CN101121726A - Chiral dinaphtholsiloxane derivatives and preparation method thereof - Google Patents

Chiral dinaphtholsiloxane derivatives and preparation method thereof Download PDF

Info

Publication number
CN101121726A
CN101121726A CNA2007101289131A CN200710128913A CN101121726A CN 101121726 A CN101121726 A CN 101121726A CN A2007101289131 A CNA2007101289131 A CN A2007101289131A CN 200710128913 A CN200710128913 A CN 200710128913A CN 101121726 A CN101121726 A CN 101121726A
Authority
CN
China
Prior art keywords
chiral
naphthol
linking
siloxane derivative
silicone derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CNA2007101289131A
Other languages
Chinese (zh)
Inventor
王晓梅
高连勋
姬相玲
邱雪鹏
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Institute of Applied Chemistry of CAS
Original Assignee
Changchun Institute of Applied Chemistry of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Institute of Applied Chemistry of CAS filed Critical Changchun Institute of Applied Chemistry of CAS
Priority to CNA2007101289131A priority Critical patent/CN101121726A/en
Publication of CN101121726A publication Critical patent/CN101121726A/en
Pending legal-status Critical Current

Links

Abstract

The invention relates to a chiral linking naphthol siloxane derivative connected by the 6, 6-propylamine amide methyl and the preparation method. The invention is characterized in the structural formula; therein, R is chosen from the - CH2OCH3,-CH3, -C12H25 or - C16H33. After the later graft or copolycondensation to be loaded on the mesoporous silicon dioside, the chiral linking naphthol siloxane derivative provided in the invention can be used in a plurality of catalytic reactions, such as the asymmetric synthetic reaction of the diethyl zinc and the benzaldehyde, the asymmetric Baylis-Hillman reaction, and so on. Therein, the linking naphthol siloxane derivative protected by the methoxy methyl can be used to prepare the mesoporous material after the copolycondensation or the later graft to protect the easy doffing of the base groups, and can be directly used in the catalytic reaction; the linking naphthol siloxane derivative protected by the long-chain alkyl can be used as the siloxane modifying reagent and the surfactant at the same time to prepare the complex mesoporous material. In the synthesis method of the chiral linking naphthol siloxane derivative, the raw materials are easy to access; the synthesis process is simple and easy.

