CN111499551A - β -hydroxy substituted alkyl dithio carbamate preparation method - Google Patents

β -hydroxy substituted alkyl dithio carbamate preparation method Download PDF

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CN111499551A
CN111499551A CN202010382653.6A CN202010382653A CN111499551A CN 111499551 A CN111499551 A CN 111499551A CN 202010382653 A CN202010382653 A CN 202010382653A CN 111499551 A CN111499551 A CN 111499551A
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武志勇
赵铭钦
来苗
郝帅
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Henan Agricultural University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/14—Dithiocarbamic acids; Derivatives thereof
    • C07C333/18—Esters of dithiocarbamic acids
    • C07C333/20—Esters of dithiocarbamic acids having nitrogen atoms of dithiocarbamate groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C07D277/26—Radicals substituted by sulfur atoms

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Abstract

The invention provides a preparation method of β -hydroxy-substituted alkyl dithiocarbamate, which belongs to the technical field of organic synthesis and comprises the following steps of (1) adding an alkali catalyst, a styrene derivative and thiuram disulfide into an organic solvent for reaction, and then cooling to room temperature to obtain a reaction liquid, and (2) concentrating, separating and purifying the reaction liquid obtained in the step (1) to obtain the product.

Description

β -hydroxy substituted alkyl dithio carbamate preparation method
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of β -hydroxy-substituted alkyl dithiocarbamate.
Background
In the last decade, transition metal-catalyzed olefin dual-functionalization is an effective method for introducing two functional groups into olefin through one-step reaction, and has the advantages of high efficiency, good regioselectivity and stereoselectivity, strong tolerance to the functional groups and the like. However, the use of transition metals may cause potential contamination of the product, which is particularly important in the pharmaceutical industry.
Although numerous synthetic results of selective bifunctional of olefins have been obtained, methods for synthesizing β -hydroxy-substituted alkyldithiocarbamates have not been described so far, mainly because of the lack of an efficient method, the product of the reaction is β -hydroxy-substituted alkyldithiocarbamates, which are a class of widely used organic synthetic intermediates having important application values in the fields of pharmaceutical production, organic synthesis, and rubber production.
Disclosure of Invention
The invention aims to provide a preparation method of β -hydroxy-substituted alkyl dithiocarbamate, which synthesizes β -hydroxy-substituted alkyl dithiocarbamate through the regioselective bifunctional reaction of thiuram disulfide and styrene.
In order to achieve the purpose, the technical scheme adopted by the preparation method of β -hydroxy-substituted alkyl dithiocarbamate is that the preparation method of β -hydroxy-substituted alkyl dithiocarbamate comprises the following steps:
(1) adding an alkali catalyst, a styrene derivative and thiuram disulfide into an organic solvent for reaction, and then cooling to room temperature to obtain a reaction solution;
(2) concentrating, separating and purifying the reaction liquid obtained in the step (1) to obtain β -hydroxy dithiocarbamate.
Further, the molar ratio of the alkali catalyst, the styrene derivative and the thiuram disulfide is 0.2: 0.2: 0.1.
Further, the alkali catalyst is one or more of cesium carbonate, sodium carbonate, potassium bicarbonate, potassium phosphate, sodium bicarbonate, potassium acetate, sodium ethoxide, lithium methoxide, lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, lithium hydroxide, sodium hydroxide and potassium hydroxide.
Further, the styrene derivative is styrene, 3-chlorostyrene, 4-chlorostyrene, 3-bromostyrene, 4-fluorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-tert-butylstyrene or 4-methyl-5-vinylthiazole.
Further, the thiuram disulfide is one or more of tetramethylthiuram disulfide, tetraethylthiuram disulfide and tetrabutylthiuram disulfide.
Further, the organic solvent is one or more of 1, 4-dioxane, toluene, xylene, mesitylene, tetrahydrofuran, acetonitrile, ethanol and tert-butyl methyl ether.
Further, the amount of the organic solvent used is 10L per mole of thiuram disulfide
Further, the reaction temperature in the step (1) is 80 ℃, and the reaction time is 48 h.
Further, the separation and purification in the step (2) comprises the following specific steps: and (3) concentrating the reaction solution to obtain a concentrate, and performing thin-layer chromatography by using petroleum ether/ethyl acetate volume ratio 5/1 as a developing agent.
