CN100364999C - Chiral binaphthol silicone derivative and its preparing method - Google Patents

Chiral binaphthol silicone derivative and its preparing method Download PDF

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CN100364999C
CN100364999C CNB2006100166214A CN200610016621A CN100364999C CN 100364999 C CN100364999 C CN 100364999C CN B2006100166214 A CNB2006100166214 A CN B2006100166214A CN 200610016621 A CN200610016621 A CN 200610016621A CN 100364999 C CN100364999 C CN 100364999C
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binaphthol
silicone derivative
derivative
chiral binaphthol
chiral
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CN1814604A (en
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王晓梅
高连勋
姬相玲
邱雪鹏
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Changchun Institute of Applied Chemistry of CAS
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Abstract

The present invention relates to a chirality binaphthol siloxane derivative and a preparation method thereof. Particularly, the chirality binaphthol siloxane derivative has a general formula, wherein R is selected from-CH2 OCH3,-CH3,-C12 H25 or-C16 H33. The chirality binaphthol siloxane derivative of the present invention has different influences on catalytic reactions, wherein the binaphthol siloxane derivative protected by methoxyl methyl is used for preparing a mesopore material after being processed by copolycondensation or post grafting, so base groups can be protected being removed easily, and the derivative can be directly used for the catalytic reactions. The binaphthol siloxane derivative protected by alkyl with a long chain can be simultaneously used as a siloxane modifier and a surfactant to be used for preparing a composite mesopore material. The method for synthesizing the chirality binaphthol siloxane derivative has the advantages of easy raw material obtainment, and simple and easy synthesis process.

