CN103553933A - Method for preparing multifunctional conjugated compound - Google Patents
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- CN103553933A CN103553933A CN201310481384.9A CN201310481384A CN103553933A CN 103553933 A CN103553933 A CN 103553933A CN 201310481384 A CN201310481384 A CN 201310481384A CN 103553933 A CN103553933 A CN 103553933A
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- 0 CC(*(C=C1)N)C=C1C(C1=C**C=C1)=C Chemical compound CC(*(C=C1)N)C=C1C(C1=C**C=C1)=C 0.000 description 5
- HTGHBAQOMRGGNQ-UHFFFAOYSA-N CN(C)C1C=CC(C(C(C=C2)=CCC=C2N(C)C)=C)=CC1 Chemical compound CN(C)C1C=CC(C(C(C=C2)=CCC=C2N(C)C)=C)=CC1 HTGHBAQOMRGGNQ-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a method for preparing a multifunctional conjugated compound. The method comprises the following step: carrying out an addition reaction by uniformly mixing a compound as shown in the formula II, aldehyde as shown in the formula III, a catalytic system and a solvent so as to obtain a compound as shown in the formula I after the reaction is finished, wherein the catalytic system is composed of a compound as shown in the formula IV and protonic acid. The synthetic method has advantages of mild condition, easy operation, wide usable range of a substrate and mass production of the reaction. In addition, a recrystallization method which is easy for industrial production can be adopted for purification.
Description
Technical field
The invention belongs to organic functional molecular field of material synthesis technology, relate to a kind of method of preparing multi-functional conjugated compound.
Background technology
Molecule based on compd A and derivative thereof is in occupation of very important status in organic functional material molecule field, and this quasi-molecule has very large using value at multiple fields, is a kind of polyfunctional molecule (Chem.Rev.1992,92,1197.).The molecule of this structure can be used for the charge transfer material in organic photoconductor material, also can be used for replying the charge control agent printing in toning agent by cable, also can be applicable to dyestuff aspect (EP0289122A1).Particularly because it has this special optical absorption property of strong absorption in 800nm left and right; this quasi-molecule also has very large application space ((a) Canon Co. in optical data storing technology field; Jpn.KokaiTokkyoKoho JP58219090,1983; Chem.Abstr.1984,101,81728; (b) Sato, T.; Abe, M.; Oba, H.; Ueda, Y.; Umehara, M.Jpn.KokaiTokkyoKoho JP60252344,1986, Chem.Abstr.1986,105,15349f.), can be used as the charge transfer material in presser sensor recording materials, also can be used in the optical data stored materials such as thermal recording medium and carbon-free print copying field (US4870050).Also having research is will this quasi-molecule structure be transformed, further to expand the practical value (J.Chem.Soc.Chem.Commun., 1993,299.) of molecule.At actual field of industrial production, about this quasi-molecule, in the applied research aspect recording materials, mainly come from Japanese hillside plot chemical industry Co., Ltd..In general, about the research of the molecule of this class formation no matter be theory property aspect or industrial application very important all.
Comparatively ripe about the applied research of this quasi-molecule, however for the synthetic method of this quasi-molecule limitation very, existing report is considerably less, and method is more single, the harsher (EP0289122A1 of condition; EP0519474A1; JP58219090A; JP60252344A; JP63160876A; JP63272581A; JP63280682A; JP2012092188A; US4870050).Method used is all under acid anhydrides, mineral acid or organic acid effect, is generally all the condition of reflux, obtain lower or medium productive rate, and acid anhydrides used, mineral acid or organic acid consumption is all larger.On objective, such synthetic method is not good methodology of organic synthesis, therefore, is necessary to seek a kind of efficient catalyzer and explores a kind of simple efficient synthetic compound A and the method for derivative thereof.
Summary of the invention
The object of this invention is to provide a kind of method of preparing multi-functional conjugated compound.
