CN105384773A - Catalytic synthesis method for phosphorus-containing aromatic heterocyclic compound - Google Patents
Catalytic synthesis method for phosphorus-containing aromatic heterocyclic compound Download PDFInfo
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- CN105384773A CN105384773A CN201510884256.8A CN201510884256A CN105384773A CN 105384773 A CN105384773 A CN 105384773A CN 201510884256 A CN201510884256 A CN 201510884256A CN 105384773 A CN105384773 A CN 105384773A
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Abstract
The invention relates to a catalytic synthesis method for a phosphorus-containing aromatic heterocyclic compound as shown in a formula (III) which is described in the specification. The method comprises the following steps: in a nitrogen atmosphere, successively adding a compound as shown in a formula (I) which is described in the specification, a compound as shown in a formula (II) which is described in the specification, a catalyst and an auxiliary agent into an organic solvent; then carrying out a reaction at 70 to 80 DEG C under stirring for 40 to 50 min; carrying out heating to 90 to 105 DEG C and then carrying out a reaction under stirring for 6 to 8 h with the temperature maintained; and carrying out after-treatment after completion of the reaction so as to obtain the compound as shown in the formula (III). In the formula (III), R1 is a C1-6 alkyl or benzyl group, and R2 is an adamantyl group. The method constructs a composite catalysis system by selecting reagents, screens out appropriate varieties/combination of the catalyst and the auxiliary agent and the organic solvent, and adopts a unique two-stage reaction manner, so high-efficiency implementation of the reaction is realized and good product yield is achieved; and the method has good application prospects and industrial production potential in the field of organic synthesis.
Description
Technical field
The present invention relates to a kind of process for catalytic synthesis of phosphorous heteroaromatic ring compounds, belong to organic chemical synthesis field.
Background technology
Aromatic ring compounds is extensively present among natural product and medical compounds, such as phenyl ring, pyridine ring, furan nucleus etc.Wherein, phosphorous heteroaromatic ring compounds is also one of very important aromatic substance, thus exploitation about the Novel synthesis technology of phosphorous heteroaromatic ring compounds of great advantage for the demand of satisfied medicine, chemical field.
Up to now, in prior art, report the multiple synthesis technique of phosphorous heteroaromatic ring compounds, such as:
MiaoYanli etc. (" ANewRoutetoa2-Phosphanaphthalene ", OrganicLetters, 2012,14,4974 – 4975) report a kind of synthetic method of 2-phosphorus naphthalene compounds, and its reaction formula is as follows:
ChenXiaodan etc. (" SodiumPhosphaethynolateasaBuildingBlockforHeterocycles) ", Angew.Chem.Int.Ed., 2014,53,1641-1645) report a kind of synthetic method of phosphorous heterocyclic compound, its reaction formula is as follows:
FancoisMathey etc. (" Phospha-OrganicChemistry:PanoramaandPerspectives ", Angew.Chem.Int.Ed., 2003,42,1578-1604) there was reported correlative study summary and the vision of the future of organophosphorus chemistry.
But the product species synthesized by these methods existing is limited, need the synthesis technique of other species compound of developing further, and reaction yield also needs further raising.
These defects are overcome in order to reach, the present inventor takes the investigation summary that a large amount of time carries out document, and carried out sufficient trial and checking by experiment, thus propose a kind of process for catalytic synthesis of phosphorous heteroaromatic ring compounds, this kind of method have employed iron-based composite catalyst and other co catalysis component, achieve the high yield preparation of phosphorous heteroaromatic ring compounds, and reaction conditions is gentle, technique is simple, possesses wide industrial prospect.
Summary of the invention
In order to overcome above-mentioned pointed many defects, present inventor has performed deep research and exploration, after having paid enough creative works, thus completing the present invention.
Specifically, technical scheme of the present invention and content relate to the process for catalytic synthesis of phosphorous heteroaromatic ring compounds shown in a kind of following formula (III), described method comprises: under nitrogen atmosphere, following formula (I) compound, following formula (II) compound, catalyzer and auxiliary agent is added successively in organic solvent, then stirring reaction 40-50 minute at 70-80 DEG C, be warming up to 90-105 DEG C again and insulated and stirred reaction 6-8 hour, described formula (III) compound is obtained after completion of the reaction through aftertreatment
Wherein, R
1for C
1-C
6alkyl or benzyl;
R
2namely for 1-adamantyl (also formula (II) compound is that 1-adamantyl phosphine is mixed acetylene, and its No. CAS is 101055-70-3).
