JPH05501884A - Organosilicon compounds, electro-optical materials and devices containing them - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Organosilicon compounds, electro-optical materials and devices containing them The present invention relates to a novel organosilicon compound, its preparation method, and its use in nonlinear optics. In particular, the organic Targets lower homologs of ion compounds.

This main patent application is directed to homologs of organosilicon compounds of the following general formula: do: (In the formula, n is an integer from 1 to 20, R1 represents an electron donating group, R2 represents an electron-withdrawing group, R1 is an alkyl group having 1 to 8 carbon atoms, hydrogen, an aryl group, a group R1 or represents R2, R4 is an alkyl group having 1 to 8 carbon atoms, hydrogen, an aryl group, or R1 the group R+ if does not represent the group R2, or the group R2 if R1 does not represent the group R8 The research leading up to this French patent application has focused on the best electron-donating groups, i.e. It has been clarified that the group defined by R4 is advantageously a group represented by the following general formula. Ta.

-R, -D.

(In the formula, R3 represents an arylene group, and D is the same or different, hydrogen, or is an amino group, alkylamino group, dialkylamino group, arylamino group, hydrogen Roxy group, thiolo group, alkylthio group, alkoxy group, aryloxy group, halo represents an electron donating group selected from a genoalkyl group and an oxy group, m is an integer from 1 to 3, D is aryl in which the group R4 is not substituted by one or more electron-withdrawing groups (If it is a group, it does not represent hydrogen) As an electron donating group, J, March 8d vanced Organic Chemi-stry (John Wiley and 5on), 3rd edition, P, 242-244. is negative, preferably more negative than -0,20, or at least to be understood as all aromatic groups substituted by one of these electron-donating groups is convenient.

The electron-withdrawing group is characterized in that the Hammett constant δ is positive, preferably greater than 0.40. characteristic group, or directly or indirectly by the bias of at least a double bond. in all aromatic groups substituted by at least one of these electron-withdrawing groups It is considered that there is. Unexpectedly, the invention of the previous major patent application We have found that lower homologs of compounds are particularly promising.

Here, the electron donating group is derived from an alkane or silane. re de Chin+ie Alcoyl group, aryl according to Duval definition and, when n=1, a silyl group.

The aryl group is advantageously a heterocycle, preferably a 5-membered ring.

Preferred heterocycles according to the invention are, for example, bi- and monovirol, thiophene , is a franc. It is advantageous for the point of bonding to silicon to be adjacent to a different atom. Also different species When the atom is trivalent, the bonding point can be a different atom. Without departing from this, heterocycles with two heteroatoms can be used. different As seed atoms, chalcogen is preferably the main oxygen and sulfur, as well as Compounds of group 5 that produce pnature, preferably the predominant nitrogen It is convenient to understand that. In general, the aryl group of the electron donating group has the Hammett constant is measured as a negative value, or contains a group of negative values. Of course preferred The radicals contain at the same time an aryl group and a silyl group as defined above.

The group R, is an alkyl group of 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or a carbon a silyl group having 3 to 20 elementary atoms, preferably 5 to 9 atoms and 1 silicon atom; It is advantageous to have.

In particular, one silicon atom surrounded by three, preferably identical, alkyl groups Conveniently, silyl groups consisting of trimethylsilyl or triethylsilyl A lyle group is preferred.

β is the limit value of hyperpolarizability when the frequency of the electromagnetic field is extrapolated to zero. compare the values of In particular, as shown in the following table, PDMA is a paradimethylaniline group. and R1 represents the following formula.

Experiments 6 and 7 are described in detail in the previous major patent application publication 2630442. This study was carried out on the compound obtained by the previous synthesis.

pDMA-p dimethylalinine group, i.e. p dimethylami7M P-p meth xyphenylene group The following example illustrates the invention.