Description

Chiral binaphthol silicone derivative and preparation method thereof
Technical field
The present invention relates to chiral binaphthol silicone derivative of 6,6 ' propoxy-methyl connection and preparation method thereof.
Background technology
Has C 2The chirality 1 of symmetry axis, 1 '-union-2-naphthol and derivative thereof have obtained widespread use { Pu, L. chemistry comment (U.S.) 1998,98,2405. at aspects such as asymmetric synthesis and molecular recognition; ChenY.; Yekta S.; Yudin A.K. chemistry comment (U.S.) 2003,103,3155.}.In recent years, chiral ligand is loaded to carry out asymmetry catalysis on the mesoporous silicon oxide and be subjected to very big concern { DirkE.D.; Dams M.; Sels B.F.; Jacobs P.A. chemistry comment (U.S.) 2002,102,3615.}.The basic load mode has copolycondensation and back graft modification two kinds of approach, and the silicone derivative of chiral ligand both can by and four alkoxyl silicone copolycondensations, again can by with blank mesoporous silicon oxide after graft reaction finish the load of chiral ligand.
Synthetic and the application of relevant chiral binaphthol silicone derivative, document is reported to some extent, mostly be that phenolic hydroxyl group is modified, the derivative 1 of dinaphthol for example, 1 '-dinaphthalene-2,2 '-diamines, respectively with the iodine propyl-triethoxysilicane, the chiral binaphthol silicone derivative that the reaction of isocyanate group triethoxyl silane obtains is used to prepare the periodic mesoporous material { chemical material (U.S.) 2004 such as Mercedes A. of chirality, 16,2222-2228}.Document { Hesemann P. and for example, Moreau J.J.E. stoichiometry journal (France) 2003,6, among the 199-207}, after phenolic hydroxyl group directly reacts with the isocyanate group triethoxyl silane in the dinaphthol, chiral binaphthol silicone derivative that obtains and cyclooctadiene base rhodium chloride (I) dimer, tetraethoxysilane loads to the title complex of dinaphthol on the silica gel under the situation of surfactant-free by sol-gel method together, but because after this mode load, the key of metal and part and power are very weak, and the specific surface area of resultant supported catalyst is little, causes the activity of catalyzed reaction and selectivity very poor.
Summary of the invention
The purpose of this invention is to provide new chiral binaphthol silicone derivative and synthetic method thereof.The contriver carries out chemically modified to 6,6 ' hydroxymethyl derivative of the dinaphthol of different phenolic hydroxyl groups protection and obtains 6,6 ' silicone derivative that the connection of propoxy-methyl is arranged.And provide the preparation method of these derivatives.
Chiral binaphthol silicone derivative among the present invention, its general structure is as follows:
Figure C20061001662100041
Wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33
Introduce the preparation method of chiral binaphthol silicone derivative below.
1. general structure is (I), and wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33The preparation method of chiral binaphthol silicone derivative as follows:
With compound 6,6 '-dihydroxymethyl-2,2 '-disubstituted dinaphthalene (R) or (S) be dissolved in the methylene dichloride, add sodium hydride under the vigorous stirring, the sodium hydride mole dosage is the former 3～4 times, adds shrend after reacting completely and goes out in batches, use ethyl acetate extraction, obtain sodium alkoxide, vacuum-drying can be avoided the influence of excessive sodium hydride to the next step; With the chloropropyl triethoxysilane of isolated sodium alkoxide and 2.5～4 times of mole dosage in dry toluene; nitrogen protection is stirred down; reflux 24～36 hours; toluene is removed in underpressure distillation; use sherwood oil: ethyl acetate=2: 1～5: 1 comes flash column chromatography to separate as eluent to purify; obtain general structure and be (I), wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33Chiral binaphthol silicone derivative.Reaction scheme is as follows:
Figure C20061001662100051
The nuclear-magnetism of the chiral binaphthol silicone derivative that contains different functional groups of the present invention's preparation, ultimate analysis prove that they are the purpose compound really, and its corresponding data are seen concrete embodiment.
Beneficial effect of the present invention and characteristics:
1. the invention provides different phenolic hydroxyl group protections and 6; go up the chiral binaphthol silicone derivative that the propoxy-methyl connects for 6 '; the blocking group of phenolic hydroxyl group has methoxymethyl, methyl, dodecyl and hexadecyl; they all are with 6; 6 '-dihydroxymethyl-2,2 '-disubstituted dinaphthalene (R) or (S) come synthetic for initiator.Wherein, the binaphthol silicone derivative of methoxymethyl protection is after preparing mesoporous material by copolycondensation or back grafting, and blocking group is easy to slough, and can be directly used in catalyzed reaction; And the binaphthol silicone derivative of chain alkyl protection can prepare complex mesoporous material as silicone-modified dose with tensio-active agent simultaneously.
2. the invention provides the method for synthetic these chiral binaphthol silicone derivatives, the raw material of these synthesis techniques all is easy to obtain, and the step of synthesis technique is simple, easily row.General structure carried out for two steps of compounds composition of (I), at first the sodium alkoxide that generates was separated, and avoided the influence of excessive sodium hydride to the back single step reaction, again with the chloropropyl siloxane reactions; These derivatives that obtain are all more stable, all can separate by column chromatography and purify, and can not decompose in separating process, also can not be difficult to wash-out with the chromatographic column reaction.
Embodiment:
Embodiment 1:
General structure is (I), and wherein, R is selected from-CH 2OCH 3Chiral binaphthol silicone derivative 6,6 '-two (the silica-based propoxy-of triethoxy) methyl-2, the preparation of 2 '-dimethoxy methoxyl group dinaphthalene.
