CN101092418A - Compound of monohedral bridging chirality porphyrin and synthetic method - Google Patents
Compound of monohedral bridging chirality porphyrin and synthetic method Download PDFInfo
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- CN101092418A CN101092418A CN 200710043739 CN200710043739A CN101092418A CN 101092418 A CN101092418 A CN 101092418A CN 200710043739 CN200710043739 CN 200710043739 CN 200710043739 A CN200710043739 A CN 200710043739A CN 101092418 A CN101092418 A CN 101092418A
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Abstract
This invention relates to a method for synthesizing single-sided bridged chiral porphyrin compound. The method comprises: synthesizing alpha2, beta2-o-amino porphyrin, performing acyl chlorination on chiral binaphthalene, forming I1 or I2 chiral porphyrin, and synthesizing chiral metal porphyrin. When the chiral porphyrin compound is used in designed synthesis of active center of simulated cell pigment P450 enzyme, the chiral porphyrin compound has ideal chiral cavity size and rigidity, and can effectively and stably perform selective catalytic oxidation reaction on the substrate.
Description
Technical field
The porphyrin compound and the method thereof in a kind of asymmetric catalytic technology field that the present invention relates to specifically are a class compound of monohedral bridging chirality porphyrin and synthetic methods thereof.
Background technology
Current in Chemical Manufacture and field of medicaments, a global problem is realized hydro carbons asymmetric oxidation at normal temperatures and pressures for how seeking chiral catalyst efficiently.Asymmetry catalysis is the most attractive and challenging in the method that obtains various optically active substances, and it is a kind of chirality multiplicative process, and promptly the chiral catalyst of a part can produce thousands of times new chiral molecules.Asymmetry catalysis has now become current internationalization educational circles heat subject, but up to now, the chiral catalyst of design and synthesizing efficient, and really be applied to industrial production, for scientist, remain stern challenge.
The chiral metal metalloporphyrin complex is because the particular structure feature, recent two decades comes, as the asymmetric oxidation catalyzer, to the asymmetric epoxidation reaction of non-functional group alkene and to the catalytic performance of the hydroxylation reaction of stable hydrocarbon, caused scientist's great attention under the mild conditions.Scientist tries hard to the corresponding katalysis of deep discussion mechanism and synthesized multiple chiral metal metalloporphyrin complex, wishes to realize the hydrocarbon selective oxidation under the mild conditions with this development of new catalyzer.But because the synthetic difficulty of chirality porphyrin title complex is bigger, Bao Dao chiral metal porphyrin catalyst in the past, enantioselectivity is not high, and the catalysis productive rate is on the low side.In fact, chiral structure is most important to catalysis of metalloporphyrin activity, selectivity and stability.In order to obtain the chiral catalyst system of efficient stable, scientist need further investigate the active centre structure and the catalytic influence of the right title of adjacent protein environment of cytochrome P 450 enzymes, thereby the synthetic chirality porphyrin of the chiral radicals of design ideal and metalloporphyrin template with suitable chirality cavity.
Synthetic chirality porphyrin catalyst structure more in the past, find catalytic performance preferably the chirality porphyrin catalyst structure have several characteristics: 1) chiral radicals should have bigger volume and enough strong rigidity, for example dinaphthalene group etc.; 2) the chirality bridge linkage group can improve the enantioselectivity of catalyzed reaction effectively; 3) size of chirality cavity is very crucial in the chirality porphyrin.Too big as cavity, chirality unit and metal center are apart from too far away, and a little less than substrate and chirality bridge interacted in the catalyzed reaction, enantioselectivity was not good; Too little as cavity, then be not enough to provide a unlimited space to help the directed convergence of substrate, and the internal oxidation decomposition reaction takes place easily, reduce the stability of catalyzer.According to above experience, we design and have synthesized the novel rigid single face bridging chirality porphyrin title complex that a class has different chirality cavity size, be oxygen source with single oxygen source under the room temperature, under the containing n-donor ligand existence condition, set up novel cytochrome P 450 enzymes catalysis simulated system.The result shows that this catalyst system has good enantioselectivity, stable catalytic life.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of compound of monohedral bridging chirality porphyrin and synthetic method thereof are provided.The present invention designs and has synthesized a series of novel chirals and how to join compound and and α
2β
2Type 5,10,15, the reaction of 20-four (o-aminophenyl) porphyrin, the novel single face bridging chirality porphyrin title complex that has obtained having different chirality cavity size.Select for use monohedral bridging chirality metal porphyrins of the present invention as catalyzer, form catalyst system jointly with nitrogenous axial ligand, at normal temperatures and pressures, the enantioselectivity epoxidation reaction of catalyzed alkene and the enantioselectivity hydroxylation reaction of stable hydrocarbon have higher enantioselectivity and good catalytic stability.
