CN102911078A - Synthetic method of dehydroabietylamine aldehydes spice Schiff base - Google Patents
Synthetic method of dehydroabietylamine aldehydes spice Schiff base Download PDFInfo
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- CN102911078A CN102911078A CN2012103952657A CN201210395265A CN102911078A CN 102911078 A CN102911078 A CN 102911078A CN 2012103952657 A CN2012103952657 A CN 2012103952657A CN 201210395265 A CN201210395265 A CN 201210395265A CN 102911078 A CN102911078 A CN 102911078A
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- dehydroabietylamine
- aldehyde
- schiff bases
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Abstract
The invention relates to a synthetic method of dehydroabietylamine aldehydes spice Schiff base. Firstly dehydroabietylamine is extracted from disproportionated rosin amine, then the dehydroabietylamine is taken as a raw material, and a target product is synthesized by virtue of a condensation reaction with aldehydes spice. According to the synthetic method provided by the invention, an ultraviolet ray absorption characteristic of a benzene ring in the dehydroabietylamine is combined with a spice characteristic of aldehydes spice which is extracted or converted from natural advantageous resource, an experimental basis is provided for application of the target product serving as an ultraviolet light absorber in sun care preparations, and a new approach is provided for deep development and utilization of dehydroabietylamine.
Description
Technical field
The invention belongs to chemical synthesis process field, specifically a kind of synthetic method of dehydroabietylamine aldehyde perfume schiff bases.
Background technology
Schiff bases is primarily referred to as the organic compound of the imines that a class contains carbon-to-nitrogen double bon or azomethine characteristic group (- C=N-), its core group-C=N- cause it is chemical with it is biologically significant.Because the N atoms on-C=N- have lone pair electrons, so it is the part of a class function admirable, schiff bases has very big flexibility in synthesis, and various functions group can be introduced in core group-C=N- left and right, make its derivatization, so that application of the schiff bases in many fields above shows unique characteristics.
Rosin is obtained by the endocrine resin in pine resin road through separated, is a kind of natural reproducible resource enriched very much of China.Rosin and its derivative are widely used in a variety of industries.Chemical modification is carried out to the functional group of rosin, the various derivatives with new function is synthesized, is one of chemistry of forest product and the study hotspot of Synthetic Organic Chemistry.The rosin of current China is mainly exported in the form of raw material, and deep processing and utilization rate is not high so that the economic benefit of itself is not fully played, so, by the modification to rosin, constantly carry out new technology, new product developmental research it is very necessary.Dehydroabietylamine can be obtained by disproportionated rosin amine separating-purifying, be a kind of optically active amines of the luxuriant and rich with fragrance structure of three ring, by carrying out chemical modification to the amino on dehydroabietylamine skeleton, can be obtained the functional form compound of different performance.
Up to the present dehydroabietylamine aldehyde perfume Schiff Base of the present invention at home and abroad having no report.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of dehydroabietylamine aldehyde perfume schiff bases.
The present invention is adopted the following technical scheme that：A kind of dehydroabietylamine aldehyde perfume schiff bases, general structure is as follows：
Wherein R is any one in Chinese cassia tree aldehyde radical, anise aldehyde radical, vanilla aldehyde radical.
A kind of method for preparing described dehydroabietylamine aldehyde perfume schiff bases, comprises the following steps：
(1) preparation of dehydroabietylamine
30g disproportionated rosin amines and the ethanol of 50ml 95%, stirring and dissolving are added in 500ml round-bottomed flasks.50ml 23.2g p-methyl benzenesulfonic acid ethanol solution is slowly added dropwise, completion of dropping is to slowly warm up to 75 DEG C of backflow 4h, terminates cooling and standings 2h after reaction.Suction filtration, filter cake is washed repeatedly with 95% ethanol.By 95% ethyl alcohol recrystallization of filter cake, 40 DEG C are dried in vacuum overnight, and obtain white solid 13.8g, i.e. dehydroabietylamine tosilate.
100ml distilled water, 150ml toluene, 1.5g NaOH and dried dehydroabietylamine tosilate 13.8g, 85 DEG C of stirring reaction 5h are added in 500ml round-bottomed flasks.Cooling and standings are layered, and are collected upper toluene layer, are repeatedly washed with distilled water, until it is in alkalescent.Collected organic layer, anhydrous MgSO4It is dried overnight.Solvent is evaporated off, pale yellow viscous liquid is obtained.A small amount of ether is added after cooling, dehydroabietylamine white solid is obtained after ether volatilizees.
