CN1250556C - Compound of diamine disilazane and preparation method - Google Patents
Compound of diamine disilazane and preparation method Download PDFInfo
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- CN1250556C CN1250556C CN 200410017175 CN200410017175A CN1250556C CN 1250556 C CN1250556 C CN 1250556C CN 200410017175 CN200410017175 CN 200410017175 CN 200410017175 A CN200410017175 A CN 200410017175A CN 1250556 C CN1250556 C CN 1250556C
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- disilane
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Abstract
The present invention discloses a compound of diamine disilanes, which has the following structure; the preparation method of the present invention is that kylhydrocarbon hydrogenous dichlorosilanes or dialkyl dichlorosilane monomers are reduced and coupled with alkali metals; then, the kylhydrocarbon hydrogenous dichlorosilanes or the dialkyl dichlorosilane monomers are directly reacted with secondary amines to decompose amines; the present invention is obtained by the steps of separating by-products, etc. The compound of diamine disilanes comprises Si-H bonds of high chemical activity, the chemical reactions, such as silicon-hydrogen addition, etc. can be further carried out, the silicon of the present invention can replace side groups to carry out functionalized modification. Thereby, the present invention can be used as disilicide alkylation reagents in synthetics chemistry materials. The present invention can be widely applied to the modern organic synthesis, the modification of chemical materials, etc.; thereby, the materials have high stability of heat resistance, optical special properties and electronics properties. The chemical structure of the compound of diamine disilanes has the following formula thatR1 and R2 represent the same ethyl or isopropyl groups; R3 and R5 are respectively H; R4 and R6 are respectively methyl groups, ethyl groups and phenyl groups.
Description
Technical field: the present invention relates to class silicoorganic compound and preparation method thereof, particularly a class and comprise disilane compound of silicon silicon key and preparation method thereof.
Background technology: prepare two amido disilane compounds method commonly used, be utilize industrial chlorosilane monomer synthetic in height boil and separate the disilane chloro monomer that obtains, and then synthetic obtaining.For example: the Padmanaban of Japan, people such as Munirathina adopt the synthetic two amido disilane compounds that obtain of this method, and carry out the condensation polymerization reaction between the various dihydric phenol, the polymkeric substance [Padmanaban, the Munirathina that contain photosensitive disilane chain link on a kind of typical main chain have been prepared; Kakimoto, Masaaki; Imai, Yoshio.J.Polym.Sci., Part A:Polym.Chem., 1990,28 (11): 2997-3005]; Or, the polymeric amide and the photosensitive material of polyimide [Padmanaban, the Munirathina that contain the disilane chain link have been prepared into to two amido disilane compounds and acid amides and the reaction of diimide group compound; Kakimoto, Masaaki; Imai, Yoshio.Polym.J., 1990,22 (7): 587-92].
In addition, two amido disilane compounds also can be by hexamethyldisilane or aminomethyl phenyl disilane, by with strong electrophilic reagent reaction, as at sulfonic acid [Kumada, M.; Yamaguchi, M.; Yamamoto, M.; Nakajima, N.; Shiina, K.J.Org.Chem., 1956,21:1264; Kumada, M.; Ishikawa, M.J.Organomet.Chem., 1963,1:153], trifluoromethane sulfonic acid [Uhlig, W.; Tzschach, A.J.Organomet.Chem., 1989,378:C1; Uhlig, W.J.Organomet.Chem., 1991,421:189], HCl/AlCl
3And MeCOCl/AlCl
3[Kumada, M.; Ishikawa, M.; Maeda, S.J.Organomet.Chem., 1964,2:478; Sakurai, H.; Tominaga, K.; Watanabe, T.; Kumada, M.Tetrahedron Lett., 1966:5493; Kumada, M.; Watanabe, T.; Sakurai, H.J.Organomet.Chem., 1967,7:15; Tamao, K.; Kumada, M.J.Organomet.Chem.1971,30:329and339] etc. exist down, carry out demethylation or go the phenylating prepared in reaction to obtain.
