JPS6058760B2 - Amines with vinylsilyl groups and their salts - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to amines having vinylsilyl groups.

In more detail, the present invention relates to raw material compounds for electrosensitive materials having good performance. Polymers that are crosslinked and rendered insolubilized by irradiation with electron beams are known as negative-tone electronic materials and are used to manufacture hologram memories, high-density integrated circuits, and the like. With the development of the information industry, electronic materials with high sensitivity and good resolution are required. It has been known to use polyvinylsiloxane as an electrosensitive material, but this polymer has poor contrast and
High resolution images cannot be obtained by irradiation with an electron beam. As a result of intensive studies aimed at producing a magnetic material with high sensitivity and good resolution, we arrived at the method of the present invention. That is, the present invention relates to an amine having a vinylsilyl group, and by bonding this compound onto a polymer through a polymer reaction, an electrophilic material with good performance can be obtained.

The compound of the present invention is an amine having a vinylsilyl group represented by the following general formula and a salt thereof.

(CH2■CH)nRA-nSi-R2-NH2(I)
[However, n = 1 to 3, R'' represents a lower alkyl group such as methyl, ethyl, propyl, etc., and R2 represents 1-(CH
2) m- is an alkylene group where m=3 to 10, and may have a lower alkyl group and/or a phenyl group as a substituent. Or, even if /-□゛・, ('2゛)1-(' ・” ゛,゛1--CH has a lower alkyl group as a substituent ~-ノ \,\,,1. good.

] To describe the content of the present invention more specifically, preferred examples of the vinylsilyl group include dimethylvinylsilyl group, methyldivinylsilyl group, trivinylsilyl group, diethylvinylsilyl group, and ethyldivinylsilyl group.

R' is preferably a lower alkyl group such as methyl, ethyl or propyl group. As R2, propylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, P-phenylene, 3-phenylpropylene, etc. are preferable.

Preferred acids that form salts with (I) include hydrohalic acids such as hydrochloric acid and hydrogen bromide, inorganic acids such as sulfuric acid and phosphoric acid, and organic acids such as carboxylic acids and organic sulfonic acids.

The compound of the present invention can be produced, for example, by the method described below.

A method using polymethylene dihalide as a raw material. (N, Rl
is the same as above, m=4 to 10, X is the same or different halogen atom, preferably chlorine or bromine) Polymethylene dihalide (■) is reacted with 2 moles or more of magnesium to form a bisgrinia reagent.3. Ru.

After reacting this with 1 mol of chlorosilanes (■),
React with carbon dioxide gas to form carboxylic acid (■). (■)
is reacted with thionyl chloride to form (·), and then reacted with ammonia to form acid amide (·). Amine (1a) is produced by reducing (■) with a reducing agent such as lithium aluminum hydride. (2) A method using phenylene dihalide as a raw material. (
N, Rl, X are the same as above) phenylene dihalide (■
) is reacted with 1 mol of magnesium to form a monogrinia reagent, and then reacted with 1 mol or more of chlorosilanes (■) to produce (■).

(■) is reacted with 1 mole or more of magnesium, um (■)
After that, carbon dioxide gas is reacted to form (X). From carboxylic acid (X) through (XI) and (XII) (Ib)
Manufacture. The manufacturing method is the same as that for manufacturing (1a) from (■). In the production of (1a) and (Ib), even if the raw materials (■) and (■) have a substituent such as lower alkyl, phenyl, alkoxy, etc., the reaction can proceed in the same way.

(3) Method using allyl chloride as a raw material (N and Rl are the same as above) Chlorosilanes (X■) and allyl chloride are reacted by hydrosilation reaction (X■), and then a vinyl Grignard reagent is reacted. (X■) is manufactured.

(RC) is produced by reacting (X) with potash phthalimide and then with hydrazine (Gabriel synthesis). (N and Rl are the same as above) Also, (XV) is reacted with magnesium to produce glycine, and cinnamonitrile (XIX) is reacted with magnesium and chlorosilanes (■) to produce (XX).

After making it into a near reagent, it is reacted with carbon dioxide gas to form carboxylic acid (
X■) is manufactured.

