CN104744337B - The synthetic method of aryl sulfonic acid alkyl esters compound - Google Patents
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Abstract
The present invention relates to a kind of synthetic method of aryl sulfonic acid alkyl esters compound, the method is concretely comprised the following steps：1. by aromatic compound, anhydrous cupric sulfate, part（A kind of C3~C8 classes carbomethoxyisopropyl isonitrate）1 is pressed with alkyl halide：3.0~4.0：3.0~5.0：2.0~3.0 mol ratio is separately added into toluene solution, in nitrogen atmosphere, is disappeared in stirring reaction at 110~130 DEG C to raw material；2. after reaction terminates, water is added after removal solvent, is extracted with ethyl acetate product, organic phase obtains crude product after the solvent in organic phase is removed through drying, with Rotary Evaporators；3. crude product purified by silica gel column chromatography purifying, solvent is selected according to the polarity situation of thin-layer chromatography situation and product, that is, obtain corresponding aryl sulfonic acid alkyl ester compound compound.The inventive method raw material is easy to get, and using copper sulphate as sulfonated reagent, can reduce the generation and the corrosion to equipment of spent acid, and using conventional reaction dissolvent, operation is very simple, and yield reaches as high as 72%, there is good development prospect in the industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of aryl sulfonic acid alkyl esters compound.
Background technology
Sulfonating reaction is that sulfonic reaction is introduced in organic matter（-SO3H）Reaction, it is in modern chemical industry field
Play a very important role, be widely used in synthetic surfactant, dyestuff and chemical intermediate.Such as, sulfonic acid and sulfuric acid alkane
Base compound is one of current most popular anion surfactant, and sulfonating toluene, sulfonation nitrobenzene are production dyes
The important intermediate of material, in Minute Organic Synthesis industry, sulfonic acid intermediate also has highly important status.Sulfonating reaction is in doctor
Also have in medicine industry and be widely applied very much, such as, when some drugses are because of poorly water-soluble, can bring that bioavilability is low, dose
Greatly, the shortcomings of absorbing slow, this kind of compound can significantly increase its water solubility, or even can strengthen its life after sulfonation
Thing activity.
Common sulfonated reagent mainly has sulfur trioxide（SO3）, the concentrated sulfuric acid, oleum, chlorosulfonic acid, sulfamic acid, Asia
Sulfate etc..The characteristics of various sulfonated reagents have different, it is adaptable to different occasions.The main of aromatic compound uses straight
The method for connecing sulfonation, frequently with sulfonated reagent have the concentrated sulfuric acid and oleum, the reaction of this class typically will be using excessive a lot
Reagent, many difficulties can be brought in last handling process, and have very strong corrosiveness to consersion unit.
The method of traditional synthesis of alkyl sulphonic acid ester generally by sulfonic acid chloride under alkalescence condition and alcohol reaction.In document
The method of other synthesizing aryl sulfonic alkyl ester compounds reported mainly has following several：
（One）Gopalan et al. has found that triethly orthoacetate and triethly orthoacetate can react with different types of sulfonic acid
Generation sulfonic acid and methyl ester product, but reaction has stronger restricted, is not easy to synthesize the sulphonic acid ester of various alkyl（See ginseng
Examine document：Trujillo, J. I.; Gopalan, A. S.Tetrahedron Lett.1993, 34, 7355）.
（Two）Kice et al. uses diazomethane as methylating reagent, can generate sulfonic acid first with sulfonic acid direct reaction
Ester, but diazomethane has certain dangerous and explosivity, while it is more complicated and uncomfortable to prepare other diazonium paraffins
Sulfonic alkyl fat is produced for being applied in practice（See reference document：Hansen, H. C.; Kice, J. L.J. Org. Chem.1983, 48, 2943.）.
（Three）Ferris et al. reports sulfonic acid silver and the reaction of alkiodide and can also prepare corresponding sulfonic alkyl
Fat, the shortcoming of this reaction is to need to prepare sulfonic acid silver from sulfonic acid in advance, can consume the silver of equivalent, and reactions steps are long,
It is uneconomical（See reference document：Emmons, W. D.; Ferris, A. F.J. Am. Chem. Soc.1953, 75,
2257.）.
In sum, although prepare the method for alkyl sulfonic acid ester compounds has several kinds, but there are some shortcomings, such as
Reagent preparation process is long, the shortcomings of high cost.Directly sulfonic alkyl fat is prepared from aromatic compound to be not yet reported that.Cause
This, it is necessary for develop efficient method carrying out synthesis of alkyl sulfonate compound.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of aryl sulfonic acid alkyl esters compound.