Yet, above in the described existing research work, except that report utilize industrial chlorosilane monomer synthetic in high boiling material separate the disilane chloro monomer that obtains as the synthesis material, second method is that employed alkyl replaces the disilane monomer in the dealkylation glycosylation reaction, the same height that be unable to do without trace in chlorosilane monomer suitability for industrialized production in its source by product that boils.As everyone knows, in chlorosilane monomer suitability for industrialized production, the height by product complicated component that boils of trace, the content of disilane monomeric products is extremely low, the monomeric source of disilane deficiency.Because two amido disilane compounds process for production thereof of the present invention are not subject to the disilane raw material monomer, the preparation method is simple, and synthesis technique is easy to control, thereby has well solved the synthetic difficulty of two amido disilane compounds; On the other hand, Padmanaban, the substituting group on the Siliciumatom of these compounds of people's synthetic such as Munirathina is methyl, is difficult to further carry out reaction kinetic.
Summary of the invention: the objective of the invention is in silicoorganic compound, to introduce the higher Si-H key of chemically reactive, can further carry out chemical reactions such as silicon hydrogen addition, significant for its functionalization.Thereby no matter be for modern organic synthesis, or chemical material modification etc. all has very big meaning.
Two amido disilane compounds of the present invention have following structural formula:
R
1, R
2Be identical ethyl or sec.-propyl; R
3With R
5Be respectively H, R
4With R
6Be selected from methyl, ethyl or phenyl respectively.
Two amido disilane compounds of the present invention follow these steps to be prepared:
(1) alkali-metal dispersion: under nitrogen protection, installing agitator additional, having in the reactor of reflux condensate device, constant pressure funnel of moisture eliminator, put into 8 weight part metal K or Na and volume 8-10 thereof organic solvent doubly, be heated to 80-100 ℃ and make metal K or Na fusion, and under high-speed stirring, metal K or Na are dispersed into trickle particle in organic solvent;
(2) dichlorosilane monomer and alkali-metal reductive coupling reaction: by monomer and basic metal reaction mol ratio is 1.05: 1, stirring, backflow, nitrogen protection are down, pass through constant pressure funnel, with dichlorosilane monomer and ORGANIC SOLVENT MIXTURES, organic solvent and monomeric weight ratio are 2-4 times, are added drop-wise in 30 minutes in the system of above-mentioned scattered metal K or Na, after dropwising, insulation reaction 10-24 hour, obtain dichloro disilane intermediate;
(3) aminolysis reaction of intermediate: after above-mentioned dichlorosilane monomer and alkali-metal reductive coupling reaction finish, reaction solution is reduced to below the room temperature (＜30 ℃), afterwards under this temperature, in 40 minutes, splash into dichlorosilane monomer molar amount 2.1-2.5 amine doubly by constant pressure funnel, stirring reaction, the hydrogen chloride gas that the monomer aminolysis reaction is emitted will be absorbed by excessive diethylamine, and under 60-100 ℃, nitrogen protection, continued stirring reaction 2-6 hour;
(4) separation of product: with above-mentioned reaction solution decompress filter, removal byproduct of reaction alkali metal chloride salt, diethylamine hydrochloride obtain containing the filtrate of product, obtain two amido disilane by underpressure distillation removal organic solvent and by product afterwards.
The monomeric structural formula of chlorosilane used in the present invention is shown below:
R
1SiR
2Cl
2
R wherein
1Be H, R
2Be selected from methyl, ethyl or phenyl.
Organic solvent used in the present invention is the aromatic hydrocarbon of the alkane of 1-8 carbon atom and derivative thereof, a 6-8 carbon atom and derivative thereof etc., that more commonly used is methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, N, dinethylformamide, benzene, monochloro-benzene, toluene, dimethylbenzene equal solvent.
In the above-mentioned preparation two amido disilane processes, the usage quantity of described organic solvent is generally 1-20 times of reactant cumulative volume, and optimum amount is 8-12 times.Wherein major part is scattered in wherein basic metal, to form basic metal fine particles (basic metal sand); The organic solvent that 1-4 doubly measures mixes with the dichlorosilane monomer, to reduce the monomeric volatility of dichlorosilane; Being more preferably 2-4 amount doubly mixes with the dichlorosilane monomer.
In the above-mentioned preparation two amido disilane processes, the amine that described aminolysis reaction uses is selected from diethylamine or diisopropylamine, and during aminolysis reaction, if when the consumption of amine is lower than 1.1 times of dichlorosilane monomer molar amount, aminolysis reaction is incomplete, and product yield is low; And when the consumption of amine is higher than 1.5 times of dichlorosilane monomer molar amount, reclaim difficulty, cause waste.
