CN1683348A - Aminobenzothiazole monomer containing alicyclic macro side group and its preparing method - Google Patents
Aminobenzothiazole monomer containing alicyclic macro side group and its preparing method Download PDFInfo
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- CN1683348A CN1683348A CN 200510024421 CN200510024421A CN1683348A CN 1683348 A CN1683348 A CN 1683348A CN 200510024421 CN200510024421 CN 200510024421 CN 200510024421 A CN200510024421 A CN 200510024421A CN 1683348 A CN1683348 A CN 1683348A
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- cycloaliphatic
- aminobenzothiazole
- lateral base
- big lateral
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Abstract
The present invention discloses aminobenzothiazole monomers containing alicyclic macro side group and its preparation process. These monomers are preparation with aniline and carbonyl compound as initial material and through two reaction steps under certain condition. Using the aminobenzene thiazole monomer as material may prepare novel polymer with both benzothiazole ring and other heterocycle, and introducing alicyclic macro side group can raise the dissolubility of the polymer while maintaining the excellent performances, including high modulus, high strength, very high stability and chemical stability, etc. The present invention will find its wide application in optics, electricity, photoelectronics, non-linear optics and other aspects.
Description
Technical field:
The present invention relates to a class organic compound and a preparation method, particularly a class contains aminobenzothiazole monomer of cycloaliphatic big lateral base and preparation method thereof.
Background technology:
Polymkeric substance group (MLBP) as far back as the SRI sixties in 20th century (Stanford Research International) material laboratory just begins to be United States Air Force research and development high-temperature polymer material, people such as the Wolfe of SRI are on the long-term basis of exploring, having released in 1981 has 2 on the main chain, the two heterocyclic contraposition aromatic polymers of 6-benzo, make this research obtain progress and success greatly, caused widely and paid attention to that this also is an immense success in the design of polymer molecule.Polybenzothiozole polymkeric substance (PBZT) has uniqueness and excellent characteristic aspect a lot, be a kind of polymer materials, especially will have very extensive studies potentiality and application prospect aspect the light of macromolecular condensed state physics, electricity, photoelectricity, the nonlinear optics with comprehensive premium properties such as ultra high modulus, superstrength, ultrahigh heat-resistant stability and chemical stability.
The monomer of preparation PBZT polymkeric substance is mainly 2 at present, the 5-diaminostilbene, 4-benzene dimercapto dihydrochloride (USPatent 4225700), the PBZT series polymer of monomer preparation is because its rigidity conjugated structure only can be dissolved in some strong protonic acids, the polyelectrolyte of protonated formation thus, reduced intermolecular attracting each other and chain rigidity, but because these protonic acids are not volatile, cause polymkeric substance easily to become fine difficult film forming, the processed and applied of family macromolecule material has caused obstacle for this reason.
Summary of the invention:
The present invention is from Molecular Structure Design and point of practical use, and the method for introducing big side group in monomer structure prepares the monomer that makes new advances, and improves the solvability of this base polymer thus.The aminobenzothiazole monomer that contains cycloaliphatic big lateral base can obtain high comprehensive performance and better deliquescent novel polymer material is arranged with dibasic acid anhydride isoreactivity molecule aggregation.
Institute of the present invention synthetic one class contains the aminobenzothiazole monomer of cycloaliphatic big lateral base, and its molecular structural formula is shown below:
Wherein X is:
The aminobenzothiazole monomer that institute of the present invention synthetic contains cycloaliphatic big lateral base is that starting raw material prepares to contain alicyclic carbonyl compound (X=0) and aniline, and its chemical equation can be expressed as follows:
The monomeric concrete preparation method of aminobenzothiazole that the present invention contains cycloaliphatic big lateral base is as follows:
(a) under protection of inert gas, mechanical stirring condition, aniline and strong acid are added in the reactor, wherein the mol ratio of aniline and strong acid is 1: 1～1: 8; Or with in aniline and the anilinechloride adding reactor, the mol ratio of aniline and anilinechloride is 1: 1～10: 1, behind the two thorough mixing, again alicyclic carbonyl compound is added, the mol ratio of wherein alicyclic carbonyl compound and aniline is 1: 4～1: 16, then mixture was reacted 12～36 hours at 120～160 ℃, solution is cooled to room temperature, in reaction soln, add the aqueous solution of alkali to pH=10, oil reservoir is separated, and wash to neutrality dry filter with water, excessive aniline is removed in underpressure distillation, obtains containing the aromatic diamines of cycloaliphatic big lateral base behind the crude product recrystallization;
(b) at rare gas element, under the mechanical stirring, the aromatic diamines that will contain cycloaliphatic big lateral base is dissolved in the Glacial acetic acid fully, containing the aromatic diamines of cycloaliphatic big lateral base and the mass ratio of Glacial acetic acid is 1: 10～1: 20, in solution, add potassium sulfocyanate or Sodium Thiocyanate 99 after the stirring and dissolving, stirring makes its dissolving, wherein containing the aromatic diamines of cycloaliphatic big lateral base and the mol ratio of potassium sulfocyanate or Sodium Thiocyanate 99 is 1: 3～1: 12, in mechanical stirring, under the ice bath refrigerative condition, the glacial acetic acid solution of dripping bromine in reaction solution, bromine is 2: 1～5: 1 with the mol ratio that contains the aromatic diamines of cycloaliphatic big lateral base, the mass ratio of bromine and Glacial acetic acid is 1: 1～5: 1, dropwised the back stirring at room 12～36 hours, in reaction solution, add water and refluxed 2～5 hours, be cooled to room temperature, filter, filtrate is poured in the big water gaging, produce precipitation, solid filtering is also extremely neutral with ammonia scrubbing, obtains containing the aminobenzothiazole monomer of cycloaliphatic big lateral base behind the crude product recrystallization.
