CN105622356A - Helicene diphenol hydride, method for preparing same and application of helicene diphenol hydride - Google Patents
Helicene diphenol hydride, method for preparing same and application of helicene diphenol hydride Download PDFInfo
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- CN105622356A CN105622356A CN201610088352.6A CN201610088352A CN105622356A CN 105622356 A CN105622356 A CN 105622356A CN 201610088352 A CN201610088352 A CN 201610088352A CN 105622356 A CN105622356 A CN 105622356A
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- 0 COc1cc(C(CCC2)=*)c2cc1 Chemical compound COc1cc(C(CCC2)=*)c2cc1 0.000 description 2
- FMMIFHYYMATLIT-UHFFFAOYSA-N COC12[BrH]C1C(C(c(c1c3Br)cccc1ccc3OC)=CCC1)=C1C=C2 Chemical compound COC12[BrH]C1C(C(c(c1c3Br)cccc1ccc3OC)=CCC1)=C1C=C2 FMMIFHYYMATLIT-UHFFFAOYSA-N 0.000 description 1
- JPINNMUFFAFJOX-UHFFFAOYSA-N COc1ccc(CCC=C2C(c3c4-c5ccccc5)=CCCc3ccc4OC)c2c1-c1ccccc1 Chemical compound COc1ccc(CCC=C2C(c3c4-c5ccccc5)=CCCc3ccc4OC)c2c1-c1ccccc1 JPINNMUFFAFJOX-UHFFFAOYSA-N 0.000 description 1
- LKQNUNKQQFTEDQ-UHFFFAOYSA-N COc1ccc(CCCC2=O)c2c1Br Chemical compound COc1ccc(CCCC2=O)c2c1Br LKQNUNKQQFTEDQ-UHFFFAOYSA-N 0.000 description 1
- QCCILMZOFGYINA-UHFFFAOYSA-N Oc1ccc(CCc2c(cccc3)c3c(CCc(c-3c4-c5ccccc5)ccc4O)c-3c2-2)c-2c1-c1ccccc1 Chemical compound Oc1ccc(CCc2c(cccc3)c3c(CCc(c-3c4-c5ccccc5)ccc4O)c-3c2-2)c-2c1-c1ccccc1 QCCILMZOFGYINA-UHFFFAOYSA-N 0.000 description 1
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- C07C39/12—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings
- C07C39/17—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic with no unsaturation outside the aromatic rings containing other rings in addition to the six-membered aromatic rings, e.g. cyclohexylphenol
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- C07C37/01—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis
- C07C37/04—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by replacing functional groups bound to a six-membered aromatic ring by hydroxy groups, e.g. by hydrolysis by substitution of SO3H groups or a derivative thereof
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Abstract
The invention discloses helicene diphenol hydride, a method for preparing the same and application of the helicene diphenol. A structural formula of the helicene diphenol hydride is shown as a formula I, wherein an R represents hydrogen atoms or bromine atoms, and an R' represents hydrogen atoms or bromine atoms. The helicene diphenol hydride, the method for preparing the helicene diphenol hydride and the application have the advantages that raw materials are low in cost and easy to synthesize, the helicene diphenol hydride is high in product yield, easy to derive and good in stability, and methods for preparing gram-grade quantities of optically pure helicene molecules with excellent heat stability can be implemented.
Description
Technical field
The present invention relates to a kind of hydrogenation helicene diphenol and preparation method thereof and application, belong to the design synthesis field of chiral catalyst.
