CN101314581B - N-sulfuryl ketimine compounds and preparation method thereof - Google Patents
N-sulfuryl ketimine compounds and preparation method thereof Download PDFInfo
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- CN101314581B CN101314581B CN2008100626791A CN200810062679A CN101314581B CN 101314581 B CN101314581 B CN 101314581B CN 2008100626791 A CN2008100626791 A CN 2008100626791A CN 200810062679 A CN200810062679 A CN 200810062679A CN 101314581 B CN101314581 B CN 101314581B
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Abstract
The invention discloses an N-sulfonylketimine compound and the preparation method thereof. The preparation method includes that alkine compound shown in formula (I) and a sulfonamide compound shown in formula (II) react in the presence of a MLYn transition metal catalyst in an inert organic solvent at 35-140 DEG C; and the reaction solution is subjected to a post-treatment to obtain the N-sulfonylketimine compound shown in formula (III). The method has the advantages that the reaction conditions is mild; the operation is convenient; the product quality is good; the yield is high; the environment friendliness is ensured; the whole production process is substantially harmless; and the operators are safe; the reaction is in accordance with the atom economic principle and has high utilization rate of the raw material. Since the N-sulfonylketimine is an excellent raw material for preparing pharmaceuticals, agricultural chemicals and chemical products, the preparation method has wide industrial application prospect.
Description
(1) technical field
The present invention relates to N-sulfuryl ketimine compounds and preparation method thereof.
(2) background technology
The N-sulfuryl ketimine compounds is widely used in synthetic fields such as agricultural chemicals, medicine as important industrial chemicals midbody.Up to the present report more about N-sulfuryl ketimine compounds compound method: 1. elder generation dewaters with the sulfinyl amine condensation under the Lewis acid condition, further oxidation prepares (Yang again through ketone compounds; Qin; Angew.Chem.Int.Ed. (2006), 45 (23), 3832-3835.; Ruano, Jose Luis Garcia, Org.Synth. (2007), 84,129-138; Ruano, Jose Luis Garcia, Org.Let. (2005), 7 (2), 179-182).2. prepare (Timokhin, Vitaliy I., J.Am.Chem.Soc. (2003), 125 (43), 12996-12997 through ketone compounds and vinylbenzene oxidation addition under palladium catalysis; Brice, Jodie L, J.Am.Chem.Soc. (2005), 127 (9), 2868-2869; ).Through sulphonamide and ketone compounds under the Lewis acid condition directly dehydrating condensation prepare (Ram, Ram N., Synth.Commun. (2001), 31 (6), 841-846).4. react with two (trimethyl silicon based) amine under the highly basic condition through ketone compounds and SULPHURYL CHLORIDE and prepare (Georg, Gunda I., J.Org.Chem. (1995), 60 (22), 7366-8).But the preparing method's complex steps that has, and generate by product easily, the yield that has is lower, and circulation ratio is bad, has therefore limited its applicability.
(3) summary of the invention
The primary technical problem that the present invention will solve has provided one type of N-sulfuryl ketimine compounds, and said compound has following general structure:
In the formula (III), R
1Independently be selected to ethylphenyl, to butyl phenyl, to amyl group phenyl, p-methoxyphenyl or to ethoxyl phenenyl; R
2Be hydrogen; R
3Independently be selected from phenyl, p-methylphenyl or to iodophenyl.
Another technical problem that the present invention will solve provides the novel method of a kind of simple, mild condition, raw material is easy to get, reaction yield is high, easy and simple to handle synthetic N-sulfuryl ketimine compounds; Said preparation method is following: under the transition-metal catalyst effect; Raw material fully reacts in 35～140 ℃ in inert organic solvents suc as formula the acetylene hydrocarbon compound shown in (I) with suc as formula sulfamide compound shown in (II), and reaction solution makes described N-sulfuryl ketimine compounds (III) through aftertreatment; Reaction formula is following:
Acetylene hydrocarbon compound (I) and sulfamide compound (II) that the present invention uses are the commercially available prod.
Further, the amount of said raw material is than sulfamide compound (II): acetylene hydrocarbon compound (I) is recommended as 1: 1.0～and 5.0, preferred 1: 3.
