CN105175402B - The synthetic method of 2- substitution -4,6- Dithiophene -1,3,5- s-triazine compounds - Google Patents
The synthetic method of 2- substitution -4,6- Dithiophene -1,3,5- s-triazine compounds Download PDFInfo
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- CN105175402B CN105175402B CN201510556004.2A CN201510556004A CN105175402B CN 105175402 B CN105175402 B CN 105175402B CN 201510556004 A CN201510556004 A CN 201510556004A CN 105175402 B CN105175402 B CN 105175402B
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Abstract
The invention discloses one kind 2 to substitute 4,6 Dithiophenes 1,3, the synthetic method of 5 s-triazine compounds, this method is using palladium complex as catalyst, using acetonitrile and water as solvent, substitutes 4 by 2,6 dichloros 1,3,5 s-triazine compounds and thienyl boric acid are reacted in alkaline conditions can synthesize 2 substitution, 4,6 Dithiophene 1,3,5 s-triazine compounds.The present invention is easy to operate, and reaction is efficient, mild condition, and good substrate applicability, can be widely used for the preparation of 2 substitution, 4,6 Dithiophene, 1,3,5 s-triazine compound.
Description
Technical field
- 4,6- bis- chloro- 1 is substituted with 2- the present invention relates to one kind, 3,5- s-triazine compounds and thienyl boric acid are substrate,
Palladium complex synthesizes 2- substitution -4,6- Dithiophenes -1,3, the side of 5- s-triazine compounds in alkaline conditions as catalyst
Method.
Background technology
1,3,5- s-triazine compound has 1,3,5- s-triazines of a variety of physiological activity, especially thiophene substitution
Compound causes the concern of researcher recently, it has extensive use in Coordinative Chemistry, optical material, electrochemical material field
On the way.At present, 2- substitutes -4,6- Dithiophenes -1,3, and the synthetic method of 5- s-triazine compounds is seldom, and it is big to be broadly divided into following three
Class：
The first kind is to be cyclized cyano thiophene and guanidine carbonate to substitute -4,6- Dithiophenes -1,3,5- equal three to obtain 2-
Piperazine class compound.The method of cyano thiophene cyclisation is by Forsberg, JohnH. et al. first
(JournalofHeterocyclicChemistry,25(3),767-70；1988) it is applied to tri- thiophene -1,3 of synthesis 2,4,6-,
5- s-triazine, subsequent Kuefner-Muehl, Ulrike et al. (Ger.Offen., 19735800,25Feb1999) were in 1999
Cyano thiophene is invented and guanidine carbonate is cyclized to obtain 2- substitution -4,6- Dithiophene -1,3,5- s-triazine compounds
Method, but target product yield is extremely low, only 5%, the reason is that the easy trimerization of cyano thiophene generates 2,4,6- tri- substituted thiophene -1,
3,5- s-triazine.
Second class is using three polychlorostyrene piperazines as starting material, under the conditions of anhydrous and oxygen-free, is carried out with thiophene organometallic reagent
Reaction, so as to obtain 2- substitution -4,6- Dithiophenes -1,3,5- s-triazine compounds.2009, Leriche, Philippe etc.
People (TetrahedronLetters, 50 (40), 5673-5676；2009) first by 2- thiophene-tetra-n-butyl tin and Cyanuric Chloride
In reflux in toluene, 2,4,6- tri- substituted thiophenes -1,3,5- s-triazine are obtained.2010, Huang, Wei et al.
(FamingZhuanliShenqing, 101717396,02Jun2010) Grignard Reagent is incorporated into the method so that its acquisition
Develop rapidly.2011, An, Zhong-Fu et al. (Chemistry-AEuropeanJournal, 17 (39), 10871-
10878,S10871/1-S10871/14；2011) Grignard Reagent is successfully passed to obtain 2- bromothiophenes and Cyanuric Chloride reaction
2- substitutes -4,6- Dithiophenes -1,3,5- s-triazine compounds, but its target product yield is not still high, and reaction condition
It is required that it is harsh, it is complicated.
Three classes are that 2- is substituted -4,6- bis- chloro- 1, and 3,5- s-triazine compounds are reacted with thienyl boric acid, so that
The method for obtaining 2- substitution -4,6- Dithiophene -1,3,5- s-triazine compounds.2010, Imai, Akira et al.
Suzuki reactive applications are substituted two thiophenes of -4,6- by (U.S.Pat.Appl.Publ., 20100234595,16Sep2010) in 2-
Fen -1,3, among 5- s-triazine compounds, and have successfully been obtained the double thiophene -1,3 of 2- methoxyl groups -4,6-, 5- s-triazine.But
Its target product yield is not still high, and only 74%.
