CN108727210A - A kind of substituted diphenylamine amine derivative and its synthetic method - Google Patents
A kind of substituted diphenylamine amine derivative and its synthetic method Download PDFInfo
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- CN108727210A CN108727210A CN201810639739.5A CN201810639739A CN108727210A CN 108727210 A CN108727210 A CN 108727210A CN 201810639739 A CN201810639739 A CN 201810639739A CN 108727210 A CN108727210 A CN 108727210A
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- substituted diphenylamine
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- alkynes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/46—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino or carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C229/50—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino or carboxyl groups bound to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups and carboxyl groups bound to carbon atoms being part of the same condensed ring system
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
- C07C227/08—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid by reaction of ammonia or amines with acids containing functional groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
- C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/08—One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention provides a kind of substituted diphenylamine amine derivative and its synthetic method, under heating condition, four alkynes are stopped into reaction in toluene solvant with 2,6- diisopropyls-N- (pyridine -2- methylene) aniline reaction, cooled to room temperature；Product purification is detached, i.e. substituted diphenylamine amine derivative.Compared with existing substituted diphenylamine, the present invention provides a series of synthetic methods of new substituted diphenylamine amine derivatives.Relative to common substituted diphenylamine, substituted diphenylamine prepared by the present invention, structure is more complicated various.Substance of the present invention may can also have wide application in medical industry, and preparation method provided by the invention is easy, efficient, and the reaction time is short, efficient.
Description
Technical field
The invention belongs to organic compound fields, are specifically related to a kind of substituted diphenylamine amine derivative and its synthetic method.
Background technology
Aniline is one of most important intermediate in dye industry, can be used in dye industry manufacture Acid Ink Blue G,
Acidic intermedium BS, acid light yellow, direct orange S, direct pink, indigo, disperse yellow brown, cationic pink fg and reactive brilliant red X-SB
Deng；Manufacture bronze red, bronze red g, pigment scarlet powder, the red, nigrosine of phenol cyanines etc. are useful in terms of organic pigment；In printing and dyeing industry
For dyestuff nigrosine；For producing many insecticides, nitrofen, propachlor etc. in pesticide industry；Aniline is rubber chemicals
Important source material, for manufacturing antioxidant A, antioxidant d, anti-aging agent, accelerating agent and CA etc.；Also it can be used as medical sulfa drug
Raw material, while being also the intermediate of production fragrance, plastics, varnish, film etc.；And it can be used as the stabilizer in explosive, in gasoline
Anti-knock agent and be used as solvent；It is other to be also used as manufacture hydroquinone, 2-phenylindone etc..Aniline is production pesticide
Important source material, can be used as fungicide sulfonat, Seedvax, insecticide Hostathion, herbicide alachlor, etc. intermediate.
Diphenylamines is mainly used for the anti-aging agent, fuel and medicine intermediate of synthetic rubber, antioxidant for lubricant oil and gunpowder
Stabilizer.The calibrating of nitrate, chlorate and other oxidizing substances.The catalytic determination of iridium.The photometering of nitrate.Oxygen
Change reduction indicator.Haploid breeding culture medium.Manufacture dyestuff.It is the stabilizer of nitrocellulose, explosive, guncotton.
Substituted diphenylamine amine antioxidants have preferable resist oxygen aging and the smelly aging of light, anti-bent rich cracking highly effective.Its
Synthetic method is generally formed by the contraposition alkylation reaction of diphenylamines and alkene hydrogen.In plastic film capicitor alkylated product pollution compared with
Gently.Its representative kind has anti-aging agent 405, antioxidant D FL etc..Increasingly increase with the demand of substituted diphenylamine amine derivative,
The synthetic method of diphenylamines is particularly important.
Invention content
The purpose of the present invention is to provide a kind of substituted diphenylamine amine derivative, easy, efficient, the reaction time is short, efficient.
Another object of the present invention is to provide a kind of synthetic methods of substituted diphenylamine amine derivative, and structure is more complicated, has
Wide application prospect.
