CN1128137C - Indole compounds and its synthetic method - Google Patents
Indole compounds and its synthetic method Download PDFInfo
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- CN1128137C CN1128137C CN 01105570 CN01105570A CN1128137C CN 1128137 C CN1128137 C CN 1128137C CN 01105570 CN01105570 CN 01105570 CN 01105570 A CN01105570 A CN 01105570A CN 1128137 C CN1128137 C CN 1128137C
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Abstract
The present invention discloses a 1, 1-dimethyl-2-formyl methylene-3-alkyl-1H-benzo [e] indole of new compound with a structure given below and a preparing method for the compound. The operation is simple, the raw material is easy to obtain, the cost low and the yield is high by using the method of the present invention to prepare the 1, 1-dimethyl-2-formyl methylene-3-alkyl-1H-benzo [e] indole. A high-purity asymmetrical cyanine dye for a DVD-R optical disc can be synthesized by using the compound as an intermediate. The structural formula of the compound is disclosed in the figure.
Description
The present invention relates to a kind of benzazolyl compounds and preparation method thereof, relate in particular to a kind of benzo [e] benzazolyl compounds and preparation method thereof.
Benzo [e] benzazolyl compounds is a kind of important organic intermediate, in dyestuff, medicine and other fields purposes is very widely arranged, and especially can be used as the starting raw material of synthetic cyanine dyes.In recent years, many patents and document disclose and have reported the application of various benzos [e] benzazolyl compounds, for example:
(1) U.S. Pat 5,489, and 593, to disclose with benzo [e] benzazolyl compounds be the piperazine that the synthetic benzindole of raw material replaces to US 5,563,142, this compound is having very important use aspect the treatment AIDS;
(2) U.S. Pat 6,180, and 085, US 6,180,086, US 6,180,087, US 6,190,641 disclose with benzo [e] indoles as raw material synthesis hydrophilic cyanine dyes, and this dyestuff can be used for optical imagery and treatment, endoscope is surveyed tumour, topical therapeutic, optoacoustic tumor imaging, detection and treatment, sound causes aspects such as fluorescence tumor imaging, detection and treatment;
(3) U.S. Pat 4,933, and 269, US 5,268,486, US 5,569,766 disclose benzo [e] the indoles synthetic dyestuff that replace with sulfonic group, this dyestuff is having very important use aspect sensitive materials, mark and the detecting material.
(4) European patent EP 946,941, U.S. Pat 5,773,193, US 5,976,658, world patent WO00/64989 etc. disclose the application as the cd-recordable recording medium of the cyanine dyes that contains benzo [e] indoles.
The n value of unsymmetrical cyanine dye is bigger, and the k value suitably (US 5,976,658; US 5,773,193), thereby as optical disc recording medium can make high-quality cd-recordable.The absorbing wavelength of three methine unsymmetrical cyanine dyes and the optical maser wavelength of DVD adapt, and especially are suitable as the recording medium of DVD-R CD.
Patent Brit.Pat.344,409; Brit.Pat.354,898; US 4,847, and 385; WO00/64989 and document J.Am.Chem.Soc., 1941,63,3192～3203; J.Chem.Soc., 1949,32～39 grades have been reported the synthetic method of unsymmetrical cyanine dye, and this method is that at first the reaction of indoles quaternary ammonium salt and condensing agent generates half cyanines, and half cyanines generate unsymmetrical cyanine dye with other indoles quaternary ammonium salt reaction more then.Adopt the synthetic asymmetric dyestuff of this method need prepare condensing agent, and always contain symmetrical dyestuff more or less in the unsymmetrical cyanine dye, purification difficult need repeatedly recrystallization, thereby purity is not high, and yield is low.And highly purified cyanine dyes is as one of DVD-R optical disc recording medium necessary conditions.
Along with developing rapidly of dyestuffs industries, the relevant scientific and technical personnel of branch of industry's expectation constantly research and develop new Benzazole compounds, to satisfy its needs.
One of purpose of the present invention is to disclose a kind of new Benzazole compounds---1,1-dimethyl-2-formyl methylene radical-3-alkyl-1H-benzo [e] indoles, purification difficult, purity is not high, yield is low defective when overcoming the synthetic unsymmetrical cyanine dye of prior art are to satisfy the needs of branch of industry;
Two of purpose of the present invention is to provide the preparation method of above-claimed cpd.
Realize the object of the invention technical scheme:
The present invention is said 1,1-dimethyl-2-formyl methylene radical-3-alkyl-1H-benzo [e] indoles, and its general structure is as follows:
Wherein: R
1For-(CH
2) mCH
2L, m are from 0～20, and L is hydrogen, sulfonic group, hydroxyl, halogen or the alkyl that contains aromatic ring;
Preferred R
1Be C
1～C
8Alkyl;
Most preferred R
1A kind of in methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl;
Preferred R
1For methyl or be butyl.
Preferred compound is 1,1-dimethyl-3-butyl-2-formyl methylene radical-1H-benzo [e] indoles or 1,1,3-trimethylammonium-2-formyl methylene radical-1H-benzo [e] indoles.
