CN105622356B - One kind hydrogenation helicene diphenol and preparation method and application - Google Patents
One kind hydrogenation helicene diphenol and preparation method and application Download PDFInfo
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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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- 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 one kind hydrogenation helicene diphenol and preparation method and application.The structural formula of present invention hydrogenation helicene diphenol is shown in formula I：Wherein, R is hydrogen atom or bromine atoms, and R ' is hydrogen atom or bromine atoms.The preparation method of present invention hydrogenation helicene diphenol compound, raw material is cheap, and synthesis is simple, and products collection efficiency is high, and easy derivatization, stability is good, realizes the preparation method that gram level amount prepares the optically pure helicene quasi-molecule with good thermal stability.
Description
Technical field
The present invention relates to one kind hydrogenation helicene diphenol and preparation method and application, belongs to the design synthesis of chiral catalyst
Field.
Background technology
Helicene is a kind of aromatic compound with helical structure at least formed by four virtue (miscellaneous) ring ortho-condenseds.Make
For a kind of Pi-conjugated systems, helicene is in molecule machine (T.B.Norsten；A.Peters,R.McDonald,M.T.Wang,
N.R.Branda,Reversible[7]-thiahelicene formation using a 1,2-
Dithienylcyclopentene photochrome, J.Am.Chem.Soc.2001,123,7447-7448), liquid crystal
(C.Nuckolls,T.J.Katz,Synthesis,Structure,and Properties of a Helical Columnar
Liquid Crystal, J.Am.Chem.Soc.1998,120,9541-9544), molecular dye (A.Mishra,
M.K.R.Fischer,P.Bauerle,Metal-free organic dyes for dye-sensitized solar
cells:from structure:property relationships to design rules,Angew.Chem.,
Int.Ed., 2009,48,2474-2499) etc. field be widely used；Using its unique spiral chirality, helicene is also answered
With for chiral Recognition (E.Anger, H.Iida, T.Yamaguchi, K.Hayashi, D.Kumano, J.Crassous,
N.Vanthuyne,C.Roussel,E.Yashima,Synthesis and chiral recognition ability of
helical polyacetylenes bearing helicene pendants,Polym.Chem.,2014,5,4909-
4914), asymmetry catalysis (K.Yavari, P.Aillard, Y.Zhang, F.Nuter, P.Retailleau, A.Voituriez,
A.Marinetti,Helicenes with Embedded Phosphole Units in Enantioselective Gold
Catalysis, Angew.Chem.Int.Ed., 2014,53,861-865) and interfacial assembly (E.Murguly, R.McDonald,
N.R.Branda,Chiral discrimination in hydrogen-bonded,Org.Lett.2000,3169-3172)
In.
Helicene is hydrogenated for a kind of new helicene skeleton caused by the endless perhydrogenating of helicene skeleton, compared with helicene its
Remain the feature of spiral chirality and conjugated system, while compared to rigid helicene skeleton, add flexibility, but still can be with table
Reveal property (M.Li, Y.Niu, X.Zhu, Q.Peng, H.Y.Lu, A.Xia, C.F.Chen, the Tetrahydro of high quantum production rate
[5]helicene-based imide dyes with intense fluorescence in both solution and
Solid state, Chem.Commun.2014,50,2993-2995), and can cell imaging (M Li, L.H.Feng,
H.Y.Lu,S.Wang,C.F.Chen,Tetrahydro[5]helicene-Based Nanoparticles for
Structure-Dependent Cell Fluorescent Imaging,Adv.Funct.Mater.2014,24,4405-
Etc. 4412) its unique characteristic is showed.
Although the report of existing many synthetic methods, the preparation of function dough helicene, either helicene skeleton are in itself
Preparation method or skeleton derivative reaction, remain limitation helicene development the main reason for.
