CN102766061B - Dehydroabietic acid base diarylamine compound, synthesis method and application thereof - Google Patents

Dehydroabietic acid base diarylamine compound, synthesis method and application thereof Download PDF

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CN102766061B
CN102766061B CN201210236120.2A CN201210236120A CN102766061B CN 102766061 B CN102766061 B CN 102766061B CN 201210236120 A CN201210236120 A CN 201210236120A CN 102766061 B CN102766061 B CN 102766061B
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dehydroabietic acid
acid base
amine compounds
amine
diaryl
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CN102766061A (en
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高宏
宋湛谦
商士斌
饶小平
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Institute of Chemical Industry of Forest Products of CAF
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Abstract

The invention discloses a dehydroabietic acid base diarylamine compound, a synthesis method and application thereof. The synthesis method comprises the following steps that in an organic solvent, by using 13-amine deisopropyl methyl dehydroabietat or a derivative thereof and a bromide as raw materials, palladium acetate as a catalyst, and an organic base and an organic phosphine as cocatalysts, a C-N coupling reaction is performed to obtain the dehydroabietic acid base diarylamine compound. The synthesis method provided by the invention has the advantages of short steps, easy obtaining of raw materials, low cost, easiness in operation, and obvious effects as a radical scavenger. When the concentration is 100 mum, the removing rate of f to diphenyl picryl hydrazinyl radical reaches to 70.8%.