Description

Chiral dinaphtholsiloxane derivatives and preparation method thereof
Technical field
The present invention relates to chiral binaphthol silicone derivative of 6,6 ' Propylamino amide 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 ' two amido derivative of the dinaphthol of different phenolic hydroxyl groups protection and obtains 6, the silicone derivative of 6 ' Propylamino amide methyl connection.And provide the preparation method of these derivatives.
Chiral binaphthol silicone derivative among the present invention, its general structure is as follows:
Wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33Introduce general structure below and be (IV), wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33The preparation method of chiral binaphthol silicone derivative, step and condition are as follows:
Compound 6; 6 '-two amidos-2; 2 '-disubstituted dinaphthalene (R) or (S) and the isocyanate group propyl-triethoxysilicane of 6～8 times of mole dosage in anhydrous chloroform, nitrogen protection is stirred down, reflux 0.5～1 hour; dissolving fully; chloroform is removed in air distillation, ℃ leaves standstill 10～16 hours in encloses container internal heating to 80 ± 10, separates obtaining general structure and be (IV) then under gravity filtration through cold normal hexane washing or by column chromatography; wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33Chiral binaphthol silicone derivative.
The nuclear-magnetism of the chiral binaphthol silicone derivative 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 Propylamino amide methyl connects for 6 '; the blocking group of phenolic hydroxyl group has methoxymethyl, methyl, dodecyl and hexadecyl; they all are with 6; 6 '-two amidos-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 this class chiral binaphthol silicone derivative, the raw material of these synthesis techniques all is easy to obtain, and the step of synthesis technique is simple, easily row.General structure is to carry out in encloses container for the derivative of (IV) is synthetic, and reaction is carried out easily.These derivatives that obtain are all more stable, and major part can be separated purification by column chromatography, 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 (IV), and wherein, R is selected from-CH 2OCH 3Chiral binaphthol silicone derivative 6,6 '-two (the silica-based Propylamino of triethoxy) amide group-2, the preparation of 2 '-dimethoxy methoxyl group dinaphthalene.
With compound (R)-6; 6 '-two amidos-2; 2 '-dimethoxy methoxyl group dinaphthalene 0.65g (1.60mmol); be dissolved in the 50mL anhydrous chloroform, heating for dissolving adds isocyanate group propyl-triethoxysilicane 2.37mL (9.60mmol) then; nitrogen protection is stirred down; reflux 0.5 hour, chloroform is removed in air distillation, and 80 ± 10 ℃ left standstill 10 hours in encloses container.Add cold normal hexane, separate out the flesh pink precipitation, action of gravity is filtered down, with cold normal hexane washing three times, collects the gluey purpose product of flesh pink 0.90g, productive rate 62.5%.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (DMSO-d 6) δ: 8.45 (s, H), 8.07 (s, 2H), 7.84-7.86 (d, 2H), and 7.48-7.50 (d, 2H), 7.07-7.09 (d, 2H), 6.77-6.79 (d, 2H), 6.14-6.17 (t, 2H), 5.01-5.13 (dd, 4H), 3.72-3.77 (m, 12H), 3.19 (s, 6H), 3.04-3.09 (m, 4H), 1.45-1.50 (m, 4H), 1.13-1.16 (m, 18H), 0.54-0.58 (t, 4H); 13C NMR (DMSO-d 6) δ: 155.4,153.2,136.1,129.4,129.1,128.1,125.1,120.3,118.9,114.8,113.2,101.1,50.2,41.8,39.6,23.4,18.3,7.3; Ultimate analysis (%, C 44H 66N 4O 12Si 2Calculated value): C, 58.75 (58.77); H, 7.42 (7.40); N, 6.21 (6.23); Si, 6.22 (6.25).
Embodiment 2:
General structure is (IV), and wherein, R is selected from-CH 3Chiral binaphthol silicone derivative 6,6 '-two (the silica-based Propylamino of triethoxy) amide group-2, the preparation of 2 '-dimethoxy dinaphthalene.