(Id) is produced from (X■) in the same manner as in the production of (1a) and (Ib). The reaction can be carried out even if a substituent such as lower alkyl or phenyl is bonded to the starting allyl cloide.

(4) By reducing method XX using cinnamonitrile as a raw material with lithium aluminum hydride etc. (Ie)
Manufacture.

(5) Method using cinnamaldehyde as raw material (N, Rl
(same as above) Cinnamaldehyde (XXI), magnesium, and chlorosilanes (■) are reacted in hexamethylphosphoryltriamide (HMPA) to produce (XXI■).

(XX■) is reacted with hydroxylamine and oxime (
XX■), and then reduced with lithium aluminum hydride or the like to obtain (If). The compound of the present invention is bonded to a polymer through the following reaction, for example, and becomes a high-performance electrosensitive material.

Poly N-acryloylbenztriazole (X4X■)
easily reacts with (1) to form polyacrylic acid (amide(
XX■). [R3 is hydrogen, 0R4 (0R4 is an alkyl group having 1 to 20 carbon atoms), a phenyl group, etc.

] Also, maleic anhydride copolymer (XX■) is similarly (
It easily reacts with 1) to form (XX■).

Examples of the present invention are shown below. Example 1 190 y of 1,4-dichlorobutane was added dropwise to a mixture of 5-(dimethylvinylsilyl)-pentylamine; 88 y of magnesium and 700 ml of tetrahydrofuran to prepare a Bisgrinia reagent.

Chlorodimethylvinylsilane 181y was added dropwise to the mixture at room temperature with stirring over 1.7 hours, and then heated under reflux for 2.5 A. After cooling the reaction mixture into finely crushed dry ice 1
It was poured into a mixture of k9 and 700 mL of ether and left overnight. After adding 600 ml of 50% hydrochloric acid to separate the two layers, the aqueous layer was extracted twice with ethyl acetate.

The organic layers were combined, washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting oil was rectified. 125-126℃/4T0rr, 159g (57
%) of 5-(dimethylvinylsilyl)-valeric acid was obtained.

Indicates the analysis value. 182 g of thionyl chloride was added to 237 g of 5-(dimethylvinylsilyl)-valeric acid, 0.3 ml of dimethylformamide was added dropwise, and the mixture was left at room temperature for 45 minutes.

Thereafter, the two powders were reacted at 80°C and distilled under reduced pressure. 67
~ Seki ℃/3.0T0rr, 245.9y (95%) of 5
Mono(dimethylvinylsilyl)-valeryl chloride was obtained.

Indicates the analysis value. 'WI?
V2▼VVVvV▼! ▼v25
-(dimethylvinylsilyl)-valeryl chloride 45.
17V was dissolved in 200 ml of methylene chloride, and ammonia gas was blown into the solution in four parts while stirring on ice.

The reaction mixture was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained crystals were mixed with 80ml of n-hexane.
was recrystallized. 30.6y (75%) of 5-(dimethylvinylsilyl)-pentanamide was obtained. Mp73
~75°C, analytical values are shown. Suspend 47.0y of lithium aluminum hydride in 300ml of ether,
(dimethylvinylsilyl)-pentanamide 91.8q
was dissolved in 700 ml of ether and stirred at room temperature.
It was added dropwise over 2 hours.

After this, heat under reflux for 1.7 hours, and add 400ml of water under ice cooling.
was added dropwise, and 4' of a saturated aqueous solution of Rothsiel's salt was added. The organic layer was separated, the aqueous layer was extracted twice with ether, the ether layers were combined, washed with a saturated aqueous solution of Rothsiel's salt, and dried over anhydrous sodium sulfate. After distilling off the ether under reduced pressure, the resulting oil was rectified. 69~70°C/5T0rr,
73.1y (74%) of 5-(dimethylvinylsilyl)
-Pentylamine was obtained.

Indicates the analysis value. Example 2 P-(dimethylvinylsilyl)-benzylamine; 390 y of paradibromobenzene was dissolved in 140 y of tetrahydrofuran.
0ml, and 36.4y of magnesium was added little by little over 15 seconds.

A Grignard reagent was prepared by reacting 2 powders under ice-cooling, 2 minutes at room temperature, and 4 powders under heating under reflux. 180.1y of chlorodimethylvinylsilane was added dropwise at room temperature with stirring, followed by heating under reflux for 3 hours.

