CN1989142A - P-electron conjugated organosilane compound and method for synthesizing same - Google Patents

Abstract

Disclosed is a pi-electron conjugated organosilane compound which enables to form an organic thin film having excellent separation resistance as well as high orderliness, crystallinity and electric conductivity. Also disclosed is a method for synthesizing such a pi-electron conjugated organosilane compound. Specifically disclosed is a pi-electron conjugated organosilane compound expressed as 1-SiX1X2X3 (wherein R1 represents an organic group containing a certain monocyclic heterocycle unit and X1-X3 respectively represent a group providing a hydroxyl group through hydrolysis). Also disclosed is a method for synthesizing such an organosilane compound wherein a compound expressed as R1-Li (wherein R1 is as defined above) or a compound expressed as R1-MgX5 (wherein R1 is as defined above and X5 represents a halogen atom) is reacted with a compound expressed as X4-SiX1X2X3 (wherein X1-X3 are as defined above and X4 represents a hydrogen atom, a halogen atom or a lower alkoxy group). Also specifically disclosed is a pi-electron conjugated organosilane compound expressed as Z-(R11)m-SiR12R13R14 (wherein Z represents an organic group derived from a certain condensed polycyclic heterocyclic compound, R11 represents a divalent organic group, m represents 0-10, and R12-R14 respectively represent a halogen atom or an alkoxy group). Also disclosed is a method for producing such an organosilane compound wherein a compound expressed as Z-(R11)m-MgX30 (wherein Z, R11 and m are as defined above, and X30 represents a halogen atom) is reacted with a compound expressed as X31-SiR12R13R14 (wherein X31 represents a hydrogen atom, a halogen atom or an alkoxy group, and R12-R14 are as defined above).

Description

πDian Zi conjugated organic silane compound and synthetic method thereof

Technical field

The present invention relates to πDian Zi conjugated organic silane compound and preparation method thereof, particularly, the present invention relates to can be as πDian Zi conjugated organic silane compound of the novelty of electricity material and preparation method thereof, and this compound has good electroconductibility or semi-conductivity.

Background technology

In recent years, it is because compare with the semi-conductor of inorganic materials that the semi-conductor (organic semiconductor) that uses organic compound is researched and developed, the organic semi-conductor preparation is simple, be easy to processing, can adapt to the amplification of device size, can allow to reduce cost, and its function is more than inorganic materials, and therefore the report of this organic semiconductor aspect has been arranged by batch process.

Particularly, the known employing organic compound that contains the πDian Zi conjugated molecule can be made the TFT with high mobility.The example of this class organic compound of report has pentacene (as non-patent literature 1).Wherein, reported by making the organic semiconductor layer of pentacene, and formed the TFT with this organic semiconductor layer, preparing the mobility of mobility greater than amorphous silicon, particularly its field-effect mobility thus is 1.5cm ²The TFT of/V.

Yet, as described in top document, when preparation organic compound semiconductor layer, when obtaining the field-effect mobility greater than above-mentioned amorphous silicon, need vacuum method such as resistive heating CVD (Chemical Vapor Deposition) method or molecular beam CVD (Chemical Vapor Deposition) method, cause manufacturing processed more complicated, have only simultaneously to obtain crystalline membrane under given conditions.In addition, organic compound thin film be physical adsorption on base material, therefore but, have the problem of easily peeling off because the adsorption strength of film on base material is low.Usually, control the molecular orientation of organic compound in the film to a certain extent, film forming base material will be orientated control by friction treatment usually in advance on it.But, make in the film by physical adsorption, report can not controlled the arrangement and the orientation of the compound molecule of physical adsorption on interface between organic compound and the base material.

On the other hand, consideration is to the far-reaching film order of field-effect mobility (crystallinity-orientation), field-effect mobility is a typical index of this TFT characteristic, recently to attracting much attention, and study the use of these films with the self-organization film of the organic compound of simple method preparation.The self-organization film is that a part of organic compound is attached to film in the functional group of substrate surface, also is that a kind of defective is very little, has high order, can crystalline film.Because the preparation of this self-organization film is extremely simple, on base material, form the film of self-organization easily.Known mercaptan film that forms on the auri material and the silicon base compound film that forms at the base material (as silicon substrate) that hydroxyl is protruded by the wetting ability processing from the surface can be used as conventional self-organization film.Especially, because the high-durability of silicon base compound film, this film attracts much attention.In the past, the silicon base compound film was always as the repellency coating, and used and have height and scold the alkyl of water effect or fluorinated alkyl to prepare this film as the silane coupling agent of organo-functional group.

Yet, though the electroconductibility of self-organization film is the organo-functional group decision by the silicon base compound that comprises in the film, but do not have commercially available having to contain the silane coupling agent of the organo-functional group of πDian Zi conjugated molecule,, be difficult to provide the self-organization film conductivity owing to this reason.Therefore, expectation can obtain being suitable for containing the silicon base compound of πDian Zi conjugated molecule as organo-functional group as the TFT device.It is the electrical properties of raw material organic molecule that field-effect mobility is had another factor of considerable influence.Generally speaking, the flow velocity of electric current in organic film depends on that obviously electronics in this organic film is sent to the efficient of another organic materials molecule from the molecule of an organic materials.Because less band gap causes electronic flow velocity to improve, the electronics flow velocity obviously depends on the molecular orbital(MO) (particularly HOMO and LUMO) of organic materials molecule.

As such silicon base compound, proposed a kind ofly have the compound of a thiphene ring as functional group in molecular end, thiphene ring wherein is connected to (as Japanese Patent 2889768, patent documentation 1) on the Siliciumatom by straight-chain alkyl.

Non-patent literature 1:IEEE Electron Device Lett., 18,606-608 (1997)

Patent documentation 1: Japanese Patent 2889768

Summary of the invention

The problem that needs solution

Yet for the compound that patent documentation 1 proposes, this compound can form the self-organization film of chemisorption on base material, but is not must form to have the organic film that can be used for as good orientation, crystallinity and the electroconductibility of the electron device of TFT.

Should have high inter-molecular attraction, to reach high orientation, i.e. high crystalline.Intermolecular forces comprises magnetism factor and repulsive force factor, and 6 powers of last factor and intermolecular distance are inversely proportional to, and then 12 of a factor and intermolecular distance powers are inversely proportional to.Therefore, intermolecular forces is that the summation of magnetism factor and repulsive force factor has relation shown in Figure 2.Lower-most point among Fig. 2 (the indicated zone of arrow among this figure) is known as van der Waals radius, promptly the time in conjunction with magnetism and repulsive force factor, and the intermolecular distance when inter-molecular attraction is maximum.Therefore, making intermolecular distance is important near van der Waals radius as far as possible., in resistive heating vapour deposition process or molecular beam vapour deposition process equal vacuum operation, have only under given conditions originally, by the molecular interaction between the abundant control πDian Zi conjugated molecule, just obtaining high orientation is crystalline film for this reason.Like this, have only by crystallinity and just can reach high conductivity based on molecular interaction.

Though described compound passes through to form the two-dimensional network structure chemisorption of Si-O-Si on base material, and be orientated by the molecular interaction between the specific chain alkyl, but, this compound is because to have only the thiophene molecule be to the effective functional group of πDian Zi conjugated system, therefore exist intermolecular interaction weak, to the very little problem of scope of the obligato πDian Zi conjugated system of electroconductibility.Even increase the quantity that above-mentioned functional group is the thiophene molecule, also be difficult to the overall equilbrium molecular interaction, this is a factor of the orientation of decision film between chain alkyl part and thiophene part.

And to conductive characteristic, in the thiophene molecule as functional group, the HOMO-LUMO energy gap is bigger, even in the organic semiconductor layer as for example TFT, can not obtain sufficient carrier mobility.Use the Devices Characteristics of organic film to be decided by two factors, the orientation of organic film and the electrical properties of material molecule, but, as mentioned above, the reports that many relevant organic films orientations are arranged, but their great majority are based on simultaneously the consideration to organic film orientation and material molecule electrical properties.

In these cases, an object of the present invention is to provide a kind of πDian Zi conjugated organic silane compound and preparation method thereof, this organic silane compound carries out crystallization by simple preparation method, can form organic film, can make the organic film of formation be adsorbed on substrate surface securely, prevent that physics from peeling off, and aspect orientation, crystallinity, electroconductibility excellent property.

Another object of the present invention provides πDian Zi conjugated organic silane compound of a kind of novelty and preparation method thereof, can guarantee sufficiently high carrier mobility when this compound is used for as the semiconducter device of TFT.

Solution to the problems described above

The present invention relates to πDian Zi conjugated organic silane compound by general formula (I) expression:

R ¹-SiX ¹X ²X ³(I)

In the formula, R ¹Expression can substituted organic group, and this group has and contains the monocyclic heterocycles unit that is selected from long (long-form) periodictable 4A, 4B, 5B and 6B family atoms of elements; X ¹To X ³Expression can produce the group of hydroxyl by hydrolysis separately.

The invention still further relates to the method for preparing πDian Zi conjugated organic silane compound, this method comprises: make compound or the compound of general formula (IV) expression and the compound reaction of general formula (III) expression by general formula (II) expression:

R ¹-Li(II)

In the formula, R ¹Expression can substituted organic group, and this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements;

R ¹-MgX ⁵(IV)

In the formula, R ¹Expression can substituted organic group, and this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements; X ⁵The expression halogen atom;

X ⁴-SiX ¹X ²X ³(III)

In the formula, X ¹To X ³Expression can produce the group of hydroxyl by hydrolysis; X ⁴Expression hydrogen or halogen atom or lower alkoxy.

The present invention relates to πDian Zi conjugated organic silane compound by general formula (α) expression:

Z-(R ¹¹) _m-SiR ¹²R ¹³R ¹⁴(α)

In the formula, Z represents to be derived from the unit price organic group of fused polycycle heterogeneous ring compound of the condensed ring of 2-10 five-ring and/or six-ring; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

The invention still further relates to the method for the above-mentioned πDian Zi conjugated organic silane compound of preparation, this method comprises: make the compound of general formula (β) expression and the compound of general formula (γ) expression carry out Ge Liya (Grignard) reaction:

Z-(R ¹¹) _m-MgX ³⁰(β)

In the formula, Z represents to be derived from the unit price organic group of fused polycycle heterogeneous ring compound of the condensed ring of 2-10 five-ring and/or six-ring; R ¹¹The expression divalent organic group; M is the integer of 0-10; X ³⁰The expression halogen atom;

X ³¹-SiR ¹²R ¹³R ¹⁴(γ)

In the formula, X ³¹Expression hydrogen or halogen atom or the alkoxyl group of 1-4 carbon atom is arranged; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

Effect of the present invention

Because general formula (I) and (α) compound of expression pass through the intermolecular formation between this compound Si-O-Si two-dimension nettedization and securely chemisorption in base material, and effectively produce the required molecular interaction of thin film crystallization (the tight filling power of molecule (tight packing force)), thus, the present invention can form has very high stability, and the film of highly crystallineization.As a result, and compare in the film of base material manufacturing, the film of gained firmly is adsorbed on the substrate surface, can prevent that physics from peeling off by physical adsorption.In addition, the compound that can prepare general formula (I) easily and (α) represent.

Because the reticulated structure that the silyl in the compound of formation organic film forms directly combines with the organic residue that constitutes film top, and, can form film with high orientation (crystallinity) from the molecular interaction of the reticulated structure and the pi-conjugated molecule of silyl.

In addition, the compound of general formula (I) expression has at least one and contains heteroatomic monocyclic heterocycles unit, described heteroatoms is selected from the element of 4A, 4B, 5B or 6B family, particularly be selected from Si, Ge, Sn, P, Se, Te, Ti or Zr, this compound has the LUMO of stabilization, promptly has the electronic structure that can easily carry out transfer transport.As a result, by the conduction of the jump in the compound molecule (hoppingconduction), described current carrier smoothly shifts.In addition, this compound to having high conductivity, not only can be used as the OTFT material at molecular axis, and can be used for various application such as solar cell, fuel cell and inductor block as electro-conductive material.

Perhaps, the organic silane compound of general formula (α) expression has the skeleton of fused polycycle heterogeneous ring compound, has stable LUMO.Therefore, can be used as N-N-type semiconductorN material.Though P-N-type semiconductorN material has been carried out many researchs, seldom to studying as those N-N-type semiconductorN materials among the present invention.By the organic silane compound of general formula (α) expression is of great use material, not only can be used as the OTFT material, and can be used for the organic assembly such as solar cell, fuel cell and inductor block.

The accompanying drawing summary

Shown in Figure 1 is the synoptic diagram of molecular orientation on the explanation organic film.

Shown in Figure 2 is the synoptic diagram of the relation of intermolecular distance and intermolecular forces.

Best mode for carrying out the invention

πDian Zi conjugated organic silane compound of the present invention be a kind of by general formula (I) or (α) expression compound.Below, πDian Zi conjugated organic silane compound (I) by general formula (I) expression and preparation method thereof is described in order, and by πDian Zi conjugated organic silane compound (α) of general formula (α) expression and preparation method thereof.

(organic silane compound (I))

πDian Zi conjugated organic silane compound of the present invention (I) is the compound by general formula (I) expression:

R ¹-SiX ¹X ²X ³(I)

Below, this compound is called organic silane compound (I).

In the general formula (I), R ¹Expression can substituted organic group, and this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements.The monocyclic heterocycles that contains this atom has low lumo energy, because at the σ of this atom position ^*π in the double bond position in track and the heterocycle, particularly its diene position ^*There is σ between the track ^*-π ^*Conjugation, obviously, this can cause the uniqueness of this compound aspect electroconductibility (semiconductor property) to improve.On the other hand, as if the compound that only contains as S, N, O and C element can not produce this σ ^*-π ^*Therefore conjugation, has unsettled LUMO, and the result causes low relatively electroconductibility (semiconductor property).

Described monocyclic heterocycles contains at least one and is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements, preferably one or two such atom as the atom that constitutes ring (below, be called Y ₀Atom).Y ₀Atom is for example to be selected from the atom of Si, Ge, Sn, P, Se, Te, Ti or Zr.

