CN111995636B - Ortho-hydroxyl-nitrogen silane compound and synthetic method thereof - Google Patents
Ortho-hydroxyl-nitrogen silane compound and synthetic method thereof Download PDFInfo
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- CN111995636B CN111995636B CN202010765831.3A CN202010765831A CN111995636B CN 111995636 B CN111995636 B CN 111995636B CN 202010765831 A CN202010765831 A CN 202010765831A CN 111995636 B CN111995636 B CN 111995636B
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 21
- 229910000077 silane Inorganic materials 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title description 4
- -1 hydroxy, amino, carbonyl Chemical group 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 238000001308 synthesis method Methods 0.000 claims abstract description 12
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 125000001188 haloalkyl group Chemical group 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- NBKDKKAKVXRRGT-UHFFFAOYSA-N Cl.[Ru].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 Chemical compound Cl.[Ru].[C]=O.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1.c1ccc(cc1)P(c1ccccc1)c1ccccc1 NBKDKKAKVXRRGT-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- WFSOQEZHBFMIPW-UHFFFAOYSA-L cycloocta-1,3-diene;ruthenium(2+);dichloride Chemical compound [Cl-].[Cl-].[Ru+2].C1CCC=CC=CC1 WFSOQEZHBFMIPW-UHFFFAOYSA-L 0.000 claims description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- CMTKJYPJPSONIT-UHFFFAOYSA-K trichlororuthenium;triphenylphosphane Chemical compound Cl[Ru](Cl)Cl.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 CMTKJYPJPSONIT-UHFFFAOYSA-K 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 abstract description 3
- 150000002148 esters Chemical class 0.000 abstract description 3
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 150000003961 organosilicon compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- AJMODWIISQEUQE-UHFFFAOYSA-N 2-[(N-triethylsilylanilino)methyl]phenol Chemical compound C1(=CC=CC=C1)N([Si](CC)(CC)CC)CC1=C(C=CC=C1)O AJMODWIISQEUQE-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000004440 column chromatography Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000012327 Ruthenium complex Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- 125000001183 hydrocarbyl group Chemical group 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- QIYHCQVVYSSDTI-UHFFFAOYSA-N 2-(phenyliminomethyl)phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=CC=C1 QIYHCQVVYSSDTI-UHFFFAOYSA-N 0.000 description 1
- VWAMOQWOPYDCQR-UHFFFAOYSA-N 2-[(4-bromophenyl)iminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=C(Br)C=C1 VWAMOQWOPYDCQR-UHFFFAOYSA-N 0.000 description 1
- COFLOZFCNFCJFM-UHFFFAOYSA-N 2-[(4-fluorophenyl)iminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NC1=CC=C(F)C=C1 COFLOZFCNFCJFM-UHFFFAOYSA-N 0.000 description 1
- GHASVSINZRGABV-UHFFFAOYSA-N Fluorouracil Chemical compound FC1=CNC(=O)NC1=O GHASVSINZRGABV-UHFFFAOYSA-N 0.000 description 1
- PDCFKPLHWJBSHJ-UHFFFAOYSA-K O[Ru](O)O.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 Chemical compound O[Ru](O)O.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1 PDCFKPLHWJBSHJ-UHFFFAOYSA-K 0.000 description 1
- 229930182555 Penicillin Natural products 0.000 description 1
- JGSARLDLIJGVTE-MBNYWOFBSA-N Penicillin G Chemical compound N([C@H]1[C@H]2SC([C@@H](N2C1=O)C(O)=O)(C)C)C(=O)CC1=CC=CC=C1 JGSARLDLIJGVTE-MBNYWOFBSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- LKCWBDHBTVXHDL-RMDFUYIESA-N amikacin Chemical compound O([C@@H]1[C@@H](N)C[C@H]([C@@H]([C@H]1O)O[C@@H]1[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O1)O)NC(=O)[C@@H](O)CCN)[C@H]1O[C@H](CN)[C@@H](O)[C@H](O)[C@H]1O LKCWBDHBTVXHDL-RMDFUYIESA-N 0.000 description 1
- 229960004821 amikacin Drugs 0.000 description 1
- XSDQTOBWRPYKKA-UHFFFAOYSA-N amiloride Chemical compound NC(=N)NC(=O)C1=NC(Cl)=C(N)N=C1N XSDQTOBWRPYKKA-UHFFFAOYSA-N 0.000 description 1
- 229960002576 amiloride Drugs 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 150000001924 cycloalkanes Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229960002949 fluorouracil Drugs 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229940049954 penicillin Drugs 0.000 description 1
- 150000002960 penicillins Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011165 process development Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 125000003039 tetrahydroisoquinolinyl group Chemical class C1(NCCC2=CC=CC=C12)* 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B47/00—Formation or introduction of functional groups not provided for in groups C07B39/00 - C07B45/00
