CN109761862A - A kind of synthetic method of β-carbonyl sulfone compound - Google Patents
A kind of synthetic method of β-carbonyl sulfone compound Download PDFInfo
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Abstract
The invention discloses a kind of β-carbonyl sulfone compound synthetic methods, it is using sulfinate and the carbonyls containing α active hydrogens is raw material, in solvent, in alkali, sodium iodide, nano-micelle and 1, under the oxidation of 2- Bromofume, it is reacted 10 ~ 12 hours under the conditions of 60 ~ 80 DEG C, isolates and purifies, obtainβ‑Carbonyl sulfone compound.Synthesis technology of the present invention is simple, easy to operate, and reaction condition is mild, at low cost, and yield is high, green safe without using transition metal-catalyzed.
Description
Technical field
The present invention relates to one kindβThe synthetic method of carbonyl sulfone compound, belongs to chemosynthesis technical field.
Background technique
β-Carbonyl sulfone due to its sterilize antibiotic property and other bioactivity and be concerned [Eur. J.Med. Chem.
2007,42,880].MeanwhileβCarbonyl sulfone be a kind of important organic synthesis intermediate [J. Am. Chem. Soc.2008,
130,9238], can be used to synthesize disubstituted alkynes, allene chirality alkene sulfone, ketone, oxinane, lycopodine, quinoline derivatives
Object and have it is photochemically reactiveβ-Hydroxy sulfone class important compound.β-The structure of carbonyl sulfone compound is as follows:
In formula, R is any one of alkyl, substitution alkyl, aromatic radical, substituted aromatic base or several；Wherein alkyl described in R
For C1-C20, such as methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl；Substituted aromatic base be halogen, nitro,
Group replaced alkoxy, benzyloxy, vinyl, alkynyl or alkyl, position on aromatic rings be contraposition, ortho position or
Position, can be monosubstituted or polysubstituted；R1, R2, R3It can be respectively hydrogen, alkyl, aromatic radical, any one in substituted aromatic base
Kind is several；Wherein alkyl is C1-C20, such as methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl；Replace
Aromatic radical is the aryl rings containing substituent groups such as halogen, nitro, alkoxy, benzyloxy, vinyl, alkynyl or alkyl.In fragrance
The position of substituent group on ring is contraposition, ortho position or meta position, can be monosubstituted or polysubstituted.
β-carbonyl sulfone compound synthetic method is very more, specifically include that (1) sulfinic acid and its derivative and alkynes or
Alkene oxidative coupling reaction [Angew. Chem. Int. Ed.2013, 52, 7156]；(2) β-carbonyl sulfide oxidation
Reaction [Tetrahedron Lett.1981, 22, 1287]；(3) ethylene sulfone compound oxidation reaction [J. Am. Chem. Soc. 2008, 130, 9238].These methods are made a general survey of, multistep reaction and metallic catalyst or organic are all made of
Solvent operates tedious, reaction cost height.Therefore, develop a kind of mild, practical, green (water is as solvent)β-Carbonyl sulfone class
The synthetic method for closing object has great importance.
Summary of the invention
The purpose of the present invention is synthesize for the prior artβ-Carbonyl sulfone compound there are the problem of, a kind of technique is provided
Simply, reaction is mild, at low cost, the high synthesis of yieldβ-The synthetic method of carbonyl sulfone compound.
Present invention synthesisβ-The method of carbonyl sulfone compound is with sulfinate and to containαThe carbonyl compound of position active hydrogen
Object is raw material, in solvent, under the action of alkali, sodium iodide, nano-micelle and 1,2- Bromofume, under the conditions of 60 ~ 80 DEG C
Reaction 10 ~ 12 hours, isolates and purifies, obtainsβ-Carbonyl sulfone compound.
The sulfinate is aliphatic sulfinate, BTX aromatic sulfinate, and structural formula is as follows:
Wherein, R is any one of alkyl, substitution alkyl, aromatic radical, substituted aromatic base or several；Wherein alkyl described in R
For C1-C20, such as methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl；Substituted aromatic base be halogen, nitro,
Group replaced alkoxy, benzyloxy, vinyl, alkynyl or alkyl, position on aromatic rings be contraposition, ortho position or
Position, can be monosubstituted or polysubstituted.