Contain Y ₀The monocyclic heterocycles of atom preferably five-ring is more preferably five-ring or six-ring to twelve-ring.

The favourable example of the unitary typical case of monocyclic five-membered ring comprises with lower unit:

In the superincumbent exemplary, Y _IAll be atom, as Si, Ge, Sn, Ti or Zr by 4A or the element representative of 4B family.

Y _IIAll be atom, as P by the element representative of 5B family.

Y _IIIAll be atom, as Se or Te by the element representative of 6B family.

When containing, a unit is selected from Y _I, Y _IIAnd Y _IIITwo or more of Y group the time, be selected from above-mentioned scope independently of one another in the Y group.

The unitary exemplary of monocyclic hexa-member heterocycle comprises with lower unit:

In these exemplary, Y _I, Y _IIAnd Y _IIIWith the Y in the monocyclic five-membered ring unit _I, Y _IIAnd Y _IIIIdentical.

In monocyclic five yuan and the unitary exemplary of hexa-member heterocycle, there is not the unit of left-right symmetry to comprise its mirror image isomer.

At a R ¹In can have one or morely, for example 1-30 contains Y ₀The monocyclic heterocycles unit of atom.Particularly, consider productive rate, cost and scale operation, R ¹Preferably contain 1-9 Y ₀The monocyclic heterocycles unit of atom.

Work as R ¹Contain a plurality of Y of containing ₀During the monocyclic heterocycles unit of atom, these unit each other can be identical, and perhaps wherein part unit or all unit differ from one another.

R ¹π-electron conjugated monocyclic heterocycles the unit and/or the mononuclear aromatics ring element that can also contain other.

The heteroatomic example that comprises in other monocyclic heterocycles unit comprises: Sauerstoffatom, nitrogen-atoms and sulphur atom.R ¹In the unitary example of other monocyclic heterocycles that comprises comprise: the heterocycle such as the furans that contain Sauerstoffatom; The heterocycle of nitrogen atom is as pyrroles, pyridine, pyrimidine, pyrroline, tetrahydroglyoxaline and pyrazoline; The heterocycle of sulfur atom-containing is as thiophene; The heterocycle ， of nitrogen atom and Sauerstoffatom such as oxazole are with isoxazole; The heterocycle of sulfur atom-containing and nitrogen-atoms is as thiazole and isothiazole etc.Wherein, preferred especially thiophene.

R ¹In the exemplary of the mononuclear aromatics ring element that comprises be phenyl ring.

Work as R ¹When containing this other monocyclic heterocycles unit and/or mononuclear aromatics ring element, this unit with contain Y ₀The unitary sum of the monocyclic heterocycles of atom is preferably at the above-mentioned Y that contains ₀The unitary quantitative range of the monocyclic heterocycles of atom.

Work as R ¹When containing a plurality of other monocyclic heterocycles unit, these unit each other can be identical, and perhaps wherein part unit or all unit differ from one another.Work as R ¹When containing a plurality of mononuclear aromatics ring element, so same.

Work as R ¹Contain Y ₀During multiple in the monocyclic heterocycles unit of atom, other monocyclic heterocycles unit and the mononuclear aromatics ring element, these unit can be connected with each other in the mode of line style or branching.Branching connects at least one unit of expression as node, has two or more unit to link to each other with this node.Consider that from the crystallinity (orientation) of film preferred line style connects.

Work as R ¹When containing the broad variety unit, polytype unit is connected with each other with the configuration of orderly repeating unit, and perhaps the configuration of arranging arbitrarily with described unit is connected with each other.

With formation R ¹The unit whether be to contain Y ₀The monocyclic heterocycles unit of atom, other monocyclic heterocycles unit or mononuclear aromatics ring element are irrelevant, and these unitary combining sites can be 2,5-, 3, and 4-, 2,3-and 2, any one in the 4-position, when being five-ring in this unit, preferably 2, the 5-position.In this case, contain Y ₀The unitary combining site of the monocyclic heterocycles of atom except above-mentioned combining site, can be 1 especially, the 1-position.When this unit was six-ring, combining site can be 1,4-, 1, and 2-, 1,3-, 2,3-, 2,4-and 2, any one is and preferred 2 in the 5-position, the 5-position.The valence mumber of above-mentioned combining site is with respect to heteroatomic valence mumber when ring contains a heteroatoms, when ring contains two or more heteroatomss, be heteroatomic valence mumber, and on ring, when not having heteroatoms, be valence mumber with respect to optional carbon atom with respect to maximum atomic wts.

Work as R ¹When containing a plurality of unit, these unit can directly interconnect, and perhaps connect indirectly as vinylidene by connecting base.Vinylidene is the unsaturated organic group of divalence of removing the following hydrocarbon of hydrogen atom from its two ends.Provide the example of the hydrocarbon of vinylidene to comprise: alkene, alkadiene, alkatriene etc.The example of alkene includes the compound of 2-4 carbon atom, as ethene, propylene and butylene, wherein optimal ethylene.The example of alkadiene includes the compound of 4-6 carbon atom, as divinyl, pentadiene, hexadiene etc.The example of alkatriene includes the compound of 6-8 carbon atom, as hexatriene, heptantriene, sarohornene etc.

Can introduce R ¹Substituent example comprise: hydroxyl, replacement and unsubstituted amino, nitro, cyano group, replacement and unsubstituted alkyl, replacement and unsubstituted alkenyl, replacement and unsubstituted cycloalkyl, replacement and unsubstituted alkoxyl group, replacement and unsubstituted aromatic hydrocarbon group, replacement and unsubstituted heterocyclic aryl, replacement and unsubstituted aralkyl, replacement and unsubstituted aryloxy, replacement and unsubstituted alkoxy carbonyl, carboxyl, ester group etc.In these substituting groups, preferably can the straight chained alkyl of 1-30 carbon atom, a particularly 1-4 carbon atom more preferably not arranged by the sterically hindered organic film crystalline group that suppresses.

In the general formula (I), X ¹To X ³Expression can produce the group of hydroxyl by hydrolysis separately.To having no particular limits by the group that hydrolysis produces hydroxyl, these groups can be, for example halogen atom, lower alkoxy etc.The example of halogen atom comprises fluorine, chlorine, iodine and bromine.The example of lower alkoxy comprises: the alkoxyl group that 1-4 carbon atom arranged, as methoxyl group, oxyethyl group, positive propoxy, 2-propoxy-, n-butoxy, sec-butoxy and tert.-butoxy, part can be replaced by another kind of functional group (as, trialkylsilkl and other alkoxyl group) in these groups in addition.X ¹, X ²And X ³Each other can be identical, perhaps wherein part or all of differing from one another, but preferably they are identical.

The exemplary of above-mentioned organic silane compound (I) comprises the compound by following general formula (1) to (11) expression.

Group and coding total in the general formula that illustrates below (1) to (11) are mutually the same.

" can introduce R if be included in ¹Substituting group " in, R then ²To R ⁴Be any group independently of one another, but preferred hydrogen atom, have 1-4 carbon atom alkyl, the cycloalkyl of 5-12 carbon atom is arranged or the aryl of 6-18 carbon atom is arranged.

A plurality of R are arranged in each general formula ³During group, each R ³Group is independently selected from above-mentioned scope.

X ¹To X ³Identical with shown in the general formula (I) those, they are represented independently of one another: fluorine atom, chlorine atom, iodine atom or bromine atoms, or methoxyl group, oxyethyl group, positive propoxy, 2-propoxy-, n-butoxy, sec-butoxy or tert.-butoxy.Preferred chlorine atom or methoxy or ethoxy.

Other group and coding in various are described respectively below.

In the general formula (1), Y ¹Expression Si, Ge, Se, Te, P, Sn, Ti or Zr, preferred Si or Se.Particularly, work as Y ¹When being Si, Ge, Sn, Ti or Zr, it is-Y ¹(R ⁴) ₂-; Work as Y ¹When being P, it is-Y ¹(R ⁴)-; Work as Y ¹When being Se or Te, it is-Y ¹-.R ⁴Be hydrogen atom or methyl, ethyl, n-propyl, 2-propyl group, normal-butyl, sec-butyl, the tertiary butyl or amyl group, preferred hydrogen atom or methyl.N1 is the integer of 1-9, the integer of preferred 2-8.

In the general formula (2), Y ²Expression Se or Te.Particularly, work as Y ²When being Se or Te, it is-Y ²-.

N1 is the integer of 1-9, the integer of preferred 2-8.

In the general formula (3), Y ³Expression Si, Ge, P, Sn, Ti or Zr, preferred Si or P.Particularly, work as Y ³When being Si, Ge, Sn, Ti or Zr, it is-Y ³(R ⁴)=, and work as Y ³When being P, it is-Y ³=.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

N1 is the integer of 1-9, the integer of preferred 2-8.

In the general formula (4), Y ⁴And Y ⁵Represent Si, Ge, Sn, Ti or Zr independently of one another, preferred Si.

N1 is the integer of 1-9, the integer of preferred 2-8.

In the general formula (5), Y ⁶To Y ⁸Represent S, N, O, Si, Ge, Se, Te, P, Sn, Ti or Zr independently of one another.Y ⁶To Y ⁸In at least one group, preferred at least Y ⁷, be Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ⁶When being Si, Ge, Sn, Ti or Zr, it is-Y ⁶(R ⁴) ₂-, work as Y ⁶When being N or P, it is-Y ⁶(R ⁴)-; Work as Y ⁶When being S, O, Se or Te, it is-Y ⁶-.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.Particularly, Y ⁷And Y ⁸All be similar to top to Y ⁶Detailed description.

N2+n3+n4 is the integer of 1-9, the integer of preferred 5-9.But n2 is more than or equal to 1, is preferably greater than or equals 2; N3 is more than or equal to 1; N4 is more than or equal to 1, is preferably greater than or equals 2.

In the general formula (6), Y ⁹Expression Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ⁹When being Si, Ge, Sn, Ti or Zr, it is-Y ⁹(R ⁴) ₂-; Work as Y ⁹When being P, it is-Y ⁹(R ⁴)-; And work as Y ⁹When being Se or Te, it is-Y ⁹-.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

Z ¹And Z ²Represent N, C, Si, Ge, P, Sn, Ti or Zr independently of one another.Particularly, work as Z ¹When being C, Si, Ge, Sn, Ti or Zr, it is-Z ¹(R ⁴)=, and work as Z ¹When being N or P, it is-Z ¹=.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.Relevant Z ²Details and Z ¹Those are identical.

N2+n3+n4 is the integer of 1-9, the integer of preferred 5-9.But n2 is more than or equal to 1, is preferably greater than or equals 2; N3 is more than or equal to 1, is preferably greater than or equals 2; N4 is more than or equal to 1, is preferably greater than or equals 2.

In the general formula (7), Y ¹⁰To Y ¹¹Represent S, N, O, Si, Ge, Se, Te, P, Sn, Ti or Zr independently of one another.But, Y ¹⁰To Y ¹¹In at least one group represent Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ¹⁰When being Si, Ge, Sn, Ti or Zr, it is-Y ¹⁰(R ⁴) ₂-; Work as Y ¹⁰Be N or P it be-Y ¹⁰(R ⁴)-; And work as Y ¹⁰When being S, O, Se or Te, it is-Y ¹⁰-.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.Relevant Y ¹¹Details and Y ¹⁰Those are identical.

N5+n6 is the integer of 1-9, the integer of preferred 5-8.But n5 is more than or equal to 0, is preferably greater than or equals 1, and n6 is more than or equal to 0, is preferably greater than or equals 1.

In the general formula (8), Y ¹²Expression Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ¹²When being Si, Ge, Sn, Ti or Zr, it is-Y ¹²(R ⁴) ₂-; Work as Y ¹²When being P, it is-Y ¹²(R ⁴)-; And work as Y ¹²When being Se or Te, it is-Y ¹²-.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

Z ³Expression N, C, Si, Ge, P, Sn, Ti or Zr.Particularly, work as Z ³When being C, Si, Ge, Sn, Ti or Zr, it is-Z ³(R ⁴)=, and work as Z ³When being N or P, it is-Z ³=.R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

N5+n6 is the integer of 1-9, the integer of preferred 5-8.But n5 is more than or equal to 1, is preferably greater than or equals 2, and n6 is more than or equal to 0, is preferably greater than or equals 1.

In the general formula (9), Y ¹³Expression Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ¹³When being Si, Ge, Sn, Ti or Zr, it is-Y ¹³(R ⁴) ₂-; Work as Y ¹³P the time, it is-Y ¹³(R ⁴)-; And work as Y ¹³When being Se or Te, it is-Y ¹³-.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

Z ⁴Expression N, C, Si, Ge, P, Sn, Ti or Zr.Particularly, work as Z ⁴When being C, Si, Ge, Sn, Ti or Zr, it is-Z ⁴(R ⁴)=, and work as Z ⁴When being N or P, it is-Z ⁴=.R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

N5+n6 is the integer of 1-9, the integer of preferred 5-8.But n5 is more than or equal to 1, is preferably greater than or equals 2, and n6 is more than or equal to 0, is preferably greater than or equals 1.

In the general formula (10), Y ¹⁴To Y ¹⁵Represent S, N, O, Si, Ge, Se, Te, P, Sn, Ti or Zr independently of one another.But, Y ¹⁴To Y ¹⁵In at least one expression Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ¹⁴When being Si, Ge, Sn, Ti or Zr, it is-Y ¹⁴(R ⁴) ₂-time; Work as Y ¹⁴When being N or P, it is-Y ¹⁴(R ⁴)-; And work as Y ¹⁴When being S, O, Se or Te, it is-Y ¹⁴-.R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.Relevant Y ¹⁵Details and Y ¹⁴Those are identical.

N5+n6 is the integer of 1-9, the integer of preferred 5-8.But n5 is more than or equal to 0, is preferably greater than or equals 1, and n6 is more than or equal to 0, is preferably greater than or equals 1.