To reach above-mentioned purpose, the reaction mechanism that the inventive method is used for：
Ar =
Wherein： R1=methyl, phenyl, p-methoxyphenyl;
R=ethyl, propyl group, isopropyl, chloroethyl；
X = Br, Cl；
Part is:A kind of C3~C8 classes carbomethoxyisopropyl isonitrate.
According to above-mentioned reaction mechanism, present invention employs following technical scheme：
A kind of synthetic method of aryl sulfonic acid alkyl esters compound, it is characterised in that the method has following steps：Will
Aromatic compound, anhydrous cupric sulfate, part and alkyl halide press 1：(3.0~4.0)：(3.0~5.0)：(2.0~3.0) mole
Than being separately added into toluene solution, in an inert atmosphere, disappeared in stirring reaction at 110~130 DEG C to raw material；After removal solvent
Water is added, product is extracted with ethyl acetate, organic phase obtains crude product after removing solvent；The crude product is separated to purify what is obtained
Aryl sulfonic acid alkyl esters compound;Described part is a kind of C3~C8 classes carbomethoxyisopropyl isonitrate.
The structural formula of above-mentioned aromatic compound is：
Ar-H, Ar=
, wherein： R1=methyl, phenyl, p-methoxyphenyl.
Above-mentioned part is：A kind of C3~C8 classes carbomethoxyisopropyl isonitrate.
The structural formula of above-mentioned alkyl halide is：RX, R=ethyl, propyl group, isopropyl, chloroethyl；X = Br, Cl.
The inventive method raw material is easy to get, and using copper sulphate as sulfonated reagent, can reduce the generation of spent acid and pair set
Standby corrosion, and using conventional reaction dissolvent, operation is very simple, and yield reaches as high as 72%, has in the industrial production
Good development prospect.
Specific embodiment
Embodiment one：The preparation of N- (4- methoxyphenyls)-indoles -3- sulfonic acids
N- (4- methoxyphenyls)-indoles -3- sulfonic acids use following step：1. added in 1000 milliliters of reactors
8.92 grams of N- (4- methoxyphenyls)-indoles, 19.14 grams of copper sulphate, 9.96 grams of parts（C3 class carbomethoxyisopropyl isonitrates）, 100 milliliters
Bromoethane and 600 milliliters of toluene, are heated to 130 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, it is former to reacting
Material disappears；2. after reaction terminates, to water is added in system, product is extracted with ethyl acetate, is removed with Rotary Evaporators after drying
Solvent, obtains crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 9.30 grams of N- (4-
Methoxyphenyl)-indoles -3- sulfonic acids, yield is 70%.Fusing point：142-143 ℃.
–1): 3111, 3054, 1518, 1345, 1244, 1175, 1010, 915, 796, 615.
1H NMR (CDCl3, 500 MHz): δ 7.99-7.98 (m, 1H), 7.89 (s, 1H), 7.43-7.32
(m, 5H), 7.08-7.05 (m, 2H), 4.19 (q, J = 7.5 Hz, 2H), 3.90 (s, 3H), 1.33 (t,J = 7.0 Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ 159.5, 137.1, 133.4, 130.5, 126.4, 124.3,
124.2, 122.9, 120.1, 115.0, 111.4, 111.1, 66.4, 55.6, 14.7
EI-MS m/z: 331 (89), 302 (63) [M+(35Cl)], 222 (100), 178 (33), 151
(17).
HRMS: m/z calcd for C17H18NO4S [M+H] + 332.0957, Found: 332.0949.
Embodiment two：The preparation of N- (4- methoxyphenyls)-indoles -3- sulfonic acid n-propyls
N- (4- methoxyphenyls)-indoles -3- sulfonic acids use following step：1. added in 1000 milliliters of reactors
8.92 grams of N- (4- methoxyphenyls)-indoles, 25.52 grams of copper sulphate, 16.60 grams of parts（C4 class carbomethoxyisopropyl isonitrates）, 100 milliliters
N-propyl bromide and 600 milliliters of toluene, are heated to 120 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, to anti-
Raw material is answered to disappear；2. after reaction terminates, to water is added in system, product is extracted with ethyl acetate, Rotary Evaporators is used after drying
Remove solvent, obtain crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 9.94 grams of N-
(4- methoxyphenyls)-indoles -3- sulfonic acids, yield is 72%.Fusing point：100-101 ℃.
