CN104876840B - One prepares dihalomethyl aryl or the method for heteroaryl sulfone based on 3,4-dihalo--2 (5H)-furanone - Google Patents
One prepares dihalomethyl aryl or the method for heteroaryl sulfone based on 3,4-dihalo--2 (5H)-furanone Download PDFInfo
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- CN104876840B CN104876840B CN201510242091.4A CN201510242091A CN104876840B CN 104876840 B CN104876840 B CN 104876840B CN 201510242091 A CN201510242091 A CN 201510242091A CN 104876840 B CN104876840 B CN 104876840B
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Abstract
The present invention relates to a kind of method preparing dihalomethyl aryl sulfone based on 3,4 dihalo-2 (5H) furanones.This preparation method is with 3,4 dihalo-2 (5H) Furanones compounds, sodium arylsulfinate and dimethyl sulfoxide are raw material, and synthesis can be used for the dihalomethyl aryl sulfone compound in herbicide, antibacterial, antibacterial, algicide and agrochemical field；Present invention firstly provides based on 3,4 dihalo-2 (5H) furanones prepare the synthetic route of dihalomethyl aryl sulfone, and define the technical conditions such as reactant ratio, reaction temperature, time, it is simple to operate, raw material is easy to get, mild condition, without any catalyst, obtained dihalomethyl aryl sulfone can have weeding, sterilization, antibacterial, kill the biological activity such as algae and parasite killing.
Description
Technical field
The present invention relates to the preparation method of many halomethyls aryl sulfone, be specifically related to based on 3,4-dihalo--2 (5H)-furanone
Preparation can be used for the method for the dihalomethyl aryl sulfone in herbicide, antibacterial, antibacterial, algicide and agrochemical field.
Background technology
Halomethyl aryl sulfone construction unit, particularly many halomethyls aryl sulfone, be widely present in many can be used for herbicide,
In the Organic substance in antibacterial, antibacterial, algicide and agrochemical field.Therefore, many halomethyls aryl sulfone compound, including
The synthesis of dihalomethyl aryl sulfone, is constantly subjected to pay close attention to.But, all there are raw material sources and be difficult to wait deficiency in these methods
[Antane S, Bernotas R, Li Y, McDevitt R, Yan Y. Synth Commun, 2004, 34, 2443-
2449；Suryakiran N, Prabhakar P, Reddy T S, Mahesh K C, Rajesh K,
Venkateswarlu Y. Tetrahedron Lett, 2007, 48, 877-881；Borys K M, Korzynski M
D, Ochal Z. Beilstein J Org Chem, 2012, 8, 259-265；Borys K M, Korzynski M D,
Ochal Z. Tetrahedron Lett, 2012, 53, 6606-6610；Korzynski M D, Borys K M,
Biaek J, Ochal Z. Tetrahedron Lett, 2014, 55, 745-748]。
3,4-dihalo--2 (5H)-furanones are a kind of raw materials being easy to get, particularly 3,4-dihalo--5-hydroxyl-2 (5H)-furan
Ketone (viscous hydracid) of muttering is commercially available raw material, and they are widely used [Tan in organic synthesis and material such as prepare at the field
Y H, Li J X, Xue F L, Qi J, Wang Z Y. Tetrahedron, 2012, 68, 2827-2843；Huo J
P, Peng P, Deng G H, Wu W, Xiong J F, Zhong M L, Wang Z Y. Macromol Rapid
Commun, 2013, 34, 1779-1784；Huo J P, Luo J C, Wu W, Xiong J F, Mo G Z, Wang Z
Y. Ind Eng Chem Res, 2013, 52, 11850-11857].Sodium arylsulfinate is also a kind of raw material being easy to get, closely
It is widely used in organic synthesis [Tang X D, Huang L B, Xu Y L, Yang J D, Wu W Q, Jiang H
F. Angew Chem Int Ed, 2014, 53, 4205-4208；Shi J, Tang X D, Wu Y C, Li H N,
Song L J, Wang Z Y. Eur J Org Chem, 2015, 1193-1197].Dimethyl sulfoxide (DMSO) is more cheap,
It is to common are machine solvent, but based on 3,4-dihalo--2 (5H)-Furanones compound and sodium arylsulfinate, dimethyl sulfoxide
Dihalomethyl aryl sulfone compound is prepared in reaction, there is no document report at present.
