CN114591376A - Synthesis method of o-alkoxy ferrocene carboxamide - Google Patents
Synthesis method of o-alkoxy ferrocene carboxamide Download PDFInfo
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- 238000001308 synthesis method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 15
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 11
- 239000010941 cobalt Substances 0.000 claims abstract description 11
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 11
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 9
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 5
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical group C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 10
- 230000002194 synthesizing effect Effects 0.000 claims description 10
- -1 8-quinolyl Chemical group 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 6
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 5
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 5
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical group C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- HHZAIOOQYMFSFC-UHFFFAOYSA-L cobalt(2+);3-oxobutanoate Chemical group [Co+2].CC(=O)CC([O-])=O.CC(=O)CC([O-])=O HHZAIOOQYMFSFC-UHFFFAOYSA-L 0.000 claims description 4
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000004202 aminomethyl group Chemical group [H]N([H])C([H])([H])* 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 238000007040 multi-step synthesis reaction Methods 0.000 abstract 1
- 229910052723 transition metal Inorganic materials 0.000 abstract 1
- 150000003624 transition metals Chemical class 0.000 abstract 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 86
- 239000000047 product Substances 0.000 description 49
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 21
- 238000005160 1H NMR spectroscopy Methods 0.000 description 20
- 230000003595 spectral effect Effects 0.000 description 20
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical group C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 150000003857 carboxamides Chemical class 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000004293 19F NMR spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000010499 C–H functionalization reaction Methods 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000005456 alcohol based solvent Substances 0.000 description 2
- 150000001345 alkine derivatives Chemical class 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- BYYUJTPNKCFZST-UHFFFAOYSA-N n-methoxyformamide Chemical compound CONC=O BYYUJTPNKCFZST-UHFFFAOYSA-N 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000012746 preparative thin layer chromatography Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- JMMPIVZDWBCEFB-UHFFFAOYSA-N cyclopenta-1,3-diene 5-iodocyclopenta-1,3-diene iron(2+) Chemical compound [Fe++].c1cc[cH-]c1.Ic1cc[cH-]c1 JMMPIVZDWBCEFB-UHFFFAOYSA-N 0.000 description 1
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- UBQKCCHYAOITMY-UHFFFAOYSA-N pyridin-2-ol Chemical class OC1=CC=CC=N1 UBQKCCHYAOITMY-UHFFFAOYSA-N 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- 230000007704 transition Effects 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
- C07F17/00—Metallocenes
- C07F17/02—Metallocenes of metals of Groups 8, 9 or 10 of the Periodic System
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of o-alkoxy ferrocene carboxamide, which comprises the following steps: under the action of a cobalt catalyst, carrying out a heat reaction on ferrocenecarboxamide shown as a formula (I), alkali, silver salt and an additive in an alcohol solvent, and carrying out post-treatment to obtain o-alkoxy ferrocenecarboxamide shown as a formula (II). The invention adopts cheap cobalt catalyst to directly carry out alkoxylation modification on the carbon-hydrogen bond on the ferrocene, thereby avoiding complex multistep synthesis, and in addition, the method has mild reaction condition, high reaction activity, strong substrate universality and good reaction yield which can reach 73 percent at most. The obtained O-alkoxy ferrocene carboxamide is a ferrocene N, O-ligand and is expected to be applied to transition metal catalytic reaction.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a synthesis method of o-alkoxy ferrocene carboxamide.
Background
Ferrocene and its derivatives are of great interest to people due to their unique structures and properties, and are widely used in the fields of organic synthesis, material science, pharmaceutical chemistry, and the like. Among them, the oxygen-containing substituent ferrocene derivatives are core skeleton structures of many bioactive molecules, ligands or catalysts. For example: chinese patent publication No. CN105693778A discloses a method for synthesizing ferrocenopyridone derivatives by guiding N-methoxy formamide, which comprises performing cyclization reaction between N-methoxy ferrocene formamide and alkyne to generate N-methoxy ferroceno [ c ] pyridine-2 (1H) -one derivatives under the conditions of palladium acetate as a catalyst, copper acetate as a cocatalyst, quaternary ammonium salt and alkali as additives. The N-methoxy-ferroceno [ c ] pyridine-2 (1H) -ketone derivative is synthesized in one step by adopting N-methoxy formamide guided carbon-hydrogen bond and nitrogen-hydrogen bond double activation reaction; chinese patent publication No. CN103788137A discloses a method for preparing a ferrocenopiperidinone compound, which comprises catalytically cyclizing ferrocenecarboxamide and alkyne under palladium acetate to form a corresponding ferrocenopiperidinone compound; the ferrocenopiperidinone compound is used for preparing medicines.
