CN109748811A - A kind of method for the naphthoquinone derivatives that synthesis of alkyl carboxylate replaces - Google Patents
A kind of method for the naphthoquinone derivatives that synthesis of alkyl carboxylate replaces Download PDFInfo
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Abstract
The present invention relates to a kind of methods for the naphthoquinone derivatives that synthesis of alkyl carboxylate replaces, under metal salt and ligand catalysis, replace quinones, alkene and alpha-halogenated carboxylic acids ester as raw material using 2- hydroxyl or 2- amino, the 2- hydroxyl or 2- amino that one-step synthesis of alkyl carboxylate replaces replace naphthoquinone derivatives.The present invention synthesizes the 2- amino that a variety of substitution structure alkyl carboxylic acid esters replace in which can be convenient or 2- hydroxyl replaces naphthoquinone derivatives, achieves the separation yield of highest 81%.The present invention has the features such as easy to operate, raw material is easy to get, wide application range of substrates.
Description
Technical field
The 2- hydroxyl or 2- amino that the present invention relates to a kind of to be replaced by the Bifunctionalized synthesis of alkyl carboxylate of alkene replace
The new method of naphthoquinone derivatives, and in particular under metal/ligand complex catalyzed, the quinones containing enamine (or enol) structure
Three component free radical tandem reactions occur for compound and alkene, alpha-halogenated carboxylic acids ester free radical reagent, and it is more to realize a kind of synthesis
It is functionalized the new method of naphthoquinone derivatives.
Background technique
Quinones structure is present in many plants, microorganism and marine organisms and some insects, and in these organisms
Life process just play irreplaceable role.Due to the special structure of quinones structure and characteristic electron, a series of quinone
Analog derivative, especially amido or hydroxyl replace 1,4-naphthoquinone analog derivative show excellent anticancer, antibacterial, it is antiviral,
The bioactivity such as antiallergy and radicals scavenging, they show huge development potentiality in medicine or pesticide developing
[(a)Sunassee,S.N.；Davies-Coleman,M.T.Nat.Prod.Rep.2012,29,513.(b)Inks,E.S.；
Josey,B.J.；Jesinkey,S.R.；Chou,C.J.ACS Chem.Biol.2012,7,331.(c)Josey,B.J.；
Inks,E.S.；Wen,X.；Chou,C.J.J.Med.Chem.2013,56,1007.].In addition, quinones is in bio-sensing
Device (Piro, B.；Reisberg.S.；Anquetin,G.；Duc,H.-T.；Pham,M.-C.Biosensors,2013,3,
58.), energy storage material (Son, E.J.；Kim,J.H.；Kim,K.；Park,C.B.J.Mater.Chem.A.2016,4,11179.)
And organic fully synthetic [(a) Mfuh, A.M.；Zhang,Y.；Stephens,D.E.；Vo,A.X.T.；Arman,H.D.；
Larionov,O.V.J.Am.Chem.Soc.2015,137,8050.(b)Zhang,Z.；Chen,J.；Yang,Z.；Tang,
Y.Org.Lett.2010,12,5554.(c)Usui,I.；Lin,D.W.；Masuda,T.；Baran,
] etc. P.S.Org.Lett.2013,15,2080. fields also show higher application value.Therefore, develop such compound
Synthetic method have important value and significance.
