CN104961727B - A kind of novel method for synthesizing of pyrrole derivatives - Google Patents
A kind of novel method for synthesizing of pyrrole derivatives Download PDFInfo
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- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
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Abstract
The present invention relates to a kind of synthetic method of pyrrole derivatives shown in lower formula (IV), methods described includes：In organic solvent, in the presence of catalyst, alkali and accelerator, lower formula (I) compound, lower formula (II) compound and lower formula (III) compound are reacted, thus obtaining described formula (IV) compound, wherein, R1For H, C1‑C6Alkyl, halogen or nitro；R2For C1‑C6Alkyl or benzyl.The method is creatively passed through compound selection using catalyst, alkali, accelerator and organic solvent and is combined, thus having reached the purpose improving reaction yield, can obtain purpose product with high yield, having extensive industrial applications prospect in organic synthesis field.
Description
Technical field
The present invention relates to a kind of synthetic method of heterocyclic compound, more particularly to a kind of three components of azole derivatives
Synthetic method, belongs to organic intermediate synthesis field.
Background technology
In heterocyclic compound, pyrroles is the important compound of a class, and it occurs frequently in substantial amounts of as mother nucleus structure
Among natural product, active alkaloid, medicine and agricultural formulations, additionally, azoles are also frequently as bioactive process
The synthetic intermediate of compound.
It is based on the so important effect of azoles, therefore, the preparation method of exploitation pyrrole derivatives
It is increasingly becoming the hot issue of organic synthesis field.
At present, there is the existing report of multiple synthesis pyrrole derivatives in prior art, for example：
CN104710339A discloses a kind of preparation method of 2,3,4- tri- substituted azole ring derivatives, belongs to chemosynthesis
Field, methods described includes：1st, connection olefin(e) acid benzyl ester is reacted with paraformaldehyde experience MBH and is obtained 2- hydroxy methylene -2,3- connection alkene
Acid benzyl ester, obtains 2- acetoxyl group methylene -2 with excess acetyl chloride, and 3- joins olefin(e) acid benzyl ester；2nd, 2- bromoacetophenone and
TsNHBoc reaction obtains N, N- (2- oxo 2-2 phenethyl)-p-toluenesulfonyl-t-butyl carbamate, sloughs Boc and obtains
N- (2- oxo -2- phenethyl) p-methylphenyl sulphonylamine；3rd, 2- acetoxyl group methylene -2,3- connection olefin(e) acid benzyl ester and N- (2- oxygen
Generation -2- phenethyl) p-methylphenyl sulphonylamine makees solvent with Isosorbide-5-Nitrae-dioxane in the presence of DABCO and inorganic base potassium carbonate, and 80
DEG C reaction 36 hours.
CN104370939A discloses a kind of preparation method of chirality pyrroline compound, and described compound is to prepare
The important intermediate of antitumor drug MK-0731, described preparation method with vinyl ethylene carbonate and isocyanates as raw material,
With the asymmetric decarboxylation cycloaddition reaction of palladium chtalyst as committed step, by the chiral pyrrolin class of four step chemical conversion preparations
Compound.This preparation method step is short, and reaction condition is gentle, and reaction yield is high, and enantioselectivity is excellent.
CN104086542A disclose a kind of cough up and quinolinones compound preparation method it is characterised in that concrete steps
As follows：(1) primary amine of 1-1.5 equivalent is added the various substituted 3- bromo- 4- alkynyl quinolinone of 1 equivalent, 2.5-3.5 equivalent
K3PO4、Pd(OAc)2With R- (+) in the solution of the N,N-dimethylacetamide of-BINAP, stir 8- at a temperature of 120-130 DEG C
24 hours, TLC monitoring terminated；Wherein, Pd (OAc)2Consumption be whole reaction system 3-6%, R- (+) consumption of-BINAP
For the 6-12% of whole reaction system, (2) wash reactant liquor with water, are extracted with ethyl acetate, and are dried, and concentrate, and column chromatography divides
From obtaining pyrroloquinoline ketone compounds.
CN103864661A discloses a kind of synthesis technique of 2- Amino 3 cyano azole derivatives, and described technique is with third
Dintrile, benzaldehyde, aminoacetaldehyde dimethyl acetal are initiation material, obtain through reduction amination, closed loop, amino derivatization, de- benzyl
Target product, such compound has potential biological activity.
As described above, the method disclosing multiple synthesis azole derivatives in prior art, but for azole derivatives
Novel method for synthesizing, still suffers from continuing necessity of research.Based on this, the present inventor is intended to by the component to catalytic reaction system
Research and component collocation, and propose a kind of novel method for synthesizing of pyrrole derivatives, and it in many experiments screening and is explored
On the basis of drawn optimal catalytic reaction system it is achieved that the efficiently synthesizing of pyrrole derivatives, and can fast reaction, tool
There is great market application foreground.