With compound (R)-6,6 '-dihydroxymethyl-2,2 '-dimethoxy methoxyl group dinaphthalene 0.70g (1.60mmol) is dissolved in the 15mL methylene dichloride, add the about altogether 0.19g of sodium hydride (4.80mmol) under the vigorous stirring in batches, adding shrend after reacting completely goes out, use ethyl acetate extraction, obtain sodium alkoxide, vacuum-drying.This sodium alkoxide is dissolved in the dry toluene; add the about 1.00mL of chloropropyl triethoxysilane (4.00mmol); nitrogen protection is stirred down; reflux 24 hours; toluene is removed in underpressure distillation; use sherwood oil: ethyl acetate=2: 1 obtains colorless oil purpose product 0.76g for eluent comes flash column chromatography to separate, two step productive rates 56.4%.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (CDCl 3) δ: 8.04-8.06 (d, 2H), 7.87 (s, 2H), 7.60-7.64 (d, 2H), and 7.31-7.33 (d, 2H), 7.21-7.24 (d, 2H), 5.00-5.13 (dd, 4H), 4.88 (s, 4H), 3.80-3.85 (m, 12H), 3.50-3.54 (m, 4H), 3.19 (s, 6H), 1.45-1.51 (m, 4H), 1.10-1.16 (m, 18H), 0.54-0.58 (t, 4H); 13C NMR (CDCl 3) δ: 154.5,135.8,135.2,133.8,129.1,126.1,125.6,125.3,120.7,116.1,101.2,69.7,65.5,57.2,51.2,23.1,18.2,8.3; Ultimate analysis (%, C 44H 66O 12Si 2Calculated value): C, 62.60 (62.68); H, 7.95 (7.89); Si, 6.59 (6.66).
Embodiment 2:
General structure is (I), and wherein, R is selected from-CH 3Chiral binaphthol silicone derivative compound 6,6 '-two (the silica-based propoxy-of triethoxy) methyl-2, the preparation of 2 '-dimethoxy dinaphthalene.
With compound (R)-6,6 '-dihydroxymethyl-2,2 '-dimethoxy dinaphthalene 0.60g (1.60mmol) is dissolved in the 15mL methylene dichloride, add the about altogether 0.20g of sodium hydride (5.00mmol) under the vigorous stirring in batches, add shrend after reacting completely and go out, use ethyl acetate extraction, obtain sodium alkoxide, vacuum-drying.This sodium alkoxide is dissolved in the dry toluene; add the about 1.25mL of chloropropyl triethoxysilane (5.00mmol); nitrogen protection is stirred down; reflux 28 hours; toluene is removed in underpressure distillation; use sherwood oil: ethyl acetate=3: 1 obtains colorless oil purpose product 0.64g, productive rate 50.7% for eluent comes flash column chromatography to separate.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (CDCl 3) δ: 8.01-8.04 (d, 2H), 7.83 (s, 2H), 7.56-7.60 (d, 2H), 7.30-7.32 (d, 2H), 7.17-7.20 (d, 2H), 4.86 (s, 4H), 3.82-3.87 (m, 12H), 3.50-3.54 (m, 4H), 3.66 (s, 6H), 1.44-1.50 (m, 4H), 1.06-1.12 (m, 18H), 0.55-0.59 (t, 4H); 13C NMR (CDCl 3) δ: 154.4,135.6,135.2,133.6,129.0,126.0,125.6,125.2,120.5,116.0,69.7,65.4,56.3,51.2,23.0,18.3,8.1; Ultimate analysis (%, C 42H 62O 10Si 2Calculated value): C, 64.50 (64.42); H, 8.03 (7.98); Si, 7.09 (7.17).
Embodiment 3:
General structure is (I), and wherein, R is selected from-C 12H 25Chiral binaphthol silicone derivative 6,6 '-two (the silica-based propoxy-of triethoxy) methyl-2, the preparation of 2 '-two (dodecyloxy) dinaphthalene.
With compound (R)-6,6 '-dihydroxymethyl-2,2 '-two (dodecyloxy) dinaphthalene 0.83g (1.20mmol) is dissolved in the 15mL methylene dichloride, add the about altogether 0.18g of sodium hydride (4.50mmol) under the vigorous stirring in batches, adding shrend after reacting completely goes out, use ethyl acetate extraction, obtain sodium alkoxide, vacuum-drying.This sodium alkoxide is dissolved in the dry toluene; add the about 1.13mL of chloropropyl triethoxysilane (4.50mmol); nitrogen protection is stirred down; reflux 30 hours; toluene is removed in underpressure distillation; use sherwood oil: ethyl acetate=5: 1 obtains colorless oil purpose product 0.86 g, productive rate 65.6% for eluent comes flash column chromatography to separate.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (CDCl 3) δ: 7.93-7.96 (d, 2H), 7.85 (s, 2H), 7.42-7.45 (d, 2H), 7.20-7.22 (d, 2H), 7.14-7.17 (d, 2H), 4.82 (s, 4H), and 3.94-4.01 (m, 12H), 3.82-3.87 (m, 4H), 3.50-3.54 (t, 4H), 1.88-1.93 (m, 2H), 1.64-1.70 (m, 4H), and 1.41-1.46 (m, 4H), 1.15-1.30 (m, 32H) 1.04-1.10 (m, 18H), and 0.84-0.89 (t, 6H), 0.54-0.59 (t, 4H); 13C NMR (CDCl 3) δ: 154.6,135.7,135.1,133.7,129.0,126.1,125.8,125.4,120.6,116.0,69.7,65.5,64.8,58.6,47.4,31.9,29.5,29.2,26.4,25.6,22.7,18.3,14.1,8.1; Ultimate analysis (%, C 64H 106O 10Si 2Calculated value): C, 70.36 (70.41); H, 9.83 (9.79); Si, 5.12 (5.15).
Embodiment 4:
General structure is (I), and wherein, R is selected from-C 16H 33Chiral binaphthol silicone derivative 6,6 '-two (the silica-based propoxy-of triethoxy) methyl-2, the preparation of 2 '-two (n-Hexadecane oxygen base) dinaphthalene.
With compound (R)-6,6 '-dihydroxymethyl-2,2 '-two (n-Hexadecane oxygen base) dinaphthalene 0.95g (1.20mmol) is dissolved in the 15mL methylene dichloride, add the about altogether 0.19g of sodium hydride (4.80mmol) under the vigorous stirring in batches, adding shrend after reacting completely goes out, use ethyl acetate extraction, obtain sodium alkoxide, vacuum-drying.This sodium alkoxide is dissolved in the dry toluene; add the about 1.20mL of chloropropyl triethoxysilane (4.80mmol); nitrogen protection is stirred down; reflux 36 hours; toluene is removed in underpressure distillation; use sherwood oil: ethyl acetate=5: 1 obtains white oily purpose product 0.82g, productive rate 57.0% for eluent comes flash column chromatography to separate.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (CDCl 3) δ: 7.91-7.94 (d, 2H), 7.82 (s, 2H), 7.41-7.44 (d, 2H), 7.19-7.21 (d, 2H), 7.13-7.16 (d, 2H), 4.81 (s, 4H), and 3.93-4.00 (m, 12H), 3.81-3.86 (m, 4H), 3.50-3.54 (t, 4H), 1.89-1.92 (M, 2H), 1.65-1.69 (m, 4H), and 1.41-1.46 (m, 4H), 1.15-1.33 (m, 48H) 1.04-1.10 (m, 18H), and 0.82-0.87 (t, 6H), 0.54-0.59 (t, 4H); 13C NMR (CDCl 3) 13C NMR (CDCl 3) δ: 154.8,135.7,135.2,133.8,129.1,126.2,125.9,125.4,120.7,116.1,69.8,65.6,64.89,58.7,47.5,31.9,29.6,29.3,26.5,25.7,22.8,18.5,14.3,8.3; Ultimate analysis (%, C 72H 122O 10Si 2Calculated value): C, 71.72 (71.83); H, 10.32 (10.21); Si, 4.58 (4.67).