Summary of the invention
Present invention aims to during dihalomethyl aryl sulfone compou nd synthesis in prior art raw material sources not
The defect such as easily, it is provided that a kind of dihalomethyl virtue in herbicide, antibacterial, antibacterial, algicide and agrochemical field
Base sulfone compound preparation method, this preparation method is simple, and raw material is easy to get, and the change of target compound structure is various, has preferably
Industrial applications prospect.The present invention is achieved through the following technical solutions.
A kind of based on 3, the method that 4-dihalo--2 (5H)-furanone prepares dihalomethyl aryl sulfone, with 3,4-dihalo--2
(5H) in-Furanones compound, sodium arylsulfinate and dimethyl sulfoxide, one reacts, prepare have weeding, sterilization, antibacterial,
Kill the bioactive dihalomethyl aryl sulfone compound such as algae and parasite killing.
Having optimal enforcement ground further, described preparation method specifically includes following steps:
(1) 3,4-dihalo--2 (5H)-Furanones compound and sodium arylsulfinate are by a certain percentage in dimethyl sulfoxide
After mixing, under conditions of temperature is 40 ~ 130 DEG C, one reacts 2 ~ 18 hours；
(2) after reaction terminates, add water dilution, then ethyl acetate extracts three times, collects the supernatant.Through anhydrous magnesium sulfate
After drying, thick product, through column chromatography for separation, obtains target compound.
Optimizing further, in step (1), described 3,4-dihalo--2 (5H)-Furanones compound is sub-with aryl
The amount ratio of the material of sodium sulfonate is 2 ~ 0.5 1.
Optimizing further, in step (1), the temperature carrying out reacting is 60 ~ 120 DEG C, and the response time is 8 ~ 15
Hour,
Preferably, in step (1), described 3,4-dihalo--2 (5H)-furanone has a following structural formula:
Wherein, X=Cl, Br；R1For H, CH3、CH3CH2。
Preferably, in step (1), described sodium arylsulfinate has a following structural formula:
Wherein, when aryl is phenyl ring, R2For H, CH3、CH3CH2、i-C3H7、CH3O, F, Cl, Br, I, and its position can position
In ortho position, meta or para position, substituent group is one or more (such as 2,4,6-trimethylphenyl sulfinic acid sodium)；Aryl is heteroaromatic
Time, during such as five-ring heterocycles, Y is O, S, NH.
The present invention compared with prior art, has the advantage that
1, propose first based on 3,4-dihalo--2 (5H)-Furanones compound and sodium arylsulfinate, dimethyl sulfoxide anti-
(part representative compound structural formula, and structural characterization data, be shown in should to prepare the method for dihalomethyl aryl sulfone compound
" embodiment 1 " etc.).
2, can be according to raw material mix that is easy to get such as 3,4-dihalo--2 (5H)-Furanones compound and sodium arylsulfinates
Difference, is combined and synthesizes the dihalomethyl aryl sulfone compound of different structure, it is simple to the application in terms of its biological activity.
3, correlated response is without the catalyst used, and solvent is easy to get, easy temperature control, and technique is simple, and quickly, product is easy in synthesis
In purification, it is suitable for commercial production of magnifying.
Detailed description of the invention
It is embodied as being described further to the present invention below in conjunction with example, but the enforcement of the present invention and protection domain are not
Being limited to this, describing part the most especially in detail if having below, be all that those skilled in the art can refer to prior art realization.
