CN109096162A - A kind of nucleophilic addition method of the scandium catalysis mercaptan to o-quinone methides - Google Patents
A kind of nucleophilic addition method of the scandium catalysis mercaptan to o-quinone methides Download PDFInfo
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- CN109096162A CN109096162A CN201810995702.6A CN201810995702A CN109096162A CN 109096162 A CN109096162 A CN 109096162A CN 201810995702 A CN201810995702 A CN 201810995702A CN 109096162 A CN109096162 A CN 109096162A
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- nucleophilic addition
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/14—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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Abstract
The present invention relates to a kind of scandium catalysis mercaptan to the nucleophilic addition method of o-quinone methides, 2- (hydroxyl (phenyl) methyl) phenol compound and sulfur alcohol compound are dissolved in solvent, Sc (III) catalyst is added, is stirred to react 5-10h at 30-70 DEG C；Reaction solution after reaction is extracted, by organic layer washing, drying, except solvent, residue silica gel column chromatography are up to product.This method utilizes trivalent scandium catalyst, and synthesis condition is mild, neutral reaction, the substitution type of functional group are limited smaller, high income, realizes a kind of thia Michael addition reaction of high-efficiency environment friendly.
Description
Technical field
The present invention relates to a kind of thia Michael addition reaction, in particular to a kind of Sc (III) (scandium) catalysis mercaptan is to neighbour
The nucleophilic addition method of methylene benzoquinones, belongs to technical field of organic synthesis.
Background technique
O-quinone methides compound is a kind of very active and important intermediate, be widely used in natural products and
In pharmaceutical chemistry.Because o-quinone methides compound is widely used, preparation method research is always that organic synthesis expert is closed
The hot spot of note has had many methods now to prepare this kind of compound: being for example pyrolyzed, photochemical reaction, acid, alkaline condition
Etc., reaction condition is more harsh.Reaction type about o-quinone methides is broadly divided into three classes: nucleophilic addition, ring
Addition reaction and 6 π electrocyclic reaction.The repercussion study of o-quinone methides has had longer history, and miscellaneous based on P, S and N
The Michael addition reaction of atom is also more mature, but most reaction method still needs using acid-base property catalyst,
Such reaction method is not suitable for preparation containing the compound to soda acid susceptible functionality, and system needs after the completion of reaction
It is neutralized to neutrality, post-processing operation is cumbersome.
The building of carbon-sulfur bond has a wide range of applications in the synthesis of many sulfur-bearing natural products and drug molecule, wherein
Thia Michael addition reaction is a kind of synthetic method of synthesis organic compounds containing sulfur being simple and efficient.In recent years, chemical
Family mainly by precious metal, acid and basic catalyst come the progress that promotes such to react, such as (IMesPr) AuCl,
[LNi2(CH3CN)(THF)](ClO4)3,[Ru(acetone)(R,R-BIPHOP-F)Cp][SbF6],NEt3,SDS/NaHCO3,
Co/SBA-15. a kind of method for the thia Michael addition reaction for therefore developing high-efficiency environment friendly has great importance.
Therefore, developing new simply and efficiently mercaptan has weight to the method for the nucleophilic addition of o-quinone methides
The meaning wanted.
Summary of the invention
The purpose of the present invention is overcoming above-mentioned insufficient a kind of scandium catalysis mercaptan is provided, the nucleophilic of o-quinone methides is added
At reaction method.This method synthesis condition is mild, neutral reaction, the substitution type of functional group are limited smaller, high income.
The technical scheme adopted by the invention is as follows:
A kind of scandium catalysis mercaptan comprises the following steps that the nucleophilic addition method of o-quinone methides
2- (hydroxyl (phenyl) methyl) phenol compound and sulfur alcohol compound are dissolved in solvent, are added Sc (III)
Catalyst is stirred to react 5-10h at 30-70 DEG C；Reaction solution after reaction is extracted, by organic layer washing, drying, except molten
Agent, residue silica gel column chromatography are up to product；Described 2- (hydroxyl (phenyl) methyl) phenol compound, thio-alcohol chemical combination
Object, Sc (III) catalyst molar ratio be 1:1.5-3:0.05-0.2.