The structural formula of the α active hydrogen carbonyls is as follows:
Wherein R1, R2, R3Respectively any one of hydrogen, alkyl, aromatic radical, substituted aromatic base or several；Wherein alkyl is
C1-C20, such as methyl, ethyl, propyl, isopropyl, normal-butyl, sec-butyl, tert-butyl；Substituted aromatic base is to contain halogen, nitre
The aryl rings of the substituent groups such as base, alkoxy, benzyloxy, vinyl, alkynyl or alkyl.It is preferred that acetone, acetophenone.
The solvent is methyl phenyl ethers anisole, DMAC N,N' dimethyl acetamide, 1,4- dioxane, N,N-dimethylformamide, two
At least one of first sulfoxide, water, PEG-400.
Alkali used is inorganic base K2CO3、Na2CO3Or organic base diisopropyl ethyl amine.It acts as abjection carbonyl compounds
α Labile protons of object promote the progress of reaction.The dosage of alkali is 1 ~ 1.5 containing α active hydrogen carbonyls moles
Times.The oxidant is 1,2- Bromofume (EDB), and it acts as the iodide ions of oxidation catalysis amount to become elemental iodine, is promoted anti-
The generation answered.The dosage of oxidant is 2 ~ 3 times containing α active hydrogen carbonyls moles.
The catalyst is iodide ion, and preferably sodium iodide, dosage are 0.2 ~ 0.4 times of carbonyl containing compound herein.
Nano-micelle is vitamin E polyethylene glycol succinic acid ester (TPGS-750-M).It functions as surfactant
(promoting organic phase and inorganic phase haptoreaction), dosage are 1% ~ 2 % containing α active hydrogen carbonyls moles.
Product prepared by the present invention is characterized through magnetic resonance spectroscopy, and confirming synthesized compound is target compound.
Specific embodiment
Below by specific embodiment to the present inventionβ-The synthesis of carbonyl sulfone compound is described further.
The synthesis of embodiment 1:2- tolysulfonyl benzoylformaldoxime
Successively by sodium toluene sulfinate (267 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
10 mL reaction is added in (376 mg, 2 mmol), potassium carbonate (173 mg, 1.25 mmol), acetophenone (120 mg, 1.0mmol)
Guan Zhong is added the 4 mL water for containing 2 mmol % TPGS-750-M as solvent later, is stirred to react at 80 DEG C 10 hours.
Remove heating bath.NH is saturated with 20mL4Cl solution quenching reaction, and extracted with methylene chloride (20mL × 3 time).Organic phase is successively used
Water, saturation NaCl aqueous solution washing.Decompression boils off solvent, the isolated product 237mg of rapid column chromatography, yield 87%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm): 7.95 (d, J = 7.2 Hz, 2H),
7.76 (d, J = 7.8 Hz, 2H), 7.62 (t, J = 7.2 Hz, 1H), 7.48 (t, J = 7.8 Hz, 2H),
7.33 (d, J = 7.8Hz, 2H), 4.72(s,2H), 2.44(s,3H). 13C NMR (151 MHz, CDCl3) δ
(ppm): 188.3, 145.5, 135.9, 134.5, 120.0, 129.5, 129.0, 128.8, 63.8, 21.9。
The synthesis of embodiment 2:1- p-toluenesulfonyl propyl- 2- ketone
Successively by sodium toluene sulfinate (267 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), potassium carbonate (173 mg, 1.25 mmol), acetone (58 mg, 1.0mmol) is added to dried
In 10mL reaction tube, water of 4 mL containing 2 mmol % TPGS-750-M is added as solvent, it is small at 80 DEG C to be stirred to react 12