The reaction principle of the β -hydroxy-substituted alkyl dithiocarbamate preparation method is as follows (taking 4-chlorostyrene as an example):
Figure DEST_PATH_IMAGE001
the invention has the beneficial effects that:
(1) the invention adopts a one-pot method, sodium ethoxide is taken as a catalyst, 4-chlorostyrene and tetramethylthiuram disulfide which are economic and easy to obtain are taken as raw materials, the raw materials are directly subjected to coupling reaction in the air to generate corresponding 2- (4-chlorphenyl) -2-hydroxyethyl dimethyl amino dithio acid ester, and the product 2- (4-chlorphenyl) -2-hydroxyethyl dimethyl amino dithio acid ester can be taken as an antibacterial agent, an anticancer agent, a vulcanization accelerator and the like;
(2) the synthesis system has wide application range and is compatible with functional groups such as halogenated groups, alkyl groups, alkoxy groups and the like.
(3) The preparation method has the advantages of simple process, convenient operation, mild reaction conditions, wide substrate range, higher yield and suitability for popularization and application.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1
The preparation method of the 2- (4-chlorphenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 4-chlorostyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture into a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 15.8mg of a target product.
The target product yield of this example was 58%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.46-7.39(d, J = 8.4Hz, 2H), 7.36-7.31 (d, J = 8.5Hz, 2H), 5.09-4.98 (d, J = 8.4Hz, 1H), 3.90-3.79 (dd, J =14.5, 3.4Hz, 1H), 3.59 (s, 3H), 3.58-3.50 (t, J =14.5, 6.0 Hz,1H), 3.42 (s, 3H), 3.28-3.18 (d, J = 2.6 Hz,1H), 13C NMR (100MHz, Cl3)197.4, 141.4, 133.5, 128.6, 127.3, 72.6, 45.9, 45.6, (41.8), (IR KBr) 3394, 2983, 2883, 2920, 2949, 1645, 1495, 13749, 1144, 1087, 976cm-1, HRMS (ESI) calcd. for C11H14ClNOS2, [ M + Na ] +: 298.0103, found: 298.0103.
Example 2
The preparation method of the 2- (3-chlorphenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 3-chlorostyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture into a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 14.4mg of a target product.
The target product yield of this example was 52%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.49 (s,1H), 7.39-7.34 (d, J = 7.3Hz, 1H), 7.34-7.29 (d, J = 7.8 Hz,1H), 7.29-7.24(m, 1H), 5.08-4.98 (dd, J = 8.4, 2.6 Hz,1H), 3.91-3.81 (dd, J =14.6, 3.4Hz, 1H), 3.59 (s, 3H), 3.58-3.50 (dd, J =14.6, 6.0 Hz,1H), 3.43 (s, 3H),3.35-3.25 (d, J = 4.4 Hz,1H), 13C NMR (100MHz, CDCl3)197.4, 145.0, 134.4,129.8, CDCl 359, 126.9, 7.45 Br 3.45, 7.8 K7.8, 7.8 Br (K20), 2921,2850, 1646, 1498, 1473, 1429, 1377, 1254, 1058, 972, 527 cm-1, HRMS (ESI) calcd. for C11H14ClNOS2, [ M + Na ] +: 298.0103, found: 298.0102.
Example 3
The preparation method of the 2- (4-bromophenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.4mmol of 4-bromostyrene, 0.2mmol of tetramethylthiuram disulfide and 0.4mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction solution obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 17.3 mg of a target product.
The target product yield of this example was 54%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.54-7.45(d, J = 8.4Hz, 2H), 7.41-7.32 (d, J = 8.3 Hz,2H), 5.10-4.96 (dd, J = 8.4,3.0 Hz,1H), 3.90-3.79 (dd, J =14.5, 3.5 Hz,1H), 3.59 (s, 3H), 3.58-3.48(M, 1H), 3.42 (s, 3H), 3.24 (s,1H), 13C NMR (100MHz, CDCl3)197.4, 141.9,131.6, 127.6, 121.6, 72.6, 45.9, 45.6, 41.8; IR KBr) 3392, 2922, 2850, 2367, ESI 3, 1906, 1646, 1900, 1485, 1375, 1373.6, 1257.7, 369714, 3647.14, 18H, 3619, 3619.8, 3623392, 3619, 18, 3, 18, 11, 3, 14, 3, 11, 3, 14, 3, 14, 341.9596 is found.