2- described in the above method (hydroxyl (phenyl) methyl) phenol compound structural formula is as follows:
Wherein R1、R2It is identical or different, it is respectively selected from H, C1-C5Alkyl, halogen atom, nitroso, cyano；R1、R2It is excellent
First it is respectively selected from methyl, ethyl, methoxyl group, ethyoxyl, fluorine atom, chlorine atom and bromine atom.
The sulfur alcohol compound is R3.SH, R3For benzyl, C1-C10Alkyl in any one.
Sc (III) catalyst in trifluoromethanesulfonic acid scandium, scandium chloride, scandium bromide, scandium nitrate, scandium sulfate one
Kind is a variety of.Preferably trifluoromethayl sulfonic acid scandium.
The solvent be DMF, DMSO, toluene, acetonitrile, methylene chloride, chloroform, 1,2- dichloroethanes, ethyl acetate or
One of tetrahydrofuran；It is preferred that 1,2- dichloroethanes.Solvent usage and 2- (hydroxyl (phenyl) methyl) phenol compound
Ratio is 2-10:1, ml:mmol.
Described 2- (hydroxyl (phenyl) methyl) phenol compound, sulfur alcohol compound, Sc (III) catalyst mole
Than being preferably 1:2:0.1.
The eluent of the silica gel column chromatography is preferably one of petroleum ether, n-hexane, hexamethylene or multiple combinations；
More preferably petroleum ether.
Above-mentioned scandium is catalyzed mercaptan to the nucleophilic addition method of o-quinone methides, and reaction equation is as follows:
The present invention is generated with 2- (hydroxyl (phenyl) methyl) phenol compound and sulfur alcohol compound by scandium catalysis and in situ
Simultaneously nucleophilic addition occurs for o-quinone methides, avoids the disadvantage of conventional method expensive catalyst, condition harshness, and product is easy
It isolates and purifies, there is important value to the methodological study of o-quinone methides, in the conjunction of sulfur-bearing natural products and drug molecule
Have great importance in.
The invention has the benefit that
(1) it is catalyzed in-situ preparation o-quinone methides compound in the reaction using scandium, uses sulfur alcohol compound and neighbour
Nucleophilic addition occurs for methylene benzoquinones, synthetic method mild condition, under neutrallty condition the substitution type of functional group it is limited compared with
It is small；
(2) preparation method of the invention is easy to operate, and raw materials and reagents are simple, the easily separated purifying of product, reaction yield compared with
Height, yield is up to 82%~95%；
(3) reaction is tandem reaction, is catalyzed first with catalyst containing scandium and forms intermediate o-quinone methides, and then urged
Change mercaptan thia Michael addition reaction is carried out to intermediate and obtain product, reaction efficiency is high, realizes a kind of high-efficiency environment friendly
Thia Michael addition reaction.
Specific embodiment
The present invention is further described combined with specific embodiments below.