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
- C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
- C07F7/0814—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring said ring is substituted at a C ring atom by Si
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/28—Compounds of silicon
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/36—Compounds of titanium
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- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/12—Treatment with organosilicon compounds
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- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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Abstract
The invention discloses an o-hydroxy-nitrogen silane compound and a synthesis method thereof, wherein the o-hydroxy-nitrogen silane compound has the following chemical general formula:
in the formula, Y 1 ‑Y 9 Independently selected from hydrogen atom, halogen atom, C 1‑22 Hydrocarbyl radical, C 1‑22 Haloalkyl, hydroxy, amino, carbonyl, amino, carboxyl, ester, cyano, phenyl, benzyl or nitro; r 1 Is selected from C 1‑22 An alkyl group. The synthesis method comprises the following steps: taking a salicylidene aniline compound shown as a formula II and an alkyl silicon compound shown as a formula III as reaction raw materials, and reacting under a heating condition in the presence of a ruthenium catalyst and a solvent to obtain an o-hydroxy-nitrogen silane compound shown as a formula I, wherein the reaction formula is as follows:
in the formula, R 1 Is selected from C 1‑22 An alkyl group.
Description
Technical Field
The invention relates to the technical field of organic chemistry, in particular to an o-hydroxy-nitrogen silane compound and a synthetic method thereof.
Background
Organosilicon compounds are valuable synthetic intermediates in a variety of organic reactions and have a variety of potential uses in material science. Furthermore, there have been increasing reports in the literature on the use of organosilicon compounds as therapeutically relevant molecules, such as amiloride, phthalic acid, silicon-containing analogues of tetrahydroisoquinoline, silapropyl protein and TMS-alanine in pharmaceutical chemistry (j.am. Chem. Soc. Soc.2009,131, 8350-8351.
Because the organosilicon compounds have potential biological activity and can be used as potential drug molecules in the fields of anti-blood pressure, anti-tumor, anti-depression and the like, people pay attention to the organosilicon compounds widely, and the preparation method of the organosilicon compounds also becomes a research hotspot. In recent years, the synthesis efficiency of the framework compounds can be greatly improved by using noble metal palladium and the like as a catalyst and adopting a carbon-hydrogen bond silicon-based mode, the steps for synthesizing related intermediates are reduced, and the emission of byproducts such as halogenated hydrocarbon and the like is reduced, so that the method is a better synthesis strategy of the organic silicon compounds. However, the use of palladium catalyst in the current synthesis method requires the participation of various reactants (Chemistry-A European journal.2014,30, 9250), while the use of other existing catalytic systems requires multiple steps and cannot protect the nearby hydroxyl (Catalysis Science & technology 2014,11, 3964), thereby restricting the universality of the substrate and increasing the energy consumption of the synthesis process. Therefore, there is a need to search for a method for synthesizing ortho-hydroxy-nitrogen silane compounds with high efficiency and simplicity by using a relatively economical catalyst.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the ortho-hydroxy-nitrogen silane compound, has the characteristic of stable structure, and has application advantages and potential in the fields of novel materials, new drug creation and the like.
The invention also aims to provide a synthesis method of the o-hydroxy-nitrogen silane compound, which has the advantages of simple raw materials, convenient operation, high yield, suitability for industrial production and the like.
The invention discloses an ortho-hydroxyl-nitrogen silane compound, which has the following chemical general formula:
in the formula (I), the compound is shown in the specification,
Y 1 -Y 9 independently selected from a hydrogen atom, a halogen atom, C 1-22 Hydrocarbyl radical, C 1-22 Haloalkyl, hydroxy, amino, carbonyl, amino, carboxyl, ester, cyano, phenyl, benzyl, or nitro;
R 1 is selected from C 1-22 An alkyl group.
