JPS6340435B2 - - Google Patents
Info
- Publication number
- JPS6340435B2 JPS6340435B2 JP3382382A JP3382382A JPS6340435B2 JP S6340435 B2 JPS6340435 B2 JP S6340435B2 JP 3382382 A JP3382382 A JP 3382382A JP 3382382 A JP3382382 A JP 3382382A JP S6340435 B2 JPS6340435 B2 JP S6340435B2
- Authority
- JP
- Japan
- Prior art keywords
- general formula
- novel
- compound represented
- ethynylene
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 150000001875 compounds Chemical class 0.000 claims description 20
- 229920000548 poly(silane) polymer Polymers 0.000 claims description 12
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 claims 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- -1 polyethynylene Polymers 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- ANRQGKOBLBYXFM-UHFFFAOYSA-M phenylmagnesium bromide Chemical compound Br[Mg]C1=CC=CC=C1 ANRQGKOBLBYXFM-UHFFFAOYSA-M 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910008045 Si-Si Inorganic materials 0.000 description 1
- 229910006411 Si—Si Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- CJGGOMJBAIHAED-UHFFFAOYSA-N chloro-[2-[[chloro(dimethyl)silyl]-dimethylsilyl]ethynyl-dimethylsilyl]-dimethylsilane Chemical compound C[Si](C)(Cl)[Si](C)(C)C#C[Si](C)(C)[Si](C)(C)Cl CJGGOMJBAIHAED-UHFFFAOYSA-N 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- JQZUMFHYRULBEN-UHFFFAOYSA-N diethyl(methyl)silicon Chemical compound CC[Si](C)CC JQZUMFHYRULBEN-UHFFFAOYSA-N 0.000 description 1
- KPISIPFWLMPWOU-UHFFFAOYSA-N dimethylsilyl-diethyl-methylsilane Chemical compound CC[Si](C)(CC)[SiH](C)C KPISIPFWLMPWOU-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- RQJRLVCBMAKXFG-UHFFFAOYSA-N phenyl(silyl)silane Chemical class [SiH3][SiH2]C1=CC=CC=C1 RQJRLVCBMAKXFG-UHFFFAOYSA-N 0.000 description 1
- 108091008695 photoreceptors Proteins 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Description
【発明の詳細な説明】
本発明は、新規エチニレンポリシラン系化合物
およびその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel ethynylene polysilane compound and a method for producing the same.
二価の反応性中間体であるシリレンは、極めて
反応性に富むことから、高分子の架橋剤や新しい
有機合成反応への利用が期待され、広く研究され
ている。有機シリレン（：SiR2）の発生法とし
ては、各種の方法が公知であり、例えばポリシラ
ン類を光分解する方法がある。この方法は操作が
容易であることから応用範囲が広い。 Silylene, a divalent reactive intermediate, is extremely reactive and is therefore widely studied as it is expected to be used as a crosslinking agent for polymers and in new organic synthesis reactions. Various methods are known for generating organic silylene (:SiR 2 ), such as a method of photolyzing polysilanes. This method has a wide range of applications because it is easy to operate.
上記の方法の一つに鎮状フエニルジシラン類を
光分解する方法が知られているが、この方法によ
ると１，３−ケイ素転位したシラエテンを主に生
成し、有機シリレンの生成収率は低い。またその
感光波長が紫外線領域に限られる。 One of the above-mentioned methods is known to photolyze decomposed phenyldisilanes, but according to this method, 1,3-silicon rearranged silaethene is mainly produced, and the production yield of organic silylene is low. In addition, its sensitivity wavelength is limited to the ultraviolet region.
本発明の目的は、光分解で有機シリレンを高収
率で発生する新規なエチニレンポリシラン系化合
物およびその製造方法を提供するにある。 An object of the present invention is to provide a novel ethynylene polysilane compound that generates organic silylene in high yield through photolysis, and a method for producing the same.
上記目的のために各種のポリエチニレンポリシ
ラン系化合物を合成し、有機シリレンの発生収率
を調べた結果、以下に示される新規なエチニレン
ポリシラン系化合物が有用であることを見出し
た。 As a result of synthesizing various polyethynylene polysilane compounds for the above purpose and examining the yield of organic silylene, it was found that the novel ethynylene polysilane compounds shown below are useful.
