CN105085471A - Preparation method of 2-substituted-1,3-dithiane derivative - Google Patents

Preparation method of 2-substituted-1,3-dithiane derivative Download PDF

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CN105085471A
CN105085471A CN201410206794.7A CN201410206794A CN105085471A CN 105085471 A CN105085471 A CN 105085471A CN 201410206794 A CN201410206794 A CN 201410206794A CN 105085471 A CN105085471 A CN 105085471A
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dithiane
cdcl
aldehyde
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CN105085471B (en
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唐寿初
赖俊汕
杜文斌
田丽霞
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Lanzhou University
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    • C07—ORGANIC CHEMISTRY
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    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
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Abstract

The invention provides a preparation method of a 2-substituted-1,3-dithiane derivative. The preparation method comprises the following steps: adding 1,3-dithiane (CAS:505-23-7) and 1,2-dichloroethane (DCE) or dichloromethane (DCM) into a reaction bottle, adding N-chlorosuccinimide (NCS) under ice-bath condition, and stirring for 0.5-1 h to prepare a 2-chloro-1,3-dithiane solution; and adding an aldehyde or ketone compound and a lewis acid catalyst into the above solution, and reacting to prepare the 2-substituted-1,3-dithiane derivative. By using the 1,3-dithiane solid and different types of aldehyde and keto-carbonyl compounds as raw material and using one or more of ferric trichloride, boron trifluoride diethyl etherate, methanesulfonic acid, aluminum trichloride, ferrous chloride and nickel chloride as catalysts, preparation of the 2-substituted-1,3-dithiane derivative is realized. The catalysts used in the invention are cheap and easily available, dosage of the catalysts is low and pollution of the catalysts is little. The solid raw materials used in the invention can avoid use of fetid toxic 1,3-dimercaptopropane with strong volatility, and the purpose of protecting an experimenter's body and reducing environmental pollution is realized. In addition, the preparation method has advantages of mild reaction condition, high yield, simple operation and the like.

