CN1160362C - Compound with intramolecule change transfer and its preparing process - Google Patents
Compound with intramolecule change transfer and its preparing process Download PDFInfo
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- CN1160362C CN1160362C CNB021107289A CN02110728A CN1160362C CN 1160362 C CN1160362 C CN 1160362C CN B021107289 A CNB021107289 A CN B021107289A CN 02110728 A CN02110728 A CN 02110728A CN 1160362 C CN1160362 C CN 1160362C
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Abstract
The present invention discloses a structure of a molecular assembly object of metallic phthalocyanine and substituted disulfide ethylene tetrathiafulvalene and a preparation method thereof. The molecular assembly object is a macromolecular compound which transfers charges in molecules, and has good application prospect in the field of molecular switches.
Description
Technical field
The molecule that the present invention relates to two sulphur ethylene group tetrathiafulvalenes of a kind of metal phthalocyanine and replacement is assembled thing and preparation method thereof.
Background technology
Four thio rich tile alkene (TTF) and derivative thereof are that the good π of a class-electronics is supplied with body (Donor), can generate stable radical cation.This free radical can generate the intermolecular charge transfer complex of conduction with numerous electron acceptors, and for example, the CT-complex compound (TTF-TCNQ) of four thio rich tile alkene and four cyano para benzoquinone bismethane at room temperature just has the electric conductivity as the metal.Simultaneously four thio rich tile alkene and derivative thereof are again good group of molecules package materials, can match each other with other functional materials molecule to be combined into CT-complex compound in the molecule.This intramolecular charge shifts complex compound and has multiple electricity, light, magnetic isoreactivity, can be used as the molecular electronic device material and be used for super large-scale integration or be used for photonic computer in the future, or be used for chemistry or biological transmitter as end organ as " molecular switch ".
Bryce professor's in 1996 research group has reported (Adv.Mater.8,1,63,1996) a kind of nonmetal phthalocyanine and the monomeric assembling thing of non-replacement tetrathiafulvalene, but this compound is slightly soluble in DMF and DMSO, and almost insoluble in other organic solvent, this has hindered this application of compound.The same year, Cook professor's research group reported (Chem.Commun., 1925,1996) another kind of assembling thing, and it is assembled by the tetrathiafulvalene monomer of nonmetal phthalocyanine through an ester group and a non-replacement, and this kind compound has liquid crystal property.1997, Bryce professor's research group synthesized two kinds of new compounds (J.Chem.Soc., PerkinTrans.2,1671,1997) again.They are respectively by nonmetal phthalocyanine and 4 or 8 symmetric macromole that the tetrathiafulvalene that replaces through the long-chain alkylthio assembles.And assembling compound through the tetrathiafulvalene monomer of alkoxyl group and replacement, metal phthalocyanine do not appear in the newspapers.
Summary of the invention
It is that metal phthalocyanine assembles compound and preparation method thereof through the tetrathiafulvalene monomer of alkoxyl group and replacement that the present invention discloses a kind of compound with intramolecular charge transfer.
Design of the present invention is such:
The present invention is that four TTF unit are introduced in the β position at the phthalocyanine molecule periphery that contains the different metal central atom.The two sulphur ethylene group tetrathiafulvalenes of these four TTF unit for replacing.Go up introducing long linear alkane for 4,5 at tetrathiafulvalene, and connect alkane and tetrathiafulvalene parent, can effectively increase solubleness with sulphur atom.Link to each other as spacer with alkoxyl group between the two sulphur ethylene group tetrathiafulvalenes of metal phthalocyanine and replacement, form the intramolecular charge transfering system (ICT) of D-σ-A (electronics is supplied with body-spacer-electron acceptor).
The molecule of two sulphur ethylene group tetrathiafulvalenes of metal phthalocyanine of the present invention and replacement assembles compound and has following structure:
Wherein: Me is a transition metal ion, preferably copper or zine ion; R is the straight chain saturated alkyl, is preferably C
6-8The straight chain saturated alkyl.