A kind of substituted diphenylamine amine derivative provided by the invention, structural formula are:
Wherein E is CO2R, R are straight chained alkyl, branched alkyl or unsaturated alkyl；R1For hydrogen, halogen, straight chained alkyl, branch
Alkyl, ester group, alkoxy or its corresponding derivative.
Preferably, the substituted diphenylamine amine derivative, structural formula are:
A kind of synthetic method of substituted diphenylamine amine derivative provided by the invention, includes the following steps：
It is under heating condition, four alkynes are anti-with 2,6- diisopropyls-N- (pyridine -2- methylene) aniline in toluene solvant
It answers, cooled to room temperature, stops reaction；Product purification is detached, i.e. substituted diphenylamine amine derivative.
Further, refer under the heating condition：It is carried out under conditions of 95-100 DEG C；Reaction time 8h or more.
Further, mole of the molar ratio of four alkynes, 2,6- diisopropyls-N- (pyridine -2- methylene) aniline and toluene
Than being 1：1：28-66；
The four alkynes structural formulaR is straight chained alkyl, branched alkyl or unsaturated alkyl.
The purifies and separates are specially：Products therefrom is washed with water, ethyl acetate extraction, decompression is spin-dried for, and uses volume ratio
1:40 ethyl acetate：The column chromatography for separation of petroleum ether obtains white solid, the i.e. product of substituted diphenylamine amine derivative synthesis.
Column chromatography yield is about 77%.
Further, the preparation method of four alkynes, includes the following steps：
1) using sodium hydride as catalyst, malonate and propargyl bromide is added to ice-water bath in anhydrous acetonitrile, reacted, so
Purifies and separates afterwards obtain brown solid product, i.e. compound 1；
2) compound 1 prepared by step 1) is blended in Pd (PPh with phenylacetylene bromide or substituted phenylacetylene bromide3)2Cl2In the anhydrous and oxygen-free catalyst system and catalyzing of/CuI, alkali is made with triethylamine, using anhydrous acetonitrile as solvent, is stirred to react at room temperature, is purified
After separation, product as light yellow solid is obtained to get four alkynes of product.
Further, the molar ratio of sodium hydride in step 1), malonate, propargyl bromide and anhydrous acetonitrile is 4-5：1：
2.2-3.2：20-23；
Preferably, malonate described in step 1) is selected from diethyl malonate.
In step 1) under the conditions of ice-water bath reaction temperature at 0-5 DEG C；Reaction time was at 5 hours or more；
Purifies and separates described in step 1) are specially：Product adds water washing, is extracted with ethyl acetate, and decompression is spin-dried for, and obtains
Brown solid product, i.e. compound 1.
The structural formula of compound 1 described in step 1)R is straight chained alkyl, branched alkyl or not
Saturated hydrocarbyl.
Compound 1 described in step 2) and phenylacetylene bromide or substituted phenylacetylene bromide, Pd (PPh3)2Cl2/ CuI, three
The amount ratio of the substance of ethamine and anhydrous acetonitrile is 1:2.2-3.2：0.03-0.04：4-5：30-45；
Step 2) is described to be stirred to react, and the reaction time was at 10 hours or more；The substituted phenylacetylene base bromine substituent is
Halogen, straight chained alkyl, branched alkyl, ester group, alkoxy or its corresponding derivative；
Purifies and separates described in step 2) are specially：Product is washed with water, and is extracted with ethyl acetate, and decompression is spin-dried for, and uses body
Product is than being 1:60 ethyl acetate：Petroleum ether column chromatography for separation obtains product as light yellow solid, i.e. four alkynes of product.
Pd (PPh described in step 2)3)2Cl2In the anhydrous and oxygen-free catalyst system and catalyzing of/CuI, molar ratio Pd (PPh3)2Cl2:CuI
=3:1.
Four alkynes structural formula described in step 2)R is straight chained alkyl, branched alkyl or insatiable hunger
And alkyl.
Compared with existing substituted diphenylamine, the present invention provides a series of synthesis sides of new substituted diphenylamine amine derivatives
Method.Relative to common substituted diphenylamine, substituted diphenylamine prepared by the present invention, structure is more complicated various.Substance of the present invention
May can also have wide application in medical industry, and preparation method provided by the invention is easy, efficient, the reaction time
It is short, it is efficient.