In the general formula (11), Y ¹⁶Expression Si, Ge, Se, Te, P, Sn, Ti or Zr.Particularly, work as Y ¹⁶When being Si, Ge, Sn, Ti or Zr, it is-Y ¹⁶(R ⁴) ₂-; Work as Y ¹⁶When being P, it is-Y ¹⁶(R ⁴)-; And work as Y ¹⁶When being Se or Te, it is-Y ¹⁶-time.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

Z ⁵Expression N, C, Si, Ge, P, Sn, Ti or Zr.Particularly, work as Z ⁵When being C, Si, Ge, Sn, Ti or Zr, it is-Z ⁵(R ⁴)=, and work as Z ⁵When being N or P, it is-Z ⁵=.But, R ⁴Identical with in the formula (1) those, and preferably hydrogen atom or methyl.

N5+n6 is the integer of 1-9, the integer of preferred 5-8.But n5 is more than or equal to 1, is preferably greater than or equals 2, and n6 is more than or equal to 0, is preferably greater than or equals 1.

(method for preparing organic silane compound (I))

Below, the method for preparing organic silane compound of the present invention (I) is described.

Organic silane compound of the present invention (I) is to adopt compound prepared in reaction that the compound make general formula (II) expression and general formula (III) represent:

R ¹-Li(II)

In the formula, R ¹Identical with in the formula (I);

X ⁴-SiX ¹X ²X ³(III)

In the formula, X ¹, X ²And X ³Identical with in the formula (I) those; X ⁴Expression hydrogen atom, halogen atom (as, fluorine, chlorine, iodine or bromine) or lower alkoxy (as, methoxyl group, oxyethyl group, positive propoxy, 2-propoxy-, n-butoxy, sec-butoxy or tert.-butoxy);

Or the compound of the compound by general formula (IV) expression and general formula (III) expression carries out, and Grignard reaction prepares:

R ¹-MgX ⁵(IV)

In the formula, R ¹Identical with in the formula (I); X ⁵The expression halogen atom.

General formula (II) or the compound of (IV) representing are by for example making formula R ¹H (in the formula, R ¹Identical with in the formula (I)) compound of expression and lithium alkylide prepared in reaction are perhaps by making formula R ¹X ⁵(in the formula, R ¹Identical with in the formula (I); X ⁵The expression halogen atom is as fluorine, chlorine, iodine or bromine) with prepared in reaction such as alkyl magnesium halide, MAGNESIUM METAL.

Employed lithium alkylide comprises low alkyl group lithium (1-4 carbon atom arranged) in the above-mentioned reaction, as n-Butyl Lithium, s-butyl lithium and tert-butyl lithium.Formula R with respect to 1 mole ¹The compound of H, the preferred 1-5 mole of the add-on of lithium alkylide, more preferably 1-2 mole.Alkyl magnesium halide for example is ethyl-magnesium-bromide, methylmagnesium-chloride etc.Formula R with respect to 1 mole ¹X ⁵Starting compound, the consumption of alkyl magnesium halide is preferably the 1-10 mole, more preferably the 1-4 mole.

Temperature preference during reaction between the reaction between the compound of the compound of general formula (II) expression and general formula (III) expression or the compound of general formula (IV) expression and compound that general formula (III) is represented is as-100 ℃ to 150 ℃, more preferably-20 ℃ to 100 ℃.Reaction times for example is about 0.1-48 hour.Reaction is carried out in to the organic solvent of this reactionlessness usually.Organic solvent to reactionlessness comprises aliphatic hydrocrbon or aromatic hydrocarbons, as hexane, pentane, benzene and toluene, and ether solvent, as diethyl ether, dipropyl ether, diox and tetrahydrofuran (THF) (THF) etc., these solvents can use separately or use as liquid mixture.In these solvents, preferred diethyl ether and THF.Can use any catalyzer in this reaction.Can use any known catalyzer, as platinum catalyst, palladium catalyst or nickel catalyzator.

Below, with reference to conventional embodiment described below (synthetic route 1 to 5), be described as obtaining the compound of general formula (II) expression and prepare compound R ¹The method of H.Be used to prepare the compound R of the compound of general formula (IV) expression ¹X ⁵Be by using halogenating agent such as N-bromosuccinimide or N-chlorosuccinimide to R ¹H carries out the halogenation preparation.

The compound of general formula (1) expression has the silyl that is replaced by H

Below, describe preparation and have and contain Se or Si as the element (Y that is selected from long period table the 4A, 4B, 5B and 6B family ₀) atom (Y ₀Atom) the unitary compound R of monocyclic heterocycles ¹The method of H still, clearly, adopts similar method to prepare and has the unitary compound R of monocyclic heterocycles that contains other heteroatoms such as Ge, Te, P, SN, Ti or Zr ¹H.

Reported that in " Polymer (2003,44,5597-5603) " preparation is used to be derived from the pentacyclic precursor (R of selenophen ring ¹H) method, the method described in the document can be used for the present invention.

Preparation is derived from the precursor (R that thiophene is coughed up (silole) ring ¹H) method is reported among " Journal ofOrganometallic Chemistry (2002; 653; 223-228) ", " Journal ofOrganometallic Chemistry (1998; 559; 73-80) " and " the CoordinationChemistry Reviews (2003; 244,1-44) ", and the method described in these documents can be used for the present invention.

Contain Y ₀The quantity of the monocyclic heterocycles unit of atom (coughing up the unit of ring as selenophen ring and thiophene) can be by to the Y that contains as raw material ₀The specific position of the unitary compound of monocyclic heterocycles of atom repeats halogenating reaction, and makes the halogenated compound that is obtained and contain Y ₀The unitary Grignard reagent of the monocycle of atom carry out Grignard reaction controlled (referring to, for example, the 1st to the 4th reaction formula in the synthetic route 1; First to second reaction formula in the synthetic route 2; Following reaction formula A, and first reaction formula in the synthetic route 3).

Reaction formula A

In first to fourth reaction formula of synthetic route 1, the precursor (R that preparation has only the selenophen ring is shown ¹H) and by the dipolymer or the trimeric method of this monomer preparation.In this method, the quantity of selenophen ring increases successively, therefore, repeats above-mentioned reaction similarly, also can prepare tetramer or longer precursor.

First reaction formula of synthetic route 2, top reaction formula A and first reaction formula of synthetic route 3 show preparation have only thiophene cough up ring precursor method and prepare thiophene by this monomer or dipolymer and cough up the reaction of dipolymer or tetramer to sexamer.In these methods, the quantity that thiophene is coughed up ring increases successively, therefore, repeats top reaction similarly, also can prepare trimer, heptamer or higher precursor.

Except the reaction of using Grignard reagent, can be by in the presence of suitable metal catalyzer (Cu, Al, Zn, Zr, Sn etc.), carrying out coupling, at control R ¹In the monocyclic heterocycles element number time produce R ¹H.

The compound of the general formula that its silyl is replaced by H (5) or (6) expression

Contain R ¹Three kinds of unitary block type R in the block unit ¹H can link to each other by two ends of compound that will contain end-blocks and the compound that contains central block and prepare.The example of these methods comprises Suzuki coupling, Grignard reaction etc.

For example, be derived from thiophene-or benzene-the unit be connected respectively to and have thiophene when coughing up two ends of the compound of ring (referring to first to the 3rd reaction formula of synthetic route 4 and first reaction formula of synthetic route 5), by n-BuLi and B (O-iPr) ₃Addition has compound that thiophene coughs up ring at first debrominateization (debrominated) and boration (borated).Used solvent is ether solvents preferably.The reaction of this boration is a two-step reaction, and the first step is carried out at-78 ℃, so that be reflected at initial stablely in mutually, second step carried out during temperature is elevated to room temperature gradually from-78 ℃.Subsequently, make the compound of the have halide end group simple benzene of (for example, bromine) or thiophene compound and above-mentioned boration for example in toluene solvant, at Pd (PPh ₃) ₄And Na ₂CO ₃React to each other under existing, temperature of reaction is 85 ℃, finishes up to the reaction that forms coupled product between them.Have the compound that thiophene is coughed up ring though described to use, to contain Ge, Se, Te, P, Sn, Ti or Zr and also have the thiophene of being similar to as heteroatomic monocyclic heterocycles compound and cough up 2 the reactive behavior of 5-position.Therefore, adopt the above-mentioned method that is similar to, also can be derived from thiophene-or benzene-the unit be attached to and contain Ge, Se, Te, P, Sn, Ti or Zr two ends as heteroatomic monocyclic heterocycles compound.Though described above to be derived from thiophene-or benzene-the unit combination, be derived from thiophene-or benzene-cellular zone can be derived from that to contain Si, Ge, Se, Te, P, Sn, Ti or Zr be that the unit of heteroatomic monocyclic heterocycles compound replaces.

In the above to R ¹In the described any synthetic method of H, have the required substituting group raw material of (as, alkyl) by using at specific position, can be at R ¹Last this substituting group of introducing of H.For example in synthetic route 1,, can obtain 2-octadecyl three selenophens (the 4th reaction formula) by using 2-octadecyl selenophen as raw material.Silane compound with general formula (III) expression reacts subsequently, is created in specific position and has required substituent organic silane compound (I).

The example that the present invention prepares the method for organic silane compound (I) is shown in following synthetic route 1 to 5.

Synthetic route 1

Synthetic route 2

Synthetic route 3

Synthetic route 4

Synthetic route 5

Adopt known any method such as resolubilization, concentrate, solvent extraction, fractionation, crystallization, recrystallization, chromatography etc., the organic silane compound that makes (I) can separate also purifying from reaction solvent.

(organic silane compound (α))

πDian Zi conjugated organic silane compound of the present invention (α) is a kind of compound by general formula (α) expression:

Z-(R ¹¹) _m-SiR ¹²R ¹³R ¹⁴(α)

Below, this compound is known as organic silane compound (α).

In general formula (α), Z is the unit price organic group that is derived from the fused polycycle heterogeneous ring compound of π-electron conjugated, and any one atom that promptly constitutes ring from this fused polycycle heterogeneous ring compound is removed the unit price residue behind the hydrogen atom.Term " π-electron conjugated " is illustrated in π-electronics delocalization on σ and π key of π key in the compound.

Fused polycycle heterogeneous ring compound to organic group Z is made of five-ring and/or six-ring, and has at least one heterocycle, preferably one or two heterocycle.Heteroatomic example comprises on the heterocycle: silicon (Si), germanium (Ge), tin (Sn), titanium (Ti), zirconium (Zr), nitrogen (N), phosphorus (P), oxygen (O), sulphur (S), selenium (Se) and tellurium (Te) atom.Productive rate when considering preparation fused polycycle heterogeneous ring compound, heteroatoms is N, O or S preferably.

Five yuan of the fused polycycle heterogeneous ring compound-and six-ring comprise ring shown below.When following ring formed the fused polycycle heterogeneous ring compound by catalysis, two atoms on the common ring were total by another ring.

Above in all exemplary, Y _VIAll represent Si, Ge, Sn, Ti or Zr.

Y _VIIAll represent N or P.

Y _VIIIAll represent O, S, Se or Te.

The condensed ring quantity that constitutes the fused polycycle heterogeneous ring compound is 2-10, considers the preferred 2-5 of the quantity of condensed ring from productive rate.

The exemplary that is derived from the organic group of fused polycycle heterogeneous ring compound comprises following group:

In the formula, X ¹¹Expression C, N, O or S; X ¹²Expression C or N (still, X ¹¹And X ¹²Can not be C simultaneously); N11 is the integer of 0-8.

In the formula, X ¹³Expression N, O or S; N12 and n13 are the integers that satisfies 0≤n12+n13≤7).

In the formula, X ¹⁴And X ¹⁵Represent C or N (still, X independently of one another ¹⁴And X ¹⁵Can not be C simultaneously); N14 is the integer of 0-8)

In the formula, X ¹⁶And X ¹⁷Represent C or N (still, X independently of one another ¹⁶And X ¹⁷Can not be C simultaneously); N15 is the integer of 0-8.

In the formula, X ¹⁸And X ¹⁹Represent C, N, O or S (still, X independently of one another ¹⁸And X ¹⁹Can not be C simultaneously); N16 and n17 are the integers that satisfies 0≤n16+n17≤7.

In the formula, X ²⁰And X ²¹Represent C or N (still, X independently of one another ²⁰And X ²¹Can not be C simultaneously); N18 and n19 are the integers that satisfies 0≤n18+n19≤7.

Organic silane compound (α) has divalent organic group between organic group Z and silyl described below; So in formula (α), R ¹¹The expression divalent organic group; M is the integer of 0-10.

Organic group R ¹¹Particularly be derived from the divalent organic group of π-electron conjugated molecule or non-πDian Zi conjugated molecule, promptly remove residue of divalent or its compound group (composite group) of two hydrogen atoms from πDian Zi conjugated molecule or non-πDian Zi conjugated molecule.

Organic group R ¹¹Be derived from the πDian Zi conjugated molecule, the example of πDian Zi conjugated molecule comprises: monocyclic aromatic hydroxy compound, monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound etc.

The example of monocyclic aromatic hydroxy compound is a benzene.

The heteroatoms that comprises in the monocyclic heterogeneous ring compound comprises: N, O, S, Si, Ge, Se, Te, P, Sn, Ti, Zr etc., and from the production cost angle, preferred N, O and S.

The example of monocyclic heterogeneous ring compound comprises: furans, pyrroles, pyridine, pyrimidine, pyrroline, tetrahydroglyoxaline, pyrazoline, thiophene, oxazole, isoxazole, thiazole, isothiazole etc.

The fused polycycle aromatic hydroxy compound is the condensed compounds of two or more phenyl ring, considers from electroconductibility, and is preferably symmetric, the special symmetric compound of preferred axes.The preferred example of this compound comprise the compound of representing by following general formula, non-that alkene (phenalene), perylene, coronene and ovalene (and fourth of the twelve Earthly Branches benzene, ovalene).

In the formula, n20 is the integer of 0-8.

The example of the fused polycycle aromatic hydroxy compound of being represented by top general formula comprises: naphthalene, anthracene, tetracene (naphthacene), pentacene, hexacene, heptacene and and eight benzene.