Of the present invention being achieved through the following technical solutions:
The compound of monohedral bridging chirality porphyrin that the present invention relates to, the chemical structural formula of this compound is as follows:
Wherein M representative: 2H or Fe
3+Or Mn
2+Or Co
2+Or Zn
2+N representative: 0 or 1.
Described compound of monohedral bridging chirality porphyrin, the difference of its M, n specifically can be divided into:
| Compound | M | n |
| I 1 I 2 | 2H 2H | 0 1 |
| I 3 I 4 I 5 I 6 I 7 I 8 I 9 I 10 | Fe 3+ Fe 3+ Mn 2+ Mn 2+ Co 2+ Co 2+ Zn 2+ Zn 2+ | 0 1 0 1 0 1 0 1 |
Described compound of monohedral bridging chirality porphyrin, its chirality unit is a R-type dinaphthalene derivatives, chemical structural formula is as follows:
Described monohedral bridging porphyrin compound, the difference of its R-type dinaphthalene derivatives specifically can be divided into again:
| Compound | R 1 | R 2 |
| I 11 I 12 I 13 I 14 I 15 I 16 I 17 I 18 I 19 I 20 | OH OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 OCH 3 | H H CHO CH 2OH CH 2Br CH 2CN CH 2CO 2H CH 2COCl CO 2H COCl |
The synthetic method of the compound of monohedral bridging chirality porphyrin that the present invention relates to specifically comprises the steps:
(1) α
2β
2The building-up reactions of the adjacent amino porphyrin of type:
Ortho Nitro Benzaldehyde is dissolved in the Glacial acetic acid, and reflux dropwise splashes into the pyrroles, continues to add CH behind the reflux cooling
2Cl
2, continuing cooling, suction filtration gets purple crystals, CH
2Cl
2Washing is colourless until filtrate.The dry raw product gets the adjacent nitro porphyrin of product.Under the room temperature adjacent nitro porphyrin is dissolved in the concentrated hydrochloric acid, adds excessive SnCl
2.2H
2O stirs reaction mixture, spends the night, and adds CH
2Cl
2, utilize strong aqua neutralization reaction mixture, separate organic phase, and use CH
2Cl
2Aqueous phase extracted merges organic phase, and drying is filtered, and rotary evaporation obtains four kinds of isomer (α
4, α
3β, α
2β
2, the adjacent amino porphyrin of α β α β type), utilize silica gel column chromatography to separate again and obtain α
2β
2The adjacent amino porphyrin of type.
(2) acyl chloride reaction of chiral binaphthyl
At N
2Under the protection, I
17Or I
19With (CH
3COCl)
2Stirring and refluxing, vacuum extraction is dissolved in the anhydrous tetrahydro furan (THF), gets I
18Or I
20Solution.
(3) I
1Or I
2The formation of chirality porphyrin
α with above-mentioned (one) step
2β
2The product I of the adjacent amino porphyrin of type, (two) step
18Or I
20Solution drips in organic solvent according to 1: 1 ratio of mol ratio, and low temperature reacted 1 hour down, and backflow is spent the night, and reaction finishes after separation and purification obtains I
1Or I
2Compound.
(4) the chiral metal porphyrin is synthetic
The Compound I that (three) are obtained
1Or I
2Be dissolved in the organic solvent, add soluble metal salt, reaction solution refluxes, and reactant obtains product monohedral bridging chirality metal porphyrins I through cooling, separation
3-I
10
In the step (), described synthetic method, resulting product α
2β
2The adjacent amino porphyrin of type, its structural formula is as follows:
In the step (three), described organic solvent is meant: acetate, chloroform, methylene dichloride, tetrahydrofuran (THF), dimethyl formamide, ether, pyridine, dimethyl sulfoxide (DMSO), benzene any.
In the step (four), described soluble metal salt is meant; Co (acac)
2, Zn (acac)
2, Fe (acac)
2, MnCl
2Any.