With C21,1- union -2-naphthols (BINOL) part of symmetrical axial chirality is due to C2Symmetric characteristics, which reduce, to be competed
Cross number (T.V.RajanBabu, A.L Casalnuovo, Role of electronic asymmetry the in the of state
design of new ligands:The asymmetric hydrocyanation reaction,
J.Am.Chem.Soc.1996,118,6325), thus at present can the chirality most excellent as Bronsted acid catalyst lure
Stem.Existing many chiral Bronsted acid catalysts are to use 1,1 '-connection beta naphthal derivative, and find that it can be catalyzed not
Symmetrical Friedel-Crafts reactions, Aldol condensations, Mannich reactions, miscellaneous Diels-Alder addition reactions and asymmetry
Epoxidation etc. reacts, and all obtains good catalytic activity and enantioselectivity effect, shows wide application prospect
(J.D.Chen,L.Fang,C.F.Chen,Recent Progress in BINOL Mediated Asymmetric
Reactions,Mini-Rev.Org.Chem.2015,12,310-327)。
The content of the invention
It is an object of the invention to provide one kind hydrogenation helicene diphenol and preparation method and application.Helicene is hydrogenated in the present invention
Diphenol has good thermal stability, and its preparation method is simple, the high income of product.
Present invention also offers one kind to hydrogenate helicene diphenol, and its structural formula is 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 ' it is 1 when being hydrogen atom, 1 '-diphenyl hydrogenation [5] helicene diphenol,
Its structural formula is as shown in formula II；
As R and R ' it is 1 when being bromine atoms, 1 '-diphenyl -3,3 '-dibromo hydrogenation [5] helicene diphenol, its structural formula is such as
Shown in formula III；
Present invention also offers the preparation method of the hydrogenation helicene diphenol, comprise the following steps：
Present invention also offers above-mentioned 1, the preparation method of 1 '-diphenyl [5] helicene diphenol, comprise the following steps：1) exist
In solvent I, tetralone and N- bromo-succinimides carry out halogenating reaction, obtain bromination product B；
2) the bromination product B and zinc powder are dissolved in tetrahydrofuran, add trim,ethylchlorosilane and concentrated hydrochloric acid reaction,
Obtain compound C；
3) under the conditions of existing for catalyst, the compound C and phenyl boric acid, alkali soluble are carried out instead in organic solvent II
Should, obtain compound D；
4) the compound D and o- benzoic acid diazonium hydrochloride are dissolved in organic solvent III, are heated to reflux carrying out addition
Reaction, gained solid dissolving add Boron tribromide and carry out demethylating reaction, the rear deionized water that adds is quenched in organic solvent IV
Above-mentioned reaction, separate out yellow solid；The yellow solid is dissolved in organic solvent V, adds trifluoromethanesulfanhydride anhydride and three second
Amine carries out esterification, obtains light yellow liquid；Gained solid dissolving carries out oxygen in organic solvent VI, with DDQ
Change reaction, be heated to reflux, obtain compound E；
5) the compound E is dissolved in organic solvent VII, with tetraethyl ammonium hydroxide reactant aqueous solution, it is molten adds watery hydrochloric acid
Liquation goes out precipitation, filters precipitation, that is, obtains described 1,1 '-diphenyl hydrogenation [5] helicene diphenol；
6) the 1,1 '-diphenyl is hydrogenated into [5] helicene diphenol and the N- bromo-succinimides is dissolved in organic solvent
In VIII, and add molecular sieve and carry out halogenation, that is, obtain described 1,1 '-diphenyl -3,3 '-dibromo hydrogenates [5] helicene.
In above-mentioned preparation method, above-mentioned steps 1) in, the solvent I be in acetonitrile, dichloromethane and acetic acid at least
It is a kind of；
The mol ratio of the tetralone and the N- bromo-succinimides can be 1：1~1.2, concretely 1:1；
The catalyst of the halogenating reaction is lewis acid, and the lewis acid is ferric trichloride；
The halogenating reaction time can be 2~8h, concretely 4h, 2~4h, 4~8h or 3~6h；The halogenating reaction
Temperature 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, the bromination product B, the zinc powder, the trim,ethylchlorosilane
Can be 1 with the concentrated hydrochloric acid mol ratio：1.5~3：3~4：2~6, concretely 1：1.5：4：2；The quality of the concentrated hydrochloric acid is dense
Degree can be 36.0~38.0%；
The reaction time can be 2~10h, concretely 3h；The reaction temperature can be -30 DEG C~-80 DEG C, specifically may be used
For -78 DEG C.
