CN103864831A - Aromatic boric acid ester compound and synthetic method thereof - Google Patents
Aromatic boric acid ester compound and synthetic method thereof Download PDFInfo
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Abstract
The invention relates to boric acid ester compounds, and particularly relates to an aromatic boric acid ester compound and a synthetic method thereof, belonging to the technical field of organic synthesis. The synthetic method comprises the steps: under protection of inert gases or nitrogen gas, adding 1,3-disubstituted aromatic compounds in an anhydrous organic solvent at minus 70 DEG C-minus 90 DEG C, then sequentially adding TMEDA (tetramethylethylenediamine) and DIPA (diisopropanolamine), and stirring for 5-15 minutes; adding lithium base in the system, reacting for one to two hours, then adding an electrophilic reagent, and heating to 20-30DEG C, wherein the electrophilic reagent is i-PrOBPin or (Bpin)2. The prepared target compound is high in isomer selectivity, convenient to separate, and high in product yield, the aromatic boric acid ester compound is a potential bioactive molecule intermediate, and can be synthesized into pyrimidine derivatives which can be used as a herbicide for use, the synthetic method is simple in synthetic technique, mild in reaction conditions, economic and easily available in raw materials, low in preparation cost, and green and environment-friendly.
Description
Technical field
The present invention relates to boric acid ester compound, particularly a kind of areneboronic acid ester compound and synthetic method thereof, belong to technical field of organic synthesis.
Background technology
The range of application of boric acid ester compound is very extensive, not only can be used as polymeric additive, and gasoline dope, disinfectant, fire retardant use, and also play an important role in pharmaceutical chemistry field.Boric acid ester compound structural unit is present in bioactive molecules, sees document:
[1]Jana,R.;Pathak,T.P.;Sigman,M.S.Chem.Rev.2011,111,1417.
[2]Boronic?Acids:Preparation?and?Applications?in?Organic?Synthesis?and?Medicine(Eds.:D.G.Hall),Wiley-VCH,Weinheim,2005.
[3]Suzuki,A.Angew.Chem.2011,123,6854.
[4] N.Miyaura, A.Suzuki.Chem.Rev.1995,95,2457 report.
Although the Application Areas of boric acid ester compound is very wide, its preparation method is very limited, and existing preparation method adopts heavy metal catalyst, and not only low, the separation difficulty of yield, and synthesis step complexity, is shown in document
[5]Maderna?A.;Pritzkow?H.;Siebert?W.Angew.Chem.1996,108,1664.
[6]Okada?H.,K.;Kawashima?S.;Tanino?K.;Ohshita?J.Chem.Commun.2010,46,1763
[7] Yoshida H.; Kawashima S.; Takemoto Y.; Okada K.; Ohshita J.; Takaki K.Angew.Chem.2012,124,239 report.
And for the preparation of fragrant boric acid ester compound participating in without metal, have not yet to see all reports.Because the synthetic field of medicine and environmental science have the requirement of the feature of environmental protection to the synthetic isomer selectivity of organic molecule now, so the preparation method of above-mentioned areneboronic acid ester compound exists universality defect, can not meet the needs of relevant field development.
Summary of the invention
The object of this invention is to provide a kind of areneboronic acid ester compound, the isomer selectivity of this target compound is high, be convenient to separate, yield is high, is conducive to industrializing implementation.
Another object of the present invention is to provide the synthetic method of above-mentioned areneboronic acid ester compound, this synthesis technique is simple, synthesis condition Wen He ﹑ raw material economics be easy to get.
The present invention seeks to be achieved through the following technical solutions.
A kind of areneboronic acid ester compound, is characterized in that: its general structure is suc as formula shown in I or II,
Wherein, R1, R2 is halogen, halohydrocarbon or alkoxyl group, Bpin is
In the structural formula of described areneboronic acid ester compound, R1 is F, Cl, C1～C4 alkoxyl group or trifluoromethyl, and R2 is F, Cl, trifluoromethyl, C1～C4 alkoxyl group.
R1=F in structural formula I, R2=F, trifluoromethyl, C1～C4 alkoxyl group; R1=Cl, R2=Cl, C1～C4 alkoxyl group; R1=C1～C4 alkoxyl group, R2=trifluoromethyl;
R1=Cl or trifluoromethyl in structural formula II, R2=trifluoromethyl.