The catalyst system of being made up of the monohedral bridging chirality metal porphyrins that the present invention relates to is the chiral catalysis system as asymmetric oxidation reaction.Asymmetric catalysis is the asymmetric hydroxylation reaction of epoxidation reaction of olefines and stable hydrocarbon.
Catalysate of the present invention detects and quantitative analysis with Capillary GC, and reaction yield is calculated according to the iodosobenzene that has consumed, and turn over number is the mol ratio of reaction product/catalyzer, and enantioselectivity (ee value) uses the kapillary chiral column to analyze.
Chiral metal metalloporphyrin complex provided by the present invention, chirality cavity with ideal dimensions, as Primary Catalysts, simulate the active centre structure and the adjacent protein environment of cytochrome P 450 enzymes, under the containing n-donor ligand existence condition, set up novel cytochrome P 450 enzymes catalysis simulated system.Axial part has been controlled the directed convergence of reaction substrate to catalyzer chirality cavity in such catalyst system, thereby has improved the chiral catalysis performance effectively.Catalytic result shows that this catalyst system has good catalytic performance.As to cinnamic asymmetric epoxidation reaction, enantioselectivity is 80%, and reaction yield is 92%, speed of reaction be 6.5 turn over number/minute.
Description of drawings
Fig. 1 is the synoptic diagram of cytochrome P 450 enzyme activity of the present invention center (A) and single face bridging porphyrin/nitrogenous axial ligand catalysis simulated system (B).
Embodiment
Below embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
(1) metalloporphyrin complex I
2Structure:
(2) porphyrin I
2Synthetic:
(1) I
12Synthetic
0 ℃, under the argon shield, 5gNaH is dissolved in the mixing solutions of anhydrous THF and DMF, and 9g is dissolved in I among the anhydrous THF
11In 0.5 hour, add in the mixed solution.Reaction mixture adds MeI 0 ℃ of stirring after 1 hour, continues at room temperature to stir to spend the night, and can be observed white precipitate.In reaction mixture impouring frozen water, suction filtration obtains product 9.7g, productive rate 98%.
Its characterization parameter:
MS m/z 314.13；IR(KBr)：1620，1600，1500cm
-1；
1H NMR 200MHz(CDCl
3)：δ3.76(s，6H，OCH
3)，7.08(d，2H，Ar-4H)，7.20(t，2H，Ar-7H)，7.30(t，2H，Ar-6H)，7.45(d，2H，Ar-3H)，7.85(d，2H，Ar-8H)，7.97(d，2H，Ar-5H)。
(2) I
13Synthetic
Room temperature is under the argon shield, with 9g I
12Be dissolved in the 700ml anhydrous diethyl ether, add the new N that steams, N, N ', N '-Tetramethyl Ethylene Diamine.After reaction mixture is cooled to 0 ℃, dropwise add BuLi, stirring is spent the night.Take out a small amount of reaction mixture next day, utilize
1H NMR detection reaction fully after, DMF was added in 1 hour in the reaction mixture under 0 ℃, stir after 5 hours in the impouring frozen water, the thermal agitation mixture is after the layering, with the 200ml methylene dichloride with the water extraction several times, collect organic phase, dewater rotary evaporation in vacuo.Utilize silica gel column chromatography that thick product is carried out purifying, methylene dichloride/sherwood oil is made eluent, collects main colour band, rotary evaporation, and vacuum-drying obtains the 7.2g product, productive rate 71%.
Its characterization parameter:
MS m/z 370.12；IR(KBr)：1678(C＝O)，1460，1390，1254cm
-1；
1H NMR200MHz(CDCl
3)：δ3.42(s，6H，OCH
3)，7.17(d，2H，Ar-8H)，7.46(t，2H，Ar-7H)，7.56(t，2H，Ar-6H)，8.09(d，2H，Ar-5H)，8.97(s，2H，Ar-4H)，10.56(s，2H，CHO)。
(3) I
14Synthetic
Room temperature is under the argon shield, with 3.93g I
13Be dissolved in new steaming ethanol and the THF mixed solution, add the NaBH of 0.88g
4, stirring is spent the night, and rotary evaporation is dissolved in the white solid that obtains in the concentrated hydrochloric acid, utilizes the dichloromethane extraction organic phase, Na2SO
4Drying is filtered, and rotary evaporation obtains the 3.93g product, productive rate 99%.
