CN116410108A - Cyclic 1, 3-diketone diimine compound and synthesis method and application thereof - Google Patents
Cyclic 1, 3-diketone diimine compound and synthesis method and application thereof Download PDFInfo
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- CN116410108A CN116410108A CN202111676575.1A CN202111676575A CN116410108A CN 116410108 A CN116410108 A CN 116410108A CN 202111676575 A CN202111676575 A CN 202111676575A CN 116410108 A CN116410108 A CN 116410108A
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- cyclic
- compound
- diketone
- general formula
- organic acid
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- 125000004122 cyclic group Chemical group 0.000 title claims abstract description 52
- 229910000071 diazene Inorganic materials 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000002904 solvent Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 17
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 15
- 150000002367 halogens Chemical class 0.000 claims abstract description 15
- 150000007524 organic acids Chemical class 0.000 claims abstract description 15
- 150000001298 alcohols Chemical class 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000010992 reflux Methods 0.000 claims abstract description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 22
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001448 anilines Chemical class 0.000 claims description 11
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 10
- KVNYFPKFSJIPBJ-UHFFFAOYSA-N 1,2-diethylbenzene Chemical compound CCC1=CC=CC=C1CC KVNYFPKFSJIPBJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 8
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 8
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 8
- UOHMMEJUHBCKEE-UHFFFAOYSA-N prehnitene Chemical compound CC1=CC=C(C)C(C)=C1C UOHMMEJUHBCKEE-UHFFFAOYSA-N 0.000 claims description 8
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 7
- 239000000460 chlorine Substances 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 6
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 claims description 4
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940117389 dichlorobenzene Drugs 0.000 claims description 4
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical compound C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011630 iodine Substances 0.000 claims description 2
- 229910052740 iodine Inorganic materials 0.000 claims description 2
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 2
- 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 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims 1
- 235000019253 formic acid Nutrition 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 18
- 238000003786 synthesis reaction Methods 0.000 abstract description 12
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 125000002490 anilino group Chemical class [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 abstract 2
- 150000003839 salts Chemical class 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 34
- QRDAPCMJAOQZSU-KQQUZDAGSA-N (e)-3-[4-[(e)-3-(3-fluorophenyl)-3-oxoprop-1-enyl]-1-methylpyrrol-2-yl]-n-hydroxyprop-2-enamide Chemical compound C1=C(\C=C\C(=O)NO)N(C)C=C1\C=C\C(=O)C1=CC=CC(F)=C1 QRDAPCMJAOQZSU-KQQUZDAGSA-N 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 17
- 239000000243 solution Substances 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 8
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 238000002844 melting Methods 0.000 description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 7
- 125000001424 substituent group Chemical group 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
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- 239000007787 solid Substances 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- -1 lithium aluminum hydride Chemical compound 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
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- 238000004809 thin layer chromatography Methods 0.000 description 5
- 238000004896 high resolution mass spectrometry Methods 0.000 description 4
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- 239000008346 aqueous phase Substances 0.000 description 3
- HJSLFCCWAKVHIW-UHFFFAOYSA-N cyclohexane-1,3-dione Chemical compound O=C1CCCC(=O)C1 HJSLFCCWAKVHIW-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 2
- KWVPRPSXBZNOHS-UHFFFAOYSA-N 2,4,6-Trimethylaniline Chemical compound CC1=CC(C)=C(N)C(C)=C1 KWVPRPSXBZNOHS-UHFFFAOYSA-N 0.000 description 2
- WKBALTUBRZPIPZ-UHFFFAOYSA-N 2,6-di(propan-2-yl)aniline Chemical compound CC(C)C1=CC=CC(C(C)C)=C1N WKBALTUBRZPIPZ-UHFFFAOYSA-N 0.000 description 2
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 1
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- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/20—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups being part of rings other than six-membered aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
- C07B63/02—Purification; Separation; Stabilisation; Use of additives by treatment giving rise to a chemical modification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C221/00—Preparation of compounds containing amino groups and doubly-bound oxygen atoms bound to the same carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C225/00—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones
- C07C225/20—Compounds containing amino groups and doubly—bound oxygen atoms bound to the same carbon skeleton, at least one of the doubly—bound oxygen atoms not being part of a —CHO group, e.g. amino ketones having amino groups bound to carbon atoms of rings other than six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
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Abstract
The invention relates to a cyclic 1, 3-diketone diimine compound and a synthesis method and application thereof. The cyclic 1, 3-diketiminate compound has a structure shown in the following general formula I, II or III:wherein R is 1 ‑R 8 Each independently selected from H, halogen, C 1 ‑C 10 N=0 or 1 or 2. The synthesis process includes reflux reaction of annular beta-diketone, substituted aniline and organic acid in benzene solvent to obtain enaminone, repeating the steps with substituted aniline and organic acid, and final salt decomposing treatmentThe corresponding cyclic beta-diimine is obtained in a higher separation yield. The cyclic beta-diimine has strong binding capacity to alcohol compounds, can completely remove alcohol molecules at 95 ℃ under vacuum after being combined with the alcohol compounds in a hydrogen bond mode, and can be applied to removing trace alcohol compounds in the compounds.