Background technology
Helicene is that a class is at least by the aromatic with helical structure of four virtue (assorted) ring ortho-condenseds. as a class Pi-conjugated systems, helicene is at molecule machine (T.B.Norsten, A.Peters, R.McDonald, M.T.Wang, N.R.Branda, Reversible [7]-thiaheliceneformationusinga1, 2-dithienylcyclopentenephotochrome, J.Am.Chem.Soc.2001, 123, 7447-7448), liquid crystal (C.Nuckolls, T.J.Katz, Synthesis, Structure, andPropertiesofaHelicalColumnarLiquidCrystal, J.Am.Chem.Soc.1998, 120, 9541 9544), molecular dye (A.Mishra, M.K.R.Fischer, P.Bauerle, Metal-freeorganicdyesfordye-sensitizedsolarcells:fromstr ucture:propertyrelationshipstodesignrules, Angew.Chem., Int.Ed., 2009, 48, 2474 2499) etc. field is widely used, utilize the spiral chirality of its uniqueness, helicene has also been employed for chiral Recognition (E.Anger, H.Iida, T.Yamaguchi, K.Hayashi, D.Kumano, J.Crassous, N.Vanthuyne, C.Roussel, E.Yashima, Synthesisandchiralrecognitionabilityofhelicalpolyacetyle nesbearinghelicenependants, Polym.Chem., 2014, 5, 4909-4914), asymmetry catalysis (K.Yavari, P.Aillard, Y.Zhang, F.Nuter, P.Retailleau, A.Voituriez, A.Marinetti, HeliceneswithEmbeddedPhospholeUnitsinEnantioselectiveGol dCatalysis, Angew.Chem.Int.Ed., 2014, 53, 861-865) and interfacial assembly (E.Murguly, R.McDonald, N.R.Branda, Chiraldiscriminationinhydrogen-bonded, Org.Lett.2000, in 3169-3172).
Hydrogenation helicene is not exclusively hydrogenating produced a kind of novel helicene skeleton for helicene skeleton, it remains the feature of spiral chirality and conjugated system compared with helicene, simultaneously compared to the helicene skeleton of rigidity, add flexibility, but still the character (M.Li of high quantum production rate can be shown, Y.Niu, X.Zhu, Q.Peng, H.Y.Lu, A.Xia, C.F.Chen, Tetrahydro [5] helicene-basedimidedyeswithintensefluorescenceinbothsolu tionandsolidstate, Chem.Commun.2014, 50, 2993-2995), and can at cell imaging (MLi, L.H.Feng, H.Y.Lu, S.Wang, C.F.Chen, Tetrahydro [5] helicene-BasedNanoparticlesforStructure-DependentCellFlu orescentImaging, Adv.Funct.Mater.2014, 24, 4405-4412) etc. represent the characteristic of its uniqueness.
Although the report of existing many synthetic methods, but the preparation of functionalization helicene, it is no matter preparation method or the derivative reaction of skeleton of helicene skeleton itself, remains the main cause that restriction helicene develops.
There is C21,1-union-2-naphthol (BINOL) part of axis of symmetry chirality is due to C2Symmetric characteristics decreases the number (T.V.RajanBabu of competition transition state, A.LCasalnuovo, Roleofelectronicasymmetryinthedesignofnewligands:Theasym metrichydrocyanationreaction, J.Am.Chem.Soc.1996,118,6325), so at present can as the most excellent chiral induction source of Bronsted acid catalyst. Existing many chirality Bronsted acid catalysts are uses 1,1 '-Lian beta naphthal derivant, and find that it can the reaction such as catalysis asymmetric Friedel-Crafts reaction, Aldol condensation, Mannich reaction, assorted Diels-Alder additive reaction and asymmetric Epoxidation, all obtain good catalysis activity and enantioselectivity effect, demonstrate wide application prospect (J.D.Chen, L.Fang, C.F.Chen, RecentProgressinBINOLMediatedAsymmetricReactions, Mini-Rev.Org.Chem.2015,12,310-327).
Summary of the invention
It is an object of the invention to provide a kind of hydrogenation helicene diphenol and preparation method thereof and application. Hydrogenating helicene diphenol in the present invention and have good thermal stability, its preparation method is simple, and the yield of product is high.
Present invention also offers a kind of hydrogenation helicene diphenol, its structural formula shown in formula I:
Wherein, R is hydrogen atom or bromine atoms, and R ' is hydrogen atom or bromine atoms.