However, under the requirement of current development Green Sustainable synthetic technology, it is existing about multiple functionalized quinones
There is also serious defects for the synthetic method of derivative: classical synthetic method will be first by paradimethoxybenzene class compound
It is functionalized, corresponding naphthoquinone derivatives is then oxidized in the presence of excessive strong oxidizer.Such methods need to expend
A large amount of manpower and material resources, the presence of strong oxidizer can also generate serious environmental problem, and such methods are not suitable for oxygen
Agent sensitivity functional group [(a) Guti é ttez-Bonet,Remeur,C.；Matsui,J.K.；Molander,
G.A.J.Am.Chem.Soc.2017,139,12251.(b)Galloway,J.D.；Mai,D.N.；Baxter,
R.D.Org.Lett.2017,19,5772.(c)Naturale,G.；Lamblin,M.；Commandeur,C.；Felpin,F.-
X.；Dessolin,J.Eur.J.Org.Chem.2012,5774.(d)Ilangovan,A.；Saravanakumar,S.；
Malayappasamy,S.Org.Lett.2013,15,4968.(e)Baral,E.R.；Kim,S.H.；Lee,Y.R.Asian
J.Org.Chem.2016,5,1134.(f)Devari,S.；Shah,B.A.Chem.Commun.2016,52,1490.(g)Li,
G.-X.；Morales-Rivera,C.A.；Wang,Y.；Gao,F.；He,G.；Liu,P.；Chen,G.Chem.Sci.2016,7,
6407.].In addition, in terms of developing new naphthoquinone derivatives synthetic technology, there are also problems: since quinones has oxidation
Property and stronger metal coordination, transition metal-catalyzed method it is usually and uncomfortable in the reaction that quinones participates in
With [(a) Jardim, G.A.M.；da Silva Júnior,E.N.；Bower,J.F.Chem.Sci.2016,7,3780.(b)
Fujiwara,Y.；Domingo,V.；Seiple,I.B.；Gian-atassio,R.；Del Bel,M.；Baran,
P.S.J.Am.Chem.Soc.2011,133,3292.]。
For alkene as a kind of large industrialization product, abundance is cheap, can be with using alkene as reaction raw materials
Synthesis cost is substantially reduced, alkene industrial expansion is pushed.To the carbon-to-carbon double bond of alkene directly carry out it is Bifunctionalized can be efficient
Synthesis there is polyfunctional compound, and be further used as the organic molecule of synthesis material preparation structure multiplicity, reaction efficiency
Height has obtained great concern in recent years and has developed [(a) Tian, Y.；Chen,S.；Gu,Q.-S.；Lin,J.-S.；Liu,X.-
Y.Tetrahedron Lett.2018,59,203.(b)Wu,Z.；Zhang,W.Chin.J.Org.Chem.2017,37,2250.
(c)Lan,X.-W.；Wang,N.-X.；Xing,Y.Eur.J.Org.Chem.2017,5821.(d)Yi,G.；Mu,X.；Liu,
G.Acc.Chem.Res.2016,49,2413.(e)Wu,K.；Liang,Y.；Jiao,N.Molecules,2016,21,352.
(f)Koike,T.；Akita,M.Org.Chem.Front.2016,1345.(g)Courant,T.；Masson,
G.J.Org.Chem.2016,81,6945.(h)Cao,M.-Y.；Ren,X.；Lu,Z.Tetrahedron,2015,56,3732.
(i)Shimizu,Y.；Kanai,M.Tetrahdedron,2014,55,3727.(j)Romero,R.M.；T.H.；K.Chem.Asian J.2014,9,972.(k)Egami,H.；Sodeoka,M.Angew.Chem.Int.Ed.2014,
53,8294.(l)Chemler,S.R.；Bovino, M.T.ACS Catal.2013,3,1076.] therefore., develops with alkene
To synthesize naphthoquinone derivatives, synthesized multiple functionalized naphthoquinone derivatives will be to medicine, pesticide, bio-sensing for Bifunctionalized reaction
The fields such as device, energy storage material generate impetus, will greatly improve combined coefficient, save production cost, reduce waste discharge,
With important science and economic value.
Summary of the invention
The object of the present invention is to provide a kind of new methods for the naphthoquinone derivatives that synthesis of alkyl carboxylate replaces.Present invention tool
There is raw material to be easy to get, easy to operate, the features such as reaction condition is mild, and reaction efficiency is high.
The 2- hydroxyl or 2- amino that the present invention is replaced by the Bifunctionalized synthesis of alkyl carboxylate of alkene replace quinones derivative
Object, under metal/ligand complex catalyzed, the quinones containing enamine (or enol) structure and alkene, alpha-halogenated carboxylic acids
Three component free radical tandem reactions occur for ester free radical reagent, realize a kind of new side for synthesizing multiple functionalized naphthoquinone derivatives
Method.