Description
Technical Field
The invention belongs to the field of organic synthetic chemistry, and particularly relates to a cyclic 1, 3-diketone diimine compound, a synthetic method and application thereof.
Background
Open-chain beta-diketondiimides are a class of ligands widely studied over the last two decades, which, because of their easy variation of the framework, nitrogen substituents, have multifunctional tunability in terms of electronics and space requirements, and are therefore widely used for stabilizing low-valence, low-coordination-number metals, many of which are active catalysts, for example in the fields of catalytic polymerization, organic synthesis and catalysis.
The synthesis of cyclic 1, 3-diketiminate compounds is rarely reported and is limited to some less sterically hindered fatty amines, and the application of the compounds is rarely reported.
In organic chemistry, it is inevitable to use some metal organic reagents such as grignard reagents, organolithium reagents, alkylzinc, alkylaluminum reagents, etc. They are very reactive in chemical nature and are susceptible to reaction with compounds having active hydrogen, such as water, alcohols, etc., which results in their failure, and thus the purity requirements for the reaction solvent are very high. At present, most of commercially available high-purity solvents are prepared by adsorbing small molecular compounds such as water, alcohol and the like through molecular sieves, the water content can reach below 100ppm, but the effects of water removal and alcohol removal are good only after the molecular sieves are baked at a high temperature (at least 350 ℃ for 4 hours), and the method has the defects of more power consumption and higher cost. Secondly, adding active metal reagents such as sodium metal, lithium aluminum hydride and the like for reflux preparation, but the method has high risk coefficient and is easy to cause accidents.
Some alcohol impurities are difficult to avoid in some chemical raw materials, but the impurities can greatly influence the quality of products, such as methyl methacrylate, are important monomers for producing organic glass, water in the organic glass can be removed through metal sodium reflux, but the reactivity of alcohol compounds with the metal sodium is low, so that the alcohol compounds are difficult to remove.
Disclosure of Invention
In order to solve the problems, the invention aims to provide a cyclic 1, 3-diketone diimine compound and a synthesis method thereof, and the cyclic 1, 3-diketone diimine compound containing a large steric hindrance substituent is successfully prepared by using the method. The method is also suitable for synthesizing the cyclic 1, 3-diketone diimine with small steric hindrance, has wide applicable substrate range and simple experimental operation, and can be applied to water and alcohol removal of solvents or chemical raw materials.
In order to achieve the above object, the present invention provides a cyclic 1, 3-diketiminate compound formed by condensing a cyclic 1, 3-diketiminate and a substituted aniline, which has a structure represented by general formula I, II or III:
the cyclic 1, 3-diketone diimine compound shown in the general formula I has tautomerism, and the molecule of the compound has two other tautomers, namely the structures shown in the general formula II and the general formula III, and the compound is shown in the general formula I in the patent. Wherein R is 1 -R 8 Each independently selected from H, halogen, C 1 -C 10 N=0 or 1 or 2.
Among the above compounds, it is preferable that: r is R 1 、R 8 Each independently selected from H, C 1 -C 5 Preferably selected from H or methyl; r is R 2 -R 7 Selected from H, halogen, C 1 -C 10 Preferably selected from H, halogen (preferably including fluorine)Bromine, chlorine, iodine), methyl, isopropyl, ethyl, propyl, n-butyl, t-butyl; n=1.
Among the above compounds, it is preferable that: n=1; r is R 1 =R 8 =h; when R is 3 =R 6 When=h, R 2 、R 4 、R 5 、R 7 Is one of methyl, ethyl, propyl, n-butyl, tertiary butyl, isopropyl and halogen, and is the same or different from each other; when R is 3 =R 6 Is one of methyl, ethyl, propyl, tertiary butyl, isopropyl and halogen, R 2 、R 4 、R 5 、R 7 Is one of methyl, ethyl, propyl, n-butyl, tert-butyl, isopropyl and halogen, and is the same or different from each other.
In the above compounds, preferably, the substituent is specifically R 1 =R 3 =R 6 =R 8 =H;R 2 =R 4 =R 5 =R 7 =iPr;n=1。
In the above compounds, preferably, the substituent is specifically R 1 =R 3 =R 6 =R 8 =H;R 2 =R 4 =R 5 =R 7 =CH 3 ;n=1。
In the above compounds, preferably, the substituent is specifically R 1 =R 8 =H;R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =CH 3 ;n=1。
In the above compounds, preferably, the substituent is specifically R 1 =R 6 =R 8 =H;R 2 =R 3 =R 4 =H;R 5 =R 7 =iPr;n=1。
In the above compounds, preferably, the substituent is specifically R 1 =R 6 =R 8 =H;R 2 =R 3 =R 4 =CH 3 ;R 5 =R 7 =iPr;n=1。
In the above compound, preferably, n=1, r 1 =R 8 =h; when (when)R 3 =R 6 When=h, R 2 =R 4 =R 5 =R 7 Methyl or isopropyl; when R is 3 =R 6 =CH 3 When R is 2 =R 4 =R 5 =R 7 All are methyl groups.