In above-mentioned hydrogenation helicene diphenol, as R and R ' when being hydrogen atom, it is 1,1 '-diphenyl hydrogenation [5] helicene diphenol, its structural formula is such as shown in formula II;
As R and R ' when being bromine atoms, it is 1,1 '-diphenyl-3,3 '-dibromo hydrogenation [5] helicene diphenol, its structural formula is such as shown in formula III;
The preparation method that present invention also offers described hydrogenation helicene diphenol, comprises the steps:
Present invention also offers above-mentioned 1, the preparation method of 1 '-diphenyl [5] helicene diphenol, comprise the steps: 1) in solvent I, tetralone and N-bromo-succinimide carry out halogenating reaction, obtain bromination product B;
2) described bromination product B and zinc powder are dissolved in oxolane, add trim,ethylchlorosilane and concentrated hydrochloric acid reaction, obtain compound C;
3) under catalyst existent condition, described compound C is reacted with phenylboric acid, alkali-soluble in organic solvent II, obtains compound D;
4) described compound D and o-benzoic acid diazol hydrochlorate are dissolved in organic solvent III, being heated to reflux carrying out additive reaction, gained solid is dissolved in organic solvent IV, adds Boron tribromide and carries out demethylating reaction, the rear addition above-mentioned reaction of deionized water cancellation, precipitates out yellow solid; Described yellow solid is dissolved in organic solvent V, adds trifluoromethanesulfanhydride anhydride and carry out esterification with triethylamine, obtain light yellow liquid; Gained solid is dissolved in organic solvent VI, carries out oxidation reaction with DDQ, is heated to reflux, and obtains compound E;
5) described compound E being dissolved in organic solvent VII, with tetraethyl ammonium hydroxide reactant aqueous solution, addition dilute hydrochloric acid solution precipitates out precipitation, and sucking filtration precipitates, and namely obtains described 1,1 '-diphenyl hydrogenation [5] helicene diphenol;
6) by described 1,1 '-diphenyl hydrogenation [5] helicene diphenol and described N-bromo-succinimide are dissolved in organic solvent VIII, and add molecular sieve and carry out halogenation, namely obtain described 1,1 '-diphenyl-3,3 '-dibromo hydrogenation [5] helicene.
In above-mentioned preparation method, above-mentioned steps 1) in, described solvent I is at least one in acetonitrile, dichloromethane and acetic acid;
The mol ratio of described tetralone and described N-bromo-succinimide can be 1:1��1.2, concretely 1:1;
The catalyst of described halogenating reaction is lewis acid, and described lewis acid is ferric chloride;
The described halogenating reaction time can be 2��8h, concretely 4h, 2��4h, 4��8h or 3��6h; The temperature of described halogenating reaction can be 15��30 DEG C, concretely 25 DEG C, 15��25 DEG C or 25��30 DEG C.
In above-mentioned preparation method, above-mentioned steps 2) in, described bromination product B, described zinc powder, described trim,ethylchlorosilane and described concentrated hydrochloric acid mol ratio can be 1:1.5��3:3��4:2��6, concretely 1:1.5:4:2; The mass concentration of described concentrated hydrochloric acid can be 36.0��38.0%;
The described response time can be 2��10h, concretely 3h; Described reaction temperature can be-30 DEG C��-80 DEG C, concretely-78 DEG C.
In above-mentioned preparation method, above-mentioned steps 3) in, described catalyst is two (triphenylphosphine) palladium chloride and/or tetrakis triphenylphosphine palladiums;
Described alkali is potassium carbonate or sodium carbonate;
Described organic solvent II is at least one in toluene, dimethylbenzene, second alcohol and water; Described organic solvent II is toluene, ethanol and water mixed liquid or dimethylbenzene, ethanol and water mixed liquid; Concretely toluene, ethanol can be that 4��1:4��1:1 mixes or dimethylbenzene, ethanol and water volume ratio are 4��1:4��1:1 with water volume ratio, it is preferable that toluene, ethanol mix according to 2:2:1 volume ratio with water;
The mol ratio of described catalyst, described compound C, described phenylboric acid and described alkali can be 0.02��0.1:1:3��5:5��10, concretely 0.1:1:5:10;
The time of described reaction can be 2��10h, concretely 4��6h, and the temperature of described reaction can be 60��100 DEG C, concretely 70��80 DEG C.
In above-mentioned preparation method, above-mentioned steps 4) in, described organic solvent III is 1,2-dichloroethanes and/or expoxy propane;
Described organic solvent IV is dichloromethane;
Described organic solvent V is dichloromethane and/or dichloroethanes, and concretely 1,2-dichloroethanes and expoxy propane ratio are 10��5:1, it is preferable that 10:1;
Described organic solvent VI is dimethylbenzene;
Described o-benzoic acid diazol hydrochlorate is 2-carboxyl benzenediazonium chloride;
Described compound D, described o-benzoic acid diazol hydrochlorate, Boron tribromide, trifluoromethanesulfanhydride anhydride, triethylamine and described DDQ mol ratio can be 2:2��6:15��25:2��6:2��6:5��15, concretely 2:3:20:6:6:20;
The time of described additive reaction can be 2��10h, concretely 2��4h; The temperature of described additive reaction can be 60��80 DEG C, concretely 65��70 DEG C;
Described demethylating reaction temperature can be-5 DEG C��5 DEG C, concretely 0 DEG C; The time of described demethylating reaction can be 15��60min, concretely 20��35min; Described demethylating reaction needs to carry out in anhydrous conditions;
In described esterification, the temperature adding described trifluoromethanesulfanhydride anhydride and described triethylamine can be-5 DEG C��0 DEG C, and then rising to reaction temperature is 18��30 DEG C, is specially 20��25 DEG C; The time of described esterification can be 2��10h, concretely 4h, 2��4h or 2��8h;
The temperature of described oxidation reaction can be 145��180 DEG C, concretely 160��165 DEG C, and the time of described oxidation reaction can be 4��20h, concretely 12h; Described oxidation reaction needs to carry out under anhydrous condition.