Its characterization parameter:
MS m/z 374.15；IR(KBr)：3320，1620，1600，1500cm
-1；
1H NMR 400MHz(CDCl
3)：δ2.47(s，2H，OH)，3.30(s，6H，OCH
3)，4.89(d，2H，benzyl-CH
2)，5.03(d，2H，benzyl-CH
2)，7.14(d，2H，Ar-8H)，7.25(t，2H，Ar-7H)，7.40(t，2H，Ar-6H)，7.89(d，2H，Ar-5H)，8.00(s，2H，Ar-4H)。
(4) I
15Synthetic
0 ℃, under the argon shield, 3.9g I
14Be dissolved in the anhydrous THF of the 350ml that contains pyridine, add the 1.0ml phosphorus tribromide, stirred reaction mixture under the room temperature spends the night.Rotary evaporation, with white residue water-soluble/the benzene mixed solution in, utilize benzene extraction, thick product purification by silica gel column chromatography, CH
2Cl
2/ cyclohexane give eluent is collected main colour band, rotary evaporation, productive rate 82%.
Its characterization parameter:
MS m/z 497.98；IR(KBr)：1610，1590，1500cm
-1；
1H NMR 200MHz(CDCl
3)：δ3.34(s，6H，OCH
3)，4.73(d，2H，benzyl-CH
2)，4.95(d，2H，benzyl-CH
2)，7.22(d，2H，Ar-8H)，7.27(t，2H，Ar-7H)，7.43(t，2H，Ar-6H)，7.89(d，2H，Ar-5H)，8.07(s，2H，Ar-4H)。
(5) I
16Synthetic
4.27gI
15Be dissolved among the DMSO of 20ml with the 1.90g sodium cyanide, reaction mixture descends heating after 48 hours at 50 ℃, impouring H
2O/CH
2Cl
2In the mixture, vigorous stirring is utilized CH
2Cl
2Extraction merges organic layer, Na
2SO
4Drying, rotary evaporation, the thick product of purification by silica gel column chromatography, CH
2Cl
2Make eluent, obtain product, productive rate 84%.
Its characterization parameter:
MS m/z 392.15；Anal.Calcd for C
26H
20N
2O
2：C，79.57；H，5.14；N，7.14；
1H NMR 400MHz(CDCl
3)：δ3.24(s，6H，OCH
3)，4.00(s，4H，benzyl-CH
2)，7.15(d，2H，Ar-8H)，7.30(t，2H，Ar-7H)，7.45(t，2H，Ar-6H)，7.91(d，2H，Ar-5H)，8.09(s，2H，Ar-4H)；
13C NMR 200MHz(CDCl
3)：153.0；141.8；138.1；137.5；136.9；135.8；135.0，133.3；132.8；131.6；125.2；68.1；27.5。
(6) I
17Synthetic
2.6gI
16Be dissolved in the 30ml sodium hydroxide solution, reaction mixture heated 36 hours down in 100 ℃, formed yellow mercury oxide, and suction filtration obtains the 2.51g product, productive rate 88%.
Its characterization parameter:
MS m/z 430.08；Anal.Calcd for C
26H
22O
6：C，72.55；H，5.15；
1H NMR 200MHz(CDCl
3)：δ3.23(s，6H，OCH
3)，3.99(s，2H，benzyl-CH
2)，4.01(s，2H，benzyl-CH
2)，7.19(d，2H，Ar-8H)，7.30(t，2H，Ar-7H)，7.45(t，2H，Ar-6H)，7.87(d，2H，Ar-5H)，7.91(s，2H，Ar-4H)，8.75(2H，S，COOH)；
13C NMR 200MHz(CDCl
3)：179.8；154.1；134.0；132.9；131.7；130.7；128.1；127.3；126.4；125.8；61.0；36.9。
(7) I
18Synthetic
21.3mg I
17With 5ml (CH
3COCl)
2At N
2Protection down, 50 ℃ of stirring and refluxing 8 hours are used the water vapour getter device.Vacuum extraction is dissolved in the anhydrous THF of 10ml stand-by afterwards.
(8) adjacent nitro porphyrin is synthetic
Ortho Nitro Benzaldehyde 50.5g is dissolved in the 1L Glacial acetic acid, and reflux dropwise splashes into 23.2ml pyrroles, and strict control oil bath temperature continues to reflux 20 minutes.The cooling back adds the CHCl of 125ml
3, ice-water bath continues to be cooled to 35 ℃, and suction filtration gets purple crystals, CHCl
3Washing is colourless until filtrate.Thick product is dry under 100 ℃, gets product 8.4g, productive rate 13%.
