CN1513843A - Cyano substituted heterocyclic ketene semiamine contained molecular material and its preparation method - Google Patents
Cyano substituted heterocyclic ketene semiamine contained molecular material and its preparation method Download PDFInfo
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Abstract
A cyano substituted heterocyclic ketenamine as a molecular material with high smelting point higherer than 300 deg.C, electric bistable nature and special dielectric characteristics is prepared through reaction between dicyano (or aza-cyano) substituted ketene methyl thiol and diamine.
Description
Technical field
The invention belongs to organic functional molecular and molecule electronic material technical field, be specifically related to heterocyclic ketene semiamine contained molecular material of cyano group replacement and preparation method thereof.
Technical background
The organic molecule that some structure is special under light, electricity or magnetic action, can become another kind of state by a kind of state-transition, thus " 0 " and " 1 " two states in configuration information processing and the information storage, i.e. bistable state.Wherein, have the molecular material of electrical bistable property, can be used as the core material in microelectronic device and the molecular electronic device, have purposes widely aspect many at molecular based logical gate, transistor, memory etc.We found once that a class contained heterocyclic 1, and 1-dicyano ethene derivatives has electrical bistable property, can be used for making the thin-film device of electrically-erasable.This class material can also be used as dielectric substance, and inferior capacitance material has special purposes in the differentiating circuit element.This quasi-molecule is a kind of ketenes amine condensation derivatives from structure.(xuwei, Lv Yinxiang, Central China one, a kind of molecular based bi-stable electric organic film device and manufacture craft thereof of electrically-erasable, application for a patent for invention number: 01132374.4)
The present invention on the basis of early-stage Study, further design and synthetic cyano group replaces, contain heterocyclic ketene semiamine functional molecular.
Summary of the invention
The objective of the invention is to propose a kind of new molecule electronic material good electric bistable behavior or special dielectric properties and preparation method thereof that has.
The molecule electronic material that the present invention proposes is to be prepared with diamine reactant respectively by the ketenes that cyano group the replaces thiomethyl alcohol that contracts, replace for cyano group, contain heterocyclic ketene semiamine functional molecule material.
The molecule electronic material that the present invention proposes, the ketenes that adopts dicyano the to replace thiomethyl alcohol (being called for short DDCN) that contracts, (dimethylthiomethylene) methane-1,1-dicarbonitrile, respectively and diamines (Diamine) reaction, then be prepared into that dicyano replaces, contain heterocyclic ketene semiamine molecule, its structure is as follows shown in the formula:
(structure 1)
The molecule electronic material that the present invention proposes, the ketenes that adopts azepine one cyano group the to replace thiomethyl alcohol that contracts, 2-aza-3,3-dimethylthioprop-2-enenitrile (is called for short: DNCN) respectively and diamines (diamine) reaction, then be prepared into that azepine one cyano group replaces, contain heterocyclic ketene semiamine molecule, its structural formula is as follows shown in the formula:
Among the present invention, adopt DDCN or DNCN respectively with different diamine reactants, can obtain the ketene semiamine functional molecular that cyano group replaces, specific as follows:
(1) DDCN and 4-methyl-o-phenylenediamine reaction obtains compound (A).
Chinese: 2-(5-methyl isophthalic acid, 3-dihydrobenzo imidazoles)-propane dinitrile,
Have another name called: (5-methyl-3-hydrogen benzimidazolyl-2 radicals-subunit) methane-1, the 1-dintrile,
English name: 2-(5-methyl-1,3-dihydro-benzoimidazol-2-ylidene)-malononitrile,
The IUPAC title: (5-methyl-3-hydrobenzimidazol-2-ylidene) methane-1,1-dicarbonitrile,
The molecular formula of this compound is C
11H
8N
4Structural formula is shown below:
(2) DDCN and 4-chlorine O-Phenylene Diamine reaction obtains compound (B).