In above-mentioned preparation method, above-mentioned steps 3) in, the catalyst is two (triphenylphosphine) palladium chlorides and/or four
(triphenylphosphine) palladium；
The alkali is potassium carbonate or sodium carbonate；
The organic solvent II is at least one of toluene, dimethylbenzene, second alcohol and water；The organic solvent II is first
Benzene, ethanol and water mixed liquid or dimethylbenzene, ethanol and water mixed liquid；Concretely toluene, ethanol and water volume ratio can be 4~
1：4~1：1 mixing or dimethylbenzene, ethanol and water volume ratio are 4~1：4~1：1, preferably toluene, ethanol and water are according to 2：2：1 body
Product is than mixing；
The catalyst, the compound C, the mol ratio of the phenyl boric acid and the alkali can be 0.02~0.1：1：3~
5：5~10, concretely 0.1：1：5：10；
The time of the reaction can be 2~10h, concretely 4~6h, and the temperature of the reaction can be 60~100 DEG C, tool
Body can be 70~80 DEG C.
In above-mentioned preparation method, above-mentioned steps 4) in, the organic solvent III is 1,2- dichloroethanes and/or epoxy third
Alkane；
The organic solvent IV is dichloromethane；
The organic solvent V is dichloromethane and/or dichloroethanes, concretely 1,2- dichloroethanes and expoxy propane
Ratio is 10~5：1, preferably 10：1；
The organic solvent VI is dimethylbenzene；
The o- benzoic acid diazonium hydrochloride is 2- carboxyl benzenediazonium chlorides；
The compound D, the o- benzoic acid diazonium hydrochloride, Boron tribromide, trifluoromethanesulfanhydride anhydride, triethylamine with it is 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 the addition reaction can be 2~10h, concretely 2~4h；The temperature of the addition reaction can be 60~
80 DEG C, concretely 65~70 DEG C；
The demethylating reaction temperature can be -5 DEG C~5 DEG C, concretely 0 DEG C；The time of the demethylating reaction can be
15~60min, concretely 20~35min；The demethylating reaction needs to carry out in anhydrous conditions；
In the esterification, the temperature for adding the trifluoromethanesulfanhydride anhydride and the triethylamine can be -5 DEG C~0 DEG C, so
After rise to reaction temperature as 18~30 DEG C, specially 20~25 DEG C；The time of the esterification can be 2~10h, concretely
4h, 2~4h or 2~8h；
The temperature of the oxidation reaction can be 145~180 DEG C, concretely 160~165 DEG C, the oxidation reaction when
Between can be 4~20h, concretely 12h；The oxidation reaction needs to carry out under anhydrous condition.
In above-mentioned preparation method, above-mentioned steps 5) in, the organic solvent VII is Isosorbide-5-Nitrae-dioxane；
The mol ratio of the compound F and the tetraethyl ammonium hydroxide can be 1：20~50, concretely 1：40；
The time of the reaction can be 2~10h, concretely 8h；The temperature of the reaction can be 15~30 DEG C, specifically may be used
For 20~25 DEG C.
In above-mentioned preparation method, above-mentioned steps 6) in, the organic solvent VIII is anhydrous methylene chloride；
The mol ratio of described 1,1 '-diphenyl hydrogenation [5] helicene diphenol and the N- bromo-succinimides can be 1：2~
4, concretely 1：3；Described 1,1 '-diphenyl hydrogenation [5] helicene diphenol can be 20~50 with the molecular sieve quality ratio：1, tool
Body can be 25：1；The halogenation needs lucifuge to carry out；The particle diameter of the molecular sieve isConcretely
The time of the halogenation can be 2~10h, concretely 3~4h, the temperature of the halogenation can be 15~
30 DEG C, concretely 20~25 DEG C.
Application of the hydrogenation helicene diphenol of the present invention in chiral Recognition and/or chiral catalysis field.