The preparation of above-claimed cpd comprises the steps:
(1) 1,1, the aqueous solution of 2-trimethylammonium-3-alkyl-1H-benzo [e] indoles salt and sodium hydroxide reacts in solvent, generates 1,1-dimethyl-2-methylene radical-3-alkyl-1H-benzo [e] indoles;
Said 1,1,2-trimethylammonium-3-alkyl-1H-benzo [e] indoles salt is the compound with following general structure:
Wherein: R
1For-(CH
2) mCH
2L, m are from 0～20, and L is hydrogen, sulfonic group, hydroxyl, halogen or the alkyl that contains aromatic ring; X is I, p-C
6H
4-SO
3Or R
1OSO
3Deng in a kind of;
Preferred R
1Be C
1～C
8Alkyl;
Most preferred R
1A kind of in methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl;
Preferred R
1Be methyl or butyl;
Said compound can adopt the commercially available prod or with reference to Soobshch Akad.Nauk.Gruz.SSR, 1968,50 (1), 77～82 (CA69:106526) institute reported method is synthesized.
Temperature of reaction is 0～60 ℃, reaction times is 1～20 hour, reaction solvent is toluene, dimethylbenzene, ether, chloroform, methylene dichloride, chloroform etc. and the immiscible organic solvent of water or its mixture, 1,1, the mol ratio of 2-trimethylammonium-3-alkyl-1H-benzo [e] indoles salt and sodium hydroxide was with 1: 1～1: 4; Be preferably 1: 1～1: 2.
(2) under stirring and cooling off, in dimethyl formamide, drip phosphorus oxychloride, the control rate of addition makes temperature remain on 0～50 ℃, drips 1 then under uniform temp, and 1-dimethyl-2-methylene radical-3-alkyl-1H-benzo [e] indoles is dissolved in the solution that dimethyl formamide forms;
The mol ratio of dimethyl formamide and phosphorus oxychloride is 1: 1～10: 1;
1, the mol ratio of 1-dimethyl-2-methylene radical-3-alkyl-1H-benzo [e] indoles and phosphorus oxychloride is 1: 1～1: 2;
Dropwise, insulation continues reaction 10 minutes to 5 hours.Then reaction solution is poured in a certain amount of mixture of ice and water, added NaOH solution adjusting pH and be about 10～11.With extracted with diethyl ether three times, use anhydrous sodium sulfate drying, then ether is spin-dried for, can obtain product 1,1-dimethyl-2-formyl methylene radical-3-alkyl-1H-benzo [e] indoles, its reaction expression is as follows:
Above-mentioned compound can be used to prepare the asymmetric three methine cyanine dyes with following general structure:
Wherein: R
1, R
2For-(CH
2) mCH
2L, m are from 0～20, and L is hydrogen, sulfonic group, hydroxyl, halogen or the alkyl that contains aromatic ring; R
3Be respectively a kind of in H, methyl, ethyl, methoxyl group, the halogen etc.; Y is respectively I, ClO
4, PF
6Deng.
By above-mentioned disclosed technical scheme as seen; of the present invention 1; 1-dimethyl-2-formyl methylene radical-3-alkyl-1H-benzo [e] indoles; because what adopt in preparation process is that the complex compound that generates of dimethyl formamide and phosphorus oxychloride is as acylating reagent; do not have any dyestuff and generate, thereby the purity height.Utilize 1,1-dimethyl-2-formyl methylene radical-3-alkyl-1H-benzo [e] indoles is as intermediate, easily three methine unsymmetrical cyanine dyes of synthesis of high purity.
Further set forth the present invention below in conjunction with example, but example does not limit protection scope of the present invention.
Embodiment 11,1,3-trimethylammonium-2-methylene radical-1H-benzo [e] indoles synthetic:
In the 1000ml there-necked flask, add 100g 1,1,2, aqueous sodium hydroxide solution and the 250ml toluene of 3-tetramethyl--1H-benzo [e] indoles salt compounded of iodine, 300g5%, at room temperature stirred fast 2 hours, and filtered then, tell the organic layer in the filtrate, dry, toluene rotation evaporate to dryness, obtain solid 61.3g, yield 96.5%.
Embodiment 21,1-dimethyl-2-methylene radical-3-butyl-1H-benzo [e] indoles synthetic:
With 1,1,2-trimethylammonium-3-butyl-1H-benzo [e] indoles salt compounded of iodine replaces 1,1,2 among the embodiment 1,3-tetramethyl--1H-benzo [e] indoles salt compounded of iodine, and other is identical with embodiment 1, and the product that obtains is an oily matter, yield 97%.