In above-mentioned preparation method, above-mentioned steps 5) in, described organic solvent VII is Isosorbide-5-Nitrae-dioxane;
The mol ratio of described compound F and described tetraethyl ammonium hydroxide can be 1:20��50, concretely 1:40;
The time of described reaction can be 2��10h, concretely 8h; The temperature of described reaction can be 15��30 DEG C, concretely 20��25 DEG C.
In above-mentioned preparation method, above-mentioned steps 6) in, described organic solvent VIII is anhydrous methylene chloride;
Described 1, the mol ratio of 1 '-diphenyl hydrogenation [5] helicene diphenol and described N-bromo-succinimide can be 1:2��4, concretely 1:3; Described 1,1 '-diphenyl hydrogenation [5] helicene diphenol can be 20��50:1, concretely 25:1 with described molecular sieve mass ratio; Described halogenation needs lucifuge to carry out; The particle diameter of described molecular sieve isConcretely
The time of described halogenation can be 2��10h, concretely 3��4h, and the temperature of described halogenation can be 15��30 DEG C, concretely 20��25 DEG C.
The hydrogenation helicene diphenol of the present invention application in chiral Recognition and/or chiral catalysis field.
The preparation method that the present invention hydrogenates helicene diphenol compound, cheaper starting materials, synthesis is simple, products collection efficiency is high, easy derivatization, detects gained compound structure through instrument correct, good stability, it is achieved that the preparation method that gram level amount preparation has the optically pure helicene quasi-molecule of good thermal stability. the present invention hydrogenates helicene diphenol and dinaphthol axial chirality replaces with the spiral chirality of helicene, retain the catalytic site of two phenolic hydroxyl groups simultaneously, become a kind of novel helicene class diphenol, it is possible not only to similar to dinaphthol, the asymmetric advantage of skeleton can be played, also remain two compared to the dinaphthol catalytic site apart from farther phenolic hydroxyl group simultaneously, such that it is able to realize the double, two substrate activated catalysis pattern that dinaphthol is difficult to, substrate is placed in spiral pocket, reach good asymmetric recognition function and asymmetry catalysis effect, it is applied in asymmetry catalysis, molecular recognition, chirality self assembly, material science, in life sciences and nano science.
Accompanying drawing explanation
Fig. 1 is the nucleus magnetic hydrogen spectrum of compound B.
Fig. 2 is the nuclear-magnetism carbon spectrum of compound B.
Fig. 3 is the nucleus magnetic hydrogen spectrum of compound C.
Fig. 4 is the nuclear-magnetism carbon spectrum of compound C.
Fig. 5 is the nucleus magnetic hydrogen spectrum of compound D.
Fig. 6 is the nuclear-magnetism carbon spectrum of compound D.
Fig. 7 is the nucleus magnetic hydrogen spectrum of compound E.
Fig. 8 is the nuclear-magnetism carbon spectrum of compound E.
Fig. 9 is the nucleus magnetic hydrogen spectrum of compound formula II.
Figure 10 is the nuclear-magnetism carbon spectrum of compound formula II.
Figure 11 is the mono-crystalline structures of compound formula II.
Figure 12 is the nucleus magnetic hydrogen spectrum of compound formula III.
Figure 13 is the nuclear-magnetism carbon spectrum of compound formula III.
Figure 14 is compound formula III1Absorption spectrum.
Figure 15 is compound formula III1Absorption spectrum.
Figure 16 is compound formula III2Absorption spectrum.
Figure 17 is compound formula III2Absorption spectrum.
Figure 18 is compound formula III1And formula III2Circular dichroism spectra.