The O-alkoxy ferrocene carboxamide is an important ferrocene N, O-ligand, and therefore, the introduction of carbon-oxygen bond on ferrocene is very important. The traditional method adopts copper-mediated Ullman coupling reaction of iodoferrocene and sodium alkoxide to introduce a carbon-oxygen bond, however, the method needs to use stoichiometric lithium alkyl reagent, and has poor functional group tolerance and complex operation. Compared with the prior art, the method for directly constructing the carbon-oxygen bond on the ferrocene skeleton structure by utilizing the carbon-hydrogen bond activation is undoubtedly a simpler and more efficient method, the previous research mainly focuses on using the second or third transition period noble metals Rh and Ir to complete the carbon-hydrogen bond functionalization at a specific position based on a guiding strategy, but the cost is higher, and meanwhile, the method still has great challenges in constructing the carbon-oxygen bond due to the instability of the oxoferrocene and the like.
Disclosure of Invention
The invention provides a synthesis method of o-alkoxy ferrocene carboxamide, which utilizes an economic cobalt catalyst to realize the activation of carbon-hydrogen bonds on various ferrocene carboxamides and directly construct carbon-oxygen bonds on a ferrocene skeleton.
The technical scheme is as follows:
a method for synthesizing o-alkoxy ferrocene formamide comprises the following steps: under the action of a cobalt catalyst, carrying out a heat reaction on ferrocenecarboxamide shown as a formula (I), alkali, silver salt and an additive in an alcohol solvent, and carrying out post-treatment to obtain o-alkoxy ferrocenecarboxamide shown as a formula (II);
wherein Q is 8-quinolyl, and the structural formula is
Represents a substitution position;
R1is hydrogen atom, alkyl, alkenyl, substituted aminomethyl, substituted oxymethyl or substituted benzyl, R is C1-C5Alkyl, halogen or methoxy substituted C1-C5Alkyl, deuterated alkyl or benzyl.
The invention takes 8-aminoquinoline substituted ferrocene carboxamide as a starting material, synthesizes a series of o-alkoxy ferrocene carboxamide by using a cobalt-catalyzed alkoxylation mode, and has the reaction principle that: under the guiding action of 8-aminoquinoline, the cobalt catalyst selectively activates carbon-hydrogen bonds at the ortho position of the amide group, and the obtained cobalt intermediate and an alcohol solvent undergo carbon-oxygen bond coupling reaction under the action of a silver salt oxidant.
The electronic and steric properties of the catalytically active intermediate are key factors in determining the activity of the chemical reaction. In the invention, 8-aminoquinoline is selected as a guide group, so that high reactivity of target reaction is ensured. In addition, the reactivity is also closely related to the reaction conditions of the catalyst, alkali, silver salt, etc.
Preferably, the cobalt catalyst is cobalt acetoacetate (Co (acac)2). Since the product is a strong tridentate ligand, the common monodentate anion is difficult to dissociate, so that catalytic cycling cannot be realized, and the acetoacetate anion is a strong coordination bidentate anion and is beneficial to catalytic cycling.
Preferably, the base is triethylamine.
Preferably, the silver salt is silver carbonate.
Preferably, the additive is hexamethylenetetramine. The reaction process involves the process of taking out and giving protons, the preferable triethylamine base has larger steric hindrance, and the process of taking out and giving protons can be accelerated by selecting hexamethylenetetramine with small steric hindrance.
Preferably, the alcohol solvent comprises any one of the following formulas (III):
preferably, the reaction temperature is 10-100 ℃ and the reaction time is 1-48 hours.
The reaction equation of the present invention is shown as the following formula, wherein, Q, R1And R is as defined above.
Preferably, the mole ratio of the ferrocenecarboxamide shown in the formula (I) to the cobalt catalyst, alkali, silver salt and additive is 1: 0.05-0.5: 0.5-5: 0.5-5: 0.05-3.
Preferably, the proportion of the ferrocenecarboxamide shown in the formula (I) to the alcohol solvent is 1 mol: 0.1-50L.
Preferably, the post-treatment mode is thin layer chromatography.
Compared with the prior art, the invention has the beneficial effects that:
(1) the synthesis method provided by the invention realizes the synthesis of the o-alkoxy ferrocene carboxamide, has high synthesis efficiency, is environment-friendly and has less pressure on production environment protection.
(2) The synthetic method has the advantages of simple operation, mild reaction conditions and good reaction yield, and the highest reaction yield reaches 73%.
(3) The substrate has wide application range, is suitable for various 8-aminoquinoline substituted ferrocenecarboxamides, has the yield of 32-73 percent, and has wide application range.
Drawings
FIG. 1 is a NMR spectrum of o-alkoxyferrocene carboxamide product 3a of example 1.
FIG. 2 is a NMR carbon spectrum of o-alkoxyferrocene carboxamide product 3a of example 1.
Detailed Description
The invention is further elucidated with reference to the figures and the examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
In a reactor, 8-aminoquinoline-substituted ferrocenecarboxamide (0.1mmol), cobalt acetoacetate catalyst (0.02mmol), hexamethylenetetramine (0.03mmol), silver carbonate (0.15mmol), triethylamine (0.2mmol) and methanol (1.5mL) were added, reacted at 30 ℃ for 18 hours under an air atmosphere, cooled, diluted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by preparative thin layer chromatography using petroleum ether: ethyl acetate ═ 8: the eluent 1 is the product 3a shown in the following formula, the yield is 71%, and the nuclear magnetic resonance hydrogen spectrum and the nuclear magnetic resonance carbon spectrum of the product 3a are respectively shown in figure 1 and figure 2.