Example 4
The preparation method of the 2- (3-bromophenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 3-bromostyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 15.3mg of a target product.
The target product yield of this example was 48%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.64 (s,1H), 7.46-7.36 (t, J = 15.3, 7.7 Hz,2H), 7.28-7.20 (t, J = 15.8, 8.0 Hz,2H), 5.08-4.98 (dd, J = 8.5, 3.2 Hz,1H), 3.91-3.81 (dd, J =14.6, 3.4Hz, 1H), 3.59 (s, 3H), 3.58-3.50 (dd, J =14.6, 6.0 Hz,1H), 3.43 (s, 3H), 3.29(s, 1H), 13C NMR (100MHz, CDCl3) 197.3, 145.2, 130.8, 130.0,129.0, 124.6,122.6, 72.6, 45.9, 45.5, IR 338, 298, 2984, 2950, 2984: 16420 (Br), 1469, 1423, 1379, 1253, 1060, 970 cm-1, HRMS (ESI) calcd, forC11H14BrNOS2, [ M + Na ] +:341.9598, found:341.9597.
Example 5
The preparation method of the 2- (4-fluorophenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 4-fluorostyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 12.2mg of a target product.
The target product yield of this example was 47%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.50-7.40(m, 2H), 7.10-7.00 (m,2H), 5.10-4.98 (dd, J = 8.4, 2.8 Hz,1H), 3.90-3.78(dd, J =14.5, 3.4Hz, 1H), 3.59 (s, 3H), 3.58-3.50 (m,1H), 3.43 (s, 3H),3.17 (s,1H), 13C NMR (100MHz, CDCl3)197.4, 162.3(d, J = 244.1 Hz), 138.7(d, J = 2.9 Hz), 127.5 (d, J = 8.1 Hz), 115.3 (d, J = 21.2 Hz), 72.7, 45.9,45.8, 41.8; KCl 3; IR 3397, Br 2897, 2920, 1508: 50,1508, 1468, 1378, 1254,1224, 1155, 1060, 973, 830 cm-1, HRMS (ESI) calcd. for C11H14FNOS2: [ M + Na ] +:282.0399, found: 282.0400.
Example 6
The preparation method of the 2- (4-methoxyphenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 4-methoxystyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 13.6mg of a target product.
The target product yield of this example was 50%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.45-7.36(d, J = 8.6 Hz,2H), 6.95-6.85 (d, J = 8.8 Hz,2H), 5.05-4.94 (dd, J = 8.7,3.4 Hz,1H), 3.86-3.77 (M, 4H), 3.67-3.54 (M, 4H), 3.42 (S, 3H), 3.01 (S,1H), 13C NMR (100MHz, CDCl3)197.6, 159.3, 135.1, 127.1, 113.9, 72.9, 55.3,45.8, 41.8; IR (KBr): 3389, 2995, 2955, 2920, 2850, 1611, 1511, 1465, 1377,1302, ESI, 1249, 1174, 6, 1032, 6cm, 1032, Na-971, 539H 2 + Na 17H: [ 11 ] No. (19H, 11,17,17,17,11,11,17,11,201,17,11,11,11,11,11,201,11,11,000,973,12,12,01,833,12,11,11,11,11,11,11,11, 294.0597 is found.
Example 7
The preparation method of the 2- (4-tert-butylphenyl) -2-hydroxyethyl dimethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 4-tert-butylstyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 14.4mg of a target product.
The target product yield of this example was 48%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm: 7.40 (s,4H), 5.10-4.90 (dd, J = 9.0, 3.3Hz, 1H), 3.90-3.80 (dd, J = 14.4, 3.4Hz, 1H), 3.70-3.60 (dd, J = 14.4, 9.1 Hz,1H), 3.59 (s, 3H), 3.42 (s, 3H), 3.02(s, 1H), 13C NMR (100MHz, CDCl3)197.6, 150.8, 140.0, 125.6, 125.4, 73.1,45.8, 45.7, 41.8, 34.6, 31.4; IR (KBr): 3415, 2959, 2925, 2867, 1660, 1502,1408, 1375, 1254, 1145, 1108, 1057, 977, 838 cm-1, HRMS (ESI) calcd. for 15H23NOS2: [ M + Na ] +:320.1119, found: 320.1118.
example 8
The preparation method of 2-hydroxy-2- (4-methylthiazol-5-yl) dimethyl ethyl carbamate comprises the following steps:
(1) taking 0.2mmol of 4-methyl-5-vinyl thiazole, 0.1mmol of tetramethyl thiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at the temperature of 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction solution obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 14.9mg of a target product.
