CN1403460A - Synthesis of monocrystal porphyrin - Google Patents
Synthesis of monocrystal porphyrin Download PDFInfo
- Publication number
- CN1403460A CN1403460A CN 02131357 CN02131357A CN1403460A CN 1403460 A CN1403460 A CN 1403460A CN 02131357 CN02131357 CN 02131357 CN 02131357 A CN02131357 A CN 02131357A CN 1403460 A CN1403460 A CN 1403460A
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- CN
- China
- Prior art keywords
- porphyrin
- monocrystal
- phenyl aldehyde
- pyrroles
- reactor
- Prior art date
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- 150000004032 porphyrins Chemical class 0.000 title claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000003935 benzaldehydes Chemical class 0.000 claims abstract description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 18
- -1 phenyl aldehyde Chemical class 0.000 claims description 18
- 150000003233 pyrroles Chemical class 0.000 claims description 16
- 235000019260 propionic acid Nutrition 0.000 claims description 9
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 150000002632 lipids Chemical class 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 7
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- 235000014493 Crataegus Nutrition 0.000 claims description 4
- 241001092040 Crataegus Species 0.000 claims description 4
- ZRSNZINYAWTAHE-UHFFFAOYSA-N p-methoxybenzaldehyde Chemical compound COC1=CC=C(C=O)C=C1 ZRSNZINYAWTAHE-UHFFFAOYSA-N 0.000 claims description 4
- FXLOVSHXALFLKQ-UHFFFAOYSA-N p-tolualdehyde Chemical compound CC1=CC=C(C=O)C=C1 FXLOVSHXALFLKQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- ZRYZBQLXDKPBDU-UHFFFAOYSA-N 4-bromobenzaldehyde Chemical compound BrC1=CC=C(C=O)C=C1 ZRYZBQLXDKPBDU-UHFFFAOYSA-N 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical class C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 abstract 2
- 235000014113 dietary fatty acids Nutrition 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 229930195729 fatty acid Natural products 0.000 abstract 1
- 239000000194 fatty acid Substances 0.000 abstract 1
- 150000004665 fatty acids Chemical class 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 238000010583 slow cooling Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000001186 cumulative effect Effects 0.000 description 5
- 239000004744 fabric Substances 0.000 description 5
- 239000012456 homogeneous solution Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 125000004799 bromophenyl group Chemical group 0.000 description 2
- VCRBUDCZLSQJPZ-UHFFFAOYSA-N porphyrinogen Chemical compound C1C(N2)=CC=C2CC(N2)=CC=C2CC(N2)=CC=C2CC2=CC=C1N2 VCRBUDCZLSQJPZ-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- AVPYQKSLYISFPO-UHFFFAOYSA-N 4-chlorobenzaldehyde Chemical compound ClC1=CC=C(C=O)C=C1 AVPYQKSLYISFPO-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- VQEFBUZTGUJCHS-UHFFFAOYSA-N benzaldehyde 4-bromobenzaldehyde Chemical class BrC1=CC=C(C=O)C=C1.C(C1=CC=CC=C1)=O VQEFBUZTGUJCHS-UHFFFAOYSA-N 0.000 description 1
- 150000004054 benzoquinones Chemical class 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses synthesis of monocrystal porphyrin as one organic monocrystal. The materials benzaldehyde or substituted benzaldehyde and pyrrole are reacted through heating in low molecular weight fatty acid as reaction medium inside one sealed reactor; and through slow cooling pure lump monocrystal porphyrin may be prepared. The process produces no tar, needs no additional oxidant and catalyst, and needs relatively lower temperature and shorter time. It has no environmental pollution and is simple, easy to control and suitable for industrial production.
Description
Technical field
The invention belongs to the organic single-crystal synthesis technical field, particularly the synthetic method of monocrystal porphyrin.
Background technology
The method of existing synthetic porphyrin, reactions steps is more, and product purity is not high, and later stage purifying workload is big.Reported that phenyl aldehyde and pyrroles are that solvent is in sealed tube with the pyridine for 267 pages at U.S.'s " JACS " (Journal of the American Chemical Society) magazine nineteen forty-one the 63rd volume, react 24-48h down at 150 ℃, the gained productive rate is very low, and the substituted benzaldehyde that can be used for this understanding, reactant is few; 1967 the 32nd volumes of U.S.'s " organic chemistry magazine " (Joumal of Organic Chemistry) have reported that phenyl aldehyde and pyrroles react for 476 pages in the propionic acid that refluxes, prepare the polycrystalline porphyrin, but generate a large amount of tar in the reaction, the purifying of product is a problem; This magazine the 52nd volume had reported again that phenyl aldehyde and pyrroles were under nitrogen protection for 827 pages in 1987, in methylene dichloride, with the etherate of trifluoroboron complex catalysis, reaction (generation porphyrinogen) under the room temperature, with dichloro dinitrile benzoquinones or tetrachlorobenzoquinone Oxidation of porphyrinogen is obtained the final product porphyrin then, the main shortcoming of this method is to need chromatographer to purify; In the domestic correlative study, " organic chemistry " rolled up 416 pages of the 2nd phases in 1991 the 11st and reported that with DMF (N, dinethylformamide) be solvent, anhydrous AlCl
3Be catalyzer, phenyl aldehyde and pyrroles's condensation generate TTP (tetraphenylporphyrin), but catalyst A lCl
3Be easy to the water reaction, cause difficulty for the separation of product.Above-mentioned domestic and international correlative study, reactions steps is more, and product purity is not high, and later stage purifying workload is big, and the research that single step reaction makes the pure product of monocrystal porphyrin there is no report at home and abroad.