Further, in the formula, Y 1 -Y 9 Independently selected from C 1-10 Hydrocarbyl radicals or C 1-10 A haloalkyl group; r is 1 Is selected from C 1-10 An alkyl group.
Further, in the formula, R 1 Selected from ethyl.
Further, in the formula, Y 6 -Y 8 In (1), at least two are simultaneously hydrogen atoms; y is 1 -Y 5 At least 2 of which are simultaneously hydrogen atoms.
The invention also discloses a synthesis method of the o-hydroxy-nitrogen silane compound, which comprises the following steps: taking a salicylidene aniline compound shown as a formula II and an alkyl silicon compound shown as a formula III as reaction raw materials, and reacting under a heating condition in the presence of a ruthenium catalyst and a solvent to obtain an o-hydroxy-nitrogen silane compound shown as a formula I, wherein the reaction formula is as follows:
in the formula (I), the compound is shown in the specification,
Y 1 -Y 9 independently selected from hydrogen atom, halogen atom, C 1-22 Hydrocarbyl radical, C 1-22 Haloalkyl, hydroxy, amino, carbonyl, amino, carboxyl, ester, cyano, phenyl, benzyl, or nitro;
R 1 is selected from C 1-22 An alkyl group.
Further, the ruthenium catalyst is selected from one of triphenylphosphine ruthenium chloride, tris (triphenylphosphine) hydroxyruthenium dihydroxide, cyclooctadiene ruthenium dichloride or tris (triphenylphosphine) carbonyl ruthenium hydrochloride. The invention adopts the relatively cheap ruthenium complex as the catalyst, and can improve the yield and reduce the cost.
Further, the solvent is selected from one of N-hexane, 1, 2-dichloroethane, toluene, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran or acetonitrile.
Further, the temperature of the heating reaction is 100-120 ℃.
Further, the heating reaction time is 8-36 hours.
Further, the molar weight ratio of the salicylideneaniline compound, the alkyl silicon compound and the ruthenium catalyst is 1:1-4:0.01-0.10.
The invention has the following beneficial effects:
the synthesis method disclosed by the invention has the advantages that the initial raw materials are simple to prepare and convenient to operate, other byproducts are not generated in a series of conversion processes except for the final product, separation and purification are not required, only one reaction step is required, the amount of the used ruthenium catalyst is small, the price is low, the investment of capital and labor force can be reduced, the synthesis efficiency of the skeleton compound is greatly improved, the steps of synthesizing related intermediates are reduced, the emission of byproducts such as halogenated hydrocarbon is reduced, and a simple and efficient synthesis method is provided for the o-hydroxy-silazane compound.
The o-hydroxy-nitrogen silane compound prepared by the invention can be used for special organic synthesis. Silylation in the synthesis process of amikacin, penicillin, cefamycin, fluorouracil and various penicillin derivatives. The method can also be used for surface treatment of diatomite, white carbon black, titanium and other powders, and the action mechanism is condensation of silicon-nitrogen bonds and silicon hydroxyl. Are used as bonding aids for photoresists in the semiconductor industry.
Herein, the term "hydrocarbyl" includes alkyl, alkenyl, and alkynyl groups; "C 1-22 The hydrocarbon group "means a straight, branched or cyclic alkane group having 1 to 22 carbon atoms.
“C 1-10 The "alkyl group" means an alkyl group having a carbon number of 1 to 10, and is meant to include a branched, straight-chain or cyclic saturated aliphatic hydrocarbon group having the specified carbon number. E.g. C 1-10 E.g. in "C 1-10 Alkyl is defined to include groups having 1,2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms in a straight or branched chain structure. For example, "C 1-10 The alkyl group "specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
“C 1-4 The "alkyl group" represents an alkyl group having 1 to 4 carbon atoms, and includes, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group and the like.
Similarly, "C 1-22 Haloalkyl "," C 1-10 Haloalkyl "or" C 1-4 Haloalkyl "denotes an alkyl group as defined above substituted by one or more halogen atoms.