The preparation method of present invention hydrogenation helicene diphenol compound, raw material is cheap, and synthesis is simple, and products collection efficiency is high, Yi Yan
Biochemistry, correct through instrument detection gained compound structure, stability is good, realizes gram level amount and prepares with good thermal stability
The preparation method of optically pure helicene quasi-molecule.Present invention hydrogenation helicene diphenol replaces with dinaphthol axial chirality on the spiral of helicene
Chirality, while retain the catalytic site of two phenolic hydroxyl groups, turn into a kind of new helicene class diphenol, not only can be with dinaphthol phase
Seemingly, the asymmetric advantage of skeleton can be played, at the same also remain two compared to dinaphthol urging apart from farther phenolic hydroxyl group
Change site, so as to realize double substrate activated catalysis patterns that dinaphthol is difficult to, substrate be placed in spiral pocket,
Reach good asymmetric identification function and asymmetry catalysis effect, apply in asymmetry catalysis, molecular recognition, chiral from group
In dress, material science, life science and nano science.
Brief description of the drawings
Fig. 1 is compound B nucleus magnetic hydrogen spectrum.
The nuclear-magnetism carbon that Fig. 2 is compound B is composed.
Fig. 3 is compound C nucleus magnetic hydrogen spectrum.
The nuclear-magnetism carbon that Fig. 4 is compound C is composed.
Fig. 5 is compound D nucleus magnetic hydrogen spectrum.
The nuclear-magnetism carbon that Fig. 6 is compound D is composed.
Fig. 7 is compound E nucleus magnetic hydrogen spectrum.
The nuclear-magnetism carbon that Fig. 8 is compound E is composed.
Fig. 9 is the nucleus magnetic hydrogen spectrum of Formula II.
Figure 10 is that the nuclear-magnetism carbon of Formula II is composed.
Figure 11 is the mono-crystalline structures of Formula II.
Figure 12 is the nucleus magnetic hydrogen spectrum of Formula III.
Figure 13 is that the nuclear-magnetism carbon of Formula III is composed.
Figure 14 is Formula III1Absorption spectrum.
Figure 15 is Formula III1Absorption spectrum.
Figure 16 is Formula III2Absorption spectrum.
Figure 17 is Formula III2Absorption spectrum.
Figure 18 is Formula III1With formula III2Circular dichroism spectra.
Figure 19 is Formula III1Pictorial diagram.
Figure 20 is Formula III2Pictorial diagram.
Embodiment
Experimental method used in following embodiments is conventional method unless otherwise specified.
Material used, reagent etc., unless otherwise specified, are commercially obtained in following embodiments.
The synthesis of embodiment 1,1,1 '-diphenyl [5] helicene diphenol
1,1 '-diphenyl [5] helicene diphenol synthesizes according to following reaction scheme：
1) 99g tetralones, 100g N- bromo-succinimides, 4g tri-chlorinations are sequentially added in 1000mL round-bottomed flasks
Iron and 500mL acetonitriles, normal-temperature reaction 4 hours, 300mL water is added into reaction system, separate out white solid 143g product B, production
Rate is more than 99%.
The structure detection result of the compound is as follows：
1H NMR(500MHz,CDCl3) δ 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)
13C NMR(126MHz,CDCl3)δ197.26,155.5,138.7,132.5,128.4,111.7,56.9,40.1,
30.1,22.8.
HRMS(APCI):calcd.for C11H11BrO2[M+H]+:254.9942,found:255.0015.
It is correct from above-mentioned testing result, the compound structure.