After starting the reaction by adding 43.7y1 of magnesium and a small amount of iodine, the two powders were reacted under ice cooling, and then heated under reflux for 1 hour.

After cooling with ice, the reaction mixture was poured into finely crushed dry ice 2K9 and left overnight. After adding 500 g of ice, add 40 g of concentrated hydrochloric acid.
After adding 0ml of the mixture and separating the two layers, the aqueous layer was extracted three times with ethyl acetate, washed with saturated brine, and dried over anhydrous sodium sulfate. When the solvent was distilled off under reduced pressure, an oil containing crystals was obtained. 200 ml of petroleum benzine was added, and the mixture was allowed to stand at room temperature for 1 hour, then filtered under reduced pressure to remove crystals, and the mother liquor was concentrated under reduced pressure. The resulting oil was rectified. 137-138℃/03T0
rr, mp89-91°C.

143.3 Da (46%) of P-(dimethylvinylsilyl) monobenzoic acid was obtained. Indicates the analysis value. P-(dimethylvinylsilyl)-benzoyl chloride was obtained from P-(dimethylsilyl)monobenzoic acid in the same manner as in Example 1. Yield 94% 83-86°C/0.5T0rr, analytical values are shown. Dark? Ice-cool Nmore water 1.5e and mix it with ice.
C7Z+1=P-(dimethylvinylsilyl)-benzoyl chloride 146y was dissolved in 500 ml of dichloromethane and added dropwise over 45 minutes. The organic layer was separated from the reaction mixture, and the aqueous layer was extracted twice with dichloromethane. The organic layers were combined, washed with water, dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained crystals were recrystallized from 50 ml of ethanol and 350 ml of petroleum benzine.

55.3y (73%) of P-(dimethylvinylsilyl)
-benzamide was obtained.

Mpll 6-118°C, analytical values are shown. In the same manner as in Example 1, p-JJP7 (vinylsilyl)-benzamide was reduced with lithium aluminum hydride to give P-
(dimethylvinylsilyl)-benzyl ryo S son melon f-1
! VhongQQO/'0k197%/3T'0rr, is shown. P-(dimethylvinylsilyl)-benzylamine hydrochloride P-(dimethylvinylsilyl)-benzylamine 3.
Dissolve 51y in 30 mt of methanol and add 1.5 ml of concentrated hydrochloric acid.
3 mt was dissolved in 10 ml of methanol and added dropwise.

50 ml of benzene was added, the solvent was distilled off under reduced pressure, and the mixture was dried under reduced pressure using a vacuum pump. The obtained crystals were recrystallized from ethanol-n-hexane. 2.0y (48%) of the desired product was obtained.

Mp245-248°C, analytical values are shown. Example-4 P-(dimethylvinylsilyl)-benzylaminebenzoic acid; P-(dimethylvinylsilyl)-benzylamine 5
．． 3.64 V of 70y1 benzoic acid was dissolved in 30 ml of methanol, 50 mt of benzene was added, and the solvent was distilled off under reduced pressure.

The obtained crystals were recrystallized from ethanol-n-hexane. 6.54y (70%) of the desired product was obtained.

Mpl44-146°C, analytical values are shown. Example-53-
(Methyldivinylsilyl)-propylamine; acryl chloride and dichloromethylsilane were prepared by J. W. The method of Ryan et al. [J. An. ChemSOc. ,82,36Ol
(1960)] to obtain 3-(dichloromethylsilyl)-propyl chloride.

Vinylbromide 156.3y dissolved in 650 ml of tetrahydrofuran was added dropwise to a mixture of 43y of magnesium and 130 ml of tetrahydrofuran to prepare a Grignard reagent.

After cooling, the supernatant was decanted and transferred to another 2e three-meter flask. 107.5y of 3-(dichloromethylsilyl)-propyl chloride was added dropwise for 30 minutes while stirring,
Thereafter, the mixture was heated under reflux for 1 hour.

After standing overnight, add 50 mt of water under ice cooling, and then add 5% hydrochloric acid 1e.