(9) under the room temperature the adjacent nitro porphyrin of 8.4g is dissolved in the 400ml concentrated hydrochloric acid; Add excessive SnCl
22H
2O.Reaction mixture is stirred, spend the night, add CH
2Cl
2, utilize strong aqua neutralization reaction mixture, color is become brown by green.Separate organic phase, and use CH
2Cl
2Aqueous phase extracted merges organic phase, anhydrous Na
2SO
4Drying is filtered, and rotary evaporation utilizes silica gel column chromatography to separate four kinds of foreign body objects, and leacheate is CH
2Cl
2/ MeOH, α
2β
2-product accounts for original stock 19%.
Its characterization parameter:
Uv-vis (CH
2Cl
2): 419,515,590,650nm;
1H NMR 200MHz (CDCl
3): δ 8.89 (s, 8H, β); 7.87 (d, 4H, Ar-3H); 7.63 (t, 4H, Ar-4H); 7.20 (t, 3H, Ar-5H); 7.12 (d, 4H, Ar-6H); 3.50 (s, 8H, NH
2);-2.62 (s, 2H, NH
Pyridine).
(10) I
2Synthetic
Under 0 ℃ of nitrogen protection with N, N-diethyl-aniline (250 μ L) and α
2β
2The amino porphyrin of type (300mg) is dissolved in anhydrous CH
2Cl
2(30ml), with the I of prepared fresh
18(40.0mmol) be dissolved in the THF solution. lentamente above-mentioned two kinds of solution are added in THF (60ml) solution simultaneously.Dropwise under back 0 ℃ reaction mixture is continued to stir 1 hour, rise to room temperature afterwards, stirring is spent the night.Rotary evaporation is removed THF, and residue is dissolved in CH
2Cl
2In.Washing is to remove unreacted amine, Na
2SO
4Drying, suction filtration, silica gel column chromatography separates, and leacheate is CH
2Cl
2/ CH
3OH gets product, productive rate 50%.
Its characterization parameter:
Uv-vis(CH
2Cl
2)λ
max：423，517，550，590，650nm；
1H NMR(CDCl
3，500MHz)δ：8.88(d，2H，βH)，8.72(d，2H，βH)，8.68(d，2H，βH)，8.59(d，2H，βH)，8.48(d，2H，ArH)，8.14(d，2H，ArH)，7.90(t，2H，ArH)，7.83(t，2H，ArH)，7.75(s，2H，NH)，7.66(t，2H，ArH)，7.57(d，2H，ArH)，7.52(d，2H，ArH)，7.44(s，1H，ArH)，7.39(d，1H，ArH)，7.23(t，1H，ArH)，7.15(t，1H，ArH)，7.04(d，1H，ArH)，6.86(s，1H，ArH)，6.68(d，1H，ArH)，6.32(t，1H，ArH)，6.19(t，1H，ArH)，5.83(d，1H，ArH)，3.75(d，2H，CH
2Ph)，3.45(s，4H，NH
2)，3.05(d，2H，CH
2 Ph)，2.06(s，3H，OCH
3)，-0.40(s，3H，OCH
3)，-2.92(s，2H，NH)；Anal.calcd for C
70H
52N
8O
4：C 78.63，H 4.90，N 10.48；found C 78.98，H 5.02，N 10.26；HRMS calcd for C
70H
52N
8O
4 1069.42，found 1069.4192。
Embodiment 2
(1) chirality porphyrin I
1Structure
(2) chirality porphyrin I
1Synthetic
(1) I
12Synthetic
0 ℃, under the argon shield, 5gNaH (125mmol) is dissolved in the mixing solutions of anhydrous THF and DMF, and 9g is dissolved in I among the anhydrous THF of 240ml
11In 0.5 hour, add in the mixed solution.Reaction mixture adds a spot of MeI 0 ℃ of stirring after 1 hour, continue at room temperature to stir to spend the night, and can be observed white precipitate.In reaction mixture impouring frozen water, suction filtration obtains product 9.7g, productive rate 98%.