[1-(Experiment 5) Synthesis: Cll3 CH3 ■) Reaction: ■) Experimental method 1) Synthesis of 1.1: 24.3 g (1 mol) of Mg was added to a 3-hole flask in a nitrogen atmosphere and dried. 250 ml of ether were introduced. Reflux and introduce one iodine crystal, 189 g (1 mol) was gradually introduced into the solution and refluxed for 16 hours.

In a second IE three-loaf flask, add 600 g of Mg5SizCI□ in a nitrogen atmosphere and dry 250 ml of dry ether were introduced. Maintaining the temperature at approximately 10°C, the initial solution The mixture was poured slowly and allowed to react overnight at ambient temperature.

It was filtered under a nitrogen atmosphere, the solvent was evaporated and distilled in vacuo. 127.3g of colorless liquid Recovered. Boiling point = 132-133°C/1mm11g, by spectral analysis The structure of the product (1,1) was determined.

2) Synthesis of 1.2: 1! 300 ml of dry ether in a nitrogen atmosphere and 12. 15 g (0.5 mol) was introduced, and 119 g (0.5 mol) was gradually added. It was introduced in various After refluxing for 30 minutes, 127 g of compound (1) was introduced and the mixture was heated for 18 hours. It refluxed.

Water was added, extracted with ether, dried over MgS04, and filtered. Evaporate the solvent 204 g of viscous oil was recovered. Elution with silica column using hexane as eluent 127 g of compound (2) was recovered with a yield of 66%.

The structure of (1,2) was determined by spectral analysis.

3) Synthesis of 1.3 In a nitrogen atmosphere, add 250% tetrahydrofuran (THF) to a 1j2 three-ring flask. ml, 1 grain of iodine, and 0-order introducing Mg 8.74 g (0.33 mol) 126 g of compound (2) was introduced into the solution, refluxed to start the reaction, refluxed overnight, and then refluxed again. After returning to ambient temperature and adding 200 ml of ether, 73 g of DMF (lI Ilol) was gradually introduced into the reaction for 16 hours at 0 ambient temperature, water 500+++1 was added and extracted with ether. Dry with MgS Oa, filter, and evaporate the solvent. did. 104.1 g of oil was recovered and diluted with ethyl acetate/hexane 1:1 (V/ V) Yellow oil (1,3)84 in a chromatographic column using the mixture as eluent ．． 1 g was collected.

4) Synthesis of 1.4 In a 500 ml flask, add 12 g of yellow oil (1,3) 1 methanol under nitrogen atmosphere. 2.25 g of 28g5NCCHZ CN and 2 drops of piperidine were introduced. surroundings The reaction was allowed to take place at temperature for 1 hour. A yellow precipitate formed, which was filtered and washed with methanol. .

8 g of this solid was recrystallized from 95% ethanol to recover 6.7 g of a yellow solid.

As a result of spectral analysis, the structure of the product (1,4) was determined.

Melting point: 280°C 1 (Imperial Mad Lord) Synthesis: Bis(4-bromophenyl)-quaromethylsilane (2,1) ether 100 Add one iodine crystal to 24 liquids containing 24.3 g (1 mol) of mfl and Mg. , 1,4-dibromo in 400 ml of a 1:1 (V/V) mixture of ether/THF. 236 g (1 mol) of Hensen's solution was gradually introduced over 40 minutes.

The temperature was maintained at approximately 35°C during the introduction. The mixture was refluxed for 2 hours and methyltrichloro 77 g (0.51 mol) of silane was gradually added over 50 minutes. During addition, warm The temperature was maintained at 0-5°C to allow a good reaction. The mixture was heated to reflux for 16 hours.

After filtration, the solvent was removed to obtain a crude product, which was distilled under reduced pressure. get yellow oil (76g).

Boiling point: 195”C10,25alnHg, this product can be used without further purification. (Purity: 94% CC).

Yield: 18.4%.

Mass spectrum (CI) m/e 3BB (M+) FT IR (KBr) 1560 -1490cm-' (aryl), 1250cm-' (v 5iCHz ).