Embodiment 1
With 0.258 gram of 3,4-bis-bromo-5-hydroxyl-2 (5H)-furanone and 0.178 gram of p-methylphenyl sulfinic acid sodium are former
Material, by the amount ratio of materialn(furanone): n(sodium arylsulfinate)=1:1 mix homogeneously, is 100 DEG C, 16 milliliter two in temperature
Under conditions of first sulfoxide is solvent (reactant of holding concurrently), one reacts 12 hours, through water dilution, ethyl acetate extraction, anhydrous slufuric acid
Magnesium is dried, after column chromatography for separation, obtain the dibromo methyl aryl sulfone 0.276 gram of yellow oily liquid, productivity 84%, the knot of product
Structure is confirmed through Organic substance characterizing methods such as infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, elementary analysis, mass spectrums.Should
The dihalomethyl aryl sulfone of method synthesis is expected to be applied to herbicide, antibacterial, antibacterial, algicide and agrochemical field
In.
The structure of product following (alphabetic flag on structural formula is corresponding with the label in nuclear-magnetism test data):
Characterization of compound data:1H NMR (CDCl3-TMS, 400 MHz): δ= 7.93 (d, J = 8.0 Hz,
2H, ArH-3,7), 7.42 (d, J = 8.0 Hz, 2H, ArH-4,6), 6.23 (s, 1H, CH-1), 2.50 (s,
3H, CH3-8); 13C NMR (100 MHz, CDCl3-TMS), δ, ppm: 146.9 (C-5), 131.2 (C-4,6),
129.9 (C-3,7), 129.1 (C-2), 50.8 (C-1), 21.9 (C-8); IR (film), ν, cm-1:
3039.96 (phenyl ring C-H stretching vibrations), 2973.99 (saturated C-H stretching vibrations), 1592.27,1494.55 (phenyl ring
Skeleton stretching vibration), 1330.83 (-SO2-asymmetric absorption), 1150.02 (-SO2-symmetrical absorption), 814.06 (benzene
Ring is to two replacements), 643.03 (C-S stretching vibrations), 544.07 (C-Br stretching vibrations); ESI-MS, m/z (%):
Calcd for C8H7Br2O2S- ([M-H]-): 326.85 (100.0), Found: 326.96 (30.0); Anal.
Calcd for C8H8Br2O2S: C 29.29, H 2.46, O 9.76, Found: C 29.17, H 2.56, O 9.67。
Embodiment 2
With 0.258 gram of 3,4-bis-bromo-5-hydroxyl-2 (5H)-furanone and 0.194 gram of p-methoxyphenyl sulfinic acid sodium are
Raw material, by the amount ratio of materialn(furanone): n(sodium arylsulfinate)=1:1 mix homogeneously, is 100 DEG C, 16 milliliters in temperature
Under conditions of dimethyl sulfoxide is solvent (reactant of holding concurrently), one reacts 12 hours, through water dilution, ethyl acetate extraction, anhydrous sulfur
Acid magnesium is dried, after column chromatography for separation, obtain the dibromo methyl aryl sulfone 0.308 gram of yellow oily liquid, productivity 90%, product
Structure is confirmed through Organic substance characterizing methods such as infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, elementary analysis, mass spectrums.
The dihalomethyl aryl sulfone of the method synthesis is expected to be applied to herbicide, antibacterial, antibacterial, algicide and agrochemical field
In.