Compound of the present invention adopts following method synthetic:
(1) 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1, the preparation of 3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes:
At first the mol ratio of zinc salt (Zincate) and N-Hexyl Bromide is 1: 5.3 in the popular response device, with acetone is that solvent reacts under reflux state, reaction times is 2-4 hour, after separating purification, conventional method gets reaction product 4,5-di-n-hexyl sulphur-1,3-dithia cyclopentenes-2-thioketones.
Wherein: the preparation of zinc salt (Zincate) is open in document " Ute Scherer; Ausgedehnte Donoren mitTetrathiafulvalen-Untereinheiten als Basis fuer elektrisch leitfaehigeLadungsuebertragungskomplexe.PhDThesis; derJohannes-Gutenberg-Universitaet (Maiz); 1992 ", and the present invention repeats no more.
Next Zincate and 2 in the popular response device, 3-dibromoacetic acid propyl ester mol ratio is 1: 8, is that solvent reacts under reflux state with acetone, the reaction times is 2-4 hour.After separating purification, conventional method gets reaction product 5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-thioketones.Is stirring under 10-30 ℃ in acetic acid and chloroform in 1: 3 with this compound and mercuric acetate with mol ratio, gets 5 after conventional method is separated purification, 6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-ketone.
At last with 4,5-di-n-hexyl sulphur-1,3-dithia cyclopentenes-2-thioketones and 5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] to place the popular response device with 1: 1 mol ratio be solvent with the triethyl-phosphite to two sulphur hexanaphthene-2-ketone, 110-120 ℃ of down reaction 5 hours, through conventional method separate after purifying 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-acetyl oxygen methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes.This compound and hydrazine hydrate mixed with mol ratio at 1: 15 to place volume ratio be that 1: 3 chloroform and methanol mixture stirred 36 hours down at 10-30 ℃, after separating purification, conventional method gets 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes.
(2) 4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-preparation of phthalic nitrile:
With 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes, 4-nitro phthalic nitrile and carbonate (or lithium hydroxide) is to mix at 1: 2: 5 with mol ratio, with N, dinethylformamide is that solvent places the popular response device, stirs 14 days down in 75 ℃.Through separate with prior art purify 4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-phthalic nitrile.
Wherein said carbonate is yellow soda ash or salt of wormwood.
(3) preparation of the finished product:
In the mixture of amylalcohol sodium/Pentyl alcohol (in the 30mL Pentyl alcohol, preparing), add 4-{2-[4 by 2.34 gram sodium Metal 99.5s; 5-di-n-hexyl sulphur-1; 3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1; 3-two sulphur [4; 5-b]-[1; 4] two sulphur hexanaphthenes }-phthalic nitrile, stir down and be heated to 130-135 ℃, under nitrogen protection reaction after 5 hours underpressure distillation except that desolvating.In resistates, add 80mL ethanol and 80mL acetate, standing over night.Obtain blackish green solid behind the suction filtration.Solid dissolves with chloroform after the ebullient washing with alcohol.Solution is by diatomite filtration, and filtrate concentrates, and steaming desolventizes.Again resulting unformed solids is dissolved in the solvent Pentyl alcohol, adds and the equimolar metal acetate salt heating of this unformed solids, under refluxad reacted 1 hour after ordinary method promptly gets the finished product after separating purification.
Wherein said metal acetate salt is neutralized verdigris or zinc acetate.
Embodiment
Preparation method to compound of the present invention is described further below:
(1) 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1, the preparation of 3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes:
Zinc salt (Zincate) is to drip the bromohexane that is dissolved in the acetone in boiling state behind the acetone solution, and wherein zinc salt (Zincate) is 1: 5.3 with the mol ratio of bromohexane, continues backflow 2-4 hour, and suction filtration is removed insolubles.Distillation desolventizes, and resistates is purified through column chromatography and obtained one of required raw material of coupled reaction 4,5-di-n-hexyl sulphur-1, and 3-dithia cyclopentenes-2-thioketones, its reaction formula is as follows:
Refluxed 20 hours after purification obtains another raw material 5 of coupled reaction, 6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-thioketones by identical method.