Bis(4-bromophenyl)-4-dimethylaminophenyl-methylsilane (2 ,2) One iodine crystal was added to a suspension of Mg 6.1 g (0.25 mol) in THF. In addition, 50 g of 4-bromodimethylaniline (0,25 a+ol) solution was added gradually over 30 minutes.

The mixture was heated at reflux for 6 hours and then the 94% pure compound (2, 1) A solution of 97.6 g (0.25 mol) was gradually added over 30 minutes. Guidance The temperature was maintained at approximately 40°C during the incubation. The mixture was refluxed for 16 hours. Stir the solvent; Ether 200. ml was added. After filtration, pour the organic layer into 60IIll of water to dissolve the solution. Reposition the agent and transfer the residue to ether/hexafluoride using a column packed with silica gel. Chromatography was performed with a 1:1 (V/V) mixture of 1:1 (V/V), and a yellow oil (2, 2) 90g was obtained.

Yield near 6%.

This product was used without further purification.

Mass spectrum (CI) m/e 473 (M+) FT IR (KBr) 286 0cm-' Cp N (CHs)z)' HRMN (CDCh), 0.72 (s, 5iCH3, 38).

2.93 (S, N ((CH3)!+6H).

Bis(4-formylphenyl)-4-dimethylaminophenyl-methylsilane ( 2,3) Iodine was added to a suspension of 9.72 g (0.4 mol) of Mg in 50 μl of THF. Add 1 crystal to 90 g of compound (2,2) in 200 ml of THF (0,19 mol) solution was gradually added over 30 minutes. Mixture at 15-20°C for 16 hours Heated under reflux, then added to 30 g (0.4 mol) of dimethylformamide. . The mixture was stirred at ambient temperature for 3 hours.

After hydrolysis, the organic layer was separated and the aqueous layer was extracted three times with ether. Complete organic layer A portion was collected and concentrated. With a 1/1 to O/1 (V/V) mixture of hexane/ether Silica gel chromatography was performed to obtain 22.6 g of a yellow oil. This product is It was used without further purification.

Yield: 31.8%.

Mass spectrum (CI) m/e 373 (M+) FT IR (KBr) 1 700cm-' (ν CHO)' HRMN (CDC13), 0.90 (S , 5iCH3,3H).

2.93 (S, N (CH3) 2.68).

7.79-7.62 (AA' BB', C6H, CHo, 8H).

7.28-6.68 (AA' BB', C, HlN (CH3), 4H) .

9.98 (s, CIo, 2H).

Bis(4-(2,2-dicyanoethynyl)phenyl-4-dimethylaminopheny) 10 g of compound (2,3) in 50 ml of methanol (2,4) (27 msmol) solution, add 3.6 g of malonodinitrile (54o++no 1) and 5 drops of piperidine were added. This mixture was stirred at ambient temperature for 16 hours.

The solvent was removed in vacuo and 20 ml of ether were added. The crude product is cyclohexane chromatography using silica gel with an 80/20 (V/V) mixture of /ethyl acetate. (HPLC) to obtain an orange product with a yield of 75%. Ta.

Mass spectrum (CI) m/e 469 (M+) FT IR (KBr) 2 230cm-' (νCN)'HRMN (CDC1i) 0.81 (s, 5iCHffI3H) 12.94 (s, N(CHi)z, 6H).

7.28 6.69 (AA' BB', CJ4N(CHs)z), 4H ).

7.80-7.61 (AA' BB', C, H4-HC=C(CN)2. 8)1).

7.72 (s, CH=C(CN)z, 2)1).

"Si RMN (CDCb): -10.94 ppm.