In described process for catalytic synthesis of the present invention, unless otherwise prescribed, from start to finish, described C
1-C
6the implication of alkyl refers to the straight or branched alkyl with 1-6 carbon atom, such as can be methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl or n-hexyl etc. in non-limiting manner.
In described process for catalytic synthesis of the present invention, described catalyzer is mol ratio is the iron cpd of 4:1 and the mixture of metal halide.
Wherein, described iron cpd most preferably is Fe (acac)
2(ferric acetyl acetonade), described metal halide most preferably is butter of antimony.
In described process for catalytic synthesis of the present invention, nano yttrium oxide and the Cu (OTf) of described auxiliary agent to be mol ratio be 1:1
2the mixture of (copper trifluoromethanesulfcomposite), wherein the granularity of nano yttrium oxide is 100-200 order.
In described process for catalytic synthesis of the present invention, described organic solvent is DMF (N, dinethylformamide), DMAc (N, N-N,N-DIMETHYLACETAMIDE), any one in toluene, benzene, o-Xylol, para-Phthalonitrile or Macrogol 200 (PEG-200), most preferably be DMAc.
Wherein, the consumption of described organic solvent strict restriction, and those skilled in the art can carry out suitable selection according to practical situation and determine, such as its consumption size is carried out and aftertreatment to facilitate reaction, is no longer described in detail at this.
In described process for catalytic synthesis of the present invention, the mol ratio of described formula (I) compound and formula (II) compound is 1:2-2.5, such as, can be 1:2,1:2.3 or 1:2.5.
In described process for catalytic synthesis of the present invention, the mol ratio of described formula (I) compound and catalyzer is 1:0.15-0.25, i.e. the mole dosage of described formula (I) compound and the Fe (acac) of formation catalyzer
2the ratio of total mole dosage of (ferric acetyl acetonade) and butter of antimony is 1:0.15-0.25, such as, can be 1:0.15,1:0.2 or 1:0.25.
In described process for catalytic synthesis of the present invention, the mol ratio of described formula (I) compound and auxiliary agent is 1:0.1-0.16, i.e. the mole dosage of described formula (I) compound and the nano yttrium oxide of formation auxiliary agent and Cu (OTf)
2the ratio of total mole dosage be 1:0.1-0.16, such as can be 1:0.1,1:0.12,1:0.14 or 1:0.16.
In described process for catalytic synthesis of the present invention, aftertreatment after reaction terminates can be specific as follows: after reaction terminates, reaction system is filtered, the filtrate obtained carries out flushing washing with saturated sodium bicarbonate aqueous solution, isolate organic phase, then use dried over mgso, upper 300-400 order silica gel column chromatography, be that chloroform and the petroleum ether mixtures of 1:2 carries out wash-out with volume ratio, thus obtain described formula (III) compound.
In described process for catalytic synthesis of the present invention, the reaction mass of employing or reagent all prepare by prior art and/or buy use.
In sum, the invention provides a kind of process for catalytic synthesis of phosphorous heteroaromatic ring compounds, the method is by building composite catalyst system, and screen suitable catalyzer, auxiliary agent, organic solvent and use two-part reaction, thus facilitate efficiently carrying out of reaction, make to obtain target product with high yield in the short period of time, possess willing feature, show good market potential.
Embodiment
Below by specific embodiment, the present invention is described in detail; but the purposes of these exemplary embodiments and object are only used for exemplifying the present invention; not any type of any restriction is formed to real protection scope of the present invention, more non-protection scope of the present invention is confined to this.
Wherein, in all embodiments below, radicals R
2be 1-adamantyl.
Embodiment 1
Under nitrogen atmosphere, in appropriate organic solvent DMAc, add 100mmol above formula (I) compound successively, 200mmol above formula (II) compound, 15mmol catalyzer (be 12mmolFe (acac)
2the mixture of (ferric acetyl acetonade) and 3mmol butter of antimony) and 10mmol auxiliary agent (be granularity 100-200 object 5mmol nano yttrium oxide and 5mmolCu (OTf)
2the mixture of (copper trifluoromethanesulfcomposite)), then stirring reaction 50 minutes at 70 DEG C, then be warming up to 90 DEG C and insulated and stirred reacts 8 hours;
After reaction terminates, reaction system is filtered, the filtrate obtained carries out flushing washing with saturated sodium bicarbonate aqueous solution, isolate organic phase, using dried over mgso again, upper 300-400 order silica gel column chromatography, is that chloroform and the petroleum ether mixtures of 1:2 carries out wash-out with volume ratio, thus obtaining above formula (III) compound, productive rate is 94.6%.
