CN102153455B - Method for synthesizing multi-substituted 3-phenyl four-membered-ring ketene compounds - Google Patents
Method for synthesizing multi-substituted 3-phenyl four-membered-ring ketene compounds Download PDFInfo
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- CN102153455B CN102153455B CN 201110041029 CN201110041029A CN102153455B CN 102153455 B CN102153455 B CN 102153455B CN 201110041029 CN201110041029 CN 201110041029 CN 201110041029 A CN201110041029 A CN 201110041029A CN 102153455 B CN102153455 B CN 102153455B
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 150000002561 ketenes Chemical class 0.000 title abstract description 32
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000003379 elimination reaction Methods 0.000 claims abstract description 5
- LZSZSURMDPHQQA-UHFFFAOYSA-N 1,1'-biphenyl;zinc Chemical compound [Zn].C1=CC=CC=C1C1=CC=CC=C1 LZSZSURMDPHQQA-UHFFFAOYSA-N 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 5
- OWQUYBAASOSGNO-CDNKMLFNSA-N 2-[[(Z)-N-(2-hydroxy-5-sulfoanilino)-C-phenylcarbonimidoyl]diazenyl]benzoic acid Chemical compound C1=CC=C(C=C1)/C(=N/NC2=C(C=CC(=C2)S(=O)(=O)O)O)/N=NC3=CC=CC=C3C(=O)O OWQUYBAASOSGNO-CDNKMLFNSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 229940043798 zincon Drugs 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical class [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000007259 addition reaction Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012074 organic phase Substances 0.000 claims description 2
- 229940125782 compound 2 Drugs 0.000 claims 3
- 229940125904 compound 1 Drugs 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000011925 1,2-addition Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- MKRVHLWAVKJBFN-UHFFFAOYSA-N diphenylzinc Chemical compound C=1C=CC=CC=1[Zn]C1=CC=CC=C1 MKRVHLWAVKJBFN-UHFFFAOYSA-N 0.000 abstract 1
- 238000007363 ring formation reaction Methods 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 12
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 12
- 150000001336 alkenes Chemical class 0.000 description 11
- 150000002148 esters Chemical class 0.000 description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- -1 enamine salt Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- CDCPVNFFXXQLQP-UHFFFAOYSA-N CCCCC=C=C(C(C)(C)C)C(=O)OC Chemical class CCCCC=C=C(C(C)(C)C)C(=O)OC CDCPVNFFXXQLQP-UHFFFAOYSA-N 0.000 description 1
- YDRWVAFIHJGNSB-UHFFFAOYSA-N COC(=O)C(=C=C(C)C)C1=CC=CC=C1 Chemical class COC(=O)C(=C=C(C)C)C1=CC=CC=C1 YDRWVAFIHJGNSB-UHFFFAOYSA-N 0.000 description 1
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 description 1
- 150000001345 alkine derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a method for synthesizing multi-substituted 3-phenyl four-membered-ring ketene compounds. In the method, 2,3-allenoates and diphenyl zinc perform 1,4-addition/cyclization and 1,2-addition/elimination reactions in toluene to generate a series of multi-substituted 3-phenyl four-membered-ring ketene compounds in one step. The method is simple to operate, and the used raw materials and regents are easy to obtain; in addition, the method has the advantages of high reaction yield and good reaction regioselectivity, and can be used for avoiding the detects that a precursor is difficult to obtain and is unstable and regioselectivity is difficult to control in the traditional method; the products obtained through the method are easy to separate and purify; therefore, the method is suitable for the synthesis of multi-substituted 3-phenyl four-membered-ring ketene compounds.
Description
Technical field
The present invention relates to a kind of method of 3-phenyl tetra-atomic ring ketene compounds of synthetic various replacements, namely by 2,3-connection olefin(e) acid ester and phenylbenzene zinc occur 1 in toluene, 4-addition/cyclisation 1,2-addition/elimination reaction, single stage method generates the 3-phenyl tetra-atomic ring ketene compounds of a series of various replacements.