Nuclear magnetic data for product 3 a:
1H NMR(400MHz,CDCl3)δ11.40(s,1H),9.01–8.61(m,2H),8.16(d,J＝8.1Hz,1H),7.57(t,J＝7.9Hz,1H),7.50(d,J＝8.2Hz,1H),7.45(dd,J＝8.3,4.1Hz,1H),4.81(s,1H),4.34(s,1H),4.26(s,5H),4.12(s,1H),4.02(s,3H)。
13C NMR(101MHz,CDCl3)δ169.2,148.4,139.1,136.3,135.8,128.2,127.7,125.8,121.5,121.0,116.8,70.3,65.8,64.8,63.1,58.8,55.2。
mass spectral data for product 3 a:
HRMS(ESI)m/z:[M+H]+calc.for C21H19FeN2O2:387.0790,Found:387.0792。
examples 2 to 11
Examples 2-11 were the same as example 1 except that the starting materials were each selected from different ferrocenecarboxamides of the formula:
the structural formula of each of the obtained o-alkoxyferrocene carboxamide products 3b-3k is shown below, and the yields are 72%, 73%, 61%, 43%, 62%, 60% (dr ═ 1:1), 64% (dr ═ 1:1), 46% (dr ═ 1:1), 50% (dr ═ 1:1), 42%, respectively.
Nuclear magnetic data for product 3 b:
1H NMR(400MHz,CDCl3)δ11.37(s,1H),9.08–8.66(m,2H),8.16(d,J＝8.3Hz,1H),7.84–7.36(m,3H),4.74(s,1H),4.32(s,1H),4.17(s,4H),4.08(s,1H),4.01(s,3H),2.65(t,J＝7.3Hz,1H),1.13(t,J＝7.5Hz,6H)。
13C NMR(101MHz,CDCl3)δ169.0,148.2,139.0,136.1,135.8,128.1,127.6,125.5,121.4,120.8,116.7,98.5,69.7,69.4,68.7,67.4,65.8,65.3,63.6,58.7,55.6,27.0,23.6,23.6。
mass spectral data for product 3 b:
HRMS(ESI)m/z:[M+H]+calc.for C24H25FeN2O2:429.1260,Found:429.1262。
nuclear magnetic data for product 3 c:
1H NMR(400MHz,CDCl3)δ11.37(s,1H),8.90(dd,J＝32.0,5.8Hz,2H),8.16(d,J＝8.2Hz,1H),7.56(t,J＝7.9Hz,1H),7.49(d,J＝8.2Hz,1H),7.44(dd,J＝8.3,4.2Hz,1H),4.74(d,J＝2.7Hz,1H),4.32(s,1H),4.15(t,J＝9.3Hz,4H),4.06(s,1H),4.00(s,3H),2.24(td,J＝7.5,3.9Hz,1H),1.65–1.55(m,2H),1.50–1.41(m,2H),0.74(dt,J＝17.2,7.4Hz,6H)。
13C NMR(101MHz,CDCl3)δ169.2,148.3,139.1,136.2,135.9,128.2,127.7,125.5,121.5,120.9,116.8,96.9,69.6,69.5,69.2,68.6,65.9,65.4,63.9,58.8,55.9,40.0,26.4,11.1。
mass spectral data for product 3 c:
HRMS(ESI)m/z:[M+H]+calc.for C26H29FeN2O2:457.1573,Found:457.1574。
nuclear magnetic data for product 3 d:
1H NMR(400MHz,CDCl3)δ11.39(s,1H),8.94(d,J＝7.5Hz,1H),8.80(d,J＝4.1Hz,1H),8.16(d,J＝8.2Hz,1H),7.55(t,J＝7.9Hz,1H),7.49(d,J＝8.2Hz,1H),7.43(dd,J＝8.3,4.1Hz,1H),7.12(d,J＝5.7Hz,3H),7.00–6.91(m,2H),4.75(s,1H),4.31(s,1H),4.19–4.11(m,4H),4.08(s,1H),4.00(s,3H),2.68(d,J＝7.9Hz,2H),2.65–2.50(m,2H)。
13C NMR(101MHz,CDCl3)δ168.9,148.3,141.9,139.0,136.2,135.8,128.3,128.2,127.7,125.7,125.6,121.5,121.0,116.9,90.4,70.4,70.2,69.3,69.2,66.0,65.3,63.6,58.8,55.8,37.5,30.0。
mass spectral data for product 3 d:
HRMS(ESI)m/z:[M+H]+calc.for C29H27FeN2O2:491.1416,Found:491.1417。
nuclear magnetic data for product 3 e:
1H NMR(400MHz,CDCl3)δ11.33(s,1H),8.94(dd,J＝7.7,1.3Hz,1H),8.86(dd,J＝4.2,1.7Hz,1H),8.16(dd,J＝8.3,1.6Hz,1H),7.56(t,J＝7.9Hz,1H),7.49(dd,J＝8.3,1.3Hz,1H),7.45(dd,J＝8.2,4.2Hz,1H),5.21–4.99(m,1H),4.80–4.75(m,1H),4.74(dd,J＝2.8,1.6Hz,1H),4.48(q,J＝2.0Hz,2H),4.31(t,J＝1.9Hz,2H),4.27(dd,J＝2.7,1.6Hz,1H),4.05(t,J＝2.8Hz,1H),3.99(s,3H),1.97(s,3H)。