Chinese: 2-(5-chloro-1,3-dihydrobenzo imidazoles-2-subunit)-propane dinitrile,
Have another name called: (5-chloro-3-hydrogen benzimidazolyl-2 radicals-subunit) methane-1, the 1-dintrile,
English name: 2-(5-chloro-1,3-dihydro-benzoimidazol-2-ylidene)-malononitrile,
The IUPAC title: (5-chloro-3-hydrobenzimidazol-2-ylidene) methane-1,1-dicarbonitrile,
The molecular formula of this compound is C
10H
5ClN
4Structural formula is shown below:
(3) DDCN and N-phenyl O-Phenylene Diamine reaction obtains compound (C).
Chinese: 2-(1-phenyl-1,3-dihydro-benzimidazolyl-2 radicals-subunit)-propane dinitrile,
Have another name called: (1-phenyl-3-hydrogen benzimidazolyl-2 radicals-subunit)-methane-1, the 1-dintrile,
English name: 2-(1-phenyl-l, 3-dihydro-benzoimidazol-2-ylidene)-malononitrile,
The IUPAC title: (1-phenyl-3-hydrobenzimidazol-2-ylidene) methane-1,1-dicarbonitrile,
The molecular formula of this compound is C
16H
10N
4Structural formula is shown below:
(4) DDCN and 2, the reaction of 3-diaminonaphthalene obtains compound (D).
Chinese: 2-(1,3-dihydro-naphtho-[2,3-d] imidazoles-2-subunit)-propane dinitrile,
Have another name called: (4, the 6-diaza tricyclic [7.4.0.0＜3,7 〉] 13 carbon-1 (2), 3 (7), 8,10,12-pentaene-5-subunit) methane-1, the 1-dintrile,
English name: 2-(1,3-dihydro-naphtho[2,3-d] imidazol-2-ylidene)-manonitrile,
The IUPAC title:
(4，6-diazatricyclo[7.4.0.0<3，7>]trideca-1(2)，3(7)，8，10，12-pentaen-5-ylidene)methane-1，1-dicarbonitrile
The molecular formula of this compound is C
14H
8N
4Structural formula is shown below:
(5) DDCN and 1, the reaction of 8-diaminonaphthalene obtains compound (E).
Chinese: 2-(1H, 3H-perimidine-2-subunit) propane dinitrile,
Have another name called: 3-hydrogen perimidine-2-subunit methane-1, the 1-dintrile,
English name: 2-(1H, 3H-perimidin-2-ylidene)-malononitrile,
IUPAC title: 3-hydroperimidin-2-ylidenemethane-1,1-dicarbonitrile,
The molecular formula of this compound is C
14H
8N
4Structural formula is shown below:
(6) DDCN and 3,3 ', 4, the reaction of 4 '-biphenyl tetramine obtains compound (F).
Chinese: 2-(2 '-dicyano methylene radical-1,3,2 ', 3 '-tetrahydrochysene-1 ' H-[5,5 '] connection (benzoglyoxaline)-2-subunit) propane dinitrile,
Have another name called: (5-(2-(dicyano methylene radical)-1,3-dihydrobenzo imidazoles-5-yl)-1,3-dihydrobenzo imidazoles-2-subunit) methane-1, the 1-dintrile,
English name: 2-(2 '-dicyanomethylene-1,3,2 ', 3 '-tetrahydro-1 ' H-[5,5 '] bibenzoimidazolyl-2-ylidene)-malononitrile,
The IUPAC title:
(5-(2-(dicyanomethylene)-1，3-dihydrobenzimidazol-5-yl)-1，3-dihydrobenzimidazol-2-ylidene)methane-1，1-dicarbonitrile，
The molecular formula of this compound is C
20H
10N
8Structural formula is shown below:
(7) DDCN and 1, the reaction of 2-propylene diamine obtains compound (G).
Chinese: 2-(4-methylimidazole alkane-2-subunit) propane dinitrile,
Have another name called: (4-methylimidazole alkane-2-subunit) methane-1, the 1-dintrile,
English name: 2-(4-methylimidazolidin-2-ylidene)-malononitrile,
The IUPAC title: (4-methylimidazolidin-2-ylidene) methane-1,1-dicarbonitrile,
The molecular formula of this compound is C
7H
8N
4Structural formula is shown below:
(8) DNCN and O-Phenylene Diamine reaction obtains compound (H).