When organic group was derived from non-πDian Zi conjugated molecule, this non-πDian Zi conjugated molecule was the aliphatic hydrocarbon compounds that for example straight chain is saturated etc.Group-(CH ₂) _m-just be derived from the saturated aliphatic hydrocarbon compounds of straight chain.

When m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them.

In the top formula (α), constitute the radicals R of silyl ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.The preferred straight chain group of alkoxyl group.

The exemplary of alkoxyl group comprises: methoxyl group, oxyethyl group, positive propoxy, 2-propoxy-, n-butoxy, sec-butoxy, tert.-butoxy etc.Part hydrogen atom in the alkoxyl group can be by another substituting group such as trialkylsilkl (alkyl has 1-4 carbon atom) or alkoxyl group (1-4 carbon atom arranged) replacement.

The example of halogen atom comprises: fluorine, chlorine, iodine, bromine etc., consider preferred chlorine atom from reactive behavior.

Preferably, R ¹²To R ¹⁴Represent the chlorine atom independently of one another or the alkoxyl group of 1-2 carbon atom is arranged.

The organic silane compound that the typical preferred following general formula of example of organic silane compound (α) is represented.

(1) the πDian Zi conjugated organic silane compound of general formula (α I) expression:

In the general formula (α I), X ¹¹Expression C, N, O or S, preferred N, O or S, more preferably N; Particularly, work as X ¹¹When being C, it is-CH ₂-, work as X ¹¹When being N, it is-NH-, and works as X ¹¹When being O or S, it is-X ¹¹-; X ¹²Expression C or N, preferred N; Particularly, work as X ¹²When being C, it is-CH=, and works as X ¹²When being N, it is-N=; But, X ¹¹And X ¹²Can not be C simultaneously; N11 is the integer of 0-8, the integer of preferred 0-3.

In general formula (α I), R ¹¹To R ¹⁴Identical with in m and the general formula (α).Particularly, R ¹¹The expression divalent organic group, promptly remove in the described monocyclic aromatic hydroxy compound of general formula (α), monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound or the saturated aliphatic hydrocarbon compounds behind two hydrogen atoms residue of divalent, perhaps their compound group.Preferably, R ¹¹Be the divalent organic group that is selected from by the group of following general formula (i) to (iV) expression:

In the formula, n20 is the integer of 0-8, preferred 0 or 1.

Most preferred R ¹¹Example is to the group of (iii) representing by general formula (i); When following described m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them;

M is the integer of 0-10, and is preferred 0 to 7, more preferably 0 to 3;

R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged, preferred chlorine atom or methoxy or ethoxy.

Other example of the organic silane compound of general formula (α I) expression comprises following compound:

(2) the πDian Zi conjugated organic silane compound of representing by general formula (α II):

In the general formula (α II), X ¹³Expression N, O or S, preferred N or O; Particularly, work as X ¹³Be N, it is-NH-, and works as X ¹³When being O or S, it is-X ¹³-; N12 and n13 are the integers that satisfies 0≤n12+n13≤7, preferably satisfy 0≤n12+n13≤2.

In general formula (α II), R ¹¹To R ¹⁴Identical with in m and the general formula (α);

Particularly, R ¹¹The expression divalent organic group is promptly removed two residue of divalent or its compound groups behind the hydrogen atom in the described monocyclic aromatic hydroxy compound of general formula (α), monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound or the saturated aliphatic hydrocarbon compounds.Preferred divalent organic group is selected from top general formula (i) to the group of (iv) representing (among the q, n20 is the integer of 0-8, preferred 0 or 1).Most preferred radicals R ¹¹Be by general formula (i) and (iii) the expression group; When following described m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them;

M is the integer of 0-10, and is preferred 0 to 2, more preferably 0 or 1;

R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged, preferred chlorine atom or methoxy or ethoxy.

Other exemplary of the organic silane compound of general formula (α II) expression comprises following compound:

(3) the πDian Zi conjugated organic silane compound of general formula (α III) expression:

In the general formula (α III), X ¹⁴And X ¹⁵Represent C or N independently of one another; Preferred X ¹⁴Be N and X ¹⁵Be C; Particularly work as X ¹⁴Be C, it is-CH=, works as X ¹⁴When being N, it is-N=, and works as X ¹⁵When being C, it is-CH=, works as X ¹⁵When being N, it is-N=:

But, X ¹⁴And X ¹⁵Can not be C simultaneously; With

N14 is the integer of 0-8, and is preferred 0 to 3, more preferably 0 or 1.

In general formula (α III), R ¹¹To R ¹⁴Identical with m with in the general formula (α) those.

Particularly, R ¹¹The expression divalent organic group, promptly by removing the residue of divalent that two hydrogen atoms obtain in the described monocyclic aromatic hydroxy compound of general formula (α), monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound or the saturated aliphatic hydrocarbon compounds, perhaps their compound group.Preferred divalent organic group is selected from general formula (i) to the group of (iv) representing (wherein, n20 is the integer of 0-8, preferred 0 or 1).Most preferred radicals R ¹¹It is (ii) and the (iii) group of expression of general formula; When following described m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them;

M is the integer of 0-10, and is preferred 0 to 2, more preferably 0 or 1; With

R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged, preferred chlorine atom or methoxy or ethoxy.

Other exemplary of the organic silane compound of general formula (α III) expression comprises following compound:

(4) the πDian Zi conjugated organic silane compound of general formula (α IV) expression:

In the general formula (α IV), X ¹⁶And X ¹⁷Represent C or N independently of one another, preferred X ¹⁶And X ¹⁷Be N simultaneously; Particularly, work as X ¹⁶When being C, it is-CH=, and works as X ¹⁶When being N, it is-N=; Work as X ¹⁷When being C, it is-CH=, and works as X ¹⁷When being N, it is-N=:

But, X ¹⁶And X ¹⁷Can not be C simultaneously; With

N15 is the integer of 0-8, and is preferred 0 to 3, more preferably 0 or 1.

In general formula (α IV), R ¹¹To R ¹⁴Identical with m with in the general formula (α) those.

Particularly, R ¹¹The expression divalent organic group is promptly removed the residue of divalent that two hydrogen atoms obtain in the described monocyclic aromatic hydroxy compound of general formula (α), monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound or the saturated aliphatic hydrocarbon compounds, perhaps their compound group.Preferred divalent organic group is selected from general formula (i) to the group of (iv) representing (wherein, n20 is the integer of 0-8, preferred 0 to 3).Most preferred radicals R ¹¹It is the group of general formula (i) expression; When following described m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them;

M is the integer of 0-10, preferred 0 to 3; With

R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged, preferred chlorine atom or methoxy or ethoxy.

In the general formula (α IV), when m is 0, condenses benzene or heterocycle and can have hydrophobic group, if any the alkyl of 1-30 carbon atom.

Other exemplary of the organic silane compound of general formula (α IV) expression comprises following compound:

(5) the πDian Zi conjugated organic silane compound of general formula (α V) expression:

In the general formula (α V), X ¹⁸And X ¹⁹Represent C, N, O or S independently of one another; X ¹⁸And X ¹⁹The preferred N-S of combination, N-O, S-O, N-N or C-N, more preferably N-S; Particularly, work as X ¹⁸When being C, it is-CH ₂-, work as X ¹⁸When being N, it is-NH-, and works as X ¹⁸When being O or S, it is-X ¹⁸-; Work as X ¹⁹When being C, it is-CH ₂-, work as X ¹⁹When being N, it is-NH-, and works as X ¹⁹When being O or S, it is-X ¹⁹-;

But, X ¹⁸And X ¹⁹Can not be C simultaneously; With

N16 and n17 are the integers that satisfies 0≤n16+n17≤7, preferably satisfy 0≤n16+n17≤2.

In general formula (α V), R ¹¹To R ¹⁴Identical with m with in the general formula (α) those.

Particularly, R ¹¹The expression divalent organic group is promptly removed the residue of divalent that two hydrogen atoms obtain in the described monocyclic aromatic hydroxy compound of general formula (α), monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound or the saturated aliphatic hydrocarbon compounds, perhaps their compound group.Preferred divalent organic group is selected from general formula (i) to the group of (iv) representing (wherein, n20 is the integer of 0-8, preferred 0 to 3).Most preferred radicals R ¹¹Be that general formula (i) is to the group of (iii) representing; When following described m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them;

M is the integer of 0-10, preferred 0 to 4; With

R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged, preferred chlorine atom or methoxy or ethoxy.

Other exemplary of the organic silane compound of general formula (α V) expression comprises following compound:

(6) the πDian Zi conjugated organic silane compound of general formula (α VI) expression;

In the general formula (α VI), X ²⁰And X ²¹Representing C or N independently of one another, preferably is N simultaneously; Particularly, work as X ²⁰When being C, it is is-CH=, works as X ²¹When being N, it is-N=; Work as X ²¹When being C, it is-CH=, and works as X ²¹When being N, it is-N=;

But, X ²⁰And X ²¹Can not be C simultaneously; With

N18 and n19 are the integers that satisfies 0≤n18+n19≤7, preferably satisfy 0≤n18+n19≤2.

In the general formula (α VI), R ¹¹To R ¹⁴Identical with m with in the general formula (α) those.

Particularly, R ¹¹Be divalent organic group, promptly remove the residue of divalent that two hydrogen atoms obtain in the described monocyclic aromatic hydroxy compound of general formula (α), monocyclic heterogeneous ring compound, fused polycycle aromatic hydroxy compound or the saturated aliphatic hydrocarbon compounds, perhaps their compound group.Preferred divalent organic group is selected from general formula (i) to the group of (iv) representing (wherein, n20 is the integer of 0-8, preferred 0 to 3).Most preferred radicals R ¹¹It is the group that top general formula is (iii) represented; When following described m more than or equal to 2 the time, a plurality of organic group R ¹¹Each other can be identical, perhaps partly or entirely all differing from one another in them;

M is the integer of 0-10, preferred 0 to 2; With

R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged, preferred chlorine atom or methoxy or ethoxy.

In the general formula (α VI), when m was 0, fused benzene rings or heterocycle can have hydrophobic group, if any the alkyl of 1-30 carbon atom.

Other exemplary of the organic silane compound of general formula (α VI) expression comprises following compound:

(method for preparing organic silane compound (α))

Organic compound of the present invention (α) is to carry out the Grignard reaction preparation by the compound that compound that makes general formula (β) expression and general formula (γ) are represented:

Z-(R ¹¹) _m-MgX ³⁰(β)

In the formula, Z, R ¹¹Identical with in the general formula (α) those respectively with m; X ³⁰The expression halogen atom):

X ³¹-SiR ¹²R ¹³R ¹⁴(γ)

In the formula, X ³¹Expression hydrogen or halogen atom or the alkoxyl group of 1-4 carbon atom is arranged; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.The organic silane compound of general formula (α I) to (α VI) expression also can be according to this method preparation.

The temperature of reaction preference is as being-100 ℃ to 150 ℃, more preferably-20 ℃ to 100 ℃.Preferably about 0.1-48 hour of reaction times.This reaction is carried out in to the organic solvent of this reactionlessness usually.Representative examples of organic to this reactionlessness comprises aliphatic hydrocrbon or aromatic hydrocarbons, as hexane, pentane, benzene and toluene; Ether solvents is as diethyl ether, dipropyl ether, diox and tetrahydrofuran (THF) (THF) etc.; These solvents can use separately, perhaps use with liquid mixture.Wherein, preferred diethyl ether and THF.Can use catalyzer according to reaction needed.The catalyzer that uses can be any catalyzer, for example platinum catalyst, palladium catalyst or nickel catalyzator etc.

Adopt known any method such as resolubilization, concentrate, solvent extraction, fractionation, crystallization, recrystallization, chromatography etc., the organic silane compound of the present invention (α) that makes can separate also purifying from reaction solvent.

The compound of general formula (β) expression (below, be called compound (β); Grignard reagent) compound that can be by making general formula (β-1) expression and MAGNESIUM METAL with top similar organic solvent in react and make;

Z-(R ¹¹) _m-X ³⁰(β-1)

In the formula, Z, R ¹¹, m and X ³⁰Identical with in the general formula (β) those respectively (below, be called compound (β-1)).

When m is 0, compound (β-1) can be by in the solvent as tetracol phenixin, and the compound that uses N-chlorosuccinimide (NCS), N-bromosuccinimide (NBS) etc. to represent at specific position mutual-through type (β-2) or (β-3) carries out halogenation and prepares:

Z-H (β-2)

Z-OH (β-3)

In the formula, Z all with general formula (β) in identical (below, be called compound (β-2) or (β-3) respectively).

M is that 0 o'clock compound (β-1) can be buied.

For example, 2-chloro benzimidazole (CAS.No.7228-38-8), 2-chloro phenothiazine (CAS.No.92-39-7) and 2-chloroquinoline (CAS.No.612-62-4) can be buied from Sigma AldrichCorporation respectively.

Compound (β-2) and (β-3) also can buy usually.

For example, 4,7-dimethyl-1,10-phenanthroline (CAS.No.3248-05-3), 2-hydroxyl diphenylene-oxide (CAS.No.86-77-1), 2-hydroxycarbazole (CAS.No.86-79-3) and 2,3-dimethyl quinoxaline (CAS.No.2379-55-7) can be buied from Sigma AldrichCorporation respectively.

When m is a Grignard reagent by the compound of preparation compound (β-2) or general formula (β-4) expression for the compound (β-1) more than or equal to 1 time, and the halide reaction of this Grignard reagent and other compound is made,

H-(R ¹¹) _m-H(β-4)

In the formula, R ¹¹Identical with in the general formula (β) those respectively with m (below, be called compound (β-4).

Special when Grignard reagent be by compound (β-4) when forming, generally by carrying out pair halogenations at two end, and a halogen atom of metal such as magnesium and end is reacted prepare.Then, make the halide reaction of Grignard reagent and compound (β-2).

Some compound (β-4) can be buied, and some needs to prepare by currently known methods.

For example, benzene, biphenyl, terphenyl, thiophene, thiophthene, three thiophthenes, four thiophthenes and naphthalene, or its single halogenide or dihalide etc. all can be buied.