(2) dehydroabietylamine aldehyde perfume schiff bases is synthesized
17.5mmol aldehyde perfumes, 20ml absolute ethyl alcohols are added in 100ml round-bottomed flasks, magnetic agitation is uniform, and the 17.5mmol dehydrogenation fir abietyl amines for being dissolved in 20ml absolute ethyl alcohols, 0.5h completion of dropping are slowly added dropwise at ambient temperature, it is to slowly warm up to 75 DEG C of backflow 3h, TLC tracking extent of reactions[91].Stop after reaction, be cooled to room temperature, filtering reacting liquid, precipitation is recrystallized with absolute ethyl alcohol, vacuum drying obtains dehydroabietylamine aldehyde perfume schiff bases.
Wherein described aldehyde perfume is any one of cinnamic acid, anisic aldehyde and vanillic aldehyde.
Beneficial effects of the present invention：
The present invention is using renewable resource rosin derivative ----dehydroabietylamine and can as obtained by natural product extraction or conversion aldehyde perfume as raw material, the fragrance characteristics of spices by the ultraviolet radiation absorption feature of phenyl ring in dehydroabietylamine with being obtained from inherent advantage Resource Access or conversion are combined, for using target product, as ultra-violet absorber, applying in sun care preparations provides experimental basis, so that the deep development and utilization for dehydroabietylamine provide new approach.
Brief description of the drawings
Fig. 1 is target compound a of the present invention IR spectrograms.
Fig. 2 is target compound a of the present invention1H NMR spectras.
Fig. 3 is target compound a of the present invention13C NMR spectras.
Fig. 4 is target compound a of the present invention MS spectrograms.
Fig. 5 is target compound b of the present invention IR spectrograms.
Fig. 6 is target compound b of the present invention1H NMR spectras.
Fig. 7 is target compound b of the present invention13C NMR spectras.
Fig. 8 is target compound b of the present invention MS spectrograms.
Fig. 9 is target compound c of the present invention IR spectrograms.
Figure 10 is target compound c of the present invention1H NMR spectras.
Figure 11 is target compound c of the present invention13C NMR spectras.
Figure 12 is target compound c of the present invention MS spectrograms.
Embodiment
Technical scheme is described further below by way of specific embodiment, embodiment described below is to citing of the invention, rather than limitation of the invention.
It is prepared by compound a：
17.5mmol cinnamic acids, 20ml absolute ethyl alcohols are added in 100ml round-bottomed flasks, magnetic agitation is uniform, and the 17.5mmol dehydrogenation fir abietyl amines for being dissolved in 20ml absolute ethyl alcohols, 0.5h completion of dropping are slowly added dropwise at ambient temperature, it is to slowly warm up to 75 DEG C of backflow 3h, TLC tracking extent of reactions.Stop after reaction, be cooled to room temperature, filtering reacting liquid, precipitation is recrystallized with absolute ethyl alcohol, vacuum drying obtains compound a.Light yellow crystal, m.p.116-118 DEG C.IR(KBr,cm-1)ν:2929,2880 (C-H), 1635 (C=N), 1450,1495 (Ar-C=C), 983 (C=C), 822,747,690.Elementary analysis C29H37N, measured value (calculated value)/%:C 87.36(87.16),H 9.24(9.33),N 3.4(3.51).1H