CN104529683B - The preparation method of 1-phenylpropene derivatives - Google Patents
The preparation method of 1-phenylpropene derivatives Download PDFInfo
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- CN104529683B CN104529683B CN201410842598.9A CN201410842598A CN104529683B CN 104529683 B CN104529683 B CN 104529683B CN 201410842598 A CN201410842598 A CN 201410842598A CN 104529683 B CN104529683 B CN 104529683B
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Abstract
The invention discloses the preparation method of a kind of 1 phenylpropene derivatives, the method with the halobenzene derivant rolled into a ball containing different substituents and propylene (gas) as raw material, with the palladium of trace as catalyst, utilize Hack reaction principle, by the most Olefination important intermediate 1 phenylpropene derivatives being synthesized in organic synthesis, pharmaceutical synthesis of halobenzene derivant.The present invention is raw materials used cheap and easily-available, and simply, easily operate, reaction condition is gentle for preparation process, and response speed is very fast, and 1 phenylpropene derivatives yield is higher, up to 68%～91%, has preferable application prospect.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, be specifically related to the preparation of a kind of 1-phenylpropene derivatives
Method.
Background technology
Phenylpropen compounds is the organic synthesis intermediate that a class is important, and hydro-reduction can occur
(Gaertner, D.Angew.Chem., Int.Ed.2014,53 (14), 3722-3726), oxidation (Morandi,
B.Angew.Chem., Int.Ed.2013,52 (10), 2944-2948), epoxidation (Nieto, N.Synlett
2008, (18), 2856-2858), C-C coupling (Xiang, J.；CN102126933A, 2011), parent
Electricity addition (Khazaei, A.Synth.Commun.2010,40 (19), 2954-2962), amination (Yamashita,
T.Tetrahedron Lett.1993,34 (32), 5131-4) etc. multiple reaction, close at organic synthesis, medicine
The aspects such as one-tenth all show important effect.
Industrially 2-phenylpropen (or referred to as α-methyl styrene) preparation technology it has been reported that as China
Patent of invention CN1764616A discloses in the presence of activated alumina, utilizes the dehydration of cumyl alcohol to enter
The methods such as row is industrially prepared.But the commercial synthesis side of 1-phenylpropen (or referred to as Beta-methyl styrene) derivant
Method has no report.The laboratory synthetic method of the most seen 1-phenylpropene derivatives mainly uses more special
Different reagent or catalyst could be prepared, as Mohammad reports under microwave radiation with palladium for catalysis
Agent catalysis pi-allyl three Potassium borofluoride and the halobenzene preparation method (US by Suzuki cross-coupling reaction
2012/0010298A)；Rakesh Kumar reports and utilizes under microwave-assisted with ionic liquid for catalyst benzyl
The dehydration preparation method of alcohol (Eur.J.Org.Chem.2008, (33), 5577)；Green, I.R.Trends
Report the bromination triphenyl ethyl phosphine being catalyzed with the titanium tetrachloride of macromolecule silicon materials support and substituted benzaldehyde
The preparation method (Org.Chem.2009,13,45-64) of isomerization reaction, the method needs-78 DEG C anti-
Answer condition.Because the above method needing the reaction condition of special, expensive reagent or harshness cause 1-phenyl
The preparation method of acryloyl derivative fails there is big breakthrough.
Summary of the invention
The technical problem to be solved is to overcome existing 1-phenylpropene derivatives preparation method to exist
Problem, it is provided that a kind of raw material is cheap and easily-available, simply, easily operate, reaction condition is gentle, reaction speed for preparation process
Degree is very fast, the preparation method that product 1-phenylpropene derivatives yield is higher.