Figure 19 is compound formula III1Pictorial diagram.
Figure 20 is compound formula III2Pictorial diagram.
Detailed description of the invention
The experimental technique used in following embodiment if no special instructions, is conventional method.
Material used in following embodiment, reagent etc., if no special instructions, all commercially obtain.
Embodiment 1,1,1 '-diphenyl [5] helicene diphenol synthesis
1,1 '-diphenyl [5] helicene diphenol synthesizes according to following reaction scheme:
1) in 1000mL round-bottomed flask, 99g tetralone, 100gN-bromo-succinimide, 4g ferric chloride and 500mL acetonitrile it are sequentially added into, normal-temperature reaction 4 hours, adding 300mL water in reaction system, precipitate out white solid 143g product B, productivity is more than 99%.
The structure detection result of this compound is as follows:
1HNMR(500MHz,CDCl3) �� 7.18 (d, J=8.4Hz, 1H), 7.01 (d, J=8.4Hz, 1H), 3.91 (s, 3H), 2.93 2.87 (m, 2H), 2.73 2.67 (m, 2H), 2.08 (p, J=6.5Hz, 2H).
13CNMR(126MHz,CDCl3)��197.26,155.5,138.7,132.5,128.4,111.7,56.9,40.1,30.1,22.8.
HRMS(APCI):calcd.forC11H11BrO2[M+H]+:254.9942,found:255.0015.
By above-mentioned testing result it can be seen that this compound structure is correct.
2) in 1000mL round-bottomed flask, add B70g, zinc powder 24g, oxolane 500mL, after tetralone dissolves, bottle is placed in the liquid nitrogen-acetone bath of-78 DEG C. After treating that temperature reduces, in bottle, add 72mL trim,ethylchlorosilane and 36mL concentrated hydrochloric acid with vigorous stirring. Reaction nature rises to room temperature afterwards, after mixture is stirred for 3 hours, obtain a clear yellow solution, sometimes have a little white solid to precipitate out, sucking filtration can obtain white solid, and mother solution rotation is evaporated off major part solvent, adds 300mL dichloromethane and 300mL water, extract and separate, organic facies anhydrous magnesium sulfate dries. Remove solvent, the yellow solid obtained petroleum ether/dichloromethane (v/v, 100:1) recrystallization, obtain white solid, merge with white solid before, there are 42g solid C, productivity 67%.
The structure detection result of this compound is as follows:
1HNMR(500MHz,CDCl3) �� 7.12 (d, J=8.2Hz, 2H), 6.72 (d, J=8.2Hz, 2H), 6.10 (t, J=5.2Hz, 2H), 3.84 (s, 6H), 2.85 2.65 (m, 4H), 2.26 2.12 (m, 4H).
13CNMR(126MHz,CDCl3)��155.31,138.8,136.1,133.8,130.4,126.5,111.6,109.4,56.4,29.0,23.2.
HRMS(APCI):calcd.forC23H20Br2O2[M+H]+:476.9810,found:476.9873.
By above-mentioned testing result it can be seen that this compound structure is correct.
3) take 5g compound C, 6.4g phenylboric acid and 14.5g potassium carbonate adds in bis-mouthfuls of bottles of 500mL; add 150mL toluene and 150mL ethanol and 75mL deionized water with syringe under argon shield; catalyst two (triphenylphosphine) palladium chloride 736mg is added after ventilating 5 minutes; reflux 3 hours; take organic layer, MgSO4Dry, filter, be spin-dried for, obtain the product D4.7g that phenyl replaces, productivity 95% through pillar layer separation.
The structure detection result of this compound is as follows:
1HNMR(500MHz,CDCl3) �� 7.16 (t, J=7.4Hz, 2H), 7.00 (s, 4H), 6.79 (m, J=11.4Hz, 4H), 6.63 (d, J=8.2Hz, 2H), 6.40 (s, 2H), 6.04 5.97 (m, 2H), 3.47 (s, 6H), 2.09 1.99 (m, 2H), 1.87 (s, 4H), 1.27 (m, 2H).
13CNMR(126MHz,CDCl3)��155.0,141.4,136.8,134.4,133.7,133.0,132.0,130.8,129.1,126.5,126.2,125.9,125.7,109.4,56.2,28.2,22.7.
HRMS(APCI):calcd.forC34H30O2[M+H]+:471.2246,found:471.2319.