Embodiment 1:
2.00g (10mmol) compound I-1,1.24g (20mmol) compound II- is added in the round-bottomed flask of 100mL
1,0.49g (1mmol) solid trifluoromethanesulfonic acid scandium Sc (OTf)3, it is eventually adding dry 1, the 2- dichloroethanes of 20mL, gained mixing
Object is stirred to react 10 hours at 30 DEG C.It after reaction mixture is cooled to room temperature, is poured into ice water, with the dichloromethane of 50mL × 3
Alkane extraction merges extraction organic phase, washed once with saturated salt solution, anhydrous Na2SO4Dry, concentration removes solvent and obtains slightly
Product obtain the sterling of compound III-1 through column chromatography for separation.Oily liquids, 2.17g, yield 92%.1H NMR(400MHz,
CDCl3) δ: 7.40 (d, J=7.4Hz, 2H), 7.32-7.16 (m, 5H), 7.05 (dd, J=7.6Hz, 1.2Hz, 1H), 6.91
(dd, J=8.0Hz, 0.7Hz, 1H), 6.88-6.82 (m, 1H), 5.39 (s, 1H), 2.49-2.43 (m, 2H), 1.23 (t, J=
7.4Hz,3H)；13C NMR(CDCl3,100MHz)δ:155.15,139.31,130.17,129.21,128.69,128.67,
128.53,128.51,127.55,125.16,120.76,117.60,50.47,26.36,14.20；HRMS(ESI)calcd
for C15H17OS[M+H]+245.0995,found 245.0996。
Embodiment 2:
2.00g (10mmol) compound I-1,1.52g (20mmol) compound II-2 is added in the round-bottomed flask of 100mL,
0.98g (2mmol) solid Sc (OTf)3, it is eventually adding the dry DMF of 25mL, gained mixture stirs 3 hours at 40 DEG C to reaction
Completely.Reaction mixture is cooled to room temperature, and is poured into water, stirring, is extracted with the methylene chloride of 50mL × 3, and merging extraction has
Machine phase, washed once with saturated salt solution, anhydrous Na2SO4Dry, concentration removes solvent and obtains crude product, obtains through column chromatography for separation
The sterling of compound III-2.Oily liquids, 2.32g, yield 90%.1H NMR(400MHz,CDCl3) δ 7.40 (d, J=
7.4Hz, 2H), 7.34-7.29 (m, 2H), 7.21 (ddd, J=15.4Hz, 10.6Hz, 4.4Hz, 2H), 7.03 (dd, J=
7.6Hz, 1.3Hz, 1H), 6.95-6.89 (m, 1H), 6.84 (td, J=7.6Hz, 1.0Hz, 1H), 5.35 (s, 1H), 2.48-
2.39 (m, 2H), 1.61 (dd, J=14.6Hz, 7.3Hz, 2H), 0.95 (t, J=7.4Hz, 3H)；13C NMR(CDCl3,
100MHz)δ:155.22,139.30,130.18,129.21,128.66,128.48,127.53,125.11,120.70,
117.64,50.97,34.33,22.32,13.49；HRMS(ESI)calcd for C16H19OS[M+H]+259.1151,found
259.1150。
Embodiment 3:
2.00g (10mmol) compound I-1,1.35g (15mmol) compound II-3 is added in the round-bottomed flask of 100mL,
0.12g (0.5mmol) solid Sc (NO3)3, it is eventually adding the dry DMSO of 50mL, it is small that gained mixture is vigorously stirred 5 at 50 DEG C
When.It after reaction mixture is cooled to room temperature, is poured into water, stirs, extracted with the methylene chloride of 50mL × 3, merging extraction has
Machine phase, washed once with saturated salt solution, anhydrous Na2SO4Dry, concentration boils off solvent and obtains crude product, obtains through column chromatographic purifying
The sterling of compound III-3.Oily liquids, 2.37g, yield 87%.1H NMR(400MHz,CDCl3) δ: 7.40 (d, J=
7.4Hz, 2H), 7.31 (dd, J=13.8Hz, 6.6Hz, 3H), 7.21 (ddd, J=11.3Hz, 8.7Hz, 4.4Hz, 2H), 7.03