Shown in preparation formula I provided by the invention, the method for multi-functional conjugated compound, comprises the steps:
Aldehyde shown in compound shown in formula II, formula III, catalyst system and solvent are mixed and carry out addition reaction, react the complete compound shown in described formula I that obtains;
In described formula I and formula II, R
1alkyl, the aryl that to be hydrogen atom, carbonatoms be 1-12, contain substituent aryl, thienyl, furyl or pyridyl;
R
2alkyl, the aryl that to be hydrogen atom, carbonatoms be 1-12, containing substituent aryl, morpholine base, Pyrrolidine base or heterocyclic substituent, be specially the alkyl of C1-C6, is more specifically methyl or ethyl;
R
3for hydrogen atom, carbonatoms be 1-12 alkyl, aryl, contain substituent aryl,
the alkoxyl group that nitro, carboxyl, halogen, cyano group, carbonatoms are 1-12;
Described
in, R be carbonatoms be 1-12 alkyl, aryl, contain substituent aryl, morpholine base, Pyrrolidine base or heterocyclic substituent, be specially the alkyl of C1-C6, be more specifically methyl or ethyl;
Described formula I contains in substituent aryl to formula III, and substituting group is all selected from alkyl, nitro, the alkoxyl group of C1-C12, the N of halogen, C1-C12, N-methyl and-CF
3in at least one; Wherein, the alkyl of described C1-C12 is specially the alkyl of C1-C6 or the alkyl of C1-C4, is more specifically selected from least one in methyl, ethyl, propyl group and butyl;
Described aryl is specially phenyl;
Described catalyst system is comprised of compound shown in formula IV and protonic acid;
In described formula IV, R
4, R
5and R
6all be selected from any one in the aryl substituent of hydrogen atom, alkyl that carbonatoms is 1-12 and replacement; N is the integer of 0-3.
Described containing in substituent aryl, substituting group is all selected from alkyl, nitro, the alkoxyl group of C1-C12, the N of halogen, C1-C12, N-methyl and-CF
3in at least one; Wherein, the alkyl of described C1-C12 is specially the alkyl of C1-C6 or the alkyl of C1-C4, is more specifically selected from least one in methyl, ethyl, propyl group and butyl;
In aforesaid method, described solvent is selected from least one in ethanol, Isosorbide-5-Nitrae-dioxane and methylene dichloride;
Described protonic acid is selected from trifluoroacetic acid, trichoroacetic acid(TCA), acetic acid, trifluoromethanesulfonic acid, methylsulfonic acid, Tetrafluoroboric acid, hexafluoro phosphonic acids, perchloric acid, Phenylsulfonic acid and contains at least one in substituent Phenylsulfonic acid; Described containing in substituent Phenylsulfonic acid, substituting group is selected from least one in methyl, nitro and halogen;
Shown in described formula IV, the mol ratio of compound and protonic acid is 1:0.5-2, is specially 1:1;
Total mole dosage of described catalyst system is the feed intake 10-50% of mole dosage of compound shown in described formula II, is specially 10%;
Shown in described solvent and formula II, the amount ratio of compound is 0.2mL-0.5mL:0.2mmol-1mmol, is specially 0.4mL:1mmol, 0.5mL:1mmol or 0.4mL-0.5mL:1mmol;
Aldehyde shown in described formula III than for 1-5:2, is specially 1:2,1.2:2,1.7:1,1-1.7:1,1-1.2:1 or 1.2-1.7:1 with the mole dosage that feeds intake of compound shown in formula II.
In described addition reaction step, temperature is 20-80 ℃, is specially 20 ℃, 40 ℃, 80 ℃, 20-40 ℃ or 40-80 ℃; Time is 5 hours-96 hours, is specially 5,10,12,22,24,30,36,40,48,5-48,10-40,12-40,30-48 hour or 10-96 hour.
Concrete, compound shown in described formula I be as shown in the formula Ia to any one in compound shown in formula Im:
The present invention compared with prior art has the following advantages:
1, the invention provides a kind of catalyzer very efficiently, catalyzer simple in structure, synthetic simple and effective, raw material is cheaply easy to get;
2, synthesising method reacting condition involved in the present invention is gentle, does not need strong acidic condition, easy handling;
3, synthetic method involved in the present invention is efficient, substrate applied widely;
4, the synthetic method of the finished product involved in the present invention can adopt this Methods For Purification that is easy to suitability for industrialized production of recrystallization, simple to operate efficient;
5, method involved in the present invention is easy to scale operation, and scale is amplified rear productive rate maintenance.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum that embodiment 1a prepares gained compound.
Fig. 2 is the nuclear-magnetism carbon spectrum that embodiment 1a prepares gained compound.
Fig. 3 is the nucleus magnetic hydrogen spectrum that embodiment 1b prepares gained compound.
Fig. 4 is the nuclear-magnetism carbon spectrum that embodiment 1b prepares gained compound.
Fig. 5 is the nucleus magnetic hydrogen spectrum that embodiment 1c prepares gained compound.