NMR(150MHz,CDCl3)δ/ppm：8.01(d,J=7.1Hz,1H,H-21),7.51(m,2H,H-25,29),7.39(m,2H,H-26,28),7.33(m,1H,H-12),7.21(d,J=8.2Hz,1H,H-27),7.01(d,J=8.1Hz,1H,H-11),6.95(m,2H,H-22,23),6.90(d,J=7.4Hz,1H,H-14),3.36(m,2H,H-18),2.86(m,3H,H-7,H-15),2.30(m,1H,He-1),1.76(m,1H,H-5),1.69(m,5H,H-2,3,He-6),1.46(m,2H,Ha-1,Ha-6),1.25(m,9H,H-16,17,20),1.04(m,3H,H-19).13C NMR(150MHz,CDCl3)δ/ppm：162.92(C-21),147.66(C-13),145.55(C-9),141.32(C-8),136.05(C-12),135.04(C-24),129.12(C-27),128.92(C-22),128.65(C-23),127.34(C-25,29),126.97(C-26,28),124.48(C-14),123.93(C-11),73.89(C-18),45.56(C-4),38.59(C-5),38.25(C-7),37.70(C-1),36.84(C-10),33.57(C-3),30.42(C-15),25.63(C-20),24.11(C-16,17),19.65(C-6),19.04(C-2),18.84(C-19).UV(EtOH)λmax/nm(lgε):336(4.54)。ESI-MS m/z:400.3([M+H]+)。
Embodiment 2
Compound b preparation：
17.5mmol anisic aldehydes, 20ml absolute ethyl alcohols are added in 100ml round-bottomed flasks, magnetic agitation is uniform, and the 17.5mmol dehydrogenation fir abietyl amines for being dissolved in 20ml absolute ethyl alcohols, 0.5h completion of dropping are slowly added dropwise at ambient temperature, it is to slowly warm up to 75 DEG C of backflow 3h, TLC tracking extent of reactions.Stop after reaction, be cooled to room temperature, filtering reacting liquid, precipitation is recrystallized with absolute ethyl alcohol, vacuum drying obtains compound b.White needle-like crystals, m.p.106-108 DEG C.IR(KB r,cm-1)ν:2929,2890 (C-H), 1646 (C=N), 1600,1511 (Ar-C=C), 1251 (C-O), 828.Elementary analysis C28H37NO, measured value (calculated value)/%:C83.40(83.33),H 9.18(9.24),N 3.6(3.47),O 3.82(3.96).1H NMR(150MHz,CDCl3)δ/ppm：8.15(d,J=9.2Hz,1H,H-21),7.67-7.63(m,2H,H-24,26),7.18(d,J=8.2Hz,1H,H-12),6.98(m,J=8.1,1.7Hz,1H,H-11),6.94-6.88(m,2H,H-23,27),6.87(s,1H,H-14),3.84(m,J=9.4Hz,3H,H-28),3.50-3.32(m,2H,H-18),2.90-2.76(m,3H,H-7,H-15),2.26(m,J=12.5Hz,1H,He-1),1.96-1.88(m,1H,H-5),1.76-1.61(m,5H,H-2,3,He-6),1.46-1.36(m,2H,Ha-1,Ha-6),1.23-1.02(m,9H,H-16,17,20),0.99(s,3H,H-19).13C NMR(150MHz,CDCl3)δ/ppm：161.56(C-21),160.09(C-25),147.70(C-13),145.46(C-9),135.17(C-8),129.74(C-24,26),129.68(C-23,27),126.99(C-14),124.56(C-12),123.91(C-11),114.04(C-22),73.43(C-18),55.48(C-28),45.91(C-4),38.62(C-5),38.26(C-7),37.80(C-1),36.82(C-10),33.55(C-3),30.68(C-15),25.80(C-20),24.12(C-16,17),19.72(C-6),19.09(C-2),18.97(C-19).UV(EtOH)λmax/nm(lgε):303(4.79)。ESI-MS m/z:404.3([M+H]+)。
Compound c preparation：
17.5mmol vanillic aldehydes, 20ml absolute ethyl alcohols are added in 100ml round-bottomed flasks, magnetic agitation is uniform, and the 17.5mmol dehydrogenation fir abietyl amines for being dissolved in 20ml absolute ethyl alcohols, 0.5h completion of dropping are slowly added dropwise at ambient temperature, it is to slowly warm up to 75 DEG C of backflow 3h, TLC tracking extent of reactions.Stop after reaction, be cooled to room temperature, filtering reacting liquid, precipitation is recrystallized with absolute ethyl alcohol, vacuum drying obtains compound c.Pale yellow powder, m.p.146-148 DEG C.IR(KBr,cm-1)ν:3275 (OH), 2957,2897 (C-H), 1646 (C=N), 1594,1462 (Ar-C=C), 1283 (C-O), 822,738.Elementary analysis C28H37NO2, measured value (calculated value)/%:C 80.40(80.15),H 9.02(8.89),N 3.4(3.34),O 7.42(7.63).1HNMR(150MHz,CDCl3)δ/ppm：8.11(s,1H,H-21),7.38(s,1H,H-26),7.18(d,J=8.2Hz,1H,H-12),7.12-7.06(m,1H,H-23),6.98(d,J=8.1Hz,1H,H-11),6.92(t,J=6.1Hz,1H,H-27),6.86(s,1H,H-14),3.94(d,J=14.4Hz,3H,H-28),3.42(m,2H,H-18),2.91-2.72(m,3H,H-7,15),2.26(d,J=12.7Hz,1H,He-1),1.92(m,1H,H-5),1.84-1.68(m,5H,H-2,3,He-6),1.48-1.34(m,2H,Ha-1,Ha-6),1.26-1.18(m,9H,H-16,17,20),1.04(s,3H,H-19).13C NMR(150MHz,CDCl3)δ/ppm：160.54(C-21),148.16(C-25),147.69(C-13),146.99(C-24),145.52(C-9),135.14(C-12),129.49(C-8),126.97(C-27),124.56(C-14),123.92(C-11),123.70(C-22),114.12(C-26),108.63(C-23),73.49(C-18),56.13(C-28),45.98(C-4),38.61(C-5),38.30(C-7),37.80(C-1),36.85(C-10),33.55(C-3),30.64(C-15),25.79(C-20),24.11(C-16,17),19.66(C-6),19.07(C-2),18.97(C-19).UV(EtOH)λmax/nm(lgε):304(4.49)。ESI-MS m/z:420.3([M+H]+)。