2), will after tetralone dissolving toward addition B 70g, zinc powder 24g, tetrahydrofuran 500mL in 1000mL round-bottomed flasks
Bottle is placed in -78 DEG C of liquid nitrogen-acetone bath.After treating temperature reduction, with vigorous stirring toward addition 72mL trimethyls in bottle
Chlorosilane and 36mL concentrated hydrochloric acids.Reaction nature is warmed to room temperature afterwards, after mixture is stirred for 3 hours, obtains a clear yellow solution,
Sometimes have a little white solid to separate out, filter and can obtain white solid, mother liquor removes most of solvent with revolving, added
300mL dichloromethane and 300mL water, extract and separate, organic phase are dried with anhydrous magnesium sulfate.Solvent is removed, obtained yellow is consolidated
Body with petroleum ether/dichloromethane (v/v, 100:1) recrystallize, obtain white solid, merge with white solid before, 42g is obtained
Solid C, yield 67%.
The structure detection result of the compound is as follows：
1H NMR(500MHz,CDCl3) δ 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)
13C NMR(126MHz,CDCl3)δ155.31,138.8,136.1,133.8,130.4,126.5,111.6,
109.4,56.4,29.0,23.2.
HRMS(APCI):calcd.for C23H20Br2O2[M+H]+:476.9810,found:476.9873.
It is correct from above-mentioned testing result, the compound structure.
3) take 5g compounds C, 6.4g phenyl boric acid and 14.5g potassium carbonate to add in bis- mouthfuls of bottles of 500mL, used under argon gas protection
Syringe adds 150mL toluene and 150mL ethanol and 75mL deionized waters, and ventilation adds the (triphenyl of catalyst two after 5 minutes
Phosphine) palladium chloride 736mg, flows back 3 hours, takes organic layer, MgSO4Dry, filtering, be spin-dried for, phenyl is obtained through pillar layer separation
Substituted product D 4.7g, yield 95%.
The structure detection result of the compound is as follows：
1H NMR(500MHz,CDCl3) δ 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).
13C NMR(126MHz,CDCl3)δ155.0,141.4,136.8,134.4,133.7,133.0,132.0,130.8,
129.1,126.5,126.2,125.9,125.7,109.4,56.2,28.2,22.7.
HRMS(APCI):calcd.for C34H30O2[M+H]+:471.2246,found:471.2319.
It is correct from above-mentioned testing result, the compound structure.
4) 10g D and 200mL dichloroethanes is added in 500mL round-bottomed flasks, treats to add 20mL rings after diene dissolving
Ethylene Oxide, 6g o- benzoic acid diazonium hydrochlorides.It is heated to reflux 2 hours, obtains an orange solution.Reaction is cooled to room temperature, used
Revolving remove solution, gained yellow oil with petroleum ether/dichloromethane (v/v, 10:1) recrystallize, obtain light yellow solid.Will
Gained solid dissolving is cooled to 0 DEG C in dry 100mL dichloromethane, adds 10mL Boron tribromides.Solution colour is by yellow
Immediately it is changed into darkviolet.Monitored by TLC, upon reaction completion, add deionized water and reaction is quenched.With the progress of reaction,
Constantly there is yellow solid precipitation.Filter, obtained solid is washed with substantial amounts of deionized water, is dried to obtain product.In argon gas bar
Under part, product is dissolved in 200mL dichloromethane, trifluoromethanesulfanhydride anhydride 10mL, Zhi Houjia is added dropwise under ice bath (0 DEG C)
Enter triethylamine 10mL.Naturally it is warmed to room temperature (20-25 DEG C), reaction stirring 4h.Reaction solution is washed with water three times.Organic phase is dried,
Yellow liquid is obtained after being spin-dried for.Rapidly purified with neutral alumina column chromatography, obtain light yellow liquid.It is dissolved in dimethylbenzene
In (500mL), DDQ 41g is added, with vigorous stirring heated overnight at reflux.Reaction solution is cooled to room temperature,
Heated overnight at reflux with vigorous stirring.Reaction solution is cooled to room temperature, rapidly purifies, obtains pale yellow through neutral alumina column chromatography
Color solid 10g E, four step yields 61%.
The structure detection result of the compound is as follows：
1H NMR(500MHz,CDCl3) δ 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)
13C NMR(126MHz,CDCl3)δ148.0,136.0,135.7,135.6,135.0,131.2,130.7,130.4,
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.for C40H26F6O6S2[M+H]+:781.1075,found:781.1138.