Background technology
The tetra-atomic ring ketene compounds is one of intermediate important in the organic synthesis, can be used to synthetic cyclopentanone, 1, and the Cycloene derivate of 3-conjugated diolefine, phenolic compound and a series of replacements also is structural unit common in the natural product simultaneously.Because structure is special, in the tetra-atomic ring of tension force, contain simultaneously the two keys of carbon-carbon double bond and carbon oxygen, this compounds is difficult synthetic in the document, and existing method mainly prepares by alkynes [2+2] reaction with ketenes and enamine salt.But this method has that ketenes and enamine salt precursor are difficult to preparation and unstable, regioselectivity is difficult to the shortcomings such as control, has limited the synthetic development of polysubstituted tetra-atomic ring ketenes.This patent provide a kind of utilization be simple and easy to phenylbenzene zinc directly and 2,3-connection olefin(e) acid ester one step of reaction obtains the method for polysubstituted 3-phenyl tetra-atomic ring ketenes.
Summary of the invention
Purpose of the present invention just provides a kind of method of effectively synthesizing the 3-phenyl tetra-atomic ring ketene compounds of various replacements under simple condition.
Concrete technical scheme of the present invention is as follows:
The present invention is a kind of method of synthetic polysubstituted 3-phenyl tetra-atomic ring ketene compounds, by 2,3-connection olefin(e) acid ester
1With phenylbenzene zinc Isosorbide-5-Nitrae-addition/cyclisation 1 occurs in toluene, 2-addition/elimination is reacted, and generates the 3-phenyl tetra-atomic ring ketene compounds of a series of various replacements, and reaction formula is as follows:
R
1/ R
2Be H or alkyl; R
3Be alkyl or phenyl; The very strong allenic compound of functional group's loading property and the phenylbenzene zinc that is easy to prepare are adopted in reaction, and in 2,3,4 functional groups that introducing is different of tetra-atomic ring ketenes, the phenyl group of phenylbenzene zinc is introduced in 3 of tetra-atomic ring ketenes, 2,3-connection olefin(e) acid ester
12,4 groups be introduced in 2 and 4 of tetra-atomic ring ketenes, the steps include:
(1) in glove box, in reaction tubes, adds phenylbenzene zincon (1.2 mmole), under nitrogen protection, add the solvent of reaction, under agitation in reaction tubes, add raw material 2,3-connection olefin(e) acid ester
1The toluene solution of (0.4 mmole) (2 milliliters) finishes and places oil bath to react;
(2) after step (1) reacts completely, reaction tubes is back to room temperature and is cooled to zero degree, drip 1 milliliter of saturated ammonium chloride and do the cancellation reaction, use extracted with diethyl ether, organic phase is used 5% hydrochloric acid successively, and saturated sodium bicarbonate, saturated aqueous common salt are respectively washed one time, with anhydrous sodium sulfate drying, filtration, concentrated, rapid column chromatography, obtain 3-phenyl tetra-atomic ring ketene compounds again
2
Of the present invention 2,3-connection olefin(e) acid ester
1For: 4 bit substituents are two 2, the 3-of the replacement connection of 2,4 of alkyl olefin(e) acid ester
1Or entirely replace 2,3-connection olefin(e) acid ester
1
The temperature that places oil bath to react of the present invention is 100 degrees centigrade.
The solvent of reaction of the present invention is toluene (3 milliliters).
Phenylbenzene zincon of the present invention and 2,3-connection olefin(e) acid ester
1Equivalence ratio be 3: 1.
The 3-phenyl tetra-atomic ring ketene compounds that the present invention obtains
2To introduce three different substituents 2,3,4 of 3-phenyl tetra-atomic ring ketenes; The phenyl of described phenylbenzene zincon is incorporated into 3 of tetra-atomic ring ketenes, 2,3-connection olefin(e) acid ester
12,4 groups be introduced in 2 and 4 of tetra-atomic ring ketenes.
The present invention relates to a kind of synthetic method of polysubstituted 3-phenyl tetra-atomic ring ketene compounds, under 100 degrees centigrade, take toluene as solvent, phenylbenzene zinc and 2,3-connection olefin(e) acid ester
1Isosorbide-5-Nitrae-addition/cyclisation 1 occurs, and 2-addition/elimination reaction obtains a series of 3-phenyl tetra-atomic ring ketene compounds
2Present method is simple to operate, raw material and reagent are easy to get, reaction yield is higher, the regioselectivity of reaction is fine, avoided that the traditional method precursor is not easy to obtain, the unstable and unmanageable shortcoming of regioselectivity, the easily separated purifying of product is applicable to synthesize the 3-phenyl tetra-atomic ring ketene compounds of various replacements.