The structure of product following (alphabetic flag on structural formula is corresponding with the label in nuclear-magnetism test data):
Characterization of compound data: gray solid, m.p. 90.0 ~ 91.3 DEG C;1H NMR (CDCl3-TMS, 400 MHz):δ= 7.90 (d, J = 8.0 Hz, 2H, ArH-3,7), 7.00 (d, J = 8.0 Hz, 2H, ArH-4,6), 6.16
(s, 1H, CH-1), 3.85 (s, 3H, OCH3-8); 13C NMR (100 MHz, CDCl3-TMS), δ, ppm:
165.2 (C-5), 133.5 (C-3,7), 123.0 (C-2), 114.5 (C-4,6), 55.9 (C-8), 51.1 (C-
1); IR (film), ν, cm-1: 3086.03 (unsaturated C-H stretching vibrations), 2979.68,2840.40 (saturated C-H
Stretching vibration), 1586.96,1498.33,1456.55 (phenyl ring skeleton stretching vibration), 1338.80 (-SO2-asymmetric
Absorb), 1264.10 (C-O stretching vibrations), 1155.22 (-SO2-symmetrical absorption), 820.97 (phenyl ring is to two replacements),
651.31 (C-S stretching vibrations), 555.09 (C-Br stretching vibrations); ESI-MS, m/z (%): Calcd for
C8H7Br2O3S- ([M-H]-): 342.85 (100.0), Found: 343.05 (30.7); Anal. Calcd for
C8H8Br2O3S: C 27.93, H 2.34, O 13.95, Found: C 27.98, H 2.45, O 13.89。
Embodiment 3
With 0.258 gram of 3,4-bis-bromo-5-hydroxyl-2 (5H)-furanone and 0.170 gram of 2-thienyl sulfinic acid sodium are raw material,
By the amount ratio of materialn(furanone): n(sodium arylsulfinate)=0.9:1 mix homogeneously, is 100 DEG C, 16 milliliter two in temperature
Under conditions of first sulfoxide is solvent (reactant of holding concurrently), one reacts 12 hours, through water dilution, ethyl acetate extraction, anhydrous slufuric acid
Magnesium is dried, after column chromatography for separation, obtain the dibromo methyl aryl sulfone 0.336 gram of yellow oily liquid, productivity 77%, the knot of product
Structure is confirmed through Organic substance characterizing methods such as infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, elementary analysis, mass spectrums.Should
The dihalomethyl aryl sulfone of method synthesis is expected to be applied to herbicide, antibacterial, antibacterial, algicide and agrochemical field
In.
The structure of product following (alphabetic flag on structural formula is corresponding with the label in nuclear-magnetism test data):
Characterization of compound data: gray solid, m.p. 120.9 ~ 122.8 DEG C;1H NMR (CDCl3-TMS, 400
MHz): δ= 7.88~7.83 (m, 2H, ArH-3,5), 7.21~7.18 (m, 1H, ArH-4), 6.27 (s, 1H,
CH-1); 13C NMR (100 MHz, CDCl3-TMS), δ, ppm: 139.0 (C-3), 137.4 (C-4), 131.4
(C-2), 128.2 (C-5), 51.0 (C-1); IR (film), ν, cm-1: 3094.89 (unsaturated C-H is flexible to shake
Dynamic), 2922.70 (saturated C-H stretching vibrations), 1503.40,1456.55 (heteroaromatic skeleton stretching vibration),
1338.80 (-SO2-asymmetric absorption), 1155.22 (-SO2-symmetrical absorption), 743.74 (heteroaromatic one replacements),
627.25 (C-S stretching vibrations), 576.61 (C-Br stretching vibrations); ESI-MS, m/z (%): Calcd for
C5H3Br2O2S2 - ([M-H]-): 318.79 (100.0), Found: 319.36 (64.7); Anal. Calcd for
C5H4Br2O2S2: C 18.77, H 1.26, O 10.00, Found: C 18.88, H 1.37, O 10.26。
Embodiment 4
With 0.272 gram of 3,4-bis-bromo-5-methoxyl group-2 (5H)-furanone and 0.178 gram of p-methylphenyl sulfinic acid sodium are
Raw material, by the amount ratio of materialn(furanone): n(sodium arylsulfinate)=1:1 mix homogeneously, is 100 DEG C, 16 milliliters in temperature
Under conditions of dimethyl sulfoxide is solvent (reactant of holding concurrently), one reacts 12 hours, through water dilution, ethyl acetate extraction, anhydrous sulfur
Acid magnesium is dried, after column chromatography for separation, obtain the dibromo methyl aryl sulfone 0.243 gram of yellow oily liquid, productivity 74%, product
Structure is confirmed through Organic substance characterizing methods such as infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, elementary analysis, mass spectrums.