The target product yield of this example was 57%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 8.66 (s,1H), 5.45-5.35 (dd, J = 7.8, 3.9 Hz,1H), 3.93-3.82 (dd, J = 14.4, 4.0 Hz,1H), 3.67 (s,1H), 3.65-3.60 (d, J = 7.9 Hz,1H), 3.59 (s, 3H), 3.43 (s, 3H),2.49 (s, 3H), 13C NMR (100MHz, CD36Cl 42) 196.8, 151.0, 148.9, 134.2, 67.1,45.9, 45.1, 41.8, 15.7; IR (KBr): 3361, 3199, 2955, 2922, 2851, 1657, 368, ESI 1, 1502, 1376, 1374, 1415, 1147, 1258, 977, Na 978, 539M + OS [ 14: 14H ] (19H ), 285.0168 is found.
Example 9
The preparation method of the 2- (4-chlorphenyl) -2-hydroxyethyl diethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 4-chlorostyrene, 0.1mmol of tetraethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing agent to obtain 12mg of a target product.
The target product yield of this example was 40%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.44-7.39(d, J = 8.4Hz, 2H), 7.36-7.31 (d, J = 8.5Hz, 2H), 5.08-5.01 (dd, J = 8.4,3.4 Hz,1H), 4.12-3.99 (m,2H), 3.89-3.81 (dd, J =14.5, 3.5 Hz,1H), 3.81-3.74 (m,2H), 3.60-3.51 (dd, J =14.5, 8.4Hz, 1H), 3.37 (s,1H), 1.38-1.23(m, 6H), 13C NMR (100MHz, CDCl3)195.8, 141.5, 133.4, 128.6, 127.3, 72.7,50.2, 47.45, 1.45, 335, 299: 7, 299, 7, 7.5, 7, 7.9, 7, 7.9, 7,77,58,58,58,58,58,58,77, 1458, 1418,1379, 1354, 1299, 1269, 1204, 1090, 1069, 831, 527 cm-1, HRMS (ESI) calcd. for C13H18ClNOS2: [ M + Na ] +:324.0416, found:324.0414.
Example 10
The preparation method of the 2- (3-chlorphenyl) -2-hydroxyethyl diethyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 3-chlorostyrene, 0.1mmol of tetraethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 12.4mg of a target product.
The target product yield of this example was 41%.
Nuclear magnetic characterization of the target product was performed by 1H NMR (400 MHz, CDCl3) ppm, 7.49 (m,1H), 7.39-7.33 (d, J = 7.3Hz, 1H), 7.33-7.29 (d, J = 7.8 Hz,1H), 7.29-7.23(m, 1H), 5.10-4.99 (dd, J = 8.4,3.2 Hz,1H), 4.13-3.98 (m,2H), 3.93-3.84(dd, J =14.6, 3.4Hz, 1H), 3.84-3.73 (m,2H), 3.63-3.51 (dd, J =14.6, 8.5Hz, 1H), 3.43 (s,1H), 1.40-1.20 (m, 6H), 13C (100MHz, CDCl 195.7,145.1, 3652.52H), 129.7, 127.8, 126.1, 124.1, 72.8, 50.2, 47.2, 45.0, 12.5,11.6, IR (KBr) 3364, 2974, 2921,2850, 1647, 1489, 1459, 1419, 1379, 1355, 1270,1205, 1070, 983, 789, 689 cm-1, HRMS (ESI) calcd. for C13H18ClNOS2, [ M + Na ] +:324.0416, found:324.0414.
Example 11
The preparation method of 2- (3-bromophenyl) -2-hydroxyethyl diethylamino dithio acid ester comprises the following steps:
(1) taking 0.2mmol of 3-bromostyrene, 0.1mmol of tetraethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48h, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 11mg of a target product.