The term "halogen" includes F, cl, br or I.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2- ((phenyl (triethylsilyl) amino) methyl) phenol in example 1 of the present invention;
FIG. 2 is a NMR carbon spectrum of 2- ((phenyl (triethylsilyl) amino) methyl) phenol in example 1 of the present invention;
FIG. 3 is a NMR chart of 2- (((((4-fluorophenyl) (triethylsilyl) amino) methyl) phenol in example 2 of this invention;
FIG. 4 is a NMR carbon spectrum of 2- (((((4-fluorophenyl) (triethylsilyl) amino) methyl) phenol in example 2 of this invention;
FIG. 5 is a NMR hydrogen spectrum of 2- (((((4-bromophenyl) (triethylsilyl) amino) methyl) phenol of example 3;
FIG. 6 is a NMR carbon spectrum of 2- (((((4-bromophenyl) (triethylsilyl) amino) methyl) phenol of example 3.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments.
Example 1: preparation of 2- ((phenyl (triethylsilyl) amino) methyl) phenol
In a 15mL reaction tube, salicylideneaniline (98mg, 0.5mmo 1), triethylsilane (116mg, 1.0mmo 1) and tris (triphenylphosphine) carbonyl ruthenium hydrochloride (23.8mg, 0.025mmol) were sequentially added, and the reaction was electromagnetically stirred at a reaction temperature of 120 ℃ for 8 hours under toluene (2 mL) and nitrogen conditions. After completion of the reaction, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography eluting with ethyl acetate and petroleum ether (ethyl acetate: petroleum ether = 1) to give a yellow oil body (138mg, 88%) after separation.
The product detection data were as follows:
1 H NMR(300MHz,CDCl 3 )δ＝7.36-7.16(m,4H),6.97-6.67(m,5H),4.36(s,2H),1.05(t,9H,J＝8.1Hz),0.88-0.80(m,6H)。
13 C NMR(75MHz,CDCl 3 )δ＝153.9,148.5,129.6,129.3,129.2,128.2,121.3,118.5,117.5,113.1,43.9,6.9,5.5。
example 2:2- (((((4-fluorophenyl) (triethylsilyl) amino) methyl) phenol
4-fluoro-N-o-hydroxyphenylmethyleneaniline (165mg, 0.5 mmo1), triethylsilane (116mg, 1.0 mmo1) and tris (triphenylphosphine) carbonyl ruthenium hydrochloride (23.8mg, 0.025 mmol) were sequentially charged into a 15mL reaction tube, and the reaction was electromagnetically stirred under the conditions of toluene (2 mL) and nitrogen at a reaction temperature of 120 ℃ for 8 hours. After completion of the reaction, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography eluting with ethyl acetate and petroleum ether (ethyl acetate: petroleum ether =1 = 10) to give a pale yellow oil body (85mg, 51%) after separation.
The product detection data were as follows:
1H NMR(500MHz,CDCl3)δ＝7.34-7.32(d,1H,J＝7.5Hz),7.21-7.17(m,1H),7.03-6.99(m,2H),6.98-6.94(m,1H),6.88-6.76(m,1H),6.74-6.73(m,1H),6.67-6.62(m,1H),4.39(s,2H),1.06-1.03(m,9H),0.85-0.83(m,6H).
13C NMR(126MHz,CDCl3)δ＝153.7,152.6(d,JCF＝239.4Hz),136.8(d,JCF＝11.3Hz),129.0(d,JCF＝10.1Hz),128.3,124.5(d,JCF＝3.8Hz),121.1,118.2,116.5(d,JCF＝6.3Hz),114.4(d,JCF＝18.9Hz),112.4(d,JCF＝2.5Hz),43.4,6.7,5.3.
example 3:2- (((((4-bromophenyl) (triethylsilyl) amino) methyl) phenol
4-bromo-N-o-hydroxyphenylmethyleneaniline (137mg, 0.5 mmo1), triethylsilane (116mg, 1.0 mmo1) and tris (triphenylphosphine) carbonyl ruthenium hydrochloride (23.8mg, 0.025 mmol) were sequentially added to a 15mL reaction tube, and the mixture was electromagnetically stirred under the conditions of toluene (2 mL) and nitrogen at a reaction temperature of 120 ℃ for a reaction time of 8 hours. After completion of the reaction, the solvent was removed by rotary evaporation, and the mixture was separated by column chromatography eluting with ethyl acetate and petroleum ether (ethyl acetate: petroleum ether = 1) to give a yellow oil body (170mg, 87%) after separation.