It is as follows that the 2- hydroxyl or 2- amino that alkyl carboxylic acid ester involved in the present invention replaces replace naphthoquinone derivatives to have
Structural formula:
In formula: R1, R2, R3, R4, R5, R6, R7, R8, R9, R10Containing in the C1~C40 such as H, alkyl and naphthenic base or not
The aromatic radical with or without functional groups such as N, S, O, P including the C7-C60 such as fat group, benzyl containing functional groups such as N, S, O, P
The aromatic group with or without functional groups such as N, S, O, P of group and fat-based combined in the C4-C60 such as group, aryl；X is selected from N
Or O；R1,R2It is also possible in C4-C60 member ring two groups with or without C, N, S, O, P.
2- hydroxyl involved in the present invention or 2- amino replace quinones to have the following structure formula:
In formula: R1, R2, R3, R4In the C1~C40 such as H, alkyl and naphthenic base with or without functional groups such as N, S, O, P
The C7-C60 such as fat group, benzyl including the aromatic group with or without functional groups such as N, S, O, P and fat-based combination
The aromatic group with or without functional groups such as N, S, O, P, R in the C4-C60 such as group, aryl1,R2It is also possible to C4-C60 member ring
In two groups with or without C, N, S, O, P；X is selected from N or O；.
Alkene involved in the present invention has the following structure formula:
In formula: R5, R6, R7, R8In the C1~C40 such as H, alkyl and naphthenic base with or without functional groups such as N, S, O, P
The C7-C60 such as fat group, benzyl including the aromatic group with or without functional groups such as N, S, O, P and fat-based combination
The aromatic group with or without functional groups such as N, S, O, P in the C4-C60 such as group, aryl；In addition, double bond is also possible to C3-
C60 cyclic olefinic bond, R5, R6, R7, R8For the group with or without C, N, S, O, P in the substituent group or ring of ring.
Alpha-halogenated carboxylic acids ester involved in the present invention has the following structure formula:
In formula: R9,R10The fat with or without functional groups such as N, S, O, P in the C1~C40 such as alkyl and naphthenic base
Combination group, the virtue of the aromatic group with or without functional groups such as N, S, O, P including the C7-C60 such as group, benzyl and fat-based
The aromatic group with or without functional groups such as N, S, O, P in the C4-C60 such as base；Y is Cl, Br or I；In addition, R9It can also be H
Or F.
For the purpose for realizing compound described in composite structure Formulas I, the present invention is with the complex that metal salt and ligand are formed
Catalyst, reaction equation are as follows:
Reaction condition is as follows:
The proportion of reaction raw materials is that compound III is 1 equivalent (mol), and compound II and IV is relative to compound III mistake
Amount.Optimal proportion is II:III:IV=1.2:1:1.2.
Temperature: -78 DEG C -200 DEG C, preferable reaction temperature is at -75 DEG C of room temperature.
Solvent: polar solvent, preferably ethyl alcohol, methanol, n,N-Dimethylformamide.The dosage of solvent will make compound
The concentration of III is 0-50mol/L, is preferably 0.1mol/L.
Alkali: mainly inorganic base, preferably potassium carbonate, potassium phosphate.The dosage of alkali is the 0-100 equivalent of compound III, excellent
It is selected as 1.2 equivalents.
Pressure: 0-100 atmospheric pressure, preferably normal pressure.
Time: > 0.1 hour, preferred reaction time was 12 hours.
The metal salt catalyst includes various mantoquitas, silver salt, molysite.Mantoquita includes but is not limited to be hydrated copper acetate, water
Close copper sulphate, Salicylaldoxime, anhydrous cupric sulfate, trifluoromethanesulfonic acid ketone, copper chloride, cuprous acetate, stannous chloride, iodate Asia
Copper, perchloric acid are cuprous, the sub- ketone of trifluoromethanesulfonic acid etc., preferably hydration copper acetate, trifluoromethanesulfonic acid ketone.Silver salt mainly includes but not
It is limited to silver acetate, silver nitrate, silver carbonate, silver oxide, silver trifluoromethanesulfonate, Silver hexafluorophosphate, silver hexafluoroantimonate etc..Molysite includes
But it is not limited to ferric trichloride, ferric bromide, ferric sulfate, ferric nitrate, frerrous chloride, ferrous perchlorate, frerrous chloride, oxalic acid Asia
Iron, ferrocene etc..The dosage of metal salt is the 0-1 equivalent of compound III, preferably 0.1 equivalent.