13C NMR(101MHz,CDCl3)13C NMR(101MHz,CDCl3)δ168.4,148.2,140.0,139.0,136.2,135.8,128.1,127.6,125.8,121.4,120.9,116.8,109.9,88.2,71.1,70.8,67.6,67.5,66.2,65.6,64.3,58.7,56.4,21.5。
mass spectral data for product 3 e:
HRMS(ESI)m/z:[M+H]+calc.for C24H24FeN2O2:427.1103,Found:427.1106。
nuclear magnetic data for product 3 f:
1H NMR(400MHz,CDCl3)δ11.33(s,1H),8.89(dd,J＝7.5,1.4Hz,1H),8.81(d,J＝4.1Hz,1H),8.19–8.07(m,1H),7.55(t,J＝7.9Hz,1H),7.50(d,J＝8.1Hz,1H),7.43(dd,J＝8.2,4.2Hz,1H),7.16(d,J＝6.1Hz,3H),7.04(d,J＝13.1Hz,2H),4.73(s,1H),4.26(d,J＝17.7Hz,4H),4.22–4.10(m,4H),4.05(s,2H),3.96(d,J＝18.4Hz,3H),1.37(s,9H)。
13C NMR(101MHz,CDCl3)δ168.8,168.5,155.6,148.3,139.0,138.3,136.2,135.7,128.4,128.2,127.7,127.2,127.1,125.7,121.5,121.1,116.8,85.1,79.8,71.5,70.9,70.4,70.0,65.8,65.2,63.8,63.5,58.7,56.1,55.7,49.6,49.1,44.3,28.5。
mass spectral data for product 3 f:
HRMS(ESI)m/z:[M+H]+calc.for C34H36FeN3:606.2050,Found:606.2054。
nuclear magnetic data of product 3 g:
1H NMR(400MHz,CDCl3)δ11.38(d,J＝4.0Hz,1H),8.96(dd,J＝7.8,1.3Hz,1H),8.86(ddd,J＝4.4,3.0,1.7Hz,1H),8.16(dt,J＝8.3,1.8Hz,1H),7.57(t,J＝7.9Hz,1H),7.49(dt,J＝8.3,1.4Hz,1H),7.44(ddd,J＝8.3,4.2,1.9Hz,1H),7.21–7.13(m,2H),7.12–7.05(m,2H),7.03–6.97(m,1H),4.77(dd,J＝6.7,2.5Hz,1H),4.41–4.26(m,2H),4.22(d,J＝2.5Hz,1H),4.18–4.14(m,1H),4.07(dt,J＝7.8,2.0Hz,2H),3.97(d,J＝16.3Hz,3H),3.86(tt,J＝7.1,3.5Hz,1H),1.49(dd,J＝10.2,7.1Hz,3H)。
13C NMR(101MHz,CDCl3)δ168.8,148.2,147.5,147.4,139.0,136.2,135.7,128.2,128.2,128.1,127.6,127.2,127.1,126.0,125.9,125.5,121.4,120.9,116.8,116.7,95.8,70.8,70.3,70.3,69.5,69.3,68.9,68.7,67.7,66.1,65.9,65.6,65.5,63.8,58.8,58.7,56.0,55.7,39.0,38.7,22.6,22.2。
mass spectral data for product 3 g:
HRMS(ESI)m/z:[M+H]+calc.for C29H27FeN2O2:491.1416,Found:491.1419。
nuclear magnetic data of product 3 h:
1H NMR(400MHz,CDCl3)δ11.43(d,J＝12.6Hz,1H),8.99(dt,J＝7.6,1.6Hz,1H),8.86(dd,J＝4.2,1.7Hz,1H),8.16(dt,J＝8.3,2.0Hz,1H),7.57(t,J＝7.9Hz,1H),7.49(dd,J＝8.3,1.3Hz,1H),7.44(ddd,J＝8.3,4.2,2.1Hz,1H),7.08–6.90(m,3H),6.81(dt,J＝7.4,2.9Hz,1H),4.79(q,J＝2.1Hz,1H),4.41–4.37(m,1H),4.36–4.31(m,1H),4.23–4.16(m,2H),4.15–4.09(m,2H),4.08–4.03(m,1H),4.00(d,J＝2.6Hz,3H),2.22(s,1.5H),2.04(s,1.5H),1.45(d,J＝7.0Hz,1.5H),1.38(d,J＝7.0Hz,1.5H)。
13C NMR(101MHz,CDCl3)δ168.8,148.4,148.3,146.5,146.3,139.1,136.3,135.9,135.9,134.6,134.6,130.1,130.0,128.2,127.7,126.9,126.9,126.2,126.1,125.7,125.7,125.6,121.5,121.0,121.0,116.9,96.3,96.2,71.0,70.5,70.4,69.7,68.9,68.8,68.2,68.1,66.6,66.1,65.7,65.6,63.8,63.7,58.9,58.8,56.0,55.6,34.2,34.2,21.1,20.9,19.5,19.2。
mass spectral data for product 3 h:
HRMS(ESI)m/z:[M+H]+calc.for C30H29FeN2O:505.1573,Found:505.1573。
nuclear magnetic data of product 3 i:
1H NMR(400MHz,CDCl3)δ11.39(d,J＝4.3Hz,1H),8.96(ddd,J＝7.7,4.4,1.3Hz,1H),8.87(dt,J＝4.2,2.1Hz,1H),8.16(dt,J＝8.3,1.8Hz,1H),7.58(t,J＝7.9Hz,1H),7.52–7.49(m,1H),7.46–7.43(m,1H),7.04–6.95(m,3H),6.90(d,J＝8.1Hz,1H),4.78–4.75(m,1H),4.38–4.26(m,2H),4.24–4.19(m,1H),4.15(q,J＝2.0Hz,1H),4.06(dt,J＝6.0,3.2Hz,2H),4.00(s,1.5H),3.96(s,1.5H),3.84(qd,J＝7.2,2.4Hz,1H),2.25(d,J＝7.4Hz,3H),1.48(dd,J＝8.4,7.1Hz,3H)。
13C NMR(101MHz,CDCl3)δ168.8,148.2,144.6,144.4,139.0,136.2,135.8,135.4,135.3,128.9,128.9,128.1,127.6,127.0,126.9,125.5,121.4,120.9,116.8,116.7,96.1,96.1,70.8,70.3,69.4,69.3,68.9,68.6,67.6,66.1,65.8,65.5,65.5,63.8,58.8,58.7,56.0,55.7,38.6,38.3,22.6,22.3,21.0,20.9。
mass spectral data for product 3 i:
HRMS(ESI)m/z:[M+H]+calc.for C30H29FeN2O2:505.1573,Found:505.1572。
nuclear magnetic data for product 3 j:
1H NMR(400MHz,CDCl3)δ11.38(s,1H),8.96(ddd,J＝7.6,4.6,1.4Hz,1H),8.86(dd,J＝3.9,1.8Hz,1H),8.16(dt,J＝8.3,1.8Hz,1H),7.57(t,J＝7.9Hz,1H),7.50(dt,J＝8.2,1.5Hz,1H),7.46–7.43(m,1H),7.07–6.98(m,1H),6.97–6.90(m,1H),6.89–6.76(m,2H),4.77–4.75(m,1H),4.36–4.32(m,1H),4.29(dd,J＝2.8,1.7Hz,1H),4.23–4.21(m,1H),4.17(dt,J＝3.4,2.2Hz,1H),4.07–4.03(m,,2H),3.99(s,1.5H),3.97(s,1.5H),3.87(qd,J＝7.2,2.5Hz,1H),1.46(dd,J＝14.6,7.2Hz,3H)。
13C NMR(101MHz,CDCl3)δ168.7,160.2(d,C-F,1JC-F＝242Hz),161.1(d,C-F,1JC-F＝242Hz),148.3,143.3,143.3,143.1,143.1,139.0,139.0,136.2,135.7,128.5,128.4(d,C-F,3JC-F＝8Hz),128.4,(d,C-F,3JC-F＝8Hz),127.6,125.5,125.5,121.4,121.0,116.8,116.7,114.91(d,C-F,2JC-F＝21Hz),114.89(d,C-F,2JC-F＝21Hz),95.7,95.7,70.9,70.3,70.2,69.5,69.3,68.8,68.6,67.4,66.2,65.9,65.7,65.6,63.8,58.8,58.7,55.9,55.7,38.2,37.9,22.6,22.3。
mass spectral data for product 3 j:
HRMS(ESI)m/z:[M+H]+calc.for C29H26FFeN2O2:509.1322,Found:509.1324。
nuclear magnetic data for product 3 k:
1H NMR(400MHz,CDCl3)δ11.43(s,1H),8.97(d,J＝7.5Hz,1H),8.88–8.79(m,1H),8.17(dt,J＝8.1,1.6Hz,1H),7.58(t,J＝7.9Hz,1H),7.51(d,J＝8.1Hz,1H),7.47–7.41(m,1H),6.97(dd,J＝8.4,3.3Hz,1H),6.58–6.38(m,2H),4.83(t,J＝2.0Hz,1H),4.70(d,J＝2.4Hz,2H),4.41(d,J＝7.2Hz,3H),4.29(s,2H),4.16(t,J＝2.8Hz,1H),4.04(s,3H),2.77–2.62(m,2H),2.50(dd,J＝18.9,8.7Hz,1H),2.33(dd,J＝9.3,4.1Hz,1H),2.18–2.07(m,2H),2.04–2.01(m,1H),1.99–1.88(m,2H),1.69–1.56(m,3H),1.55–1.47(m,2H),1.42–1.32(m,1H),0.90(s,3H)。
13C NMR(101MHz,CDCl3)δ168.6,156.8,148.4,139.1,137.6,136.3,135.8,132.0,128.3,127.8,126.2,125.8,121.6,121.2,116.9,114.6,114.6,112.2,112.1,84.3,84.2,71.3,71.2,70.9,70.5,70.4,70.3,66.1,65.4,65.3,63.6,58.8,55.9,50.5,48.1,44.1,38.4,36.0,31.7,29.7,26.6,26.0,21.7,14.0。
mass spectral data for product 3 k:
HRMS(ESI)m/z:[M+H]+calc.for C40H41FeN2O4:669.2410,Found:669.2413。
examples 12 to 16
Examples 12-16 were run under the same conditions as example 1 except that the starting material was selected from different alcohol solvents, each selected from:
HOCD3 
the structural formulas of the o-alkoxy ferrocene carboxamide products 4a-4e are shown as the following formula, and the yields are 63%, 60%, 55%, 34% and 52% respectively.