Described areneboronic acid ester compound is with one of compound in following formula:
The synthetic method of above-mentioned areneboronic acid ester compound, is characterized in that, step comprises:
1), under-70～-80 DEG C, nitrogen or protection of inert gas, in anhydrous organic solvent, add suc as formula 1,3 di-substituted aryl hydrocarbon shown in III, then add successively TMEDA, DIPA, stir 5-15 minute; Add lithium alkali in system after, react 1-2 hour, then add electrophilic reagent, be warming up to 20-30 DEG C;
R1 in formula III is F, Cl, C1～C4 alkoxyl group or trifluoromethyl, and R2 is F, Cl, trifluoromethyl, C1～C4 alkoxyl group.
Described electrophilic reagent is Virahol tetramethyl ethylene ketone boric acid ester or connection boric acid pinacol ester;
Described boric acid pinacol ester [(Bpin)
2], its structural formula as shown in IV,
Shown in Virahol tetramethyl ethylene ketone boric acid ester (i-PrOBPin), its structural formula as shown in V,
2) in the reaction system, in step (1), add saturated ammonium chloride solution to carry out cancellation reaction, extraction, dry, separation.
In described step (1), the add-on proportioning of anhydrous organic solvent, 1,3 di-substituted aryl hydrocarbon, TMEDA and DIPA is 2-5mL:1mmol:1-2mmol:0.05mmol.
In described step (1), the mol ratio of 1,3 di-substituted aryl hydrocarbon, lithium alkali and electrophilic reagent is 1:1-1.5:1.
Anhydrous organic solvent in described step (1) is anhydrous tetrahydro furan, and lithium alkali is n-Butyl Lithium.
In described step (2), extraction agent is ethyl acetate, and the add-on of extraction agent and 1,3 di-substituted aryl hydrocarbon is than being 7-15mL:1mmol; The saturated ammonium chloride solution adding in reaction system and the volume of anhydrous organic solvent are 1-2:1.
Described 1,3 di-substituted aryl hydrocarbon is the one in m-difluorobenzene, three fluorochlorobenzenes, a fluoride trifluoro toluene, meta-methoxy methyl ether fluorobenzene, meta-methoxy benzene fluorine, Meta Dichlorobenzene, meta-methoxy chlorobenzene, meta-methoxy methyl ether chlorobenzene, m-trifluoromethyl anisole, meta-chlorobenzotrifluoride, two-phenylfluoroform.
Gained target product, except meta-chlorobenzotrifluoride, two substrates of two-phenylfluoroform, due to sterically hindered reason, obtains the target product at ortho position, the target product of position between other products are.
Areneboronic acid ester compound prepared by the present invention, is a kind of potential bioactive molecules pharmaceutical intermediate, can be used as important intermediate and is used for synthesizing boric acid compound, for substituted arene especially substituted benzene ring being added to the molecule of target compound.
Beneficial effect of the present invention: the target compound isomer selectivity that 1, the present invention prepares is high, be convenient to separation, product yield also far away higher than prior art, be conducive to industrializing implementation, described areneboronic acid ester compound is a kind of potential bioactive molecules intermediate, can synthesize pyrimidine derivatives, this pyrimidine derivatives can be used as weedicide and uses.2, this synthesis technique is simple, and reaction conditions gentleness, is easy to get at raw material economics, and preparation cost is low, and does not adopt heavy metal as catalyzer in synthetic, environmental protection.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with specific embodiment.
Embodiment 1:
The preparation of compound 1b
At the temperature of-78 DEG C, reaction system is done Non-aqueous processing, inflated with nitrogen protection, get anhydrous THF10mL, add the substrate m-difluorobenzene of 3mmol, then add successively the TMEDA(Tetramethyl Ethylene Diamine of 3.3mmol), the DIPA(2 of 0.15mmol, 6-diisopropyl aniline), magnetic agitation 10 minutes, add the n-Butyl Lithium of 3.6mmol, at being-78 DEG C, temperature of reaction reacts 1.5 hours, add the electrophilic reagent Virahol tetramethyl ethylene ketone boric acid ester (i-PrOBPin) of 3mmol, slowly rise to 25 DEG C, in reaction system, add 10mL saturated ammonium chloride solution to carry out cancellation reaction, with the ethyl acetate of 30mL the most extraction agent extract, coextraction 3 times, organic phase is with after anhydrous magnesium sulfate drying, decompression is lower to desolventizing, with the separation of ethyl acetate/petroleum ether post, obtain target compound 1b, yield is 67%.
The characterization data of compound 1b:
Target compound is yellow solid, and fusing point is 50.1-51.8 DEG C.
1H?NMR(400MH
z,CDCl
3)δ,7.38(m,1H),6.86(t,J=8.0Hz,2H),1.41(s,12H),
13C?NMR(100MHz,CDCl
3)δ167.8,165.3,133.1,111.1,84.3,77.0,24.8,
19FNMR(376MHz,CDCl
3)δ,-100.7.HR-MS(ESI)C
12H
16BF
2O
2[M+H]
+calcd.241.1133,found241.1211.