The molecule that contains the benzene skeleton can be by for example following method preparation.But the molecule that contains N, Si, Ge, P, Sn, Ti or Zr that contains the heterocycle skeleton also can adopt and be similar to the method preparation that contains the benzene molecule of the skeleton.

The branch period of the day from 11 p.m. to 1 a.m that preparation contains the benzene skeleton carries out effectively adopting Grignard reaction after the halogenation to the avtive spot on the benzene.Adopt this method can control the quantity of phenyl ring.Perhaps, can adopt and use the coupling of suitable metal catalyst (Cu, Al, Zn, Zr, Sn etc.) to substitute Grignard reagent, prepare this molecule.

Below with a method of coming the self-described preparation to contain the benzene molecule of the skeleton.Below shown in the preparation example by of the unique reaction of benzene trimer to (3+m)-oligopolymer.But,, can prepare the molecule that contains the benzene skeleton except that 4-to 7-oligopolymer by using the raw material of different units quantity.

For example, the molecule that contains the thiophene skeleton can prepare by the following method.But, adopt the method that is similar to the molecule that contains the thiophene skeleton, also can prepare the molecule that contains O or N that contains the heterocycle skeleton.

The branch period of the day from 11 p.m. to 1 a.m that preparation contains the thiophene skeleton after the avtive spot of thiophene carries out halogenation, can effectively adopt Grignard reaction.Adopt this method can control the quantity of thiphene ring.Perhaps, adopt the coupling of using suitable metal catalyzer (Cu, Al, Zn, Zr, Sn etc.), substitute Grignard reagent, can prepare this molecule.

Contain the branch period of the day from 11 p.m. to 1 a.m of thiophene skeleton in preparation, can also adopt following preparation method, substitute the method for using Grignard reagent.

Particularly, 2 of thiophene '-position or 5 '-position is at first by halogenation (for example, chlorination).An example of chlorination method is with 1 equivalent N-chlorosuccinimide or phosphoryl chloride (POCl ₃) handle.Solvent for use for example is the liquid mixture or the DMF of chloroform-acetate (AcOH).Perhaps, by at catalyzer three (triphenylphosphine) nickel ((PPh ₃) ₃Ni) under the existence halogenated thiophene is reacted in the DMF solvent, can the thiophene molecule be interconnected in halogenated site.

Halogenated thiophene and divinylsulfone coupling can obtain its 1, the 4-derovatives.Subsequently, at Lawesson reagent (LR) or P ₄S ₁₀Carrying out anhydrous toluene solution under existing refluxes, last compound situation, anhydrous toluene solution refluxes and spends the night, back one compound situation, anhydrous toluene solution refluxed about 3 hours, to cause ring closed, the thiphene ring quantity of the molecule that contains the thiophene skeleton of acquisition increases by one than thiphene ring total amount in the link coupled thiophene.

Therefore, adopt above-mentioned thiophene reaction can increase thiphene ring quantity.

With an example method that preparation contains the thiophene molecule of the skeleton is shown below.Describe by the thiophene dipolymer to tetramer with by of the reaction of thiophene trimer in the preparation example below to 6-or 7-oligopolymer.But, in the reaction of the thiophene of different units quantity, can form except that 4-, 6-or 7-oligopolymer other and contain the molecule of thiophene skeleton.For example, the coupling by the 2-chlorothiophene, with NCS the 2-chlorothiophene is carried out chlorination and make chlorizate and the trimeric 2-chlorinated derivatives reaction of thiophene subsequently, can form the thiophene pentamer.In addition, the thiophene tetramer is carried out chlorination, also can obtain 8-or 9-thiophene oligomers with NCS.

For example, the method that preparation is contained the benzene molecule of the skeleton combines with the method that preparation contains the molecule of thiophene skeleton, can also prepare the molecule that contains benzene and thiophene skeleton.

Perhaps, adopt following method can prepare the molecule that contains the acene skeleton.

Preparation contains the method for the molecule of acene skeleton, for example be, replace the hydrogen atom that links to each other with carbon atom at the predetermined site of initial compounds, repeat this step with triflate (triflate) base, itself and furans or furan derivatives are reacted, and the method for product being carried out oxidation.It is as follows to adopt this method to prepare the example of method of acene skeleton.

(organic film and preparation method thereof)

Use organic silane compound of the present invention (I) or organic silane compound (α), can form organic film (particularly unimolecular film).Unimolecular film is preferably formed on the base material.

Organic silane compound (I) or (α) chemical bond by silyl (particularly silanol bonds (Si-O-)) is adsorbed on the base material.Therefore, in organic silane compound (I) or unimolecular film (α), compound molecule on substrate surface with its silyl and the lip-deep R of film ¹Or Z group orientation.As a result, the orientation of the compound molecule of this unimolecular film (crystallinity) is higher, has good stripper-resistance.In addition, because organic silane compound (I) has π-electron conjugated R ¹Group, and organic silane compound (α) has π-electron conjugated Z group, for example, when described unimolecular film was used as the organic layer (film) in the organic assembly of organic transistor, organic photoelectric converter or organic electroluminescent device, the electrology characteristic of the unimolecular film that is obtained such as carrier mobility efficient were good.

The example of the raw material of base material comprises: element semiconductor such as silicon and germanium; Compound semiconductor such as gallium arsenide and zinc selenide; Silica glass; And polymer materials, as polyethylene, polyethylene terephthalate and tetrafluoroethylene.Perhaps, base material can be made of the inorganic materials that is used as the electrode of semiconducter device usually, can also have the organic materials film on its surface.Base material among the present invention is preferably at substrate surface possess hydrophilic property group, as hydroxyl or carboxyl, particularly hydroxyl, hydrophilic radical can adopt following method to form, if promptly there is not hydrophilic radical, can be by substrate surface be handled, and form hydrophilic radical.Base material is carried out the wetting ability processing for example can be undertaken by base material being immersed in hydrogen peroxide-sulfuric acid mixed solution or by irradiation UV light.

Below, the method for using organic silane compound (I) or (α) forming organic film is described.

At first, when forming organic film,, make the reaction of organic silane compound (I) or silyl (α) and substrate surface, form directly absorption (combination) to the unimolecular film of base material by hydrolysis.Particularly, can adopt such as so-called LB method (Langmuir Blodgett method), pickling process or coating process.

More specifically, for example in the LB method, be dissolved in the nonaqueous organic solvent, obtaining solution dropwise be applied on the surface of the water of having regulated pH in advance, on this water surface, form film with organic silane compound (I) or (α).Radicals X in the silyl of organic silane compound (I) ¹To X ³The perhaps radicals R in the silyl of organic silane compound (α) ¹²To R ¹⁴Be hydrolyzed into then and be hydroxyl.Subsequently, on the water surface of this state, exert pressure, and be retracted in the base material of lip-deep possess hydrophilic property group (particularly hydroxyl), cause organic silane compound (I) or (α) in silyl and this base material reaction, obtain being attached to the unimolecular film of this base material by chemical bond (particularly, silanol bonds).Dropwise use this solution on the water surface, the pH of this water surface should be adjusted to and can make radicals X ¹To X ³Or R ¹²To R ¹⁴The scope of hydrolysis takes place.

Perhaps, for example in dipping or coating method, be dissolved in the nonaqueous organic solvent with organic silane compound (I) or (α), the base material of possess hydrophilic property group on the surface (particularly hydroxyl) is flooded in the solution that is obtained, then it is extracted out, perhaps the solution that is obtained is coated in the surface of this base material.Radicals X in the silyl of organic silane compound (I) ¹To X ³The perhaps radicals R in the silyl of organic silane compound (α) ¹²To R ¹⁴Be hydrolyzed to hydroxyl by the trace water in existence and the non-aqueous solvent.Then, when the base material of dipping keeps specified time, organic silane compound (I) or (α) in silyl and base material reaction, formation chemical bond (particularly silanol bonds), the result obtains unimolecular film.Work as radicals X ¹To X ³Perhaps radicals R ¹²To R ¹⁴During not hydrolysis, preferably in this solution, add the water of having regulated pH on a small quantity.

Non-aqueous organic solvent is had no particular limits, as long as organic solvent and water is incompatible and can be dissolved with organic silane compound (α), this class representative examples of organic comprises hexane, chloroform, tetracol phenixin etc.

After forming unimolecular film, use non-aqueous organic solvent to remove unreacted organic silane compound usually from this unimolecular film.After organic film washed with water, in drying at room temperature, perhaps heat drying made its curing.

The organic film that obtains can directly be used as electricity material, perhaps handles in addition, for example, handles by electrolytic polymerization.Use organic silane compound of the present invention (I) or (α) can form Si-O-Si reticulated structure in the organic film shown in Figure 1, shorten the distance between adjacent molecule, and increase orientation (crystallinity).In addition, work as unit R ¹Or Z-(R ¹¹) _mWhen line style connected, the mutual debond in the unit in the adjacent molecule caused the distance between adjacent molecule further to shorten, and obtains the organic film of highly crystalline.

Below, with reference to embodiment organic silane compound of the present invention and preparation method thereof is described more specifically.

Embodiment

Preparation example 1

Three selenophen trichlorosilane (terselenophenetrichlorosilane) (X of general formula (1) expression above the preparation ¹=X ²=X ³=Cl; Y=Se; R ²=R ³=H and n1=3) (Ge Liya method)

According to synthetic route 1 this compound of preparation.Particularly, at first, 50ml chloroform and 70mM selenophen are put into the round-bottomed flask of a 100-ml, cool off this mixture to 0 ℃ temperature; Add the NBS (N-bromosuccinimide) of 20M therein, stirred this mixture 1 hour.After product extracts with purifying waste water, under reduced pressure carry out purifying, acquisition 2-bromine selenophen in 80 ℃.Then, in nitrogen atmosphere, anhydrous THF of 5ml and 30mM 2-bromine selenophen are put into a 50-ml round-bottomed flask; Add magnesium therein; Stirred the mixture 2 hours.Then, adding contains catalyst n i (dppp) Cl therein ₂The 5ml anhydrous THF solution of (dichloro [1,3-two (diphenylphosphino) propane] nickel (II)) and 30mM 2-bromine selenophen makes this mixture in 0 ℃ of reaction 12 hours.Product by by the flash chromatography purifying, obtains two selenophens with after the extraction of purifying waste water.

Then, 50ml chloroform and 70mM two selenophens are put into the round-bottomed flask of a 100-ml; Cool off this mixture to 0 ℃; Add 70M NBS (N-bromosuccinimide); Stirred this mixture 1 hour.Product under reduced pressure carries out purifying, acquisition 2-bromine two selenophens (productive rate: 50%) in 80 ℃ with after the extraction of purifying waste water.Then, under nitrogen atmosphere, the anhydrous THF of 5ml and 7mM are put into the round-bottomed flask of a 50-ml for the 2-bromine selenophen of the intermediate of preparation two selenophens; Add magnesium; Stirred this mixture 2 hours.Then, adding contains catalyst n i (dppp) Cl ₂The anhydrous THF solution of the 5ml of (dichloro [1,3-two (diphenylphosphino) propane] nickel (II)) and 3mM 2-bromine two selenophens; Make this mixture in 0 ℃ of reaction 12 hours.Product by the flash chromatography purifying, obtains three selenophens (30%) with after the extraction of purifying waste water.

In addition, 50ml chloroform and 5mM three selenophens are put into the round-bottomed flask of a 100-ml; Cooling mixture to 0 ℃ temperature; The NBS that adds 20M therein; Stirred this mixture 1 hour.Product under reduced pressure carries out purifying, acquisition 2-bromine three selenophens in 80 ℃ with after the extraction of purifying waste water.In addition, under nitrogen atmosphere, the anhydrous THF of 5ml, 2-bromine three selenophens and magnesium are put into the round-bottomed flask of a 200-ml, stirred this mixture 2 hours, obtain Grignard reagent.

With 20mM SiCl ₄(tetrachloro silicane) and 50ml toluene are put into the round-bottomed flask of a 200-ml, and this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; This mixture of cooling in ice bath; Under 20 ℃ or lower internal temperature, in 2 hours, drip Grignard reagent; Then, this mixture is in 30 ℃ aging 1 hour (Grignard reactions).

Then, the filtration under diminished pressure reaction soln is to remove magnesium chloride; Stripping toluene and unreacted tetrachloro silicane from filtrate; Solution is distilled, obtain title compound, productive rate is 40%.

The infrared absorption spectrometry of the compound that obtains is presented at 1080cm ^-1The absorption that is derived from the SiC key, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.Can not carry out direct NMR owing to the high reaction activity of the compound that obtains and measure, make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring, the chlorine end group be replaced by oxyethyl group.

(s) 7.7ppm (1H is derived from the selenophen ring)

7.2ppm to 7.1ppm (m) (6H is derived from the selenophen ring)

3.8ppm to 3.7ppm (m) (6H is derived from the methylene radical in the oxyethyl group)

1.30ppm to 1.20ppm (m) (9H is derived from the methyl in the oxyethyl group)

These results determine that the compound that obtains is a title compound.

Preparation example 2

Four selenophen Trimethoxy silane (X of preparation general formula (1) expression ¹=X ²=X ³=OCH ₃Y=Se, R ²=R ³=H; N1=4)

At first, under nitrogen atmosphere, intermediate 2-bromine two selenophens that the anhydrous THF of 5ml and 5mM obtain are put into a 50ml round-bottomed flask in preparation example 1; Add magnesium therein; Stirred this mixture 2 hours.Then, adding contains catalyst n i (dppp) Cl ₂With the 5ml anhydrous THF solution of 5mM 2-bromine two selenophens, make this compound in 0 ℃ of reaction 10 hours.Product by the flash chromatography purifying, obtains four selenophens (35%) with after the extraction of purifying waste water.

Then, intermediate four selenophens of 50ml chloroform and 2 acquisitions of 70mM preparation example are put into a 100-ml round-bottomed flask; Cool off this mixture to 0 ℃, add 70M NBS after, stirred 1 hour.Product under reduced pressure carries out purifying, acquisition 2-bromine four selenophens (productive rate 40%) in 80 ℃ with after the extraction of purifying waste water.Under nitrogen atmosphere, the anhydrous THF of 5ml, 2-bromine four selenophens and magnesium are put into a 200-ml round-bottomed flask, stirred this mixture 2 hours, obtain Grignard reagent.