Nuclear magnetic data for product 4 a:
1H NMR(400MHz,CDCl3)δ11.40(s,1H),8.94(dd,J＝7.6,1.4Hz,1H),8.87(dd,J＝4.2,1.7Hz,1H),8.16(dd,J＝8.2,1.7Hz,1H),7.57(t,J＝7.9Hz,1H),7.53–7.49(m,1H),7.45(dd,J＝8.2,4.2Hz,1H),4.81(dd,J＝2.9,1.6Hz,1H),4.34(dd,J＝2.7,1.6Hz,1H),4.26(s,5H),4.12(t,J＝2.8Hz,1H)。
13C NMR(101MHz,CDCl3)δ169.1,148.3,139.0,136.2,135.7,128.1,127.6,125.7,121.4,121.0,116.8,70.2,65.7,64.7,63.0,57.6(h,C-D,JC-D＝21.4Hz,12.6Hz,8.5Hz),55.1。
mass spectral data for product 4 a:
HRMS(ESI)m/z:[M+H]+calc.for C21H16D3FeN2O2:390.0979,Found:390.0980。
nuclear magnetic data for product 4 b:
1H NMR(400MHz,CDCl3)δ11.41(s,1H),9.00(dd,J＝7.7,1.4Hz,1H),8.82(dd,J＝4.2,1.7Hz,1H),8.16(dd,J＝8.2,1.7Hz,1H),7.57(t,J＝7.9Hz,1H),7.50(dd,J＝8.2,1.4Hz,1H),7.45(dd,J＝8.3,4.2Hz,1H),4.81(dd,J＝2.9,1.6Hz,1H),4.38–4.29(m,1H),4.25–4.20(m,6H),4.15–4.03(m,2H),1.72(t,J＝7.0Hz,3H)。
13C NMR(101MHz,CDCl3)δ169.4,147.9,139.1,136.2,136.1,128.2,127.7,124.7,121.5,121.0,116.9,70.2,67.5,65.4,64.7,63.1,55.6,15.4。
mass spectral data for product 4 b:
HRMS(ESI)m/z:[M+H]+calc.for C22H21FeN2O2:401.0947,Found:401.0949。
nuclear magnetic data for product 4 c:
1H NMR(400MHz,CDCl3)δ11.39(s,1H),9.01(dd,J＝7.6,1.4Hz,1H),8.89(dd,J＝4.2,1.7Hz,1H),8.20(dd,J＝8.3,1.7Hz,1H),7.60(t,J＝7.9Hz,1H),7.54(dd,J＝8.2,1.4Hz,1H),7.49(dd,J＝8.3,4.2Hz,1H),5.17(t,J＝4.1Hz,1H),5.05(t,J＝4.1Hz,1H),4.87(dd,J＝2.9,1.6Hz,1H),4.55–4.34(m,3H),4.30(s,5H),4.16(t,J＝2.8Hz,1H)。
13C NMR(101MHz,CDCl3)δ168.9,147.9,139.0,136.3,135.8,128.2,127.6,124.2,121.6,121.1,116.8,82.1(d,C-F,JC-F＝171Hz),77.4,77.3,77.1,71.1,70.9,70.3,65.9,65.1,63.2,55.7。
19F NMR(376MHz,CDCl3)δ-222.26。
mass spectral data for product 4 c:
HRMS(ESI)m/z:[M+H]+calc.for C22H20FFeN2O2:419.0853,Found:419.0855。
nuclear magnetic data for product 4 d:
1H NMR(400MHz,CDCl3)δ11.14(s,1H),8.93(dd,J＝7.5,1.5Hz,1H),8.84(dd,J＝4.2,1.7Hz,1H),8.16(dd,J＝8.3,1.7Hz,1H),7.57(t,J＝7.9Hz,1H),7.52(dd,J＝8.2,1.5Hz,1H),7.46(dd,J＝8.3,4.2Hz,1H),4.87(dd,J＝3.0,1.6Hz,1H),4.50(p,J＝8.1Hz,2H),4.33(t,J＝2.1Hz,1H),4.30(s,5H),4.16(t,J＝2.8Hz,1H)。
13C NMR(101MHz,CDCl3)δ168.1,148.4,139.0,136.2,135.5,128.2,127.5,124.6,123.9,121.9,121.7,121.4,116.9,70.7,69.2(q,C-F,JC-F＝36.1Hz),66.6,65.8,63.6,56.7。
19F NMR(376MHz,CDCl3)δ-73.50。