The target product yield of this example was 32%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.64 (s,1H), 7.45-7.36 (m,2H), 7.29-7.20 (m,1H), 5.10-4.98 (t, J = 8.4, 4.2 Hz,1H), 4.14-3.97 (m,2H), 3.92-3.84 (dd, J =14.6, 3.4Hz, 1H), 3.84-.3.70 (m,2H), 3.63-3.50 (dd, J =14.6, 8.4Hz, 1H), 3.47-3.37 (d, J = 3.6 Hz,1H), 1.36-1.27 (m, 6H), 13C NMR (100MHz, CDCl3) 195.7, 145.4, 130.8, 130.0,129.0, 124.6,122.6, 72.7, 2.47, 2.5, 3345 Br (Kb, 11, 11,47,47,47,47,5,47,47,47,47,47,47,47,47,45,47,47,12, 2957,2922, 2850, 1645, 1489, 1468, 1419, 1379, 1354, 1269, 1205, 1141, 1067, 982cm-1, HRMS (ESI) calcd. for C13H18BrNOS2, [ M + Na ] +:369.9911, found: 369.9911.
Example 12
The preparation method of 2- (4-fluorophenyl) -2-hydroxyethyl diethylamino dithio acid ester comprises the following steps:
(1) taking 0.2mmol of 4-fluorostyrene, 0.1mmol of tetramethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction solution obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 8.9mg of a target product.
The target product yield of this example was 31%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.50-7.40(m, 2H), 7.10-7.00 (t, J = 17.5, 8.8 Hz,2H), 5.10-4.98 (d, J = 7.7 Hz,1H), 4.15-3.96 (m,2H), 3.90-3.82 (dd, J =14.5, 3.5 Hz,1H), 3.82-3.73 (m,2H),3.64-3.50 (dd, J =14.5, 8.6 Hz,1H), 3.31 (s,1H), 1.37-1.20 (m, 6H), 13CNMR (100MHz, CDCl3)195.8, 162.3(d, J = 244.1 Hz), 138.8 (d, J = 2.3 Hz), 115.6 (d = 115.8, 1 Hz), 3.6 (d, 115.3 Hz), j = 21.4 Hz), 72.7,50.2, 47.1, 45.3, 12.5,11.6, IR (KBr) 3394, 2920, 2848, 1644, 1488, 1467, 1418, 1269, 1207, 1142,1068, 982, 835, 541, 525, 509 cm-1, HRMS (ESI) calcd. for C13H18FNOS2: [ M + Na ] +: 310.0712, found: 310.0713.
Example 13
The preparation method of 2- (4-methylphenyl) -2-hydroxyethyl diethylamino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 3-bromostyrene, 0.1mmol of tetraethylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48h, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction solution obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 7.4mg of a target product.
The target product yield of this example was 26%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.41-7.33(d, J = 8.0 Hz,2H), 7.23-7.13 (d, J = 7.9 Hz,2H), 5.08-4.93 (t, J = 8.6,5.0 Hz,1H), 4.15-3.95 (m,2H), 3.89-3.81 (dd, J = 14.4, 3.6 Hz,1H), 3.81-3.72 (m,2H), 3.69-3.57 (dd, J = 14.4, 8.7 Hz,1H), 3.20-3.08 (d, J = 3.5 Hz,1H), 2.40-2.30 (s, 3H), 1.40-1.20 (m, 6H), 13C NMR (100MHz, Cl3)196.0,140.1, 137.4, 137.125, 1.73, 2.73, 50.73, 47.1, 45.3, 21.2, 12.5,11.6, IR (KBr): 3394, 2977, 2921, 2849, 1646, 1489, 1463, 1419, 1379, 1355, 1268,1205, 1142, 1067, 982, 736 cm-1, HRMS (ESI) calcd. for C14H21NOS2 [ M + Na ] +:306.0962, found: 306.0963.
Example 14
The preparation method of the 2- (4-chlorphenyl) -2-hydroxyethyl dibutyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 4-chlorostyrene, 0.1mmol of tetrabutylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture into a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 15.1mg of a target product.