Claims (2)

1. chiral binaphthol silicone derivative is characterized in that, general structure is:
Figure C2006100166210002C1
Wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33
2. the preparation method of a chiral binaphthol silicone derivative as claimed in claim 1 is characterized in that, its step and condition are as follows:
With compound 6,6 '-dihydroxymethyl-2,2 '-disubstituted dinaphthalene (R) or (S) be dissolved in the methylene dichloride, add sodium hydride under the vigorous stirring, the sodium hydride mole dosage is the former 3～4 times, adds shrend after reacting completely and goes out in batches, use ethyl acetate extraction, obtain sodium alkoxide, vacuum-drying; With the chloropropyl triethoxysilane of isolated sodium alkoxide and 2.5～4 times of mole dosage in dry toluene; nitrogen protection is stirred down; reflux 24～36 hours; toluene is removed in underpressure distillation; use sherwood oil: ethyl acetate=2: 1～5: 1 comes flash column chromatography to separate as eluent to purify; obtain general structure and be (I), wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33Chiral binaphthol silicone derivative.
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CN101992076B (en) * 2010-10-29 2012-05-30 华东理工大学 Chiral binaphthyl chromatogram immobile phase, and preparation method and application thereof
CN107629184B (en) * 2017-09-26 2020-06-23 东北师范大学 R-binaphthol polyurethane, preparation method and application
CN113416162B (en) * 2021-07-29 2023-02-10 南开大学 Double-chiral binaphthyl O-N-N tridentate ligand and preparation method thereof
CN114870892B (en) * 2022-02-07 2023-04-28 上海交通大学 Chiral binaphthyl catalyst and preparation method and application thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6479708B1 (en) * 1998-11-18 2002-11-12 The Regents Of The University Of California Biphasic catalysis in water/carbon dioxide micellar systems
JP2003261680A (en) * 2002-03-08 2003-09-19 National Institute Of Advanced Industrial & Technology Binaphthylsiloxane based polymer and its production method
CN1463266A (en) * 2001-04-19 2003-12-24 株式会社上野制药应用研究所 Binaphthol derivative and method for producing same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6479708B1 (en) * 1998-11-18 2002-11-12 The Regents Of The University Of California Biphasic catalysis in water/carbon dioxide micellar systems
CN1463266A (en) * 2001-04-19 2003-12-24 株式会社上野制药应用研究所 Binaphthol derivative and method for producing same
JP2003261680A (en) * 2002-03-08 2003-09-19 National Institute Of Advanced Industrial & Technology Binaphthylsiloxane based polymer and its production method

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