Content of the invention
As described above, for the novel method for synthesizing developing azole derivatives, present inventor has performed in-depth study and
Explore, after having paid enough creative works, thus completing the present invention.
Specifically, technical scheme and content are related to a kind of synthesis of pyrrole derivatives shown in lower formula (IV)
Method,
Methods described includes：In organic solvent, in the presence of catalyst, alkali and accelerator, lower formula (I) compound, under
Formula (II) compound and lower formula (III) compound are reacted, thus obtaining described formula (IV) compound,
Wherein, R1For H, C1-C6Alkyl, halogen or nitro；
R2For C1-C6Alkyl or benzyl.
In the described synthetic method of the present invention, described C1-C6The implication of alkyl refers to the straight chain with 1-6 carbon atom
Or branched alkyl, can be for example methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, isobutyl group, uncle in non-limiting manner
Butyl, n-pentyl, isopentyl or n-hexyl etc..
In the described synthetic method of the present invention, the implication of described halogen refers to halogen, can be for example non-exclusively
F, Cl, Br or I.
In the described synthetic method of the present invention, described catalyst is Pd (PhCN)2Cl2(two (cyano group benzene) palladium chloride),
Pd(acac)2(palladium acetylacetonate), Pd (dba)2(double (two subunit acetone) palladium), Pd (MeCN)2Cl2(di acetonitrile palladium chloride),
Pd(OAc)2Any one in (acid chloride), most preferably Pd (MeCN)2Cl2.
In the described synthetic method of the present invention, described alkali is sodium bicarbonate, potassium carbonate, sodium acetate, potassium acetate, phosphoric acid
Any one in sodium, potassium tert-butoxide, diisopropanolamine (DIPA), triethylamine, N- (4- picolyl) ethamine etc., most preferably N- (4-
Picolyl) ethamine.
In the described synthetic method of the present invention, described accelerator is 1 for mol ratio:Copper trifluoromethanesulfcomposite (the Cu of 3-4
(OTf)2) and Yttrium trinitrate mixture.
In the described synthetic method of the present invention, described organic solvent is DMA (N,N-dimethylacetamide), DMF (N, N-
Dimethylpropionamide), DMSO (dimethyl sulfoxide), toluene, ethanol, NMP (N-Methyl pyrrolidone), benzene, 1,4- dioxane,
Any one in acetonitrile etc., most preferably acetonitrile.
The consumption of described organic solvent does not have strict restriction, and those skilled in the art can be carried out suitably to its consumption
Select, for example can be appropriately selected according to making post processing be easy to carry out, reacting the amount being smoothed out to carry out.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of formula (II) compound:1-
1.5, can be for example 1:1、1:1.1、1:1.2、1:1.3、1:1.4 or 1:1.5.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of formula (III) compound:1-
1.3, can be for example 1:1、1:1.1、1:1.2 or 1:1.3.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of catalyst:0.04-
0.08, can be for example 1 in non-limiting manner:0.04、1:0.06 or 1:0.08.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of alkali:2-3, indefiniteness
Ground can be for example 1:2、1:2.5 or 1:3.
In the described synthetic method of the present invention, described formula (I) compound is 1 with the mol ratio of accelerator:0.1-0.2,
I.e. the mole dosage of described formula (I) compound and the ratio of the total moles consumption of two kinds of components of described accelerator are 1:0.1-0.2,
Can be for example 1 in non-limiting manner:0.1、1:0.15 or 1:0.2.
In the described synthetic method of the present invention, reaction temperature is 60-90 DEG C, for example, can be 60 DEG C, 70 DEG C, 80 DEG C or 90
℃.
In the described synthetic method of the present invention, the response time is 4-8 hour, for example can be little for 4 hours, 6 hours or 8
When.
In the described synthetic method of the present invention, the post processing after reaction terminates is specific as follows：After reaction terminates, will react
Mixture is poured in deionized water, fully vibrates, is then extracted with ethyl acetate 2-3 time, merges organic faciess, organic faciess are divided
Not Yong saturated aqueous common salt, deionized water wash, then with anhydrous magnesium sulfate be dried, concentrating under reduced pressure, residue crosses 200-300 mesh silicon
Glue pillar layer separation, with volume ratio for 1:2 acetone and the mixed liquor of petroleum ether are eluent, thus obtain described formula (IV) changing
Compound.