Solve above-mentioned technical problem to be the technical scheme is that with N-Methyl pyrrolidone (NMP) as solvent,
Halobenzene derivant shown in formula I, palladium, triethylamine are joined in autoclave, are passed through propylene gas,
Pressure be 1～2MPa, temperature be at 90～120 DEG C react, wherein halobenzene derivant, propylene, palladium,
The mol ratio of triethylamine is 1: 3～8: 0.002～0.020: 0.5～2, and isolated and purified product obtains shown in formula II
1-phenylpropene derivatives, its reaction equation is as follows:
R in formula1、R2、R3Any in the most independent representative H, alkoxyl, hydroxyl, nitro, amino, cyano group
One, X represents Br or I.
Above-mentioned halobenzene derivant, propylene, palladium, the mol ratio preferably 1: 4 of triethylamine～6: 0.004～
0.005: 1～1.5, most preferably 1: 5: 0.004: 1.1.
The preparation method of above-mentioned 1-phenylpropene derivatives preferably pressure be 1.6MPa, temperature be 100～120
At DEG C react 1～8 hour, more preferably pressure be 1.6MPa, temperature be at 110 DEG C react 2～6 hours.
The present invention with the halobenzene derivant rolled into a ball containing different substituents and propylene (gas) as raw material, with trace
Palladium is catalyst, utilizes Hack reaction principle, and the most Olefination by halobenzene derivant is synthesized
1-phenylpropene derivatives.The present invention is raw materials used cheap and easily-available, preparation process simply, easily operate, reaction condition
Gentleness, response speed is very fast, and 1-phenylpropene derivatives yield is higher, up to 68%～91%, has preferably
Application prospect.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in more detail, but protection scope of the present invention is not limited only to these
Embodiment.
Embodiment 1
As a example by preparing the following 1-of structural formula (4-nitro) propenyl benzene, concrete preparation method is:
2.02g (10mmol) 4-bromo nitrobenzene, 0.008g it is sequentially added in 100mL autoclave
(0.04mmol) palladium, 1.11g (11mmol) triethylamine, 15mL N-Methyl pyrrolidone, room temperature
Stirring, to dissolving, after carrying out gas displacement by nitrogen, propylene gas successively, is passed through propylene gas to reaction under high pressure
In still, pressure is 1.6MPa, is warming up to 110 DEG C, isothermal reaction 2 hours.It is cooled to room temperature, adds 30mL
Distilled water, with dichloromethane extract (3 × 20mL), organic facies merge after successively with 1mol/L aqueous hydrochloric acid solution,
Distilled water, saturated aqueous common salt wash, be then dried through anhydrous magnesium sulfate, be concentrated in vacuo after column chromatography for separation (wash
De-agent is the mixed liquor that volume ratio is 1: 30 of dichloromethane and petroleum ether), obtain yellow needle-like crystals 1-(4-
Nitro) propenyl benzene, its yield is 87%, mp:89.3～90.7 DEG C, and structural characterization data are:1H NMR(300
MHz, CDCl3) δ: 8.14 (d, J=8.7Hz, 2H), 7.43 (d, J=8.7Hz, 2H), 6.45
(m, 2H), 1.98-1.90 (m, 3H)；13C NMR (101MHz, CDCl3) δ: 146.4,144.4,
131.3,129.4,126.2,123.9,18.7.
Embodiment 2
In embodiment 1, reaction temperature is 90 DEG C, and the response time extends to 6 hours, other steps and enforcement
Example 1 is identical, obtains 1-(4-nitro) propenyl benzene, and its yield is 63%.
Embodiment 3
In embodiment 1, reaction temperature is increased to 120 DEG C, and other steps are same as in Example 1, obtain 1-
(4-nitro) propenyl benzene, its yield is 80%.
Embodiment 4
In embodiment 1, palladium consumption changes 0.004g (0.02mmol) into, and it is little that the response time extends to 6
Time, other steps are same as in Example 1, obtain 1-(4-nitro) propenyl benzene, and its yield is 71%.
Embodiment 5
In embodiment 1, palladium consumption changes 0.01g (0.05mmol), other steps and embodiment 1 into
Identical, obtain 1-(4-nitro) propenyl benzene, its yield is 80.5%.