The dihalomethyl aryl sulfone of the method synthesis is expected to be applied to herbicide, antibacterial, antibacterial, algicide and agrochemical field
In (structure of product with " embodiment 1 ", therefore its structural characterization data are omited herein).
Embodiment 5
With 0.169 gram of 3,4-bis-chloro-5-hydroxyl-2 (5H)-furanone and 0.178 gram of p-methylphenyl sulfinic acid sodium are former
Material, by the amount ratio of materialn(furanone): n(sodium arylsulfinate)=1:1 mix homogeneously, is 80 DEG C, 10 milliliter two in temperature
Under conditions of first sulfoxide is solvent (reactant of holding concurrently), one reacts 10 hours, through water dilution, ethyl acetate extraction, anhydrous slufuric acid
The post processings such as magnesium is dried, column chromatography for separation, obtain the dichloromethyl aryl sulfone 0.096 gram of yellow oily liquid, productivity 40%, produce
The structure of thing is through Organic substance characterizing method institutes such as infrared spectrum, proton nmr spectra, carbon-13 nmr spectra, elementary analysis, mass spectrums
Confirmation.The dihalomethyl aryl sulfone of the method synthesis is expected to be applied to herbicide, antibacterial, antibacterial, algicide and insecticide
Deng (product is similar to that " embodiment 1 ", and bromine atoms the most therein becomes chlorine atom, therefore related data is slightly) in field.
Claims (4)
1. prepare dihalomethyl aryl or heteroaryl sulfone compound based on 3,4-dihalo--2 (5H)-Furanones compound for one kind
Method, it is characterised in that 3,4-dihalo--2 (5H)-Furanones compounds, aryl or heteroaryl sulfinic acid sodium are held concurrently anti-at solvent
Answer in thing dimethyl sulfoxide one to react, prepare have weeding, sterilization, antibacterial, kill the dihalomethyl virtue of algae and insecticidal bioactivity
Base or heteroaryl sulfone compound；Described 3,4-dihalo--2 (5H)-Furanones compound has a following structural formula:
Wherein, X=Cl, Br；R1For H, CH3、CH3CH2；
Described aryl or heteroaryl sulfinic acid sodium have a following structural formula:
Wherein, R2For H, CH3、CH3CH2、i-C3H7、CH3O, F, Cl, Br or I；Y is O, S or NH.
The most according to claim 1 based on 3,4-dihalo--2 (5H)-Furanones compound prepare dihalomethyl aryl or
The method of heteroaryl sulfone compound, it is characterised in that comprise the steps:
After (1) 3,4-dihalo--2 (5H)-Furanones compound mixes in dimethyl sulfoxide with aryl or heteroaryl sulfinic acid sodium,
Under conditions of temperature is 40～130 DEG C, one reacts 2～18 hours；
(2), after reaction terminates, add water dilution, then be extracted with ethyl acetate three times, collect the supernatant, do through anhydrous magnesium sulfate
After dry, thick product, through column chromatography for separation, obtains described dihalomethyl aryl or heteroaryl sulfone compound.
The most according to claim 1 and 2 prepare dihalomethyl aryl based on 3,4-dihalo--2 (5H)-Furanones compound
Or the method for heteroaryl sulfone compound, it is characterised in that described 3,4-dihalo--2 (5H)-Furanones compound and aryl or
The amount ratio of the material of heteroaryl sulfinic acid sodium is 2～0.5 1.
The most according to claim 2 based on 3,4-dihalo--2 (5H)-Furanones compound prepare dihalomethyl aryl or
The method of heteroaryl sulfone compound, it is characterised in that in step (1), the temperature of described reaction is 60～120 DEG C, during reaction
Between be 8～15 hours.
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