mass spectral data for product 4 d:
HRMS(ESI)m/z:[M+H]+calc.for C22H18F3FeN2O2:455.0664,Found:455.0667。
nuclear magnetic data for product 4 e:
1H NMR(400MHz,CDCl3)δ11.40(s,1H),9.30–8.98(m,1H),8.86(dd,J＝4.2,1.7Hz,1H),8.22(dd,J＝8.2,1.7Hz,1H),7.63(t,J＝7.9Hz,1H),7.58–7.54(m,1H),7.51(dd,J＝8.3,4.2Hz,1H),4.86(t,J＝2.1Hz,1H),4.38(t,J＝2.1Hz,1H),4.29(s,5H),4.23–4.14(m,2H),4.06(dt,J＝8.5,6.1Hz,1H),2.19(h,J＝6.9Hz,2H),1.28(t,J＝7.4Hz,3H)。
13C NMR(101MHz,CDCl3)δ169.4,147.7,139.1,136.2,136.0,128.2,127.7,124.8,121.4,121.0,117.0,73.4,70.2,65.2,64.8,63.0,55.5,22.9,11.2。
mass spectral data for product 4 e:
HRMS(ESI)m/z:[M+H]+calc.for C23H23FeN2O2:415.1103,Found:455.1105。
example 17
In a reactor, 8-aminoquinoline-substituted ferrocenecarboxamide (0.1mmol), cobalt acetoacetate catalyst (0.02mmol), hexamethylenetetramine (0.03mmol), silver carbonate (0.15mmol), triethylamine (0.2mmol) and 1.5mL of n-butanol were added, reacted at 100 ℃ for 18 hours under an air atmosphere, cooled, diluted with ethyl acetate, washed with saturated brine, dried over anhydrous sodium sulfate, filtered, concentrated, and purified by preparative thin layer chromatography using petroleum ether: ethyl acetate ═ 8: eluent 1 gave the product 4f, shown below, in 47% yield.
Nuclear magnetic data for product 4 f:
1H NMR(400MHz,CDCl3)δ11.31(s,1H),8.99(dt,J＝7.6,1.1Hz,1H),8.82(dt,J＝4.2,1.2Hz,1H),8.17(dt,J＝8.2,1.2Hz,1H),7.57(t,J＝7.9Hz,1H),7.51(dt,J＝8.3,1.1Hz,1H),7.46(dd,J＝8.2,4.1Hz,1H),4.81(dt,J＝2.5,1.1Hz,1H),4.32(dt,J＝2.5,1.2Hz,1H),4.24(s,5H),4.17(dt,J＝8.8,6.6Hz,1H),4.11(td,J＝2.8,0.8Hz,1H),4.04(dt,J＝8.6,6.5Hz,1H),2.18–2.02(m,2H),1.70–1.60(m,4H),1.13–0.98(m,3H)。
13C NMR(101MHz,CDCl3)δ169.5,147.9,139.2,136.3,136.1,128.3,127.7,124.9,121.5,121.1,117.1,71.6,70.3,65.3,64.8,63.1,55.6,31.7,19.6,14.1。
mass spectral data for product 4 f:
HRMS(ESI)m/z:[M+H]+calc.for C24H25FeN2O2:429.1260,Found:429.1261。
examples 18 to 21
Examples 18-21 were run under the same conditions as example 17 except that the starting material was selected from different alcohol solvents, each selected from:
the structural formula of the obtained product 4g-4i is shown as the following formula, and the yield is 37%, 35% and 32% respectively.