It is correct from above-mentioned testing result, the compound structure.
5) toward adding 2.5g E, 100mL Isosorbide-5-Nitrae-dioxanes in 250mL round-bottomed flasks, after E is completely dissolved, then to its
The middle tetraethyl ammonium hydroxide aqueous solution of addition 41mL 20%, after reacting 24 hours, 100mL is added dropwise into reaction system
1mol/L dilute hydrochloric acid solutions, with the progress of reaction, constantly there is faint yellow solid precipitation.Filter, obtained solid is with largely
Deionized water is washed, desired hydrogenation helicene diphenol (Formula II) 1.6g of drying to obtain, yield 98%.
The structure detection result of the compound is as follows：
1H NMR(500MHz,CDCl3) δ 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)
13C NMR (126MHz, CDCl3) δ 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.for C38H28O2[M-H]+:515.2089,found:515.2005.
It is correct from above-mentioned testing result, the compound structure.
6) 100mL round-bottomed flasks are taken, 1.2g Formula II is added thereto and 1.0g N- bromo-succinimides is dissolved in 20mL and done
In dry dichloromethane, while add 50mgMolecular sieve, react 2 hours, be spin-dried for, through pillar layer separation under the conditions of lucifuge
Obtain the 1.5g of final product formula III, yield 82%.
The structure detection result of the compound is as follows：
1H NMR(500MHz,CDCl3) δ 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)
13C NMR(126MHz,CDCl3)δ148.0,136.0,135.7,135.6,135.0,131.2,130.7,130.4,
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.for C38H26Br2O2[M-H]+:673.0279,found:673.0204.
It is correct from above-mentioned testing result, the compound structure.
HPLC is passed through to obtained two bromo- tetrahydro benzo [5] helicenes of 1,1- diphenyl -2,2- dihydroxy -3,3- simultaneously
Optical voidness fractionation is carried out, has respectively obtained 3.50g enantiomters formula III1With 3.90g enantiomters formula III2, realize optics
Prepared by gram level amount of pure helicene, then its specific rotatory power is measured, enantiomer formula III1With formula III2Specific rotatory power difference
For -456 ° and+435 °, illustrate that the compounds of this invention has optical activity.
Claims (9)
1. one kind hydrogenation helicene diphenol, its structural formula is as shown in formula II or formula III：
2. hydrogenating the preparation method of helicene diphenol described in claim 1, comprise the following steps：1) in solvent I, 7- methoxyl groups-
1- tetralones and N- bromo-succinimides carry out halogenating reaction, obtain bromination product B；
2) the bromination product B and zinc powder are dissolved in tetrahydrofuran, add trim,ethylchlorosilane and concentrated hydrochloric acid reaction, obtain
Compound C；
3) under the conditions of existing for catalyst, the compound C and phenyl boric acid, alkali soluble are reacted in organic solvent II,
Obtain compound D；
4) the compound D and o- benzoic acid diazonium hydrochloride are dissolved in organic solvent III, are heated to reflux carrying out addition reaction,
Gained solid dissolving adds Boron tribromide and carries out demethylating reaction, rear addition deionized water is quenched above-mentioned in organic solvent IV
Reaction, separate out yellow solid；The yellow solid is dissolved in organic solvent V, trifluoromethanesulfanhydride anhydride is added and enters with triethylamine
Row esterification, obtains light yellow liquid；Gained solid dissolving in organic solvent VI, with DDQ aoxidize instead
Should, it is heated to reflux, obtains compound E；
5) the compound E is dissolved in organic solvent VII, with tetraethyl ammonium hydroxide reactant aqueous solution, adds dilute hydrochloric acid solution analysis
Go out precipitation, filter precipitation, that is, obtain described 1,1 '-diphenyl hydrogenation [5] helicene diphenol；
6) described 1,1 '-diphenyl is hydrogenated into [5] helicene diphenol and the N- bromo-succinimides is dissolved in organic solvent VIII,
And add molecular sieve and carry out halogenation, that is, described 1 is obtained, 1 '-diphenyl -3,3 '-dibromo hydrogenates [5] helicene.