Summary, present inventors have proposed a kind of novel method for synthesizing of pyrrole derivatives, the method is creatively
By using catalyst, alkali, accelerator and organic solvent compound selection with combine, thus reached improve reaction yield mesh
, purpose product can be obtained with high yield, in organic synthesis field, there is extensive industrial applications prospect.
Specific embodiment
Below by specific embodiment, the present invention is described in detail, but the purposes of these exemplary embodiments and
Purpose is only used for enumerating the present invention, and not the real protection scope of the present invention is constituted with any type of any restriction, more non-general
Protection scope of the present invention is confined to this.
Embodiment 1
Under room temperature, in the appropriate organic solvent acetonitrile in reactor, add 100mmol on formula (I) compound,
100mmol upper formula (II) compound, 100mmol upper formula (III) compound, 4mmol catalyst Pd (MeCN)2Cl2, 200mmol alkali
N- (4- picolyl) ethamine and the (mixing for 2.5mmol copper trifluoromethanesulfcomposite and 7.5mmol Yttrium trinitrate of 10mmol accelerator
Thing), then heat to 60 DEG C, and stirring reaction 8 hours at such a temperature；
After reaction terminates, reactant mixture is poured in deionized water, fully vibrates, be then extracted with ethyl acetate 2-
3 times, merge organic faciess, organic faciess are used respectively saturated aqueous common salt, deionized water wash, be then dried with anhydrous magnesium sulfate, subtract
Pressure concentrates, and residue is crossed 200-300 mesh silica gel column chromatography and separated, with volume ratio for 1:2 acetone and the mixed liquor of petroleum ether are
Eluent, thus obtaining formula (IV) compound, yield is 96.9%.
1H NMR(CDCl3,400MHz):δ 1.47 (s, 9H), 2.29 (s, 3H), 4.52 (s, 2H), 6.33 (d, J=
3.1Hz, 1H), 6.87 (d, J=7.8Hz, 1H), 6.97 (d, J=3.0Hz, 1H), 7.03-7.12 (m, 3H), 7.19 (d, J=
7.8Hz, 2H), 7.54 (dt, J=7.7Hz＆1.5Hz, 1H), 8.55 (d, J=4.2Hz, 1H).
HRMS(ESI)([M+H]+):304.1.
Embodiment 2
Under room temperature, in the appropriate organic solvent acetonitrile in reactor, add 100mmol on formula (I) compound,
120mmol upper formula (II) compound, 110mmol upper formula (III) compound, 6mmol catalyst Pd (MeCN)2Cl2, 250mmol alkali
N- (4- picolyl) ethamine and 15mmol accelerator (for the mixture of 3mmol copper trifluoromethanesulfcomposite and 12mmol Yttrium trinitrate),
Then heat to 70 DEG C, and stirring reaction 6 hours at such a temperature；
After reaction terminates, reactant mixture is poured in deionized water, fully vibrates, be then extracted with ethyl acetate 2-
3 times, merge organic faciess, organic faciess are used respectively saturated aqueous common salt, deionized water wash, be then dried with anhydrous magnesium sulfate, subtract
Pressure concentrates, and residue is crossed 200-300 mesh silica gel column chromatography and separated, with volume ratio for 1:2 acetone and the mixed liquor of petroleum ether are
Eluent, thus obtaining formula (IV) compound, yield is 97.3%.
1H NMR(CDCl3,400MHz):δ 2.34 (s, 3H), 4.33 (s, 2H), 4.99 (s, 2H), 6.38 (d, J=
2.7Hz, 1H), 6.72 (d, J=2.7Hz, 1H), 6.88-7.45 (m, 11H), 7.52 (t, J=7.6Hz, 1H), 8.49 (d, J=
4.2Hz,1H).
HRMS(ESI)([M+H]+):338.2.
Embodiment 3
Under room temperature, in the appropriate organic solvent acetonitrile in reactor, add 100mmol on formula (I) compound,
150mmol upper formula (II) compound, 120mmol upper formula (III) compound, 8mmol catalyst Pd (MeCN)2Cl2, 300mmol alkali
N- (4- picolyl) ethamine and the (mixing for 4.5mmol copper trifluoromethanesulfcomposite and 15.5mmol Yttrium trinitrate of 20mmol accelerator
Thing), then heat to 90 DEG C, and stirring reaction 4 hours at such a temperature；
After reaction terminates, reactant mixture is poured in deionized water, fully vibrates, be then extracted with ethyl acetate 2-
3 times, merge organic faciess, organic faciess are used respectively saturated aqueous common salt, deionized water wash, be then dried with anhydrous magnesium sulfate, subtract
Pressure concentrates, and residue is crossed 200-300 mesh silica gel column chromatography and separated, with volume ratio for 1:2 acetone and the mixed liquor of petroleum ether are
Eluent, thus obtaining formula (IV) compound, yield is 97.2%.