Fig. 6 is the nuclear-magnetism carbon spectrum that embodiment 1c prepares gained compound.
Fig. 7 is the nucleus magnetic hydrogen spectrum that embodiment 1d prepares gained compound.
Fig. 8 is the nuclear-magnetism carbon spectrum that embodiment 1d prepares gained compound.
Fig. 9 is the nucleus magnetic hydrogen spectrum that embodiment 1e prepares gained compound.
Figure 10 is the nuclear-magnetism carbon spectrum that embodiment 1e prepares gained compound.
Figure 11 is the nucleus magnetic hydrogen spectrum that embodiment 1f prepares gained compound.
Figure 12 is the nuclear-magnetism carbon spectrum that embodiment 1f prepares gained compound.
Figure 13 is the nucleus magnetic hydrogen spectrum that embodiment 1g prepares gained compound.
Figure 14 is the nuclear-magnetism carbon spectrum that embodiment 1g prepares gained compound.
Figure 15 is the nucleus magnetic hydrogen spectrum that embodiment 1h prepares gained compound.
Figure 16 is the nuclear-magnetism carbon spectrum that embodiment 1h prepares gained compound.
Figure 17 is the nucleus magnetic hydrogen spectrum that embodiment 1i prepares gained compound.
Figure 18 is the nuclear-magnetism carbon spectrum that embodiment 1i prepares gained compound.
Figure 19 is the nucleus magnetic hydrogen spectrum that embodiment 1j prepares gained compound.
Figure 20 is the nuclear-magnetism carbon spectrum that embodiment 1j prepares gained compound.
Figure 21 is the nucleus magnetic hydrogen spectrum that embodiment 1k prepares gained compound.
Figure 22 is the nuclear-magnetism carbon spectrum that embodiment 1k prepares gained compound.
Figure 23 is the nucleus magnetic hydrogen spectrum that embodiment 1l prepares gained compound.
Figure 24 is the nuclear-magnetism carbon spectrum that embodiment 1l prepares gained compound.
Figure 25 is the nucleus magnetic hydrogen spectrum that embodiment 1m prepares gained compound.
Figure 26 is the nuclear-magnetism carbon spectrum that embodiment 1m prepares gained compound.
Embodiment
Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.
The preparation method of following embodiment reactant used is as follows:
Synthesizing of 4,4 '-bis-(N, N-diethyl) toluylene:
Reaction formula is as follows:
Argon shield under condition of ice bath, adds the ether that 100mL is dry in 250mL round-bottomed flask, slowly adds 4.8mL (2.5mol/L) n-BuLi, and then 4.3g methyl wittig reagent joins in above-mentioned system in batches; Stirring at room 4h, slowly adds 3.24g4,4 '-bis-(N, N-diethyl) benzophenone, 60 ℃ of reflux 12h, TLC detection reaction.After reaction finishes, saturated NaCl solution cancellation reaction, dichloromethane extraction once, is isolated organic phase, and water is extracted organic phase repeatedly, anhydrous Na
2sO
4dry organic phase, vacuum is revolved to steam and is removed organic solvent, and thick product is purified (leacheate-ethyl acetate/petroleum ether 1:10v/v) with silica gel column chromatography, obtains faint yellow solid sprills (yield:80%).
Synthesizing of 4,4 '-bis-morpholine toluylene:
Reaction formula is as follows:
1) by 4 of 3.3g, the morpholine of 4 '-difluoro benzophenone and 5.2mL joins in the solution of tetramethylene sulfone, 140 ℃ of reflux 30h, after reaction finishes, question response system is cooled to room temperature, adds a large amount of water, filter, vacuum-drying, re-crystallizing in ethyl acetate, products obtained therefrom is needle-like solid (yield:70%).
2) argon shield under condition of ice bath, adds dry 100mL ether in 250mL round-bottomed flask, slowly adds 4mL (2.5mol/L) n-BuLi, and then 3.5g methyl wittig reagent joins in above-mentioned system in batches; Stirring at room 4h, slowly adds 2.3g, 4,4 '-bis-morpholine benzophenone, 60 ℃ of reflux 12h, TLC detection reaction.After reaction finishes, saturated NaCl solution cancellation reaction, dichloromethane extraction once, is isolated organic phase, and water is extracted organic phase repeatedly, anhydrous Na
2sO
4dry, vacuum is revolved to steam and is removed organic solvent, and thick product is purified (leacheate-ethyl acetate/petroleum ether 1:1v/v) with silica gel column chromatography, obtains brown solid sprills (yield:75%).