In order to improve the selectivity of coupled reaction, this thioketones and mercuric acetate were stirred 24 hours under room temperature in acetic acid and chloroform with 1: 3 (mol ratio).Behind the suction filtration filtrate is washed, and used anhydrous sodium sulfate drying through washing, saturated sodium carbonate.Rotary evaporation can obtain 5 after removing chloroform, 6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-ketone.Shown under its structural formula:
Above-mentioned thioketones and ketone are placed reactor with 1: 1 mol ratio, and triethyl-phosphite is a solvent, and 110-120 ℃ of reaction 5 hours down, the decompression rotary evaporation removes and desolvates.Resistates obtains 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-acetyl oxygen methylene radical-5-hydrogen-6-dihydro-1 after column chromatography for separation, 3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes, and its structural formula is as follows.
This compound stir about 36 hours under the normal temperature in chloroform, methyl alcohol and hydrazine hydrate.Rotary evaporation is removed low boiling point solvent, uses chloroform extraction, the oil reservoir anhydrous sodium sulfate drying.Filter, rotary evaporation is removed chloroform.After column chromatography for separation, get 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes.
(2) 4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-preparation of phthalic nitrile, its structural formula is as follows:
With 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes and 4-nitro phthalic nitrile are mixed in the reactor through DMF with 1: 2 (mol ratio), add salt of wormwood, stir about is 14 days under the 75C.Rotary evaporation is removed DMF, uses chloroform extraction, the anhydrous magnesium sulfate drying after-filtration, and rotary evaporation is removed chloroform.Resistates gets 4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene after column chromatography is purified]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-phthalic nitrile.
(3) in mixture, add 4-{2-[4 by amylalcohol sodium/Pentyl alcohol; 5-di-n-hexyl sulphur-1; 3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1; 3-two sulphur [4; 5-b]-[1; 4] two sulphur hexanaphthenes }-phthalic nitrile, to stir down and be heated to 130-135 ℃, nitrogen protection is reacted down hour.Underpressure distillation removes and desolvates.In resistates, add ethanol and acetate, standing over night.Obtain blackish green solid behind the suction filtration.Solid dissolves with chloroform after ebullient ethanol is washed.Solution is by diatomite filtration, and filtrate concentrates, and steaming desolventizes, and obtains blackish green unformed solid.Solid is dissolved in the Pentyl alcohol, adding waits the neutralized verdigris of gram amount, is heated to backflow, reacts 1 hour again.Underpressure distillation removes and desolvates.Wash with ebullient ethanol again after residual solid washes with water, obtain blackish green solid, promptly get target compound.
The molecule assembling thing of two sulphur ethylene group tetrathiafulvalenes of said metal phthalocyanine of the present invention and replacement is a kind of macromolecular cpd that intramolecular charge shifts that has, and it has good prospects for application in the molecular switch field.
Below will the invention will be further described by embodiment, but embodiment does not limit protection scope of the present invention.
Embodiment
4,5-di-n-hexyl sulphur-1,3-dithia cyclopentenes-2-thioketones
8g zinc salt (Zincate) (11.2mmol) is dissolved in the 100mL acetone, is heated to backflow under stirring, and drips the 50mL acetone soln that contains 9.4mL (60mmol) bromohexane, refluxes 4 hours.Suction filtration is removed insolubles.Rotary evaporation is removed acetone.Resistates obtains 8g orange oil, productive rate 98% through column chromatography (with chloroform: sherwood oil=1: 2 is a developping agent) and after revolving developping agent.