In the above compound, preferably, R 2 -R 7 Selected from H, halogen, C 1 -C 10 Saturated alkyl groups of (2) are preferably selected from H, halogen, C 1 -C 5 More preferably from the group consisting of H, chloro, methyl, isopropyl.
In the above compound, preferably, R 1 、R 8 Each independently selected from H, C 1 -C 5 Preferably from H, methyl.
In some embodiments of the invention, the compound is selected from one or more of the following compounds:
compound 1: in the general formula I, R 1 =R 3 =R 6 =R 8 =H,R 2 =R 4 =R 5 =R 7 =iPr,n=1;
Compound 2: in the general formula I, R 1 =R 3 =R 6 =R 8 =H,R 2 =R 4 =R 5 =R 7 =CH 3 ,n=1;
Compound 3: in the general formula I, R 1 =R 8 =H,R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =CH 3 ,n=1;
Compound 4: in the general formula I, R 1 =R 3 =R 5 =R 6 =R 7 =R 8 =H,R 2 =R 4 =iPr,n=1;
Compound 5: in the general formula I, R 1 =R 6 =R 8 =H,R 2 =R 3 =R 4 =CH 3 ,R 5 =R 7 =iPr,n=1;
Compound 6: in the general formula I, R 1 =R 3 =R 5 =R 6 =R 7 =H,R 2 =R 4 =iPr,R 8 =CH 3 ,n=1;
Compound 7: in the general formula I, R 3 =R 5 =R 6 =R 7 =R 8 =H,R 2 =R 4 =iPr,R 1 =CH 3 ,n=1;
Compound 8: in the general formula I, R 1 =R 3 =R 6 =R 8 =H,R 2 =R 4 =R 5 =R 7 =Cl,n=1;
Compound 9: in the general formula I, R 1 =R 8 =H,R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =CH 3 ,n=1。
There are few reports about cyclic beta-diketone diimines. In 1958, chen De reported the synthesis of 1, 3-cyclohexanedione aminoguanidine and applied it to antibacterial experiments, demonstrating its inhibitory effect against typhoid bacteria, but in very low yields (chemistry report, 1958,25 (05): 349-51). The 1, 3-cyclohexanedione compound and aniline or para-substituted aniline are heated and refluxed in toluene in the presence of p-toluenesulfonic acid, and then treated by alkaline solution to obtain the annular beta-diketone diimine (Bulletin of the Korean Chemical Society,2004,25 (2): 163-4). However, the inventors of the present invention studied to find that: the substituted anilines in the 2,6 or 2,4,6 positions and the cyclic β -diketones have no sign of reaction under the same conditions as those described in the above documents even if the reaction time is prolonged to 240 hours. The inventors of the present invention tried all methods of synthesizing cyclic beta-diketone diimine in the prior literature to synthesize 2, 6-disubstituted, highly sterically hindered cyclic beta-diketone diimine, such as direct method, enaminone activated by iodoethane (Pure and Applied Chemistry,2015,87 (9-10): 979-96), enaminone intermediate activated by boron tetrafluoride (molecular, 2009,14 (6): 2278-85), enaminone activated by boron tetrafluoride ethoxysalt (Angewandte Chemie-International Edition,2017,56 (10): 2632-5), etc., but could not react aniline having substituents at the 2,6 positions with 1, 3-cyclic diketone. One of the efforts to which the present invention relates is then to explore the synthesis of the corresponding cyclic β -diketone diimines with a large steric hindrance with substitution at the 2,6 or 2,4,6 positions and to investigate their use.