Transition-metal catalyst used in the present invention is used MLY
nExpression, wherein M is Jinyang ion, and L is and the ligand of Jinyang ion coordination, and Y is a negatively charged ion, and n is the ratio of Jinyang ionic valence mumber and negatively charged ion valence mumber.Among the present invention, it is one of following that M can be selected from: monovalence Jinyang ion, trivalent Jinyang ion; It is one of following that L can be selected from: triphenyl phosphorus, trimethylammonium phosphorus, tributyl phosphorus; It is one of following that Y can be selected from: cl anion, bromine anions, nitric acid negatively charged ion.The preferred M of catalyzer of the present invention is monovalence Jinyang ion; The preferred triphenyl phosphorus of L; The preferred cl anion of Y, promptly preferred described catalyzer are that its consumption is recommended as: with respect to the sulfamide compound of 1mol suc as formula the gold trichloride-triphenyl phosphorus complex compound of (IV) expression; Use 0.001～0.2mol, preferred 0.01～0.1mol.
(PPh
3)AuCl
(IV)
Further, reaction of the present invention is except adding transition-metal catalyst MLY
nAs catalyzer, can also add silver trifluoromethanesulfonate as promotor, the consumption of said promotor silver trifluoromethanesulfonate is recommended as: with respect to the sulfamide compound of 1mol, use 0.01～0.2mol, preferred 0.02～0.1mol.
Inert organic solvents of the present invention can be selected halogenated aliphatic hydrocarbon class, substituted benzene or ether compound for use, specifically can select for use one of following: methylene dichloride, ethylene dichloride, toluene, chlorophenetole, THF, dioxane.Be best with ethers as solvent wherein, its consumption is recommended as: with respect to the sulfamide compound of 1mol, use 1～12L, preferred 2～6L.
Temperature of reaction according to the invention is preferably 50～120 ℃.
The present invention is through TLC detection reaction terminal point, and the general reaction times is 0.5～20h, preferred 2～10h.
Described aftertreatment can be adopted following steps: reaction solution is cooled to room temperature, adds saturated NaHCO
3Solution is used ethyl acetate extraction, organic layer with the anhydrous sodium sulfate drying after-filtration, boil off solvent, can obtain the pure article of N-sulphonyl ketoimine through column chromatography is refining.
Concrete recommendation N-sulfuryl ketimine compounds according to the invention prepares according to following steps: with acetylene hydrocarbon compound, sulfamide compound, catalyzer (PPh)
3AuCl) and silver trifluoromethanesulfonate in organic solvent, mix; Gold trichloride-triphenyl phosphorus the complex compound, silver trifluoromethanesulfonate, the acetylene hydrocarbon compound that add are 0.01～0.1: 0.02～0.1 with the amount of substance ratio of sulfamide compound: 1.0～5.0: 1; Mix the back controlled temperature at 50～120 ℃ of reaction 2～10h; Reaction solution is cooled to room temperature, adds saturated NaHCO
3, use ethyl acetate extraction then, organic layer is used anhydrous sodium sulfate drying, filters, and concentrates column chromatography (sherwood oil: the refining target compound that obtains ETHYLE ACETATE=20: 1).
Of the present invention have the compound of N-sulfimide structure and a preparation method of verivate thereof, and its key has been to select for use the compound of containing metal gold to make catalyzer, and reaction generates compound and the verivate thereof with N-sulfimide structure.Its advantage is: (1) reaction conditions is gentle, and easy to operate, product quality is good, and yield is high.(2) to environment-friendly, the basic toxicological harmless of whole process of production produces, to operator also safety.(3) this reaction meets the atom economy principle, and raw material availability is high.Seeing that the N-sulfonyl imide compounds as one type of important organic intermediate, is the good raw material of synthetic medicine intermediate, agricultural chemicals and Chemicals, so the present invention has the wide industrial application prospect.The concrete application as follows: the 1.N-sulfuryl ketimine compounds can generate oxaza propane through the Davis oxygenizement; This compound is a good oxygenant; The reactive hydrogen of oxidation carbonyl alpha-position optionally; Generation has the alcohol of chirality, synthetic this method that all adopts of some Macrolide antitumour drug Epothilone B, quinazolin allkaloids compound (-)-Fumiquinazoline; 2. reduction N-sulphonyl ketoimine becomes the substituted sulphonamide of N; Generate ethylenimine through benzyl position hydroxylation, DIAD dehydration again; Under Louis acid acid catalysis, generate imidazolines at last, have the important medical meaning with anti rheumatism action with the reaction of benzene nitrile.
(4) embodiment
To be further described the present invention through embodiment below, but protection scope of the present invention is not limited thereto.