Embodiment 2
The preparation of compound 2b
Substrate m-difluorobenzene in embodiment 1 is replaced to three fluorochlorobenzenes, and other raw materials and reaction conditions are all constant, obtain target compound 2b, and yield is 69%.
The characterization data of compound 2b:
Target compound is yellow solid, and fusing point is 68.3-69.6 DEG C.
1H?NMR(400MHz,CDCl
3):δ7.29(m,1H),7.15(d,J=8.0Hz,1H),6.94(t,J=8.0Hz,1H)1.43(s,12H),
13C?NMR(100MHz,CDCl
3)δ166.7,164.2,138.4,131.9,124.7,113.2,84.8,77.0,24.7
19F?NMR(376MHz,CDCl
3)δ-102.6.HRMS(ESI)C
12H
16BClFO
2.[M+H]
+calcd.257.0838,found257.0895.
Embodiment 3
The preparation of compound 3b
Substrate m-difluorobenzene in embodiment 1 is replaced to a fluoride trifluoro toluene, and other raw materials and reaction conditions are all constant, obtain target compound 3b, and yield is 57%.
The characterization data of compound 3b:
Target compound is yellow oil.
1H?NMR(400MHz,CDCl
3)δ7.47(m,2H),7.22(d,J=8.0Hz,H),1.42(s,12H),
13C?NMR(100MHz,CDCl3)δ131.54,131.45,121.26,118.36,118.12,85.07,24.63.
19F?NMR(376MHz,CDCl3)δ-59.94(3F),-103.1(F).HRMS(ESI)C
13H
16BF
4O
2[M+H]
+calcd.291.1101,found291.1168.
Embodiment 4
The preparation of compound 4b
Substrate m-difluorobenzene in embodiment 1 is replaced to meta-methoxy methyl ether fluorobenzene, and other raw materials and reaction conditions are all constant, obtain target compound 4b, and yield is 52%.
The characterization data of compound 4b:
Target compound is yellow solid, and fusing point is 96.3-97.2 DEG C.
1H?NMR(400MHz,CDCl
3)δ7.27(m,1H),6.82(d,J=8.4Hz,1H),6.70(t,J=8.0Hz,1H),5.18(s,2H),3.49(s,3H),1.40(s,12H),
13C?NMR(100MHz,CDCl
3)δ167.4,164.9,161.3,161.2,132.1,109.6,94.6,83.5,77.0,56.6,25.0.
19F?NMR(376MHz,CDCl
3)δ-103.88.EI-MS:m/z=281.87(20%).
Embodiment 5
The preparation of compound 5b
Substrate m-difluorobenzene in embodiment 1 is replaced to meta-methoxy benzene fluorine, and other raw materials and reaction conditions are all constant, obtain target compound 5b, and yield is 63%.
The characterization data of compound 5b:
Target compound is yellow solid, and fusing point is 68.6-70.1 DEG C.
1H?NMR(400MHz,CDCl
3):δ/ppm,7.29(m,1H),6.64(m,2H),1.41(s,12H),
13CNMR(100MHz,CDCl
3):δ/ppm,167.5,165.1,164.0,132.1,107.7,105.8,84.1,77.0,56.0,24.7.
19F?NMR(376MHz,CDCl
3)δ-104.17.HRMS(ESI)C
13H
19BFO
3[M+H]
+calcd.253.1333,found253.1400.
Embodiment 6
The preparation of compound 6b
Substrate m-difluorobenzene in embodiment 1 is replaced to Meta Dichlorobenzene, and other raw materials and reaction conditions are all constant, obtain target compound 6b, and yield is 68%.
The characterization data of compound 6b:
Target compound is yellow solid, and fusing point is 78.5-79.6 DEG C.
1H?NMR(400MHz,CDCl
3)δ7.24(s,3H),1.45(s,12H),
13C?NMR(100MHz,CDCl
3)δ138.1,131.2,126.8,85.0,77.0,24.8.ESI-MS:[M+Na]
+,295.1.HRMS(ESI)C
12H
16BCl
2O
2[M+H]
+calcd.273.0542,found273.0610.
Embodiment 7
The preparation of compound 7b
Substrate m-difluorobenzene in embodiment 1 is replaced to meta-methoxy chlorobenzene, and other raw materials and reaction conditions are all constant, obtain target compound 6b, and yield is 64%.
The characterization data of compound 7b:
Target compound is yellow solid, and fusing point is 78.4-79.7 DEG C.