–1): 3116, 2975, 1517, 1344, 1244, 1172, 919, 878, 777, 582.
1H NMR (CDCl3, 500 MHz): δ 7.99-7.97 (m, 1H), 7.89 (s, 1H), 7.43-7.31
(m, 5H), 7.07-7.06 (m, 2H), 4.07 (t, J = 7.0 Hz, 2H), 3.89 (s, 3H), 1.74-1.67
(m, 2H), 0.92 (t, J = 7.5 Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ 159.5, 137.1, 133.3, 130.5, 126.4, 124.3,
124.2, 122.9, 120.1, 115.0, 111.4, 111.1, 71.8, 55.6, 22.3, 10.0.
EI-MS m/z: 345 (68) [M+], 303 (100), 222 (96), 178 (32), 144 (37).
HRMS: m/z calcd for C18H20NO4S [M+H] + 346.1113, Found: 346.1106.
Embodiment three：The preparation of N- (4- methoxyphenyls)-indoles -3- sulfonic acid N-butyls
N- (4- methoxyphenyls)-indoles -3- sulfonic acids use following step：1. added in 1000 milliliters of reactors
8.92 grams of N- (4- methoxyphenyls)-indoles, 20.83 grams of copper sulphate, 16.60 grams of parts（C6 class carbomethoxyisopropyl isonitrates）, 100 milliliters
Bromination of n-butane and 600 milliliters of toluene, are heated to 110 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, to anti-
Raw material is answered to disappear；2. after reaction terminates, to water is added in system, product is extracted with ethyl acetate, Rotary Evaporators is used after drying
Remove solvent, obtain crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 10.34 grams
N- (4- methoxyphenyls)-indoles -3- sulfonic acids, yield is 72%.Fusing point：78-80 ℃.
-13112, 2963, 1520, 1346, 1247, 1173, 1019, 958, 827, 613.
1H NMR (CDCl3, 500 MHz): δ 7.99-7.97 (m, 1H), 7.88 (s, 1H), 7.43-7.32
(m, 5H), 7.08-7.06 (m, 2H), 4.11 (t, J = 6.5 Hz, 2H), 3.90 (s, 3H), 1.68-1.63
(m, 2H), 1.40-1.33 (m, 2H), 0.85 (t, J = 7.5 Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ 159.5, 137.1, 133.3, 130.5, 126.4, 124.3,
124.2, 122.9, 120.2, 115.0, 111.4, 111.1, 111.1, 70.0, 55.6, 30.8, 18.6,
13.4.
EI-MS m/z: 359 (34) [M+], 303 (45), 225 (100), 143 (31), 105 (32).
HRMS: m/z calcd for C19H22NO4S [M+H] + 360.1270, Found: 360.1259.
Example IV：The preparation of N- phenyl -7- azaindole -3- sulfonic acid n-propyls
N- phenyl -7- azaindole -3- sulfonic acid n-propyls use following step：1. added in 1000 milliliters of reactors
7.76 grams of N- phenyl -7- azaindoles, 25.52 grams of copper sulphate, 14.68 grams of parts（C5 class carbomethoxyisopropyl isonitrates）, 100 milliliters of bromos
N-propane and 600 milliliters of toluene, 130 DEG C are heated under nitrogen protection.Tracked with thin-layer chromatography method and reacted, it is former to reacting
Material disappears；2. after reaction terminates, to water is added in system, product is extracted with ethyl acetate, is removed with Rotary Evaporators after drying
Solvent, obtains crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 5.31 grams of N- benzene
Base -7- azaindole -3- sulfonic acid n-propyls, yield is 42%.Fusing point：137-138 ℃.
–1): 3128, 2975, 1524, 1355, 1173, 933, 842, 762, 592.
1H NMR (CDCl3, 500 MHz): δ 8.51 (dd, J = 5.0, 1.5 Hz, 1H), 8.32 (dd, J
= 8.0, 2.0 Hz, 1H), 8.14 (s, 1H), 7.73-7.71 (m, 2H), 7.60-7.56 (m, 2H), 7.48-
7.44 (m, 1H), 7.35 (dd, J = 8.0, 4.5 Hz, 1H), 4.09 (t, J = 6.5 Hz, 2H), 1.75-
1.68 (m, 2H), 0.92 (t, J = 6.5 Hz, 3H).