3. preparation method according to claim 2, it is characterised in that：Above-mentioned steps 1) in, the solvent I is acetonitrile, two
At least one of chloromethanes and acetic acid；
The mol ratio of the 7- methoxyl groups -1- tetralones and the N- bromo-succinimides is 1：1~1.2；
The catalyst of the halogenating reaction is lewis acid, and the lewis acid is ferric trichloride；
The halogenating reaction time is 2~8h；The temperature of the halogenating reaction is 15~30 DEG C.
4. the preparation method according to Claims 2 or 3, it is characterised in that：Above-mentioned steps 2) in, the bromination product B, institute
It is 1 to state zinc powder, the trim,ethylchlorosilane and the concentrated hydrochloric acid mol ratio：1.5~3：3~4：2~6；The matter of the concentrated hydrochloric acid
It is 36.0~38.0% to measure concentration；
The reaction time is 2~10h；The reaction temperature is -30 DEG C~-80 DEG C.
5. preparation method according to claim 4, it is characterised in that：Above-mentioned steps 3) in, the catalyst is two (triphens
Base phosphine) palladium chloride and/or tetrakis triphenylphosphine palladium；
The alkali is potassium carbonate or sodium carbonate；
The organic solvent II is at least one of toluene, dimethylbenzene, second alcohol and water；
The catalyst, the compound C, the mol ratio of the phenyl boric acid and the alkali are 0.02~0.1：1：3~5：5~
10；
The time of the reaction is 2~10h, and the temperature of the reaction is 60~100 DEG C.
6. preparation method according to claim 5, it is characterised in that：Above-mentioned steps 4) in, the organic solvent III is 1,
2- dichloroethanes and/or expoxy propane；
The organic solvent IV is dichloromethane；
The organic solvent V is dichloromethane or dichloroethanes；
The organic solvent VI is dimethylbenzene；
The o- benzoic acid diazonium hydrochloride is 2- carboxyl benzenediazonium chlorides；
The compound D, the o- benzoic acid diazonium hydrochloride, Boron tribromide, trifluoromethanesulfanhydride anhydride, triethylamine and the dichloro
Dicyano benzoquinone mol ratio is 2：2~6：15~25：2~6：2~6：5~15；
The time of the addition reaction is 2~10h；The temperature of the addition reaction is 60~80 DEG C；
The demethylating reaction temperature is -5 DEG C~5 DEG C；The time of the demethylating reaction is 15~60min；The demethylation
Reaction needs to carry out in anhydrous conditions；
In the esterification, the temperature for adding the trifluoromethanesulfanhydride anhydride and the triethylamine is -5 DEG C~0 DEG C, is then risen to
Reaction temperature is 18~30 DEG C；The time of the esterification is 2~10h；
The temperature of the oxidation reaction is 145~180 DEG C, and the time of the oxidation reaction is 4~20h；The oxidation reaction needs
Want to carry out under anhydrous condition.
7. preparation method according to claim 6, it is characterised in that：Above-mentioned steps 5) in, the organic solvent VII is 1,
6- dioxanes；
The mol ratio of the compound F and the tetraethyl ammonium hydroxide is 1：20~50；
The time of the reaction is 2~10h；The temperature of the reaction is 15~30 DEG C.
8. preparation method according to claim 7, it is characterised in that：Above-mentioned steps 6) in, the organic solvent VIII is nothing
Water dichloromethane；
The mol ratio of described 1,1 '-diphenyl hydrogenation [5] helicene diphenol and the N- bromo-succinimides is 1：2~4；It is described
It is 50~20 that 1,1 '-diphenyl, which hydrogenates [5] helicene diphenol with the molecular sieve quality ratio,：1；The halogenation needs lucifuge to enter
OK；The particle diameter of the molecular sieve is
The time of the halogenation is 2~10h, and the temperature of the halogenation is 15~30 DEG C.
9. application of the helicene diphenol in chiral Recognition and/or chiral catalysis field is hydrogenated described in claim 1.
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