When.Remove heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time).Organic phase
Successively use water, saturation NaCl solution washing.Decompression boils off solvent, the isolated product 169mg of rapid column chromatography, yield 80%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):7.76 (d, J = 8.4 Hz, 2H), 7.37
(d, J = 7.8 Hz, 2H),4.14 (s,2H),2.45(s,3H),2.40(s,3H).13C NMR (151 MHz, CDCl3)
δ (ppm):196.1,145.6, 135.6, 130.0, 128.3, 68.0, 31.5, 21.7。
The synthesis of embodiment 3:2- p-toluenesulfonyl -2,3- dihydro -1H- 1-Indanone
Successively by sodium toluene sulfinate (267 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2mmol), 1- indone (132 mg, 1.0mmol), potassium carbonate (173 mg, 1.25 mmol) are added to dried
In 10 mL reaction tubes, water of 4 mL containing 2 mmol % TPGS-750-M is added as solvent, is stirred to react 10 at 80 DEG C
Hour.Remove heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time).It is organic
Mutually successively use water, saturation NaCl aqueous solution washing.Decompression boils off solvent, the isolated product 223mg of rapid column chromatography, yield
78%。
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):7.81 (d, J = 7.8 Hz, 2H), 7.72
(d, J = 7.8 Hz, 1H), 7.63(t, J = 7.2Hz, 1H), 7.50 (d, J = 7.8 Hz, 1H), 7.39
(d, J = 7.8Hz, 1H), 7.36 (d, J = 8.1 Hz, 2H), 4.26 (dd, J = 3.6, 3.6 Hz, 1H),
3.83 (dd, J = 3.6, 3.6 Hz, 1H), 3.54 (dd, J = 8.4, 8.4 Hz, 1H), 2.45 (s, 3H)
.13C NMR (151 MHz, CDCl3) δ (ppm):194.6, 151.9, 145.4, 135.9, 135.9, 134.6,
129.8 , 129.3, 128.2, 126.4, 124.9, 68.8, 28.2, 21.8。
Embodiment 4:2-(methane sulfonyl) acetophenone synthesis
Successively by methane sulfinic acid sodium (153 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), acetophenone (120 mg, 1.0mmol), potassium carbonate (138 mg, 1.0mmol) are added to dried
In 10mL reaction tube, water of 4 mL containing 2 mmol % TPGS-750-M is added as solvent, it is small at 80 DEG C to be stirred to react 12
When, remove heating bath.Use NH4Cl saturated aqueous solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time).It is organic
Mutually successively use water, saturation NaCl solution washing.Decompression boils off solvent, the isolated product 128mg of rapid column chromatography, yield 65%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):8.00 (d, J = 7.8 Hz, 2H), 7.66
(t, J = 7.2 Hz, 1H), 7.53 (t, J = 8.4 Hz, 2H), 4.61 (s, 2H), 3.15 (s,3H).13C
NMR (151 MHz, CDCl3) δ (ppm): 189.2, 135.6, 134.7, 129.2, 129.0, 61.3, 41.8。
Embodiment 5:1-(1- naphthalene) -2- p-toluenesulfonyl ethyl ketone synthesis
Successively by sodium toluene sulfinate (153 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), 1- acetonaphthone (170 mg, 1.0mmol), potassium carbonate (173 mg, 1.25 mmol) are added to dried
10 mL reaction tubes in, add 4 mL containing 2 mmol % TPGS-750-M water as solvent, be stirred to react at 80 DEG C
12 hours, remove heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time).Have
Machine mutually successively uses water, saturation NaCl aqueous solution washing.Decompression boils off solvent, the isolated product 249mg of rapid column chromatography, yield