UV: CHCl3: 317 nm (ε: 55200) Cll1OII : 310nm (t: 55200) 5↓ limit 4-Bromophenyl-dichloromethylsilane (3,1) in 100 ml of ether Add one iodine crystal to Mg 12.15g (0.5no!) Q suspension, 118 g (0.5 no!) of 1,4-dibromobenzene dissolved in 200 ml of The liquid was added gradually. The temperature was kept at approximately 35°C. After the addition, the mixture was refluxed for 3 hours. , poured one drop at a time into 224.2 g (1,5n+ol) of methyltrichlorosilane. I entered. During the introduction, the temperature was kept at 0-5°C.

The reaction mixture was refluxed for 16 hours, then cooled, filtered and finally hydrolyzed with 100 ml of water. I understand. The organic phase was dried over MgS04 and the solvent was driven off. 91g colorless oil I got it. This product was used without further purification (90% purity).

Yield: 61%.

Mass spectrum (CI) m/e 268 (M+) peak m/e 253 (M- CH3)+bis(4-dimethylaminophenyl)-4-bromophenyl-methyl Silane (3,2) A suspension of Mg 18 g (0.74 no!) in THF 80+al is Add 1 grain of elementary crystal, 140 4-bromodimethylaniline in 200 ml of THF 　g　(0.7no!) solution was added gradually.

The mixture was refluxed for 4 hours and cooled to ambient temperature. This Grignard reagent was added to THF 88 g of compound (3,1) with a purity of 90% in 50 ml (0.3 no!) Add slowly to the solution and reflux for 16 hours.

After cooling, the solvent was exposed to light for 30 minutes at 70°C. Add ether and filter the mixture , the solvent was expelled. After adding 200ml of hexane, crystallize at 5°C for 2 days. 66 g (50%) of an orange-yellow solid was obtained. FP19~100°C mass Spectrum (CI) m/e 438 (M+).

FT IR (Kbr) 2800cm-' (N(CH3)Z).

'HRMN (CDC13) 0.67 (S, 5iCH3, 3H).

2.91 (s, N(C)Ii)z, 12H).

Bis(4-dimethylaminophenyl)-4-formylphenyl-methylsilane ( 3,3) A suspension of 4.4 g (0.18 no!) of Mg in 50 ml of THF is One elementary crystal and 66 g of compound (3,2) in 200 ml of THF (0,15 No! ) The solution was added gradually over 1 hour.

The mixture was heated under reflux for 1 hour and 14.6 g of dimethylformamide (0.2 no. ) added to the solution.

During the introduction, the temperature was kept at about 30 °C, and the mixture was stirred at ambient temperature for 3 hours, then poured into brine. Added 100ml. The organic phase was separated and concentrated.

Chromatography on silica gel with a 75/25 mixture of ether/hexane It was confirmed that 158 g of yellow oil (yield 26.5%) was obtained.

Mass spectrum (CI) m/e 39 B (M+).

FT IR2800co+-' (νN(CH3)z)11700c+i-' (νCHO).

'HRMN (CDC13) 0.70 (S, 5iCHs, 3H).

2.91 (s, N(CHz)z, 12)1).

6.66-7.28 (AA' BB', C6H, N (CH3)!, 8H ).

7.61-7.73 (AA' BB', C,)1. CHO, 4H), 9 ．． 98 (s, CHO1).

Bis(4-dimethylaminophenyl)-4-(2,2-dicyanoethynylphenyl )-Methylsilane (3,4) Compound (3,3) in 100ml methanol 1 5.8 g (40 mmol) of malonodinitrile 2.65 g (4 (l) smol) and 4 drops of piperidine were added. The mixture was stirred at ambient temperature for 4 hours.

The solvent was stirred in vacuo and the crude product was purified with ether/hexane 1/. My husband is me Isolated as 13.95 g of a dark red solid, yield: 80%, mp: 158° C0*m spectrum (CI) m/e 436 (M+) FT IR (KBr) 2 230cm-' (νCN)'II RMN (CDC13) 0.70 (S , 5iCHx1311).

2.91 Ga, N(Clh)z, 1211).

6.65-7.28 (48' BB' + Cbll, N (Clh) z + 8 11) +7.62-7.74 (48' BB', C611 (C1l = C(Cll)z, 411).