Strong acid used in the present invention comprises hydrochloric acid, Phenylsulfonic acid or p-chlorobenzenesulfonic acid.。
Alkali used in the present invention comprises sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus.
Alicyclic carbonyl compound used in the present invention comprises: pimelinketone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,5-dimethylcyclohexanon, 3,4-dimethylcyclohexanon, 2,5-dimethylcyclohexanon, 3,5-dimethylcyclohexanon, 3,5,5-trimethylcyclohexanone, 4-tertiary butyl pimelinketone, suberone, cyclooctanone, ring ketone in the third of the twelve Earthly Branches, ring decanone, cycloundecanone, cyclododecanone, cyclotridecanone, cyclotetradecanone or diamantane ketone.
The aminobenzothiazole monomer that contains cycloaliphatic big lateral base that the present invention is prepared can synthesize and contain benzothiazole ring and other heterocyclic new polymerss simultaneously, because the introducing of cycloaliphatic big lateral base can improve the solubility property of this base polymer and can keep many-sided premium propertiess such as its high-modulus, high strength, high thermal stability and chemical stability.
Description of drawings:
Fig. 1: 1, the infrared spectra IR (KBr) of 1-two (2-aminobenzothiazole base) hexanaphthene (BABTCH)
Fig. 2: 1,1-two (2-aminobenzothiazole base) hexanaphthene (BABTCH)
1H NMR (DMSO-d
6)
Fig. 3: 1, the mass spectrum of 1-two (2-aminobenzothiazole base) hexanaphthene (BABTCH)
Embodiment:
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
(a) with 37.3g (0.4mol) aniline, 37mL of 35wt% HCl solution joins magnetic agitation is housed, in the three-necked bottle of nitrogen gangway and reflux condensing tube, 60 ℃ of following stirring and dissolving.Solution clarification back drips 9.8g (0.1mol) pimelinketone.Mixture was 120 ℃ of reactions 24 hours.Solution is cooled to room temperature, and the sodium hydroxide solution of adding 10% is to pH=10, and the organic layer separation also washes with water to neutrality.Anhydrous magnesium sulfate drying, underpressure distillation are removed excessive aniline, and crude product gets 1 with the toluene recrystallization, 1-two (4-aminophenyl) hexanaphthene 22.1g (productive rate 83.1%).
(b) with 26.6g (0.1mol) 1,1-two ((4-amino) phenyl) hexanaphthene, the 398mL Glacial acetic acid joins in the three-necked bottle that mechanical stirring, nitrogen inlet and dropping funnel are housed, and adds 48.5g (0.51mol) potassium sulfocyanate after the stirring and dissolving.In the ice bath cooling, under the churned mechanically condition, drip the 10mL glacial acetic acid solution of 38.4g (0.24mol) bromine.There is the orange solid to produce in the dropping process.The mixture stirring at room adds 330mL water after 12 hours, mixture heating up refluxed 2 hours, was cooled to the room temperature after-filtration.Filtrate is poured in the big water gaging, filters and collects light yellow solid.Crude product 200mL ammonia scrubbing washes with water to neutrality again.Product gets 24.2g 1,1-two (2-aminobenzothiazole base) hexanaphthene (BABTCH) (productive rate 63.6%) after using the tetrahydrofuran (THF) recrystallization.Fig. 1 represents the infrared spectra IR (KBr) of BABTCH: 3369 (m, N-H), 2932,2855 (m,
), 1627 cm
-1(m, C=N).Fig. 2 represents the proton nmr spectra of BABTCH
1H NMR (DMSO-d
6): δ (ppm)=1.51 (br s, 6H), 2.17 (br s, 4H), 7.11-7.13 (dd, 2H), 7.17-7.19 (d, 2H), 7.29 (s, 4H), 7.56 (d, 2H).MS(70eV)：
Fig. 3 represents the mass spectrum m/z=380 (M of BABTCH
+).