77%。
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):8.56 (d, J = 9.0Hz, 1H), 8.03
(dd, J = 8.4, 7.8 Hz, 2H), 7.88 (d, J = 7.8 Hz, 1H), 7.73 (d, J = 8.4 Hz,
2H), 7.60-7.57 (m, 1H), 7.56 – 7.54 (m, 1H), 7.52 – 7.50 (m, 1H), 7.27 (d, J
= 7.8 Hz, 2H), 4.84 (s, 2H), 2.42 (s, 3H).13C NMR (151 MHz, CDCl3) δ (ppm):
190.6, 145.3, 135.9, 134.7, 134.0, 133.5), 130.9, 130.5, 129.9, 128.8, 128.7,
128.7, 126.9, 125.7, 124.3, 66.4, 21.8。
Embodiment 6:1-(4- nitrobenzophenone) -2- p-toluenesulfonyl ethyl ketone synthesis
Successively by sodium toluene sulfinate (153 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), p-nitroacetophenone (165 mg, 1.0mmol), potassium carbonate (138 mg, 1.0mmol) and 1,2- dibromo
Ethane (282 mg, 1.5mmol) is added in 10 dried mL reaction tubes, adds 4 mL containing 2 mmol % TPGS-
The water of 750-M is stirred to react 10 hours as solvent at 80 DEG C.Remove heating bath.Use NH4Cl saturated aqueous solution (20mL) is quenched
Reaction, and extracted with methylene chloride (20mL × 3 time).Organic phase washed with water, saturation NaCl aqueous solution washing.Decompression boils off molten
Agent, the isolated product 280mg of rapid column chromatography, yield 88%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):8.33 (d, J = 8.4Hz, 2H), 8.15
(d, J = 9.0Hz, 2H), 7.75 (d, J = 7.8Hz, 2H), 7.37 (d, J = 8.4 Hz, 2H), 4.76
(s, 2H), 2.46 (s, 3H).13C NMR (151 MHz, CDCl3) δ (ppm): 187.0, 145.9, 139.9,
130.5, 130.3, 130.0, 128.5, 128.1, 123.9, 64.1, 21.8。
The synthesis of embodiment 7:2- tolysulfonyl cycloheptanone
Successively by sodium toluene sulfinate (153 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), cycloheptanone (112 mg, 1.0mmol), potassium carbonate (173 mg, 1.25 mmol) are added to dried
In 10mL reaction tube, water of 4 mL containing 2 mmol % TPGS-750-M is added as solvent, it is small at 80 DEG C to be stirred to react 12
When, remove heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time), it remains with
Machine phase, successively uses water, and saturation NaCl solution is respectively washed three times.It depressurizes and boils off solvent, isolated 181 mg of product of rapid column chromatography,
Yield 68%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):7.70 (d, J = 8.3 Hz, 2H), 7.33
(d, J = 8.0 Hz, 2H), 3.87 (dd, J = 12.1, 5.4 Hz, 1H), 2.83 (td, J = 12.2, 3.1
Hz, 1H), 2.49 – 2.45 (m, 1H), 2.44 (s, 3H), 2.42 – 2.38 (m, 1H), 2.12 – 2.05
(m, 2H), 1.97 – 1.89 (m, 2H), 1.39 (dt, J = 32.2, 13.3 Hz, 2H), 1.21 – 1.13
(m, 1H).13C NMR (151 MHz, CDCl3) δ (ppm):204.7, 145.2, 134.8, 129.7, 128.9,
76.3, 42.4, 29.9, 26.4, 26.1, 24.1, 21.7。
Embodiment 8:2-(methyl sulphonyl) -2,3- dihydro -1H- 1-Indanone synthesis
It successively will be to methane sulfinic acid sodium (153 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), 1- indone (132 mg, 1.0mmol), potassium carbonate (138 mg, 1.0mmol) are added to dried
In 10mL reaction tube, water of 4 mL containing 2 mmol % TPGS-750-M is added as solvent, is stirred under the conditions of 80 DEG C of temperature
Reaction overnight, removes heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time).