7.68 (s, CI=C(CN)z, l1l).

“Si RMN (CDCl2): 11.87 ppm.

UV: CIICh: 319nm (ε: 33600) 112.7 Base land 4-(2,2-dicyanoethynyl)trimethylsilylbenzemethanol 50ml 6.3 g (35.3 mmol) of 4-trimethylsilylbenzenaldehyde in ) solution, add 1 drop of piperidine and 2.5 g (37.8 mmol) of malononitrile. ) was added. The mixture was stirred at ambient temperature for 4 hours. Filter to white creamy solid Collected.

It was recrystallized twice from hexane to obtain 3.1 g of a white solid in a yield of 39%. mP:93° C0 According to the 1t spectrum, molecular ion (70eV) 226m/e, peak 211 m/　e　(M　CHz　) 10 was given.

'HRMN (CDC1z): 0.25 (s, 5iC1h, 9H).

7.79-7.62 (48' 111B', CbH-, 411).

7.70 (s, CH=C (CNh, III) 2qSi RMN (CDC 1z): +2.60ppm.

150.3 131.0 160. O UV: ClICl3: 320 nm (t’: 27950).

CH: +OH: 316 nm (ε: 2 (i760).

±dan 1 Kawado: Synthesis: C.N. ■) Reaction: 5.1 5.2 5.3 ■) Experimental method 1) Synthesis of 5.2 In a nitrogen atmosphere, 3200 g of ClzSi OCH (1 mol) was introduced. Next, 100 ml of ether and 1 mol were introduced, and the temperature The mixture was kept at about 30-40°C and refluxed overnight.

Filter and evaporate the solvent. 165 g of viscous oil was recovered by vacuum distillation.

Boiling point: 147-148°C/0.8 mnMg.

2) Synthesis of 5.2 In a three-hole flask of No. 21, 150 ml of THF dried in a nitrogen atmosphere and Mg 13. 05 g (5,37・10-'mol) was introduced, and 5 ml of dry THF was added. 163 g of compound (5,1) was gradually added and the mixture was refluxed overnight.

After cooling, water If was added and extracted with ethyl acetate. M　g　S　evaporate and dry with Oa After drying, 220 g of yellow oil was recovered. Eluent hexane/ethyl acetate 90/10 Chromatography was performed on a silica column using the mixture, and 183 g of yellow oil was obtained. Recovered. Yield: 88%.

3) Synthesis of 5.3 Nitrogen atmosphere T: M g 9.6 g (0,395+* ol), 200 ml of THF, and 1 grain of iodine crystal were introduced.

Then 155 g of compound (5,2) in 100 IIll of dry THF were added. 1 night It refluxed. Cool, add 50ml of THF, add 100ml of dry THF and Add 43 g (0,589 mol) of chillformamide and bring to ambient temperature at 16:00. I paused. Add water, ether 2! was added, extracted, dried over Mg5o, and evaporated. 120 g of a very viscous oil was recovered. Ethyl acetate/hexane as eluent Chromatography on silica using a 20/80 mixture yields the pure compound ( 5,3) 47g was collected.

4) Synthesis of 5.4 In a 100 d flask, 6.9 g of compound (3) (2.10-2 ma t), CN　CHz　CN　1.32g (2・10-”mol　), CH30H 30+111 and 2 drops of piperidine were introduced. React for 48 hours at ambient temperature, Evaporation and CLHP purification isolated 2.4 g of pure compound (5,4).

Spectral analysis was performed on compounds (1), (2), (3) and (4), and the The structure of the product was determined.