Embodiment 2:
(a) with 15.4g (0.1mol) 4-tertiary butyl pimelinketone, 51.8g (0.4mol) anilinechloride and 102.3g (1.1mol) aniline joins in the three-necked bottle of magnetic agitation, nitrogen inlet, mixture was 140 ℃ of C stirring and refluxing 36 hours, solution is cooled to room temperature, the potassium hydroxide solution that adds 10wt% is to pH=10, mixture refluxed 10 minutes, and organic layer separates and washes with water to neutrality.Anhydrous magnesium sulfate drying, underpressure distillation are removed excessive aniline, and crude product gets 1 with the benzene recrystallization, 1-two (4-aminophenyl)-4-tertiary butyl hexanaphthene 20.6g (productive rate 63.9%).
(b) with 16.1g (0.05mol) 1,1-two (4-aminophenyl)-4-tertiary butyl hexanaphthene, the 240mL Glacial acetic acid joins in the three-necked bottle that mechanical stirring, nitrogen inlet and dropping funnel are housed, and adds 29.1g (0.3mol) potassium sulfocyanate after the stirring and dissolving.In the ice bath cooling, under the churned mechanically condition, drip the 5mL glacial acetic acid solution of 19.2g (0.12mol) bromine.There is the orange solid to produce in the dropping process.The mixture stirring at room adds 170mL water after 12 hours, mixture heating up refluxed 4 hours, is cooled to room temperature and filters.Filtrate is poured in the big water gaging, filters and collects white solid.Crude product 120mL ammonia scrubbing washes with water to neutrality again.Product gets 15.7g 1,1-two (2-aminobenzothiazole base)-4-tertiary butyl hexanaphthene (BABTTCH) (productive rate 72.0%) after using the tetrahydrofuran (THF) recrystallization.IR(KBr)：3367(m，N-H)，2941，2864(m，
)，1615cm
-1(m，C＝N)。
1H?NMR(DMSO-d
6)：δ(ppm)＝0.77(s，9H)，1.07-1.77(m，7H)，2.84-2.81(d，2H)，7.02-7.10(d，2H)，7.13(d，2H)，7.23-7.29(d，4H)，7.46-7.66(d，2H)MALDI-TOF-MS：m/z＝437(M
++1)。
Embodiment 3:
(a) with 18.2g (0.1mol) cyclododecanone, 51.8g (0.4mol) anilinechloride and 120.9g (1.3mol) aniline joins in the three-necked bottle that magnetic agitation, nitrogen inlet are housed, mixture was 140 ℃ of stirring and refluxing 36 hours, solution is cooled to room temperature, the potassium hydroxide solution that adds 10wt% is to pH=10, mixture refluxed 10 minutes, and organic layer separates and washes with water to neutrality.Anhydrous magnesium sulfate drying, underpressure distillation are removed excessive aniline, and crude product gets 1 with the toluene recrystallization, 1-two (4-aminophenyl) cyclododecane 23.0g (productive rate 65.6%).
(b) with 17.5g (0.05mol) 1,1-two (4-aminophenyl) cyclododecane, the 260mL Glacial acetic acid joins in the three-necked bottle that mechanical stirring, nitrogen inlet and dropping funnel are housed, and adds 38.8g (0.4mol) potassium sulfocyanate after the stirring and dissolving.In the ice bath cooling, under the churned mechanically condition, drip the 5mL glacial acetic acid solution of 19.2g (0.12mol) bromine.There is the orange solid to produce in the dropping process.The mixture stirring at room adds 200mL water after 12 hours, mixture heating up refluxed 4 hours, is cooled to room temperature and filters.Filtrate is poured in the big water gaging, filters and collects white solid.Crude product 120mL ammonia scrubbing washes with water to neutrality again.Product gets 15.9g1,1-two ((2-amino) benzothiazolyl) cyclododecane (BABTCD) (productive rate 68.4%) IR (KBr) after using the tetrahydrofuran (THF) recrystallization: 3366 (m, N-H), 2909,2930 (m,
), 1623cm
-1(m, C=N).