The ligand includes but is not limited to various Phosphine ligands, nitrogen ligand, phosphine-nitrogen ligand etc..Such as triphenylphosphine, BINAP (L-
1), DPPF (L-2), DPPE (L-3), DPPP (L-4), DPPB (L-5), 2.2 '-bipyridyls (L-6), 1,10- Phen (L-
7) etc..The dosage of ligand is the 0-100 equivalent of metal, preferably 1 equivalent.
The invention has the following advantages that
1. reactivity is high, reaction condition is mild.Product can obtain alkyl carboxylic acid ester through simple post separation in high yield
Substituted naphthoquinone derivatives.
2. starting material alkene, quinones are cheap and easy to get.
3. catalyst is cheap and easy to get, dosage is few.
Compare traditional method, reaction step can be greatly reduced, avoided using strong oxidizer, to reduce labour
Consumption reduces waste discharge, improves combined coefficient and finished product yield.
Specific embodiment
The present invention is described in detail below by embodiment, but the present invention is not limited to the following embodiments:
Embodiment 1CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-1
Reaction flask containing stirrer is vacuumized, nitrogen is replaced.Claim that compound II-1 is added in reaction flask
(0.24mmol, 59.8mg), III-1 (0.2mmol, 23.6mg), IV-1 (0.24mmol, 56.8mg), CuCl (0.02mmol,
2.0mg),DPPF(0.02mmol,11.1mg),K2CO32mL ethyl alcohol is then added in (0.24mmol, 33.2mg).Reaction flask is set
Enter and is stirred overnight in 75 DEG C of oil bath.Reaction system is spin-dried for, residue carries out column chromatography, and (eluant, eluent is petroleum ether/acetic acid second
Ester=15/1), obtain target product I-1, red solid, yield 80%.1H NMR(300MHz,CDCl3): δ 8.15 (dd, J=
7.7,1.4Hz, 1H), 8.04 (dd, J=7.6,1.4Hz, 1H), 7.74 (td, J=7.6,1.4Hz, 1H), 7.64 (td, J=
7.5,1.4Hz, 1H), 7.29 (s, 1H), 7.23-6.96 (m, 8H), 6.82-6.90 (m, 2H), 4.01 (dd, J=8.3,
4.6Hz, 1H), 3.80-3.52 (m, 2H), 2.63 (dd, J=14.6,8.3Hz, 1H), 2.37 (dd, J=14.5,4.7Hz,
1H),1.10(s,3H),1.07–0.94(m,6H).HRMS calcd.for C30H30NO4[M+H]+:468.2619,found:
468.2617。
Embodiment 2: with BINAP (L-1) ligand replacement DPPF (L-2), remaining obtains compound I-1 with embodiment 1,
76% yield.
Embodiment 3: ligand DPPF (L-2) is replaced with 2,2 '-bipyridyls (L-6), remaining obtains compound with embodiment 1
I-1,78% yield.
Embodiment 4: ligand DPPF (L-2) is replaced with 1,10- Phen (L-7), remaining obtains chemical combination with embodiment 1
Object I-1,78% yield.
Embodiment 5: CuCl is replaced with AgOAc, remaining obtains compound I-1,77% yield with embodiment 1.
Embodiment 6: changing CuCl with CuOAc, remaining obtains compound I-1,75% yield with embodiment 1.
Embodiment 7: FeCl is used2CuCl is changed, remaining obtains compound I-1,61% yield with embodiment 1.
Embodiment 8: replacing ethyl alcohol with n,N-Dimethylformamide, remaining obtains compound I-1 with embodiment 1, and 72% receives
Rate.
Embodiment 9: replacing potassium carbonate with potassium phosphate, remaining obtains compound I-1,70% yield with embodiment 1.
Catalyst amount: being increased to 0.2 equivalent of compound III by embodiment 10, remaining obtains chemical combination with embodiment 1
Object I-1,78% yield.