Synthesis: 2) SiMe2-SjMe3 1): MgOSinew-SiMe3■ )experimental method 1) Synthesis of 6.1 In a 500ml flask, dry THF 200ml in a nitrogen atmosphere, Mg06 g (2,6·10-'mol) and one iodine crystal were introduced. Br-0 -Br 58.5 g (2,47-10-'mol) was gradually introduced. 1 o'clock Reflux for a while, return to ambient temperature, and add 41 g of CI-3iMez-Cl-3i (2,4 610-'mol) was gradually added. Reflux for 2 hours, cool and hydrolyze.

Extracted with ether, dried over MgS Oa, concentrated and vacuum distilled to a colorless liquid. 22g was collected.

Ambient temperature 282°C/0.2 mnlIg, yield: 31%.

The structure of the product was determined by spectral analysis.

2) Synthesis of 6.2 In a 250+I11 flask, 60 ml of dry THF and 1 Mg were added in a nitrogen atmosphere. 8 g (7,8·10-”mol) and 1 grain of iodine crystal were introduced.60 °C, compound (6,,1) 22 g (7,6' 6・10-"mol ) was introduced. Reflux for 3 hours, cool to ambient temperature, dry DMF 10.6 g (1,4·, -'mol) was introduced and kept at ambient temperature for 16 hours. Add water; Extracted with ethyl acetate, dried over Mg5On, filtered and evaporated the solvent to a yellow oil. was recovered.

Filter with a silica gel column using a 90/10 mixture of hexane/ethyl acetate as eluent. Romatography was performed and 11.21 g of yellow oil was recovered. Yield %i: 61.4 The structure of the 5% mini-61.45% spectra was determined.

3) Synthesis of 6.3 In a 100 ml flask, 11.10 g of compound (2) (4,72 ・10-"mol　), NCCHz CN 3.11　g(4,7・10-" mol), 50 ml of methanol and 2 drops of piperidine and brought to ambient temperature. I kept it for 2 hours. A gray-yellow precipitate formed. Filtered and washed with hexane. Hexa CLHP purification was carried out on two silica columns using a 9515 mixture of chlorine/ethyl acetate. The product was manufactured. 2.3 g of a yellow solid with a melting point of 81.5"C was recovered. Spectrum Analysis confirmed the structure of the product.

Earthwork 8 people 1.88 g (5.10-3 mo 1) and 20ml of 50% ethanol, heated and completely dissolved in 5 minutes. Ta. Add ACNO, 65 g (10-”mol), then add 2 ml of acetic acid and HzO The solution with LOML was slowly added to 0 and stirred for 1 hour at ambient temperature to form a rubber. Next, P b (OAC) 4 2.2 g (5 10-ffmol) and acetic acid 5o1 was reacted for 3 hours at 0 ambient temperature to form a red precipitate. filtered Then, hexane/ethyl acetate 1:1 (V/V) was used as the eluent. Chromatography was performed on a silica gel column, and 0.62 g of red solid was collected. and recrystallized with hexane at ambient temperature 122-122.5°C, spectral fraction. The structure of the product was determined by analysis.

1. tlO people's mu MiL: ■) 1 piece of soup 1) Synthesis of 8.1 In a 500 ml flask, add 200 ml of dry THF in a nitrogen atmosphere. Mg’6 g (2,6·10-'mol) and one grain of iodine crystal were introduced.

BrSotor Gradually add 58.5 g (2,47·10-'ff1ol) and reflux for 1 hour. did. Return to ambient temperature and remove CI-S iMe, -3iMez 41g (2,4 6·10-'mol) was gradually added and refluxed for 2 hours.

Cooled, hydrolyzed, extracted with ether, dried over MgSO4, and concentrated. . After vacuum distillation, 22 g of colorless liquid was recovered.

Ambient temperature = 82°C/0.2 mmog.

Yield: 31% The structure of 9.1 was determined by spectral analysis.

II) Synthesis of 8.2 In a 250+sl flask, dry THF 60ml in nitrogen atmosphere, Mg 1.8 g (7,8·10-"mol) and one iodine crystal were introduced. 60 °C and introduced 22 g of compound (8,1) (7,66・10-”+*ol) and refluxed for 3 hours. Cooled to ambient temperature and held for 16 hours. Add water and ethyl acetate The yellow oil was recovered by extraction with a Ta.