本発明の新規エチニレンポリシラン系化合物
は、以下の一般式(1)で示される。 The novel ethynylene polysilane compound of the present invention is represented by the following general formula (1).
（但し、一般式(1)中のＲはアルキル基を表わす。）
本発明の新規エチニレンポリシラン系化合物と
しては、例えば、７，７，８，８，９，９−ヘキ
サメチル−７，８，９−トリシラシクロ−１，５
−ノナジインなどがあげられる。 (However, R in general formula (1) represents an alkyl group.) Examples of the novel ethynylene polysilane compounds of the present invention include 7,7,8,8,9,9-hexamethyl-7,8, 9-trisilacyclo-1,5
- Examples include nonadiine.
本発明による新規ポリエチニレンポリシラン系
化合物は、例えば次のような反応により合成でき
る。 The novel polyethylene polysilane compound according to the present invention can be synthesized, for example, by the following reaction.
３，３，４，４，７，７，８，８，11，11，
12，12−ドデカメチル−３，４，７，８，11，12
−ヘキサシラシクロドデカ−１，５，９−トリイ
ン（一般式４においてＲ＝メチル基、ｎ＝１であ
る化合物）は、エーテル溶液中３，３，４，４−
テトラメチル−３，４−ジシラ−１，５−ヘキサ
ジインとフエニルマグネシウムブロマイドから導
びかれるジグリニヤール試薬を１，６−ジクロロ
−１，１，２，２，５，５，６，６−オクタメチ
ル−１，２，５，６−テトラシラヘキサン−３−
インを加え、室温にて反応させ、さらに還流させ
ることにより合成できる。 3, 3, 4, 4, 7, 7, 8, 8, 11, 11,
12,12-dodecamethyl-3,4,7,8,11,12
-Hexasilacyclododeca-1,5,9-triyne (a compound in which R=methyl group and n=1 in general formula 4) is 3,3,4,4-triyne in an ether solution.
The digrinard reagent derived from tetramethyl-3,4-disilyl-1,5-hexadiyne and phenylmagnesium bromide was converted into 1,6-dichloro-1,1,2,2,5,5,6,6-octamethyl. -1,2,5,6-tetrasilahexane-3-
It can be synthesized by adding yne, reacting at room temperature, and further refluxing.
実施例 １
200ml３つ口フラスコを窒素置換した後、その
中に３，３，４，４−テトラメチル−３，４−ジ
シラ−１，５−ヘキサジイン2g（0.012モル）を入
れ、40mlのジエチルエーテルを加え、フラスコを
氷冷した。次にこの溶液を撹拌しながら、フエニ
ルマグネシウムブロマイドの２規定THF溶液12
ml（フエニルマグネシウムブロマイドとして
0.024モル）を約10分間で滴下し、さらに室温で
20分間撹拌した。これに１，６−ジクロロ−１，
１，２，２，５，５，６，６−オクタメチル−
１，２，５，６−テトラシラヘキサン−３−イン
3.93（0.012モル）とジエチルエーテル20mlの混合
溶液を一度に添加し、室温にて１時間撹拌した
後、１時間還流させた。反応混合物を常法により
処理した後、粗生成物を再結晶により精製し、白
色固体を得た。この固体が本発明の３，３，４，
４，７，７，８，８，11，11，12，12−ドデカメ
チル−３，４，７，８，11，12−ヘキサシラシク
ロドデカ−１，５，９−トリインであることは核
磁気共鳴スペクトル（1H−NMR）および高分解
能マススペクトルにおける以下の結果から確認さ
れた。収率55％mp.145〜147℃
(1) 1H−NMR（δppm／CDCl3）
0.25（36H、シングレツト、メチル基）
(2) 高分解能マススペクトル
C18H36Si6の計算値＝421.002
実測値＝421.001
実施例 ２
実施例１の方法により合成した３，３，４，
４，７，７，８，８，11，11，12，12−ドデカメ
チル−３，４，７，８，11，12−ヘキサシラシク
ロドデカ−１，５，９−トリイン2gをベンゼン
50mlに溶かし、さらにシリレン捕捉剤としてジエ
チルメチルシラン2.9gを加え、300W低圧水銀燈
で10分間光照射した。反応混合物をガスクロマト
グラフイーで分離し、標準試料との比較ならびに
マススペクトルによつて分析した。その結果、シ
リレンの捕捉によつて生じた１，１−ジエチル−
１，２，２−トリメチルジシラン（シリレン捕捉
剤に対して、収率85％）を得た。Example 1 After purging a 200 ml three-necked flask with nitrogen, 2 g (0.012 mol) of 3,3,4,4-tetramethyl-3,4-disilyl-1,5-hexadiyne was added thereto, and 40 ml of diethyl ether was added. was added and the flask was cooled on ice. Next, while stirring this solution, a 2N THF solution of phenylmagnesium bromide 12
ml (as phenylmagnesium bromide)
0.024 mol) was added dropwise over about 10 minutes, and then further heated at room temperature.