Chinese: 1,3-dihydrobenzo imidazoles-2-subunit-cyanamide,
Have another name called: 2-azepine-2-(3-hydrogen benzimidazolyl-2 radicals-subunit) acetonitrile,
English name: 1,3-dihydro-benzoimidazol-2-ylidene-cyanamide,
IUPAC title: 2-aza-2-(3-hydrobenzimidazol-2-ylidene) ethanenitrile,
The molecular formula of this compound is C
8H
6N
4Structural formula is shown below:
(9) DNCN and 1, the reaction of 8-diaminonaphthalene obtains compound (I).
Chinese: 1H, 3H-perimidine-2-subunit-nitrile amine,
Have another name called: 2-azepine-2-(3-hydrogen perimidine-2-subunit) acetonitrile,
English name: 1H, 3H-perimidin-2-ylidene-cyanamide,
IUPAC title: 2-aza-2-(3-hydroperimidin-2-ylidene) ethanenitrile,
The molecular formula of this compound is C
12H
8N
4Structural formula is shown below:
(10) DNCN and 1, the reaction of 2-propylene diamine obtains compound (J).
Chinese: 4-methyl-imidazolidine-2-subunit-nitrile amine,
Have another name called: 2-azepine-2-(4-methylimidazole alkane-2-subunit) acetonitrile,
English name: 4-methyl-imidazolidin-2-ylidene-cyanamide,
IUPAC title: 2-aza-2-(4-methylimidazolidin-2-ylidene) ethanenitrile,
The molecular formula of this compound is C
5H
8N
4Structural formula is shown below:
(11) DNCN and N-phenylethylenediamine reaction obtains compound (K).
Chinese: 1-phenylimidazolidines,-2-subunit-cyanamide,
Have another name called: 2-azepine-2-(1-phenylimidazolidines,-2-subunit) acetonitrile,
English name: 1-phenyl-imidazolidin-2-ylidene-cyanamide,
IUPAC title: 2-aza-2-(1-phenylimidazolidin-2-ylidene) ethanenitrile,
The molecular formula of this compound is C
10H
10N
4Structural formula is shown below:
(12) DNCN and 3,3 ', 4, the reaction of 4 '-biphenyl tetramine obtains compound (L).
Chinese: 5-(2-(cyano group aza-methylene) (1,3-dihydrobenzo imidazoles-5-yl)) (1,3-dihydrobenzo imidazoles-2-subunit)-cyanamide,
Have another name called: 2-(5-(2-(cyano group aza-methylene) (1,3-dihydrobenzo imidazoles-5-yl)) (1,3-dihydrobenzo imidazoles-2-subunit))-2-azepine acetonitrile,
English name:
5-(2-(cyanoazamethylene)(1，3-dihydrobenzimidazol-5-yl))(1，3-dihydrobenzimidazol-2-ylidene)-cyanamide
The IUPAC title:
2-(5-(2-(cyanoazamethylene)(1，3-dihydrobenzimidazol-5-yl))(1，3-dihydrobenzimidazol-2-ylidene))-2-aza-ethanenitrile
The molecular formula of this compound is C
10H
10N
4Structural formula is shown below;
The present invention also proposes the synthetic method of above-mentioned organic molecule:
(1) DCN and diamine reactant prepare that dicyano replaces contains heterocyclic ketene semiamine molecule:
Contract thiomethyl alcohol (DDCN) and diamines (diamine) of the ketenes that dicyano is replaced is dissolved in the dehydrated alcohol.The mol ratio of DDCN and diamines is 0.9～3; The concentration of diamines all is 0.05～0.5 mol.With mixing solutions reflux 6～24 hours, boil off most of ethanol then, cooling is filtered, and use washing with alcohol, must crude product.Crude product N, dinethylformamide (DMF) recrystallization, with ethanol and ether washing, drying gets product again.Productive rate 65～98%.