Description of the drawings
Fig. 1 is the structural formula of substituted diphenylamine amine derivative of the present invention；
Fig. 2 is the structural formula of substituted diphenylamine amine derivative prepared by embodiment 1；
Fig. 3 is the nuclear magnetic resonance spectroscopy of substituted diphenylamine amine derivative prepared by embodiment 1；
Fig. 4 is the carbon-13 nmr spectra of substituted diphenylamine amine derivative prepared by embodiment 1；
Fig. 5 is 1 preparation process reaction equation of embodiment；
Fig. 6 is the reaction mechanism of embodiment 1.
Specific implementation mode
Embodiment 1
A kind of substituted diphenylamine amine derivative, structural formula are：
The synthetic method of above-mentioned substituted diphenylamine amine derivative, includes the following steps：
(1) using 830mmol sodium hydrides as catalyst, 200mmol diethyl malonates and 440mmol propargyl bromides are added
To ice-water bath in 210mL anhydrous acetonitriles, it is stirred to react 8 hours, product adds water washing, is extracted with ethyl acetate, and decompression is spin-dried for, and obtains
To yellow-brown solid product, i.e. compound 1；
(2) 80mmol compounds 1 and 200mmol phenylacetylene bromides are blended in Pd (PPh3)2Cl2The anhydrous and oxygen-free of/CuI
In catalyst system and catalyzing (2.56mmol/0.85mmol), molar ratio Pd (PPh3)2Cl2:CuI=3:1, alkali is made with 336mmol triethylamines,
It using 150mL anhydrous acetonitriles as solvent, is stirred to react at room temperature 12 hours, product is washed with water, and is extracted with ethyl acetate, decompression rotation
It is dry, it is 1 with volume ratio:60 ethyl acetate：Petroleum ether column chromatography for separation obtains product as light yellow solid, i.e. four alkynes of product.
(3) under conditions of 100 DEG C, tetra- alkynes of 1mmol prepared by step (2) is in 5mL toluene solvants and 1mmol 2,6-
Diisopropyl-N- (pyridine -2- methylene) aniline reaction 8 hours, obtains compound 3, the i.e. crude product of substituted diphenylamine amine derivative；
The crude product with water of the substituted diphenylamine amine derivative of preparation is washed, ethyl acetate extraction, decompression is spin-dried for, with volume ratio acetic acid second
Ester：Petroleum ether=1:40 column chromatography for separation, obtain white solid product, i.e. substituted diphenylamine amine derivative, and column chromatography yield is about
77%.
White solid product structure passes through；1H NMR；13C NMR are measured.
White solid product:
1H NMR(500 MHz,CDCl3)δ7.47-7.19(m,13H),6.04(s,1H)5.03(s,1H),4.32-4.27
(q,4H),3.89(s,2H),3.63(s,2H),3.19-3.16(m,2H)1.34-1.31(t,6H),1.19-1.14(m,12H)。
13C NMR(125 MHz,CDCl3) δ 172.08,147.77,145.25,144.77,144.22,141.39,
134.56,131.39,127.76,,124.68,122.81,117.40,111.32,107.36,96.43,93.96,88.55,
62.98,60.07,41.82,38.25,28.75,24.93,23.58,14.48。
Claims (10)
1. a kind of substituted diphenylamine amine derivative, which is characterized in that the substituted diphenylamine derivant structure formula is:
Wherein E is CO2R, R are straight chained alkyl, branched alkyl or unsaturated alkyl；R1For hydrogen, halogen, straight chained alkyl, branched alkane
Base, ester group, alkoxy or its corresponding derivative.
2. substituted diphenylamine amine derivative according to claim 1, which is characterized in that the substituted diphenylamine derivant structure
Formula is:
3. a kind of synthetic method of substituted diphenylamine amine derivative as claimed in claim 1 or 2, which is characterized in that the synthesis side
Method is：
Under heating condition, by four alkynes in toluene solvant with 2,6- diisopropyls-N- (pyridine -2- methylene) aniline reaction, from
It is so cooled to room temperature, stops reaction；Product purification is detached, i.e. substituted diphenylamine amine derivative.