1HNMR(CDCl
3,400MHz):δ8.51(d,
2J
P-H＝39.7Hz,1H),7.77(d,
3J
P-H＝5.7Hz,1H),3.74(s,6H),3.67-3.66(m,4H),2.11-2.03(m,9H),1.77(brs,6H)。
Embodiment 2
Under nitrogen atmosphere, in appropriate organic solvent DMAc, add 100mmol above formula (I) compound successively, 230mmol above formula (II) compound, 20mmol catalyzer (be 16mmolFe (acac)
2the mixture of (ferric acetyl acetonade) and 4mmol butter of antimony) and 13mmol auxiliary agent (be granularity 100-200 object 6.5mmol nano yttrium oxide and 6.5mmolCu (OTf)
2the mixture of (copper trifluoromethanesulfcomposite)), then stirring reaction 45 minutes at 75 DEG C, then be warming up to 100 DEG C and insulated and stirred reacts 7 hours;
After reaction terminates, reaction system is filtered, the filtrate obtained carries out flushing washing with saturated sodium bicarbonate aqueous solution, isolate organic phase, using dried over mgso again, upper 300-400 order silica gel column chromatography, is that chloroform and the petroleum ether mixtures of 1:2 carries out wash-out with volume ratio, thus obtaining above formula (III) compound (wherein n-Pr is n-propyl), productive rate is 94.3%.
1HNMR(CDCl
3,400MHz):δ8.53(d,
2J
P-H＝40.0Hz,1H),7.76(d,
3J
P-H＝5.7Hz,1H),4.11(t,J＝6.5Hz,4H),3.67-3.66(m,4H),2.12-2.05(m,9H),1.82-1.59(m,10H),0.92(t,J＝7.3Hz,6H)。
Embodiment 3
Under nitrogen atmosphere, in appropriate organic solvent DMAc, add 100mmol above formula (I) compound successively, 250mmol above formula (II) compound, 25mmol catalyzer (be 20mmolFe (acac)
2the mixture of (ferric acetyl acetonade) and 5mmol butter of antimony) and 16mmol auxiliary agent (be granularity 100-200 object 8mmol nano yttrium oxide and 8mmolCu (OTf)
2the mixture of (copper trifluoromethanesulfcomposite)), then stirring reaction 40 minutes at 80 DEG C, then be warming up to 105 DEG C and insulated and stirred reacts 6 hours;
After reaction terminates, reaction system is filtered, the filtrate obtained carries out flushing washing with saturated sodium bicarbonate aqueous solution, isolate organic phase, using dried over mgso again, upper 300-400 order silica gel column chromatography, is that chloroform and the petroleum ether mixtures of 1:2 carries out wash-out with volume ratio, thus obtaining above formula (III) compound (wherein n-Bu is normal-butyl), productive rate is 94.2%.
1HNMR(CDCl
3,400MHz):δ8.51(d,2JP-H＝39.7Hz,1H),7.76(d,3JPH＝5.7Hz,1H),4.15(t,J＝6.5Hz,4H),3.65-3.64(m,4H),2.12-2.05(m,9H),1.82-1.55(m,10H),1.42-1.26(m,4H),0.91(t,J＝7.3Hz,6H)。
Embodiment 4
Under nitrogen atmosphere, in appropriate organic solvent DMAc, add 100mmol above formula (I) compound successively, 220mmol above formula (II) compound, 18mmol catalyzer (be 14.4mmolFe (acac)
2the mixture of (ferric acetyl acetonade) and 3.6mmol butter of antimony) and 12mmol auxiliary agent (be granularity 100-200 object 6mmol nano yttrium oxide and 6mmolCu (OTf)
2the mixture of (copper trifluoromethanesulfcomposite)), then stirring reaction 45 minutes at 75 DEG C, then be warming up to 95 DEG C and insulated and stirred reacts 7 hours;
After reaction terminates, reaction system is filtered, the filtrate obtained carries out flushing washing with saturated sodium bicarbonate aqueous solution, isolate organic phase, using dried over mgso again, upper 300-400 order silica gel column chromatography, is that chloroform and the petroleum ether mixtures of 1:2 carries out wash-out with volume ratio, thus obtaining above formula (III) compound (wherein Bn is benzyl), productive rate is 94.4%.