Embodiment 31,1-dimethyl-3-butyl-2-formyl methylene radical-1H-benzo [e] indoles synthetic:
Under stirring and cooling off, Dropwise 5 2.5g phosphorus oxychloride in the 100ml dimethyl formamide, the control rate of addition makes temperature remain on 10～15 ℃, drip 70g1 then under same temperature, 1-dimethyl-2-methylene radical-3-butyl-1H-benzo [e] indoles is dissolved in the solution that the 25ml dimethyl formamide forms.Dropwise, be incubated 35 ℃ and continue reaction 40 minutes.Under agitation reaction solution is poured in the 600g mixture of ice and water, adding 20% NaOH solution regulates PH and is about 10～11, with extracted with diethyl ether three times, use anhydrous sodium sulfate drying, then ether is spin-dried for, can obtain product 1,1-dimethyl-3-butyl-2-formyl methylene radical-1H-benzo [e] indoles 71.2g, yield 92%.m.p.112～113.5℃。
1H-NMR(CDCl
3)(ppm)：0.98(t，3H)，1.47(m，2H)，1.72(m，2H)，1.97(s，6H)，3.78(t，2H)，5.46(d，1H)，7.18(d，1H)，7.37(t，1H)，7.53(t，1H)，7.84(d，1H)，7.88(d，1H)，8.07(d，1H)，10.14(d，1H)。
Embodiment 41,1,3-trimethylammonium-2-formyl methylene radical-1H-benzo [e] indoles synthetic:
With 1,1,3-trimethylammonium-2-methylene radical-1H-benzo [e] indoles replaces 1 among the embodiment 3,1-dimethyl-2-methylene radical-3-butyl-1H-benzo [e] indoles, and other is identical with embodiment 3, and product is the brown crystallization, yield 94%.m.p.156～161℃。
1H-NMR(CDCl
3)(ppm)：1.97(s，6H)，3.43(s，3H)，5.42(d，1H)，7.20(d，1H)，7.37(t，1H)，7.53(t，1H)，7.85(d，1H)，7.88(d，1H)，8.07(d，1H)，10.13(d，1H)。
Claims (9)
1. Benzazole compounds is characterized in that having following chemical structure of general formula:
Wherein: R
1For-(CH
2) mCH
2L, m are from 0～20, and L is hydrogen, sulfonic group, hydroxyl, halogen or the alkyl that replaced by aromatic ring.
2. compound as claimed in claim 1 is characterized in that R
1Be C
1～C
8Alkyl.
3. compound as claimed in claim 2 is characterized in that R
1A kind of in methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl.
4. compound as claimed in claim 3 is characterized in that R
1For methyl or be butyl.
5. compound as claimed in claim 1 is characterized in that, said compound is 1,1-dimethyl-3-butyl-2-formyl methylene radical-1H-benzo [e] indoles.
6. compound as claimed in claim 1 is characterized in that, said compound is 1,1,3-trimethylammonium-2-formyl methylene radical-1H-benzo [e] indoles.
7. as the preparation method of the arbitrary described compound of claim 1～6, it is characterized in that comprising the steps:
(1) 1,1, the aqueous solution of 2-trimethylammonium-3-alkyl-1H-benzo [e] indoles salt and sodium hydroxide reacts in solvent, generates 1,1-dimethyl-2-methylene radical-3-alkyl-1H-benzo [e] indoles;
Temperature of reaction is 0～60 ℃, and the reaction times is 1～20 hour, and reaction solvent is and the immiscible organic solvent of water or its mixture;
(2) drip phosphorus oxychloride in dimethyl formamide, controlled temperature is 0～50 ℃, then under uniform temp to wherein dripping 1,1-dimethyl-2-methylene radical-3-alkyl-1H-benzo [e] indoles is dissolved in the solution that dimethyl formamide forms;
The mol ratio of dimethyl formamide and phosphorus oxychloride is 1: 1～10: 1;
1, the mol ratio of 1-dimethyl-2-methylene radical-3-alkyl-1H-benzo [e] indoles and phosphorus oxychloride is 1: 1～1: 2;
Insulation reaction 10 minutes to 5 hours collects 1 then from reaction product, 1-dimethyl-2-formyl methylene radical-3-alkyl-1H-benzo [e] indoles.
8. method as claimed in claim 7 is characterized in that, 1,1, and the mol ratio of 2-trimethylammonium-3-alkyl-1H-benzo [e] indoles salt and sodium hydroxide is 1: 1～1: 4.
9. method as claimed in claim 7 is characterized in that, said solvent is toluene, dimethylbenzene, ether, chloroform, methylene dichloride and/or chloroform.
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|---|---|---|---|
| CN 01105570 CN1128137C (en) | 2001-03-06 | 2001-03-06 | Indole compounds and its synthetic method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01105570 CN1128137C (en) | 2001-03-06 | 2001-03-06 | Indole compounds and its synthetic method |
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|---|---|
| CN1311184A CN1311184A (en) | 2001-09-05 |
| CN1128137C true CN1128137C (en) | 2003-11-19 |
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| CN 01105570 Expired - Fee Related CN1128137C (en) | 2001-03-06 | 2001-03-06 | Indole compounds and its synthetic method |
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Granted publication date: 20031119 Termination date: 20110306 |