CN1257896C - Funcitonal molecule material containing four tertiary amine branches and preparation method - Google Patents

Funcitonal molecule material containing four tertiary amine branches and preparation method Download PDF

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CN1257896C
CN1257896C CN 200310108272 CN200310108272A CN1257896C CN 1257896 C CN1257896 C CN 1257896C CN 200310108272 CN200310108272 CN 200310108272 CN 200310108272 A CN200310108272 A CN 200310108272A CN 1257896 C CN1257896 C CN 1257896C
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CN1539833A (en
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徐伟
吕银祥
周辉
蓝碧健
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Fudan University
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Abstract

The present invention relates to a four-branch functional molecule material, a preparation method and an application method thereof, which belongs to the technical field of organic functional molecule materials and nanometer organic materials. The four-branch functional molecule material structurally uses teera pentacite as a basic structure framework, and has four functional branches, and each branch is a tertiary amine structure. Organic compound prepared by the present invention can be used for the nanometer organic materials, molecule semiconductors, current carrier transmission materials, luminescent materials, nonlinear optical materials, etc., and has wide application in the technical fields of organic electroluminescent devices, organic field effect transistors, non-linear optical devices, rub resistance nanometer organic medium materials, etc.

Description

Contain four branched functional molecule materials of tertiary amine and preparation method thereof
Technical field
The invention belongs to organic functional molecular material and nanometer organic materials technical field, be specifically related to a class and contain four branched functional molecule materials of tertiary amine and preparation method thereof.
Technical background
The size of organic molecule is at nanoscale, and the nanometer organic materials has the characteristics of size homogeneous, and this is that general metal nanoparticle or inorganic nano-particle can't be accomplished.Therefore the organic molecule of sphere or torispherical can be regarded nanoparticle as, and this class material has nanometer size effect, and many special functional propertys are arranged, such as: can be used as the lubricant, nanometer dielectric materials of nanometer dielectric material, the bearing of rub resistance etc.The functional unit of ad hoc structure is incorporated in the organic molecule molecule of torispherical, can also makes up organic nano-functional material, such as being used as molecular semiconductor, carrier transmission material, luminescent material etc.To push away in electronics base and the electron withdrawing group introducing conjugated organic molecule and can also constitute nonlinear optical material.In each branch of molecule, introduce electron donor(ED), each molecule just contains four electron donor(ED)s simultaneously like this, this electron donor(ED) can be simultaneously and four electron acceptors constitute organic charges and shift complex compounds, so can be used as molecule electronic material and use.Therefore, the design and the organic molecule material of synthetic special construction can further be expanded the functional property of organic molecule.
Summary of the invention
The objective of the invention is to propose the preparation method that a class has functional molecule material and this molecular material of four apparatus derivatoriuses.
The four branch functional molecule materials that the present invention proposes are skeleton with the Ji Wusi base, and each molecule contains four identical branches, and each branch contains the tertiary amine structural unit.It is starting raw material that this quasi-molecule material adopts tetramethylolmethane four benzene sulfonates or four halo neopentanes, by preparing with the reactive organic molecule that contains active hydrogen.Wherein, four halo neopentanes adopt the tetraiodo for neopentane or tetrabromo for neopentane, the organic molecule with active hydrogen can adopt various secondary amine and derivative thereof.This quasi-molecule material has constructional feature as follows:
Figure C20031010827200051
Wherein X is various heteroatomss or methylene radical, R 2Be various substituting groups or hydrogen atom.When X is the N atomic time, R 1Be various substituting groups; When X is O, S, then there is not R 1Substituting group.
The secondary amine that the functional molecule material that the present invention proposes, its precursor contain active hydrogen adopts different materials, can obtain the organic molecule material of different structure.
The following several four branch functional organic molecule materials of the special proposition of the present invention:
(1) English name: Tetrakis (morpholin-4-ylmethyl) methane
Chinese: four (morphine quinoline-4-ylmethyl) methane
Molecular formula is C 21H 40N 4O 4, chemical structural formula is as follows:
Figure C20031010827200061
(2) English name: Tetrakis (piperidin-1-ylmethyl) methane
Chinese: four (piperidines-1-ylmethyl) methane
Molecular formula is C 25H 48N 4, chemical structural formula is as follows:
(3) English name: Tetrakis (2-(1,2,3,4-tetrahydroisoquinol) ylmethyl) methane
Chinese: four (2-(1,2,3, the 4-tetrahydro isoquinolyl) methyl) methane
Molecular formula is C 41H 48N 4, chemical structural formula is as follows:
Figure C20031010827200063
(4) English name: Tetrakis ((4-phenylpiperazinyl) methyl) methane
Chinese: four ((4-Phenylpiperazinyl) methyl) methane
Molecular formula is C 45H 60N 8, chemical structural formula is as follows:
Figure C20031010827200071
(5) methane English name: Tetrakis (4-(4-nitrophenyl) piperazinyl) methyl)
Chinese: four ((4-(4-nitrophenyl) piperazinyl) methyl) methane
Molecular formula is C 45H 56N 12O 8, chemical structural formula is as follows:
Figure C20031010827200072
(6) English name: Tetrakis ((4-(diphenylmethyl) piperazinyl) methyl) methane
Chinese: four ((4-(diphenyl methyl) piperazinyl) methyl) methane
Molecular formula is C 56H 84N 8, chemical structural formula is as follows:
Figure C20031010827200073
A kind of universal method for preparing above-mentioned four branch functional molecule materials is: adopting tetramethylolmethane four benzene sulfonates or four halo neopentanes is starting raw material, by preparing with the various reactive organic molecules that contain active hydrogen.Wherein, four halo neopentanes adopt the tetraiodo for neopentane or tetrabromo for neopentane; Organic molecule with active hydrogen can adopt secondary amine molecule and various derivatives etc.Concrete steps are as follows:
In nitrogen atmosphere, in reaction flask, add salt of wormwood, secondary amine, four halo neopentane and organic solvents.The mol ratio of secondary amine and salt of wormwood, four halo neopentanes is respectively 0.9～1.1,4.5～6.Solvent adopts DMF or TG, and the amount ratio of secondary amine and solvent is 0.5～2 mol.Stir, and be heated to 130～170 ℃, reacted 6～24 hours.Cooling is filtered, and solid is washed with massive laundering, and oven dry is again with ethanol or DMF recrystallization.
In the aforesaid method, four halo neopentanes can adopt the tetraiodo for neopentane or tetrabromo for neopentane.
In above-mentioned steps,, obtain compound (A) if secondary amine adopts morpholine (Morpholine).
In above-mentioned steps,, obtain compound (B) if secondary amine adopts piperidines (Piperidine).
In above-mentioned steps, if secondary amine adopts 1,2,3, the 4-tetrahydroisoquinoline (1,2,3,4-Tetrahydroisoquinoline), obtain compound (C).
In above-mentioned steps,, obtain compound (D) if secondary amine adopts 1-phenylpiperazine (1-Phenylpiperazine).
In above-mentioned steps,, obtain compound (E) if secondary amine adopts 1-(4-nitrophenyl) piperazine (1-(4-Nitrophenyl) piperazine).
In above-mentioned steps,, obtain compound (F) if secondary amine adopts 1-(diphenyl methyl) piperazine (1-(Diphenylmethyl) piperazine).
The four branch molecular materials that made by the present invention can pass through vacuum thermal evaporation method film forming.These organic molecules can also by further grafting and functionalization, can make up the more function molecular material as required as organic medium and organic synthesis intermediate.Through suitably handling, these organic materialss can also use as the nanometer organic materials.