The product detection data were as follows:
1 H NMR(500MHz,CDC1 3 )δ＝7.32-7.28(m,3H),7.23-7.21(t,1H,J＝7.5Hz),6.98-6.95(t,1H,J＝7Hz),6.90-6.89(d,1H,J＝8Hz),6.56-6.55(t,2H,J＝4.5Hz),4.33(s,2H),1.08-1.05(m,9H),0.88-0.83(m,6H)。
13 C NMR(126MHz,CDC1 3 )δ＝153.8,147.4,131.9,129.3,129.1,129.0,128.4,121.3,118.4,114.6,113.0,108.9,43.9,6.8,5.4。
in conclusion, the synthesis method of the o-hydroxy-nitrogen silane compound provided by the invention has high yield, and the o-hydroxy-nitrogen silane compound is synthesized by taking a relatively cheap ruthenium complex as a catalyst and catalyzing a salicylidene aniline compound and an alkyl silicon compound to be heated and stirred under the condition of no other additives; the synthetic method has good practical value and social and economic efficiency, and has good reference significance for process development of similar products and downstream products.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (7)
1. A method for synthesizing an ortho-hydroxy-nitrogen silane compound, wherein the compound has the following general chemical formula:
in the formula (I), the compound is shown in the specification,
Y 1 -Y 8 independently selected from C 1-10 Hydrocarbyl radical, C 1-10 A haloalkyl group, a hydrogen atom or a halogen atom;
R 1 is selected from C 1-10 An alkyl group;
the synthesis method of the ortho-hydroxyl-nitrogen silane compound comprises the following steps: taking a salicylidene aniline compound shown as a formula II and an alkyl silicon compound shown as a formula III as reaction raw materials, and reacting under a heating condition in the presence of a ruthenium catalyst and a solvent to obtain an o-hydroxy-nitrogen silane compound shown as a formula I, wherein the reaction formula is as follows:
in the formula (I), the compound is shown in the specification,
the ruthenium catalyst is selected from one of triphenylphosphine ruthenium chloride, tri (triphenylphosphine) hydroxyl ruthenium dihydrogen, cyclooctadiene ruthenium dichloride or tri (triphenylphosphine) carbonyl ruthenium hydrochloride.
2. The method of claim 1, wherein R is 1 Selected from ethyl.
3. The synthesis process according to claim 1, wherein, in the formula,
Y 6 -Y 8 in (b), at least two of them are hydrogen atoms at the same time;
Y 1 -Y 5 at least 2 of which are simultaneously hydrogen atoms.
4. The method of claim 1, wherein the solvent is selected from the group consisting of N-hexane, 1, 2-dichloroethane, toluene, N-methylpyrrolidone, N-dimethylformamide, tetrahydrofuran, and acetonitrile.
5. The synthesis method according to claim 1, wherein the temperature of the heating reaction is 100-120 ℃.
6. The synthesis method according to claim 1, wherein the heating reaction time is 8-36 hours.
7. The synthesis method according to claim 1, wherein the molar weight ratio of the substances of the salicylideneaniline compound, the alkyl silicon compound and the ruthenium catalyst is 1:1-4:0.01-0.10.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS49110632A (en) * | 1973-03-07 | 1974-10-22 | ||
| JPS505331A (en) * | 1973-05-30 | 1975-01-21 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49110632A (en) * | 1973-03-07 | 1974-10-22 | ||
| JPS505331A (en) * | 1973-05-30 | 1975-01-21 |
Non-Patent Citations (3)
| Title |
|---|
| HYDROSILYLATION OF (HETERO)-AROMATIC ALDIMINES IN THE PRESENCE OF A Pd(I) COMPLEX;I. Iovel 等;《Chemistry of Heterocyclic Compounds》;20041231;第40卷(第6期);第701-714页 * |
| I. Iovel 等.HYDROSILYLATION OF (HETERO)-AROMATIC ALDIMINES IN THE PRESENCE OF A Pd(I) COMPLEX.《Chemistry of Heterocyclic Compounds》.2004,第40卷(第6期),第701-714页. * |
| Reaction of benzylideneaniline with triethylsilane;K. A. Andrianov 等;《Seriya Khimicheskaya》;19751231(第9期);第2128-2129页 * |
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