Therefore 2- substitution -4,6- Dithiophenes -1,3 of existing literature report, the synthesis side of 5- s-triazine compounds
Either the required condition of method is harsh, complicated, or substrate applicability is poor and yield is all relatively low.
The content of the invention
The technical problems to be solved by the invention are to overcome existing 2- substitutions -4,6- Dithiophene -1,3,5- s-triazines
Compounds process for production thereof there are the shortcomings that, there is provided it is a kind of it is easy to operate, reaction is gentle, efficiently synthesizes 2- substitute -4,6- Dithiophenes -
The method of 1,3,5- s-triazine compounds.
Technical solution is used by solving above-mentioned technical problem：It is catalyst using water and acetonitrile as solvent, palladium complex,
The chloro- 1,3,5- s-triazines compounds of -4,6- two, thienyl boric acid, alkali is substituted to be 1 in molar ratio the 2- shown in Formulas I:1.5~
3:2~4, reacted at 50~60 DEG C, obtain 2- substitution -4,6- Dithiophenes -1,3,5- s-triazine compounds；
R represents C in formula1~C2Any one in alkoxy, phenylol, naphthols base, diphenylamino, morpholinyl.
Above-mentioned thienyl boric acid is 2- thienyl boric acids or 3 thienylboronic acid.
Above-mentioned palladium complex is double Phenylphosphine palladium chlorides, its addition is 2- substitutions -4,6- bis- chloro- 1,3,5- equal three
The 3%~5% of piperazine class compound mole.
Above-mentioned alkali is sodium carbonate or potassium carbonate.
The present invention substitutes -4,6- bis- chloro- 1,3,5- s-triazines using acetonitrile and water as solvent, with palladium complex catalyst 2-
Compound synthesizes 2- substitution -4,6- Dithiophenes -1,3 with the reaction of thienyl boric acid, and 5- s-triazine compounds, have below beneficial to effect
Fruit：
1st, cosolvent water is nontoxic, and securely and reliably, the addition of water reduces the use of organic solvent, meets Green Chemistry
It is required that.
2nd, for than the poly- method of substrate ring, target product is easy to get, and substitution number is easily controllable, efficiently.
3rd, for than organometallic reagent method, reaction carries out in atmosphere, easy to operate, mild condition, to equipment
It is required that it is low, it is securely and reliably, cost-effective.
4th, good substrate applicability.
Embodiment
With reference to embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these realities
Apply example.
Embodiment 1
To prepare following formula: compound 2- methoxyl groups -4,6- bis- (2- thienyls) -1, exemplified by 3,5- s-triazine, it is raw materials used and
Its preparation method is as follows：
By two chloro- 1,3,5- s-triazine of 0.1780g (1.0mmol) 2- methoxyl groups -4,6-, 0.3199g (2.5mmol) 2- thiophenes
The double Phenylphosphine palladium chlorides of fen boric acid, 0.0281g (0.04mmol) are added in 5mL acetonitriles, by 0.1590g sodium carbonate
(3.0mmol) is dissolved in 2mL water, and adds reaction system, when 60 DEG C of reactions 1 are small, is extracted with ethyl acetate, with petroleum ether and
The volume ratio of ethyl acetate is 40:1~20:1 mixed liquor gradient elution, through column chromatography for separation product, obtains white solid 2-
Methoxyl group -4,6- bis- (2- thienyls) -1,3,5- s-triazine, its yield are 99%.Products therefrom is surpassed with BrukerAvance types
Lead Fourier digitizing nuclear magnetic resonance spectrometer to be characterized, characterize data is：1H NMR (400MHz, CDCl3)δ(ppm)：8.24
(s, 2H), 7.61 (s, 2H), 7.19 (s, 2H), 4.16 (s, 3H)；13C NMR (101MHz, CDCl3)δ(ppm)：170.11
168.40,140.01,131.45,130.82,127.36,53.99.
Embodiment 2
To prepare following formula: compound 2- phenylols -4,6- bis- (2- thienyls) -1, exemplified by 3,5- s-triazine, it is raw materials used and
Its preparation method is as follows：
In embodiment 1,2- methoxyl groups -4,6- bis- chloro- 1 used, equimolar 2- phenylol -4 of 3,5- s-triazine,
6- bis- chloro- 1,3,5- s-triazine are replaced, the reaction time extend to 2 it is small when, other steps are same as Example 1, and it is solid to obtain white
Body 2- phenylols -4,6- bis- (2- thienyls) -1,3,5- s-triazine, its yield are 80%.Products therefrom BrukerAvance
Type superconduction Fourier digitizing nuclear magnetic resonance spectrometer is characterized, and characterize data is：1H NMR (400MHz, CDCl3)δ(ppm)：
8.15 (s, 2H), 7.62 (s, 2H), 7.48 (s, 2H), 7.33 (s, 3H), 7.17 (s, 2H)；13C NMR (101MHz, CDCl3)δ
(ppm)：172.41,171.32,153.42,142.14,134.35,133.69,130.77,129.91,127.17,123.18.