The target product yield of this example was 42%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.47-7.37(d, J = 8.4Hz, 2H), 7.37-7.30 (d, J = 8.5Hz, 2H), 5.10-4.96 (d, J = 6.7 Hz,1H), 4.07-3.89 (m,2H), 3.89-3.80 (dd, J =14.6, 3.4Hz, 1H), 3.76-3.61 (m,2H), 3.60-3.50 (dd, J =14.6, 8.5Hz, 1H), 3.37 (s,1H), 1.80-1.64 (m, 4H),1.45-1.30 (m, 4H), 1.03-0.90 (m, 6H), 13C NMR (100MHz, CDCl3)196.0, 141.6,133.4, 6.6, 127.55, 7.55, 7.52, 45.2, 29.4, 28.4, 20.1,13.8, 13.7, IR (KBr) 3358, 2958, 2926, 2857, 1488, 1464, 1415, 1369, 1290, 1218, 1185,1091, 1064, 1013, 980, 945, 828, 755 cm-1, HRMS (ESI) calcd, for 17H26ClNOS2: [ M + H ] +: 360.1223, found: 360.1223.
Example 15
The preparation method of the 2- (3-chlorphenyl) -2-hydroxyethyl dibutyl amino dithio-acid ester comprises the following steps:
(1) taking 0.2mmol of 3-chlorostyrene, 0.1mmol of tetrabutylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture into a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 16.5mg of a target product.
The target product yield of this example was 46%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.48 (s,1H), 7.38-7.33 (m,1H), 7.33-7.28 (m,1H), 7.28-7.23 (m,1H), 5.10-4.98 (t, J = 8.3, 4.9 Hz,1H), 4.04-3.92 (m,2H), 3.90-3.80 (dd, J =14.6, 3.4Hz, 1H),3.75-3.64 (m,2H), 3.62-3.50 (dd, J =14.6, 8.4Hz, 1H), 3.46-3.36 (d, J = 3.3Hz, 1H), 1.80-1.66(m, 4H), 1.45-1.32 (m, 4H), 1.02-0.93 (m, 6 MHz, 13C 100 MHz), CDCl3)196.0, 145.1, 134.4, 129.7, 127.8, 126.1, 124.1, 72.8, 55.7,52.9, 45.1, 29.4, 28.4, 20.1,13.8, 13.7, IR (KBr) 3358, 2959, 2927, 2855,1657, 1632, 1597, 1537, 1468, 1415, 1367, 1290, 1217, 1184, 1140, 1095, 1061cm-1, HRMS (ESI) calcd. for C17H26ClNOS2: [ M + H ] +: 360.1223, found: 360.1221.
Example 16
The preparation method of the 2- (4-bromophenyl) -2-hydroxyethyl dibutylamino dithio-ester comprises the following steps:
(1) taking 0.2mol of 4-bromostyrene, 0.1mmol of tetrabutylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48h, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 15.1mg of a target product.
The target product yield of this example was 38%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.55-7.45(d, J = 8.4Hz, 2H), 7.40-7.30 (d, J = 8.4Hz, 2H), 5.08-4.98 (dd, J = 8.4,3.2 Hz,1H), 4.06-3.90 (m,2H), 3.89-3.80 (dd, J =14.6, 3.4Hz, 1H), 3.78-3.62 (m,2H), 3.60-3.50 (dd, J =14.6, 8.5Hz, 1H), 3.38 (s,1H), 1.80-1.66(m, 4H 127), 1.44-1.30 (m, 4H), 1.03-0.90 (m, 6H), 13C NMR (100MHz, CDCl3) ppm 7.52, 131.635 NMR, 7.121, 72.8, 55.7,52.9, 45.1, 29.4, 28.4, 20.1,13.8, 13.7, IR (KBr) 3360, 2958, 2928, 2869, 1485, 1414, 1368, 1290, 1250,1218, 1069, 1010, 521 cm-1, HRMS (ESI) calcd, for C17H26BrNOS2: [ M + Na ] +:426.0537, found: 426.0535.
Example 17
The preparation method of the 2- (3-bromophenyl) -2-hydroxyethyl dibutylamino dithio-ester comprises the following steps:
(1) taking 0.2mmol of 3-bromostyrene, 0.1mmol of tetrabutylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48h, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction solution obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 17.6mg of a target product.