Its characterization parameter:
MS m/z 314.13；IR(KBr)：1620，1600，1500cm
-1；
1H NMR 200MHz(CDCl
3)：δ3.76(s，6H，OCH
3)，7.08(d，2H，Ar-4H)，7.20(t，2H，Ar-7H)，7.30(t，2H，Ar-6H)，7.45(d，2H，Ar-3H)，7.85(d，2H，Ar-8H)，7.97(d，2H，Ar-5H)。
(2) I
19Synthetic
0 ℃, under the nitrogen protection, the I of 1.0g
12Be dissolved in 200ml with the TEMED of 2.0ml and newly steam in the ether stirring and refluxing.Dropwise add a spot of n-BuLi, temperature of reaction rises to the room temperature backflow afterwards, and the afterreaction mixture was cooled to 0 ℃ once more in 24 hours, fed dry CO
2One hour, after continuing to reflux one hour, utilize Rotary Evaporators to remove ether, add 200ml distilled water, mixture benzene extracting twice.Water utilizes concentrated hydrochloric acid acidifying, CHCl
3Extraction, NaSO
4Drying, recrystallization get thick product, productive rate 65%.
Its characterization parameter:
1H NMR(CDCl
3，400MHz)δ：8.95(s，2H，COOH)，8.07(d，2H，Ar-4H)，7.98(d，2H，Ar-5H)，7.54(t，2H，Ar-6H)，7.45(t，2H，Ar-7H)，7.15(d，2H，Ar-8H)；
13C NMR(CDCl
3，400MHz)δ：166.52，153.89，143.80，136.38，136.14，130.04，129.95，126.57，125.31，124.42，121.36；MS m/z(％)：402.1(M+H)
+；Anal.calcdfor C
24H
18O
6：C，71.64，H，4.51；found C 71.46，H 4.70。
(3) I
20Synthetic
The I of 90mg
19With SOCl
2Refluxed 8 hours, vacuum-drying is dissolved in the anhydrous THF stand-by.
(4) adjacent nitro porphyrin is synthetic
Ortho Nitro Benzaldehyde 50.5g is dissolved in the 1L Glacial acetic acid, and reflux dropwise splashes into 23.2ml pyrroles, and strict control oil bath temperature continues to reflux 20 minutes, and the cooling back adds the CHCl of 125ml
3, ice-water bath continues to be cooled to 35 ℃, and suction filtration gets purple crystals, CHCl
3Washing is colourless until filtrate.Thick product is dry under 100 ℃, gets product 8.4g, productive rate 13%.
(5) under the room temperature the adjacent nitro porphyrin of 8.4g is dissolved in the 400ml concentrated hydrochloric acid, adds excessive SnCl
22H
2O.Reaction mixture is stirred, spend the night, add CH
2Cl
2, utilize strong aqua neutralization reaction mixture, color is become brown by green.Separate organic phase, and use CH
2Cl
2Aqueous phase extracted merges organic phase, anhydrous Na
2SO
4Drying is filtered, and rotary evaporation utilizes silica gel column chromatography to separate four kinds of foreign body objects, and leacheate is CH
2Cl
2/ MeOH, α
2β
2-product accounts for original stock 19%.
Its characterization parameter:
Uv-vis (CH
2Cl
2): 419,515,590,650nm;
1H NMR 200MHz (CDCl
3): δ 8.89 (s, 8H, β); 7.87 (d, 4H, Ar-3H); 7.63 (t, 4H, Ar-4H); 7.20 (t, 3H, Ar-5H); 7.12 (d, 4H, Ar-6H); 3.50 (s, 8H, NH
2);-2.62 (s, 2H, NH
Pyridine).
(6) I
1Synthetic
With N, N-diethyl-aniline (250 μ l) and adjacent amino porphyrin 300mg are dissolved in anhydrous CH under 0 ℃ of nitrogen protection
2Cl
2(30ml), with the I of prepared fresh
2040.0mmol be dissolved in the THF solution.Utilize syringe pump lentamente above-mentioned two kinds of solution to be added in THF (60ml) solution simultaneously in 1 hour. dropwise under back 0 ℃ reaction mixture continuation stirring was risen to room temperature after 1 hour, stirring is spent the night.Rotary evaporation is removed THF, and residue is dissolved in CH
2Cl
2In.Washing is to remove unreacted amine, Na
2SO
4Drying, suction filtration, silica gel column chromatography separates, and leacheate is CH
2Cl
2/ CH
3OH gets product, productive rate 55%.