13C NMR (CDCl3, 125 MHz): 147.2, 145.8, 136.6, 132.7, 129.7, 128.9,
128.2, 124.6, 119.1, 117.4, 110.4, 72.1, 22.3, 10.0.
EI-MS m/z: 316 (26) [M+], 274 (100), 193 (42), 165 (19), 77 (27).
HRMS: m/z calcd for C16H17N2O3S [M+H] + 317.0960, Found: 317.0940.
Embodiment five：The preparation of N- phenylpyrrole -2- sulfonic acid chloroethyl fat
N- phenylpyrrole -2- sulfonic acid chloroethyl fat uses following step：1. 5.72 grams are added in 1000 milliliters of reactors
N- phenylpyrroles, 25.52 grams of copper sulphate, 14.68 grams of parts（C4 class carbomethoxyisopropyl isonitrates）, 100 milliliters of dichloroethanes and 600 milliliters
Toluene, is heated to 130 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, disappeared to reaction raw materials；2. reaction is tied
Shu Hou, to water is added in system, is extracted with ethyl acetate product, and solvent is removed with Rotary Evaporators after drying, and obtains crude product；③
Crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 7.31 grams of N- phenylpyrrole -2- sulfonic acid chloroethenes
Base fat, yield is 64%.
–1): 3136, 1511, 1355, 1190, 1153, 1005, 895, 763, 624.
1H NMR (CDCl3, 500 MHz): δ 7.65 (t, J = 2.0 Hz, 1H), 7.51-7.48 (m,
2H), 7.40-7.37 (m, 3H), 7.11 (t, J = 2.5 Hz, 1H), 6.69 (dd, J = 3.0, 1.5 Hz,
1H), 4.29 (t, J = 6.0 Hz, 2H), 3.70 (t, J = 6.0 Hz, 2H).
13C NMR (CDCl3, 125 MHz): 139.0, 130.0, 127.8, 124.1, 122.1, 121.4,
119.6, 110.1, 68.7, 40.8.
EI-MS m/z: 286 (9) [M+(37Cl)], 284 (26) [M+(35Cl)], 195 (31), 132
(100).
HRMS: m/z calcd for C12H13ClNO3S [M+H] + 286.0305, Found: 286.0304.
Embodiment six：The preparation of 3,5- dimethyl-N-phenyl pyrazoles -4- sulfonic acid chloroethyl fat
3,5- dimethyl-N-phenyl pyrazoles -4- sulfonic acid chloroethyl fat uses following step：1. in 1000 milliliters of reactors
Add 6.88 grams of 3,5- dimethyl-N-phenyl pyrazoles, 23.12 grams of copper sulphate, 16.60 grams of parts（C7 class carbomethoxyisopropyl isonitrates）, 100
Milliliter dichloroethanes and 600 milliliters of toluene, are heated to 120 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, extremely
Reaction raw materials disappear；2. after reaction terminates, to water is added in system, product is extracted with ethyl acetate, rotary evaporation is used after drying
Instrument removes solvent, obtains crude product；3. crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 6.41 grams
3,5- dimethyl-N-phenyl pyrazoles -4- sulfonic acid chloroethyl fat, yield is 51%.
–1): 2927, 1725, 1533, 1418, 1352, 1191, 1006, 895, 766, 690.
1H NMR (CDCl3, 500 MHz): δ 7.55-7.47 (m, 3H), 7.41-7.39 (m, 2H), 4.31
(t, J = 6.0 Hz, 2H), 4.06 (s, 3H), 3.75 (t, J = 6.0 Hz, 2H), 2.51 (s, 3H),
2.50 (s, 3H).
13C NMR (CDCl3, 125 MHz): δ 149.5, 143.8, 138.0, 129.4, 129.2, 125.6,
113.0, 68.4, 41.0, 13.0, 11.8.
EI-MS m/z: 316 (3) [M+(37Cl)], 314 (8) [M+(35Cl)], 172 (22), 149 (100).
HRMS: m/z calcd for C13H16ClN2O3S [M+H] + 315.0570, Found: 315.0565.
Embodiment seven：The preparation of positive third fat of N- methyl indol -3- sulfonic acid
Positive third fat of N- methyl indol -3- sulfonic acid uses following step：1. 5.24 grams of N- are added in 1000 milliliters of reactors
Methyl indol, 25.52 grams of copper sulphate, 11.90 grams of parts（C5 class carbomethoxyisopropyl isonitrates）, 100 milliliters of n-propyl bromides and 600 milliliters
Toluene, is heated to 130 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, disappeared to reaction raw materials；2. reaction is tied
Shu Hou, to water is added in system, is extracted with ethyl acetate product, and solvent is removed with Rotary Evaporators after drying, and obtains crude product；③
Crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 5.97 grams of N- methyl indols -3- sulfonic acid positive third
Fat, yield is 59%.Fusing point：80-81 ℃.