The target product yield of this example was 44%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.64 (s,1H), 7.46-7.36 (t, J = 16.1, 8.1 Hz,2H), 7.27-7.18 (m,1H), 5.08-4.98 (d, J = 8.2 Hz,1H), 4.07-3.90 (m,2H), 3.90-3.81 (dd, J =14.6, 3.4Hz, 1H), 3.78-3.61 (m,2H), 3.61-3.50 (dd, J =14.6, 8.4Hz, 1H), 3.49-3.40 (d, J = 2.8 Hz,1H), 1.80-1.66(m, 4H), 1.44-1.30 (m, 4H), 1.03-0.90 (m, 6H), 13C (3 MHz, CDCl) NMR, 0.196, 145.4, 130.7, 130.0, 129.1, 124.6,122.6, 72.7, 55.7,52.9, 45.0, 29.4, 28.4, 20.1,13.8, 13.7, IR (KBr) 3394, 2957, 2923, 2851,1645, 1484, 1417, 1369, 1291, 1251, 1217, 1186, 1093, 1063 cm-1, HRMS (ESI) calcd. for C17H26BrNOS2: [ M + Na ] +:426.0537, found: 426.0536.
Example 18
The preparation method of the 2- (4-fluorophenyl) -2-hydroxyethyl dibutylamino dithio-ester comprises the following steps:
(1) taking 0.2mmol of 4-fluorostyrene, 0.1mmol of tetrabutylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture into a 5ml Schlenk tube, placing the tube in an oil bath at the temperature of 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 14.6mg of a target product.
The target product yield of this example was 43%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.51-7.41(m, 2H), 7.13-6.99 (t, J = 17.4, 8.7 Hz,2H), 5.10-4.98 (dd, J = 8.5, 3.3Hz, 1H), 4.06-3.88 (m,2H), 3.88-3.78 (dd, J =14.5, 3.4Hz, 1H), 3.78-3.62 (m,2H), 3.62-3.50 (dd, J =14.5, 8.6 Hz,1H), 3.33 (s,1H), 1.80-1.66(m, 4H),1.45-1.31 (m, 4H), 1.04-0.90 (m, 6H), 13C NMR (100MHz, CDCl3)196.0, 162.196 (J = 3.138 Hz), 1.244 d (244.138 Hz), j = 3.0 Hz), 127.6 (d, J = 8.1 Hz), 115.2 (d, J = 21.4 Hz), 72.8, 55.7,52.9, 45.3, 29.4, 28.4, 20.1,13.8, 13.7, IR (KBr):3360, 2958, 2923, 2852, 1509, 1485, 1467, 1415, 1369, 1290, 1221, 1186, 837cm-1, MS (ESI) calcd. for C17H26FNOS2: [ M + Na ] +: 366.1338, ufound: 366.1339.
Example 19
The preparation method of the 2-hydroxy-2-phenylethyl dimethyl amino dithio acid ester comprises the following steps:
(1) taking 0.2mmol of styrene, 0.1mmol of tetrabutylthiuram disulfide and 0.2mmol of sodium ethoxide, adding 1ml of 1.4-dioxane to obtain a mixture, placing the mixture in a 5ml Schlenk tube, placing the tube in an oil bath at 80 ℃ for heating, reacting for 48 hours, and cooling to room temperature to obtain a reaction solution;
(2) directly concentrating the reaction liquid obtained in the step (1) to obtain a concentrate, and performing thin-layer chromatography on the concentrate by using ethyl acetate/petroleum ether =1/5(v/v) as a developing solvent to obtain 15.6mg of a target product.
The target product yield of this example was 23%.
Performing nuclear magnetism characterization on a target product, and comprising the following steps: 1H NMR (400 MHz, CDCl3) ppm 7.53-7.46(d, J = 7.36 Hz,2H), 7.42-7.34 (t, J = 14.9, 7.2 Hz,2H), 7.33-7.27 (t, J =14.6, 7.3Hz, 1H), 5.10-4.98 (d, J = 8.6 Hz,1H), 3.92-3.80 (dd, J =14.5, 3.4Hz, 1H), 3.67-3.60 (t, J = 14.7, 8.8 Hz,1H), 3.59 (s,1H), 3.42 (s,1H), 3.15 (s,1H), 13C NMR (100MHz, CDCl3)197.6, 142.9, 128.5, 127.8, 125.9,73.3, 45.3029, 45.41, 3208, R, 21 Br), 1491, 1451, 1373, 1254,1079, 974, 724, 692 cm-1, HRMS (ESI) calcd. for C11H15NOS2, [ M + Na ] +:246.0493, found:264.0485.