In aforesaid method, if diamines is the 4-methyl-o-phenylenediamine, then obtain compound (A), its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is a 4-chlorine O-Phenylene Diamine, then obtain compound (B), its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is a N-phenyl O-Phenylene Diamine, then obtain compound (C), its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 2, the 3-diaminonaphthalene then obtains compound (D), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 1, the 8-diaminonaphthalene then obtains compound (E), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 3,3 ', 4,4 '-biphenyl tetramine then obtains compound (F), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 1, the 2-propylene diamine then obtains compound (G), and its structural formula and molecular formula are equal to aforementioned.
(2) DNCN and diamine reactant prepare that azepine one cyano group replaces contains heterocyclic ketene semiamine molecule:
Contract thiomethyl alcohol (DNCN) and diamines (diamine) of the ketenes that azepine one cyano group is replaced is dissolved in the dehydrated alcohol, adds triethylamine or pyridine in addition again.The mol ratio of DNCN and diamines is 0.9～3; The concentration of diamines is 0.05～0.5 mol; The concentration of triethylamine or pyridine is 0.1～1 mol.With mixing solutions reflux 6～24 hours, boil off most of ethanol then, cooling is filtered, with ethanol and ether washing, crude product.Crude product N, dinethylformamide (DMF) and ethyl alcohol recrystallization, with ethanol and ether washing, drying gets product again.Productive rate 60～95%.
In aforesaid method, if diamines is an O-Phenylene Diamine, then obtain compound (H), its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 1, the 8-diaminonaphthalene then obtains compound (I), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 1, the 2-propylene diamine then obtains compound (J), and its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is the N-phenylethylenediamine, then obtain compound (K), its structural formula and molecular formula are equal to aforementioned.
In aforesaid method, if diamines is 3,3 ', 4,4 '-biphenyl tetramine then obtains compound (L), and its structural formula and molecular formula are equal to aforementioned.
The ketene semiamine molecule great majority of the present invention's preparation have good thermostability, and wherein the fusing point of many molecules is more than 300 ℃.These functional moleculars have electrical bistable property a bit, and some has special dielectric properties, can be used for making multiple functional device, such as: electric memory, molecular switch, logical gate, transistor, electrical condenser and differentiating circuit element etc.In addition, this class organic molecule can also also have special purpose in the organic chemical industry field as organic synthesis intermediate.
Embodiment
The invention is further illustrated by the following examples
Embodiment 1, the ketenes that 10 mmole 4-methyl-o-phenylenediamines, 10 mmole dicyanos the are replaced thiomethyl alcohol (DDCN) that contracts is dissolved in 50 milliliters of dehydrated alcohols reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get light yellow solid, i.e. compound (A) again.
Productive rate 86%; Fusing point (m.p.):＞300 ℃;
IR(cm
-1)：3161，2983，2216，2175，1638，1605，1509，1474，796，691.
1H-NMR(500MHz，DMSO-d
6，δ)：12.7(d，2H)，7.0-7.2(m，3H)，2.4(s，3H).
Embodiment 2,10 mmole 4-chlorine O-Phenylene Diamines, 10 mmole DDCN are dissolved in 50 milliliters of dehydrated alcohols reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get beige solid, i.e. compound (B) again.
Productive rate 86%; Fusing point (m.p.):＞300C;
IR(cm
-1)：3147，2970，2218，2197，2178，1639，1602，1474，1363，926，798，688.
1H-NMR(500MHz，DMSO-d
6，δ)：13.0(s，2H)，7.2-7.3(m，3H).
Embodiment 3,10 mmole N-phenyl O-Phenylene Diamines, 10 mmole DDCN are dissolved in 50 milliliters of dehydrated alcohols reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get Off-white solid, i.e. compound (C) again.
Productive rate 80%; Fusing point (m.p.): 282-284 ℃;
IR(cm
-1)：3148，3103，2946，2212，2187，1624，1573，1502，1256，758，690.
1H-NMR(500MHz，DMSO-d
6，δ)：13.0(s，2H)，7.6(d，5H)，6.8-7.4(m，4H).