After separating the two layers, the organic layer was taken, and the solvent was distilled off under reduced pressure to reduce the volume to about half. The aqueous layer was extracted three times with ether, combined with the organic layer, and washed with an aqueous sodium bicarbonate solution and saturated brine.
It was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The resulting oil was distilled under reduced pressure. 94-95℃/3π0rr
, 73.5y (80%) of 3-(methyldivinylsilyl)-propyl chloride was obtained.

Indicates the analysis value. 3-(Methyldivinylsilyl)-propyl chloride 141.9y1 Phthalimide 81y was dissolved in 670ml of dimethylformamide and heated to 90℃ for 4 hours.
I stirred it for an hour.

After standing overnight, 1.5 f of ice water was added and extracted three times with ethyl acetate. Wash with 0.2N aqueous sodium hydroxide solution and water,
After drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure.

234.41 N-[3-(methyldivinylsilyl)-
Propyl]-phthalimide was obtained as a yellow oil.

Crude N-[3-(methyldivinylsilyl)-propyl]-
Phthalimide 234.4f1 Hydrazine 80% aqueous solution 7
0.3y was dissolved in methanol 2e and heated under reflux for 2.5 hours.

The solvent was distilled off under reduced pressure, 1.2e1 of water and 120mL of concentrated hydrochloric acid were added, and the mixture was stirred at 80'C for 20 minutes. After cooling with ice, remove the colorless crystals that precipitate by filtration, and add 1 ml of sodium hydroxide under ice cooling.
27y was dissolved in 500 ml of water and added dropwise. The extract was extracted three times with chloroform, washed with saturated brine, and dried over anhydrous sodium sulfate.

After the solvent was distilled off under reduced pressure, the residue was distilled under reduced pressure. 75-76 pressure C/1
The target product of 31'0rr, 76.3V (61%) was obtained.

Indicates the analysis value. Example 6 3-(methyldivinylsilyl)-propylamine hydrochloride 3-(methyldivinylsilyl)-propylamine hydrochloride was obtained in the same manner as in Example 3.

Recrystallization yield 90% from benzene-n-hexane, Mp1
67-169'C analysis values are shown. Example 7 3-(methyldivinylsilyl)-propylamine benzoate; 3-(methyldivinylsilyl)-propylamine was prepared from 3-(methyldivinylsilyl)-propylamine and benzoic acid in the same manner as in Example 4. Benzoate was obtained.

Recrystallized from benzene-n-hexane. Yield 75%, Mp
7l~72'C analysis values are shown. Example 8 A mixture consisting of 3-(dimethylvinylsilyl)-3-phenylpropylamine; 10.95y of magnesium) 10.95y of chlorodimethylvinylsilane) 240ml of hexamethylphosphoryltriamide was heated to 70°C,
While stirring, 38.7 y of cinnamonitrile was dissolved in 90 mL of hexamethylphosphoryl triamide and added dropwise over 2.7 hours.

After this, the mixture was stirred at 70 to 7'C for 4 hours.

After cooling, the mixture was poured into 600 g of ice and extracted twice with ether. The ether layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and the ether was distilled off under reduced pressure.

The resulting colored oil was distilled under reduced pressure. 124-126
°C/0. n'0, 2.3- of 44.04y (49%)
Bis(dimethylvinylsilyl)-3-phenylpropiononitrile was obtained.

Indicates the analysis value. 2.74 da of lithium aluminum hydride was suspended in 100 mι of ether to form 2,3-bis(
21.5 Da of dimethylvinylsilyl-3-phenylpropiononitrile was dissolved in 100 ml of ether and added dropwise.

Thereafter, the mixture was heated and refluxed for three times. After cooling on ice, 30 ml of water was added dropwise, 500 ml of a saturated aqueous solution of Rothsiel's salt was added, and after separating into two layers, the aqueous layer was extracted three times with ether.

Claims (1)

[Claims] 1 General formula (CH_2=CH)n(R^1)_3_-_
nSi-R^2-NH_2(I) [however, n=1 to 3
:R^1 is a lower alkyl group; R^2 is (1)-(CH
_2) m- is an alkylene group where m=3 to 10, and may have a lower alkyl group and/or a phenyl group as a substituent. or (2) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ and may have a lower alkyl group as a substituent. ] and its salts having a vinylsilyl group.