Description

Dehydroabietic acid base diaryl-amine compounds and synthetic method and application
One. technical field
The present invention relates to a class diaryl-amine free-radical scavengers, particularly class dehydroabietic acid base diaryl-amine free-radical scavengers and a synthetic method thereof.
Two. background technology
Dehydroabietic acid, is a kind of diterpenes monobasic resinous acid with the luxuriant and rich with fragrance skeleton of three rings, mainly by nilox resin separating-purifying, is obtained.The feature of dehydroabietic acid maximum is the existence of aromatic ring in skeleton, it has not only improved the unstable of abietic acid type sylvic acid conjugated double bond, and can carry out multiple electrophilic substitution reaction as other fragrant cluster compound, introduce substituting group or active group, and then the physicochemical property of change dehydroabietic acid, establish the basis of further transforming on aromatic ring.At present, for the modification of dehydroabietic acid aromatic ring, mainly comprise Friedel-Crafts reaction, bromo, the electrophilic substitution reaction such as nitrated, and to the further series derivates such as synthetic nitrogen heterocyclic ring, arylamine and phenol, quinone of nitrated substitution product.
Main method based on the synthetic diaryl-amine compound of dehydroabietic acid phenyl ring is at present: 12 or 14 at dehydroabietic acid phenyl ring are carried out nitrated, reduction generation aniline, then generate serial dehydroabietic acid base diaryl-amine compound with acetic acid benzene bismuth or the plumbous N-aryl-response that occurs of acetic acid virtue, as compound and the performance of their removing free radical is tested, contrast is conventional free-radical scavengers 2,6-di-t-butyl 4-methylphenol (BHT) and N-sec.-propyl-N,-diphenyl-para-phenylene diamine (IPPD) [M.A.Esteves, N.Narender, J.Nat.Prod.64 (2001) 761-766.].
Although the N-aryl-response method yield of above-mentioned bibliographical information is high, the reaction times is short, the reagent preparation difficulties such as acetic acid benzene bismuth used or acetic acid virtue lead.Consider that again the steric effect of 13 sec.-propyls of dehydroabietic acid phenyl ring can affect the performance of diaryl-amine compound.
Three. summary of the invention
The object of the present invention is to provide a kind of dehydroabietic acid base diaryl-amine type free base scavenging agent and synthetic method thereof, by 13-amine-Tuo sec.-propyl methyl dehydroabietate and fragrant halogen compound, by C-N linked reaction, generate compound, have the performance of removing free radical, step of the present invention is brief, raw material is easy to get, cost is low, easy handling.
Technical scheme of the present invention is: a kind of dehydroabietic acid base diaryl-amine compounds, structural formula is
Figure BDA00001865347600021
wherein R is phenyl, with the aryl of supplied for electronic or electron-withdrawing substituent, or any one in quinoline, naphthalene, halogenated biphenyl, anthracene.
Described electron donating group is any one in methoxyl group, methyl, ethyl, sec.-propyl or phenyl; Described electron-withdrawing substituent is any one in nitro, cyano group, bromine, chlorine, iodine, trifluoromethyl.
The position of substitution of described-NH-R is 12,13 or 14.
The method of the dehydroabietic acid base diaryl-amine compounds that preparation is described, under nitrogen exists, with
Figure BDA00001865347600022
with fragrant halogen compound be starting raw material, palladium is that catalyzer, organic bases and organic phosphine are promotor, carries out C-N linked reaction and obtain product in organic solvent, is shown below:
Figure BDA00001865347600023
Described R is phenyl, with the aryl of supplied for electronic or electron-withdrawing substituent, or any one in quinoline, naphthalene, halogenated biphenyl, anthracene.
Described electron donating group is any one in methoxyl group, methyl, ethyl, sec.-propyl or phenyl; Described electron-withdrawing substituent is any one in nitro, cyano group, bromine, chlorine, iodine, trifluoromethyl or trifluoromethoxy.
RBr and 13-amine-Tuo sec.-propyl methyl dehydroabietate's molar ratio of material is 10:1 to 1:10.
Described organic solvent is any one or a few in DMF, tetrahydrofuran (THF), ethanol, chloroform, toluene, dimethylbenzene, o-Xylol or dioxane.
Described organic bases is a kind of in sodium alkoxide, potassium alcoholate, positive fourth lithium, isobutyl lithium, tertiary Ding Li; Described organic phosphine is any one in triphenylphosphine, triphenylphosphine oxide, tributylphosphine, tributylphosphine oxide, tri-butyl phosphine, diphenylphosphine.
Temperature of reaction is 50-200 ℃, and the reaction times is 1-24 hour.
Described dehydroabietic acid base diaryl-amine compounds is as the application of free-radical scavengers.
Beneficial effect:
1. cost is low.Raw material of the present invention is simple, be easy to get, and only uses the commercially available bromide that price is lower.
2. reaction conditions is gentle, simple to operate, is conducive to large-scale industrial production.
3. reactions steps is short, and technology difficulty is low.
4. product separation purifying is easy.For 13-amine-Tuo sec.-propyl methyl dehydroabietate, at 13, there is C-N linked reaction and generate diaryl-amine compound in the present invention.
5. the present invention discloses a class dehydroabietic acid base diaryl-amine free-radical scavengers, wherein remarkable with the effect of compound f.When concentration is 100 μ M, f reaches 70.8% to hexichol for the clearance rate of bitter taste diazanyl free radical (DPPH), substantially reaches the effect of 2,6-di-t-butyl 4-methylphenol (BHT); When concentration is 120 μ M, f is 80.9% to the clearance rate of DPPH, be better than BHT 77.6% and IPPD 72.3%.
Four, accompanying drawing explanation
Fig. 1 is the clearance rate graphic representation of diaryl-amine to free radical (DPPH).
Five. embodiment
Below by embodiment in detail the present invention is described in detail, yet the invention is not restricted to the following example.
The present invention 13-amine-Tuo sec.-propyl methyl dehydroabietate (1), 12-amine-Tuo sec.-propyl methyl dehydroabietate, 14-amine-Tuo sec.-propyl methyl dehydroabietate used be take dehydroabietic acid as raw material, through ester, nitrated, reduction reaction, according to document [M.A.Esteves, N.Narender, J.Nat.Prod.64 (2001) 761-766.] method synthetic.
Under nitrogen exists, take 13-amine-Tuo sec.-propyl methyl dehydroabietate and Fang halogen compound is starting raw material, and palladium is that catalyzer, organic bases and organic phosphine are promotor, in organic solvent, in flask with three necks,round bottom, reacts, and reaction formula is as follows:
Figure BDA00001865347600041
13-amine-Tuo sec.-propyl methyl dehydroabietate 1NH 2base the position of substitution can be 13 of phenyl ring, can be also 12,14; R in bromide 2 can be phenyl, can be also the aryl with supplied for electronic or electron-withdrawing substituent, can be also quinoline, naphthalene, halogenated biphenyl, anthracene etc.; Bromide 2 is 10:1 to 1:10 with 13-amine-Tuo sec.-propyl methyl dehydroabietate 1 molar ratio of material; The consumption of catalyzer, promotor is catalyst levels, and the mole dosage of palladium is the 0.01-1% of the less side of mole dosage in 13-amine-Tuo sec.-propyl methyl dehydroabietate and bromide; Organic bases mole dosage is the 0.1-10% of the less side of mole dosage in 13-amine-Tuo sec.-propyl methyl dehydroabietate and bromide; Organic phosphine mole dosage is the 0.1-20% of the less side of mole dosage in 13-amine-Tuo sec.-propyl methyl dehydroabietate and bromide; Temperature of reaction is 20-200 ℃; Reaction times is 1-24 hour.
On R in wherein said reactant bromide is methoxyl group, methyl, ethyl, sec.-propyl or phenyl etc. to electron substituent group; Electron-withdrawing substituent is nitro, cyano group, bromine, chlorine, iodine, trifluoromethyl or trifluoromethoxy etc.; Wherein said organic bases is sodium alkoxide, potassium alcoholate, positive fourth lithium, isobutyl lithium, tertiary Ding Li etc.; Wherein said organic phosphine is triphenylphosphine, triphenylphosphine oxide, tributylphosphine, tributylphosphine oxide, tri-butyl phosphine, diphenylphosphine etc.; Wherein said organic solvent, polar solvent is DMF, tetrahydrofuran (THF), ethanol, chloroform; Non-utmost point inertia solvent is any one in toluene, dimethylbenzene, o-Xylol or dioxane.
Embodiment 1
In 100ml there-necked flask, add 13-amine-Tuo sec.-propyl methyl dehydroabietate (0.1mmol), to bromobenzene (0.11mmol), sodium tert-butoxide (0.12mmol), tributylphosphine (0.01mmol) and palladium catalyzer, add successively in 5ml dimethylbenzene, stir, logical nitrogen, be warming up to 130 ℃, reaction 8h.Be chilled to room temperature, by extracted with diethyl ether, in organic phase, add anhydrous magnesium sulfate, place 4h, filter, remove dimethylbenzene under reduced pressure.Through column chromatography purification, eluent is sherwood oil and ethyl acetate (8 ﹕ 1), concentrated remove eluent and obtains product, and product is
Figure BDA00001865347600051
productive rate is 67%.
Embodiment 2
Bromide is para-bromoanisole, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600052
productive rate is 71%.
Embodiment 3
Bromide is para-bromo toluene, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600053
productive rate is 69%.
Embodiment 4
Bromide is 8-bromoquinoline, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600054
productive rate is 65%.
Embodiment 5
Bromide is α-bromonaphthalene, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600055
productive rate is 55%.
Embodiment 6
Bromide is Isosorbide-5-Nitrae-'-dibromobiphenyl, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600061
productive rate is 63%.
Embodiment 7
Bromide is p-Nitrobromobenzene, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600062
productive rate is 23%.
Embodiment 8
Bromide is 9-bromine anthracene, and other test method and condition are with embodiment 1, and product is
Figure BDA00001865347600063
productive rate is 21%.
Embodiment 9
Raw material aniline is 12-amine-Tuo sec.-propyl methyl dehydroabietate, and bromide is bromobenzene, and other test method and condition be with embodiment 1, and product is,
Figure BDA00001865347600064
productive rate is 73%.
Embodiment 10
Raw material aniline is 12-amine-Tuo sec.-propyl methyl dehydroabietate, and bromide is bromo quinoline, and other test method and condition be with embodiment 1, and product is,
productive rate is 68%.
Embodiment 11
Raw material aniline is 14-amine-Tuo sec.-propyl methyl dehydroabietate, and bromide is Isosorbide-5-Nitrae-'-dibromobiphenyl, and other test method and condition be with embodiment 1, and product is,
Figure BDA00001865347600072
productive rate is 43%.
Embodiment 12
Raw material aniline is 14-amine-Tuo sec.-propyl methyl dehydroabietate, and bromide is 9-bromine anthracene, and other test method and condition be with embodiment 1, and product is,
Figure BDA00001865347600073
productive rate is 22%.
Embodiment 13
Organic bases is potassium tert.-butoxide, and other test method and condition are with embodiment 1, and productive rate is 61%.
Embodiment 14
Organic phosphine is tri-butyl phosphine, and other test method and condition are with embodiment 1, and productive rate is 64%.
Embodiment 15
Organic solvent is o-Xylol, and other test method and condition are with embodiment 1, and productive rate is 67%.
Embodiment 16
Temperature of reaction is 100 ℃, and other test method and condition are with embodiment 1, and productive rate is 51%.
Embodiment 17
Reaction times is 3h, and other test method and condition are with embodiment 1, and productive rate is 54%.
Application Example
Really take DPPH free radical, [DPPH] ethanolic soln that configuration concentration is 0.04mM.Take ethanol as solvent, the sample solution of configuration different concns, samples liquid 2 μ l, adds [DPPH] ethanolic soln of 198 μ l0.04mM, make sample (a, b, c, d, e, f, g) final concentration be respectively 0,10,20,40,60,80,100,120 μ M, with solvent, make blank.After mixing, 30 ° of C effect 30-60min, with the full wave length detector of Tecan SafireII, at 515nm wavelength place, measure it at the absorbance of different time.According to the relation curve of the mass concentration of [DPPH] and absorbancy, can by add free-radical scavengers rear side absorbancy be scaled the mass concentration of [DPPH], thereby calculate the DPPH residual rate [DPPH] adding after free-radical scavengers rEM, its calculation formula is as follows:
[DPPH] REM=[DPPH]T/[DPPH] t＝0×100％
Wherein:
[DPPH] is the quality volume fraction in a certain moment [DPPH] in free radical scavenging process, [DPPH] t=0original quality volume fraction for [DPPH].
Adopt contrast for conventional free-radical scavengers: 2,6-di-t-butyl 4-methylphenol (BHT) and N-sec.-propyl-N '-diphenyl-para-phenylene diamine (IPPD).
By Fig. 1, found out, when concentration is 100 μ M, f reaches 70.8% to hexichol for the clearance rate of bitter taste diazanyl free radical (DPPH), substantially reaches the effect of 2,6-di-t-butyl 4-methylphenol (BHT); When concentration is 120 μ M, f is 80.9% to the clearance rate of DPPH, is better than BHT and IPPD, and both are respectively 77.6% and 72.3% afterwards.The free radical scavenging activity of compound a and e is lower, is only 20% left and right.

