CN117624001A - Method for synthesizing thioester compound by ring opening of photocatalytic indenone in water - Google Patents
Method for synthesizing thioester compound by ring opening of photocatalytic indenone in water Download PDFInfo
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- CN117624001A CN117624001A CN202210977665.2A CN202210977665A CN117624001A CN 117624001 A CN117624001 A CN 117624001A CN 202210977665 A CN202210977665 A CN 202210977665A CN 117624001 A CN117624001 A CN 117624001A
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- indenone
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- -1 thioester compound Chemical class 0.000 title claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims abstract description 11
- SNWQUNCRDLUDEX-UHFFFAOYSA-N inden-1-one Chemical compound C1=CC=C2C(=O)C=CC2=C1 SNWQUNCRDLUDEX-UHFFFAOYSA-N 0.000 title claims description 6
- 230000002194 synthesizing effect Effects 0.000 title claims description 4
- 230000001699 photocatalysis Effects 0.000 title claims description 3
- 238000007142 ring opening reaction Methods 0.000 title claims description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 45
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 claims abstract description 14
- SEACYXSIPDVVMV-UHFFFAOYSA-L eosin Y Chemical compound [Na+].[Na+].[O-]C(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C([O-])=C(Br)C=C21 SEACYXSIPDVVMV-UHFFFAOYSA-L 0.000 claims abstract description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 5
- 238000004587 chromatography analysis Methods 0.000 claims abstract description 3
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 9
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000010025 steaming Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 229910052717 sulfur Inorganic materials 0.000 claims 1
- 239000011593 sulfur Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 14
- 238000003756 stirring Methods 0.000 abstract description 2
- 150000007970 thio esters Chemical class 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 238000005481 NMR spectroscopy Methods 0.000 description 12
- 238000004440 column chromatography Methods 0.000 description 12
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 12
- 239000011541 reaction mixture Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 3
- JNPGUXGVLNJQSQ-BGGMYYEUSA-M (e,3r,5s)-7-[4-(4-fluorophenyl)-1,2-di(propan-2-yl)pyrrol-3-yl]-3,5-dihydroxyhept-6-enoate Chemical compound CC(C)N1C(C(C)C)=C(\C=C\[C@@H](O)C[C@@H](O)CC([O-])=O)C(C=2C=CC(F)=CC=2)=C1 JNPGUXGVLNJQSQ-BGGMYYEUSA-M 0.000 description 3
- VAVHMEQFYYBAPR-ITWZMISCSA-N (e,3r,5s)-7-[4-(4-fluorophenyl)-1-phenyl-2-propan-2-ylpyrrol-3-yl]-3,5-dihydroxyhept-6-enoic acid Chemical compound CC(C)C1=C(\C=C\[C@@H](O)C[C@@H](O)CC(O)=O)C(C=2C=CC(F)=CC=2)=CN1C1=CC=CC=C1 VAVHMEQFYYBAPR-ITWZMISCSA-N 0.000 description 3
- HIHOEGPXVVKJPP-JTQLQIEISA-N 5-fluoro-2-[[(1s)-1-(5-fluoropyridin-2-yl)ethyl]amino]-6-[(5-methyl-1h-pyrazol-3-yl)amino]pyridine-3-carbonitrile Chemical compound N([C@@H](C)C=1N=CC(F)=CC=1)C(C(=CC=1F)C#N)=NC=1NC=1C=C(C)NN=1 HIHOEGPXVVKJPP-JTQLQIEISA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- VZXOZSQDJJNBRC-UHFFFAOYSA-N 4-chlorobenzenethiol Chemical compound SC1=CC=C(Cl)C=C1 VZXOZSQDJJNBRC-UHFFFAOYSA-N 0.000 description 2
- 241000123650 Botrytis cinerea Species 0.000 description 2
- 241000228143 Penicillium Species 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000001212 derivatisation Methods 0.000 description 2
- 229930014626 natural product Natural products 0.000 description 2
- 125000002560 nitrile group Chemical group 0.000 description 2
- 150000002825 nitriles Chemical group 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PHDIJLFSKNMCMI-ITGJKDDRSA-N (3R,4S,5R,6R)-6-(hydroxymethyl)-4-(8-quinolin-6-yloxyoctoxy)oxane-2,3,5-triol Chemical compound OC[C@@H]1[C@H]([C@@H]([C@H](C(O1)O)O)OCCCCCCCCOC=1C=C2C=CC=NC2=CC=1)O PHDIJLFSKNMCMI-ITGJKDDRSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- ZCYMRZHNYXPSKC-UHFFFAOYSA-N 1,5-dimethyl-7-thiabicyclo[4.1.0]hepta-2,4-diene Chemical compound CC1=CC=CC2(C)SC12 ZCYMRZHNYXPSKC-UHFFFAOYSA-N 0.000 description 1
- CVQSDGUQZODCKQ-UHFFFAOYSA-N 1-(trifluoromethyl)-4-[4-(trifluoromethyl)phenyl]sulfanylbenzene Chemical compound C1=CC(C(F)(F)F)=CC=C1SC1=CC=C(C(F)(F)F)C=C1 CVQSDGUQZODCKQ-UHFFFAOYSA-N 0.000 description 1