Compound (A), (B), (C) and (F) can be used as organic medium and lubricant uses.Compound (D) is a kind of good electron donor, can and electron acceptor (such as TCNQ) constitute charge transfer complex; Compound (D) also has the hole transport performance, can be used for being manufactured with the hole transmission layer in the organic electroluminescence devices.Compound (E) is a kind of good nonlinear optical material, can also be used as the luminescent material in the organic electroluminescence device.
Embodiment
The invention is further illustrated by the following examples
Embodiment 1
In nitrogen atmosphere, in reaction flask, add 0.06 mole of salt of wormwood (or yellow soda ash), 0.06 mole of morpholine (Morpholine), 0.01 mole of tetrabromo for neopentane and 60 milliliters of DMF.Stir, be heated to 150 ℃ of reactions 12 hours.Cooling is filtered, and solid is dried with 100 ml waters washing three times, uses ethyl alcohol recrystallization again, promptly gets compound (A), productive rate 78%.
Fusing point (m.p.): 220-222 ℃.
IR(KBr，cm -1)：2959，2849，2796，1464，1279，1261，1114，1067，1008，920，858，800.
1H?NMR(500MHz，CDCl 3，δ)：3.6(t，16H)，2.5(d，16H)，2.4(t，8H).
Embodiment 2
In nitrogen atmosphere, in reaction flask, add 0.06 mole of salt of wormwood (or yellow soda ash), 0.06 mole of piperidines (Piperidine), 0.01 mole of tetrabromo for neopentane and 60 milliliters of DMF.Stir, be heated to 150 ℃ of reactions 12 hours.Cooling is filtered, and solid is dried with 100 ml waters washing three times, uses ethyl alcohol recrystallization again, promptly gets compound (B), productive rate 70%.
Fusing point (m.p.): 140～142 ℃.
IR(KBr，cm -1)：2931，2852，2776，1471，1304，1104，997.
1H?NMR(500MHz，CDCl 3，δ)：1.35(s，8H)，1.48(t，16H)，2.29(s，8H)，2.39(s，16H)；
Embodiment 3
In nitrogen atmosphere, add 0.06 mole of salt of wormwood (or yellow soda ash), 0.06 mole 1,2,3 in the reaction flask, the 4-tetrahydroisoquinoline (1,2,3,4-tetrahydroisoquinoline), 0.01 mole of tetrabromo is for neopentane and 60 milliliters of DMF.Stir, be heated to 150 ℃ of reactions 12 hours.Cooling is filtered, and solid is dried with 100 ml waters washing three times, uses the DMF recrystallization again, promptly gets compound (C), productive rate 85%.
Fusing point (m.p.): 200-202 ℃.
IR(KBr，cm -1)：2952，2788，1673，1451，1353，1281，1131，1034，936，831，746，738.
1H?NMR(500MHz，CDCl 3，δ)：6.9-7.3(m，16H)，3.7(s，8H)，2.7-3.0(m，24H).
Embodiment 4
In nitrogen atmosphere, in reaction flask, add 0.06 mole of salt of wormwood (or yellow soda ash), 0.06 mole of 1-phenylpiperazine (1-phenylpiperazine), 0.01 mole of tetrabromo for neopentane and 60 milliliters of DMF.Stir, be heated to 150 ℃ of reactions 12 hours.Cooling is filtered, and solid is dried with 100 ml waters washing three times, uses the DMF recrystallization again, promptly gets compound (D), productive rate 87%.
Fusing point (m.p.): 174-176 ℃.
IR(KBr，cm -1)：2954，2794，1600，1502，1382，1236，1155，1010，925，754，687，520.
1H?NMR(500MHz，CDCl 3，δ)：6.8-7.3(m，20H)，3.17(s，16H)，2.72(s，16H)，2.5-2.6(d，8H).
Embodiment 5
In nitrogen atmosphere, in reaction flask, add 0.06 mole of salt of wormwood (or yellow soda ash), 0.06 mole of 1-(4-nitrophenyl) piperazine (1-(4-nitrophenyl) piperazine), 0.01 mole of tetrabromo for neopentane and 60 milliliters of DMF.Stir, be heated to 150 ℃ of reactions 12 hours.Cooling is filtered, and solid is dried with 100 ml waters washing three times, uses the DMF recrystallization again, promptly gets compound (E), productive rate 65%.
Fusing point (m.p.):＞300 ℃.
IR(KBr，cm -1)：2840，1597，1508，1321，1239，1113，1000，925，827，752，655.
1H?NMR(500MHz，CDCl 3，δ)：8.12-8.15(d，8H)，6.80-6.84(d，8H)，2.59-3.60(m，40H).
Embodiment 6
In nitrogen atmosphere, in reaction flask, add 0.06 mole of salt of wormwood (or yellow soda ash), 0.06 mole of 1-(diphenyl methyl) piperazine (1-(diphenylmethyl) piperazine), 0.01 mole of tetrabromo for neopentane and 60 milliliters of DMF.Stir, be heated to 150 ℃ of reactions 12 hours.Cooling is filtered, and solid is dried with 100 ml waters washing three times, uses the DMF recrystallization again, promptly gets compound (F), productive rate 75%.
Fusing point (m.p.):＞300 ℃.
IR(KBr，cm -1)：2840，1597，1508，1321，1239，1113，1000，925，827，752，655.
1H?NMR(500MHz，CDCl 3，δ)：8.12-8.15(d，8H)，6.80-6.84(d，8H)，2.59-3.60(m，40H).