By above-mentioned testing result it can be seen that this compound structure is correct.
4) in 500mL round-bottomed flask, add 10gD and 200mL dichloroethanes, treat that diene adds 20mL expoxy propane, 6g o-benzoic acid diazol hydrochlorate after dissolving. It is heated to reflux 2 hours, obtains an orange solution. Reaction is cooled to room temperature, solution, gained yellow oil petroleum ether/dichloromethane (v/v, 10:1) recrystallization is evaporated off with rotation, obtains light yellow solid. Gained solid is dissolved in dry 100mL dichloromethane, is cooled to 0 DEG C, add 10mL Boron tribromide. Solution colour is immediately become darkviolet from yellow. Monitored by TLC, upon reaction completion, add deionized water cancellation reaction. Along with the carrying out of reaction, yellow solid is constantly had to precipitate out. Sucking filtration, the substantial amounts of deionized water wash of the solid obtained, dry and obtain product. When argon, product is dissolved in 200mL dichloromethane, under ice bath (0 DEG C), is added dropwise over trifluoromethanesulfanhydride anhydride 10mL, add triethylamine 10mL afterwards. Naturally room temperature (20-25 DEG C), reaction stirring 4h are risen to. Reactant liquor washes three times with water. Organic facies dries, and obtains yellow liquid after being spin-dried for. With neutral alumina column chromatography fast purifying, obtain light yellow liquid. It is dissolved in dimethylbenzene (500mL), adds DDQ 41g, with vigorous stirring heated overnight at reflux. Reactant liquor is cooled to room temperature, with vigorous stirring heated overnight at reflux. Reactant liquor is cooled to room temperature, through neutral alumina column chromatography fast purifying, obtains light yellow solid 10gE, four step productivity 61%.
The structure detection result of this compound is as follows:
1HNMR(500MHz,CDCl3) �� 8.13 (dd, J=6.5,3.4Hz, 2H), 7.56 (dd, J=6.5,3.2Hz, 2H), 7.20 7.04 (m, 8H), 6.77 (td, J=7.6,1.7Hz, 2H), 6.53 (d, J=7.7Hz, 2H), 6.02 (d, J=7.8Hz, 2H), 3.39 3.31 (m, 2H), 2.43 (dd, J=13.4,10.4Hz, 3H), 1.57 1.51 (m, 3H).
13CNMR(126MHz,CDCl3)��148.0,136.0,135.7,135.6,135.0,131.2,130.7,130.4,130.1,129.1,128.2,128.0,127.6,127.1,125.8,124.4,108.1,53.4,29.1,24.8.
HRMS(APCI):calcd.forC40H26F6O6S2[M+H]+:781.1075,found:781.1138.
By above-mentioned testing result it can be seen that this compound structure is correct.
5) in 250mL round-bottomed flask, 2.5gE is added, 100mL1,4-dioxane, after E is completely dissolved, it is added thereto to 41mL20% tetraethyl ammonium hydroxide aqueous solution again, after reacting 24 hours, in reaction system, is added dropwise over 100mL1mol/L dilute hydrochloric acid solution, along with the carrying out of reaction, faint yellow solid is constantly had to precipitate out. Sucking filtration, the substantial amounts of deionized water wash of the solid obtained, drying to obtain desired hydrogenation helicene diphenol (Formula II) 1.6g, productivity 98%.
The structure detection result of this compound is as follows:
1HNMR(500MHz,CDCl3) �� 8.11 (dd, J=6.3,3.2Hz, 2H), 7.50 (dd, J=6.4,3.2Hz, 2H), 7.18 7.09 (m, 4H), 6.88 (q, J=7.8Hz, 4H), 6.80 (d, J=8.0Hz, 2H), 6.58 6.52 (m, 2H), 6.08 (d, J=7.4Hz, 2H), 3.70 (s, 2H), 3.30 (d, J=13.6Hz, 2H), 2.40 (t, J=15.1Hz, 2H), 2.30 (d, J=15.5Hz, 2H), 1.41 (d, J=12.6Hz, 3H).
13CNMR(126MHz,CDCl3)��151.3,136.1,135.5,135.2,134.4,131.7,131.5,130.3,128.9,128.8,127.7,126.9,126.2,125.4,113.4,29.3,25.0.
HRMS(ESI):calcd.forC38H28O2[M-H]+:515.2089,found:515.2005.
By above-mentioned testing result it can be seen that this compound structure is correct.