Based on the above, the invention also provides a synthesis method of the compound, and the compound with the structure of the general formula I is prepared by two-step reaction of the following equation:
step one, carrying out reflux reaction on cyclic 1, 3-diketone with a structure shown in a general formula IV and substituted aniline with a structure shown in a general formula V in a molar ratio of 1:1 to 1:5 (preferably 1:1 to 1.2) in benzene solvent under the catalysis of organic acid with a molar amount of 0.01 to 5 times (preferably 1 to 2.5 times) of that of the cyclic 1, 3-diketone, and adopting alkaline solution with an equimolar amount of the organic acid to treat the cyclic 1, 3-diketone with the substituted aniline with the structure shown in the general formula V for 1 to 24 hours to obtain enaminone with the structure shown in the general formula VI;
reflux-reacting enaminone with a structure shown in a general formula VI and substituted aniline with a structure shown in a general formula VII in a molar ratio of 1:1 to 1:5 (preferably 1:1-1.2) in a benzene solvent under the catalysis of 0.01-5 times of organic acid (preferably 1-2.5 times of molar amount) for 10-120 hours to obtain a corresponding cyclic 1, 3-diketone diimine organic acid salt, and treating the corresponding cyclic 1, 3-diketone diimine organic acid salt with an alkaline solution with an equimolar amount of the organic acid of 0.1-10M to obtain the cyclic 1, 3-diketone diimine;
according to a specific embodiment of the present invention, preferably, the above synthesis method may be performed according to the following specific steps:
step one as shown in the following equation 1 (the reaction conditions of the present invention are not limited to the specific conditions shown in equation 1), the cyclic 1, 3-diketone with general formula IV and the substituted aniline with general formula V are reflux reacted in benzene solvent under the catalysis of organic acid with the molar ratio of 0.01-5 times of the molar ratio of 1:1 to 1:5 for 1-24 hours to obtain enaminone with general formula VI;
compounds 1a-1j are some representative enaminone compounds having the structure of formula VI, but the enaminone compounds of the present invention are not limited to the following compounds:
step two, as shown in the following equation 2 (only examples, the reaction conditions of the invention are not limited to the specific conditions shown in equation 2), the enaminone with the structure of the general formula VI prepared in the first step and the substituted aniline with the structure of the general formula VII are subjected to reflux reaction in benzene solvent under the catalysis of organic acid with the molar ratio of 0.01-5 times of the molar ratio of 1:1 to 1:5 for 10-120 hours (preferably 30-120 hours) to obtain the corresponding cyclic 1, 3-diketone diimine salt, and the corresponding cyclic 1, 3-diketone diimine is obtained by adopting 1M alkaline solution with the equimolar ratio of the organic acid to treat the cyclic 1, 3-diketone diimine with the general formula I;
it is noted that compounds of formula I may exist in solid or solution as tautomers as shown in the following equation 3, the three tautomeric structures being the same compound:
the compounds 2a-2k are representative compounds having the structure of formula I, but the compounds of formula I to which the present invention relates are not limited to these compounds:
in the above synthesis method, preferably, in the first step, the benzene solvent is one or a combination of two or more of benzene, toluene, xylene, diphenyl ether, trimethylbenzene, tetramethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1, 2-diphenylethane, ethylbenzene and diethylbenzene; the reaction temperature is 100-200 ℃.
In the above synthesis method, preferably, in the step one and the step two, the alkaline solution is one or a combination of more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium tert-butoxide, sodium tert-butoxide, diethylamine, triethylamine and pyridine.
In the above synthesis method, preferably, in the second step, the benzene solvent is mesitylene or a benzene solvent having a boiling point higher than or equal to that of mesitylene.
In the above synthesis method, preferably, the benzene solvent having a boiling point higher than or equal to that of mesitylene includes one or a combination of two or more of tetramethylbenzene, dichlorobenzene, trichlorobenzene or diethylbenzene, and the reaction temperature is 160-230 ℃.
In the above synthetic method, preferably, the organic acid includes one or a combination of two or more of p-toluenesulfonic acid, benzenesulfonic acid, methanesulfonic acid and trifluoroacetic acid.
The invention also provides a method for removing water and alcohol compounds in the compound, which is performed by the cyclic 1, 3-diketone diimine provided by the invention.
When the cyclic 1, 3-diketone diimine is adopted to contact with water and small molecular alcohol compounds, the water and the small molecular alcohol compounds are embedded in the cyclic 1, 3-diketone diimine compound in a ratio of 1:1, and the crystal structure shows that the water and the small molecular alcohol compounds interact with the cyclic beta-diimine of two molecules in a hydrogen bond way; and the alcohol can be completely removed only at 95℃or higher under vacuum, which proves that hydrogen bonds formed between the cyclic 1, 3-diketiminate compound and the alcohol molecule are very strong. The characteristic of the compound is used for removing trace water and alcohol compounds in solvents and chemical raw materials, a certain amount of cyclic 1, 3-diketone diimine is added into the solvents or chemical raw materials containing trace micromolecular alcohol compounds, standing is carried out for more than 1-10 hours, filtration is carried out, the trace alcohol compounds in the solvents or the chemical raw materials can be removed, and the water content or the alcohol content can reach the level lower than 50ppm through a Karl fei water content tester or a gas chromatograph.
Drawings
FIG. 1 is a gas chromatogram of a Hex (n-hexane) solution of 0.1mol/LMeOH not treated with the cyclic 1, 3-diketiminate compound 2f obtained in example 4;
FIG. 2 is a gas chromatogram of a 0.1mol/L MeOH Hex (n-hexane) solution treated with the cyclic 1, 3-diketo diimine compound 2f obtained in example 4;
FIG. 3 shows the combination of the cyclic 1, 3-diketiminate compound 2f obtained in example 4 with one molecule of methanol 1 H-NMR spectrum.