1H?NMR(400MHz,CDCl
3)δ7.23(d,J=8.0Hz,1H),6.93(d,J=8.0Hz,1H),6.72(d,J=8.4Hz,1H),3.8(s,3H),1.42(s,12H),
13C?NMR(100MHz,CDCl
3)δ163.1,137.8,132.6,131.3,121.2,108.0,84.4,77.0,55.8,24.7.HRMS(ESI)C
13H
19BClO
3[M+H]
+calcd.269.1038,found269.1101.
Embodiment 8
The preparation of compound 8b
Substrate m-difluorobenzene in embodiment 1 is replaced to: meta-methoxy methyl ether chlorobenzene, other raw materials and reaction conditions are all constant, obtain target compound 8b, and yield is 53%.
The characterization data of compound 8b:
Target compound is yellow solid, and fusing point is 100.6-101.3 DEG C.
1H?NMR(400MHz,CDCl
3)δ7.22(t,J=8.0Hz,1H),6.98(d,J=8.0Hz,1H),6.93(d,J=8.4Hz,1H),5.16(s,2H),3.48(s,3H),1.42(s,12H),
13C?NMR(100MHz,CDCl
3)δ160.4,137.7,131.2,122.2,111.6,94.3,77.0,56.1,29.7,24.7.EI-MS:m/z=297.83(20%).
Embodiment 9
The preparation of compound 9b
Substrate m-difluorobenzene in embodiment 1 is replaced to m-trifluoromethyl anisole, and other raw materials and reaction conditions are all constant, obtain target compound 9b, and yield is 55%.
The characterization data of compound 9b:
Target compound is yellow oil.
1H?NMR(400MHz,CDCl
3)δ7.43(t,J=8.0Hz,1H),7.22(d,J=8.0Hz,1H),7.00(d,J=8.0Hz,1H),3.85(s,3H),1.41(s,12H),
13C?NMR(100MHz,CDCl
3)δ24.6,55.9,77.0,84.5,112.9,117.7,130.8,134.4,162.7.
19F?NMR(376MHz,CDCl3)δ-63.24.HRMS(ESI)C
14H
19BF
3O
3[M+H]
+calcd.303.1301,found303.1365.
Embodiment 10
The preparation of compound 10c
Substrate m-difluorobenzene in embodiment 1 is replaced to meta-chlorobenzotrifluoride, and other raw materials and reaction conditions are all constant, obtain target compound 10c, and yield is 56%.
The characterization data of compound 10c:
Target compound is yellow oil.
1H?NMR(400MHz,CDCl3)δ7.82(d,J=7.6Hz,1H),7.63(s,1H),7.50(d,J=7.6Hz,1H),1.40(s,12H),13C?NMR(100MHz,CDCl3)δ140.1,136.8,133.9,133.5,126.1,122.4,84.6,77.0,24.8.19F?NMR(376MHz,CDCl3)δ-63.21.ESI-MS:[M+H]+,306.9.
By areneboronic acid ester compound (10c) synthetic in the present embodiment, synthetic pyrimidine derivatives, this derivative is suc as formula shown in VII, and concrete operation step is as follows:
Under nitrogen protection, in organic solvent DMF, add suc as formula shown in pyrimidines V I, then add successively alkali CsF(1eq.); Catalyst P d(dppf) Cl
2(0.001%eq.), in system, add areneboronic acid ester compound 10c(1.5eq. synthetic in the present embodiment) after, back flow reaction 1 hour, cooling process.Chromatographic column separates, the target compound VII that just can arrive, and this pyrimidines can be used as weedicide and uses.
Embodiment 11
The preparation of compound 11c
Two-phenylfluoroform between substrate m-difluorobenzene in embodiment 1 is replaced to, other raw materials and reaction conditions are all constant, obtain target compound 11c, and yield is 59%.
The characterization data of compound 11c:
Target compound is yellow oil.
1H?NMR(400MHz,CDCl3)δ7.93(s,1H),7.89(d,J=8.0Hz,1H),7.79(d,J=8.0Hz,1H),1.40(s,12H),13C?NMR(100MHz,CDCl3)δ24.6,77.0,85.0,122.2,124.9,127.3,132.2,134.7,135.5.19F?NMR(376MHz,CDCl3)δ-60.13,-63.27.ESI-MS:[M+Na]+,363.1.
By areneboronic acid ester compound (11c) synthetic in the present embodiment, synthetic pyrimidine derivatives, this derivative is suc as formula shown in VIII, and concrete operation step is as follows:
Under nitrogen protection, in organic solvent DMF, add suc as formula shown in pyrimidines V I, then add successively alkali CsF(1eq.); Catalyst P d(dppf) Cl
2(0.001%eq.), in system, add areneboronic acid ester compound 11c(1.5eq. synthetic in the present embodiment) after, back flow reaction 1 hour, cooling process.Chromatographic column separates, the target compound VIII that just can arrive, and this pyrimidines can be used as weedicide and uses.