Embodiment 11: ethyl alcohol is replaced with methanol, remaining obtains compound I ' -2,73% yield with embodiment 1.1H NMR
(300MHz,CDCl3): δ 8.13 (dd, J=7.7,1.4Hz, 1H), 8.03 (dd, J=7.6,1.4Hz, 1H), 7.74 (td, J=
7.6,1.4Hz, 1H), 7.64 (td, J=7.5,1.4Hz, 1H), 7.38 (s, 1H), 7.22-6.95 (m, 8H), 6.82-6.90
(m, 2H), 4.02 (dd, J=8.3,4.6Hz, 1H), 3.25 (s, 3H), 2.56 (dd, J=14.6,8.3Hz, 1H), 2.41 (dd,
J=14.5,4.7Hz, 1H), 1.11 (s, 3H), 0.99 (s, 3H) .HRMS calcd.for C29H28NO4[M+H]+:
454.2013,found:454.2013。
Embodiment 12:CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-2
Alkene III-1 in embodiment 1 is replaced with alkene III-2, remaining is the same as embodiment 1.Reaction obtains compound I-
2.Red solid, yield 73%.1H NMR(300MHz,CDCl3) δ 8.14 (dd, J=7.7,1.3Hz, 1H), 8.06 (dd, J=
7.6,1.4Hz, 1H), 7.75 (td, J=7.5,1.4Hz, 1H), 7.66 (td, J=7.5,1.4Hz, 1H), 7.43 (s, 1H),
7.17-7.02 (m, 5H), 7.02-6.92 (m, 2H), 6.92-6.80 (m, 2H), 3.81 (dt, J=9.5,4.8Hz, 1H),
3.76-3.49 (m, 2H), 2.60 (dd, J=14.6,8.3Hz, 1H), 2.27 (dd, J=14.7,4.6Hz, 1H), 1.07 (s,
3H),1.06–0.96(m,6H).HRMS calcd.for C30H29ClNO4[M+H]+:502.1780,found:502.1781。
Embodiment 13:CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-3
Alkene III-1 in embodiment 1 is replaced with alkene III-3, remaining is the same as embodiment 1.Reaction obtains compound I-
3.Red solid, yield 80%.1H NMR(300MHz,CDCl3) δ 8.14 (dd, J=7.7,1.4Hz, 1H), 8.06 (dd, J=
7.6,1.4Hz, 1H), 7.75 (td, J=7.6,1.5Hz, 1H), 7.66 (td, J=7.5,1.4Hz, 1H), 7.44 (s, 1H),
7.31–7.23(m,2H),7.12–7.01(m,3H),6.96–6.84(m,4H),3.86–3.77(m,1H),3.77–3.51(m,
2H), 2.60 (dd, J=14.7,8.3Hz, 1H), 2.26 (dd, J=14.6,4.6Hz, 1H), 1.07 (s, 3H), 1.05-0.94
(m,6H).HRMS calcd.for C30H29BrNO4[M+H]+:546.1274,found:546.1275。
Embodiment 14:CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-4
Compound III-1 in embodiment 1 is replaced with compound III-4, remaining is the same as embodiment 1.Reaction obtains chemical combination
Object I-4.Red solid, yield 70%.1H NMR(300MHz,CDCl3) δ 8.16 (dd, J=7.8,1.3Hz, 1H), 8.05 (dd,
J=7.6,1.4Hz, 1H), 7.75 (td, J=7.5,1.5Hz, 1H), 7.66 (td, J=7.5,1.4Hz, 1H), 7.29 (d, J=
2.6Hz, 1H), 7.13 (dd, J=8.3,6.6Hz, 2H), 7.08-6.98 (m, 3H), 6.91 (dd, J=7.6,1.8Hz, 2H),
6.83-6.68 (m, 2H), 3.98 (dd, J=8.0,5.1Hz, 1H), 3.78 (s, 3H), 3.77-3.54 (m, 2H), 2.58 (dd, J
=14.5,8.0Hz, 1H), 2.41 (dd, J=14.5,5.1Hz, 1H), 1.11 (s, 3H), 1.05 (t, J=7.1Hz, 3H),
1.01(s,3H).HRMS calcd.for C31H32NO4[M+H]+:498.2275,found:498.2274。
Embodiment 15:CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-5
Alkene III-1 in embodiment 1 is replaced with alkene III-5, remaining is the same as embodiment 1.Reaction obtains compound I-
5.Red solid, yield 67%.1H NMR(300MHz,CDCl3) δ 8.10-8.05 (m, 2H), 7.74 (td, J=7.5,1.4Hz,
1H), 7.65 (td, J=7.5,1.4Hz, 1H), 7.43-7.35 (m, 3H), 7.32-7.19 (m, 3H), 7.19-7.09 (m, 3H),
7.09-7.01(m,2H),3.77–3.51(m,2H),2.84-2.14(m,5H),1.82-1.56(m,2H),1.05(s,3H),
1.04–0.93(m,6H).HRMS calcd.for C32H34NO4[M+H]+:496.2482,found:496.2479。
Embodiment 16:.CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-6
