CN1108305C - Method for preparing 1,3-dichloro-1,1,3,3-tetraphenyl disilazane - Google Patents
Method for preparing 1,3-dichloro-1,1,3,3-tetraphenyl disilazane Download PDFInfo
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- CN1108305C CN1108305C CN 99123988 CN99123988A CN1108305C CN 1108305 C CN1108305 C CN 1108305C CN 99123988 CN99123988 CN 99123988 CN 99123988 A CN99123988 A CN 99123988A CN 1108305 C CN1108305 C CN 1108305C
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- Prior art keywords
- dichloro
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- reaction
- tetraphenyldisilazane
- nmr spectrum
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- XTMUAAIZPSSJGN-UHFFFAOYSA-N [chloro-[[chloro(diphenyl)silyl]amino]-phenylsilyl]benzene Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)N[Si](Cl)(C=1C=CC=CC=1)C1=CC=CC=C1 XTMUAAIZPSSJGN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- FIADVASZMLCQIF-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octamethyl-1,3,5,7,2,4,6,8-tetrazatetrasilocane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N[Si](C)(C)N1 FIADVASZMLCQIF-UHFFFAOYSA-N 0.000 claims abstract description 6
- WGGNJZRNHUJNEM-UHFFFAOYSA-N 2,2,4,4,6,6-hexamethyl-1,3,5,2,4,6-triazatrisilinane Chemical compound C[Si]1(C)N[Si](C)(C)N[Si](C)(C)N1 WGGNJZRNHUJNEM-UHFFFAOYSA-N 0.000 claims abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000001953 recrystallisation Methods 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 description 13
- 238000000921 elemental analysis Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 3
- SHWQWXGIWFEYTA-UHFFFAOYSA-N 2,2,4,4,6,6-hexakis-phenyl-1,3,5,2,4,6-triazatrisilinane Chemical compound N1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)N[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)N[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 SHWQWXGIWFEYTA-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 101100438134 Rattus norvegicus Cabs1 gene Proteins 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- LBAQSKZHMLAFHH-UHFFFAOYSA-N ethoxyethane;hydron;chloride Chemical compound Cl.CCOCC LBAQSKZHMLAFHH-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
Abstract
本发明1，3-二氯-1，1，3，3-四苯基二硅氮烷的制备方法是将六甲基环三硅氮烷或八甲基环四硅氮烷与二苯基二氯硅烷以1∶6～1∶10的摩尔比在搅拌下进行反应，在140℃-200℃下反应共进行45-60小时，经过滤，重结晶制得。本发明提供的方法具有操作简便，产率高(78%)的优点。The preparation method of 1,3-dichloro-1,1,3,3-tetraphenyldisilazane of the present invention is to combine hexamethylcyclotrisilazane or octamethylcyclotetrasilazane with diphenyl Dichlorosilane is reacted with stirring at a molar ratio of 1:6 to 1:10, and the reaction is carried out at 140°C-200°C for 45-60 hours, filtered and recrystallized. The method provided by the invention has the advantages of simple operation and high yield (78%).
Description
The invention relates to 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane (ClPh)2Si-NH-SiPh2Cl) (I)and processes for the preparation thereof.
For the preparation of (I), the document "1.3-dihalogengdilizane (Beitrage)Zur Chemie der silicon-sticksttoff-verindungen) "(mona. chem., 1971, 102: 1806) two methods are used. One method is hexaphenylcyclotrisilazane ((Ph)2SiNH)3) Reacting with Hydrogen Chloride (HCL), but this method requires the preparation of a hydrogen chloride-ether solution of precise concentration in advance and the work-up of by-product NH4Cl is not easy to remove, so the whole operation process is complicated; process II hexaphenylcyclotrisilazane ((Ph)2SiNH)3) With diphenyldichlorosilane (Ph)2SiCl2) However, the yield of this process was low, only 21%.
The invention overcomes the defects of complex operation or low yield in the prior art, and provides a preparation method of 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane, which has simple operation and high yield (78%).
The reaction equation for preparing 1, 3-dichloro-1, 1, 3, 3-tetraphenyldisilazane according to the invention is as follows:
or
The preparation method of the invention is carried out according to the following sequence:
the hexamethylcyclotrisilazane or octamethylcyclotetrasilazane and diphenyldichlorosilane are reacted under stirring at a molar ratio of 1: 6 to 1: 10, and the reaction is carried out at 140-200 ℃ for 45-60 hours, wherein dimethyldichlorosilane (Me) generated by the reaction is continuously evaporated2SiCl2). After the reaction, the crystals were obtained by filtration. The crystals are recrystallized from organic solvents including: alkane with 6-12C atoms, aromatic hydrocarbon with 6-9C atoms and the like.
The method provided by the invention has the advantages of simple operation and high yield (78%), and the effect is shown in table 1.
Table 1: EXAMPLES 123456 yield (%) 78.077.269.969.970.473.0 melting point (. degree. C.) 117.1117.0117.0117.1117.2117.2
Example 1:
0.1mol of octamethylcyclotetrasilazane and 0.8mol of diphenyldichlorosilane were added to a three-necked flask, and reacted at 200 ℃ for 45 hours while dimethyldichlorosilane produced by the reaction was continuously distilled off. Cooling, filtering to obtain crystal, and recrystallizing with mixed solution of toluene and n-hexane (volume ratio of 1: 3) to obtain white crystal140.4g, 78.0% yield, mp 117.1 ℃. Elemental analysis: c63.70%, H4.56%, N2.91%, cl15.49% (the observed values of elemental analysis are in line with the theoretical values). Of the product29The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.75(TMS scale).1H-NMR spectrum has peaks (-C) at delta 7.2-7.66H5) And a single peak (-NH) at 2.5.