1HNMR(CDCl
3,400MHz):δ8.52(d,
2J
P-H＝39.7Hz,1H),7.75(d,
3J
P-H＝5.7Hz,1H),7.32-7.18(m,10H),5.13(s,4H),3.68-3.67(m,4H),2.12-2.04(m,9H),1.76(brs,6H)。
Embodiment 5-13: the investigation of catalyzer
Except the different catalysts used in following table 1, other operation all identical can, thus respectively to obtain embodiment 5-13 with the same way of embodiment 1-4, the catalyzer used, corresponding relation and products collection efficiency see the following form 1.
Table 1
Note: "--represent and do not exist.
As can be seen here, as iron cpd, most preferably be Fe (acac)
2(ferric acetyl acetonade), and as metal halide, most preferably be butter of antimony.Also can find out, when being used alone Fe (acac)
2when (ferric acetyl acetonade) or butter of antimony, products collection efficiency has significant reduction (especially butter of antimony).This proves to only have to use Fe (acac) simultaneously
2the mixture of (ferric acetyl acetonade) and butter of antimony, as catalyzer, has just unexpectedly played concerted catalysis effect between the two, thus has achieved best products collection efficiency.
Embodiment 14-25: the investigation of auxiliary agent
Embodiment 14-17: except auxiliary agent being replaced with one-component nano yttrium oxide that consumption is the total consumption sum of original two kinds of components, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 14-17 in turn.
Embodiment 18-21: except auxiliary agent is replaced with the one-component Cu (OTf) that consumption is the total consumption sum of original two kinds of components
2outward, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 18-21 in turn.
Embodiment 22-25: except being omitted by auxiliary agent, other operation is all constant, thus repeats to implement embodiment 1-4, obtains embodiment 22-25 in turn.
The results are shown in following table 2.
Table 2
As can be seen here, when being used alone nano yttrium oxide or Cu (OTf)
2time (copper trifluoromethanesulfcomposite), productive rate all has remarkable reduction (but nano yttrium oxide reduces more obvious); It can also be seen that, when not using any auxiliary agent, its productive rate is higher than productive rate when only using nano yttrium oxide on the contrary, and this proves not play any facilitation effect when being used alone nano yttrium oxide.Demonstrate thus and ought use nano yttrium oxide and Cu (OTf) simultaneously
2when the mixture of (copper trifluoromethanesulfcomposite) is as auxiliary agent, competence exertion works in coordination with facilitation effect.
Embodiment 26-31: the investigation of organic solvent
Except the different organic solvents used in following table 3, other operation all identical can, thus respectively to obtain embodiment 26-31 with the same way of embodiment 1-4, the organic solvent used, corresponding relation and products collection efficiency see the following form 3.
Table 3
As can be seen here, the kind of organic solvent can the final products collection efficiency of remarkably influenced, and wherein DMAc has best effect, even if the DMF very similar with it, its productive rate also reduced, and other organic solvent then reduces more obvious.
Embodiment 32-: the investigation of temperature of reaction
Embodiment 32-35: respectively embodiment 1-4 is reacted under first paragraph temperature of reaction, time is the total time (namely reacting at the temperature of second segment) that original two-part reacts, other operation is all constant, thus obtains embodiment 32-35 in turn.
Embodiment 36-39: respectively embodiment 1-4 is reacted under second segment temperature of reaction, time is the total time (namely reacting at the temperature of first paragraph) that original two-part reacts, other operation is all constant, thus obtains embodiment 36-39 in turn.
The results are shown in following table 4.
Table 4
As can be seen here, when carrying out two-part of the present invention reaction, products collection efficiency can be improved significantly.When only carrying out first paragraph reaction, then productive rate reduces remarkable especially.Although productive rate when only carrying out the second segmentation is also higher than 90%, obviously will lower than the productive rate of embodiment 1-4.These all demonstrate the unobviousness and the unexpected property of effect that adopt two-part of the present invention reaction.