In the above examples, 1.4-dioxane was used as the organic solvent. In other embodiments, the 1, 4-dioxane can also be replaced by one or more of toluene, xylene, mesitylene, tetrahydrofuran, acetonitrile, ethanol, and tert-butyl methyl ether; of course, the organic solvent may also be 1, 4-dioxane in combination with any one or more of toluene, xylene, mesitylene, tetrahydrofuran, acetonitrile, ethanol, tert-butyl methyl ether.
In the above examples, sodium ethoxide was the base catalyst. In other embodiments, the sodium ethoxide can be replaced by one or more of cesium carbonate, sodium carbonate, potassium bicarbonate, potassium phosphate, sodium bicarbonate, potassium acetate, sodium acetate, lithium methoxide, lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide; of course, the base catalyst can also be a combination of sodium ethoxide and any one or more of cesium carbonate, sodium carbonate, potassium bicarbonate, potassium phosphate, sodium bicarbonate, potassium acetate, sodium acetate, lithium methoxide, lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, lithium hydroxide, sodium hydroxide, and potassium hydroxide.
In the above examples, styrene, 3-chlorostyrene, 4-chlorostyrene, 3-bromostyrene, 4-fluorostyrene, 4-methoxystyrene, 4-tert-butylstyrene, 4-methyl-5-vinylthiazole were styrene derivatives. In other embodiments, the styrene derivative may also be 4-methylstyrene.
Although the present invention has been described in detail with reference to the embodiments, it will be understood by those skilled in the art that various changes in the specific parameters of the embodiments may be made without departing from the spirit of the present invention, and a plurality of specific embodiments are formed, which are common variations of the present invention, and will not be described in detail herein.

Claims (9)

  1. A process for the preparation of β -hydroxy-substituted alkyldithiocarbamates characterized by the steps of:
    (1) adding an alkali catalyst, a styrene derivative and thiuram disulfide into an organic solvent for reaction, and then cooling to room temperature to obtain a reaction solution;
    (2) concentrating, separating and purifying the reaction liquid obtained in the step (1) to obtain β -hydroxy dithiocarbamate.
  2. 2. The method of claim 1, wherein the molar ratio of the base catalyst, the styrene derivative, and the thiuram disulfide is 0.2: 0.2: 0.1.
  3. 3. The method of β -hydroxy-substituted alkyldithiocarbamates according to claim 1 wherein said base catalyst is one or more of cesium carbonate, sodium carbonate, potassium bicarbonate, potassium phosphate, sodium bicarbonate, potassium acetate, sodium ethoxide, lithium methoxide, lithium tert-butoxide, potassium tert-butoxide, sodium tert-butoxide, lithium hydroxide, sodium hydroxide, potassium hydroxide.
  4. 4. The method of claim 1, wherein the styrene derivative is styrene, 3-chlorostyrene, 4-chlorostyrene, 3-bromostyrene, 4-fluorostyrene, 4-methylstyrene, 4-methoxystyrene, 4-tert-butylstyrene or 4-methyl-5-vinylthiazole.
  5. 5. The method of claim 1, wherein the thiuram disulfide is one or more selected from the group consisting of tetramethylthiuram disulfide, tetraethylthiuram disulfide, and tetrabutylthiuram disulfide.
  6. 6. The method of claim 1, wherein the organic solvent is one or more selected from the group consisting of 1, 4-dioxane, toluene, xylene, mesitylene, tetrahydrofuran, acetonitrile, ethanol, and tert-butyl methyl ether.
  7. 7. The method of claim 1, wherein the amount of said organic solvent is 10L per mole of thiuram disulfide.
  8. 8. The method of β -hydroxysubstituted alkyldithiocarbamates according to any of claims 1-8, wherein the reaction temperature in step (1) is 80 ℃ and the reaction time is 48 hours.
  9. 9. The method for preparing β -hydroxy-substituted alkyldithiocarbamates according to any of claims 1 to 8, wherein said separation and purification in step (2) is carried out by subjecting a concentrate obtained by concentrating the reaction mixture to thin layer chromatography using petroleum ether/ethyl acetate in a volume ratio of 5/1 as a developing solvent.
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