Embodiment 1:
N-(1-(4-ethylphenyl) second subunit) benzsulfamide:
Will to ethylbenzene acetylene (195.3mg, 1.5mmol), benzsulfamide (78.6mg, 0.5mmol), gold trichloride complex compound ((PPh)
3AuCl) (5mg, 0.01mmol), (10mg 0.04mmol) mixes in THF (2.0mL) silver trifluoromethanesulfonate, and 6h is reacted in 100 ℃ of oil bath heating.Be cooled to room temperature, add saturated NaHCO
3, use ETHYLE ACETATE (50mL * 3) extraction then, the organic layer anhydrous sodium sulfate drying filters, and concentrates, and (sherwood oil: ETHYLE ACETATE=20: 1), obtain target compound 77mg, yield is 53.6% to column chromatography, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ8.06-8.03(m，2H)，7.84(d，J＝8.5Hz，2H)，7.60-7.54(m，3H)，7.23(d，J＝8.5Hz，2H)，2.98(s，3H)，2.68(q，J＝7.5Hz，2H)，1.23(t，J＝7.5Hz，3H).
Embodiment 2:
N-(1-(4-ethylphenyl) second subunit)-4-iodobenzene sulphonamide:
Operation is just used the iodobenzene sulphonamide is replaced benzsulfamide with reference to embodiment 1, obtains title product 130mg, and yield is 63%, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ7.90(d，J＝8.0Hz，2H)，7.83(d，J＝8.0Hz，2H)，7.75(d，J＝8.0Hz，3H)，7.24(d，J＝8.0Hz，2H)，2.97(s，3H)，2.69(q，J＝7.5Hz，2H)，1.23(t，J＝7.5Hz，3H).
Embodiment 3:
4-iodo-N-(1-(4-p-methoxy-phenyl) second subunit) benzsulfamide:
Operation is just used anisole acetylene is replaced ethylbenzene acetylene is replaced benzsulfamide to the iodobenzene sulphonamide with reference to embodiment 1, and THF changes toluene into, obtains title product 207mg, and yield is 99.7%, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ7.92-7.89(m，4H)，7.75(d，J＝8.5Hz，2H)，6.90(d，J＝9.0Hz，2H)，3.87(s，3H)，2.95(s，3H).
Embodiment 4:
N-(1-(4-butyl phenyl) second subunit)-4-methyl benzenesulfonamide:
Operation is just used butylbenzene-acetylene is replaced ethylbenzene acetylene with reference to embodiment 1, and para toluene sulfonamide replaces benzsulfamide, obtains title product 126.6mg, and yield is 80.3%, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ7.92(d，J＝8.5Hz，2H)，7.82(d，J＝8.0Hz，2H)，7.32(d，J＝8.0Hz，3H)，7.20(d，J＝8.5Hz，2H)，2.95(s，3H)，2.63(t，J＝7.5Hz，2H)，1.61-1.54(m，2H)，1.35-1.30(m，2H)，0.91(t，J＝7.5Hz，3H).
Embodiment 5:
N-(1-(4-ethylphenyl) second subunit)-4-methyl benzenesulfonamide:
Operation just replaces benzsulfamide with para toluene sulfonamide with reference to embodiment 1, obtains title product 112.2mg, and yield is 78%, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ7.92(d，J＝8.0Hz，2H)，7.83(d，J＝8.5Hz，2H)，7.32(d，J＝8.0Hz，2H)，7.22(d，J＝8.0Hz，2H)，2.95(s，3H)，2.67(q，J＝7.5Hz，2H)，2.42(s，3H)，1.22(t，J＝7.5Hz，3H).
Embodiment 6:
N-(1-(4-ethoxyl phenenyl) second subunit)-4-methyl benzenesulfonamide:
Operation is just used phenetole acetylene is replaced ethylbenzene acetylene with reference to embodiment 1, and para toluene sulfonamide replaces benzsulfamide, and THF changes toluene into, obtains title product 158.5mg, and yield is 99.8%, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ7.93-7.89(m，4H)，7.34(d，J＝8.5Hz，2H)，6.87(d，J＝9.0Hz，2H)，4.08(q，J＝7.0Hz，2H)，2.94(s，3H)，2.44(s，3H)，1.43(t，3H).
Embodiment 7:
4-methyl-N-(1-(4-amyl group phenyl) second subunit) benzsulfamide:
Operation is just used amylbenzene acetylene is replaced ethylbenzene acetylene with reference to embodiment 1, and para toluene sulfonamide replaces benzsulfamide, obtains title product 133mg, and yield is 77.4%, yellow oily liquid.
1H NMR(500MHz，CDCl
3)：δ7.94-7.91(m，2H)，7.83-7.81(m，2H)，7.33(d，J＝8.0Hz，2H)，7.20(d，J＝8.5Hz，2H)，2.96(s，3H)，2.63(t，J＝7.8Hz，2H)，2.43(s，3H)，1.63-1.57(m，2H)，1.34-1.26(m，4H)，0.87(t，J＝7.0Hz，3H).