In addition, 10mM trimethoxy chlorosilane and 30ml toluene are put into a 100-ml round-bottomed flask, and this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel, cools off in ice bath; The past Grignard reagent that wherein drips in 2 hours; Described mixture is 30 ℃ down aging 1 hour (Grignard reactions).

Filtering reacting solution under reducing pressure then is to remove magnesium chloride; Stripping toluene and unreacted trimethoxy chlorosilane from filtrate; And described solution distilled, obtaining title compound, productive rate is 45%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

And, this compound is carried out nucleus magnetic resonance (NMR) measure.

(s) 7.8ppm (1H is derived from the selenophen ring)

7.4ppm to 7.3ppm (m) (8H is derived from the selenophen ring)

(m) 3.50ppm (9H is derived from methyl)

These results determine that the compound that obtains is a title compound.

Preparation example 3

Eight selenophen triethoxyl silane (X of preparation general formula (1) expression ¹=X ²=X ³=OC ₂H ₅Y=Se; R ²=R ³=H; N1=8)

At first, under nitrogen atmosphere, intermediate 2-bromine four selenophens that the anhydrous THF of 5ml and 5mM obtain are put into a 50ml round-bottomed flask in preparation example 2; Add magnesium therein; Stirred this mixture 3 hours.Then, adding contains catalyst n i (dppp) Cl ₂With the 5ml anhydrous THF solution of 5mM 2-bromine four selenophens, make this compound in 0 ℃ of reaction 12 hours.Product by the flash chromatography purifying, obtains eight selenophens (30%) with after the extraction of purifying waste water.

Then, 50ml chloroform and above-mentioned eight selenophens of 70mM are put into a 100-ml round-bottomed flask; Cool off this mixture to 0 ℃, add 10M NBS after, stirred this mixture 1 hour.Product under reduced pressure carries out purifying, acquisition 2-bromine four selenophens in 80 ℃ with after the extraction of purifying waste water.

Under nitrogen atmosphere, the anhydrous THF of 5ml, 2-bromine eight selenophens and magnesium are put into a 200-ml round-bottomed flask in addition, stirred this mixture 2 hours, obtain Grignard reagent.In addition, 10mM triethoxy chlorosilane and 30ml toluene are put into a 100-ml round-bottomed flask, and this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel, cools off in ice bath; The past Grignard reagent that wherein drips in 2 hours; Described mixture is 30 ℃ down aging 1 hour (Grignard reactions).Filtering reacting solution under reducing pressure then is to remove magnesium chloride; Stripping toluene and unreacted triethoxy chlorosilane from filtrate; And described solution distilled, obtaining title compound, productive rate is that 35% infrared absorption spectrometry that obtains compound is presented at 1080cm ^-1The absorption that is derived from the SiC key, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(s) 7.7ppm (1H is derived from the selenophen ring)

7.2ppm to 7.1ppm (m) (16H is derived from the selenophen ring)

3.8ppm to 3.7ppm (m) (6H is derived from the methylene radical in the oxyethyl group)

1.3ppm to 1.2ppm (m) (9H is derived from the methyl in the oxyethyl group)

These results determine that the compound that obtains is a title compound.

Preparation example 4

The thiophene with substituting group (methyl) of preparation general formula (1) expression is coughed up (silole) compound (X ¹=X ²=X ³=Cl; Y=Si; R ²=H; R ³=CH ₃N1=2)

According to synthetic route 2 these compounds of preparation.Particularly, at first, with 20mM 2,5-bromo-3,4-dimethyl-1H-thiophene is coughed up and is dissolved in the alcohol solvent; This solution adding is contained in the ethanolic soln of 22mM butyllithium, the 5-bromo is converted into the Li group; Copper oxidation addition takes place in the TFH solution that adds 12mM CuCN in this solution.Subsequently, add 30mM trimethylammonium quadrol and 100mM right-dinitrobenzene, with two molecule couplings, obtain 5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up (bisilolyl), productive rate is 60%

Then, under nitrogen atmosphere, in the 200ml round-bottomed flask, add the anhydrous THF of 5ml, above 5,5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up and magnesium, and stirs 1 hour, obtains only to have in the 5-position Grignard reagent of Mg.In addition, 10mM trimethylchlorosilane and 30ml THF are put into one at ice bath refrigerative 100-ml round-bottomed flask, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; Add Grignard reagent therein; This mixture was worn out 1 hour in 30 ℃.Then, the reaction soln decompression is filtered down, to remove magnesium chloride; Go out toluene and unreacted trimethylchlorosilane from this filtrate stripping, acquisition 5-trimethyl silyl-5 '-bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up.Subsequently, with 5-trimethyl silyl-5 '-bromo-3,4,3 ', 4 '-tetramethyl--1H, connection thiophene in 1H '-[2,2 '] is coughed up and is dissolved among the 20ml THF; Use PHN ⁺Me ₃F ^-Eliminate trimethyl silyl, acquisition 5-bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up.In addition, under nitrogen atmosphere with the anhydrous THF of 5ml, 5-bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up with magnesium and is put into the 200-ml round-bottomed flask, stirs the acquisition Grignard reagent 1 hour; 10mM tetrachloro silicane and 30ml THF are put into one at ice bath refrigerative 100-ml round-bottomed flask, and this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; Add Grignard reagent therein; This mixture wore out 1 hour in 30 ℃.Filtering reacting solution under reducing pressure then is to remove magnesium chloride; Go out TFH and unreacted tetrachloro silicane from this filtrate stripping, obtain title compound, productive rate is 30%.

The infrared absorption spectrometry of the compound that obtains is presented at 1080cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.In addition, obtaining compound being carried out nucleus magnetic resonance (NMR) measures.

Because the high reaction activity of the compound that obtains can not directly carry out NMR and measure, and can make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring the chlorine end group is replaced by oxyethyl group.

(m) 4.5ppm (1H is derived from thiophene and coughs up ring)

(m) 4.3-4.2ppm (4H is derived from the hydrogen that directly is connected with Si)

3.8ppm to 3.7ppm (m) (6H is derived from the methylene radical in the oxyethyl group)

2.0ppm to 1.9ppm (m) (12H is derived from thiophene and coughs up methyl on the ring)

1.5ppm to 1.4ppm (m) (9H is derived from the methyl in the oxyethyl group)

These results determine that the compound that obtains is a title compound.

Preparation example 5

Preparation is coughed up compound (X by the thiophene with substituting group (methyl) of general formula (1) expression ¹=X ²=X ³=Cl; Y=Si; R ²=H; R ³=CH ₃N1=6)

At first, according to the mode that is similar to preparation example 4, preparation intermediate 5,5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up.Then, handle according to 3 pairs of these intermediates of synthetic route.Particularly, at first, under nitrogen atmosphere, with the anhydrous THF of 5ml, 5mM 5,5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up with magnesium and is put into a 200-ml round-bottomed flask, stirs the acquisition Grignard reagent 5 hours.Then, with 10mM 5-bromo-3,4,3 ', 4 '-tetramethyl--1H, connection thiophene in 1H '-[2,2 '] is coughed up with 30ml THF and is put into one at ice bath refrigerative 100-ml round-bottomed flask, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; Add Grignard reagent therein; Make this compound in 0 ℃ of reaction 15 hours.Product by the flash chromatography purifying, obtains intermediate (A) with after the extraction of purifying waste water.

Subsequently, 50ml chloroform and 10mL intermediate (A) are put into a 100-ml round-bottomed flask, be cooled to 0 ℃ of temperature, behind the interpolation 10M NBS, stirred this mixture 1 hour.Product under reduced pressure carries out purifying in 80 ℃ with after the extraction of purifying waste water, and obtains the intermediate (A) that its terminal hydrogen atom is replaced by bromine.Under nitrogen atmosphere, the intermediate (A) and the magnesium of the anhydrous THF of 5ml, 5mM bromine end group are put into a 200-ml round-bottomed flask, stirred 1 hour, obtain Grignard reagent.5 mM tetrachloro silicanes and 30ml THF are placed in the ice bath in the refrigerative 100-ml round-bottomed flask, and this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; Add Grignard reagent therein; Mixture wore out 1 hour in 30 ℃.Filtering reacting solution under reducing pressure then is to remove magnesium chloride; Go out TFH and unreacted tetrachloro silicane from this filtrate stripping, obtain title compound, productive rate is 20%.

The infrared absorption spectrometry of the compound that obtains is presented at the absorption that is derived from the SiC key, shows that this compound has the SiC key.

In addition, obtaining compound being carried out nucleus magnetic resonance (NMR) measures.Because the high reaction activity of the compound that obtains can not directly carry out NMR and measure, and can make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring the chlorine end group is replaced by oxyethyl group.

(m) 4.4ppm (1H is derived from thiophene and coughs up ring)

4.3ppm to 4.2ppm (m) (12H is derived from the hydrogen that directly is connected with Si)

3.8ppm to 3.7ppm (m) (6H is derived from the methylene radical in the oxyethyl group)

2.1ppm to 2.0ppm (m) (36H is derived from thiophene and coughs up methyl on the ring)

1.5ppm to 1.4ppm (m) (9H is derived from the methyl in the oxyethyl group)

These results determine that the compound that obtains is a title compound.

Preparation embodiment 1

Preparation 2-bromine three thiophene

In the 100-ml glass flask, 1mM three thiophene are dissolved in the tetracol phenixin, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; In flask, add NBS and AIBN (Diisopropyl azodicarboxylate); Stirred this mixture 2.5 hours, then, decompression is filtered down, obtains 2-bromine three thiophene.

Preparation example 6

The thiophene with substituting group (methyl) of preparation general formula (5) expression is coughed up compound (X ¹=X ²=X ³=OC ₂H ₅, Y ⁶=Y ⁸=S; Y ⁷=Si; R ²=H; R on the five-ring of center ³=CH ₃R on the five-ring endways ³=H; N2=n4=3; N3=2)

At first, according to the mode that is similar to preparation example 4, preparation intermediate 5,5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up.According to second reaction formula of synthetic route 4 or the reaction formula of back, to this intermediate handle (m=3, n=2).Particularly, the 0.5mM n-Butyl Lithium is put into a 500-ml glass flask be cooled to-78 ℃, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; In 30 minutes, from this dropping funnel Dropwise 5,5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up, and this compound is converted into its lithium compound; Add 1.5mM two (any acid group (pinacolato) frequently) two boron; When flask Nei Wen-78 ℃ is heated to room temperature gradually, make this mixture reaction 12 hours, after the reaction, adding 2M hydrochloric acid, preparing two boron compounds (C).Then, (C) is dissolved in the toluene solution with two boron compounds, and this solution is added a 200-ml glass flask, and this flask equipped has agitator, reflux exchanger, thermometer and contains 3 moles of %pd (PPh) ₃Dropping funnel with the small amount of carbon acid sodium aqueous solution; Be added in the toluene solution of 2-bromine three thiophene of preparation embodiment 1 preparation from this dropping funnel; Mixture is 85 ℃ of reactions 12 hours, obtains to have the intermediate (D) that the thiophene that directly is attached to three thiophene in 2-position and 5-position is coughed up ring.

Subsequently, 50ml chloroform and 5mM intermediate (D) are put into a 100-ml round-bottomed flask, be cooled to 0 ℃ of temperature; Add 5M NBS therein; Stirred this mixture 1 hour.Product with purify waste water the extraction after, and under 80 ℃ of decompressions purifying, make intermediate (E).Under nitrogen atmosphere, the anhydrous THF of 5ml, 5mM intermediate (E) and magnesium are put into a 200-ml round-bottomed flask, stirred 1 hour, obtain Grignard reagent.Then, 5mM triethoxy chlorosilane and 30ml THF are put into one at ice bath refrigerative 100-ml round-bottomed flask, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; Add Grignard reagent therein; Mixture wore out 1 hour in 30 ℃.Filtering reacting solution under reducing pressure then is to remove magnesium chloride; Go out TFH and unreacted tetrachloro silicane from this filtrate stripping, obtain title compound, productive rate is 15%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, obtaining compound being carried out nucleus magnetic resonance (NMR) measures.

(s) 7.7ppm (1H is derived from thiphene ring)

7.3ppm to 7.2ppm (m) (12H is derived from thiphene ring)

4.5ppm to 4.3ppm (m) (4H is derived from the hydrogen that directly is connected with Si)

3.7ppm to 3.6ppm (m) (6H is derived from the methylene radical in the oxyethyl group)

2.2ppm to 2.1ppm (m) (12H is derived from thiophene and coughs up methyl on the ring)

1.4ppm to 1.3ppm (m) (9H is derived from the methyl in the oxyethyl group)

These results determine that the compound that obtains is a title compound.

Preparation embodiment 2

Preparation 4-bromine quaterphenyl

A 100-ml glass flask, the 0.5mM quaterphenyl is dissolved in the tetracol phenixin, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; Add NBS and AIBN; Stirred this mixture 3 hours, decompression is filtered down, obtains the bromine quaterphenyl.

Preparation example 7

The thiophene with substituting group (methyl) of preparation general formula (6) expression is coughed up compound (X ¹=X ²=X ³=Cl; Y ⁹=Si; Z ¹=Z ²=C; R on the five-ring of center ³=CH ₃R on the six-ring endways ³=H; N2=n4=4; N3=1)

According to synthetic route 5 preparation compounds (m=4, n=1).Particularly, prepare title compound, except substituting 2-bromine three thiophene with 4-bromine quaterphenyl according to the mode that is similar to preparation example 6, substituted in 15 hours 85 ℃ of reactions 12 hours 80 ℃ of reactions, with 2,5-two bromo-3,4-dimethyl-1H-thiophene is coughed up and is substituted 5,5 '-two bromo-3,4,3 ', 4 '-tetramethyl--1H, 1H '-[2,2 '] connection thiophene is coughed up, and substitutes outside the triethoxy chlorosilane with tetrachloro silicane.