1H NMR(C6D6,400MHz):δ 1.48 (s, 9H), 4.53 (s, 2H), 6.29 (d, J=3.1Hz, 1H), 6.87 (d,
J=7.8Hz, 1H), 6.94-7.29 (m, 6H), 7.53 (t, J=6.0Hz, 1H), 8.53 (d, J=4.5Hz, 1H).
HRMS(ESI)([M+H]+):324.
Embodiment 4
Under room temperature, in the appropriate organic solvent acetonitrile in reactor, add 100mmol on formula (I) compound,
140mmol upper formula (II) compound, 130mmol upper formula (III) compound, 5mmol catalyst Pd (MeCN)2Cl2, 220mmol alkali
N- (4- picolyl) ethamine and the (mixing for 4.5mmol copper trifluoromethanesulfcomposite and 13.5mmol Yttrium trinitrate of 18mmol accelerator
Thing), then heat to 80 DEG C, and stirring reaction 5 hours at such a temperature；
After reaction terminates, reactant mixture is poured in deionized water, fully vibrates, be then extracted with ethyl acetate 2-
3 times, merge organic faciess, organic faciess are used respectively saturated aqueous common salt, deionized water wash, be then dried with anhydrous magnesium sulfate, subtract
Pressure concentrates, and residue is crossed 200-300 mesh silica gel column chromatography and separated, with volume ratio for 1:2 acetone and the mixed liquor of petroleum ether are
Eluent, thus obtaining formula (IV) compound, yield is 97.5%..
1H NMR(CDCl3,400MHz):δ 4.22 (s, 2H), 5.13 (s, 2H), 6.42 (d, J=2.5Hz, 1H), 6.79
(d, J=2.5Hz, 1H), 6.92 (d, J=8.0Hz, 1H), 6.99 (d, J=7.5Hz, 2H), 7.06-7.31 (m, 4H), 7.48
(t, J=8.0Hz, 1H), 7.57 (dt, J=8.0Hz＆2.0Hz, 1H), 7.74 (d, J=5.5Hz, 1H), 8.05 (d, J=
5.0Hz, 1H), 8.298 (s, 1H), 8.54 (d, J=4.0Hz, 1H).
HRMS(ESI)([M+H]+):369.
Embodiment 5-20
Embodiment 5-8：Remove and respectively catalyst is replaced with Pd (PhCN)2Cl2Outward, other operations are all constant, thus according to reality
The same procedure applying a 1-4 is carried out a 5-8.
Embodiment 9-12：Remove and respectively catalyst is replaced with Pd (acac)2Outward, other operations are all constant, thus according to reality
The same procedure applying a 1-4 is carried out a 9-12.
Embodiment 13-16：Remove and respectively catalyst is replaced with Pd (dba)2Outward, other operations are all constant, thus according to reality
The same procedure applying a 1-4 is carried out a 13-16.
Embodiment 17-20：Remove and respectively catalyst is replaced with Pd (OAc)2Outward, other operations are all constant, thus according to reality
The same procedure applying a 1-4 is carried out a 17-20.
Experimental result is as shown in table 1 below.
Table 1
From table 1, in all of palladium catalyst, Pd (MeCN)2Cl2There is best catalytic effect, even with it
Very similar Pd (PhCN)2Cl2, its yield also has obvious reduction, and other palladium compound then reduces and becomes apparent from.
Embodiment 21-28
In addition to using different alkali, to implement embodiment 21-28 respectively with embodiment 1-4 identical mode, made
As shown in table 2 below with alkali, corresponding relation and experimental result.
Table 2
From upper table 2 data, in the compound reaction system of the present invention, as alkali, N- (4- picolyl) ethamine has
There is a best effect, and the yield of other alkali all has and substantially even significantly reduces.
Embodiment 29-40
Embodiment 29-32：In addition to dispensing accelerator therein respectively, other operations are all constant, thus according to embodiment
The same way of 1-4, is carried out a 29-32.
Embodiment 33-36：Remove accelerator respectively by copper trifluoromethanesulfcomposite (Cu (OTf)2) and the mixture of Yttrium trinitrate replace
It is changed to the copper trifluoromethanesulfcomposite (Cu (OTf) that consumption is the total consumption of original two kinds of components2) outward, other operations are all constant, thus pressing
According to the same way of embodiment 1-4, it is carried out a 33-36.