Alkene III-1 in embodiment 1 is replaced with alkene III-6, remaining is the same as embodiment 1.Reaction obtains compound I-
6.Red solid, yield 75%.1H NMR(300MHz,CDCl3) δ 8.14-8.08 (m, 2H), 7.76 (td, J=7.6,1.5Hz,
1H), 7.66 (td, J=7.5,1.4Hz, 1H), 7.61 (br, 1H), 7.33-7.16 (m, 3H), 7.16-7.07 (m, 3H), 6.83
(dd, J=5.2,3.5Hz, 1H), 6.52 (dt, J=3.5,1.1Hz, 1H), 4.02 (m, 1H), 3.80-3.52 (m, 2H), 2.64
(dd, J=14.6,8.3Hz, 1H), 2.38 (dd, J=14.5,4.7Hz, 1H), 1.11 (s, 3H), 1.06-0.93 (m, 6H)
.HRMS calcd.for C28H28NSO4[M+H]+:474.1734,found:474.1734。
Embodiment 17:CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-7
The derivative I I-2 of the derivative I I-1 quinone of quinone in embodiment 1 is replaced, remaining is the same as embodiment 1.It reacts
To compound I-7.Red solid, yield 75%.1H NMR(300MHz,CDCl3)δ8.03-8.11(m,2H),7.64-7.70
(m, 2H), 7.14-7.38 (m, 5H), 5.95 (m, 1H), 3.99 (m, 1H), 3.78-3.50 (m, 4H), 2.60 (dd, J=14.7,
8.3Hz, 1H), 2.26 (dd, J=14.6,4.6Hz, 1H), 1.75-1.56 (m, 2H), 1.41-1.18 (m, 6H), 1.11 (s,
3H),1.09-0.89(m,9H).HRMS calcd.for C30H38NO4[M+H]+:476.2795,found:476.2791。
Embodiment 18:CuCl and DPPF catalysis reaction generate 1,4- naphthoquinone derivatives I-8
The derivative I I-3 of the derivative I I-1 quinone of quinone in embodiment 1 is replaced, remaining is the same as embodiment 1.It reacts
To compound I-8.Red solid, yield 75%.1H NMR(300MHz,CDCl3)δ8.03-8.11(m,2H),7.64-7.70
(m, 2H), 7.14-7.38 (m, 5H), 4.78 (m, 1H), 3.82-3.50 (m, 2H), 2.81 (dd, J=14.7,8.3Hz, 1H),
2.40 (dd, J=14.6,4.6Hz, 1H), 1.12 (s, 3H), 1.06-0.96 (m, 6H) .HRMS calcd.for C24H25O5[M+
H]+:393.1697,found:393.1695。
Embodiment 19-32: the applicability of reaction substrate
The present invention has extensive substrate applicability, according to the reaction condition in embodiment 1, has various structures and electronics
The quinones substrate and olefin substrate of property can successfully be reacted, and the naphthoquinone derivatives that alkyl carboxylic acid ester replaces are generated,
It is shown in Table 1.
Table 1: embodiment 19-32
The present invention can be efficiently synthesized the naphthoquinone derivatives of alkyl carboxylic acid ester's substitution, product by three component reaction of a step
Separation yield be up to 81%.The present invention is avoided using strong oxidizer, and is easy to get with reaction raw materials, easy to operate, reacts item
The features such as part is mild, and reaction efficiency is high.This method is applied to the derivatization of multiple biological activities molecule in which can be convenient.
Claims (8)
1. a kind of method for the naphthoquinone derivatives that synthesis of alkyl carboxylate replaces, it is characterised in that: in metal salt and ligand catalysis
Under, replace quinones, alkene and alpha-halogenated carboxylic acids ester as raw material using 2- hydroxyl or 2- amino, one-step synthesis of alkyl carboxylic acid
The 2- hydroxyl or 2- amino that ester replaces replace naphthoquinone derivatives.