1HNMR(DMSO-d
6)：δ(ppm)＝0.956-1.973(m，22H)，7.13-7.15(dd，2H)，7.18-7.21(d，2H)，7.28(s，4H)，7.58(d，2H)MS：m/z＝464(M
+)。
Claims (5)
1. aminobenzothiazole monomer that contains cycloaliphatic big lateral base is characterized in that the molecular structural formula of this compound is:
Wherein X is:
2. the monomeric preparation method of aminobenzothiazole who contains cycloaliphatic big lateral base as claimed in claim 1 is characterized in that the preparation method is as follows:
(a) under protection of inert gas, mechanical stirring condition, aniline and strong acid are added in the reactor, wherein the mol ratio of aniline and strong acid is 1: 1～1: 8; Or with in aniline and the anilinechloride adding reactor, the mol ratio of aniline and anilinechloride is 1: 1～10: 1, behind the two thorough mixing, again alicyclic carbonyl compound is added, the mol ratio of wherein alicyclic carbonyl compound and aniline is 1: 4～1: 16, then mixture was reacted 12～36 hours at 120～160 ℃, solution is cooled to room temperature, in reaction soln, add the aqueous solution of alkali to pH=10, oil reservoir is separated, and wash to neutrality dry filter with water, excessive aniline is removed in underpressure distillation, obtains containing the aromatic diamines of cycloaliphatic big lateral base behind the crude product recrystallization;
(b) at rare gas element, under the mechanical stirring, the aromatic diamines that will contain cycloaliphatic big lateral base is dissolved in the Glacial acetic acid fully, containing the aromatic diamines of cycloaliphatic big lateral base and the mass ratio of Glacial acetic acid is 1: 10～1: 20, in solution, add potassium sulfocyanate or Sodium Thiocyanate 99 after the stirring and dissolving, stirring makes its dissolving, wherein containing the aromatic diamines of cycloaliphatic big lateral base and the mol ratio of potassium sulfocyanate or Sodium Thiocyanate 99 is 1: 3～1: 12, in mechanical stirring, under the ice bath refrigerative condition, the glacial acetic acid solution of dripping bromine in reaction solution, bromine is 2: 1～5: 1 with the mol ratio that contains the aromatic diamines of cycloaliphatic big lateral base, the mass ratio of bromine and Glacial acetic acid is 1: 1～5: 1, dropwised the back stirring at room 12～36 hours, in reaction solution, add water and refluxed 2～5 hours, be cooled to room temperature, filter, filtrate is poured in the big water gaging, produce precipitation, solid filtering is also extremely neutral with ammonia scrubbing, obtains containing the aminobenzothiazole monomer of cycloaliphatic big lateral base behind the crude product recrystallization.
3. the monomeric preparation method of aminobenzothiazole who contains cycloaliphatic big lateral base according to claim 2 is characterized in that strong acid comprises hydrochloric acid, Phenylsulfonic acid or p-chlorobenzenesulfonic acid.
4. the monomeric preparation method of aminobenzothiazole who contains cycloaliphatic big lateral base according to claim 2 is characterized in that alkali comprises sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate, salt of wormwood or saleratus.
5. the monomeric preparation method of aminobenzothiazole who contains cycloaliphatic big lateral base according to claim 2, it is characterized in that alicyclic carbonyl compound comprises: pimelinketone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 2,5-dimethylcyclohexanon, 3,4-dimethylcyclohexanon, 2,5-dimethylcyclohexanon, 3,5-dimethylcyclohexanon, 3,3,5-trimethylcyclohexanone, 4-tertiary butyl pimelinketone, suberone, cyclooctanone, ring ketone in the third of the twelve Earthly Branches, ring decanone, cycloundecanone, cyclododecanone, cyclotridecanone, cyclotetradecanone or diamantane ketone.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387636C (en) * | 2005-12-22 | 2008-05-14 | 上海交通大学 | Benzothiazole-carbamide polymer containing aliphatics lateral group and method for preparing the same |
| CN109336843A (en) * | 2018-11-08 | 2019-02-15 | 南京医科大学康达学院 | A kind of double benzothiazole compounds and its synthetic method |
-
2005
- 2005-03-17 CN CN 200510024421 patent/CN1683348A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100387636C (en) * | 2005-12-22 | 2008-05-14 | 上海交通大学 | Benzothiazole-carbamide polymer containing aliphatics lateral group and method for preparing the same |
| CN109336843A (en) * | 2018-11-08 | 2019-02-15 | 南京医科大学康达学院 | A kind of double benzothiazole compounds and its synthetic method |
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