Embodiment 37-40：Remove accelerator respectively by copper trifluoromethanesulfcomposite (Cu (OTf)2) and the mixture of Yttrium trinitrate replace
It is changed to outside the Yttrium trinitrate that consumption is the total consumption of original two kinds of components, other operations are all constant, thus identical according to embodiment 1-4
Mode, is carried out a 37-40.
Experimental result is as shown in table 3 below.
Table 3
From table 3, when not using accelerator, then yield significantly reduces；And work as and simply use copper trifluoromethanesulfcomposite
(Cu(OTf)2) or during Yttrium trinitrate, yield reduces and becomes apparent from.This demonstrate that two facts：1st, the presence of accelerator can be notable
Improve products collection efficiency；2nd, when being used one-component as accelerator, its yield even will be less than when not using any accelerator
Yield, thus illustrating only simultaneously using copper trifluoromethanesulfcomposite (Cu (OTf)2) and Yttrium trinitrate as accelerator, just can take
Obtain the excellent effect of the present invention, also demonstrate the collaborative facilitation having played uniqueness between the two.
Embodiment 41-48
In addition to using different organic solvents, to implement embodiment 41- respectively with embodiment 1-4 identical mode
48, used organic solvent, corresponding relation and experimental result are as shown in table 4 below.
Table 4
From upper table 4 data, the species of organic solvent is capable of the yield of appreciable impact product, wherein acetonitrile have best
Solvent effect, and other organic solvent all leads to products collection efficiency to decrease.
Summary, the present invention creatively proposes a kind of novel method for synthesizing of pyrrole derivatives, and the method is created
The property made by using catalyst, alkali, accelerator and organic solvent compound selection with combine, thus reached raising reaction receive
The purpose of rate, can obtain purpose product with high yield, have extensive industrial applications prospect in organic synthesis field.
It should be appreciated that the purposes of these embodiments is merely to illustrate the present invention and is not intended to limit the protection model of the present invention
Enclose.Additionally, it will also be appreciated that after the technology contents having read the present invention, those skilled in the art can make each to the present invention
Plant and change, change and/or modification, all these equivalent form of value equally falls within the guarantor that the application appended claims are limited
Within the scope of shield.
Claims (6)
1. the synthetic method of pyrrole derivatives shown in a kind of lower formula (IV),
Methods described includes：In organic solvent, in the presence of catalyst, alkali and accelerator, lower formula (I) compound, following formula
(II) compound and lower formula (III) compound are reacted, thus obtaining described formula (IV) compound,
Wherein, R1For H, C1-C6Alkyl, halogen or nitro；
R2For C1-C6Alkyl or benzyl；
Described catalyst is di acetonitrile palladium chloride；
Described alkali is N- (4- picolyl) ethamine；
Described accelerator is 1 for mol ratio:The copper trifluoromethanesulfcomposite of 3-4 and the mixture of Yttrium trinitrate；
Described organic solvent is acetonitrile.
2. synthetic method as claimed in claim 1 it is characterised in that：Described formula (I) compound is rubbed with formula (II) compound
That ratio is 1:1-1.5.
3. synthetic method as claimed in claim 1 it is characterised in that：Described formula (I) compound is rubbed with formula (III) compound
That ratio is 1:1-1.3.
4. synthetic method as claimed in claim 1 it is characterised in that：Described formula (I) compound with the mol ratio of catalyst is
1:0.04-0.08.
5. synthetic method as claimed in claim 1 it is characterised in that：Described formula (I) compound is 1 with the mol ratio of alkali:2-
3.
6. the synthetic method as described in any one of claim 1-5 it is characterised in that：Described formula (I) compound and accelerator
Mol ratio is 1:0.1-0.2.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370939A (en) * | 2014-10-14 | 2015-02-25 | 上海交通大学 | Preparation method of chiral dihydropyrrole compound |
| CN104710339A (en) * | 2015-01-22 | 2015-06-17 | 华东理工大学 | Preparation method of 2,3,4-trisubstituted pyrrole ring derivative |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104370939A (en) * | 2014-10-14 | 2015-02-25 | 上海交通大学 | Preparation method of chiral dihydropyrrole compound |
| CN104710339A (en) * | 2015-01-22 | 2015-06-17 | 华东理工大学 | Preparation method of 2,3,4-trisubstituted pyrrole ring derivative |
Non-Patent Citations (1)
| Title |
|---|
| Palladium-Catalyzed One-Pot Sonogashira Coupling, exo-dig Cyclization and;SHEKARRAO KOMMURI et al.;《Advanced Synthesis & Catalysis》;20150309;第357卷(第6期);1187-1192 * |
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