Stir for 20 minutes. To this, 1,6-dichloro-1,
1,2,2,5,5,6,6-octamethyl-
1,2,5,6-tetrasilahexane-3-yne
A mixed solution of 3.93 (0.012 mol) and 20 ml of diethyl ether was added at once, stirred at room temperature for 1 hour, and then refluxed for 1 hour. After the reaction mixture was treated in a conventional manner, the crude product was purified by recrystallization to obtain a white solid. This solid is the 3, 3, 4,
4,7,7,8,8,11,11,12,12-dodecamethyl-3,4,7,8,11,12-hexasilacyclododeca-1,5,9-triyne is nuclear magnetic. This was confirmed from the following results in resonance spectra ( 1H -NMR) and high-resolution mass spectra. Yield 55%mp.145-147℃ (1) 1 H-NMR (δppm/CDCl 3 ) 0.25 (36H, singlet, methyl group) (2) High-resolution mass spectrum Calculated value of C 18 H 36 Si 6 = 421.002 Actual value = 421.001 Example 2 3, 3, 4, synthesized by the method of Example 1
2 g of 4,7,7,8,8,11,11,12,12-dodecamethyl-3,4,7,8,11,12-hexasilacyclododeca-1,5,9-triyne in benzene
The mixture was dissolved in 50 ml, 2.9 g of diethylmethylsilane was added as a silylene scavenger, and the mixture was irradiated with a 300 W low-pressure mercury lamp for 10 minutes. The reaction mixture was separated by gas chromatography and analyzed by comparison with standard samples and mass spectroscopy. As a result, the 1,1-diethyl-
1,2,2-trimethyldisilane (85% yield based on silylene scavenger) was obtained.
以上述べたように、本発明の新規エチニレンポ
リシラン系化合物は、σ（Si−Si）−π共役に基づ
く強い吸収を紫外線領域に有するため光分解によ
る有機シリレンの発生効率が高く、新しいシリレ
ン発生剤として有用である。 As described above, the novel ethynylene polysilane compound of the present invention has strong absorption in the ultraviolet region based on σ(Si-Si)-π conjugation, so it has a high efficiency in generating organic silylene through photolysis, and generates new silylene. It is useful as a drug.
また、次のように光電変換膜の形成に使用でき
る。例えば、３，３，４，４，７，７，８，８，
11，11，12，12−ドデカメチル−３，４，７，
８，11，12−ヘキサシラシクロドデカ−１，５，
９−トリインのトルエン溶液（５〜10重量％）を
導電性基板上に塗布し、乾燥成膜の後、全面を低
圧水銀燈で照射すれば不溶性の光電変換薄膜を形
成できる。 Moreover, it can be used to form a photoelectric conversion film as follows. For example, 3, 3, 4, 4, 7, 7, 8, 8,
11,11,12,12-dodecamethyl-3,4,7,
8,11,12-hexasilacyclododeca-1,5,
An insoluble photoelectric conversion thin film can be formed by applying a toluene solution (5 to 10% by weight) of 9-triine on a conductive substrate, drying it, and then irradiating the entire surface with a low-pressure mercury lamp.