Claims (5)
1. a kind of dehydroabietylamine aldehyde perfume schiff bases, it is characterised in that the structural formula of the compound is：
Wherein R is any one in Chinese cassia tree aldehyde radical, anise aldehyde radical, vanilla aldehyde radical.
2. preparing the method for the dehydroabietylamine aldehyde perfume schiff bases described in claim 1, include the isolation and purification of dehydroabietylamine, it is characterised in that react as the following formula：
3. the method as claimed in claim 2 for preparing dehydroabietylamine aldehyde perfume schiff bases, it is characterised in that：Described aldehyde perfume is any one in cinnamic acid, anisic aldehyde, vanillic aldehyde.
4. the method as claimed in claim 2 for preparing dehydroabietylamine aldehyde perfume schiff bases, it is characterised in that this method is also comprised the steps of：
It is 1 by the mol ratio of dehydroabietylamine and aldehyde perfume：1 feeds intake, 17.5mmol aldehyde perfumes, 20ml absolute ethyl alcohols are added in 100ml round-bottomed flasks, magnetic agitation is uniform, and the 17.5mmol dehydrogenation fir abietyl amines for being dissolved in 20ml absolute ethyl alcohols are slowly added dropwise at ambient temperature, 0.5h completion of dropping, 75 DEG C of backflow 3h, TLC tracking extent of reactions are to slowly warm up to, are stopped after reaction, it is cooled to room temperature, filtering reacting liquid, precipitation is recrystallized with absolute ethyl alcohol, and vacuum drying obtains dehydroabietylamine aldehyde perfume schiff bases.
5. the dehydroabietylamine aldehyde perfume schiff bases described in claim 1 in sun care preparations as ultra-violet absorber purposes.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922961A (en) * | 2014-04-09 | 2014-07-16 | 南京林业大学 | Alkyl diol diphenyl ether dehydroabietylamine bis-Schiff base compound and synthetic method thereof |
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2012
- 2012-10-17 CN CN2012103952657A patent/CN102911078A/en active Pending
Non-Patent Citations (4)
| Title |
|---|
| 《Heteroatom Chemistry》 20081231 Xiaoping Rao et al. Synthesis and Antitumor Activity of Novel alpha-Aminophosphonates from Diterpenic Dehydroabietylamine 512-516 1-5 第19卷, 第5期 * |
| LING-YING LIN ET AL.: "N-Benzoyl-12-nitrodehydroabietylamine-7-one, a novel dehydroabietylamine derivative, induces apoptosis and inhibits proliferation in HepG2 cells", 《CHEMICO-BIOLOGICAL INTERACTIONS》 * |
| XIAOPING RAO ET AL.: "Synthesis and Antitumor Activity of Novel α-Aminophosphonates from Diterpenic Dehydroabietylamine", 《HETEROATOM CHEMISTRY》 * |
| 雷茜等: "两类脱氢松香胺Schiff碱类衍生物的合成及其离子识别性能", 《有机化学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922961A (en) * | 2014-04-09 | 2014-07-16 | 南京林业大学 | Alkyl diol diphenyl ether dehydroabietylamine bis-Schiff base compound and synthetic method thereof |
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Application publication date: 20130206 |