- RFCQDOVPMUSZMN-UHFFFAOYSA-N 2-Naphthalenethiol Chemical compound C1=CC=CC2=CC(S)=CC=C21 RFCQDOVPMUSZMN-UHFFFAOYSA-N 0.000 description 1
- WLHCBQAPPJAULW-UHFFFAOYSA-N 4-methylbenzenethiol Chemical compound CC1=CC=C(S)C=C1 WLHCBQAPPJAULW-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- DOUHZFSGSXMPIE-UHFFFAOYSA-N hydroxidooxidosulfur(.) Chemical compound [O]SO DOUHZFSGSXMPIE-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001766 physiological effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a thioester compound and a product thereof, wherein the method comprises the steps of adding 1-indenone acetoxime ester, thiophenol, eosin Y, lithium carbonate and MPEG-550 into water, and stirring for 0.5-4 h under the irradiation of blue LED (lambda=440-480 nm) at room temperature. Extracting with ethyl acetate, and performing rotary evaporation chromatography to obtain the target product. The method for preparing the thioester compound has the characteristics of simplicity, high efficiency, mildness and environment friendliness.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and particularly relates to a preparation method of a thioester compound and a product thereof.
Background
Thioesters are present in large amounts in natural compounds, and their specific structure can lead to certain compounds having physiological activities, so that they are very widely used in medical treatment, pesticides, etc. Thioesters also relate to various fields such as polymers and additives. Also, since-SR is a good leaving group, thioesters are an important class of intermediates in organic synthesis as mild acylating agents. Because of the important biological properties and multifunctional reactivity of thioesters, thioesters have become a research hotspot for synthetic chemists, exploring many construction methods. The synthesis of thioesters using visible light is a new and promising technology.
Kim and Oh team 2019 reported a method for free radical coupling of acyl chloride and sodium aryl sulfinate to thioester under visible light promotion. Later, liao published studies on the formation of thioesters by deamination or decarboxylation thioesterification under visible light. However, these reactions typically rely on organic solvents (dichloromethane, dichloroethane, etc.) as well as expensive metal photocatalysts and/or reducing agents. Heretofore, there has been no method for synthesizing thioesters using inexpensive photocatalysts in water. Therefore, the development of a novel thioester synthesis method without metal catalysis and environmental friendliness has great significance.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the invention and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description summary and in the title of the application, to avoid obscuring the purpose of this section, the description summary and the title of the invention, which should not be used to limit the scope of the invention.
The present invention has been made in view of the above and/or the technical blank of the prior art for producing thioester compounds.
Therefore, one of the purposes of the invention is to solve the defects in the prior art and provide a preparation method of high-yield and high-purity thioester compounds.
In order to solve the technical problems, the invention provides the following technical scheme: a preparation method of a thioester compound comprises the steps of adding 1-indenone acetoxime ester, thiophenol, eosin Y, lithium carbonate and MPEG-550 into water, and stirring for 0.5-4 h under the irradiation of blue LED (lambda=440-480 nm) at room temperature. Extracting with ethyl acetate, and performing rotary evaporation chromatography to obtain the target product.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: deionized water is used as a solvent.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the blue LED: λ=440-480 nm, p=3-15W.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the 1-indenone acetoxime ester compound comprises a compound shown in a formula I:
wherein R is 1 、R 2 、R 3 Is a substituent group comprising: hydrogen, halogen, methoxy, cyano, trifluoromethyl, and the like; x is C or O atom; n=1 or 3.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the thiophenol compound includes the formula II
R 4 -SH
II
Wherein R is 4 Including phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, alkyl, t-butyl, trifluoromethyl, etc.), heterocycle, and naphthyl.