Organic phase washed with water, saturation NaCl solution washing.Decompression boils off solvent, and isolated 164 mg of product of rapid column chromatography is produced
Rate 78%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):7.81 (d, J = 7.6 Hz, 1H),
7.68 (t, J = 7.5 Hz, 1H), 7.56 (d, J = 7.8 Hz, 1H), 7.46 – 7.43 (m, 1H), 4.15
(dd, J = 8.5, 3.6 Hz, 1H), 3.80 (dd, J = 18.1, 3.6 Hz, 2H), 3.51 (dd, J =
18.2, 8.5 Hz, 1H), 3.27 (s, 3H).13C NMR (151 MHz, CDCl3)δ (ppm): 195.6, 152.5,
136.3, 135.4, 128.4, 126.6, 125.1, 67.1, 40.2, 26.1。
Embodiment 9:2-(phenyl sulfonyl) acetophenone synthesis
Successively by benzene sulfinic acid sodium salt (246 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume (376
Mg, 2 mmol), acetophenone (120 mg, 1.0mmol), it is anti-that potassium carbonate (138 mg, 1.0mmol) is added to dried 10mL
Ying Guanzhong adds water of 4 mL containing 2 mmol % TPGS-750-M as solvent, was stirred to react under the conditions of 80 DEG C of temperature
Night removes heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time).Organic phase
Successively use water, saturation NaCl solution washing.Decompression boils off solvent, isolated 179 mg of product of rapid column chromatography, yield 69%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm): 7.94 (d, J = 7.1 Hz, 2H),
7.90 (d, J = 7.1 Hz, 2H), 7.66 (t, J = 7.6 Hz, 1H), 7.62 (t, J = 7.4 Hz, 1H),
7.57 – 7.53 (m, 2H), 7.50 – 7.46 (m, 2H), 4.74 (s, 2H).13C NMR (151MHz, CDCl3)
δ (ppm):187.9, 138.7,135.7,134.4, 134.2, 129.3, 129.2, 128.8, 128.6, 63.5。
The synthesis of embodiment 10:2-(to benzotrifluoride sulfonyl) acetophenone
It successively will be to fluoroform benzene sulfinic acid sodium salt (346 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- dibromo
Ethane (376 mg, 2 mmol), acetophenone (120 mg, 1.0mmol), potassium carbonate (138 mg, 1.0mmol) are added to dried
10 mL reaction tubes in, add 4 mL containing 2 mmol % TPGS-750-M water as solvent, under the conditions of 80 DEG C of temperature
It is stirred to react overnight, removes heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time)
It takes.Organic phase washed with water, saturation NaCl solution washing.Decompression boils off solvent, isolated 194 mg of product of rapid column chromatography
Yield 59%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):8.05 (d, J = 8.1 Hz, 2H),
7.93 (d, J = 7.3 Hz, 2H), 7.82 (d, J = 8.2 Hz, 2H), 7.65 (t, J = 7.4 Hz, 1H),
7.50 (t, J = 7.8 Hz, 2H), 4.78 (s, 2H).13C NMR (151MHz, CDCl3)δ (ppm):187.6,
142.1, 135.9, 135.5, 134.6, 129.4, 129.2, 129.0, 126.3(q, J = 3.7 Hz), 123.9,
63.1.19F NMR (376 MHz, CDCl3) δ (ppm):-68.42。
Embodiment 11:2-(8- quinoline sulfonyl) -1-(o-tolyl) ethyl ketone synthesis
Successively by 8- quinoline sulfinic acid sodium (323 mg, 1.5mmol), sodium iodide (45 mg, 0.3 mmol), 1,2- Bromofume
(376 mg, 2 mmol), o-methyl-benzene ethyl ketone (134 mg, 1.0mmol), potassium carbonate (138 mg, 1.0mmol) are added to drying
In the 10mL reaction tube crossed, water of 4 mL containing 2 mmol % TPGS-750-M is added as solvent, under the conditions of 80 DEG C of temperature
It is stirred to react overnight, removes heating bath.With saturation NH4Cl solution (20mL) quenching reaction, and extracted with methylene chloride (20mL × 3 time)
It takes.Organic phase washed with water, saturation NaCl solution washing.It depressurizes and boils off solvent, isolated 247 mg of product of rapid column chromatography,
Yield 76%.
Spectroscopic data:1H NMR (600 MHz, CDCl3) δ (ppm):9.11 (s, 1H), 8.45 (d, J =
7.4 Hz, 1H), 8.28 (d, J = 8.3 Hz, 1H), 8.10 (d, J = 8.2 Hz, 1H), 7.66 (q, J =
7.8 Hz, 2H), 7.57 (dd, J = 8.3, 4.2 Hz, 1H), 7.31 (t, J = 7.6 Hz, 1H), 7.15
(d, J = 7.9 Hz, 2H), 5.57 (s, 2H), 2.31 (s, 3H). 13C NMR (151MHz, CDCl3)δ
(ppm):191.6, 151.5, 144.0, 139.3, 136.8, 136.3, 136.0, 134.6, 132.3, 132.1,
132.0, 129.7, 128.9, 122.3, 65.0, 26.4。
Claims (9)
1. a kind ofβ-The synthetic method of carbonyl sulfone compound is with sulfinate and to containαPosition active hydrogen carbonyls be
Raw material under the action of alkali, sodium iodide, nano-micelle and 1,2- Bromofume, reacts in solvent under the conditions of 60 ~ 80 DEG C
It 10 ~ 12 hours, isolates and purifies, obtainsβ-Carbonyl sulfone compound.