さらに、同様の方法により、レーザービームパ
ターニングシステムにおける感光体として用いう
る。即ち上記と同様の方法により作製した本新規
物質薄膜に対して、レーザービーム照射により光
電導性の不溶性薄膜パターンを形成できる。 Furthermore, it can be used as a photoreceptor in a laser beam patterning system in a similar manner. That is, a photoconductive insoluble thin film pattern can be formed by laser beam irradiation on a thin film of the novel substance produced by the same method as above.
Claims (1)
で表される化合物よりなることを特徴とする新規
エチニレンポリシラン系化合物。 ２ ３，３，４，４，７，７，８，８，11，11，
12，12−ドデカメチル−３，４，７，８，11，12
−ヘキサシラシクロドデカ−１，５，９−トリイ
ンであることを特徴とする特許請求の範囲第１項
記載の新規エチニレンポリシラン系化合物。 ３ 一般式(2)で表される化合物と、一般式(3)で表
される化合物とを反応させて、一般式(1)で示され
る化合物を得ることを特徴とする新規エチニレン
ポリシラン系化合物の製造方法。 但し、一般式(1)〜(3)中のＲはアルキル基であ
り、一般式(2)〜(4)中のＸはClもしくはBrである。 ４ 一般式(2)で示される化合物が 【式】もしくは 【式】であり、一般式(3)で表 される化合物が ClSi（CH3）2Si（CH3）2−Ｃ≡Ｃ−Si（CH3）2Si
（CH3）2Cl もしくは BrSi（CH3）2Si（CH3）2−Ｃ≡Ｃ−Si（CH3）2Si
（CH3）2Br であり、一般式(1)で表される化合物が、 であることを特徴とする特許請求の範囲第３項記
載の新規エチニレンポリシラン系化合物の製造方
法。[Claims] 1 General formula (1) (However, R in general formula (1) represents an alkyl group.)
A novel ethynylene polysilane compound characterized by comprising a compound represented by: 2 3, 3, 4, 4, 7, 7, 8, 8, 11, 11,
12,12-dodecamethyl-3,4,7,8,11,12
The novel ethynylene polysilane compound according to claim 1, which is -hexasilacyclododeca-1,5,9-triyne. 3. A novel ethynylene polysilane system characterized by reacting a compound represented by general formula (2) with a compound represented by general formula (3) to obtain a compound represented by general formula (1). Method of manufacturing the compound. However, R in general formulas (1) to (3) is an alkyl group, and X in general formulas (2) to (4) is Cl or Br. 4 The compound represented by general formula (2) is [formula] or [formula], and the compound represented by general formula (3) is ClSi(CH 3 ) 2 Si(CH 3 ) 2 -C≡C-Si ( CH3 ) 2Si
( CH3 ) 2Cl or BrSi( CH3 ) 2Si ( CH3 ) 2 -C≡C-Si( CH3 ) 2Si
(CH 3 ) 2 Br and the compound represented by general formula (1) is A method for producing a novel ethynylenepolysilane compound according to claim 3, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382382A JPS58152892A (en) | 1982-03-05 | 1982-03-05 | Novel ethynylenepolysilane compound and its preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3382382A JPS58152892A (en) | 1982-03-05 | 1982-03-05 | Novel ethynylenepolysilane compound and its preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58152892A JPS58152892A (en) | 1983-09-10 |
| JPS6340435B2 true JPS6340435B2 (en) | 1988-08-11 |
Family
ID=12397202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3382382A Granted JPS58152892A (en) | 1982-03-05 | 1982-03-05 | Novel ethynylenepolysilane compound and its preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58152892A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0227462U (en) * | 1988-08-10 | 1990-02-22 | ||
| JPH0268961U (en) * | 1988-11-14 | 1990-05-24 |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03503155A (en) * | 1988-10-28 | 1991-07-18 | ヒユーズ・エアクラフト・カンパニー | High-density filament winding and improved cross-section and internal payout formation methods |
| US4996341A (en) * | 1990-07-05 | 1991-02-26 | Kanegafuchi Chemical Industry Co., Ltd. | Condensed bicyclic disilanylene-acetylene compound and method for preparing the same |
-
1982
- 1982-03-05 JP JP3382382A patent/JPS58152892A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0227462U (en) * | 1988-08-10 | 1990-02-22 | ||
| JPH0268961U (en) * | 1988-11-14 | 1990-05-24 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58152892A (en) | 1983-09-10 |
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