MS(EI)：m/z(％)＝367(M
++1，14.119)，366(M
+，27.196)
5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-thioketones
In the 250mL there-necked flask, add 7.2g (10mmol) Zincate, 100mL acetone.Drip 11.4mL (80mmol) 2 under the stirring and refluxing, 3-dibromoacetic acid propyl ester/50mL acetone reacted about 20 hours.TLC follows the tracks of, and developping agent is an ethyl acetate: sherwood oil=1: 2.After reaction finishes, suction filtration.Filtrate is removed acetone through rotary evaporation, obtains orange red oil 3.2g altogether, productive rate 54% through column chromatography.
MS(EI)：m/z(％)＝296(M
+，32.33)；
EA For C
8H
8O
2S
5(%): calculated value: C32.43, H2.70; Experimental value: C32.22, H2.73 δ
H(CDCl
3): 4.40 (2H, d), 3.35 (3H, m), 2.10 (3H, s);
5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-ketone
Add 2.6g (8.78mmol) and go up described thioketones of step, 20mL chloroform, 20mL Glacial acetic acid, 8g (25.1mmol) mercuric acetate in 100mL single port flask, stirred one day under the room temperature, system changes taupe suspension gradually into.Behind the suction filtration filtrate is washed, and used anhydrous sodium sulfate drying through washing, saturated sodium carbonate.Rotary evaporation can obtain the pale brown look thick liquid of 2.0g, productive rate 81% after removing chloroform.
MS(EI)：m/z(％)＝280(M
+，32.33)；
EA For C
8H
8O
3S
4(%): calculated value .C34.29, H2.86; Experimental value: C34.73, H3.24 δ
H(CDCl
3): 4.35 (2H, d), 3.4 (3H, m), 2.1 (3H, s);
2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-acetyl oxygen methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes
0.28g (1mmol) 5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-ketone, 0.3mL (1mmol) 4,5-di-n-hexyl sulphur-1,3-dithia cyclopentenes-2-thioketones, the new triethyl-phosphite that steams of 5mL was in 110-120 ℃ of following heated and stirred 5 hours.The decompression rotary evaporation removes and desolvates.Through ethyl acetate: sherwood oil=column chromatography obtained the orange red oil of 0.40g, productive rate 70% in 1: 2.
MS(ESI)：m/z(％)＝598.2(M
+-1，5.45)，599.2(M
+，1.55)；
EA For C
23H
34O
2S
8(%): calculated value: C46.11, H5.72; Experimental value: C46.11, H5.73
δ
H(CDCl
3)：0.89(6H，t)，1.25-1.44(12H，m)，1.57-1.64(4H，m)，2.10(6H，s)，2.79(4H，m)，4.39-3.25(2H，m)，5.14(1H，m)，4.32(2H，d)
δ
C(CDCl
3)：14.709，21.431，23.204，28.854，30.343，30.950，31.954，32.744，37.041，42.535，65.351，77.447，77.701，77.955，108.395，114.358，114.576，115.926，128.410，171.074；
2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes
In the 250mL there-necked flask, add 2.7g (4.5mmol) 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-acetyl oxygen methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes, 45mL chloroform, 135mL methyl alcohol and 3.4mL (67mmol) hydrazine hydrate.Normal temperature stirs down up to till the no raw material of TLC check, about 36 hours.Rotary evaporation is removed low boiling point solvent, uses chloroform extraction, the oil reservoir anhydrous sodium sulfate drying.Filter, rotary evaporation is removed chloroform.Use the developping agent sherwood oil: chloroform: ethyl acetate=100: 10: 40 is made column chromatography.Obtain orange-yellow crystal 1.8g, productive rate 73% after revolving developping agent.m.p.56-58℃。
MS(ESI)：m/z(％)＝555.9(M
+-1，6.97)，556.9(M
+，1.96)，557.9(M
++1，2.91)
EA For C
21H
32OS
8(%): calculated value: C45.28, H5.79; Experimental value: C44.85, H5.64
δ
H(CDCl