(dd, J=7.6Hz, 1.3Hz, 1H), 6.92 (dd, J=8.0,0.6Hz, 1H), 6.87-6.80 (m, 1H), 5.31 (s, 1H),
2.35 (qd, J=12.5Hz, 6.8Hz, 2H), 1.83 (dt, J=13.4Hz, 6.7Hz, 1H), 0.95 (dd, J=8.0Hz,
6.8Hz,6H)；13C NMR(CDCl3,100MHz)δ:155.26,139.36,130.24,129.22,128.66,128.51,
128.48,128.45,127.54,125.12,120.69,117.65,51.54,41.27,28.24,22.22,21.98；HRMS
(ESI)calcd for C17H21OS[M+H]+273.1308,found 273.1305。
Embodiment 4:
2.00g (10mmol) compound I-1,1.86g (15mmol) compound II-4 is added in the round-bottomed flask of 100mL,
0.49g (1mmol) solid Sc (OTf)3, it is eventually adding 50mL1,2- dichloroethanes, gained mixture is vigorously stirred 7 at 40 DEG C
Hour.It after reaction mixture is cooled to room temperature, is poured into water, stirs, extracted with the methylene chloride of 50mL × 3, merge extraction
Organic phase washed once with saturated salt solution, anhydrous Na2SO4Dry, concentration removes solvent and obtains an oily residue, through column layer
Analysis purifying obtains the sterling of compound III-4.Oily liquids, 3.78g, yield 91%.1H NMR(400MHz,CDCl3)δ:7.36
(d, J=7.3Hz, 2H), 7.30 (t, J=7.3Hz, 4H), 7.27-7.22 (m, 2H), 7.18 (dd, J=12.7Hz, 4.5Hz,
3H), 6.95 (dd, J=7.7Hz, 1.3Hz, 1H), 6.90 (d, J=8.4Hz, 2H), 6.86-6.79 (m, 1H), 5.11 (s,
1H), 3.59 (d, J=3.2Hz, 2H)；13C NMR(CDCl3,100MHz)δ:155.03,138.75,137.28,130.31,
129.30,129.01,128.99,128.76,128.73,127.65,127.47,124.86,120.80,117.60,49.68,
36.54；HRMS(ESI)calcd for C20H19OS[M+H]+307.1151,found 307.1152。
Embodiment 5:
2.00g (10mmol) compound I-1,0.92g (20mmol) compound II-5 is added in the round-bottomed flask of 100mL,
0.15g (1mmol) solid ScCl3, it is eventually adding the dry DMF of 30mL, gained mixture is vigorously stirred 8 hours at 30 DEG C.Instead
It after answering mixture to be cooled to room temperature, is poured into water, stirs, extracted with the methylene chloride of 50mL × 3, merge extraction organic phase,
It washed once with saturated salt solution, anhydrous Na2SO4Dry, concentration removes solvent and obtains an oily residue, through column chromatographic purifying
Obtain the sterling of compound III-5.Oily liquids, 2.56g, yield 86%.1H NMR(400MHz,CDCl3) δ: 7.40 (d, J=
7.3Hz, 3H), 7.30 (t, J=7.4Hz, 2H), 7.26-7.13 (m, 2H), 7.03 (dd, J=7.6Hz, 1.3Hz, 1H),
6.97-6.88 (m, 1H), 6.85 (dd, J=10.8Hz, 4.1Hz, 1H), 5.36 (s, 1H), 2.91 (p, J=7.0Hz, 1H),
1.91 (dt, J=12.3Hz, 6.3Hz, 2H), 1.72-1.70 (m, 2H), 1.64-1.50 (m, 4H)；13C NMR(CDCl3,
100MHz)δ:155.33,139.37,130.05,129.15,128.64,128.46,128.44,127.47,125.36,
120.70,117.71,51.40,44.23,33.65,33.20,24.88,24.74；HRMS(ESI)calcd for C18H21OS
[M+H]+285.1308,found 285.1308。
Above-mentioned, although specific embodiments of the present invention have been described, not to the limit of the scope of the present invention
System, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art do not need to pay
The various modifications or changes that creative work can be made out are still within protection scope of the present invention.