Detailed Description
The technical solution of the present invention will be described in detail below for a clearer understanding of technical features, objects and advantageous effects of the present invention, but should not be construed as limiting the scope of the present invention.
The analytical characterization instrument used in the present invention is as follows:
NMR spectra were measured on Bruker Mercury 400MHz Nuclear magnetic resonance apparatus at the analytical test center of Beijing university of chemical industry (TMS is an internal standard, deuterated reagents except for the specific description were CDCl) 3 99.8atom% D, with0.03% (V/V) TMS), high resolution mass spectrum was measured by using a Beijing university high precision center Agilent G6500 Series Q-TOF mass spectrometer, ultraviolet visible spectrum by using a Hitachi U-3010 type ultraviolet visible spectrophotometer, infrared spectrum by using a Nicolet 8700 type infrared spectrometer, X-ray single crystal diffraction by using a Beijing university Nichikungunya Gemin E single crystal X-ray diffractometer, and melting point by using a Tianjin national Ming medicine RY-1 type melting point meter.
Example 1
This example provides the synthesis of 2g of a cyclic 1, 3-diketiminate compound, comprising the steps of:
step 1c Synthesis of Compounds
In a 250ml single flask were placed 11.21g (100 mmol) of 1, 3-cyclohexanedione, 1.90g (10.0 mmol) of p-toluenesulfonic acid monohydrate, 19.50g (110 mmol) of 2, 6-diisopropylaniline, 100ml of toluene and heated under reflux for 10h. Subsequent monitoring by thin layer chromatography (TLC, silica gel as stationary phase, methylene chloride: methanol=20:1 as developing solvent ratio) showed complete disappearance of 1, 3-cyclohexanedione starting material points and a new point was generated. The volatile substances such as toluene were removed by rotary evaporator, and the residue was taken up in methylene chloride until complete dissolution. 1M aqueous sodium hydroxide solution in an equimolar amount to the p-toluenesulfonic acid was then added and shaken well until the aqueous phase was weakly basic. The organic phase was collected, the aqueous phase was extracted three times with dichloromethane, and the organic phases were combined and dried over anhydrous sodium sulfate. After filtration, the organic solvent was removed in vacuo, and the residue was taken up in toluene and heated to dissolve, and recrystallized at-20 ℃ after returning to room temperature. The first recrystallization gave 20.63g of white needle-like crystals, and the second recrystallization gave 2.02g of white needle-like crystals after concentrating the mother liquor, which gave 1c in total: 22.65g. Theoretical yield: 27.14g, yield: 83%. Melting point: 210-213 ℃.
1 H NMR(400MHz)δ7.32–7.23(t, 3 J H-H =7.6Hz,1H,Ar-H),7.14(d, 3 J H-H =7.7Hz,2H,Ar-H),6.11(s,1H,NH),4.69(s,1H,=CH),3.09–2.86(m,2H,CH(CH 3 ) 2 ),2.56(t, 3 J H-H =6.2Hz,2H,CH 2 ),2.28(t, 3 J H-H =6.5Hz,2H,CH 2 ),2.06–1.97(m,2H,CH 2 ),1.14(m,12H,CH(CH 3 ) 2 );
13 C NMR(101MHz)δ197.38,165.12,146.53,131.93,128.70,123.87,99.12,36.43,29.19,28.44,24.51,23.22;
HR-MS m/z(%):calculated 272.2009,found 272.2056[M+H] + ;IR(KBr,cm -1 ):3433.1,3192.3,2962.8,1598.1,1535.8,1467.1,860.0,806.6,774.9.UV-Vis(CH 2 Cl 2 )λ max 281nm(ε=21740)。
Step two Synthesis of 2g of Compound
1.36g (5.0 mmol) of compound 1c,0.95g (5.0 mmol) of p-toluenesulfonic acid monohydrate, 0.68g (5.0 mmol) of 2,4, 6-trimethylaniline, 20ml of mesitylene and heated under reflux for 52 hours were put into a 100ml single flask. The starting material was found to have disappeared by thin layer chromatography TLC analysis and a new spot was generated. The solvent was removed by rotary evaporation and the residue was taken up in dichloromethane until complete dissolution (about 20 ml). 1M aqueous sodium hydroxide solution in an equimolar amount to the p-toluenesulfonic acid was then added and shaken well until the aqueous phase was weakly basic. The organic phase was separated, collected, extracted three times with 10ml of dichloromethane and the organic phases were combined and dried over anhydrous sodium sulfate. After filtration, the organic solvent was removed in vacuo, the residue was taken up in 5ml of methanol and allowed to stand, a white solid precipitated, filtered and washed with a small amount of methanol to give 1.21g of a colourless solid, theoretical yield: 1.94g, yield 62%. Blackening at 190 ℃, melting point: 208-211 ℃.