Comprehensively above-mentioned, the invention provides a kind of process for catalytic synthesis of phosphorous heteroaromatic ring compounds, the method builds composite catalyst system by selection reagent, and screen the two-part reaction of suitable catalyzer, auxiliary agent kind/combination and organic solvent and uniqueness, and achieve efficiently carrying out of reaction, achieve good products collection efficiency, have a good application prospect and industrial production potential in organic synthesis field.
Should be appreciated that the purposes of these embodiments is only not intended to for illustration of the present invention limit the scope of the invention.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various change, amendment and/or modification to the present invention, and these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (10)
1. the process for catalytic synthesis of phosphorous heteroaromatic ring compounds shown in a following formula (III), described method comprises: under nitrogen atmosphere, following formula (I) compound, following formula (II) compound, catalyzer and auxiliary agent is added successively in organic solvent, then stirring reaction 40-50 minute at 70-80 DEG C, be warming up to 90-105 DEG C again and insulated and stirred reaction 6-8 hour, described formula (III) compound is obtained after completion of the reaction through aftertreatment
Wherein, R
1for C
1-C
6alkyl or benzyl
R
2for 1-adamantyl.
2. process for catalytic synthesis as claimed in claim 1, is characterized in that: described catalyzer is mol ratio is the iron cpd of 4:1 and the mixture of metal halide.
3. process for catalytic synthesis as claimed in claim 2, is characterized in that: described iron cpd most preferably is Fe (acac)
2(ferric acetyl acetonade).
4. method as claimed in claim 2 or claim 3, is characterized in that: described metal halide most preferably is butter of antimony.
5. the method as described in any one of claim 1-4, is characterized in that: nano yttrium oxide and the Cu (OTf) of described auxiliary agent to be mol ratio be 1:1
2the mixture of (copper trifluoromethanesulfcomposite), wherein the granularity of nano yttrium oxide is 100-200 order.
6. the process for catalytic synthesis as described in any one of claim 1-5, it is characterized in that: described organic solvent is DMF (N, dinethylformamide), DMAc (N, N-N,N-DIMETHYLACETAMIDE), any one in toluene, benzene, o-Xylol, para-Phthalonitrile or Macrogol 200 (PEG-200), most preferably be DMAc.
7. the process for catalytic synthesis as described in any one of claim 1-6, is characterized in that: the mol ratio of described formula (I) compound and formula (II) compound is 1:2-2.5.
8. the process for catalytic synthesis as described in any one of claim 1-7, is characterized in that: the mol ratio of described formula (I) compound and catalyzer is 1:0.15-0.25.
9. the process for catalytic synthesis as described in any one of claim 1-8, is characterized in that: the mol ratio of described formula (I) compound and auxiliary agent is 1:0.1-0.16.
10. the process for catalytic synthesis as described in any one of claim 1-9, it is characterized in that: the aftertreatment after reaction terminates is specific as follows: after reaction terminates, reaction system is filtered, the filtrate obtained carries out flushing washing with saturated sodium bicarbonate aqueous solution, isolate organic phase, then use dried over mgso, upper 300-400 order silica gel column chromatography, be that chloroform and the petroleum ether mixtures of 1:2 carries out wash-out with volume ratio, thus obtain described formula (III) compound.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1343211A (en) * | 1999-03-17 | 2002-04-03 | 巴斯福股份公司 | Phosphabenzene compounds and theie use as ligands for hydroformylation catalysts |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1343211A (en) * | 1999-03-17 | 2002-04-03 | 巴斯福股份公司 | Phosphabenzene compounds and theie use as ligands for hydroformylation catalysts |
Non-Patent Citations (3)
| Title |
|---|
| BARBARA HELLER ET AL.: ""The fascinating construction of pyridine ring systems by transition metal-catalysed [2 + 2 + 2] cycloaddition reactions"", 《CHEM. SOC. REV.》 * |
| KAZUNARI NAKAJIMA, ET AL.: ""Synthesis of Phosphabenzenes by an Iron-Catalyzed [2+2+2] Cycloaddition Reaction of Diynes with Phosphaalkynes"", 《ANGEW. CHEM. INT. ED.》 * |
| YANLI MAO ET AL.: ""A New Route to a 2‑Phosphanaphthalene"", 《ORG. LETT.》 * |
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