Embodiment 4, with 10 mmoles 2,3-diaminonaphthalene, 10 mmole DDCN are dissolved in 50 milliliters of dehydrated alcohols, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get light yellow solid, i.e. compound (D) again.
Productive rate 80%; Fusing point (m.p.):＞300 ℃:
IR(cm
-1)：3147，2221，2197，2174，1634，1602，1515，1464，1269，857，685.
1H-NMR(500MHz，DMSO-d
6，δ)：12.9(s，2H)，8.0(m，2H)，7.7(s，2H)，7.4(m，2H)
Embodiment 5, with 10 mmoles 1,8-diaminonaphthalene, 10 mmole DDCN are dissolved in 50 milliliters of dehydrated alcohols, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get oyster solid, i.e. compound (E) again.
Productive rate 95%; Fusing point (m.p.):＞300 ℃;
IR(cm
-1)：3212，3052，2195，1653，1593，1459，1382，1267，812，761，688.
1H-NMR(500MHz，DMSO-d
6，δ)：10.9(s，2H)，7.3(m，4H)，7.0(m，2H).
Embodiment 6, with 10 mmoles 3,3 ', 4,4 '-biphenyl tetramine, 25 mmole DDCN are dissolved in 80 milliliters of dehydrated alcohols, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get pale brown look solid, i.e. compound (F) again.
Productive rate 71%; Fusing point (m.p.):＞300 ℃;
IR(cm
-1)：3136，2205，2175，1630，1589，1491，1276，1113，932，795.
1H-NMR(500MHz，DMSO-d
6，δ)：10.9(s，4H)，7.0-7.3(m，6H).
Embodiment 7, with 10 mmoles 1,2-propylene diamine, 10 mmole DDCN are dissolved in 50 milliliters of dehydrated alcohols, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use the DMF recrystallization then, with ethanol and ether washing, get white solid, i.e. compound (G) again.
Productive rate 97%; Fusing point (m.p.): 238-240 ℃;
IR(cm
-1)：3262，2978，2211，2185，1598，1530，1448，1392，1338，1153，653.
1H-NMR(500MHz，DMSO-d
6，δ)：5.7-6.0(d，2H)，4.2(m，1H)，3.9(t，1H)，
3.3-3.4(m，1H)，1.4(d，3H).
Embodiment 8, the ketenes that 10 mmole O-Phenylene Diamines, 10 mmole azepines, one cyano group the are replaced thiomethyl alcohol (DNCN) that contracts is dissolved in 50 milliliters of dehydrated alcohols, adds 1 milliliter of triethylamine again, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use DMF and ethyl alcohol recrystallization then, with ethanol and ether washing, get yellow solid, i.e. compound (H) again.
Productive rate 65%; Fusing point (m.p.): 185-187 ℃ (decomposition);
IR(cm
-1)：3059，2173，1637，1561，1509，1459，1389，1270，1229，772，742.
1H-NMR(500MHz，DMSO-d
6，δ)：7.0-9.0(m，6H).
Embodiment 9, with 10 mmoles 1,8-diaminonaphthalene, 10 mmole DNCN are dissolved in 50 milliliters of dehydrated alcohols, add 1 milliliter of triethylamine again, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use DMF and ethyl alcohol recrystallization then, with ethanol and ether washing, get pale solid, i.e. compound (I) again.
Productive rate 79%; Fusing point (m.p.):＞300 ℃;
IR(cm
-1)：3163，3007，2949，2197，1691，1676，1647，1610，1550，1449，
1383，1330，1279，1163，979，810，765，700，537，517，465.
1H-NMR(500MHz，DMSO-d
6，δ)：11.0(s，2H)，7.2-7.3(m，4H)，6.8(d，2H).
Embodiment 10, with 10 mmoles 1,2-propylene diamine, 10 mmole DNCN are dissolved in 50 milliliters of dehydrated alcohols, add 1 milliliter of triethylamine again, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use DMF and ethyl alcohol recrystallization then, with ethanol and ether washing, get white solid, i.e. compound (J) again.