The present invention has overcome the drawback of traditional method, and the beneficial effect that has is as follows:
1) reaction need not catalyzer; 2) can optionally introduce different substituents 2,3,4 of tetra-atomic ring ketene compounds; 3) intermediate need not separate; 4) the easily separated purifying of product.
Innovative point of the present invention is to have developed and a kind ofly prepares the methodology of polysubstituted 3-phenyl tetra-atomic ring ketene compounds by phenylbenzene zinc and 2,3-connection olefin(e) acid ester single stage method, and the productive rate of the corresponding polysubstituted 3-phenyl tetra-atomic ring ketene compounds of gained is 69-89%.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention.
Embodiment 1
In glove box, in reaction tubes, add phenylbenzene zinc (0.2604 gram, 1.2 mmoles), under nitrogen protection, add toluene (3 milliliters).Under agitation add 2-butyl-4-propyl group-2 in reaction tubes, the toluene solution (2 milliliters) of 3-heptadienoic acid methyl esters (0.0958 gram, 0.4 mmole) finishes, and places 100 degrees centigrade of oil baths., be back to room temperature and be down to zero degree after 3 hours 100 degrees centigrade of lower reactions, drip 1 milliliter of saturated ammonium chloride solution cancellation reaction, use extracted with diethyl ether, 5% hydrochloric acid, saturated sodium bicarbonate, saturated aqueous common salt are respectively washed once, anhydrous sodium sulfate drying.Filter, concentrated, rapid column chromatography gets 2-butyl-4,4-dipropyl-3-phenyl tetra-atomic ring ketenes 0.0794 gram, and productive rate is 69%, product is liquid.
?1H?NMR?(300?MHz,?CDCl
3)?δ?7.62-7.54?(m,?2?H,?Ar-H),?7.51-7.42?(m,?3?H,?Ar-H),?2.44?(t,?
J?=?7.7?Hz,?2?H,?CH
2),?1.88-1.75?(m,?2?H,?CH
2),?1.74-1.57?(m,?4?H,?2?×?CH
2),?1.47-1.35?(m,?2?H,?CH
2),?1.34-1.07?(m,?4?H,?2?×?CH
2),?0.93?(t,?
J?=?7.4?Hz,?3?H,?CH
3),?0.84?(t,?
J?=?7.4?Hz,?6?H,?2?×?CH
3);?
13C?NMR?(CDCl
3,?75?MHz)?198.6,?169.3,?145.6,?132.9,?130.5,?129.0,?128.0,?70.2,?36.2,?29.4,?24.0,?22.9,?18.9,?14.5,?13.8;?MS?(EI)?
m/z?(%)?284?(M
+,?6.16),?255?(100);?IR?(neat,?cm
-1)?2957,?2929,?2872,?1747,?1611,?1572,?1493,?1464,?1447,?1379,?1342,?1296;?HRMS?Calcd?for?C
20H
28O?(M
+):?284.2140,?Found:?284.2141.
Embodiment 2
Press embodiment 1 described method, different is that used substrate and reagent are: the 2-tertiary butyl-2,3-octadienoic acid methyl esters (0.0844 gram, 0.4 mmole), phenylbenzene zinc (0.2602 gram, 1.2 mmoles) gets 4-butyl-2-tertiary butyl-3-phenyl tetra-atomic ring ketenes 0.0840 gram, productive rate is 82%, and product is liquid.
1H?NMR?(300?MHz,?CDCl
3)?δ?7.50-7.36?(m,?5?H,?Ar-H),?3.78?(dd,?
J 1?=?7.2?Hz,?
J 2?=?4.5?Hz,?1?H,?CH),?1.75-1.44?(m,?2?H,?CH
2),?1.37-1.16?(m,?13?H,?2?×?CH
2?+?C(CH
3)
3),?0.82?(t,?