The infrared absorption spectrometry of the compound that obtains is presented at 1100cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, obtaining compound being carried out nucleus magnetic resonance (NMR) measures.Because the high reaction activity of the compound that obtains can not directly carry out NMR and measure, and can make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring the chlorine end group is replaced by oxyethyl group.

7.6ppm to 7.5ppm (m) (8H is derived from phenyl ring)

7.5ppm to 7.4ppm (m) (20H is derived from phenyl ring)

(m) 7.2ppm (1H is derived from phenyl ring)

(m) 7.1ppm (4H is derived from phenyl ring)

(m) 4.3ppm (2H is derived from the hydrogen that directly is connected with Si)

3.8ppm to 3.7ppm (m) (6H is derived from the methylene radical in the oxyethyl group)

2.1ppm to 2.0ppm (m) (12H is derived from thiophene and coughs up methyl on the ring)

1.5ppm to 1.4ppm (m) (9H is derived from the methyl in the oxyethyl group)

These results determine that the compound that obtains is a title compound.

The evaluation of-energy level

The lumo energy that is estimated each organic silane compound that makes by Molecular Orbital Calculation in preparation example 1-7 is-2.6eV.On the other hand, measure the lumo energy of each organic silane compound for being less than or equal to-2.5eV by photoelectron spectroscopy.These results determine that any lumo energy in these compounds is more stable than not containing heteroatomic compound.Clearly, the band gap of above-mentioned organic silane compound is not less than containing heteroatomic compound, and therefore, these organic silane compounds are the compounds with high semiconductor property.

Preparation example 8

The organic silane compound of preparation general formula (α I-I) expression

Prepare title compound according to following method.At first, under nitrogen atmosphere, 0.5 mole metal magnesium and 300ml THF (tetrahydrofuran (THF)) are put into a 500-ml glass flask, this flask equipped has agitator, reflux exchanger, thermometer and dropping funnel; In 50-60 ℃, in 2 hours, drip 0.5 mole of 2-chloro benzimidazole from this dropping funnel; After dripping end, this compound wore out the acquisition Grignard reagent 2 hours in 65 ℃.Then, with 1.0 moles of SiCl ₄(tetrachloro silicane) and 300ml toluene are put into one in 1 liter of glass flask of ice bath refrigerative; When temperature is less than or equal to 20 ℃ in the flask, in 2 hours, in flask, add Grignard reagent; After dripping end, this compound wore out 1 hour in 30 ℃.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes toluene and unreacted tetrachloro silicane from filtrate, obtains title compound, and productive rate is 50%.

The infrared absorption spectrometry of the compound that obtains is presented at 1080cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.Because the high reaction activity of the compound that obtains can not directly carry out NMR and measure, and can make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring the chlorine end group is replaced by oxyethyl group.

(m) 7.7ppm (2H, aromatic series)

(m) 7.2ppm (2H, aromatic series)

(m) 5.2ppm (1H, the directly hydrogen that links to each other with nitrogen-atoms)

(m) 3.8ppm (6H, oxyethyl group methylene radical)

(m) 1.4ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α I-1) expression.

Preparation example 9

The organic silane compound of preparation general formula (α V-I) expression

Prepare title compound according to following method.At first, according to the mode that is similar to preparation example 8, under nitrogen atmosphere, put into 0.5 mole metal magnesium and 30ml THF; Add 0.5 mole of 2-chloro phenothiazine therein; Compound obtains Grignard reagent in 60 ℃ of reactions 2 hours.Then, Grignard reagent is added the toluene solution that contains 1.0 moles of chlorine Trimethoxy silanes, this mixture was in 30 ℃ of reactions 1 hour.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes toluene and unreacted chlorine Trimethoxy silane from filtrate, obtains title compound, and productive rate is 55%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

7.0ppm to 6.1ppm (m) (7H, aromatic series)

(5.3ppm 1H, the directly hydrogen that links to each other in nitrogen-atoms)

(m) 3.7ppm (9H, methoxymethyl)

These results show that the compound that obtains is the compound of general formula (α V-1) expression.

Preparation example 10;

The organic silane compound of preparation general formula (α III-1) expression

Prepare title compound according to the methods below.According to the mode that is similar to preparation example 8, at first under nitrogen atmosphere, 0.3 mole metal magnesium and 30ml THF are put into a flask; Add 0.3 mole of 2-chloroquinoline therein; Mixture obtains Grignard reagent in 60 ℃ of reactions 1.5 hours.Then, Grignard reagent is joined in the THF solution that contains 0.5 mole of tetrachloro silicane, mixture was in 30 ℃ of reactions 1 hour.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes THF and unreacted tetrachloro silicane from filtrate, obtains title compound, and productive rate is 55%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.Because the high reaction activity of the compound that obtains can not directly carry out NMR and measure, and can make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring the chlorine end group is replaced by oxyethyl group.

7.8ppm to 7.2ppm (m) (6H, aromatic series)

(m) 3.7ppm (6H, oxyethyl group methylene radical)

(m) 1.6ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α III-1) expression.

Preparation example 11

The organic silane compound of preparation general formula (α VI-1) expression

Prepare title compound according to following method.At first, 1M NBS joined contain 0.5mM 4,7-dimethyl-1 is in the carbon tetrachloride solution of 10-phenanthroline; Stirred this mixture 2 hours, decompression is filtered down, obtains 3-bromo-4,7-dimethyl-1,10-phenanthroline.According to the mode that is similar to preparation example 8, at first, under nitrogen atmosphere, 0.3 mole metal magnesium and 30ml THF are put into a flask subsequently; Add above-mentioned 3-bromo-4 therein, 7-dimethyl-1,10-phenanthroline; Make mixture in 60 ℃ of reactions 1.5 hours, obtain Grignard reagent.Then, this Grignard reagent is joined in the THF solution that contains 0.5 mole of chlorine Trimethoxy silane; And make this mixture in 30 ℃ of reactions 1 hour.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes THF and unreacted compound from filtrate, obtains title compound, and productive rate is 50%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(m) 8.6ppm (2H, aromatic series)

(m) 7.7ppm (1H, aromatic series)

(m) 7.5ppm (2H, aromatic series)

(m) 3.6ppm (9H, methoxymethyl)

(m) 2.4ppm (6H, methyl)

These results show that the compound that obtains is the compound of general formula (α VI-1) expression.

Preparation example 12;

The organic silane compound of preparation general formula (α II-1) expression

Prepare title compound according to the methods below.At first, according to the mode that is similar to preparation example 11,1M NBS and AIBN are joined in the carbon tetrachloride solution that contains 0.5mM 2-hydroxyl diphenylene-oxide; Stirred this mixture 2 hours, decompression is filtered down, obtains 2-bromine diphenylene-oxide.Then, according to the mode that is similar to preparation example 8, under nitrogen atmosphere, 0.3 mole metal magnesium and 30ml THF are put into a flask; 2-bromine diphenylene-oxide above adding therein; Mixture obtains Grignard reagent 55 ℃ of reactions 2 hours.Then, Grignard reagent is joined in the THF solution that contains 0.5 mole of chlorine triethoxyl silane, mixture was 20 ℃ of reactions 1 hour.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes THF and unreacted compound from filtrate, obtains title compound, and productive rate is 60%.

The infrared absorption spectrometry of the compound that obtains is presented at 1080cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(m) 7.5ppm (4H, aromatic series)

(m) 7.2ppm (3H, aromatic series)

(m) 3.5ppm (6H, oxyethyl group methylene radical)

(m) 1.6ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α II-1) expression.

Preparation example 13

The organic silane compound of preparation general formula (α II-3) expression

Prepare title compound according to following method.At first, according to the mode that is similar to preparation example 11,1M NBS and AIBN are joined the carbon tetrachloride solution that contains 0.5mM 2-hydroxycarbazole; Stirred this mixture 2 hours, decompression is filtered down, obtains 2-bromine carbazole.Subsequently,, under nitrogen atmosphere, 0.3 mole metal magnesium and 30ml THF are put into a flask, the 2-bromine carbazole above adding therein according to the mode that is similar to preparation example 8; Mixture obtains Grignard reagent 60 ℃ of reactions 2 hours.Then, this Grignard reagent is joined in the THF solution that contains 0.5 mole of tetrachloro silicane, mixture was 20 ℃ of reactions 1 hour.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes THF and unreacted compound from filtrate, obtains title compound, and productive rate is 60%.

The infrared absorption spectrometry of the compound that obtains is presented at 1080cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.Because the high reaction activity of the compound that obtains can not directly carry out NMR and measure, and can make this compound and ethanol synthesis (supervening hydrogenchloride), before measuring the chlorine end group is replaced by oxyethyl group.

(m) 8.5ppm (1H, the directly hydrogen that links to each other in nitrogen-atoms)

7.6ppm to 7.5ppm (m) (4H, aromatic series)

(m) 7.2ppm (3H, aromatic series)

(m) 3.5ppm (6H, oxyethyl group methylene radical)

(m) 1.4ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α II-3) expression.

Preparation example 14

The organic silane compound of preparation general formula (α IV-1) expression.

Prepare title compound according to the methods below.At first, according to the mode that is similar to preparation example 11,1M NBS and AIBN joined contain 0.4mM 2, in the carbon tetrachloride solution of 3-dimethyl quinoxaline; Stirred this mixture 1.5 hours, decompression is filtered down, obtains 2,3-dimethyl-7-bromine quinoxaline.Then,, under nitrogen atmosphere, 0.2 mole metal magnesium and 30ml THF are put into a flask, 2 above adding therein, 3-dimethyl-7-bromine quinoxaline according to the mode that is similar to preparation example 8; Mixture obtains Grignard reagent 50 ℃ of reactions 4 hours.Then, this Grignard reagent is joined in the THF solution that contains 0.3 mole of chlorine triethoxyl silane, mixture was 20 ℃ of reactions 1.5 hours.After the reaction, the reaction soln decompression is filtered down, to remove magnesium chloride, removes THF and unreacted compound from filtrate, obtains title compound, and productive rate is 55%.

The infrared absorption spectrometry of the compound that obtains is presented at 1085cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(m) 8.0ppm (2H, aromatic series)

(m) 7.6ppm (1H, aromatic series)

(m) 3.5ppm (6H, oxyethyl group methylene radical)

(m) 2.4ppm (6H, methyl)

(m) 1.4ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α IV-1) expression.

Preparation example 15

The organic silane compound of preparation general formula (α I-2) expression

Prepare title compound according to following method.At first, 1M NBS and AIBN are joined in the carbon tetrachloride solution that contains the 0.5M terphenyl, stirred this mixture 8 hours and decompression filtration down, obtain the dibromo terphenyl.Then, under nitrogen atmosphere, 0.2 mole metal magnesium is joined in the THF solution of the dibromo terphenyl that contains above the 0.2M; Mixture obtains Grignard reagent (A) 50 ℃ of reactions 2 hours; In the THF of this Grignard reagent solution, add 0.2M 2-chloro benzimidazole; Mixture obtains intermediate (B) 20 ℃ of reactions 1 hour.

In addition, (B) is dissolved among the THF with intermediate, and this intermediate reacted 2 hours with MAGNESIUM METAL at 55 ℃, obtained Grignard reagent; Add 0.1M chlorine triethoxyl silane therein; Mixture obtains title compound 25 ℃ of reactions 2 hours, and productive rate is 40%.

The infrared absorption spectrometry of the compound that obtains is presented at 1075cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(m) 7.7ppm (2H is derived from the aromatic series of benzoglyoxaline)

7.6ppm to 7.5ppm (m) (10H is derived from the aromatic series of terphenyl)

(m) 7.4ppm (2H, the aromatic series of terphenyl)

(m) 7.3ppm (2H is derived from the aromatic series of benzoglyoxaline)

(m) 3.5ppm (6H, oxyethyl group methylene radical)

(m) 1.4ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α I-2) expression.

Adopt similar method, the organic silane compound that can prepare its phenylene different amts with and be derived from the different organic silane compound of group of fused polycycle.

Preparation example 16

The organic silane compound of preparation general formula (α V-2)

Prepare title compound according to following method.At first, 1M NBS and AIBN are joined in the carbon tetrachloride solution that contains 0.5M four thiophene; Stirred this mixture 6 hours, decompression is filtered down, obtains dibromo four thiophene.Then, under nitrogen atmosphere, 0.2 mole metal magnesium is joined the THF solution that contains dibromo four thiophene; Mixture obtains to have the Grignard reagent of the magnesium that only links to each other with a bromine group, as preparation example 15 60 ℃ of reactions 3 hours; This solution is joined in the THF solution that contains 0.2M 2-chloro phenothiazine, and mixture forms intermediate (C) 20 ℃ of reactions 1 hour.

In addition, intermediate (C) is dissolved in THF; Add MAGNESIUM METAL therein; Mixture obtains Grignard reagent 55 ℃ of reactions 2 hours; Add 0.1M chlorine Trimethoxy silane therein, mixture obtains title compound 25 ℃ of reactions 2 hours, and productive rate is 40%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(m) 8.5ppm (1H, the directly hydrogen that links to each other in nitrogen-atoms)

(m) 7.1ppm (8H, thiphene ring)

(m) 6.9ppm (5H, aromatic series)

(m) 6.8ppm (2H, aromatic series)

(m) 3.5ppm (9H, methoxymethyl)

These results show that the compound that obtains is the compound of general formula (α V-2) expression.

Adopt similar method, the organic silane compound that can prepare its thienyl different amts with and be derived from the different organic silane compound of group of fused polycycle.

Preparation example 17

The organic silane compound of preparation general formula (α II-2) expression

Prepare title compound according to following method.At first, under nitrogen atmosphere, 0.5 mole metal magnesium is joined the THF solution of the intermediate 2-bromine diphenylene-oxide that contains 0.5M preparation example 12; Mixture obtains Grignard reagent 50 ℃ of reactions 3 hours; Then, add 0.5M 1-bromonaphthalene therein; Mixture obtains 3-naphthalene-2-base-diphenylene-oxide 20 ℃ of reactions 1 hour.

In addition, top 0.5M 3-naphthalene-2-base-diphenylene-oxide is joined in the carbon tetrachloride solution that contains 1M NBS and AIBN, mixture obtains intermediate (D) 55 ℃ of reactions 2 hours.