Example 2:
0.1mol of octamethylcyclotetrasilazane and 0.9mol of diphenyldichlorosilane were added to a three-necked flask, and reacted at 180 ℃ for 47 hours while dimethyldichlorosilane produced by the reaction was continuously distilled off. After cooling, the mixture was filtered to give crystals, which were recrystallized from a mixture of toluene and n-hexane (volume ratio 1: 3) to give 139.0g of white crystals, 77.2% yield and 117.0 ℃ melting point. Elemental analysis: c63.66%, H4.46%, N2.94%, Cl 15.238% (the observed values of elementalanalysis are in agreement with the theoretical values). Of the product29The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.76(TMS scale).1H-NMR spectrum has peaks (-C) at delta 7.2-7.66H5) And a single peak (-NH) at 2.5.
Example 3:
0.1mol of octamethylcyclotetrasilazane and 1.0mol of diphenyldichlorosilane were added to a three-necked flask, and reacted at 150 ℃ for 55 hours while dimethyldichlorosilane produced by the reaction was continuously distilled off. Cooling, filtering to obtain crystal, and mixing with toluene and n-hexane (1: 3 by volume)The solution was recrystallized to give 125.8g of white crystals, 69.9% yield, mp 117.0 ℃. Elemental analysis: c63.72%, H4.55%, N2.98%, Cl 15.39%, (the observed values of elemental analysis correspond to those of theory). Of the product29The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.76(TMS scale).1H-NMR spectrum has peaks (-C) at delta 7.2-7.66H5) And a single peak (-NH) at 2.5.
Example 4:
0.1mol of hexamethylcyclotrisilazane and 0.6mol of diphenyldichlorosilane are added into a three-neck flask, and the mixture reacts for 60 hours at the temperature of 140 ℃, and dimethyldichlorosilane generated by the reaction is continuously evaporated during the reaction. After cooling, the mixture was filtered to give crystals, which were recrystallized from a mixture of toluene and n-hexane (volume ratio 1: 3) to give 94.4g of white crystals, yield 69.9%, melting point 117.1 ℃. Elemental analysis: c63.81%, H4.60%, N3.01%, Cl 15.59%, (the observed values of elemental analysis correspond to theoretical values). Of the product29The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.73(TMS scale).1H-NMR spectrum has peaks (-C) at delta 7.2-7.66H5) And a single peak (-NH) at 2.5.
Example 5:
0.1mol of hexamethylcyclotrisilazane and 0.8mol of diphenyldichlorosilane are added into a three-neck flask, and the mixture reacts for 50 hours at 170 ℃, and dimethyldichlorosilane generated by the reaction is continuously evaporated during the reaction. After cooling, the mixture was filtered to give crystals, which were recrystallized from a mixture of toluene and n-hexane (volume ratio 1: 3) to give 95g of white crystals, 70.4% yield and 117.2 ℃ melting point. Elemental analysis: c63.86%, H4.57%, N3.10%, cl15.69% (the observed values of elemental analysis are in line with the theoretical values). Of the product29The Si-NMR spectrum has only a single peak,chemical shifts are at δ -7.73(TMS scale).1H-NMR spectrum has peaks (-C) at delta 7.2-7.66H5) And a single peak (-NH) at 2.5.
Example 6:
adding 0.1mol of hexamethylcyclotrisilazane and 1.0mol of diphenyldichlorosilane into a three-neck flask, reacting for 45 hours at 200 ℃, and continuously distilling off dimethyl generated by the reactionDichlorosilane. After cooling, the mixture was filtered to obtain crystals, which were recrystallized from a mixture of toluene and n-hexane (1: 3 by volume) to obtain 98.5g of white crystals, 73.0% yield and 117.2 ℃ melting point. Elemental analysis: c63.89%, H4.56%, N3.13%, Cl 15.55%, (the observed values of elemental analysis are in line with the theoretical values). Of the product29The Si-NMR spectrum has only a single peak with a chemical shift at δ -7.75(TMS scale).1H-NMR spectrum has peaks (-C) at delta 7.2-7.66H5) And a single peak (-NH) at 2.5.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123988 CN1108305C (en) | 1999-11-23 | 1999-11-23 | Method for preparing 1,3-dichloro-1,1,3,3-tetraphenyl disilazane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99123988 CN1108305C (en) | 1999-11-23 | 1999-11-23 | Method for preparing 1,3-dichloro-1,1,3,3-tetraphenyl disilazane |
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| Publication Number | Publication Date |
|---|---|
| CN1303856A CN1303856A (en) | 2001-07-18 |
| CN1108305C true CN1108305C (en) | 2003-05-14 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN 99123988 Expired - Lifetime CN1108305C (en) | 1999-11-23 | 1999-11-23 | Method for preparing 1,3-dichloro-1,1,3,3-tetraphenyl disilazane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435810B (en) * | 2013-07-15 | 2016-01-20 | 江苏大学 | A kind of preparation method of high temperature-resistanthermoplastic thermoplastic organic polysilazane |
| TWM604421U (en) | 2020-07-02 | 2020-11-21 | 宏碁股份有限公司 | Electronic device |
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1999
- 1999-11-23 CN CN 99123988 patent/CN1108305C/en not_active Expired - Lifetime
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| CN1303856A (en) | 2001-07-18 |
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Granted publication date: 20030514 |