Its characterization parameter:
Uv-vis(CH
2Cl
2)λ
max：418，511，552，590，648nm；Anal.calcd for C
68H
48N
8O
4：C 78.44，H 4.65，N 10.76；found C 78.68，H 5.69，N 10.57；HRMS calcd for C
68H
48N
8O
4 1040.38，found 1040.3822。
Embodiment 3
(1) iron porphyrin title complex I
4Structure:
(2) iron porphyrin I
4Synthetic:
(1) I
2Synthetic
With (two) among the embodiment 1.
(2) I
4Synthetic
Add I in the 100ml round-bottomed flask
2(350mg), chloroform 20ml, Glacial acetic acid 25ml and 10g sodium-chlor, magnetic agitation refluxed 10 minutes, added the colourless iron liquor of new system rapidly, continued stirring and refluxing, the reaction process lucifuge that keeps dry.After utilizing the Uv-vis monitoring reaction fully, cooling.Add the 30ml chloroform again, with 3M salt acid elution repeatedly, be washed to ph value of aqueous phase neutrality again.Solvent distillation gets thick product after the drying.Purification by silica gel column chromatography, CH
2Cl
2/ MeOH makes eluent, collects main colour band, productive rate 90%.
Its characterization parameter:
Uv-vis(CH
2Cl
2)λ
max：417，504，576，639nm；MS m/z 1124.27(M-Cl+H)
+；Anal.calcd for C
70H
50ClFeN
8O
4：C 72.57，H 4.35，N 9.67；found C 72.84，H4.25.N 9.91。
As shown in Figure 1, by (B) as can be seen, monohedral bridging chirality iron porphyrin I
4Chiral radicals in the structure has imitated the protein hydrophobic cavity of P450 enzyme active center structure periphery; The 4-tert .-butylpyridine is as axial ligand L, same I
4The axial ligand L (cysteine residues sulphur) in the P450 enzyme active center structure in (A) has been imitated in the active centre coordination.
Under 20 ℃ and the 100Pa, with the catalyst I in the present embodiment of mass percent 0.035%
4, 14% vinylbenzene, 0.41% 4-tert .-butylpyridine and 0.88% interior mark 1,2,4-trichlorobenzene and 84% new steaming CH
2Cl
2Be dissolved in the microreactor of band water bath with thermostatic control, the nitrogen protection lower magnetic force stirs, and 0.67% iodosobenzene oxygen source gradation adds reaction system.Catalysate detects and quantitative analysis with Capillary GC, and reaction yield is calculated according to the iodosobenzene that has consumed, and turn over number is the mol ratio of epoxide/catalyzer, and enantioselectivity (ee value) uses the kapillary chiral column to analyze.Its catalytic result sees Table the project 2 in 1.
The catalysis asymmetric epoxidation reaction data of table 1 chirality porphyrin
| Project | Catalyzer | Substrate | Axial ligand | Enantioselectivity/% | Productive rate/% |
| 1 2 | I 4 I 4 | Vinylbenzene vinylbenzene | 0 4-tert .-butylpyridine | 28 7 | 80 89 |
Embodiment 4
(1) metalloporphyrin I
10Structure
(2) metalloporphyrin I
10Synthetic
(1) I
2Synthetic
With embodiment 1 (two)
(2) I
10Synthetic
Add I in the 100ml round-bottomed flask
2350mg, chloroform 20ml, Glacial acetic acid 25ml and certain zinc acetate, magnetic agitation reflux, the reaction process lucifuge that keeps dry.After utilizing the Uv-vis monitoring reaction fully, cooling.Add the 30ml chloroform, be washed to ph value of aqueous phase neutrality.The underpressure distillation solvent gets thick product after the drying.The plastic column chromatography purifying, CH
2Cl
2/ MeOH makes eluent, collects main colour band, productive rate 95%.
Its characterization parameter: Uv-vis (CH
2Cl
2) λ
Max: 427,553nm;
1H NMR (CDCl
3, 500MHz) δ: 8.76 (m, 8H, β H), 8.47 (d, 2H, ArH), 8.14 (d, 2H, ArH), 7.89 (t, 2H, ArH), 7.83 (t, 2H, ArH), 7.74 (s, 2H, NH), 7.63 (t, 2H, ArH), 7.57 (d, 2H, ArH), 7.52 (d, 2H, ArH), 7.42 (s, 1H, ArH), 7.39 (d, 1H, ArH), 7.23 (t, 1H, ArH), 7.14 (t, 1H, ArH), 7.04 (d, 1H, ArH), 6.86 (s, 1H, ArH), 6.68 (d, 1H, ArH), 6.32 (t, 1H, ArH), 6.19 (t, 1H, ArH), 5.83 (d, 1H, ArH), 3.70 (d, 2H, CH
2Ph), 3.43 (s, 4H, NH
2), 3.08 (d, 2H, CH
2Ph), 2.11 (s, 3H, OCH
3), 1.98 (s, 3H, OCH
3); Anal.calcd for C
70H
50N
8O
4Zn:C 74.23, and H 4.45, and N 9.89; Found C74.33, H 4.55, and N 10.01; HRMS calcd for C
70H
50N
8O
4Zn 1130.32, and found 1130.3187.