Reaction formula is as follows:
By total mass, be the 2.6mg compound N shown in formula IV that is 1:1 by mol ratio, the catalyst system that N-dimethyl-ethylenediamine and protonic acid tosic acid form joins in reactor, then adds 0.1mL alcohol solvent that above-mentioned catalyst system is dissolved.With compound 4 shown in 0.4mL dissolve with ethanol formula II, 4 '-bis-(N, N-dimethyl) mixture of aldehyde phenyl aldehyde (0.1mmol) shown in toluylene (0.1mmol) and formula III, join in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 22h, underpressure distillation is except desolventizing, the sherwood oil that is 10:1 by volume ratio: ethyl acetate column chromatography for separation obtains product, productive rate 93%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Fig. 1-Fig. 2) of this compound:
White?solid,Yield:93%;
1HNMR(300MHz,CDCl
3)δ7.35–7.15(m,9H),6.90(d,J=8.5Hz,4H),6.64(d,J=8.7Hz,4H),6.46(d,J=8.6Hz,4H),5.98(d,J=10.1Hz,2H),4.71(t,J=10.1Hz,1H),2.93(s,12H),2.90(s,12H);
13C?NMR(75MHz,CDCl
3)δ149.9,149.3,145.8,140.8,132.6,130.8,128.9,128.5,128.3,128.0,127.0,125.8,112.3,120.0,44.8,40.8,40.6;IR(KBr):1608,1520,947,819,748,701cm
-1;HRMS(EIS)calcd?for?C
43H
48N
4(M/2+H)
+:311.2013,found311.2011.
From above-mentioned detected result, this compound structure is correct.
Reaction formula is as follows:
By total mass, be the N that 2.4mg is 1:1 by mol ratio, the catalyst system that N-dimethyl-ethylenediamine and protonic acid trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With compound 4 shown in 0.6mL dissolve with ethanol formula II, 4 '-bis-(N, N-dimethyl) mixture of p-trifluoromethyl benzaldehyde (0.12mmol) shown in toluylene (0.2mmol) and formula III, join in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 12h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1(volume ratio) column chromatography for separation obtains product, productive rate 98%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Fig. 3-Fig. 4) of this compound:
White?solid,Yield:98%;
1HNMR(300MHz,CDCl
3)δ7.50(d,J=8.1Hz,2H),7.40(d,J=8.0Hz,2H),7.18(d,J=8.5Hz,4H),6.87(d,J=8.3Hz,4H),6.64(d,J=8.6Hz,4H),6.47(d,J=8.4Hz,4H),5.95(d,J=10.1Hz,2H),4.75(t,J=10.0Hz,1H),2.92(s,12H),2.90(s,12H);
13CNMR(75MHz,CDCl
3)δ150.1,150.0,149.4,141.6,132.1,130.7,128.9,128.2,128.2,125.9,125.3,125.2,112.2,112.0,44.9,40.8,40.5;IR(KBr):1609,1520,947,816cm
-1;HRMS(EIS)calcd?for?C
44H
47F
3N
4:689.3826,found689.3822.
From above-mentioned detected result, this compound structure is correct.
Reaction formula is as follows:
By total mass, be the N that 4.8mg is 1:1 by mol ratio, the catalyst system that N-dimethyl-ethylenediamine and protonic acid trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of toluylene (0.2mmol) and butyraldehyde-n (0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 30h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1 column chromatography for separation obtains product, productive rate 82%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Fig. 5-Fig. 6) of this compound:
White?solid,Yield:82%;
1HNMR(300MHz,CDCl
3)δ7.13(d,J=8.7Hz,4H),6.86(d,J=8.6Hz,4H),6.62(d,J=8.8Hz,4H),6.50(d,J=8.6Hz,4H),5.71(d,J=10.1Hz,2H),3.47–3.35(m,1H),2.92(s,12H),2.90(s,12H),1.49-1.41(m,2H),1.31-1.19(m,2H),0.72(t,J=7.2Hz,3H);
13CNMR(75MHz,CDCl
3)δ149.7,149.1,139.6,133.1,130.9,129.7,129.2,128.5,112.3,112.0,40.9,40.6,40.0,39.3,20.4,14.3;IR(KBr):1609,1519,1443,1349,947,817,732cm
-1;HRMS(EIS)calcd?for?C
40H
50N
4:587.4108,found587.4101.
From above-mentioned detected result, this compound structure is correct.