Embodiment 6
In embodiment 1, palladium consumption changes 0.02g (0.10mmol), other steps and embodiment 1 into
Identical, obtain 1-(4-nitro) propenyl benzene, its yield is 81%.
Embodiment 7
In embodiment 1,4-bromo nitrobenzene used is replaced with equimolar 4-iodonitrobenzene, and the response time contracts
Being as short as 1.5 hours, other steps are same as in Example 1, obtain 1-(4-nitro) propenyl benzene, and its yield is 91%.
Embodiment 8
As a example by preparing the following 1-of structural formula (2-nitro) propenyl benzene, concrete preparation method is:
In embodiment 1,4-bromo nitrobenzene used is replaced with equimolar 2-bromo nitrobenzene, and the response time prolongs
It is long that to 5 hours, other steps were same as in Example 1, obtain faint yellow solid 1-(2-nitro) propenyl benzene, its
Yield is 78%, and structural characterization data are:1H NMR (300MHz, CDCl3) δ: 7.84 (d, J=8.0Hz,
1H), 7.57-7.49 (m, 3H), 6.84 (d, J=15.4Hz, 1H), 6.24 (dq, J=15.4,
6.6Hz, 1H), 1.92 (d, J=6.6Hz, 3H)；13C NMR (75MHz, CDCl3) δ: 145.5,
133.3,132.2,129.4,127.8,126.6,126.1,124.5,17.9.
Embodiment 9
In embodiment 8,2-bromo nitrobenzene used is replaced with equimolar 2-iodonitrobenzene, and the response time contracts
Being as short as to 3 hours, other steps are the same as in Example 8, obtain faint yellow solid 1-(2-nitro) propenyl benzene,
Its yield is 75%.
Embodiment 10
As a example by preparing the following 1-of structural formula (3-nitro) propenyl benzene, concrete preparation method is:
In embodiment 1,4-bromo nitrobenzene used is replaced with equimolar 3-iodonitrobenzene, and the response time prolongs
It is long that to 6 hours, other steps were same as in Example 1, obtain faint yellow solid 1-(3-nitro) propenyl benzene, its
Yield is 68%, and structural characterization data are:1H NMR (300MHz, CDCl3) δ: 8.09-8.23 (m,
2H), 7.17-7.78 (m, 2H), 6.46 (d, J=11.7Hz, 1H), 5.95 (dq, J=11.7,
7.2Hz, 1H), 1.92 (d, J=7.2Hz, 3H)；13C NMR (75MHz, CDCl3) δ: 147.3,
141.2,132.1,129.6,129.1,126.0,122.2,17.9.
Embodiment 11
As a example by preparing the following 4-of structural formula (1-acrylic) methyl phenyl ethers anisole, concrete preparation method is:
In embodiment 1,4-bromo nitrobenzene used is replaced with equimolar 4-iodanisol, and the response time prolongs
It is long that to 5 hours, other steps were same as in Example 1, obtain white crystal 4-(1-acrylic) methyl phenyl ethers anisole, its
Yield is 88%, and structural characterization data are:1H NMR (400MHz, CDCl3) δ: 7.24 (d, J=8.7Hz,
2H), 6.81 (d, J=8.7Hz, 2H), 6.33 (d, J=14.6Hz, 1H), 6.07 (dq, J=14.6,
6.6Hz, 1H), 3.76 (s, 3H), 1.84 (d, J=6.6Hz, 3H)；13C NMR (101MHz,
CDCl3) δ: 158.6,142.6,130.4,126.9,123.4,113.9,55.2,18.4.
Embodiment 12
As a example by preparing the following 4-of structural formula (1-acrylic) phenol, concrete preparation method is:
In embodiment 1,4-bromo nitrobenzene used is replaced with equimolar 4-iodophenol, other steps and reality
Executing example 1 identical, obtain white plates crystal 4-(1-acrylic) phenol, its yield is 83%, structural characterization
Data are:1H NMR (400MHz, CDCl3) δ: 7.19 (d, J=8.6Hz, 2H), 6.75 (d, J
=8.6Hz, 2H), 6.32 (d, J=15.7Hz, 1H), 6.07 (dq, J=15.7,6.6Hz, 1H),
1.84 (d, J=6.6Hz, 3H)；13C NMR (101MHz, CDCl3) δ: 154.4,131.1,130.3,
127.1,123.6,115.4,18.4.