Embodiment 12
The preparation of compound 1b
Electrophilic reagent i-PrOBPin in embodiment 1 is replaced with to (Bpin) 2, and other raw materials and reaction conditions are all constant, obtain target compound 1b, and yield is 43%.
Embodiment 13
The preparation of compound 2b
Electrophilic reagent i-PrOBPin in embodiment 1 is replaced with to (Bpin)
2, other raw materials and reaction conditions are all constant, obtain target compound 2b, and yield is 45%.
Claims (10)
1. an areneboronic acid ester compound, is characterized in that: its general structure is suc as formula shown in I or II,
Wherein, R1, R2 is halogen, halohydrocarbon or alkoxyl group, Bpin is
2. areneboronic acid ester compound according to claim 1, is characterized in that: in the structural formula of described areneboronic acid ester compound,
R1 is F, Cl, C1～C4 alkoxyl group or trifluoromethyl, and R2 is F, Cl, trifluoromethyl, C1～C4 alkoxyl group, methoxymethyl ether.
3. areneboronic acid ester compound according to claim 1, is characterized in that:
R1=F in structural formula I, R2=F, trifluoromethyl, C1～C4 alkoxyl group; R1=Cl, R2=Cl, C1～C4 alkoxyl group or trifluoromethyl; R1=C1～C4 alkoxyl group, R2=trifluoromethyl;
R1=Cl or trifluoromethyl in structural formula II, R2=trifluoromethyl.
4. areneboronic acid ester compound according to claim 1, is characterized in that, is selected from one of following formula: compound:
5. the synthetic method of areneboronic acid ester compound claimed in claim 1, is characterized in that, step comprises:
1), under-70～-80 DEG C, nitrogen or protection of inert gas, in anhydrous organic solvent, add suc as formula 1,3 di-substituted aryl hydrocarbon shown in III, then add successively TMEDA, DIPA, stir 5-15 minute; Add lithium alkali in system after, react 1-2 hour, then add electrophilic reagent, be warming up to 20-30 DEG C;
R1 in formula III is F, Cl, C1～C4 alkoxyl group or trifluoromethyl, and R2 is F, Cl, trifluoromethyl, C1～C4 alkoxyl group or methoxymethyl ether.
Described electrophilic reagent is Virahol tetramethyl ethylene ketone boric acid ester or connection boric acid pinacol ester;
2) in the reaction system, in step (1), add saturated ammonium chloride solution to carry out cancellation reaction, extraction, dry, separation.
6. the synthetic method of areneboronic acid ester compound according to claim 3, it is characterized in that: in described step (1), anhydrous organic solvent, 1, the add-on proportioning of 3-di-substituted aryl hydrocarbon, TMEDA and DIPA is 2-5mL:1mmol:1.1mmol:0.05mmol.
7. the synthetic method of areneboronic acid ester compound according to claim 3, is characterized in that: in described step (1), the mol ratio of 1,3 di-substituted aryl hydrocarbon, lithium alkali and electrophilic reagent is 1:1.1:1.
8. according to the synthetic method of the areneboronic acid ester compound described in claim 3 or 4, it is characterized in that: the anhydrous organic solvent in described step (1) is anhydrous tetrahydro furan, lithium alkali is n-Butyl Lithium.
9. the synthetic method of areneboronic acid ester compound according to claim 3, is characterized in that: in described step (2), extraction agent is ethyl acetate, and the add-on of extraction agent and 1,3 di-substituted aryl hydrocarbon is than being 7-15mL:1mmol; The saturated ammonium chloride solution adding in reaction system and the volume of anhydrous organic solvent are 1-2:1.
10. according to the synthetic method of the areneboronic acid ester compound described in claim 5,6,7 or 9, it is characterized in that: described 1,3 di-substituted aryl hydrocarbon is the one in m-difluorobenzene, three fluorochlorobenzenes, a fluoride trifluoro toluene, meta-methoxy methyl ether fluorobenzene, meta-methoxy benzene fluorine, Meta Dichlorobenzene, meta-methoxy chlorobenzene, meta-methoxy methyl ether chlorobenzene, m-trifluoromethyl anisole, meta-chlorobenzotrifluoride, two-phenylfluoroform.
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| CN109111474A (en) * | 2018-06-29 | 2019-01-01 | 贾红琴 | The synthetic method of one kind 2,6- dichloro phenyl boric acid |
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