Embodiment 4
Reaction formula is as follows:
By total mass, be the N that 2.4mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of toluylene (0.2mmol) and 2-thiophene aldehyde (0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 10h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=3:1 column chromatography for separation obtains product, productive rate 89%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Fig. 7-Fig. 8) of this compound:
Yellow?solid,Yield:89%;
1HNMR(300MHz,CDCl
3)δ7.20(d,J=8.9Hz,4H),7.14(d,J=5.0Hz,1H),6.93(d,J=8.6Hz,5H),6.88–6.87(m,1H),6.64(d,J=8.8Hz,4H),6.47(d,J=8.7Hz,4H),5.98(d,J=10.0Hz,2H),4.83(t,J=9.9Hz,1H),2.92(s,12H),2.90(s,12H);
13CNMR(75MHz,CDCl
3)δ151.0,149.9,149.4,141.0,132.3,130.7,128.9,128.2,126.9,126.2,123.8,123.6,112.2,112.0,41.2,40.8,40.5;IR(KBr):1608,1520,947,818cm
-1;HRMS(EIS)calcd?for?C
41H
46N
4S:627.3516,found627.3512.
From above-mentioned detected result, this compound structure is correct.
Embodiment 5
Reaction formula is as follows:
By total mass, be the N that 24mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 4mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 16mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of toluylene (3mmol) and aubepine (5mmol), joins in reactor, under 40 ℃ of temperature condition, magnetic agitation is carried out addition reaction 36h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1 column chromatography for separation obtains product, productive rate 91%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Fig. 9-Figure 10) of this compound:
White?solid,Yield:91%;
1HNMR(300MHz,CDCl
3)δ7.25–7.16(m,6H),6.89(d,J=8.7Hz,4H),6.81(d,J=8.7Hz,2H),6.64(d,J=8.8Hz,4H),6.46(d,J=8.7Hz,4H),5.95(d,J=10.1Hz,2H),4.65(t,J=10.1Hz,1H),3.77(s,3H),2.92(s,12H),2.89(s,12H);
13CNMR(75MHz,CDCl3)δ157.9,149.9,149.3,140.5,137.9,132.6,130.8,128.9,128.6,127.3,113.8,112.2,112.0,55.4,43.9,40.8,40.6;IR(KBr):1607,1519,947,818,734cm
-1;HRMS(EIS)calcd?for?C
44H
503N
4O(M/2+H)
+:326.2065,found326.2062.
From above-mentioned detected result, this compound structure is correct.
Embodiment 6
Reaction formula is as follows:
By total mass, be the N that 2.4mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of toluylene (0.2mmol) and p-Fluorobenzenecarboxaldehyde (0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 24h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1 column chromatography for separation obtains product, productive rate 90%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 11-Figure 12) of this compound:
White?solid,Yield:90%;
1HNMR(300MHz,CDCl
3)δ7.25(dd,J=8.3,5.7Hz,2H),7.18(d,J=8.8Hz,4H),7.00–6.84(m,6H),6.63(d,J=8.8Hz,4H),6.47(d,J=8.7Hz,4H),5.94(d,J=10.1Hz,2H),4.67(t,J=10.1Hz,1H),2.92(s,12H),2.90(s,12H);
13CNMR(75MHz,CDCl
3)δ149.9,149.3,141.4,140.9,132.4,130.7,129.4,129.3,128.8,128.3,126.8,115.1,114.8,112.2,111.9,44.1,40.8,40.5;IR(KBr):1607,1552,947,817cm
-1;HRMS(EIS)calcd?for?C
43H
47FN
4:639.3858,found639.3856.
From above-mentioned detected result, this compound structure is correct.
Reaction formula is as follows:
By total mass, be the N that 2.4mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of toluylene (0.2mmol) and 3-nitrobenzaldehyde (0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 24h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=3:1 column chromatography for separation obtains product, productive rate 97%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 13-Figure 14) of this compound:
Yellow?solid,Yield:97%;
1HNMR(300MHz,CDCl
3)δ8.13(s,1H),8.01(d,J=8.1Hz,1H),7.60(d,J=7.7Hz,1H),7.38(t,J=7.9Hz,1H),7.24–7.15(m,4H),6.87(d,J=8.6Hz,4H),6.64(d,J=8.8Hz,4H),6.49(d,J=8.6Hz,4H),5.97(d,J=10.0Hz,2H),4.78(t,J=10.0Hz,1H),2.92(s,12H),2.91(s,12H);
13CNMR(75MHz,CDCl
3)δ150.0,149.4,148.5,148.2,142.2,134.2,131.8,130.6,129.1,128.8,127.9,125.3,122.8,121.0,112.1,111.9,44.7,40.740.5;IR(KBr):1609,1522,1349,947,818cm
-1;HRMS(EIS)calcd?for?C
43H
47N
5O
2:666.3803,found666.3799.