The compounds of this invention synthetic overcome disilane compound source to the boil dependence of by product of the height of trace in the chlorosilane monomer suitability for industrialized production, provide a kind of synthesis technique comparatively simple, have the synthetic method of two amido disilane compounds of good controllable operation, product yield is higher.
Two amido disilane compounds of the present invention's preparation, show after deliberation, this compounds has the intensive uv-absorbing, unique photoluminescence performance, good chemical reactivity and stable preferably, can further react, or carry out chemical reaction with materials such as reactive polysiloxane with other materials that contain reactive hydrogen.
Owing to introduced the higher Si-H key of chemically reactive in the two amido disilane compounds, can further carry out chemical reactions such as silicon hydrogen addition, the functional modification that replaces side group for its silicon provides feasibility; Thereby can be used as disilane base reagent in the synthetic chemistry material, be widely used in modern organic synthesis, chemical material modification etc., thereby further give heat-resistant stability, the optics of material, the property of electronics aspect.In addition, the unique texture of two amido disilane compounds of the present invention, the response capacity of having given this compounds can further be improved the chemical adhesion to base material, inorganic substrate such as glass, metal, metal oxide and with binding property of his base material etc., can be used as the coupling agent that contains the disilane base.
Description of drawings: Fig. 1. be embodiment 1 target product 1, two (diethylin)-1 of 2-, 2-dimethyl disilane
Infrared spectra;
Fig. 2. be embodiment 2 target products 1, two (diethylin)-1 of 2-, 2-dimethyl disilane
Proton nmr spectra.
Specific implementation method: the following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
(1) will 3.20 gram (0.139mol) sodium Metal 99.5s put into fill the 100mL solvent toluene, sealed stirrer, thermometer, nitrogen protection be housed, install the reactor of the reflux condensing tube of drying tube additional; under 100 ℃, nitrogen protection, high-speed stirring, sodium Metal 99.5 is separated into fine particle.
(2) with the mixture of 16.78 gram (0.146mol) methyl hydrogen dichlorosilane and 40mL toluene, under quick agitation condition, be added drop-wise in 30 minutes in the above-mentioned toluene solvant that disperses sodium Metal 99.5 by constant pressure funnel, temperature control continues reaction 18 hours for 100 ℃ afterwards.
(3) treat that monomer and sodium Metal 99.5 react completely after; reaction solution is cooled to room temperature (below 30 ℃); and control reaction temperature is below 30 ℃; stir the diethylamine that in 40 minutes, drips 26.28 grams (0.365mol) down; the hydrogen chloride gas that the monomer aminolysis reaction is emitted; to be absorbed by excessive diethylamine, under 100 ℃, nitrogen protection, continue stirring reaction 6 hours afterwards.
(4) with after the salt settling that generates in linked reaction, the aminolysis reaction process, carry out decompress filter, removal byproduct of reaction alkali metal chloride salt, diethylamine hydrochloride obtain containing the filtrate of product, afterwards by underpressure distillation (0.105MPa * 60 ℃), remove solvent toluene and by product, obtain slightly light yellow transparent liquid product 1, two (diethylin)-1 of 2-, 2-dimethyl disilane 13.10 grams, productive rate is 81%.IR (film, cm by the KBr wafer
-1): Si-Si stretching vibration 370cm
-1, Si-N vibration 1024,929cm
-1, Si-H stretching vibration (splitting branch) 2141,2097.3cm
-1, Si-CH
3Formation vibration 690,862.5,1253,1466cm
-1,-CH
3Stretching vibration 2862.5,2929.4,2963cm
-1,-CH
3Vibration such as bending 739.8,790, C-N vibration 1208.5,1410cm
-1 1HNMR (C
6D
6, δ, ppm): 2.779-2.854 (CH
3), 0.929-0.971 (CH
2), 0.190-0.210 (Si-H), 0.09-0.146 (Si-CH
3).
(1) 3.18 gram (0.082mol) potassium metals are put into fill the 80mL solvent toluene, sealed stirrer, thermometer, nitrogen protection be housed, install the reactor of the reflux condensing tube of drying tube additional; under 60 ℃, nitrogen protection, high-speed stirring, potassium metal is separated into fine particle.
(2) with the mixture of 9.90 gram (0.861mol) methyl hydrogen dichlorosilane and 30mL toluene, under quick agitation condition, be added drop-wise in 30 minutes in the above-mentioned toluene solvant that disperses potassium metal by constant pressure funnel, temperature control continues reaction 14 hours for 60 ℃ afterwards.