Chromatography was performed on a silica gel column using a 90/10 hexane/ethyl acetate solution as eluent. Matography was performed and 11.21 g of yellow oil was recovered. Yield %i: 61.45 %.

The structure of the product was determined by spectral analysis.

Synthesis of I[1)8.3 (8,2) 11.10 g (4,72・ 10-"mol), NC-CHz-CN 3.11 g (4,7・10-" mat), 0 ambient temperature with the introduction of 5 Qml of ethanol and 2 drops of piperidine. The mixture was kept for 2 hours to form a gray-yellow precipitate. Filter and wash with hexane; piperidine CLH on two silica columns using a 9515 solution of /ethyl acetate. 2.3 g of a yellow solid was recovered at an ambient temperature of 81.5'C.

The structure of the product was determined by spectral analysis.

51 1-(4-(2,2-dicyanoethynyl)]]phenyl-2-2-thiophenyl ) Synthesis and activity of tetramethylsilane (9,1) 3) CH2(CN)2 catalyst piperidine 1-(4-bromo)phenyl-2-(2-thiophenyl)tetramethyldisilane synthesis of 6.70g (276mmol) of magnesium shavings in THF 300+sl, 2- Gradually add 45 g (276 mraol) of chewy fluorine one by one. At the end of this exothermic reaction, at 60° C., the mixture was added for 12 hours. generated 1-(4-bromophenyl)-2-chlorotetramethylene in brown Grignard reagent 83.75 g (272a+mol) of Lucilan was added. After addition, the reaction mixture The mixture was further stirred at 60°C for 12 hours and then hydrolyzed with 0.1N HCl. organic The phases were collected and the aqueous phase was washed three times with hexane. Collect all the organic phase and add anhydrous Nag. Dry with SO4. Next, the solvent was expelled and the remaining liquid was chromatographed on silica gel. It was purified using After evaporating the solvent, 86.8 g of colorless oil were obtained.

Yield: 89.9%.

Mass spectrum: m/e 354 (M+).

RMN'H (CDCh): δ0.30 (s, Si (CH3) z, 1 2FI).

7.19 7.59. (AA' BB', BrC, H--4H).

7.53 7.11 7.06 (w, thiophene, 3H).

R gate NCl3 (CDC13): δ-4,12,6 (5i(CL)z).

137.3-135.4-130.9-123.4 (C, H4Br).

130.6-126.1134.5-137.6 (thiophene).

1-(2,2-dicyano-4-ethynyl)phenyl-2-(2-thiophenyl) Tetramethyldisilane THF 5.95 g magnesium shavings in 200 ml (2 45II11ol), 1-(4-bromophenyl)-2-(2-thiophenyl ) Gradually add 86.8 g (245 liters) of tetramethyldisilane one drop at a time. Ta. At the end of the reaction, the reaction mixture was heated to 60°C and stirred overnight. This Grini After adding 20 g (274 ■■ ol) of DMF dissolved in THF to Jarl's reagent, , the mixture was stirred at 60 °C for a further 6 h, then hydrolyzed with 0.1 N HCl, The aqueous phase was made slightly acidic. The organic phase was collected and the aqueous phase was washed three times with hexane. Yes The organic phase was collected and dried over anhydrous NazSO4. Evaporate the solvent and purify it. The product left over was used. Marono dissolved in ethanol 100a+s+ Add 18 g (272 wmol) of dinitrile and 2 drops of piperidine to malonodinitrile. was present as a condensation catalyst and added to the aldehyde. This mixture was stirred for 5 hours. After that, the product was crystallized in a refrigerator. The yellow crude product was isolated and diluted twice with hexane. Recrystallization gave 9 g of a yellow solid with a melting point of 98.5-99.5'C in a yield of 10%. .