2. according to the method described in claim 1, it is characterized by: metal salt is one of silver, copper or various metal salts of iron；Match
Body is one of various Phosphine ligands, nitrogen ligand or phosphine-nitrogen ligand, and the molar ratio of metal salt and ligand is between 1:10 to 10:1.
3. according to the method described in claim 1, it is characterized by: reaction dissolvent be various polar solvents, such as methanol, ethyl alcohol,
N,N-dimethylformamide.
4. according to the method described in claim 1, it is characterized by: 2- hydroxyl or 2- amino that the alkyl carboxylic acid ester replaces
Naphthoquinone derivatives are replaced to have the following structure formula:
In formula: R1, R2, R3, R4, R5, R6, R7, R8, R9, R10In the C1~C40 such as H, alkyl and naphthenic base with or without N,
S, the aromatic group with or without functional groups such as N, S, O, P including the C7-C60 such as fat group, benzyl of the functional groups such as O, P with
The aromatic group with or without functional groups such as N, S, O, P of fat-based combined in the C4-C60 such as group, aryl；X is selected from N or O；
R1,R2It is also possible in C4-C60 member ring two groups with or without C, N, S, O, P.
5. according to the method described in claim 1, it is characterized by: the 2- hydroxyl or 2- amino replace quinones tool
Just like flowering structure formula:
In formula: R1, R2, R3, R4The rouge with or without functional groups such as N, S, O, P in the C1~C40 such as H, alkyl and naphthenic base
The aromatic group with or without functional groups such as N, S, O, P including the C7-C60 such as fat group, benzyl and the combination group of fat-based,
The aromatic group with or without functional groups such as N, S, O, P, R in the C4-C60 such as aryl1,R2It is also possible to contain in C4-C60 member ring
Or two groups without C, N, S, O, P；X is selected from N or O；.
6. according to the method described in claim 1, it is characterized by: the alkene has the following structure formula:
In formula: R5, R6, R7, R8The rouge with or without functional groups such as N, S, O, P in the C1~C40 such as H, alkyl and naphthenic base
The aromatic group with or without functional groups such as N, S, O, P including the C7-C60 such as fat group, benzyl and the combination group of fat-based,
The aromatic group with or without functional groups such as N, S, O, P in the C4-C60 such as aryl；In addition, double bond is also possible in C3-C60 ring
Double bond, R5, R6, R7, R8For the group with or without C, N, S, O, P in the substituent group or ring of ring.
7. according to the method described in claim 1, it is characterized by: the alpha-halogenated carboxylic acids ester has the following structure formula:
In formula: R9,R10The fat group with or without functional groups such as N, S, O, P in the C1~C40 such as alkyl and naphthenic base,
The aromatic group with or without functional groups such as N, S, O, P including the C7-C60 such as benzyl and the combination group of fat-based, aryl etc.
The aromatic group with or without functional groups such as N, S, O, P in C4-C60；Y is Cl, Br or I；In addition, R9It can also be H or F.
8. a kind of 2- hydroxyl that the alkyl carboxylic acid ester of the synthesis of method described in one of -7 according to claim 1 replaces or 2- amino take
For naphthoquinone derivatives.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114685295A (en) * | 2020-12-25 | 2022-07-01 | 信阳师范学院 | Polyfluoroalkyl-containing 2-amino-1, 4-naphthoquinone compound and preparation method thereof |
| CN114702400A (en) * | 2022-04-27 | 2022-07-05 | 信阳师范学院 | 3-trifluoromethylalkenyl-2-phenylamino-1, 4-naphthoquinone compound and preparation method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114685295A (en) * | 2020-12-25 | 2022-07-01 | 信阳师范学院 | Polyfluoroalkyl-containing 2-amino-1, 4-naphthoquinone compound and preparation method thereof |
| CN114702400A (en) * | 2022-04-27 | 2022-07-05 | 信阳师范学院 | 3-trifluoromethylalkenyl-2-phenylamino-1, 4-naphthoquinone compound and preparation method thereof |
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