Claims (9)
1. the preparation method of the N-sulfuryl ketimine compounds of a general structure shown in (III) is characterized in that described preparation method is: at transition-metal catalyst MLY
nUnder the effect, raw material fully reacts in 35～140 ℃ in inert organic solvents suc as formula the acetylene hydrocarbon compound shown in (I) with suc as formula sulfamide compound shown in (II), and reaction solution makes described N-sulfuryl ketimine compounds (III) through aftertreatment;
R
3-SO
2NH
2 
(I) (II) (III)
In formula (I), formula (II) or the formula (III), R
1Independently be selected to ethylphenyl, to butyl phenyl, to amyl group phenyl, p-methoxyphenyl or to ethoxyl phenenyl; R
2Be hydrogen; R
3Independently be selected from phenyl, p-methylphenyl or to iodophenyl; MLY
nIn, M is Jinyang ion, and L is and the ligand of Jinyang ion coordination, and Y is a negatively charged ion, and n is the ratio of Jinyang ionic valence mumber and negatively charged ion valence mumber; Wherein M is selected from one of following: monovalence Jinyang ion, trivalent Jinyang ion; It is one of following that L is selected from: triphenyl phosphorus, trimethylammonium phosphorus, tributyl phosphorus; It is one of following that Y is selected from: cl anion, bromine anions, nitric acid negatively charged ion.
2. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 1, the amount that it is characterized in that said raw material are than sulfamide compound (II): acetylene hydrocarbon compound (I) is 1:1.0～5.0.
3. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 1; It is characterized in that described transition-metal catalyst is the gold trichloride-triphenyl phosphorus complex compound suc as formula (IV) expression, the amount of substance ratio of employed gold trichloride-triphenyl phosphorus complex compound and sulfamide compound (II) is 0.001～0.2: 1;
(PPh
3)AuCl
(IV)。
4. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 3; It is characterized in that described reaction also adds silver trifluoromethanesulfonate as promotor, the amount of substance ratio of employed promotor silver trifluoromethanesulfonate and sulfamide compound (II) is 0.01～0.2: 1.
5. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 4 is characterized in that the amount of substance ratio of employed gold trichloride-triphenyl phosphorus complex compound, silver trifluoromethanesulfonate and sulfamide compound (II) is 0.01～0.1: 0.02～0.1: 1.
6. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 1 is characterized in that described inert organic solvents selects halogenated aliphatic hydrocarbon class, substituted benzene or ether compound for use.
7. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 6 is characterized in that described inert organic solvents selects for use one of following: methylene dichloride, ethylene dichloride, toluene, chlorophenetole, THF, dioxane.
8. the preparation method of N-sulfuryl ketimine compounds as claimed in claim 1 is characterized in that described temperature of reaction is 50～120 ℃, and the reaction times is 2～10h.
9. like the preparation method of the described N-sulfuryl ketimine compounds of one of claim 1～8; It is characterized in that described aftertreatment employing following steps: reaction solution is cooled to room temperature; Add saturated sodium bicarbonate; Use ethyl acetate extraction, organic layer with the anhydrous sodium sulfate drying after-filtration, boil off solvent, through the refining pure article of N-sulphonyl ketoimine that promptly obtain of column chromatography.
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| CN101817775B (en) * | 2010-04-30 | 2012-06-27 | 浙江工业大学 | Preparation method of 2-pyrrole benzenylsulfonylamide compound |
| CN103012184B (en) * | 2012-12-17 | 2014-07-02 | 浙江大学 | Preparation method of formamide derivative |
| CN104119255B (en) * | 2013-04-23 | 2015-12-23 | 中国科学院大连化学物理研究所 | A kind of method preparing the Cycloene derivate of polyfluorinated alkyl |
| CN104151214B (en) * | 2014-07-03 | 2016-03-02 | 浙江工业大学 | A kind of method of synthesizing 2-alkylsulfonyl ketone compounds |
| CN106083662A (en) * | 2016-05-21 | 2016-11-09 | 魏东 | Sulfabenz formaldehyde derivatives preparation method |
| CN109420526B (en) * | 2017-08-21 | 2021-06-15 | 中国科学院大连化学物理研究所 | Woven mesoporous polymer silver-loaded catalyst and preparation method and application thereof |
| CN107501136B (en) * | 2017-09-19 | 2019-05-28 | 西南大学 | A method of it prepares together with diaryl methylamines |
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| Xiao Huang et al..asymmetric strecker reaction of ketoimines catalyzed by a novel chiral bifunctional N, N"-dioide.《Adv. synth. Catal.》.2006,第348卷2579-2584. * |
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