The molar ratio of the 1-indenone acetyl oxime ester compound to the 1-indenone acetyl oxime ester compound is 1-2:1.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the molar ratio of the photocatalyst eosin Y to the 1-indenone acetoxime ester compound is 0.01-0.05:1.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the molar ratio of the lithium carbonate to the 1-indenone acetyl oxime ester compound is 1-2:1.
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the mass ratio of the MPEG-550 and the deionized water is 0.02-0.1:1
As a preferable scheme of the preparation method of the thioester compound, the invention comprises the following steps: the rotary steaming is carried out at the rotating speed of 100-200 rpm, the temperature of 38-40 ℃, the vacuum of 0.08-0.12 Mpa and the treatment time of 3-5 min.
Another object of the present invention is to solve the drawbacks of the prior art and to provide a thioester compound.
In order to solve the technical problems, the invention provides the following technical scheme: comprises a thioester compound shown in a formula III,
wherein R is 1 、R 2 、R 3 Is a substituent group comprising: hydrogen, halogen, methoxy, cyano, trifluoromethyl, and the like; x is C or O atom; n=1 or 3
R 4 Including phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, alkyl, t-butyl, trifluoromethyl, etc.), heterocycle, and naphthyl.
The invention has the beneficial effects that:
(1) The preparation method of the thioester compound provided by the invention enables the ketoxime ester compound to be capable of generating the nitrile group-containing thioester compound through free radical coupling between the ketoxime ester compound and thiophenol.
(2) The whole reaction is initiated by visible light, and the water phase reaction system is used, so that the method is green, sustainable, safe, low-cost, nontoxic, nonflammable and good in environmental compatibility.
(3) Simple operation, high yield and purity of more than 98 percent.
(4) The conditions are mild, the substrate range is wide, not only the oxime ester derived from the 1-indenone natural product is applicable, but also the oxime ester derived from the 3-coumarone can react.
(5) The developed and prepared brand new compound has thioester and nitrile functional groups, has antibacterial activity of Botrytis cinerea, black mould, penicillium and the like, and can also obtain other active frameworks through subsequent derivatization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a nuclear magnetic resonance spectrum H of Compound 1 a;
FIG. 2 is a nuclear magnetic resonance spectrum C of the compound 1a, and FIGS. 1 and 2 show that the compound 1a has a correct structure;
FIG. 3 is a nuclear magnetic resonance spectrum H of Compound 1 b;
FIG. 4 is a nuclear magnetic resonance spectrum C of the compound 1b, and FIGS. 3 and 4 show that the compound 1b has a correct structure;
FIG. 5 is a nuclear magnetic resonance spectrum H of Compound 1 c;
FIG. 6 is a nuclear magnetic resonance spectrum C of the compound 1C, and FIGS. 5 and 6 show that the structure of the compound 1C is correct.
FIG. 7 is a nuclear magnetic resonance spectrum H of Compound 1 d;
FIG. 8 is a nuclear magnetic resonance spectrum C of the compound 1d, and FIGS. 7 and 8 show that the compound 1d has a correct structure.
FIG. 9 is a nuclear magnetic resonance spectrum H of Compound 1 e;
FIG. 10 is a nuclear magnetic resonance spectrum C of the compound 1e, and FIGS. 9 and 10 show that the compound 1e has a correct structure.
FIG. 11 is a nuclear magnetic resonance spectrum H of Compound 1 f;
FIG. 12 is a nuclear magnetic resonance spectrum C of the compound 1f, and FIGS. 11 and 12 show that the compound 1f has a correct structure.