2. a kind of as described in claim 1β-The synthetic method of carbonyl sulfone compound, it is characterised in that: the sulfinate is
Aliphatic sulfinate, BTX aromatic sulfinate, structural formula are as follows:
Wherein, R is any one of alkyl, substitution alkyl, aromatic radical, substituted aromatic base or several；Wherein alkyl described in R
For C1-C20；Substituted aromatic base is halogen, nitro, alkoxy, benzyloxy, vinyl, group replaced alkynyl or alkyl,
Position on aromatic rings is contraposition, ortho position or meta position.
3. a kind of as described in claim 1β-The synthetic method of carbonyl sulfone compound, it is characterised in that: the α active hydrogen
The structural formula of carbonyls is as follows:
Wherein R1、R2、R3Respectively any one of hydrogen, alkyl, aromatic radical, substituted aromatic base or several；Wherein alkyl is C1-
C20；Substituted aromatic base is the aryl rings containing halogen, nitro, alkoxy, benzyloxy, vinyl, alkynyl or alkyl substituent.
4. a kind of as described in claim 1β-The synthetic method of carbonyl sulfone compound, it is characterised in that: the raw material sulfinic acid
Salt is matched with the carbonyls containing α active hydrogens with the molar ratio of 1.5:1 ~ 2:1.
5. a kind of as described in claim 1β-The synthetic method of carbonyl sulfone compound, it is characterised in that: the solvent is benzene first
Ether, DMAC N,N' dimethyl acetamide, 1,4- dioxane, N,N-dimethylformamide, dimethyl sulfoxide, water, in PEG-400 extremely
Few one kind.
6. a kind of as described in claim 1β-The synthetic method of carbonyl sulfone compound, it is characterised in that: alkali used is inorganic base
K2CO3、Na2CO3Or the organic bases such as diisopropyl ethyl amine, the dosage of alkali are 1 containing α active hydrogen carbonyls moles
~ 1.5 times.
7. a kind of as described in claim 1β-The synthetic method of carbonyl sulfone compound, it is characterised in that: the oxidant is 1,
2- Bromofume, the dosage of oxidant are 2 ~ 3 times containing α active hydrogen carbonyls moles.
8. a kind of synthetic method of β-carbonyl sulfone compound as described in claim 1, it is characterised in that: the catalyst iodate
The dosage of sodium is 0.2 ~ 0.4 times containing α active hydrogen carbonyls moles.
9. a kind of synthetic method of β-carbonyl sulfone compound as described in claim 1, it is characterised in that: the surfactant
Nano-micelle is vitamin E polyethylene glycol succinic acid ester, and dosage is 1% ~ 2 containing α active hydrogen carbonyls moles
%。
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| CN110818600B (en) * | 2019-11-29 | 2021-07-09 | 苏州大学 | Method for preparing beta-carbonyl sulfone |
| CN110818600A (en) * | 2019-11-29 | 2020-02-21 | 苏州大学 | Method for preparing β -carbonyl sulfone |
| CN111068776A (en) * | 2020-01-16 | 2020-04-28 | 苏州大学 | Application of HEH in preparation of sulfone compound by catalyzing reaction of aryl halogen and aryl sulfinate |
| CN111068776B (en) * | 2020-01-16 | 2022-09-23 | 苏州大学 | Application of HEH in preparation of sulfone compound by catalyzing reaction of aryl halogen and aryl sulfinate |
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| CN113185435A (en) * | 2021-04-26 | 2021-07-30 | 上海应用技术大学 | Method for preparing beta-carbonyl sulfone compound by using half-sandwich iridium complex |
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Application publication date: 20190517 |