3)：0.88(6H，t)，1.25-1.44(12H，m)，1.54-1.70(4H，m)，2.71--2.91(4H，m)
δ
C(CDCl
3)：14.448，22.957，28.614，30.116，31.717，36.797，40.329，77.183，77.437，77.691，111.856，113.691，128.140，131.627；
4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-phthalic nitrile
In the 100mL there-necked flask, add 0.3g (0.5mmol) 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes, 20mL dry DMF, 0.18g (1mmol) 4-nitro phthalic nitrile, 0.35g (2.5mmol) Anhydrous potassium carbonate, 75 ℃ of following stir abouts 14 days.Rotary evaporation is removed DMF, uses chloroform extraction, the anhydrous magnesium sulfate drying after-filtration, and rotary evaporation is removed chloroform.Resistates is through sherwood oil: ethyl acetate: obtain garnet crystal 0.11g, productive rate 32.2% after chloroform=column chromatography was purified in 100: 40: 10.Mp＝87-88℃。
MS(EI)：m/z(％)＝682(M
+-1，100)，683(M
+，58.86)，684(M
++1，42.48)
EA For C
29H
34OS
8N
2(%): calculated value: C50.99, H5.02, N4.10; Experimental value: C50.67, H5.03, N3.97
δ
H(CDCl
3)：0.85-0.93(6H，t)，1.25-1.45(12H，m)，1.59-1.68(4H，m)，2.65-2.81(4H，m)，2.81-2.87(2H，m)，2.98-3.05(2H，d)，4.80-4.90(H，t)，7.17-7.72(Ar-3H，m)
δ
C(CDCl
3)：14.706，23.206，28.858，30.359，31.963，36.559，37.064，77.446，77.700，77.954，109.132，109.680，114.963，115.558，115.945，118.606，120.497，121.399，128.413，131.023，136.287，159.867
Four-β-2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes } phthalocyanine
In mixture, add 580mg (0.85mmol) 4-{2-[4 by amylalcohol sodium/Pentyl alcohol; 5-di-n-hexyl sulphur-1; 3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1; 3-two sulphur [4; 5-b]-[1; 4] two sulphur hexanaphthenes }-phthalic nitrile, be heated to 130-135 ℃ under stirring, nitrogen protection was reacted 5 hours down.Underpressure distillation removes and desolvates.In resistates, add 80mL ethanol and 80mL acetate, standing over night.Obtain blackish green solid behind the suction filtration.Solid dissolves with chloroform after ebullient ethanol is washed.Solution is by diatomite filtration, and filtrate concentrates, and steaming desolventizes, and obtains the blackish green unformed solid of 92.8mg, productive rate 16%, Mp=150-185 ℃.
MS(ESI)：m/z(％)＝145(41.68)，147(20.57)，220(24.43)，222(13.59)，258(13.52)，335(15.26)，342(12.42)，406(18.57)，426(100.00)，427(21.28)，428(64.48)，429(14.92)，430(11.32)，438(15.35)，440(10.07)，701(42.36)，702(19.19)，730(17.76)
EA For C
116H
138O
4S
32N
8(%): calculated value: C50.95, H5.09, N4.10; Experimental value: C51.31, H5.36, N3.97;
δ
H(CDCl
3)：0.75-1.08(6H，t)，1.13-1.50(12H，m)，1.50-1.75(4H，m)，2.65-3.00(4H，m)，3.13-3.20(1H，t)
δ
C(CDCl
3)：14.807，23.387，30.056，30.396，31.281，38.118，39.452，125.732，129.539，131.569，168.450；
Four-β-2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes } copper (II) phthalocyanine
The above-mentioned product of 100mg, about 100mg neutralized verdigris are dissolved in the Pentyl alcohol, are heated to backflow, reacted 1 hour.Underpressure distillation removes and desolvates.Wash with ebullient ethanol again after residual solid washes with water, obtain the blackish green solid of 92mg, productive rate 90%.
EA For CuC
116H
136O
4S
32N
8(%): calculated value: C49.83, H4.86, N4.01; Experimental value: C50.21, H4.96, N3.95.
Claims (5)
1, the molecule of two sulphur ethylene group tetrathiafulvalenes of a kind of metal phthalocyanine and replacement assembling thing is characterized by described assembling thing and has following structure:
Wherein Me is a transition metal ion, and R is the straight chain saturated alkyl.