Detailed Description
In order that the above-recited objects, features and advantages of the present invention will become more apparent, a more particular description of the invention will be rendered by reference to specific embodiments thereof.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present invention is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1:
10wt% MPEG-550/H was added to a 4mL vial 2 O (1 mL) of 1-indenone oxime ester (0.1 mmol,20.9 mg), 4-chlorophenylthiol (0.15 mmol,22.1 mg), eosin Y (1.3 mg,2 mol%) and Li 2 CO 3 (0.2 mmol,14.9 mg). The reaction mixture was stirred at room temperature under irradiation of a 2×5W blue LED (λ=440-480 nm) for 0.5h. The reaction mixture was extracted 3 times with ethyl acetate, the organic phases extracted several times were combined into a 100mL eggplant-shaped bottle, the mixture was treated for 5 minutes with a Heidolph rotary evaporator at a rotation speed of 100rpm at 38℃under a vacuum of 0.1MPa, and then subjected to column chromatography with 200 mesh column chromatography silica gel as a developing solvent of petroleum ether: ethyl acetate=10:1, to obtain the objective compound 1a (25.6 mg, yield: 89%) which was 98% in purity by HPLC analysis, and the purity of the product was extremely high in terms of nuclear magnetic pattern appearance, signal, noise and the like.
1 H NMR(600MHz，CDCl 3 )δ8.12(d，J＝7.7Hz，1H)，7.64-7.60(m，2H)，7.53-7.49(m，1H)，7.45(s，4H)，4.04(s，2H).
13 C NMR(150MHz，CDCl 3 )δ192.2，136.8，136.7，135.3，133.9，130.8，130.12，130.09，129.8，129.0，126.0，117.7，22.3.
Example 2:
10wt% MPEG-550/H was added to a 4mL vial 2 O (1 mL) 1-indenone oxime ester (0.1 mmol,20.9 mg), 4-trifluoromethylphenyl sulfide (0.15 mmol,27.3 mg), eosin Y (1.3 mg, 2)mol%) and Li 2 CO 3 (0.2 mmol,14.9 mg). The reaction mixture was stirred at room temperature under irradiation of a 2×5W blue LED (λ=440-480 nm) for 0.5h. The reaction mixture was extracted 3 times with ethyl acetate, the organic phases extracted several times were combined into a 100mL eggplant-shaped bottle, the mixture was treated for 5 minutes with a Heidolph rotary evaporator at a rotation speed of 100rpm at 38℃under a vacuum of 0.1MPa, and then subjected to column chromatography with 200 mesh column chromatography silica gel as a developing solvent of petroleum ether: ethyl acetate=10:1, to obtain the objective compound 1b (26.0 mg, yield: 81%) which was 98% in purity by HPLC analysis, and the purity of the product was extremely high in terms of nuclear magnetic pattern appearance, signal, noise and the like.
1 H NMR(600MHz，CDCl 3 )δ8.14(d，J＝7.9Hz，1H)，7.73(d，J＝8.2Hz，2H)，7.66(d，J＝8.2Hz，2H)，7.63(t，J＝8.2Hz，2H)，7.55-7.51(m，1H)，4.04(s，2H).
13 C NMR(150MHz，CDCl 3 )δ191.5，135.7，135.2，134.1，132.3，132.2(q，J＝32.9Hz)，131.0，130.2，130.1，129.1，126.6(q，J＝3.6Hz)，124.1(q，J＝272.4Hz)，117.7，22.4.
Example 3:
10wt% MPEG-550/H was added to a 4mL vial 2 O (1 mL) 1-indenone oxime ester (0.1 mmol,20.9 mg), 4-methyl thiophenol (0.15 mmol,19.0 mg), eosin Y (1.3 mg,2 mol%) and Li 2 CO 3 (0.2 mmol,14.9 mg). The reaction mixture was stirred at room temperature under irradiation of a 2×5W blue LED (λ=440-480 nm) for 0.5h. The reaction mixture was extracted 3 times with ethyl acetate, the organic phases of several extractions were combined into a 100mL eggplant-shaped bottle, the mixture was treated for 5min with a Heidolph rotary evaporator at a speed of 100rpm at 38℃under a vacuum of 0.1MPa, and column chromatography was performed on 200 mesh column chromatography silica gel with a developing solvent of petroleum ether: ethyl acetate=10:1, and the objective compound 1c (17.8 mg, yield 67%) was isolated byThe purity of HPLC analysis is 98%, and the purity of the product can be reflected in the aspects of nuclear magnetic pattern appearance, signals, noise and the like.
1 H NMR(600MHz，CDCl 3 )δ8.14(d，J＝7.7Hz，1H)，7.64-7.58(m，2H)，7.53-7.47(m，1H)，7.40(d，J＝8.0Hz，2H)，7.30(d，J＝7.9Hz，2H)，4.06(s，2H)，2.42(s，3H).