Embodiment 3
To prepare following formula: compound 2- (1- naphthols base) -4,6- bis- (2- thienyls) -1, exemplified by 3,5- s-triazine, original used
Material and preparation method thereof is as follows：
In embodiment 1,2- methoxyl groups -4,6- bis- chloro- 1 used, 3,5- s-triazine equimolar 2- (1- naphthols
Base) -4,6- bis- chloro- 1,3,5- s-triazine replace, the reaction time extend to 2 it is small when, other steps are same as Example 1, obtain
White solid 2- (1- naphthols base) -4,6- bis- (2- thienyls) -1,3,5- s-triazine, its yield are 67%.Products therefrom is used
BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers are characterized, and characterize data is：1H NMR (400MHz,
CDCl3)δ(ppm)：8.06 (s, 2H), 8.02 (s, 1H), 7.94 (s, 1H), 7.84 (s, 1H), 7.52 (dd, J=21.6,
13.1Hz, 5H), 7.42 (s, 1H), 7.12 (s, 2H)；13CNMR (101MHz, CDCl3)δ(ppm)：170.02 148.04,
140.68,134.71,132.88,132.27,128.42,127.90,127.07,126.41,125.99,125.39,121.78,
118.08。
Embodiment 4
To prepare following formula: compound 2- morpholinyls -4,6- bis- (2- thienyls) -1, exemplified by 3,5- s-triazine, it is raw materials used and
Its preparation method is as follows：
In embodiment 1,2- methoxyl groups -4,6- bis- chloro- 1 used, equimolar 2- morpholinyl -4 of 3,5- s-triazine,
6- bis- chloro- 1,3,5- s-triazine are replaced, the reaction time extend to 2 it is small when, other steps are same as Example 1, and it is solid to obtain white
Body 2- morpholinyls -4,6- bis- (2- thienyls) -1,3,5- s-triazine, its yield are 83%.Products therefrom BrukerAvance
Type superconduction Fourier digitizing nuclear magnetic resonance spectrometer is characterized, and characterize data is：1H NMR (400MHz, CDCl3)δ(ppm)：
8.12 (s, 2H), 7.52 (s, 2H), 7.15 (s, 2H), 3.99 (s, 4H), 3.80 (s, 4H)；13C NMR (101MHz, CDCl3)δ
(ppm)：168.72,165.79,143.89,132.48,131.96,129.50,68.22,45.06.
Embodiment 5
To prepare following formula: compound 2- (N, N- hexichol amido) -4,6- bis- (2- thienyls) -1, exemplified by 3,5- s-triazine, institute
It is as follows with raw material and preparation method thereof：
In embodiment 1,2- methoxyl groups -4,6- bis- chloro- 1 used, 3,5- s-triazine equimolar 2- (N, N- hexichol
Amido) -4,6- bis- chloro- 1,3,5- s-triazine replace, the reaction time extend to 2 it is small when, other steps are same as Example 1, obtain
To white solid 2- (N, N- hexichol amido) -4,6- bis- (2- thienyls) -1,3,5- s-triazine, its yield is 70%.Gained produces
Thing is characterized with BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers, and characterize data is：1H NMR
(400MHz, CDCl3)δ(ppm)：7.97 (s, 2H), 7.50 (s, 2H), 7.42 (d, J=6.7Hz, 8H), 7.29 (s, 2H),
7.10 (s, 2H)；13C NMR (101MHz, CDCl3)δ(ppm)：168.98,144.55,143.63,132.95,132.31,
130.20,129.53,129.22,127.58.
Embodiment 6
To prepare following formula: compound 2- (N, N- hexichol amido) -4,6- bis- (2- thienyls) -1, exemplified by 3,5- s-triazine, institute
It is as follows with raw material and preparation method thereof：
In embodiment 5,2- thienyl boric acids used are replaced with equimolar 3 thienylboronic acid, other steps and embodiment 5
It is identical, white solid 2- (N, N- hexichol amido) -4,6- bis- (2- thienyls) -1,3,5- s-triazine are obtained, its yield is 68%.
Products therefrom is characterized with BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers, and characterize data is：1H
NMR (400MHz, CDCl3)δ(ppm)：8.29 (s, 2H), 7.74 (s, 2H), 7.42 (s, 8H), 7.30 (d, J=5.1Hz, 4H)
；13C NMR (101MHz, CDCl3)δ(ppm)：169.48,167.73,144.80,142.28,131.80,130.24,129.15,
127.54,127.24.