Claims (10)
1. a kind of scandium catalysis mercaptan is to the nucleophilic addition method of o-quinone methides, characterized in that comprise the following steps that
2- (hydroxyl (phenyl) methyl) phenol compound and sulfur alcohol compound are dissolved in solvent, Sc (III) catalysis is added
Agent is stirred to react 5-10h at 30-70 DEG C；Reaction solution after reaction is extracted, by organic layer washing, it is dry, except solvent,
Residue silica gel column chromatography is up to product；Described 2- (hydroxyl (phenyl) methyl) phenol compound, sulfur alcohol compound, Sc
(III) molar ratio of catalyst is 1:1.5-3:0.05-0.2.
2. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the 2- (hydroxyl (phenyl) methyl) phenol compound structural formula is as follows:
Wherein R1、R2It is identical or different, it is respectively selected from H, C1-C5Alkyl, halogen atom, nitroso, cyano.
3. a kind of scandium catalysis mercaptan according to claim 2 is to the nucleophilic addition method of o-quinone methides, special
Sign is the R1、R2It is respectively selected from methyl, ethyl, methoxyl group, ethyoxyl, fluorine atom, chlorine atom and bromine atom.
4. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the sulfur alcohol compound is R3.SH, R3For benzyl, C1-C10Alkyl in any one.
5. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the Sc (III) catalyst is selected from one of trifluoromethanesulfonic acid scandium, scandium chloride, scandium bromide, scandium nitrate, scandium sulfate
Or it is a variety of.
6. a kind of scandium catalysis mercaptan according to claim 5 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the Sc (III) catalyst is trifluoromethanesulfonic acid scandium.
7. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the solvent is DMF, DMSO, toluene, acetonitrile, methylene chloride, chloroform, 1,2- dichloroethanes, ethyl acetate or tetrahydro
One of furans.
8. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the usage ratio of the solvent and 2- (hydroxyl (phenyl) methyl) phenol compound is 2-10:1, ml:mmol.
9. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is the molar ratio of the 2- (hydroxyl (phenyl) methyl) phenol compound, sulfur alcohol compound, Sc (III) catalyst
For 1:2:0.1.
10. a kind of scandium catalysis mercaptan according to claim 1 is to the nucleophilic addition method of o-quinone methides, special
Sign is that the eluent of the silica gel column chromatography is one of petroleum ether, n-hexane, hexamethylene or multiple combinations.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110437129A (en) * | 2019-08-17 | 2019-11-12 | 齐鲁工业大学 | A kind of straightforward procedure synthesizing 3- ether isoindoline ketone compound |
| CN112939830A (en) * | 2019-11-26 | 2021-06-11 | 山东省科学院新材料研究所 | Nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone |
| CN114436922A (en) * | 2022-01-26 | 2022-05-06 | 江西师范大学 | Compound containing C-S bond and preparation method and application thereof |
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2018
- 2018-08-29 CN CN201810995702.6A patent/CN109096162B/en active Active
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110437129A (en) * | 2019-08-17 | 2019-11-12 | 齐鲁工业大学 | A kind of straightforward procedure synthesizing 3- ether isoindoline ketone compound |
| CN112939830A (en) * | 2019-11-26 | 2021-06-11 | 山东省科学院新材料研究所 | Nucleophilic reaction method of alkenyl thioether to o-methylene benzoquinone |
| CN114436922A (en) * | 2022-01-26 | 2022-05-06 | 江西师范大学 | Compound containing C-S bond and preparation method and application thereof |
| CN114436922B (en) * | 2022-01-26 | 2023-09-29 | 邵阳学院 | Compound containing C-S bond, and preparation method and application thereof |
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Effective date of registration: 20221223 Address after: 250306 Room 3115, No. 135, Ward Avenue, Ping'an Street, Changqing District, Jinan City, Shandong Province Patentee after: Shandong Jiqing Technology Service Co.,Ltd. Address before: 250014 No. 19, ASTRI Road, Lixia District, Shandong, Ji'nan Patentee before: NEW MATERIAL INSTITUTE OF SHANDONG ACADEMY OF SCIENCES |