6) take 100mL round-bottomed flask, be added thereto to 1.2g Formula II and 1.0gN-bromo-succinimide is dissolved in the 20mL dichloromethane dried, be simultaneously introduced 50mgMolecular sieve, reacts 2 hours when lucifuge, is spin-dried for, obtains end product formula III 1.5g, productivity 82% through pillar layer separation.
The structure detection result of this compound is as follows:
1HNMR(500MHz,CDCl3) �� 8.10 (dd, J=6.4,3.3Hz, 2H), 7.52 (dd, J=6.5,3.2Hz, 2H), 7.18 (t, J=7.4Hz, 2H), 7.13 (m, 4H), 6.82 (t, J=7.4Hz, 2H), 6.72 (d, J=7.5Hz, 2H), 6.04 (d, J=7.7Hz, 2H), 5.39 (s, 2H), 3.31 (d, J=15.3Hz, 2H), 2.39 (td, J=15.1,3.7Hz, 2H), 2.27 (d, J=12.4Hz, 2H), 1.44 (td, J=14.6,4.1Hz, 3H).
13CNMR(126MHz,CDCl3)��148.0,136.0,135.7,135.6,135.0,131.2,130.7,130.4,130.1,129.0,128.2,128.0,127.6,127.1,125.8,124.4,108.1,29.0,24.8.
HRMS(ESI):calcd.forC38H26Br2O2[M-H]+:673.0279,found:673.0204.
By above-mentioned testing result it can be seen that this compound structure is correct.
Simultaneously to 1,1-diphenyl-2 obtained, 2-dihydroxy-3,3-bis-bromo-tetrahydro benzo [5] helicene carries out optical voidness fractionation by HPLC, has respectively obtained 3.50g enantiomer formula III1With 3.90g enantiomer formula III2, it is achieved that prepared by a gram level amount for optical voidness helicene, subsequently its specific rotatory power is measured, enantiomer formula III1And formula III2Specific rotatory power respectively-456 �� and+435 ��, illustrate that the compounds of this invention has optical activity.
Claims (10)
1. hydrogenation a helicene diphenol, its structural formula shown in formula I:
Wherein, R is hydrogen atom or bromine atoms, and R ' is hydrogen atom or bromine atoms.
2. hydrogenation helicene diphenol according to claim 1, it is characterised in that: as R and R ' when being hydrogen atom, it is 1,1 '-diphenyl hydrogenation [5] helicene diphenol, its structural formula is such as shown in formula II;
As R and R ' when being bromine atoms, it is 1,1 '-diphenyl-3,3 '-dibromo hydrogenation [5] helicene diphenol, its structural formula is such as shown in formula III;
3. the preparation method hydrogenating helicene diphenol described in claim 2, comprises the steps: 1) in solvent I, tetralone and N-bromo-succinimide carry out halogenating reaction, obtain bromination product B;
2) described bromination product B and zinc powder are dissolved in oxolane, add trim,ethylchlorosilane and concentrated hydrochloric acid reaction, obtain compound C;
3) under catalyst existent condition, described compound C is reacted with phenylboric acid, alkali-soluble in organic solvent II, obtains compound D;
4) described compound D and o-benzoic acid diazol hydrochlorate are dissolved in organic solvent III, being heated to reflux carrying out additive reaction, gained solid is dissolved in organic solvent IV, adds Boron tribromide and carries out demethylating reaction, the rear addition above-mentioned reaction of deionized water cancellation, precipitates out yellow solid; Described yellow solid is dissolved in organic solvent V, adds trifluoromethanesulfanhydride anhydride and carry out esterification with triethylamine, obtain light yellow liquid; Gained solid is dissolved in organic solvent VI, carries out oxidation reaction with DDQ, is heated to reflux, and obtains compound E;
5) described compound E being dissolved in organic solvent VII, with tetraethyl ammonium hydroxide reactant aqueous solution, addition dilute hydrochloric acid solution precipitates out precipitation, and sucking filtration precipitates, and namely obtains described 1,1 '-diphenyl hydrogenation [5] helicene diphenol;
6) by described 1,1 '-diphenyl hydrogenation [5] helicene diphenol and described N-bromo-succinimide are dissolved in organic solvent VIII, and add molecular sieve and carry out halogenation, namely obtain described 1,1 '-diphenyl-3,3 '-dibromo hydrogenation [5] helicene.