From above-mentioned detected result, this compound structure is correct.
Reaction formula is as follows:
By total mass, be the N that 2.4mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4, the mixture of 4 '-bis-(N, N-dimethyl) toluylene (0.2mmol) and 2,4-dimethoxy benzaldehyde (0.12mmol), join in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 40h, and underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1 column chromatography for separation obtains product, productive rate 85%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 15-Figure 16) of this compound:
White?solid,Yield:85%;
1H?NMR(300MHz,CDCl
3)δ7.20(d,J=8.8Hz,4H),6.91(d,J=8.7Hz,5H),6.82-6.76(m,2H),6.64(d,J=8.9Hz,4H),6.47(d,J=8.7Hz,4H),5.97(d,J=10.1Hz,2H),4.66(t,J=10.1Hz,1H),3.84(s,3H),3.80(s,3H),2.92(s,12H),2.90(s,12H);
13CNMR(75MHz,CDCl
3)δ149.8,149.3,148.8,147.2,140.8,138.4,132.5,130.8,128.9,128.5,127.1,119.5,112.2,111.9,111.5,111.1,56.0,55.9,44.2,40.7,40.5;IR(KBr):1608,1519,947,819cm
-1;HRMS(EIS)calcd?for?C
45H
52N
4O
2(M/2+H)
+:341.2118,found341.2114.
From above-mentioned detected result, this compound structure is correct.
Embodiment 9
Reaction formula is as follows:
By total mass, be the N that 24mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 4mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 16mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) toluylene (5mmol) and 4-N, the mixture of N-dimethylbenzaldehyde (3mmol), join in reactor, under 40 ℃ of temperature condition, magnetic agitation is carried out addition reaction 36h, and underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1-3:1 column chromatography for separation obtains product, productive rate 70%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 17-Figure 18) of this compound:
White?solid,Yield:70%;
1HNMR(300MHz,CDCl
3)δ7.20(d,J=8.7Hz,6H),6.91(d,J=8.6Hz,4H),6.69(d,J=8.7Hz,2H),6.63(d,J=8.8Hz,4H),6.45(d,J=8.7Hz,4H),5.96(d,J=10.2Hz,2H),4.63(t,J=10.1Hz,1H),2.91(s,12H),2.89(s,6H),2.88(s,12H);
13CNMR(75MHz,CDCl
3)δ149.8,149.2,149.1,140.2,133.8,132.8,130.8,128.9,128.7,128.5,127.7,113.0,112.2,111.9,43.7,41.1,40.8,40.6;IR(KBr):1607,1519,947,818,734cm
-1;HRMS(EIS)calcd?for?C
45H
53N
5(M/2+H)
+:332.7223,found332.7219.
From above-mentioned detected result, this compound structure is correct.
Reaction formula is as follows:
By total mass, be the N that 2.4mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of toluylene (0.2mmol) and valeral (0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 96h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=10:1 column chromatography for separation obtains product, productive rate 67%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 19-Figure 20) of this compound:
Yellow?solid,Yield:67%;
1HNMR(300MHz,CDCl
3)δ7.13(d,J=8.8Hz,4H),6.85(d,J=8.7Hz,4H),6.63(d,J=8.8Hz,4H),6.51(d,J=8.7Hz,4H),5.71(d,J=10.1Hz,2H),3.45–3.32(m,1H),2.93(s,12H),2.91(s,12H),1.46(dd,J=14.8,7.0Hz,2H),1.28–1.03(m,4H),0.79(t,J=7.0Hz,3H);
13CNMR(75MHz,CDCl
3)δ149.7,149.1,139.5,133.1,130.9,129.7,129.2,128.5,112.3,112.0,40.9,40.7,39.4,37.4,29.4,22.9,14.3;IR(KBr):1609,1519,1443,1349,947,817,732cm
-1;HRMS(EIS)calcd?for?C
41H
52N
4:601.4265,found601.4264.
From above-mentioned detected result, this compound structure is correct.