Nuclear magnetic data of 4g of product:
1H NMR(400MHz,CDCl3)δ11.38(s,1H),8.98(dd,J＝7.6,1.4Hz,1H),8.79(dd,J＝4.2,1.7Hz,1H),8.16(dd,J＝8.2,1.7Hz,1H),7.58(t,J＝7.9Hz,1H),7.51(dd,J＝8.3,1.4Hz,1H),7.44(dd,J＝8.3,4.1Hz,1H),4.81(dd,J＝2.9,1.5Hz,1H),4.28(dd,J＝2.7,1.6Hz,1H),4.24(s,5H),4.14–4.03(m,2H),3.80(dd,J＝9.8,7.4Hz,1H),1.64–1.54(m,1H),0.79–0.68(m,2H),0.52–0.45(m,2H)。
13C NMR(101MHz,CDCl3)δ169.4,147.9,139.2,136.3,136.0,128.3,127.7,124.6,121.5,121.1,117.2,70.3,65.6,64.8,63.2,56.0,10.7,4.1,3.7。
mass spectral data for product 4 g:
HRMS(ESI)m/z:[M+H]+calc.for C24H23FeN2O2:427.1103,Found:427.1103。
nuclear magnetic data of product 4 h:
1H NMR(400MHz,CDCl3)δ11.29(s,1H),8.98(d,J＝7.6Hz,1H),8.89(d,J＝4.2Hz,1H),8.18(d,J＝8.2Hz,1H),7.58(t,J＝7.9Hz,1H),7.51(d,J＝8.1Hz,1H),7.47(dd,J＝8.3,4.1Hz,1H),4.82(s,1H),4.33(t,J＝4.4Hz,2H),4.26(s,6H),4.11(dt,J＝11.3,3.5Hz,2H),4.04(dt,J＝10.3,4.8Hz,1H),3.47(s,3H)。
13C NMR(101MHz,CDCl3)δ169.2,147.8,139.1,136.3,135.9,128.2,127.7,124.5,121.5,121.1,117.1,71.1,71.0,70.3,65.8,64.8,63.2,59.3,55.8。
mass spectral data for product 4 h:
HRMS(ESI)m/z:[M+H]+calc.for C23H23FeN2O3:431.1053,Found:431.1056。
nuclear magnetic data for product 4 i:
1H NMR(400MHz,CDCl3)δ11.34(s,1H),8.95(dd,J＝7.7,1.3Hz,1H),8.20(dd,J＝4.2,1.7Hz,1H),8.10(dd,J＝8.3,1.7Hz,1H),7.67–7.62(m,2H),7.55(t,J＝7.9Hz,1H),7.48(dd,J＝8.3,1.3Hz,1H),7.45–7.38(m,3H),7.32(dd,J＝8.2,4.2Hz,1H),5.24(d,J＝11.4Hz,1H),5.15(d,J＝11.4Hz,1H),4.84(dd,J＝2.9,1.6Hz,1H),4.39(dd,J＝2.6,1.6Hz,1H),4.25(s,5H),4.14(t,J＝2.8Hz,1H)。
13C NMR(101MHz,CDCl3)δ169.1,148.1,139.0,136.6,136.0,135.8,128.7,128.4,128.4,128.1,127.6,124.7,121.4,121.1,117.0,74.0,70.4,65.8,65.0,63.3,56.5。
mass spectral data for product 4 i:
HRMS(ESI)m/z:[M+H]+calc.for C27H23FeN2O2:463.1103,Found:461.1104。
the embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A method for synthesizing o-alkoxy ferrocene formamide is characterized by comprising the following steps: under the action of a cobalt catalyst, carrying out a heat reaction on ferrocenecarboxamide shown as a formula (I), alkali, silver salt and an additive in an alcohol solvent, and carrying out post-treatment to obtain o-alkoxy ferrocenecarboxamide shown as a formula (II);
wherein Q is 8-quinolyl, and the structural formula is
Represents a substitution position;
R1is hydrogen atom, alkyl, alkenyl, substituted aminomethyl, substituted oxymethyl or substituted benzyl, R is C1-C5Alkyl, halogen or methoxy substituted C1-C5Alkyl, deuterated alkyl, or benzyl.
2. The method for synthesizing o-alkoxy ferrocene carboxamide as claimed in claim 1, characterized in that the cobalt catalyst is cobalt acetoacetate.
3. The method for synthesizing o-alkoxy ferrocene carboxamide according to claim 1, characterized in that the base is triethylamine.
4. The method for synthesizing o-alkoxy ferrocene carboxamide as claimed in claim 1, characterized in that the silver salt is silver carbonate.
5. The method for synthesizing o-alkoxy ferrocene carboxamide as claimed in claim 1, characterized in that the additive is hexamethylenetetramine.
6. The method for synthesizing o-alkoxy ferrocene carboxamide according to claim 1, characterized in that the alcohol solvent comprises any one of the following formulas (III):
7. the method for synthesizing o-alkoxy ferrocene carboxamide according to claim 1, characterized in that the reaction temperature is 10-100 ℃ and the reaction time is 1-48 hours.
8. The method for synthesizing o-alkoxy ferrocene carboxamide according to claim 1, characterized in that the mole ratio of ferrocene carboxamide shown in formula (i) to cobalt catalyst, alkali, silver salt and additive is 1: 0.05-0.5: 0.5-5: 0.5-5: 0.05-3.
9. The proportion of the ferrocenecarboxamide shown in the formula (I) to the alcohol solvent is 1 mol: 0.1-50L.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105693778A (en) * | 2016-03-21 | 2016-06-22 | 山东师范大学 | N-methoxyl formamide-orientated method for synthesizing ferrocene and pyridone derivative |
| CN109232669A (en) * | 2018-09-20 | 2019-01-18 | 五邑大学 | A kind of synthetic method of ferrocene analog derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105693778A (en) * | 2016-03-21 | 2016-06-22 | 山东师范大学 | N-methoxyl formamide-orientated method for synthesizing ferrocene and pyridone derivative |
| CN109232669A (en) * | 2018-09-20 | 2019-01-18 | 五邑大学 | A kind of synthetic method of ferrocene analog derivative |
Non-Patent Citations (1)
| Title |
|---|
| ZHUO-ZHUO ZHANG等: "Cobalt-Catalyzed C−H Alkoxylation of Ferrocenes with Alcohols under Mild Conditions", 《ADVANCED SYNTHESIS & CATALYSIS》, vol. 363, no. 16, pages 3946 - 3951 * |
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