(3) treat that monomer and potassium metal react completely after; reaction solution is cooled to room temperature (below 30 ℃); and control reaction temperature is below 30 ℃; stir the diethylamine that in 40 minutes, drips 15.5 grams (0.215mol) down; the hydrogen chloride gas that the monomer aminolysis reaction is emitted; to be absorbed by excessive diethylamine, under 60 ℃, nitrogen protection, continue stirring reaction 6 hours afterwards.
(4) with after the salt settling that generates in linked reaction, the aminolysis reaction process, carry out decompress filter, remove byproduct of reaction alkali metal chloride salt, diethylamine hydrochloride and obtain containing the filtrate of product, afterwards by underpressure distillation (0.105MPa * 60 ℃), removal solvent toluene and by product, obtain light yellow transparent liquid product 1, two (diethylin)-1,1 of 2-, 2,2-tetramethyl-disilane 5.71 grams, productive rate is 79%.IR (film, cm by the KBr wafer
-1): Si-Si stretching vibration 370cm
-1, Si-N vibration 1024,929cm
-1, Si-CH
3Formation vibration 689.6,879,1253,1466cm
-1,-CH
3Stretching vibration 2862.5,2929.4,2963cm
-1,-CH
3Vibration such as bending 773,812, C-N vibration 1208,1410.1cm
-1 1HNMR (C
6D
6, δ, ppm): 2.754-2.807 (CH
3), 0.931-0.967 (CH
2), 0.08-0.142 (Si (CH
3) 2).
Claims (4)
1. two amido disilane compounds is characterized in that its chemical structural formula is shown below:
R
1, R
2Be identical ethyl or sec.-propyl; R
3With R
5Be respectively H, R
4With R
6Be selected from methyl, ethyl or phenyl respectively.
2. the preparation method of two amido disilane compounds as claimed in claim 1 is characterized in that the preparation method is as follows:
(1) alkali-metal dispersion: under nitrogen protection, installing agitator additional, having in the reactor of reflux condensate device, constant pressure funnel of moisture eliminator, put into metal K or the Na and the volume 8-10 organic solvent doubly thereof of 8 weight parts, be heated to 80-100 ℃ and make metal K or Na fusion, and under high-speed stirring, metal K or Na are dispersed into trickle particle in organic solvent;
(2) dichlorosilane monomer and alkali-metal reductive coupling reaction: by dichlorosilane monomer and basic metal reaction mol ratio is 1.05: 1, stirring, backflow, nitrogen protection are down, pass through constant pressure funnel, with dichlorosilane monomer and ORGANIC SOLVENT MIXTURES, the monomeric volume ratio of organic solvent and dichlorosilane is 2-4 times, is added drop-wise in 30 minutes in the system of above-mentioned scattered metal K or Na, after dropwising, insulation reaction 10-24 hour, obtain dichloro disilane intermediate; Wherein the monomeric structural formula of dichlorosilane is shown below:
R
1SiR
2Cl
2
R wherein
1Be H, R
2Be selected from methyl, ethyl or phenyl;
(3) aminolysis reaction of dichloro disilane intermediate: above-mentioned reaction soln is reduced to room temperature below 30 ℃, afterwards under this temperature, in 40 minutes, splash into dichlorosilane monomer molar amount 2.1-2.5 amine doubly by constant pressure funnel, stirring reaction, the hydrogen chloride gas that the reaction of intermediate aminolysis is emitted, to be absorbed by excessive diethylamine, and under 60 ℃, nitrogen protection, continue stirring reaction 4-6 hour; Wherein amine is selected from diethylamine or diisopropylamine;
(4) separation of product: with the reaction solution decompress filter, removal byproduct of reaction alkali metal chloride salt, secondary amine hydrochloride obtain containing the filtrate of product, obtain two amido disilane compounds by underpressure distillation removal organic solvent and by product again.
3. the preparation method of two amido disilane compounds according to claim 2, the usage quantity that it is characterized in that described organic solvent are 1-20 times of reactant cumulative volume.
4. the preparation method of two amido disilane compounds according to claim 2, it is characterized in that described organic solvent is selected from methylene dichloride, trichloromethane, tetrahydrofuran (THF), dioxane, N, dinethylformamide, benzene, monochloro-benzene, toluene or dimethylbenzene.
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