13 C NMR(150MHz，CDCl 3 )δ193.3，140.8，135.7，135.4，133.6，130.7，130.7，130.1，129.7，128.9，124.0，117.9，22.3，21.2.
Example 4:
10wt% MPEG-550/H was added to a 4mL vial 2 O (1 mL) of 1-indenone oxime ester (0.1 mmol,20.9 mg), 2, 6-dimethylbenzenesulfide (0.15 mmol,21.4 mg), eosin Y (1.3 mg,2 mol%) and Li 2 CO 3 (0.2 mmol,14.9 mg). The reaction mixture was stirred at room temperature under irradiation of a 2×5W blue LED (λ=440-480 nm) for 0.5h. The reaction mixture was extracted 3 times with ethyl acetate, the organic phases extracted several times were combined into a 100mL eggplant-shaped bottle, the mixture was treated for 5 minutes with a Heidolph rotary evaporator at a rotation speed of 100rpm at 38℃under a vacuum of 0.1MPa, and then subjected to column chromatography with 200 mesh column chromatography silica gel as a developing solvent of petroleum ether: ethyl acetate=10:1, to obtain the objective compound 1d (24.3 mg, yield: 87%) which was 98% in purity by HPLC analysis, and the purity of the product was extremely high in terms of nuclear magnetic pattern appearance, signal, noise and the like.
1 H NMR(600MHz，CDCl 3 )δ8.26(d，J＝7.7Hz，1H)，7.63-7.60(m，2H)，7.55-7.51(m，1H)，7.33-7.28(m，1H)，7.23(d，J＝7.6Hz，2H)，4.05(s，2H)，2.44(s，6H).
13 C NMR(150MHz，CDCl 3 )δ192.0，143.6，136.1，133.6，130.7，130.4，129.7，129.0，128.9，126.9，117.9，22.2，21.6.
Example 5:
10wt% MPEG-550/H was added to a 4mL vial 2 O (1 mL) 1-indenone oxime ester (0.1 mmol,20.9 mg), 2-naphthalene thiol (0.15 mmol,24.5 mg), eosin Y (1.3 mg,2 mol%) and Li 2 CO 3 (0.2 mmol,14.9 mg). The reaction mixture was stirred at room temperature under irradiation of a 2×5W blue LED (λ=440-480 nm) for 0.5h. The reaction mixture was extracted 3 times with ethyl acetate, the organic phases extracted several times were combined into a 100mL eggplant-shaped bottle, the mixture was treated for 5 minutes with a Heidolph rotary evaporator at a rotation speed of 100rpm at 38℃under a vacuum of 0.1MPa, and then subjected to column chromatography with 200 mesh column chromatography silica gel as a developing solvent of petroleum ether: ethyl acetate=10:1, to obtain the objective compound 1e (14.4 mg, yield: 47%) which was 98% in purity by HPLC analysis, and the purity of the product was extremely high in terms of nuclear magnetic pattern appearance, signal, noise and the like.
1 H NMR(600MHz，CDCl 3 )δ8.20(d，J＝8.1Hz，1H)，8.06(s，1H)，7.95(d，J＝8.5Hz，1H)，7.92-7.86(m，2H)，7.66-7.62(m，2H)，7.59-7.56(m，2H)，7.55-7.52(m，2H)，4.07(s，2H).
13 C NMR(150MHz，CDCl 3 )δ193.4，136.1，135.9，134.5，134.4，134.2，132.0，131.1，130.6，130.1，129.9，129.4，128.9，128.7，128.2，127.5，125.2，118.2，22.7.
Example 6:
10wt% MPEG-550/H was added to a 4mL vial 2 O (1 mL) 3-coumarone oxime ester (0.1 mmol,21.6 mg), 4-chlorophenylthiol (0.15 mmol,22.1 mg), eosin Y (1.3 mg,2 mol%) and Li 2 CO 3 (0.2 mmol,14.9 mg). At room temperature, at 2×The reaction mixture was stirred for 0.5h under irradiation of a 5W blue LED (λ=440-480 nm). The reaction mixture was extracted 3 times with ethyl acetate, the organic phases extracted several times were combined into a 100mL eggplant-shaped bottle, the mixture was treated for 5 minutes with a Heidolph rotary evaporator at a rotation speed of 100rpm at 38℃under a vacuum of 0.1MPa, and then subjected to column chromatography with 200 mesh column chromatography silica gel as a developing solvent of petroleum ether: ethyl acetate=10:1, to obtain the objective compound 1f (2.9 mg, yield: 14%) which was 98% in purity by HPLC analysis, and the purity of the product was extremely high in terms of nuclear magnetic pattern appearance, signal, noise, etc.