Claims (6)
1. a compound of monohedral bridging chirality porphyrin is characterized in that, the chemical structural formula of this compound is as follows:
Wherein M representative: 2H or Zn
2+N representative: 0 or 1;
According to the difference of M, n, compound specifically is divided into:
2. compound of monohedral bridging chirality porphyrin as claimed in claim 1 is characterized in that, described monohedral bridging chirality metal porphyrins, and its chirality unit is a R-type dinaphthalene derivatives, chemical structural formula is as follows:
3. compound of monohedral bridging chirality porphyrin as claimed in claim 1 or 2 is characterized in that, described monohedral bridging metal porphyrins, and the difference of its R-type dinaphthalene derivatives specifically is divided into again:
4. the synthetic method of a compound of monohedral bridging chirality porphyrin as claimed in claim 1 specifically comprises the steps:
(1) α
2β
2The building-up reactions of the adjacent amino porphyrin of type: Ortho Nitro Benzaldehyde is dissolved in the Glacial acetic acid, and reflux dropwise splashes into the pyrroles, continues to add CHCl behind the reflux cooling
3, continuing cooling, suction filtration gets purple crystals, CHCl
3Washing is colourless until filtrate.The dry raw product gets product nitro porphyrin.Under the room temperature nitro porphyrin is dissolved in the concentrated hydrochloric acid, adds excessive SnCl
22H
2O stirs reaction mixture, spends the night.Add CH
2C1
2, utilize strong aqua neutralization reaction mixture, separate organic phase, and use CH
2C1
2Aqueous phase extracted merges organic phase, and drying is filtered, and rotary evaporation obtains four kinds of isomer α
4, α
3β, α
2β
2, the adjacent amino porphyrin of α β α β type, utilize silica gel column chromatography to separate again and obtain α
2β
2The adjacent amino porphyrin of type;
(2) acyl chloride reaction of chiral binaphthyl: at N
2Under the protection, I
17Or I
19With (CH
3COCl)
2Stirring and refluxing, vacuum extraction is dissolved in the anhydrous tetrahydro furan, gets I
18Or I
20Solution;
(3) I
1Or I
2The formation of chirality porphyrin: with the α of above-mentioned (one) step
2β
2The product I of the adjacent amino porphyrin of type, (two) step
18Or I
20Solution drips in organic solvent according to 1: 1 ratio of mol ratio, and low temperature reacted 1 hour down, and backflow is spent the night, and reaction finishes after separation and purification obtains I
1Or I
2Compound;
(4) the chiral metal porphyrin is synthetic: the Compound I that (three) step is obtained
1Or I
2Be dissolved in the organic solvent, add soluble metal salt, reaction solution refluxes, and reactant obtains product monohedral bridging chirality metal porphyrins through cooling, separation.
5. the synthetic method of compound of monohedral bridging chirality porphyrin as claimed in claim 4 is characterized in that, in the step (), and described α
2β
2The building-up reactions of the adjacent amino porphyrin of type, products therefrom α
2β
2The adjacent amino porphyrin of type, its structural formula is as follows:
6. the synthetic method of monohedral bridging chirality metal porphyrins as claimed in claim 4, it is characterized in that, in the step (three), described organic solvent is meant: chloroform, methylene dichloride, tetrahydrofuran (THF), dimethyl formamide, ether, pyridine, dimethyl sulfoxide (DMSO), benzene any.
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| CN103446969A (en) * | 2013-06-07 | 2013-12-18 | 南开大学 | Micro-nano reactor based on phthalocyanine bridging methylation cyclodextrin and preparation of micro-nano reactor |
| CN103446969B (en) * | 2013-06-07 | 2015-02-11 | 南开大学 | Micro-nano reactor based on phthalocyanine bridging methylation cyclodextrin and preparation of micro-nano reactor |
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