Reaction formula is as follows:
By total mass, be the N that 2.4mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-dimethyl) mixture of the chloro-5-trifluoromethylated benzaldehyde of toluylene (0.2mmol) and the fluoro-3-of 2-(0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 5h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=4:1 column chromatography for separation obtains product, productive rate 98%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 21-Figure 22) of this compound:
White?solid,Yield:98%;
1H?NMR(300MHz,CDCl
3)δ7.46(dd,J=5.9,1.5Hz,1H),7.21–7.09(m,5H),6.79(d,J=8.6Hz,4H),6.62(d,J=8.8Hz,4H),6.52(d,J=8.7Hz,4H),6.16–6.04(m,2H),4.75(t,J=9.6Hz,1H),2.93(s,12H),2.91(s,12H);
13CNMR(75MHz,CDCl
3)δ150.1,149.5,142.6,136.1,135.9,131.4,130.6,128.6,127.9,127.1,127.1,126.7,126.6,125.4,125.4,125.3,125.3,125.2,125.2,124.3,122.0,121.8,121.6,112.1,112.0,41.9,40.7,40.6;IR(KBr):1608,1520,947,817cm
-1;HRMS(EIS)calcd?forC
44H
45ClF
4N
4:741.3342,found741.3334.
From above-mentioned detected result, this compound structure is correct.
Embodiment 12
Reaction formula is as follows:
By total mass, be the N that 4.8mg, mol ratio are 1:1, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4, the mixture of 4 '-bis-morpholine toluylene (0.2mmol) and p-trifluoromethyl benzaldehyde (0.12mmol), join in reactor, under 80 ℃ of temperature condition, magnetic agitation is carried out addition reaction 48h, and underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=2:1 column chromatography for separation obtains product, productive rate 47%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 23-Figure 24) of this compound:
Yellow?solid,Yield:47%;
1HNMR(300MHz,CDCl
3)δ7.52(d,J=8.2Hz,2H),7.35(d,J=8.0Hz,2H),7.18(d,J=8.6Hz,4H),6.88(d,J=8.4Hz,4H),6.81(d,J=8.6Hz,4H),6.66(d,J=8.4Hz,4H),6.03(d,J=10.1Hz,2H),4.66(t,J=10.0Hz,1H),3.86(s,16H),3.14(m,16H);
13CNMR(75MHz,CDCl
3)δ150.6,150.1,149.3,141.2,134.7,131.1,130.7,128.8,128.1,127.0,125.4,125.4,115.1,114.9,67.0,67.0,49.2,45.0;IR(KBr):2973,1607,1515,1262,1049,927,748cm
-1;HRMS(EIS)calcd?for?C
52H
55F
3N
4O
4:857.4248,found857.4241.
From above-mentioned detected result, this compound structure is correct.
Embodiment 13
Reaction formula is as follows:
By total mass, be the N that 2.4mg is 1:1 by mol ratio, the catalyst system that N-dimethyl-ethylenediamine and trifluoromethanesulfonic acid form joins in reactor, then adds 0.2mL alcohol solvent, and above-mentioned catalyst system is dissolved.With 0.6mL dissolve with ethanol 4,4 '-bis-(N, N-diethyl) mixture of toluylene (0.2mmol) and p-trifluoromethyl benzaldehyde (0.12mmol), joins in reactor, under 20 ℃ of temperature condition, magnetic agitation is carried out addition reaction 24h, underpressure distillation is except desolventizing, with sherwood oil: ethyl acetate=2:1 column chromatography for separation obtains product, productive rate 95%, product can further be purified by the method for recrystallization, with methylene dichloride and ethyl alcohol recrystallization, once gets final product to obtain product.
The structure detection result following (with seeing Figure 25-Figure 26) of this compound:
Yellow?solid,Yield:95%;
1HNMR(300MHz,CDCl
3)δ7.50(d,J=8.3Hz,2H),7.41(d,J=8.2Hz,2H),7.17(d,J=8.8Hz,4H),6.88(d,J=8.7Hz,4H),6.58(d,J=8.8Hz,4H),6.43(d,J=8.7Hz,4H),5.92(d,J=9.9Hz,2H),4.79(t,J=9.9Hz,1H),3.31(dq,J=14.0,7.0Hz,16H),1.13(td,J=6.9,2.3Hz,24H);
13CNMR(75MHz,CDCl
3)δ150.6,147.1,146.8,141.5,131.2,131.0,129.1,128.4,127.1,125.6,125.1,125.1,111.3,111.2,44.9,44.5,44.3,12.9,12.8;IR(KBr):1608,1520,947,817,735cm
-1;HRMS(EIS)calcdfor?C
52H
63F
3N
4(M/2+H)
+:401.2575,found401.2571.