2, compound as claimed in claim 1 is characterized by wherein that Me is copper or zine ion, and R is C
6-8The straight chain saturated alkyl.
3, the method for preparation compound as claimed in claim 1 is characterized by this method and comprises the steps:
(1) 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1, the preparation of 3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes:
At first the mol ratio of zinc salt (Zincate) and N-Hexyl Bromide is 1: 5.3 in the popular response device, with acetone is that solvent reacts under reflux state, reaction times is 2-4 hour, after separating purification, conventional separating and purifying method gets reaction product 4,5-di-n-hexyl sulphur-1,3-dithia cyclopentenes-2-thioketones;
Next zinc salt (Zincate) and 2 in the popular response device, 3-dibromoacetic acid propyl ester mol ratio is 1: 8, with acetone is that solvent reacts under reflux state, reaction times is 2-4 hour, after separating purification, conventional separating and purifying method gets reaction product 5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-thioketones, with this compound and mercuric acetate with mol ratio be 1: 3 in acetic acid and solvent chloroform in stirring under the 10-30 ℃ of temperature after conventional separating and purifying method separates must 5 after purifying, 6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthene-2-ketone, at last with 4,5-di-n-hexyl sulphur-1,3-dithia cyclopentenes-2-thioketones and 5,6-dihydro-5-acetyl oxygen methylene radical-1,3-two sulphur [4,5-b] [1,4] to place the popular response device with 1: 1 mol ratio be solvent with the triethyl-phosphite to two sulphur hexanaphthene-2-ketone, reacted 5 hours down at 110-120 ℃, after separating purification, conventional separating and purifying method gets 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-acetyl oxygen methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes, with this compound and hydrazine hydrate with mol ratio mix at 1: 15 place volume ratio be 1: 3 chloroform and methanol mixture stir under the 10-30 ℃ of temperature after conventional separating and purifying method separates must 2-after purifying (4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes;
(2) 4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-preparation of phthalic nitrile:
With 2-(4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene)-5-hydroxyl methylene radical-5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b] [1,4] two sulphur hexanaphthenes, 4-nitro phthalic nitrile and carbonate or lithium hydroxide are mixing in 1: 2: 5 with mol ratio, with N, dinethylformamide is that solvent places the popular response device, in 50-90 ℃ stir down after with existing purification technique separate purify 4-{2-[4,5-di-n-hexyl sulphur-1,3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1,3-two sulphur [4,5-b]-[1,4] two sulphur hexanaphthenes }-phthalic nitrile;
(3) preparation of the finished product:
In the mixture of amylalcohol sodium/Pentyl alcohol (in the 30mL Pentyl alcohol, preparing), add 4-{2-[4 by 2.34 gram sodium Metal 99.5s; 5-di-n-hexyl sulphur-1; 3-two sulphur-2-ylide alkene]-the inferior methoxyl group of 5--5-hydrogen-6-dihydro-1; 3-two sulphur [4; 5-b]-[1; 4] two sulphur hexanaphthenes }-phthalic nitrile; be heated to 130-135 ℃ under stirring; under nitrogen protection reaction after 5 hours underpressure distillation remove and to desolvate; in resistates, add 80mL ethanol and 80mL acetate; leave standstill the back suction filtration and get solid; solid dissolves with chloroform after the ebullient washing with alcohol; solution passes through diatomite filtration; filtrate concentrates, and steaming desolventizes, and more resulting unformed solids is dissolved in the solvent Pentyl alcohol; add and the equimolar metal acetate salt heating of this unformed solids, under refluxad reacted 1 hour after conventional separating and purifying method promptly gets the finished product after separating purification.
4, method as claimed in claim 3, it is characterized by wherein said carbonate is yellow soda ash or salt of wormwood.
5, method as claimed in claim 3, it is characterized by wherein said metal acetate salt is neutralized verdigris or zinc acetate.
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