Summary of the invention
The object of the present invention is to provide a kind of synthetic method of monocrystal porphyrin, method that should synthetic monocrystal porphyrin is to be raw material with phenyl aldehyde and pyrroles, with low-molecular-weight lipid acid is medium, in closed reactor, carry out, it is characterized in that: phenyl aldehyde, pyrroles are dissolved in the low-molecular-weight lipid acid by weight 1～3: 1 mixture, under 60～160 ℃, react, reacted 5～15 hours, behind the naturally cooling, can prepare the pure product of monocrystalline of multiple porphyrin.
Its chemical equation is:
R＝-H，-OCH
3，-CH
3，-Br，-Cl，
Described phenyl aldehyde comprises that phenyl aldehyde or substituted benzaldehyde comprise p-bromobenzaldehyde, p-tolyl aldehyde and aubepine.
Described lower molecular weight lipid acid comprises propionic acid, or butyric acid.
Beneficial effect of the present invention is raw material for adopting phenyl aldehyde and the pyrroles have different substituents, and available identical experimental installation has been prepared the pure product of monocrystalline of multiple replacement tetraphenylporphyrin.No tar produces, and without catalyzer, reaction is fast, the purity height, and technology is simple, and suitability is wide, is fit to industrialized production, has broad application prospects.
Embodiment
The present invention is the synthetic method of monocrystal porphyrin, does not need additionally to add oxygenant and catalyzer, and under lower temperature and in the short time, one-step synthesis goes out the pure product of monocrystalline of porphyrin.With phenyl aldehyde or substituted benzaldehyde and pyrroles is raw material, is medium with low-molecular-weight lipid acid such as propionic acid or butyric acid, carries out in closed reactor.The mixture of phenyl aldehyde, pyrroles's weight ratio 1～3: 1 is dissolved in the low-molecular-weight lipid acid, under 60～160 ℃, reacts, reacted 5～15 hours, behind the naturally cooling, can prepare the pure product of monocrystalline of multiple porphyrin.Above-mentioned technology is implemented on identical testing apparatus.Above-mentioned phenyl aldehyde comprises phenyl aldehyde or substituted benzaldehyde p-bromobenzaldehyde, p-tolyl aldehyde and aubepine.R is R=-H in its chemical equation ,-OCH
3,-CH
3,-Br ,-Cl, chemical equation is:
For example the molecular structure of four (to the bromo phenyl) porphyrin is:
Below further specify the technological process that adopts the inventive method to prepare monocrystal porphyrin for example.
Embodiment one:
Take by weighing 0.925g analytical pure p-bromobenzaldehyde, 0.335g analytical pure pyrroles and place the withstand voltage reactor of stainless steel of 40ml, adding analytical pure propionic acid to cumulative volume is about 70% of reactor volume, stirs to form homogeneous solution.Sealed reactor is at 140 ℃ of reaction 12-15h.Naturally cool to room temperature in the baking oven, open reactor,, wash respectively, get the bluish voilet crystal with methyl alcohol and hot water with cloth formula funnel suction filtration.Product is accredited as four (to the bromo phenyl) porphyrin through the X ray single crystal diffraction.Unit cell parameters a=10.2141 (15) , b=9.0953 (13) , c=20.957 (3) belongs to oblique system, and spacer is P2
1Ln (No.14), β=100.857 (4) °, V=1912.1 (5)
3
Embodiment two:
Take by weighing 0.53g analytical pure phenyl aldehyde, 0.335g analytical pure pyrroles and place the withstand voltage reactor of stainless steel of 40ml, adding analytical pure propionic acid to cumulative volume is about 70% of reactor volume, stirs to form homogeneous solution.Sealed reactor is at 160 ℃ of reaction 12-15h.Naturally cool to room temperature in the baking oven, open reactor,, wash respectively, get the bluish voilet crystal with methyl alcohol and hot water with cloth formula funnel suction filtration.