J?=?7.1?Hz,?3?H,?CH
3);?
13C?NMR?(CDCl
3,?75?MHz)?δ?193.8,?167.1,?153.1,?133.1,?129.5,?128.6,?128.3,?61.7,?32.4,?28.7,?28.0,?22.8,?13.8;?MS?(EI)?
m/z?(%)?256?(M
+,?79.44),?185?(100);?IR?(neat,?cm
-1)?2960,?2928,?2869,?1749,?1612,?1461,?1365,?1330,?1215,?1123;?HRMS?Calcd?for?C
18H
24O?(M
+):?256.1827,?Found:?256.1817.
Embodiment 3
Press embodiment 1 described method, different is that used substrate and reagent are: 4-methyl-2-phenyl-2,3-pentadienoic acid methyl esters (0.0803 gram, 0.4 mmole), phenylbenzene zinc (0.2613 gram, 1.2 mmole), get 4,4-dimethyl-2,3-phenylbenzene tetra-atomic ring ketenes 0.0874 gram, productive rate is 89%, and product is white solid m.p. 111.6-112.4
oC (hexane/ethyl acetate).
1H?NMR?(300?MHz,?CDCl
3)?δ?7.77-7.65?(m,?4?H,?Ar-H),?7.50-7.28?(m,?6?H,?Ar-H),?1.53?(s,?6?H,?2?×?CH
3);?
13C?NMR?(CDCl
3,?75?MHz)?δ?196.7,?171.8,?138.8,?131.8,?131.1,?129.8,?128.9,?128.8,?128.6,?128.2,?127.6,?63.1,?21.2;?MS?(EI)?
m/z?(%)?248?(M
+,?59.34),?205?(100);?IR?(KBr,?cm
-1)?3047,?2960,?2924,?1741,?1615,?1446,?1384,?1345,?1317,?1177,?1100,?1074;?Anal.?Calcd?for?C
18H
16O:?C?87.06,?H?6.49,?Found:?C?86.77,?H?6.47.
Claims (2)
1. the method for a synthetic compound 2 is characterized in that by compound 1 and phenylbenzene zinc Isosorbide-5-Nitrae-addition/cyclisation 1 occuring in toluene, and 2-addition/elimination reaction generates compound 2, and reaction formula is as follows:
R
1And R
2Be H; R
3Be phenyl; The steps include:
(1) in glove box, adds the phenylbenzene zincon of 1.2 mmoles in the reaction tubes, under nitrogen protection, the solvent that adds reaction under agitation adds 2 milliliters of the toluene solutions of formula 1 compound that contains 0.4 mmole in the reaction tubes, finishes to place oil bath to react;
(2) after step (1) reacts completely, reaction tubes is back to room temperature and is cooled to zero degree, drip 1 milliliter of saturated ammonium chloride and do the cancellation reaction, use extracted with diethyl ether, organic phase is used 5% hydrochloric acid successively, and saturated sodium bicarbonate, saturated aqueous common salt are respectively washed one time, again with anhydrous sodium sulfate drying, filtration, concentrated, rapid column chromatography, acquisition formula 2 compounds.
2. the method for synthetic compound 2 according to claim 1 is characterized in that the described temperature that places oil bath to react is 100 degrees centigrade.
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| CN102382091B (en) * | 2011-09-05 | 2014-07-09 | 浙江大学 | Method for synthesizing multi-substituted chromone compound |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204311A (en) * | 1995-12-13 | 1999-01-06 | Basf公司 | Process for catalytic addition of nucleophiles to alkines or allenes |
| CN1256264A (en) * | 1998-12-08 | 2000-06-14 | 罗姆和哈斯公司 | Process for preparing 2-alkyl-3-hydroxy-benzoic acid |
-
2011
- 2011-02-21 CN CN 201110041029 patent/CN102153455B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1204311A (en) * | 1995-12-13 | 1999-01-06 | Basf公司 | Process for catalytic addition of nucleophiles to alkines or allenes |
| CN1256264A (en) * | 1998-12-08 | 2000-06-14 | 罗姆和哈斯公司 | Process for preparing 2-alkyl-3-hydroxy-benzoic acid |
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