1 H NMR(600MHz，CDCl 3 )δ7.76(d，J＝7.8Hz，1H)，7.73-7.69(m，1H)，7.56(d，J＝8.5Hz，2H)，7.40-7.36(m，2H)，7.30-7.26(m，2H).
13 C NMR(150MHz，CDCl 3 )δ176.8，163.9，146.7，139.0，135.6，134.0，129.7，127.5，125.7，125.2，121.6，113.4.
Therefore, the preparation method of the thioester compound provided by the invention enables oxime ester compounds derived from 1-indenone and the like to open loop in water under the initiation of visible light to generate thioester with a special structure containing nitrile groups. The whole reaction uses water as a solvent, metal catalysis is not needed, and the method is green, sustainable, safe, low-cost, nontoxic, nonflammable and good in environmental compatibility; the operation is simple, the yield is high, and the purity is more than 98%; the conditions are mild, the substrate range is wide, not only the 1-indenone can be suitable, but also the 3-coumarone can be modified by the method. The synthesized compound has thioester and nitrile functional groups and has antibacterial activity of Botrytis cinerea, black mould, penicillium and the like, and other active skeletons can be obtained through subsequent derivatization.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A method for synthesizing a thioester compound by ring opening of photocatalytic indenone in water is characterized by comprising the following steps:
1-indenone acetoxime ester, thiophenol, eosin Y, lithium carbonate and MPEG-550 were added to water, and stirred at room temperature under irradiation of blue LED (lambda=440-480 nm) for 0.5 to 4 hours. Extracting with ethyl acetate, and performing rotary evaporation chromatography to obtain the target product.
2. The method for producing a thioester compound according to claim 1, characterized in that: deionized water is used as a solvent.
3. The method for producing a thioester compound according to claim 1, characterized in that: the blue LED: λ=440-480 nm, p=3-15W.
4. The method for producing a thioester compound according to claim 1, characterized in that: the ketoxime ester compound comprises a compound represented by formula I:
wherein R is 1 、R 2 、R 3 Is a substituent group comprising: hydrogen, halogen, methoxy, cyano, trifluoromethyl, and the like; x is C or O atom; n=1 or 3.
5. The method for producing a thioester compound according to claim 1, characterized in that: the mercaptan compound comprises the formula II
R 4 -SH
II
Wherein R is 4 Including phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, alkyl, t-butyl, trifluoromethyl, etc.), heterocycle, and naphthyl.
The molar ratio of the 1-indenone acetyl oxime ester compound to the 1-indenone acetyl oxime ester compound is 1-2:1.
6. The method for producing a thioester compound according to claim 1, characterized in that: the molar ratio of the photocatalyst eosin Y to the 1-indenone acetoxime ester compound is 0.01-0.05:1.
7. The method for producing a thioester compound according to claim 1, characterized in that: the molar ratio of the lithium carbonate to the 1-indenone acetyl oxime ester compound is 1-2:1.
8. The method for producing a thioester compound according to claim 1, characterized in that: the mass ratio of the MPEG-550 to the deionized water is 0.02-0.1:1.
9. The method for producing a thioester compound according to claim 1, characterized in that: the rotary steaming is carried out at the rotating speed of 100-200 rpm, the temperature of 38-40 ℃, the vacuum of 0.08-0.12 Mpa and the treatment time of 3-5 min.
10. A product produced by the process for producing a sulfur ester compound according to claim 1, characterized in that: comprises a thioester compound shown in a formula III,
wherein R is 1 、R 2 、R 3 Is a substituent group comprising: hydrogen, halogen, methoxy, cyano, trifluoromethyl, and the like; x is C or O atom; n=1 or 3
R 4 Including phenyl, substituted phenyl (including mono-substituted phenyl and poly-substituted phenyl, substituents including halogen, alkyl, t-butyl, trifluoromethyl, etc.), heterocycle, and naphthyl.
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