4. preparation method according to claim 3, it is characterised in that: above-mentioned steps 1) in, described solvent I is at least one in acetonitrile, dichloromethane and acetic acid;
The mol ratio of described tetralone and described N-bromo-succinimide is 1:1��1.2;
The catalyst of described halogenating reaction is lewis acid, and described lewis acid is ferric chloride;
The described halogenating reaction time is 2��8h; The temperature of described halogenating reaction is 15��30 DEG C.
5. the preparation method according to claim 3 or 4, it is characterised in that: above-mentioned steps 2) in, described bromination product B, described zinc powder, described trim,ethylchlorosilane and described concentrated hydrochloric acid mol ratio are 1:1.5��3:3��4:2��6; The mass concentration of described concentrated hydrochloric acid is 36.0��38.0%;
The described response time is 2��10h; Described reaction temperature is-30 DEG C��-80 DEG C.
6. the preparation method according to any one of claim 3-5, it is characterised in that: above-mentioned steps 3) in, described catalyst is two (triphenylphosphine) palladium chloride and/or tetrakis triphenylphosphine palladiums;
Described alkali is potassium carbonate or sodium carbonate;
Described organic solvent II is at least one in toluene, dimethylbenzene, second alcohol and water;
The mol ratio of described catalyst, described compound C, described phenylboric acid and described alkali is 0.02��0.1:1:3��5:5��10;
The time of described reaction is 2��10h, and the temperature of described reaction is 60��100 DEG C.
7. the preparation method according to any one of claim 3-6, it is characterised in that: above-mentioned steps 4) in, described organic solvent III is 1,2-dichloroethanes and/or expoxy propane;
Described organic solvent IV is dichloromethane;
Described organic solvent V is dichloromethane or dichloroethanes;
Described organic solvent VI is dimethylbenzene;
Described o-benzoic acid diazol hydrochlorate is 2-carboxyl benzenediazonium chloride;
Described compound D, described o-benzoic acid diazol hydrochlorate, Boron tribromide, trifluoromethanesulfanhydride anhydride, triethylamine and described DDQ mol ratio are 2:2��6:15��25:2��6:2��6:5��15;
The time of described additive reaction is 2��10h; The temperature of described additive reaction is 60��80 DEG C;
Described demethylating reaction temperature is-5 DEG C��5 DEG C; The time of described demethylating reaction is 15��60min; Described demethylating reaction needs to carry out in anhydrous conditions;
In described esterification, the temperature adding described trifluoromethanesulfanhydride anhydride and described triethylamine is-5 DEG C��0 DEG C, and then rising to reaction temperature is 18��30 DEG C; The time of described esterification is 2��10h;
The temperature of described oxidation reaction is 145��180 DEG C, and the time of described oxidation reaction is 4��20h; Described oxidation reaction needs to carry out under anhydrous condition.
8. the preparation method according to any one of claim 3-7, it is characterised in that: above-mentioned steps 5) in, described organic solvent VII is 1,6-dioxane;
The mol ratio of described compound F and described tetraethyl ammonium hydroxide is 1:20��50;
The time of described reaction is 2��10h; The temperature of described reaction is 15��30 DEG C.
9. the preparation method according to any one of claim 3-8, it is characterised in that: above-mentioned steps 6) in, described organic solvent VIII is anhydrous methylene chloride;
The mol ratio of described 1,1 '-diphenyl hydrogenation [5] helicene diphenol and described N-bromo-succinimide is 1:2��4; Described 1,1 '-diphenyl hydrogenation [5] helicene diphenol is 50��20:1 with described molecular sieve mass ratio; Described halogenation needs lucifuge to carry out; The particle diameter of described molecular sieve is
The time of described halogenation is 2��10h, and the temperature of described halogenation is 15��30 DEG C.
10. described in claim 1 or 2, hydrogenate the application in chiral Recognition and/or chiral catalysis field of the helicene diphenol.
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| CN107141217A (en) * | 2017-04-26 | 2017-09-08 | 中国科学院化学研究所 | A kind of chiral organic dye molecule with blue-fluorescence and preparation method and application |
| CN111559973A (en) * | 2020-04-21 | 2020-08-21 | 中国科学院化学研究所 | Spiroalkene derivative and preparation method and application thereof |
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| CN111559973A (en) * | 2020-04-21 | 2020-08-21 | 中国科学院化学研究所 | Spiroalkene derivative and preparation method and application thereof |
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