Add 0.5M chlorine triethoxyl silane therein, mixture obtains title compound 20 ℃ of reactions 2 hours, and productive rate is 30%.

The infrared absorption spectrometry of the compound that obtains is presented at 1090cm ^-1The absorption that is derived from the SiC key is arranged, show that this compound has the SiC key.

In addition, this compound being carried out nucleus magnetic resonance (NMR) measures.

(m) 7.8ppm (4H, aromatic series)

(m) 7.5ppm (5H, aromatic series)

(m) 7.3ppm (2H, aromatic series)

(m) 7.2ppm (2H, aromatic series)

(m) 3.6ppm (6H, oxyethyl group methylene radical)

(m) 1.5ppm (9H, ethoxyl methyl)

These results show that the compound that obtains is the compound of general formula (α II-2) expression.

Adopt similar method, the organic silane compound that can prepare its acene skeleton different amts with and be derived from the different organic silane compound of group of fused polycycle.

Commercial Application

The electric conductivity of organosilan compound of the present invention (semiconduction), orientation (crystallinity and regularity) And with the cohesive aspect function admirable of base material, can be for the manufacture of such as TFT, solar cell, fuel The semi-conductor electronic device of battery and sensor.

Claims

(according to the modification of the 19th of treaty)

1. the πDian Zi conjugated organic silane compound of general formula (I) expression:

R ₁-SiX ¹X ²X ³(I)

In the formula, R ¹Expression has the unitary organic group of monocyclic heterocycles, and described monocyclic heterocycles unit contains the atom that is selected from Si, Ge, Sn, P, Se, Te, Ti or Zr; X ¹To X ³Expression can produce the group of hydroxyl by hydrolysis separately.

2. πDian Zi conjugated organic silane compound as claimed in claim 1 is characterized in that R ¹Expression also has the organic group of other monocyclic heterocycles unit and/or mononuclear aromatics ring element.

3. πDian Zi conjugated organic silane compound as claimed in claim 2 is characterized in that, described other monocyclic heterocycles unit is the thiphene ring unit, and described mononuclear aromatics ring element is the phenyl ring unit.

4. as claim 1,2 or 3 described πDian Zi conjugated organic silane compounds, it is characterized in that R ¹In the unit that comprises add up to 1-9.

5. as claim 1,2,3 or 4 described πDian Zi conjugated organic silane compounds, it is characterized in that R ¹Be illustrated in the organic group that vinylidene is arranged between the unit.

6. as each described πDian Zi conjugated organic silane compound among the claim 1-5, it is characterized in that X ¹To X ³Represent halogen atom or lower alkoxy independently of one another.

7. the method for preparing πDian Zi conjugated organic silane compound, this method comprises:

The compound of general formula (II) expression and the compound of general formula (III) expression are reacted:

R ₁-Li(II)

In the formula, R ¹The expression organic group, this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements;

X ⁴-SiX ¹X ²X ³(III)

In the formula, X ¹To X ³Expression can produce the group of hydroxyl by hydrolysis separately; X ⁴Expression hydrogen or halogen atom or lower alkoxy.

8. the method for preparing πDian Zi conjugated organic silane compound, this method comprises:

Make the compound of general formula (IV) expression and the compound of general formula (III) expression carry out Grignard reaction:

R ¹-MgX ⁵(IV)

In the formula, R ¹The expression organic group, this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements; X ⁵The expression halogen atom;

X ⁴-SiX ¹X ²X ³(III)

In the formula, X ¹To X ³Each can produce the group of hydroxyl naturally by hydrolysis; X ⁴Expression hydrogen or halogen atom or lower alkoxy.

9. as claim 7 or the 8 described methods that prepare πDian Zi conjugated organic silane compound, it is characterized in that, make to contain the atoms of elements (Y that is selected from long period table the 4A, 4B, 5B and 6B family ⁰) the unitary compound of monocyclic heterocycles at specific position by halogenation, and make the halogenated compound that makes and contain Y ₀The unitary Grignard reagent of the monocyclic heterocycles of atom carries out Grignard reaction, repeats above-mentioned halogenating reaction and Grignard reaction, with control R ¹In contain Y ₀The quantity of the monocyclic heterocyclic units of atom.

10. the πDian Zi conjugated organic silane compound of general formula (α) expression, but do not comprise 3-triethoxysilyl quinoline:

Z-(R ¹¹) _m-SiR ¹²R ¹³R ¹⁴(α)

In the formula, Z represents the unit price organic group, and this organic group is derived from the fused polycycle heterogeneous ring compound of the condensed ring of 2-10 five-ring and/or six-ring; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

11. the πDian Zi conjugated organic silane compound of general formula (α I) expression:

In the formula, X ¹¹Expression carbon atom, nitrogen-atoms, Sauerstoffatom or sulphur atom, X ¹²Expression carbon atom or nitrogen-atoms, still, X ¹¹And X ¹²Can not be carbon atom simultaneously; N11 is the integer of 0-8; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

12. the πDian Zi conjugated organic silane compound of general formula (α II) expression:

In the formula, X ¹³Expression nitrogen-atoms, Sauerstoffatom or sulphur atom; N12 and n13 are the integers that satisfies 0≤n12+n13≤7; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

13. the πDian Zi conjugated organic silane compound of general formula (α III) expression, but do not comprise 3-triethoxysilyl quinoline:

In the formula, X ¹⁴And X ¹⁵Represent carbon atom or nitrogen-atoms independently of one another, still, X ¹⁴And X ¹⁵Can not be carbon atom simultaneously; N14 is the integer of 0-8; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

14. the πDian Zi conjugated organic silane compound of general formula (α IV) expression:

In the formula, X ¹⁶And X ¹⁷Represent carbon atom or nitrogen-atoms independently of one another, still, X ¹⁶And X ¹⁷Can not be carbon atom simultaneously; N15 is the integer of 0-8; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

15. the πDian Zi conjugated organic silane compound of general formula (α V) expression:

In the formula, X ¹⁸And X ¹⁹Represent carbon atom, nitrogen-atoms, Sauerstoffatom or sulphur atom independently of one another, still, X ¹⁸And X ¹⁹Can not be carbon atom simultaneously; N16 and n17 are the integers that satisfies 0≤n16+n17≤7; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

16. the πDian Zi conjugated organic silane compound of general formula (α VI) expression:

In the formula, X ²⁰And X ²¹Represent carbon atom or nitrogen-atoms independently of one another, still, X ²⁰And X ²¹Can not be carbon atom simultaneously; N18 and n19 are the integers that satisfies 0≤n18+n19≤7; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

17., it is characterized in that R as each described πDian Zi conjugated organic silane compound among the claim 10-16 ¹¹Be to be selected from the divalent organic group of following general formula (i) to the group of (iv) representing:

In the formula, n20 is the integer of 0-8.

18. prepare the method for πDian Zi conjugated organic silane compound, this method comprises:

Make the compound of general formula (β) expression and the compound of general formula (γ) expression carry out Grignard reaction,

Z-(R ¹¹) _m-MgX ³⁰(β)

In the formula, Z represents the unit price organic group, and this organic group is derived from the fused polycycle heterogeneous ring compound of the condensed ring of 2-10 five-ring and/or six-ring; R ¹¹The expression divalent organic group; M is the integer of 0-10; X ³⁰The expression halogen atom;

X ³¹-SiR ¹²R ¹³R ¹⁴(γ)

In the formula, X ³¹Expression hydrogen or halogen atom or the alkoxyl group of 1-4 carbon atom is arranged; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

Claims (19)

1. the πDian Zi conjugated organic silane compound of general formula (I) expression:

R ¹-SiX ¹X ²X ³(I)

In the formula, R ¹The expression organic group, this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements; X ¹To X ³Each can produce the group of hydroxyl naturally by hydrolysis.

2. πDian Zi conjugated organic silane compound as claimed in claim 1 is characterized in that R ¹Expression has the unitary organic group of monocyclic heterocycles, and described monocyclic heterocycles unit contains the atom that is selected from Si, Ge, Sn, P, Se, Te, Ti or Zr.

3. πDian Zi conjugated organic silane compound as claimed in claim 1 or 2 is characterized in that R ¹Expression also has the organic group of other monocyclic heterocycles unit and/or mononuclear aromatics ring element.

4. πDian Zi conjugated organic silane compound as claimed in claim 3 is characterized in that, described other monocyclic heterocycles unit is the thiphene ring unit, and described mononuclear aromatics ring element is the phenyl ring unit.

5. as each described πDian Zi conjugated organic silane compound among the claim 1-4, it is characterized in that R ¹In the unit that comprises add up to 1-9.

6. as each described πDian Zi conjugated organic silane compound among the claim 1-5, it is characterized in that R ¹Be illustrated in the organic group that vinylidene is arranged between the unit.

7. as each described πDian Zi conjugated organic silane compound among the claim 1-6, it is characterized in that X ¹To X ³Represent halogen atom or lower alkoxy independently of one another.

8. prepare the method for each described πDian Zi conjugated organic silane compound among the claim 1-7, this method comprises:

The compound of general formula (II) expression and the compound of general formula (III) expression are reacted:

R ¹-Li(II)

In the formula, R ¹The expression organic group, this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements;

X ⁴-SiX ¹X ²X ³(III)

In the formula, X ¹To X ³Each can produce the group of hydroxyl naturally by hydrolysis; X ⁴Expression hydrogen or halogen atom or lower alkoxy.

9. prepare the method for each described πDian Zi conjugated organic silane compound among the claim 1-8, this method comprises:

Make the compound of general formula (IV) expression and the compound of general formula (III) expression carry out Grignard reaction:

R ¹-MgX ⁵(IV)

In the formula, R ¹The expression organic group, this group has and contains the monocyclic heterocycles unit that is selected from long period table the 4A, 4B, 5B and 6B family atoms of elements; X ⁵The expression halogen atom;

X ⁴-SiX ¹X ²X ³(III)

In the formula, X ¹To X ³Each can produce the group of hydroxyl naturally by hydrolysis; X ⁴Expression hydrogen or halogen atom or lower alkoxy.

10. prepare the method for πDian Zi conjugated organic silane compound as claimed in claim 8 or 9, it is characterized in that, make to contain the atoms of elements (Y that is selected from long period table the 4A, 4B, 5B and 6B family ⁰) the unitary compound of monocyclic heterocycles at specific position by halogenation, and make the halogenated compound that makes and contain Y ₀The unitary Grignard reagent of the monocyclic heterocycles of atom carries out Grignard reaction, repeats above-mentioned halogenating reaction and Grignard reaction, with control R ¹In contain Y ₀The quantity of the monocyclic heterocyclic units of atom.

11. the πDian Zi conjugated organic silane compound of general formula (α) expression:

Z-(R ¹¹) _m-SiR ¹²R ¹³R ¹⁴(α)

In the formula, Z represents the unit price organic group, and this organic group is derived from the fused polycycle heterogeneous ring compound of the condensed ring of 2-10 five-ring and/or six-ring; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

12. the πDian Zi conjugated organic silane compound of general formula (α I) expression:

In the formula, X ¹¹Expression carbon atom, nitrogen-atoms, Sauerstoffatom or sulphur atom, X ¹²Expression carbon atom or nitrogen-atoms, still, X ¹¹And X ¹²Can not be carbon atom simultaneously; N11 is the integer of 0-8; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

13. the πDian Zi conjugated organic silane compound of general formula (α II) expression:

In the formula, X ¹³Expression nitrogen-atoms, Sauerstoffatom or sulphur atom; N12 and n13 are the integers that satisfies 0≤n12+n13≤7; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

14. the πDian Zi conjugated organic silane compound of general formula (α III) expression:

In the formula, X ¹⁴And X ¹⁵Represent carbon atom or nitrogen-atoms independently of one another, still, X ¹⁴And X ¹⁵Can not be carbon atom simultaneously; N14 is the integer of 0-8; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

15. the πDian Zi conjugated organic silane compound of general formula (α IV) expression:

In the formula, X ¹⁶And X ¹⁷Represent carbon atom or nitrogen-atoms independently of one another, still, X ¹⁶And X ¹⁷Can not be carbon atom simultaneously; N15 is the integer of 0-8; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

16. the πDian Zi conjugated organic silane compound of general formula (α V) expression:

In the formula, X ¹⁸And X ¹⁹Represent carbon atom, nitrogen-atoms, Sauerstoffatom or sulphur atom independently of one another, still, X ¹⁸And X ¹⁹Can not be carbon atom simultaneously; N16 and n17 are the integers that satisfies 0≤n16+n17≤7; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

17. the πDian Zi conjugated organic silane compound of general formula (α VI) expression:

In the formula, X ²⁰And X ²¹Represent carbon atom or nitrogen-atoms independently of one another, still, X ²⁰And X ²¹Can not be carbon atom simultaneously; N18 and n19 are the integers that satisfies 0≤n18+n19≤7; R ¹¹The expression divalent organic group; M is the integer of 0-10; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

18., it is characterized in that R as each described πDian Zi conjugated organic silane compound among the claim 11-17 ¹¹Be to be selected from the divalent organic group of following general formula (i) to the group of (iv) representing:

-CH ₂- (iV)

In the formula, n20 is the integer of 0-8.

19. prepare the method for πDian Zi conjugated organic silane compound, this method comprises:

Make the compound of general formula (β) expression and the compound of general formula (γ) expression carry out Grignard reaction,

Z-(R ¹¹) _m-MgX ³⁰(β)

In the formula, Z represents the unit price organic group, and this organic group is derived from the fused polycycle heterogeneous ring compound of the condensed ring of 2-10 five-ring and/or six-ring; R ¹¹The expression divalent organic group; M is the integer of 0-10; X ³⁰The expression halogen atom;

X ³¹-SiR ¹²R ¹³R ¹⁴(γ)

In the formula, X ³¹Expression hydrogen or halogen atom or the alkoxyl group of 1-4 carbon atom is arranged; R ¹²To R ¹⁴Represent halogen atom independently of one another or the alkoxyl group of 1-4 carbon atom is arranged.

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