1 H NMR(400MHz)δ6.69–7.05(m,6H,Ar-H),5.07(s,1H,=CH),4.26(s,1H,NH),2.85(s,2H,CH(CH 3 ) 2 ),2.58(s,1H,CH 2 ),2.41(s,1H,CH 2 ),2.23-2.36(m,4H,CH 2 ),1.95(s,3H,CH 3 ),1.82(s,6H,CH 3 ),1.05-1.26(m,10H,CH(CH 3 ) 2 ),0.89(s,2H,CH(CH 3 ) 2 );
HR-MS m/z(%):calculated 389.3020,found 389.2951(M + +H);IR(KBr,cm -1 ):3442.37,2960.245,2865.749,1573.658,1598.725,1376948,1257.381,777.185.UV-Vis(CH 2 Cl 2 )λ max 295nm(ε=19780)。
Example 2
The present example provides the synthesis of a cyclic 1, 3-diketiminate compound 2f, comprising the steps of:
to a 100ml single port flask, 2.72g (10.0 mmol) of the product 1c of step one of example 1, 1.90g (10.0 mmol) of p-toluenesulfonic acid monohydrate, 1.95g (11.0 mmol) of 2, 6-diisopropylaniline, 20ml of mesitylene and heating reflux reaction were put in.
Reaction monitoring and workup procedure reference example 1 to give 4.30g of colorless 2f compound in yield: 61%. Melting point: 174-175 ℃.
1 H NMR(400MHz)δ7.27–6.82(m,6H,Ar-H),5.10(s,1H,=CH),4.32(s,1H,NH),3.17(s,1H,CH(CH 3 ) 2 ),2.84(s,3H,CH(CH 3 ) 2 ),2.58(s,3H,CH 2 ),2.05(s,2H,CH 2 ),1.86(s,1H,CH 2 ),1.09-1.17(m,20H,CH(CH 3 ) 2 ),0.89(s,4H,CH(CH 3 ) 2 );
HR-MS m/z(%):calculated 431.3421,found 431.3465(M++H);IR(KBr,cm -1 ):3422.2,3233.8,3059.8,2959.1,2865.2,1602.3,1575.0,1524.7,1467.2,1435.5,1362.7,1264.4,1197.4.UV-Vis(CH2Cl2)λ max 290nm(ε=19680)。
Example 3
The present example provides the synthesis of cyclic 1, 3-diketiminate compound 2e, comprising the steps of:
step one Synthesis of Compound 1b
In a 250ml single vial were added 11.21g (100 mmol) 1, 3-cyclohexanedione, 1.90g (10.0 mmol) p-toluenesulfonic acid monohydrate, 13.52g (110 mmol) 2,4, 6-trimethylaniline, 100ml toluene, heated under reflux for 10h, followed by TLC monitoring and working up to compound 1c. The first recrystallization gave 17.11g of orange bulk crystals, and the second recrystallization after concentrating the mother liquor gave 1.73g of orange bulk crystals, which in total gave 1b:18.84g. Theoretical yield: 22.93g, yield: 82%. Melting point: 250-252 ℃.
1 H NMR(400MHz)δ6.87(s,2H,Ar-H),5.84(s,1H,NH),4.69(s,1H,=CH),2.52(t, 3 J H-H =5.6Hz,2H,CH 2 ),2.31(t, 3 J H-H =6.5Hz,2H,CH 2 ),2.26(s,3H,p-ArCH 3 ),2.12(s,6H,o-ArCH 3 ),2.03(m,2H,CH 2 );
13 C NMR(101MHz)δ197.69,163.58,137.56,135.66,131.92,129.18,98.42,36.42,29.19,22.13,20.92,17.81;
ESI-MS m/z(%):calculated 229.32,found 230.01[M+H] + ;IR(KBr,cm -1 ):3435.6,3236.2,2943.8,2918.3,1758.8,1567.6,1521.4,1431.0,1361.6,852.7,826.1,769.6.UV-Vis(CH 2 Cl 2 )λ max 281nm(ε=23320)。
Synthesis of step 2e
The reaction was carried out as in example 2, with only the starting material 1c being replaced by 1b. Analytical data for 2 e: yield: 67%. Melting point: 199-202 ℃.