Embodiment 13
As a example by preparing the following 2-of structural formula (1-acrylic) phenol, concrete preparation method is:
In embodiment 1,4-bromo nitrobenzene used is replaced with equimolar 2-iodophenol, and the response time extends
To 6 hours, other steps were same as in Example 1, obtained colorless oil 2-(1-acrylic) phenol, its yield
Being 75%, structural characterization data are:1H NMR (300MHz, CDCl3) δ: 7.29 (dd, J=7.6,
1.3Hz, 1H), 7.07 (td, J=7.9,1.5Hz, 1H), 6.87 (t, J=7.4Hz, 1H), 6.76
(d, J=8.0Hz, 1H), 6.58 (d, J=15.8Hz, 1H), 6.19 (dq, J=15.8,6.6Hz,
1H), 1.89 (d, J=6.6Hz, 3H)；13C NMR (75MHz, CDCl3) δ: 152.4,128.3,
128.0,127.4,125.4,120.9,115.7,18.9.
Embodiment 14
As a example by preparing 2-amino-4-(1-acrylic) benzonitrile that structural formula is following, concrete preparation method is:
In embodiment 1,4-bromo nitrobenzene used equimolar 4-iodo-2-anthranilo nitrile is replaced, reaction
Time lengthening was to 6 hours, and other steps are same as in Example 1, obtained yellow solid 2-amino-4-(1-propylene
Base) benzonitrile, its yield is 71%, and structural characterization data are:1H NMR (300MHz, CDCl3) δ:
7.52-7.37 (m, 1H), 7.35-7.22 (m, 2H), 6.72 (t, J=8.9Hz, 2H), 6.22 (d,
J=15.8Hz, 1H), 6.10-5.95 (m, 1H), 1.83 (d, J=5.2Hz, 3H)；13C NMR
(75MHz, CDCl3) δ: 148.7,140.9,131.4,128.9,124.0,117.8,115.5,110.8,
95.7,17.6.
Claims (4)
1. the preparation method of a 1-phenylpropene derivatives, it is characterised in that: it is molten with N-Methyl pyrrolidone
Agent, joins in autoclave by the halobenzene derivant shown in formula I, palladium, triethylamine, is passed through propylene
Gas, pressure be 1～2MPa, temperature be at 90～120 DEG C react, wherein halobenzene derivant, propylene,
Palladium, the mol ratio of triethylamine are 1: 4～6: 0.004～0.005: 1～1.5, and isolated and purified product obtains
1-phenylpropene derivatives shown in formula II；
R in formula1、R2、R3Any in the most independent representative H, alkoxyl, hydroxyl, nitro, amino, cyano group
One, X represents Br.
The preparation method of 1-phenylpropene derivatives the most according to claim 1, it is characterised in that: described
Halobenzene derivant, propylene, palladium, the mol ratio of triethylamine be 1: 5: 0.004: 1.1.
The preparation method of 1-phenylpropene derivatives the most according to claim 1 and 2, it is characterised in that:
With N-Methyl pyrrolidone as solvent, the halobenzene derivant shown in formula I, palladium, triethylamine are joined height
Pressure reactor in, be passed through propylene gas, pressure be 1.6MPa, temperature be at 100～120 DEG C react 1～8
Hour.
The preparation method of 1-phenylpropene derivatives the most according to claim 1 and 2, it is characterised in that:
With N-Methyl pyrrolidone as solvent, the halobenzene derivant shown in formula I, palladium, triethylamine are joined height
Pressure reactor in, be passed through propylene gas, pressure be 1.6MPa, temperature be at 110 DEG C react 2～6 hours.
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