Productive rate 84%; Fusing point (m.p.): 146-148 ℃;
IR(cm
-1)：3246，2964，2187，1670，1602，1531，1406，1347，1280，1180，
1065，987，935，860，764，615.
1H-NMR(500MHz，DMSO-d
6，δ)：6.2-6.4(d，2H)，4.1-4.2(m，1H)，3.8(t，1H)，
3.2-3.3(m，1H)，1.3(d，3H).
Embodiment 11,10 mmole N-phenylethylenediamines, 10 mmole DNCN are dissolved in 50 milliliters of dehydrated alcohols, add 1 milliliter of triethylamine again, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use DMF and ethyl alcohol recrystallization then, with ethanol and ether washing, get white solid, i.e. compound (K) again.
Productive rate 90%; Fusing point (m.p.): 156-157 ℃;
IR(cm
-1)：3246，2169，1605，1554，1509，1426，1335，1284，1148，748，694.
1H-NMR(500MHz，DMSO-d
6，δ)：8.4(s，1H)，7.1(m，2H)，6.5-6.6(m，3H)，
3.4(m，2H)，3.2(t，2H).
Embodiment 12, with 10 mmoles 3,3 ', 4,4 '-biphenyl tetramine, 25 mmole DNCN are dissolved in 50 milliliters of dehydrated alcohols, add 1 milliliter of triethylamine again, reflux 18 hours.Boil off most of solvent then, cooling is filtered, and uses washing with alcohol, gets crude product.Use DMF and ethyl alcohol recrystallization then, with ethanol and ether washing, get lark solid, i.e. compound (L) again.
Productive rate 71%; Fusing point (m.p.):＞300 ℃;
IR(cm
-1)：3166，2175，1637，1601，1561，1459，1267，804.
1H-NMR(500MHz，DMSO-d
6，δ)：7.0-9.0(m).
Claims (17)
1, a kind of molecule electronic material is characterized in that being prepared with diamine reactant respectively by the ketenes that cyano group the replaces thiomethyl alcohol that contracts, replace for cyano group, contain heterocyclic ketene semiamine functional molecule material.
2, molecule electronic material according to claim 1 is characterized in that ketenes that cyano group the replaces thiomethyl alcohol that contracts is ketenes that dicyano the replaces thiomethyl alcohol that contracts, obtain be that dicyano replaces, contain heterocyclic ketene semiamine molecular material, its structural formula is:
(structure 1)
3, molecule electronic material according to claim 1, it is characterized in that ketenes that cyano group the replaces thiomethyl alcohol that contracts is ketenes that azepine one cyano group the replaces thiomethyl alcohol that contracts, obtain be that azepine one cyano group replaces, contain heterocyclic ketene semiamine molecular material, its structural formula is:
(structure 2)
4, molecule electronic material according to claim 2 is characterized in that that obtain is compound (A) with the ketenes that dicyano replaces contract thiomethyl alcohol and the reaction of 4-methyl-o-phenylenediamine,
Its Chinese name is called: 2-(5-methyl isophthalic acid, 3-dihydrobenzo imidazoles)-propane dinitrile,
English name: 2-(5-methyl-1,3-dihydro-benzoimidazol-2-ylidene)-malononitrile,
Molecular formula is C
11H
8N
4, structural formula is shown below:
5, molecule electronic material according to claim 2 is characterized in that that obtain is compound (B) with the ketenes that dicyano replaces contract thiomethyl alcohol and the reaction of 4-chlorine O-Phenylene Diamine,
Its Chinese: 2-(5-chloro-1,3-dihydrobenzo imidazoles-2-subunit)-propane dinitrile,
English name: 2-(5-chloro-1,3-dihydro-benzoimidazol-2-ylidene)-malononitrile,
Molecular formula is C
10H
5ClN
4Structural formula is shown below:
6, molecule electronic material according to claim 2 is characterized in that that obtain is compound (C) with the ketenes that dicyano replaces contract thiomethyl alcohol and the reaction of N-phenyl O-Phenylene Diamine,
Its Chinese: 2-(1-phenyl-1,3-dihydro-benzimidazolyl-2 radicals-subunit)-propane dinitrile,