1 H NMR(400MHz)δ6.79(s,4H,Ar-H),5.30(s,1H,=CH),4.80(s,1H,NH),2.50–2.24(m,4H,CH 2 ),2.22(s,6H,p-ArCH 3 ),2.02(s,12H,o-ArCH 3 ),1.88(hept, 3 J H-H =6.5Hz,2H,CH 2 ). 13 C NMR(101MHz)δ161.52,142.32,137.57,134.01,128.54,123.67,98.51,29.69,27.70,22.11,20.78,17.93;
HR-MS m/z(%):calculated 347.2482,found 347.2492(M + +H);IR(KBr,cm -1 ):3435.6,3166.7,2935.4,2862.6,1697.7,1611.0,1574.0,1531.9,1480.5,1418.2,1259.1,1211.3.UV-Vis(CH 2 Cl 2 )λ max 290nm(ε=26180)。
Example 4
The embodiment provides an application of a cyclic 1, 3-diketone diimine compound 2f for removing methanol in n-hexane, which specifically comprises the following steps:
MeOH (0.01 mol,0.32g,0.404 ml) was taken in a 100ml volumetric flask, then fixed to 100ml with n-hexane, shaken well with shaking to prepare a 0.1mol/LMeOH n-hexane (Hex) solution, and the methanol content in the 0.1mol/LMeOH n-hexane (Hex) solution was determined by gas chromatography, see FIG. 1.
10ml of a 0.1mol/LMeOH/Hex solution was taken in a 50ml round bottom flask, added (1.0 mmol,0.43 g) of compound 2f, shaken and allowed to stand for 2h, the solvent was separated from compound 2f by distillation, and then the change in methanol content was determined by gas chromatography (chromatographic column was a capillary column, detector was a hydrogen flame detector, set at a detection chamber temperature of 99℃and vaporization chamber temperature of 99℃and column chamber temperature of 79 ℃). The gas chromatography result shows that the methanol in the n-hexane is removed, and the filtered compound 2f is subjected to nuclear magnetic resonance hydrogen spectrum analysis after being vacuumized under normal pressure, wherein a characteristic peak of the methanol exists at the position of a chemical shift of 3.49ppm, so that the methanol is proved to be combined with the compound 2f, and the nuclear magnetic resonance hydrogen spectrum is shown in figure 3.
Example 5
MeOH (0.01 mol,0.32g,0.404 ml) was taken in a 100ml volumetric flask, then toluene (Tol) was used to volume 100ml, and shaken well with shaking to prepare a toluene solution of 0.1mol/L MeOH. 10ml of a 0.1mol/L MeOH/Tol solution was taken in a 50ml round bottom bottle, added (1.0 mmol,0.43 g) of compound 2f, shaken and allowed to stand for 2 hours, the solvent was separated from compound 2f by distillation, and then the change in methanol content was determined by gas chromatography (the column was a capillary column, the detector was a hydrogen flame detector, the detection chamber temperature was set at 140 ℃, the vaporization chamber temperature was set at 140 ℃, and the column chamber temperature was 120 ℃). The results of the gas chromatography showed that methanol had been removed from toluene and that compound 2f was combined with one molecule of methanol by nuclear magnetic resonance hydrogen spectroscopy.
Example 6
(0.01 mol,0.46 g) EtOH was taken in a 100ml volumetric flask, then fixed to 100ml with n-hexane, shaken well with shaking to prepare a 0.1mol/L EtOH in n-hexane (Hex). 10ml of a 0.1mol/L EtOH/Hex solution are taken in a 50ml round bottom bottle, and (1.0 mmol,0.43 g) of compound 2f is added, after shaking, and allowed to stand for 2h, after workup and detection method reference example 4. The gas chromatography result shows that the ethanol in the n-hexane is removed, and simultaneously, after the filtered compound 2f solid is vacuumized at normal pressure, nuclear magnetic resonance hydrogen spectrum analysis is performed, so that one molecule of ethanol exists.
Example 7
Take (0.01 mol,0.60 g) nPrOH in a 100ml volumetric flask, then fix volume to 100ml with n-hexane, shake well with shaking to prepare 0.1mol/L nPrOH in n-hexane (Hex). 10ml of a 0.1mol/L nPrOH/Hex solution are taken in a 50ml round-bottomed flask, and (1.0 mmol,0.43 g) of compound 2f are added, after shaking, left for 2h, the aftertreatment and detection process being described in example 4. The gas chromatography result shows that n-propanol in n-hexane is removed, and simultaneously, after the filtered compound 2f solid is vacuumized at normal pressure, nuclear magnetic resonance spectroscopy analysis is performed, so that one molecule of n-propanol exists.
Example 8
A solution of (0.01 mol,0.60 g) iPrOH in n-hexane (Hex) was prepared in a 100ml volumetric flask, then fixed to 100ml with n-hexane, and shaken well with shaking to give a 0.1mol/L iPrOH solution in n-hexane (Hex). 10ml of a 0.1mol/LiPrOH/Hex solution are taken in a 50ml round-bottomed flask, and (1.0 mmol,0.43 g) of compound 2f is added, after shaking and allowed to stand for 2h, the aftertreatment and detection method being described in example 4. The gas chromatography result shows that isopropanol in n-hexane is removed, and simultaneously, after the filtered compound 2f solid is vacuumized at normal pressure, nuclear magnetic resonance spectroscopy analysis is performed, which shows that one molecule of isopropanol exists.