Mass spectrum: m/e 352 (M+).

Fourier transform infrared (KBr) 71586 1538 1495 cm-' (ν C=C aryl), 1248 cm+-' (C5i-CH3).

792 cm-' (ν5i(CHs)z), 718 cm-' (thiophene) .

2226cs+-' (v (CH).

RMNH’ (CDCh): δ0.32 (s, Si (CL) z, 12 H).

0.34 (s, Si (C[13)z, 12H).

7.48 7.74 (AA' BB', 51 (CHz)z CbHaCH= 4H).

7.53-7.11-7°05 (ll, thiophene).

7.67 (S, C) I=C (CN) Z, LH).

R? lNC" (CDCh): δ-2, 8, 4, 53 (Si (CHz) ).

134.7 129.3 149.3-150.6 (Ar-CI(=).

130.9-128.3-134.5 (thiophene), 160.0 (CH =).

82.3 (=C(CN)ri, 112.6-113.8(CN).

RMNS, i” (CDC13): δ-23,820,4(s, 5i(C) lz)　z).

UV (CDC13): 344 nm (t = 22000).

C15Hz. S, N, Siz calculation value: C, 61, 31, H, 5, 71; S, 9.05; N, 7.94°Si, 15.93° Measured value: C, 61,00; H, 5,82; S, 8.45; N, 7.5 5; Si, 16.4゜ Essentials The present invention relates to lower homologs of organosilicon compounds of French Patent Application Box No. 8805214. Regarding.

This sub-congener has the general formula (In the formula, n is 1 to 20, R2 represents an electronic water pulling group, R3 is an alkyl group having 1 to 8 carbon atoms, hydrogen, an aryl group, a group R3 or R, represents R4 is an alkyl group having 1 to 8 carbon atoms, hydrogen, an aryl group, or R1 is If R2 does not represent the group R8, or if R1 does not represent the group R, the group R2 and/or R8 is an alkyl group, an aryl group, or a silyl group when n=1 (selected from the group consisting of groups).

Applied to nonlinear optics.

international search report 1MmMtla+tel As+++an NePCT,, 9110o33 6 International Search Report FR9100338 S^　47247

Claims (9)

[Claims] 1. The organosilicon compound according to claim 1 of patent application 8805214, A group in which R1 is an alkyl group, an aryl group, and a silyl group when n=1 An organosilicon compound characterized by being selected from. 2. The group R1 is an alcoyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or Silyl group having 3 to 20 carbon atoms, preferably 5 to 9 carbon atoms and 1 silicon atom The organosilicon compound according to claim 1. 3. The radical R1 is a silicon atom 1 surrounded by three, preferably identical, alkyl groups A silyl group consisting of, for example, trimethylsilyl or triethylsilyl The organosilicon compound according to claim 1 or 2, which is selected from the following. 4. The group R1 is at least one alkyloxyphenyl group, preferably an alkyloxyphenyl group. A silicon atom is bonded to an yloxyphenyl group, preferably a methoxyphenyl group. is a silyl group The organosilicon compound according to claim 1 or 2. 5. The material according to claim 10 of patent application 8805214, comprising claims 1 to 4 A substance characterized by containing at least one compound according to any one of the above. 6. The device according to claim 11 of patent application 8805214, A device characterized in that it contains at least one of the substances listed above. 7. The method according to any one of claims 12 to 14 of patent application 8805214. When the group R1 is an alkyl group, an aryl group, or a silyl group when n=1, A method characterized in that the method is selected from the group consisting of: 8. The group R1 is an alcoyl group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, or Silyl group having 3 to 20 carbon atoms, preferably 5 to 9 carbon atoms and 1 silicon atom The method according to claim 6. 9. The radical R1 is a silicon atom 1 surrounded by three, preferably identical, alkyl groups A silyl group consisting of, for example, trimethylsilyl or triethylsilyl The method according to claim 6 or 7, wherein the method is selected from the following.