English name: 2-(1-phenyl-1,3-dihydro-benzoimidazol-2-ylidene)-malononitrile,
Molecular formula is C
16H
10N
4Structural formula is shown below:
7, molecule electronic material according to claim 2 is characterized in that with the ketenes that dicyano replaces contract thiomethyl alcohol and 2, the reaction of 3-diaminonaphthalene, and that obtain is compound (D),
Its Chinese: 2-(1,3-dihydro-naphtho-[2,3-d] imidazoles-2-subunit)-propane dinitrile,
English name: 2-(1,3-dihydro-naphtho[2,3-d] imidazol-2-ylidene)-manonitrile,
Molecular formula is C
14H
8N
4Structural formula is shown below:
8, molecule electronic material according to claim 2 is characterized in that with the ketenes that dicyano replaces contract thiomethyl alcohol and 1, the reaction of 8-diaminonaphthalene, and that obtain is compound (E),
Its Chinese: 2-(1H, 3H-perimidine-2-subunit) propane dinitrile,
English name: 2-(1H, 3H-perimidin-2-ylidene)-malononitrile,
Molecular formula is C
14H
8N
4Structural formula is as shown below:
9, molecule electronic material according to claim 2 is characterized in that ketenes that dicyano replaces contract thiomethyl alcohol and 3,3 ', 4, and the reaction of 4 '-biphenyl tetramine, that obtain is compound (F),
Its Chinese: 2-(2 '-dicyano methylene radical-1,3,2 ', 3 '-tetrahydrochysene-1 ' H-[5,5 '] connection (benzoglyoxaline)-2-subunit) propane dinitrile,
English name: 2-(2 '-dicyanomethylene-1,3,2 ', 3 '-tetrahydro-1 ' H-[5,5 '] bibenzoimidazolyl-2-ylidene)-malononitrile,
Molecular formula is C
20H
10N
8Structural formula is shown below:
10, molecule electronic material according to claim 2 is characterized in that with the ketenes that dicyano replaces contract thiomethyl alcohol and 1, the reaction of 2-propylene diamine, and that obtain is compound (G),
Its Chinese: 2-(4-methylimidazole alkane-2-subunit) propane dinitrile,
English name: 2-(4-methylimidazolidin-2-ylidene)-malononitrile,
Molecular formula is C
7H
8N
4Structural formula is shown below:
11, molecule electronic material according to claim 3 is characterized in that that obtain is compound (H) with the ketenes that azepine one cyano group replaces contract thiomethyl alcohol and O-Phenylene Diamine reaction,
Its Chinese: 1,3-dihydrobenzo imidazoles-2-subunit-cyanamide,
English name: 1,3-dihydro-benzoimidazol-2-ylidene-cyanamide,
Molecular formula is C
8H
6N
4Structural formula is shown below:
12, molecule electronic material according to claim 3 is characterized in that with the ketenes that azepine one cyano group replaces contract thiomethyl alcohol and 1, the reaction of 8-diaminonaphthalene, and that obtain is compound (I),
Its Chinese: 1H, 3H-perimidine-2-subunit-nitrile amine,
English name: 1H, 3H-perimidin-2-ylidene-cyanamide,
Molecular formula is C
12H
8N
4Structural formula is shown below:
13, molecule electronic material according to claim 3 is characterized in that with the ketenes that azepine one cyano group replaces contract thiomethyl alcohol and 1, the reaction of 2-propylene diamine, and that obtain is compound (J),
Its Chinese: 4-methyl-imidazolidine-2-subunit-nitrile amine,
English name: 4-methyl-imidazolidin-2-ylidene-cyanamide,
Molecular formula is C
5H
8N
4Structural formula is shown below:
14, molecule electronic material according to claim 3 is characterized in that that obtain is compound (K) with the ketenes that azepine one cyano group replaces contract thiomethyl alcohol and the reaction of N-phenylethylenediamine,
Its Chinese: 1-phenylimidazolidines,-2-subunit-cyanamide,
English name: 1-phenyl-imidazolidin-2-ylidene-cyanamide,