Claims (8)

1. a dehydroabietic acid base diaryl-amine compounds, is characterized in that, structural formula is
Figure FDA0000458791840000011
or or
Figure FDA0000458791840000013
wherein R is any one in quinoline, naphthalene, halogenated biphenyl, anthracene.3
2. dehydroabietic acid base diaryl-amine compounds as claimed in claim 1, is characterized in that, the position of substitution of described-NH-R is 12,13 or 14.
3. the method for the arbitrary described dehydroabietic acid base diaryl-amine compounds of preparation claim 1 or 2, is characterized in that, under nitrogen exists, with
Figure FDA0000458791840000014
with fragrant halogen compound be starting raw material, palladium is that catalyzer, organic bases and organic phosphine are promotor, carries out C-N linked reaction and obtain product in organic solvent, is shown below:
Figure FDA0000458791840000015
Described R is any one in quinoline, naphthalene, halogenated biphenyl, anthracene.
4. the method for preparing dehydroabietic acid base diaryl-amine compounds as claimed in claim 3, is characterized in that, RBr and 13-amine-Tuo sec.-propyl methyl dehydroabietate's molar ratio of material is 10:1 to 1:10.
5. the method for preparing dehydroabietic acid base diaryl-amine compounds as claimed in claim 3, it is characterized in that, described organic solvent is any one or a few in DMF, tetrahydrofuran (THF), ethanol, chloroform, toluene, o-Xylol or dioxane.
6. the method for preparing dehydroabietic acid base diaryl-amine compounds as claimed in claim 3, is characterized in that, described organic bases is a kind of in sodium alkoxide, potassium alcoholate, positive fourth lithium, isobutyl lithium, tertiary Ding Li; Described organic phosphine is any one in triphenylphosphine, triphenylphosphine oxide, tributylphosphine, tributylphosphine oxide, tri-butyl phosphine, diphenylphosphine.
7. the method for preparing dehydroabietic acid base diaryl-amine compounds as described in as arbitrary in claim 3, is characterized in that, temperature of reaction is 50-200 ℃, and the reaction times is 1-24 hour.
8. dehydroabietic acid base diaryl-amine compounds claimed in claim 1 is as the application of free-radical scavengers.
CN201210236120.2A 2012-07-09 2012-07-09 Dehydroabietic acid base diarylamine compound, synthesis method and application thereof Active CN102766061B (en)

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CN102976964B (en) * 2012-11-30 2015-11-11 中国林业科学研究院林产化学工业研究所 Dehydroabietic acid triarylamine compounds and its preparation method and application
CN103073444B (en) * 2013-01-28 2015-04-01 中国林业科学研究院林产化学工业研究所 Application of dehydroabietic acid based arylamine compound as hole transport material
CN103215033B (en) * 2013-05-09 2015-10-28 中国林业科学研究院林产化学工业研究所 Dehydroabietic acid diaryl-amine compound is as the application of fluorescent probe
CN104535546B (en) * 2014-11-10 2017-02-15 中国林业科学研究院林产化学工业研究所 Application of dehydroabietic acid-based arylamine compounds as metal ion fluorescent probes
CN111138389B (en) * 2019-10-21 2023-02-03 中国林业科学研究院林产化学工业研究所 Dehydroabietic acid triarylamine D-pi-A type compound with furan derivative as pi bridge and synthesis method thereof

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