4. synthetic method according to claim 3, which is characterized in that refer under the heating condition：95-100 DEG C of item
It is carried out under part；Reaction time 8h or more.
5. synthetic method according to claim 3, which is characterized in that four alkynes, 2,6- diisopropyls-N- (pyridine -2- methylenes
Base) molar ratio of molar ratio of aniline and toluene is 1：1：28-66.
6. the synthetic method according to claim 3 or 5, which is characterized in that the four alkynes structural formulaR is straight chained alkyl, branched alkyl or unsaturated alkyl.
7. the synthetic method according to claim 3 or 6, which is characterized in that the preparation method of four alkynes, including following step
Suddenly：
1) using sodium hydride as catalyst, malonate and propargyl bromide is added to ice-water bath in anhydrous acetonitrile, reacted, it is then pure
Change separation, obtains brown solid product, i.e. compound 1；
2) compound 1 prepared by step 1) is blended in Pd (PPh with phenylacetylene bromide or substituted phenylacetylene bromide3)2Cl2/
In the anhydrous and oxygen-free catalyst system and catalyzing of CuI, alkali is made with triethylamine, using anhydrous acetonitrile as solvent, is stirred to react at room temperature, purifies and separates
Afterwards, product as light yellow solid is obtained to get four alkynes of product.
8. synthetic method according to claim 7, which is characterized in that sodium hydride, malonate, propargyl bromide in step 1)
Molar ratio with anhydrous acetonitrile is 4-5：1：2.2-3.2：20-23.
9. synthetic method according to claim 7, which is characterized in that the structural formula of compound 1 described in step 1)R is straight chained alkyl, branched alkyl or unsaturated alkyl.
10. synthetic method according to claim 7, which is characterized in that compound 1 described in step 2) and phenylacetylene bromide
Or phenylacetylene bromide, the Pd (PPh of substitution3)2Cl2The amount ratio of the substance of/CuI, triethylamine and anhydrous acetonitrile is 1:2.2-3.2：
0.03-0.04：4-5：30-45；Step 2) is described to be stirred to react, and the reaction time was at 10 hours or more.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369508A (en) * | 2018-11-28 | 2019-02-22 | 安徽师范大学 | A kind of polysubstituted indole derivatives and preparation method thereof |
| CN110746305A (en) * | 2019-11-19 | 2020-02-04 | 安徽师范大学 | Polysubstituted dibenzoylbenzene derivative and synthetic method thereof |
| CN113045586A (en) * | 2021-03-26 | 2021-06-29 | 安徽师范大学 | Synthetic method of benzoxazole alkane derivative |
| CN114014779A (en) * | 2021-12-14 | 2022-02-08 | 安徽师范大学 | Bisaryl oxime ether compound and preparation method thereof |
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| CN105038904A (en) * | 2015-07-15 | 2015-11-11 | 河南大学 | High-temperature anti-oxidant for lubricating oil and preparation method of high-temperature anti-oxidant |
| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
-
2018
- 2018-06-20 CN CN201810639739.5A patent/CN108727210A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105732400A (en) * | 2014-12-12 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method for (para, para)-diisopropylphenyl diphenylamine product |
| CN105038904A (en) * | 2015-07-15 | 2015-11-11 | 河南大学 | High-temperature anti-oxidant for lubricating oil and preparation method of high-temperature anti-oxidant |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109369508A (en) * | 2018-11-28 | 2019-02-22 | 安徽师范大学 | A kind of polysubstituted indole derivatives and preparation method thereof |
| CN109369508B (en) * | 2018-11-28 | 2021-08-27 | 安徽师范大学 | Polysubstituted indole derivative and preparation method thereof |
| CN110746305A (en) * | 2019-11-19 | 2020-02-04 | 安徽师范大学 | Polysubstituted dibenzoylbenzene derivative and synthetic method thereof |
| CN113045586A (en) * | 2021-03-26 | 2021-06-29 | 安徽师范大学 | Synthetic method of benzoxazole alkane derivative |
| CN114014779A (en) * | 2021-12-14 | 2022-02-08 | 安徽师范大学 | Bisaryl oxime ether compound and preparation method thereof |
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