From above-mentioned detected result, this compound structure is correct.
Embodiment 14-44
According to the step of embodiment 1, only by the R in reactant shown in formula II and formula III
1to R
3, addition reaction time according to the corresponding replacement of table 1, shown in gained formula I, the productive rate of product is also listed in table 1.
The productive rate of table 1, reaction conditions and product
Claims (6)
1. a method for compound shown in preparation formula I, comprises the steps:
Aldehyde shown in compound shown in formula II, formula III, catalyst system and solvent are mixed and carry out addition reaction, react the complete compound shown in described formula I that obtains;
Described formula I to formula III, R
1alkyl, the aryl that to be hydrogen atom, carbonatoms be 1-12, contain substituent aryl, thienyl, furyl or pyridyl;
R
2alkyl, the aryl that to be hydrogen atom, carbonatoms be 1-12, contain substituent aryl, morpholine base, Pyrrolidine base or heterocyclic substituent;
R
3for hydrogen atom, carbonatoms be 1-12 alkyl, aryl, contain substituent aryl,
the alkoxyl group that nitro, carboxyl, halogen, cyano group, carbonatoms are 1-12;
Described
in, R be carbonatoms be 1-12 alkyl, aryl, contain substituent aryl, morpholine base, Pyrrolidine base or heterocyclic substituent;
Described formula I contains in substituent aryl to formula III, and substituting group is all selected from alkyl, nitro, the alkoxyl group of C1-C12, the N of halogen, C1-C12, N-methyl and-CF
3in at least one;
Described catalyst system is comprised of compound shown in formula IV and protonic acid;
In described formula IV, R
4, R
5and R
6all be selected from any one in the aryl substituent of hydrogen atom, alkyl that carbonatoms is 1-12 and replacement; N is the integer of 0-3;
Described containing in substituent aryl, substituting group is all selected from alkyl, nitro, the alkoxyl group of C1-C12, the N of halogen, C1-C12, N-methyl and-CF
3in at least one.
2. method according to claim 1, is characterized in that: described formula I contains in substituent aryl to formula III, and the alkyl that the alkyl of described C1-C12 is C1-C6 or the alkyl of C1-C4, be specifically selected from least one in methyl, ethyl, propyl group and butyl;
Described formula IV contains in substituent aryl, and the alkyl that the alkyl of described C1-C12 is C1-C6 or the alkyl of C1-C4, be specifically selected from least one in methyl, ethyl, propyl group and butyl.
3. method according to claim 1 and 2, is characterized in that: described solvent is selected from least one in ethanol, Isosorbide-5-Nitrae-dioxane and methylene dichloride;
Described protonic acid is selected from trifluoroacetic acid, trichoroacetic acid(TCA), acetic acid, trifluoromethanesulfonic acid, methylsulfonic acid, Tetrafluoroboric acid, hexafluoro phosphonic acids, perchloric acid, Phenylsulfonic acid and contains at least one in substituent Phenylsulfonic acid; Described containing in substituent Phenylsulfonic acid, substituting group is selected from least one in methyl, nitro and halogen.
4. according to the arbitrary described method of claim 1-3, it is characterized in that: shown in described formula IV, the mol ratio of compound and protonic acid is 1:0.5-2, is specially 1:1;
Total mole dosage of described catalyst system is the feed intake 10-50% of mole dosage of compound shown in described formula II, is specially 10%;
Shown in described solvent and formula II, the amount ratio of compound is 0.2mL-0.5mL:0.2mmol-1mmol, is specially 0.4mL:1mmol;
Aldehyde shown in described formula III than for 1-5:2, is specially 1.2:2 with the mole dosage that feeds intake of compound shown in formula II.
5. according to the arbitrary described method of claim 1-4, it is characterized in that: in described addition reaction step, temperature is 20-80 ℃; Time is 5 hours-96 hours.
6. according to the arbitrary described method of claim 1-5, it is characterized in that: compound shown in described formula I for as shown in the formula Ia to any one in compound shown in formula Im:
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| LINGYUN CUI等: "Primary–Tertiary Diamine/Brønsted Acid Catalyzed C–C Coupling between para-Vinylanilines and Aldehydes", 《CHEM. EUR. J.》, vol. 19, no. 29, 3 June 2013 (2013-06-03) * |
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