Molecular formula is C
10H
10N
4Structural formula is shown below:
15, molecule electronic material according to claim 1 is characterized in that with the ketenes that azepine one cyano group replaces contract thiomethyl alcohol and 3,3 ', 4, and the reaction of 4 '-biphenyl tetramine, that obtain is compound (L),
Its Chinese: 5-(2-(cyano group aza-methylene) (1,3-dihydrobenzo imidazoles-5-yl)) (1,3-dihydrobenzo imidazoles-2-subunit)-cyanamide English name:
5-(2-(cyanoazamethylene)(1，3-dihydrobenzimidazol-5-yl))(1，3-dihydrobenzimidazol-2-ylidene)-cyanamide，
Molecular formula is C
10H
10N
4Structural formula is shown below;
16, a kind of preparation method who contains heterocyclic ketene semiamine molecular material of dicyano replacement as claimed in claim 2, it is characterized in that: contract thiomethyl alcohol and diamines of the ketenes that dicyano is replaced is dissolved in the dehydrated alcohol, the mol ratio of DDCN and diamines is 0.9～3, and the concentration of diamines is 0.05～0.5 mol; With mixing solutions reflux 6～24 hours, boil off most of ethanol then, cooling is filtered, and the DMF recrystallization use in washing, and with ethanol and ether washing, drying gets product again:
In the above-mentioned steps, diamines adopts 4-methyl-o-phenylenediamine, 4-chlorine O-Phenylene Diamine, N-phenyl O-Phenylene Diamine, 2 respectively, 3-diaminonaphthalene, 1,8-diaminonaphthalene, 3,3 ', 4,4 '-biphenyl tetramine, 1,2-propylene diamine, corresponding product are respectively compound (A), (B), (C), (D), (E), (F) and (G).
17, a kind of preparation method who contains heterocyclic ketene semiamine molecular material of azepine as claimed in claim 3 one cyano group replacement, it is characterized in that: contract thiomethyl alcohol and diamines of the ketenes that azepine one cyano group is replaced is dissolved in the dehydrated alcohol, add triethylamine or pyridine again, the mol ratio of DNCN and diamines is 0.9～3, the concentration of diamines is 0.05～0.5 mol, and the concentration of triethylamine or pyridine is 0.1～1 mol; With mixing solutions reflux 6～24 hours, boil off most of ethanol then, cooling is filtered, washing, with DMF and ethyl alcohol recrystallization, again with ethanol and ether washing, drying, product;
In the above-mentioned steps, diamines adopts O-Phenylene Diamine, 1 respectively, 8-diaminonaphthalene, 1, and 2-propylene diamine, N-phenylethylenediamine, 3,3 ', 4,4 '-biphenyl tetramine, corresponding product is respectively compound (H), (I), (J), (K), (L).
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293409B (en) * | 2008-06-19 | 2012-09-05 | 复旦大学 | Metallic-organic complex function thin film with stepped construction and uses thereof |
| CN108440543A (en) * | 2017-02-16 | 2018-08-24 | 北京鼎材科技有限公司 | Perimidine derivative |
| CN112521601A (en) * | 2020-11-24 | 2021-03-19 | 西安交通大学 | Degradable covalent cross-linked polymer and preparation process and application thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101293409B (en) * | 2008-06-19 | 2012-09-05 | 复旦大学 | Metallic-organic complex function thin film with stepped construction and uses thereof |
| CN108440543A (en) * | 2017-02-16 | 2018-08-24 | 北京鼎材科技有限公司 | Perimidine derivative |
| CN112521601A (en) * | 2020-11-24 | 2021-03-19 | 西安交通大学 | Degradable covalent cross-linked polymer and preparation process and application thereof |
| CN112521601B (en) * | 2020-11-24 | 2021-08-13 | 西安交通大学 | Degradable covalent cross-linked polymer and preparation process and application thereof |
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