Embodiment 7
To prepare following formula: compound 2- morpholinyls -4,6- bis- (3- thienyls) -1, exemplified by 3,5- s-triazine, it is raw materials used and
Its preparation method is as follows：
In example 4,2- thienyl boric acids used are replaced with equimolar 3 thienylboronic acid, other steps and embodiment 4
It is identical, white solid 2- morpholinyls -4,6- bis- (3- thienyls) -1,3,5- s-triazine are obtained, its yield is 78%.Products therefrom
Characterized with BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers, characterize data is：1H NMR
(400MHz, CDCl3)δ(ppm)：8.43 (s, 2H), 7.91 (s, 2H), 7.36 (s, 2H), 4.00 (s, 4H), 3.79 (s, 4H)；13C NMR (101MHz, CDCl3)δ(ppm)：169.25,166.40,142.52,131.35,129.01,127.21,68.23,
45.05。
Embodiment 8
To prepare following formula: compound 2- phenylols -4,6- bis- (3- thienyls) -1, exemplified by 3,5- s-triazine, it is raw materials used and
Its preparation method is as follows：
In example 2,2- thienyl boric acids used are replaced with equimolar 3 thienylboronic acid, other steps and embodiment 2
It is identical, white solid 2- phenylols -4,6- bis- (3- thienyls) -1,3,5- s-triazine are obtained, its yield is 75%.Products therefrom
Characterized with BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers, characterize data is：1H NMR
(400MHz, CDCl3)δ(ppm)：8.46 (s, 2H), 7.89 (s, 2H), 7.46 (s, 2H), 7.37-7.29 (m, 5H)；13CNMR
(101MHz, CDCl3)δ(ppm)：172.96,171.83,153.56,141.06,133.29,130.82,129.07,127.75,
127.15,123.24.
Embodiment 9
To prepare following formula: compound 2- methoxyl groups -4,6- bis- (3- thienyls) -1, exemplified by 3,5- s-triazine, it is raw materials used and
Its preparation method is as follows：
In embodiment 1,2- thienyl boric acids used are replaced with equimolar 3 thienylboronic acid, other steps and embodiment 1
It is identical, white solid 2- methoxyl groups -4,6- bis- (3- thienyls) -1,3,5- s-triazine are obtained, its yield is 95%.Products therefrom
Characterized with BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers, characterize data is：1H NMR
(400MHz, CDCl3)δ(ppm)：8.57 (s, 2H), 8.01 (s, 2H), 7.41 (s, 2H), 4.18 (s, 3H)；13C NMR
(101MHz, CDCl3)δ(ppm)：173.06,171.41,141.33,132.80,129.05,127.65,56.34.
Example 10
To prepare following formula: compound 2- (1- naphthols base) -4,6- bis- (3- thienyls) -1, exemplified by 3,5- s-triazine, original used
Material and preparation method thereof is as follows：
In embodiment 3,2- thienyl boric acids used are replaced with equimolar 3 thienylboronic acid, other steps and embodiment 3
It is identical, obtain white solid 2- (1- naphthols base) -4,6- bis- (3- thienyls) -1,3,5- s-triazine, yield 65%.Gained produces
Thing is characterized with BrukerAvance type superconduction Fourier digitizing nuclear magnetic resonance spectrometers, and characterize data is：1H NMR
(400MHz, CDCl3)δ(ppm)：8.40 (s, 2H), 7.99 (s, 1H), 7.95 (s, 1H), 7.83 (d, J=4.6Hz, 3H),
7.55 (s, 1H), 7.53 (s, 1H), 7.47 (s, 1H), 7.42 (s, 1H), 7.33 (s, 2H)；13C NMR (101MHz, CDCl3)δ
(ppm)：172.14,170.56,148.19,139.61,134.75,131.87,127.96,127.64,127.14,126.48,
126.45,126.28,126.00,125.46,121.80,118.12.
Claims (1)
1. a kind of 2- substitutes -4,6- Dithiophenes -1,3, the synthetic method of 5- s-triazine compounds, it is characterised in that：With water and
Acetonitrile is solvent, palladium complex is catalyst, and the 2- shown in Formulas I substituted -4,6- bis- chloro- 1,3,5- s-triazine compounds,
Thienyl boric acid, alkali are 1 in molar ratio:1.5~3:2~4, reacted at 60 DEG C, obtain 2- substitution -4,6- Dithiophenes -1,3,5-
S-triazine compound；
R represents C in formula1~C2Any one in alkoxy, phenylol, naphthols base, diphenylamino, morpholinyl；
Above-mentioned thienyl boric acid is 2- thienyl boric acids or 3 thienylboronic acid；
Above-mentioned palladium complex is double Phenylphosphine palladium chlorides, its addition is that 2- substitutes -4,6- bis- chloro- 1,3,5- s-triazines
The 3%~5% of compound mole；
Above-mentioned alkali is sodium carbonate or potassium carbonate.
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