With compound (R)-6; 6 '-two amidos-2; 2 '-dimethoxy dinaphthalene 0.55g (1.60mmol); be dissolved in the 60mL anhydrous chloroform, heating for dissolving adds isocyanate group propyl-triethoxysilicane 2.37mL (9.60mmol) then; nitrogen protection is stirred down; reflux 0.75 hour, chloroform is removed in air distillation, and 80 ± 10 ℃ left standstill 12 hours in encloses container.Add cold normal hexane, separate out the flesh pink precipitation, action of gravity is filtered down, with cold normal hexane washing three times, collects the gluey purpose product of flesh pink 1.02g, productive rate 75.5%.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (DMSO-d 6) δ: 8.45 (s, 2H), 8.07 (s, 2H), 7.84-7.86 (d, 2H), and 7.48-7.50 (d, 2H), 7.07-7.09 (d, 2H), 6.77-6.80 (d, 2H), 6.14-6.17 (t, 2H), 3.72-3.77 (m, 12H), 3.66 (s, 6H), 3.04-3.09 (m, 4H), 1.47-1.50 (m, 4H), 1.13-1.16 (m, 18H), 0.54-0.58 (t, 4H); 13C NMR (DMSO-d 6) δ: 155.3,153.1,136.0,129.3,129.0,128.0,125.0,120.2,118.8,114.7,113.1,56.2,41.7,39.5,23.3,18.2,7.3; Ultimate analysis (%, C 42H 62N 4O 10Si 2Calculated value): C, 60.14 (60.12); H, 7.42 (7.45); N, 6.64 (6.68); Si, 6.65 (6.69).
Embodiment 3:
General structure is (IV), and wherein, R is selected from-C 12H 25Chiral binaphthol silicone derivative 6,6 '-two (the silica-based Propylamino of triethoxy) amide group-2, the preparation of 2 '-two (dodecyloxy) dinaphthalene.
With compound (R)-6; 6 '-two amidos-2; 2 '-two (dodecyloxy) dinaphthalene 0.65g (1.20mmol); be dissolved in the 30mL anhydrous chloroform, heating for dissolving adds isocyanate group propyl-triethoxysilicane 2.08mL (8.40mmol) then; nitrogen protection is stirred down; reflux 1 hour, chloroform is removed in air distillation, and 80 ± 10 ℃ left standstill 14 hours in encloses container.The column chromatography separation obtains colorless oil purpose product 0.84g productive rate 60.5%.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1HNMR (CDCl 3) δ: 8.43 (s, 2H), 8.05 (s, 2H), 7.82-7.84 (d, 2H), 7.46-7.48 (d, 2H), 7.05-7.07 (d, 2H), 6.75-6.77 (d, 2H), 6.12-6.15 (t, 2H), 3.82-3.87 (m, 4H), 3.72-3.77 (m, 12H), 3.50-3.54 (t, 4H), 1.64-1.70 (m, 4H), 1.47-1.52 (m, 4H), 1.34-1.40 (m, 4H), 1.15-1.30 (m, 32H), 1.10-1.13 (m, 18H), and 0.84-0.89 (t, 6H), 0.54-0.58 (t, 4H); 13C NMR (CDCl 3) δ: 155.5,153.3,136.2,129.5,129.2,128.2,125.2,120.4,118.9,114.9,113.3,72.5,70.2,51.2,48.4,32.5,30.6,30.3,30.0,26.6,23.1,18.2,6.1,14.1,8.5; Ultimate analysis (%, C 64H 106N 4O 10Si 2Calculated value): C, 66.97 (66.98); H, 9.32 (9.31); N, 4.89 (4.88); Si, 4.85 (4.89).
Embodiment 4:
General structure is (IV), and wherein, R is selected from-C 16H 33Chiral binaphthol silicone derivative 6,6 '-two (the silica-based Propylamino of triethoxy) amide group-2, the preparation of 2 '-two (n-Hexadecane oxygen base) dinaphthalene.
With compound (R)-6; 6 '-two amidos-2; 2 '-two (n-Hexadecane oxygen base) dinaphthalene 0.92g (1.20mmol); be dissolved in the 40mL anhydrous chloroform, heating for dissolving adds isocyanate group propyl-triethoxysilicane 2.37mL (9.60mmol) then; nitrogen protection is stirred down; reflux 1 hour, chloroform is removed in air distillation, and 80 ± 10 ℃ left standstill 16 hours in encloses container.The column chromatography separation obtains colorless oil purpose product 0.93g productive rate 61.5%.Through nuclear-magnetism, ultimate analysis proof is the purpose compound really:
1H NMR (CDCl 3) δ: 8.44 (s, 2H), 8.06 (s, 2H), 7.83-7.85 (d, 2H), 7.47-7.49 (d, 2H), 7.06-7.08 (d, 2H), 6.76-6.78 (d, 2H), 6.14-6.17 (t, 2H), 3.82-3.87 (m, 4H), 3.72-3.77 (m, 12H), 3.50-3.54 (t, 4H), 1.64-1.70 (m, 4H), 1.47-1.52 (m, 4H), 1.34-1.40 (m, 4H), 1.15-1.30 (m, 48H), 1.10-1.13 (m, 18H), and 0.84-0.89 (t, 6H), 0.54-0.58 (t, 4H); 13C NMR (CDCl 3) δ: 155.5,153.3,136.2,129.5,129.2,128.2,125.2,120.4,118.9,114.9,113.3,72.7,70.3,51.3,48.5,32.6,30.7,30.3,30.0,26.7,23.2,18.3,16.2,14.3,8.7; Ultimate analysis (%, C 64H 106N 4O 10Si 2Calculated value): C, 68.67 (68.64); H, 9.78 (9.76); N, 4.42 (4.45); Si, 4.43 (4.46).

