-amino-acridine; the 2-amino phenol, 2; the 6-diisopropyl aniline; 2-amino-4-methylbenzothiazole; the 2-benzaminic acid.
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