Claims (15)
2. A compound according to claim 1, wherein,
R 1 、R 8 each independently selected from H, C 1 -C 5 Preferably selected from H or methyl;
R 2 -R 7 selected from H, halogen, C 1 -C 10 Preferably selected from H, halogen (preferably including fluorine, chlorine, bromine, iodine), methyl, isopropyl, ethyl, propyl, n-butyl, t-butyl;
n=1。
3. a compound according to claim 1, wherein,
n=1;
R 1 =R 8 =H;
when R is 3 =R 6 When=h, R 2 、R 4 、R 5 、R 7 Is one of methyl, ethyl, propyl, n-butyl, tertiary butyl, isopropyl and halogen, and is the same or different from each other; when R is 3 =R 6 When the compound is one of methyl, ethyl, propyl, tertiary butyl, isopropyl and halogen, R 2 、R 4 、R 5 、R 7 Is one of methyl, ethyl, propyl, n-butyl, tert-butyl, isopropyl and halogen, and is the same or different from each other.
4. A compound according to any one of claims 1 to 3, wherein R 1 =R 3 =R 6 =R 8 =H;R 2 =R 4 =R 5 =R 7 =iPr;n=1。
5. A compound according to any one of claims 1 to 3, wherein R 1 =R 3 =R 6 =R 8 =H;R 2 =R 4 =R 5 =R 7 =CH 3 ;n=1。
6. A compound according to any one of claims 1 to 3, wherein R 1 =R 8 =H;R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =CH 3 ;n=1。
7. A compound according to claim 1, wherein R 1 =R 6 =R 8 =H;R 2 =R 3 =R 4 =H;R 5 =R 7 =iPr;n=1。
8. A compound according to claim 1, wherein R 1 =R 6 =R 8 =H;R 2 =R 3 =R 4 =CH 3 ;R 5 =R 7 =iPr;n=1。
9. A compound according to claim 1, wherein n = 1, r 1 =R 8 =H;
When R is 3 =R 6 When=h, R 2 =R 4 =R 5 =R 7 Methyl or isopropyl; when R is 3 =R 6 =CH 3 When R is 2 =R 4 =R 5 =R 7 All are methyl groups.
10. The method for synthesizing a cyclic 1, 3-diketiminate compound according to any one of claims 1 to 9, characterized in that the method comprises the steps of:
step one, carrying out reflux reaction on cyclic 1, 3-diketone with a structure shown in a general formula IV and substituted aniline with a structure shown in a general formula V in a molar ratio of 1:1 to 1:5 (preferably 1:1 to 1.2) in benzene solvent under the catalysis of organic acid with a molar amount of 0.01 to 5 times (preferably 1 to 2.5 times) of that of the cyclic 1, 3-diketone, and adopting alkaline solution with an equimolar amount of the organic acid to treat the cyclic 1, 3-diketone with the substituted aniline with the structure shown in the general formula V for 1 to 24 hours to obtain enaminone with the structure shown in the general formula VI;
reflux-reacting enaminone with a structure shown in a general formula VI and substituted aniline with a structure shown in a general formula VII in a molar ratio of 1:1 to 1:5 (preferably 1:1-1.2) in a benzene solvent under the catalysis of 0.01-5 times of organic acid (preferably 1-2.5 times of molar amount) for 10-120 hours to obtain a corresponding cyclic 1, 3-diketone diimine organic acid salt, and treating the corresponding cyclic 1, 3-diketone diimine organic acid salt with an alkaline solution with an equimolar amount of the organic acid of 0.1-10M to obtain the cyclic 1, 3-diketone diimine;
11. the method according to claim 10, wherein in the first step, the benzene solvent is one or a combination of two or more of benzene, toluene, xylene, diphenyl ether, trimethylbenzene, tetramethylbenzene, chlorobenzene, dichlorobenzene, trichlorobenzene, 1, 2-diphenylethane, ethylbenzene, diethylbenzene; the reaction temperature is 100-200 ℃.
12. The method according to claim 10, wherein in the first and second steps, the alkaline solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate, potassium tert-butoxide, sodium tert-butoxide, diethylamine, triethylamine, and pyridine.
13. The method according to claim 10, wherein in the second step, the benzene solvent is mesitylene or a benzene solvent with a boiling point higher than or equal to that of mesitylene, and the reaction temperature is 160-230 ℃;
preferably, the benzene solvent having a boiling point higher than or equal to mesitylene includes one or a combination of two or more of tetramethylbenzene, dichlorobenzene, trichlorobenzene and diethylbenzene.
14. The method of claim 10, wherein the organic acid is one or a combination of two or more of p-toluene sulfonic acid, benzene sulfonic acid, methane sulfonic acid, and trifluoro formic acid.
15. A method for removing water and alcohol compounds from a compound by using the cyclic 1, 3-diketiminate according to any one of claims 1 to 9.
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