Claims (2)

1. chiral binaphthol silicone derivative is characterized in that, general structure is:
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:
Compound 6; 6 '-two amidos-2; 2 '-disubstituted dinaphthalene (R) or (S) and the isocyanate group propyl-triethoxysilicane of 6～8 times of mole dosage in anhydrous chloroform; nitrogen protection is stirred down; reflux 0.5～1 hour; dissolving fully; chloroform is removed in air distillation; ℃ left standstill 10～16 hours in encloses container internal heating to 80 ± 10; under gravity filtration, obtain chiral binaphthol silicone derivative then through cold normal hexane washing or by the column chromatography separation; its general structure is (IV), and wherein, R is selected from-CH 2OCH 3,-CH 3,-C 12H 25Or-C 16H 33
CNA2007101289131A 2006-03-03 2006-03-03 Chiral dinaphtholsiloxane derivatives and preparation method thereof Pending CN101121726A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNA2007101289131A CN101121726A (en) 2006-03-03 2006-03-03 Chiral dinaphtholsiloxane derivatives and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNA2007101289131A CN101121726A (en) 2006-03-03 2006-03-03 Chiral dinaphtholsiloxane derivatives and preparation method thereof

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
CNB2006100166214A Division CN100364999C (en) 2006-03-03 2006-03-03 Chiral binaphthol silicone derivative and its preparing method

Publications (1)

Publication Number Publication Date
CN101121726A true CN101121726A (en) 2008-02-13

Family

ID=39084246

Family Applications (1)

Application Number Title Priority Date Filing Date
CNA2007101289131A Pending CN101121726A (en) 2006-03-03 2006-03-03 Chiral dinaphtholsiloxane derivatives and preparation method thereof

Country Status (1)

Country Link
CN (1) CN101121726A (en)

Similar Documents

Publication Publication Date Title
CN103214509B (en) Cubic eight-methacryloyloxsilsesquioxane silsesquioxane crystal and preparation method thereof
CN101940947A (en) Method for preparing polystyrene resin-immobilized Salon-Co (III) catalyst
CN103627002A (en) Preparation method of double-end double-hydroxyalkyl polydimethylsiloxane
CN101501047B (en) Novel epoxy compound and process for production thereof
CN101274984B (en) Preparation of dihydroxyl-terminated polydimethylsiloxane
CN106243105A (en) Methylene-bridged 1,8 naphthyridines part and copper (I) coordination compound, preparation method and application
CN102993142B (en) Preparation method of 4-hydroxy aurone compound
CN111253425B (en) Synthesis method of 1, 3-bis [2- (3, 4-epoxycyclohexyl) ethyl ] tetramethyldisiloxane
CN102718768A (en) Chiral five-membered bicyclic guanidine compound, preparation method and application thereof
CN101585780A (en) Method for asymmetric synthesis of chiral paclitaxel lateral chain
CN101648967B (en) Preparation method of 3-(methacryloxypropyl) propyl-triethoxysilicane
CN101679641B (en) Method for the production of beta-ketocarbonyl-functional organosilicon compounds
CN101121726A (en) Chiral dinaphtholsiloxane derivatives and preparation method thereof
CN100364999C (en) Chiral binaphthol silicone derivative and its preparing method
CN101712622B (en) Method for preparing anti-asthmatic medicament of salmeterol
CN101121725A (en) Chiral dinaphtholsiloxane derivatives and preparation method thereof
CN109942418A (en) The preparation method of compound and chipal compounds
CN109485671A (en) A kind of preparation method of bis- (trimethyl silicane) oxalates
CN101879458B (en) Preparation method of polysiloxane-loaded chiral diamine derivative catalyst
CN104447588B (en) Based on Ni (II) metal organic frame and synthetic method thereof and application
CN101845055B (en) Method for purifying dichloromethyl phenylsilane by chemical coordination effect
CN102485719A (en) Preparation method of Imatinib amine
CN101693642A (en) Method for synthesizing 1,2-diphenylethylene compounds
CN101215294A (en) Chiral dinaphtholsiloxane derivatives and preparation method thereof
CN103193784B (en) A kind of containing pyrimidine group rigidity Conjugate macrocycle compound and its preparation method and application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Open date: 20080213