Embodiment three:
Take by weighing 0.70g analytical pure 4-chloro-benzaldehyde, 0.335g analytical pure pyrroles and place the withstand voltage reactor of stainless steel of 40ml, adding analytical pure propionic acid to cumulative volume is about 70% of reactor volume, stirs to form homogeneous solution.Sealed reactor is at 140 ℃ of reaction 12-15h.Naturally cool to room temperature in the baking oven, open reactor,, wash respectively, get the bluish voilet crystal with methyl alcohol and hot water with cloth formula funnel suction filtration.
Embodiment four:
Take by weighing 0.60g analytical pure p-tolyl aldehyde, 0.335g analytical pure pyrroles and place the withstand voltage reactor of stainless steel of 40ml, adding analytical pure propionic acid to cumulative volume is about 70% of reactor volume, stirs to form homogeneous solution.Sealed reactor is at 160 ℃ of reaction 12-15h.Naturally cool to room temperature in the baking oven, open reactor,, wash respectively, get the bluish voilet crystal with methyl alcohol and hot water with cloth formula funnel suction filtration.
Embodiment five:
Take by weighing 0.68g analytical pure aubepine, 0.335g analytical pure pyrroles and place the withstand voltage reactor of stainless steel of 40ml, adding analytical pure propionic acid to cumulative volume is about 70% of reactor volume, stirs to form homogeneous solution.Sealed reactor is at 140 ℃ of reaction 12-15h.Naturally cool to room temperature in the baking oven, open reactor,, wash respectively, get the bluish voilet crystal with methyl alcohol and hot water with cloth formula funnel suction filtration.
Claims (3)
1. the synthetic method of a monocrystal porphyrin, method that should synthetic monocrystal porphyrin is to be raw material with phenyl aldehyde and pyrroles, with low-molecular-weight lipid acid is medium, in closed reactor, carry out, it is characterized in that: phenyl aldehyde, pyrroles are dissolved in the low-molecular-weight lipid acid by weight 1～3: 1 mixture, under 60～160 ℃, react, reacted 5～15 hours, behind the naturally cooling, can prepare the pure product of monocrystalline of multiple porphyrin; Its chemical equation is:
R＝-H，-OCH
3，-CH
3，-Br，-Cl。
2. according to the synthetic method of the described monocrystal porphyrin of claim 1, it is characterized in that: described phenyl aldehyde comprises that phenyl aldehyde or substituted benzaldehyde comprise p-bromobenzaldehyde, p-tolyl aldehyde and aubepine.
3. according to the synthetic method of the described monocrystal porphyrin of claim 1, it is characterized in that: described lower molecular weight lipid acid comprises propionic acid, or butyric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021313571A CN1194001C (en) | 2002-10-08 | 2002-10-08 | Synthesis of monocrystal porphyrin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021313571A CN1194001C (en) | 2002-10-08 | 2002-10-08 | Synthesis of monocrystal porphyrin |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1403460A true CN1403460A (en) | 2003-03-19 |
| CN1194001C CN1194001C (en) | 2005-03-23 |
Family
ID=4746663
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021313571A Expired - Fee Related CN1194001C (en) | 2002-10-08 | 2002-10-08 | Synthesis of monocrystal porphyrin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1194001C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010130065A1 (en) * | 2009-05-15 | 2010-11-18 | Guo Cancheng | A method for synthesizing tetraaryl porphyrin and its device |
| CN101550140B (en) * | 2009-05-15 | 2011-06-15 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
| CN105080423A (en) * | 2014-05-07 | 2015-11-25 | 华东理工大学 | Quaternary ammonium salt type Gemini surfactant and preparation method therefor |
| CN111715263A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of nitrogen-doped carbon-supported monatomic catalyst |
| CN114797988A (en) * | 2022-05-16 | 2022-07-29 | 万华化学(四川)有限公司 | Synthesis of novel composite catalyst and method for preparing beta-isophorone |
-
2002
- 2002-10-08 CN CNB021313571A patent/CN1194001C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010130065A1 (en) * | 2009-05-15 | 2010-11-18 | Guo Cancheng | A method for synthesizing tetraaryl porphyrin and its device |
| CN101550140B (en) * | 2009-05-15 | 2011-06-15 | 湖南大学 | Method and apparatus for synthesis of tetaraary porphyrin |
| CN105080423A (en) * | 2014-05-07 | 2015-11-25 | 华东理工大学 | Quaternary ammonium salt type Gemini surfactant and preparation method therefor |
| CN111715263A (en) * | 2020-07-03 | 2020-09-29 | 广州志成新材料有限公司 | Preparation method of nitrogen-doped carbon-supported monatomic catalyst |
| CN114797988A (en) * | 2022-05-16 | 2022-07-29 | 万华化学(四川)有限公司 | Synthesis of novel composite catalyst and method for preparing beta-isophorone |
| CN114797988B (en) * | 2022-05-16 | 2023-08-11 | 万华化学(四川)有限公司 | Synthesis of composite catalyst and method for preparing beta-isophorone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1194001C (en) | 2005-03-23 |
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