Claims (9)

1, a kind of four branch molecular materials, it is a skeleton with the Ji Wusi base, each molecule contains four identical branches, each branch all contains the tertiary amine structure, it is characterized in that this molecular material is a starting raw material by tetramethylolmethane four benzene sulfonates or four halo neopentanes, by preparing with the reactive organic molecule that contains active hydrogen, wherein, the described organic molecule that contains active hydrogen is selected from morpholine, piperidines, 1,2,3,4-tetrahydroisoquinoline, 1-phenylpiperazine, 1-(4-nitrophenyl) piperazine or 1-(diphenyl methyl) piperazine.
2, four branch molecular materials according to claim 1, the molecular formula that it is characterized in that molecular material is C 21H 40N 4O 4, chemical structural formula is as follows:
The name of this compound is called: four (morphine quinoline-4-ylmethyl) methane.
3, four branch molecular materials according to claim 1, the molecular formula that it is characterized in that molecular material is C 25H 48N 4, chemical structural formula is as follows:
Figure C2003101082720002C2
The name of this compound is called: four (piperidines-1-ylmethyl) methane.
4, four branch molecular materials according to claim 1, the molecular formula that it is characterized in that molecular material is C 41H 48N 4, chemical structural formula is as follows:
The name of this compound is called: four (2-(1,2,3, the 4-tetrahydro isoquinolyl) methyl) methane.
5, four branch molecular materials according to claim 1, the molecular formula that it is characterized in that molecular material is C 45H 60N 8, chemical structural formula is as follows:
Figure C2003101082720003C1
The name of this compound is called: four ((4-Phenylpiperazinyl) methyl) methane.
6, four branch molecular materials according to claim 1, the molecular formula that it is characterized in that molecular material is C 45H 56N 12O 8, chemical structural formula is as follows:
The name of this compound is called: four ((4-(4-nitrophenyl) piperazinyl) methyl) methane.
7, four branch molecular materials according to claim 1, the molecular formula that it is characterized in that molecular material is C 56H 84N 8, chemical structural formula is as follows:
The name of this compound is called: four ((4-(diphenyl methyl) piperazinyl) methyl) methane.
8, the preparation method of the described four branch molecular materials of a kind of claim 1～7, it is characterized in that concrete steps are as follows: in nitrogen atmosphere, in reaction flask, add salt of wormwood, secondary amine, four halo neopentane and organic solvents, the mol ratio of secondary amine and salt of wormwood, four halo neopentanes is respectively 0.9～1.1,4.5～6, solvent adopts DMF or TG, and the amount ratio of secondary amine and solvent is 0.5～2 mol; Stir, and be heated to 130～170 ℃, reacted 6～24 hours; Cooling is filtered, and solid is washed with massive laundering, and oven dry is again with ethanol or DMF recrystallization.
9, preparation method according to claim 8, it is characterized in that described secondary amine adopts morpholine respectively, piperidines, 1,2,3, the 4-tetrahydroisoquinoline, the 1-phenylpiperazine, 1-(4-nitrophenyl) piperazine, 1-(diphenyl methyl) piperazine, obtain corresponding compound and be followed successively by (A) four (morphine quinoline-4-ylmethyl) methane, (B) four (piperidines-1-ylmethyl) methane, (C) four (2-(1,2,3, the 4-tetrahydro isoquinolyl) methane methyl), (D) four ((4-nitrophenyl) piperazinyl) methyl) methane, (E) ((4-(4-nitrophenyl) piperazinyl) methyl) methane, (F) four ((4-(diphenyl methyl) piperazinyl) methyl) methane.
CN 200310108272 2003-10-30 2003-10-30 Funcitonal molecule material containing four tertiary amine branches and preparation method Expired - Fee Related CN1257896C (en)

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