-12967, 1524, 1465, 1344, 1192, 945, 837, 738, 615.
1H NMR (CDCl3, 500 MHz): δ 7.92 (d, J = 7.55 Hz, 1H), 7.70 (s, 1H),
7.40-7.30 (m, 3H), 3.98 (t, J = 7.0 Hz, 2H), 3.86 (s, 3H), 1.69-1.62 (m, 2H),
0.87 (t, J = 7.5 Hz, 3H).
13C NMR (CDCl3, 125 MHz): δ 137.0, 134.0, 124.2, 123.8, 122.5, 120.1,
110.2, 109.1, 71.6, 33.6, 22.3, 10.0.
EI-MS m/z: 253 (21) [M+], 211 (100), 194 (11), 146 (45), 130 (14).
ESI-HRMS: m/z calcd for C12H16NO3S [M+H] + 254.0851, Found: 254.0831.
Embodiment eight：The preparation of positive third fat of N- methyl carbazole -3- sulfonic acid
Positive third fat of N- methyl carbazole -3- sulfonic acid uses following step：1. 7.24 grams of N- are added in 1000 milliliters of reactors
Methyl carbazole, 19.86 grams of copper sulphate, 13.58 grams of parts（C8 class carbomethoxyisopropyl isonitrates）, 100 milliliters of n-propyl bromides and 600 milliliters
Toluene, is heated to 110 DEG C under nitrogen protection.Tracked with thin-layer chromatography method and reacted, disappeared to reaction raw materials；2. reaction is tied
Shu Hou, to water is added in system, is extracted with ethyl acetate product, and solvent is removed with Rotary Evaporators after drying, and obtains crude product；③
Crude product column chromatography（Petroleum ether:Ethyl acetate=5: 1）Purifying, obtains 8.77 grams of N- methyl carbazoles -3- sulfonic acid positive third
Fat, yield is 72%.Fusing point：91-92 ℃.
-1 3064, 2968, 1590, 1470, 1350, 1174, 940, 851, 747.
1H NMR (500 MHz, CDCl3):δ8.65 (d, J = 1.5 Hz, 1H), 8.12 (d, J = 8.0
Hz, 1H), 7.98 (dd, J = 8.5, 1.5 Hz, 1H), 7.57 (td, J = 8.5, 1.0 Hz, 1H), 7.47
(t, J = 8.5 Hz, 2H), 7.34 (td, J = 8.0, 1.0 Hz, 1H), 4.00 (t, J = 6.5 Hz,
2H), 3.89 (s, 3H), 1.69-1.62 (m, 2H), 0.88 (t, J = 7.5 Hz, 2H).
13C NMR (125 MHz, CDCl3):δ 143.2, 141.7, 127.2, 125.5, 125.0, 122.5,
122.2, 121.3, 120.8, 120.5, 109.2, 108.8, 71.9, 29.4, 22.3, 10.0.
LC-MS (ESI) m/z: 304 [M+H].
ESI-HRMS: m/z calcd for C16H18NO3S [M+H] + 304.1007, Found: 304.0996.
Claims (1)
1. a kind of synthetic method of aryl sulfonic acid alkyl esters compound, it is characterised in that the method has following steps：By virtue
Aroma compounds, anhydrous cupric sulfate, part and alkyl halide press 1：(3.0~4.0)：(3.0~5.0)：The mol ratio of (2.0~3.0)
It is separately added into toluene solution, in an inert atmosphere, is disappeared in stirring reaction at 110~130 DEG C to raw material；Add after removal solvent
Enter water, be extracted with ethyl acetate product, organic phase obtains crude product after removing solvent；The crude product is separated to purify the virtue for obtaining
Base alkylsulfonates compound；Described part is the carbomethoxyisopropyl isonitrate of C3~C8；
The structural formula of described aromatic compound is Ar-H,
Wherein：R1=methyl, phenyl, p-methoxyphenyl；
The structural formula of described alkyl halide is：RX, R=ethyl, propyl group, isopropyl, chloroethyl；X=Br, Cl.
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