Description

A kind of 2-replaces the preparation method of-1,3-dithiane derivatives
Technical field
The invention belongs to technical field of organic synthesis, particularly relate to replacement 1,3-dithiane derivatives preparation method.
Background technology
1,3-dithiane (1,3-dithiane) derivative is a kind of important organo-functional group reagent.1; 3-dithiane not only can be used for aldehyde; the synthesis of ketone and in organic synthesis as the protecting group of carbonyl; and can be used for the preparation of multi-functional carbonyl compound; build complicated molecular skeleton and complicated molecule segment, thus realize the complete synthesis of numerous target molecule, molecule of pharmaceutical and natural product and preparation.Secondly, 1,3-dithiane can participate in numerous organic reaction research, such as: Linchpin reaction, Brook rearrangement reaction, ARC (AnionRelayChemistry) reaction and carbon lithiation etc.The preparation method of usual replacement 1,3-dithiane derivatives is prepared by 1,3-dimercaptopropane and aldoketones Reactive Synthesis, but the stench of 1,3-dimercaptopropane and toxicity, limit the application of this kind of reaction.Have now been developed different reagent and alternative 1, the 3-dimercaptopropane reagent of method, but most of preparation method is complicated, need polystep reaction synthesis, surrogate costliness and Atom economy poor.Use 2-chloro-1,3-dithiane as mercaptan surrogate herein, a step can directly realize 1,3-dithianeization reaction of aldehyde, ketone carbonyl.Chloro-1, the 3-dithiane preparation of 2-is simple, and reaction conditions is gentle, and yield is high, simple to operate, avoids the use of 1,3-dimercaptopropane of stench, toxicity.Inexpensive catalyst of the present invention is easy to get, and consumption is few and pollution-free, belongs to the method that green syt 2-replaces-1,3-dithiane derivatives, has significant using value and social effect.
Summary of the invention
The invention provides a kind of preparation method of 1,3-dithiane derivatives, the method mild condition, and operation steps is simple, has aftertreatment and avoids the advantages such as environmental pollution.
The invention provides the preparation method that a kind of 2-replaces-1,3-dithiane derivatives, mainly comprise the following steps:
A) by 1,3-dithiane and 1,2-ethylene dichloride (DCE) or methylene dichloride (DCM) add in reaction flask, and ice bath, adds N-chlorosuccinimide (NCS), obtains 2-chlorine 1,3-dithiane solution; In above-mentioned system, add aldehyde compound and catalyzer, obtain corresponding 2-after reaction and replace-1,3-dithiane derivatives.
B) by 1,3-dithiane and DCE or DCM add in reaction flask, and ice bath adds NCS, obtain 2-chlorine 1,3-dithiane solution; In above-mentioned system, add ketone compounds and catalyzer, obtain corresponding 2-after reaction and replace-1,3-dithiane derivatives.
Preferably, described catalyzer is boron trifluoride diethyl etherate, iron trichloride, methylsulfonic acid, one or both Lewis acids in aluminum chloride.
Preferably, the solvent used is 1,2-ethylene dichloride and methylene dichloride.
Preferably, replace-1,3-dithiane derivatives preparation method according to described 2-, it is characterized in that: described aldehyde compound is aromatic aldehyde and the alkanoic of different substituents, substituting group on described aromatic ring comprises methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, ethanoyl, phenyl, hydrogen, cyano group, nitro, cyano group, sulfo group, phenolic hydroxyl group, one or more in fatty alkyl, described aromatic formaldehyde comprises naphthaldehyde, phenyl aldehyde; Described alkanoic comprises the saturated aldehyde of different carbon chain, unsaturated aldehyde.
Preferably, replace-1,3-dithiane derivatives preparation method according to described 2-, it is characterized in that: the structure of described ketone is as follows:
Wherein, R 1, R 2comprise substituted-phenyl, substituted benzyl, substituted naphthyl, one or more in fatty alkyl, described substituted-phenyl, substituted benzyl, the substituting group on substituted naphthyl comprises methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, ethanoyl, phenyl, hydrogen, cyano group, nitro, phenolic hydroxyl group, sulfo group, one or more in fatty alkyl; Described aliphatic ketone comprises the saturated ketone of different carbon chain, beta-unsaturated ketone.
Preferably, described step a) in ratio of reagents used be 1,3-dithiane: NCS: aldehyde=1:1.1:0.8.
Preferably, described step b) in reagent molar ratio used be 1,3-dithiane: NCS: ketone=1:1.1:0.8.
Preferably, described step a) and step b) in temperature of reaction be 0 ~ 100 degree Celsius.
Preferably, described step a) and step b) in the reaction times be 0.5 little of 18 hours.
Preferably, described step a) and step b) in reaction times of 1,3-dithiane and NCS be 0.5 hour-1 hour.
Embodiment
The following examples can make those skilled in the art more fully understand the present invention, but do not limit the present invention in any way.The present invention is raw materials used is known compound, can be buied means known in the art synthesis maybe can be adopted to obtain by market.
Embodiment 1, in 10 milliliters of round-bottomed flasks, adds 1,3-dithiane (0.250mmol), NCS (0.300mmol), adds after 2 milliliters of DCE dissolve and reacts 0.5 ~ 1h in-10 DEG C.Add phenyl aldehyde (0.250mmol), iron trichloride (0.025mmol) after TLC monitoring question response is complete, continuation reaction 12h, TLC detection question response steams completely afterwards and desolventizes, and column chromatography obtains product.
Embodiment 3, in 10 milliliters of round-bottomed flasks, adds 1,3-dithiane (0.250mmol), NCS (0.300mmol), adds after 2 milliliters of DCE dissolve and reacts 0.5 ~ 1h in-10 DEG C.Add aubepine (0.250mmol), boron trifluoride diethyl etherate (0.025mmol) after TLC monitoring question response is complete, continuation reaction 4h, TLC detection question response steams completely afterwards and desolventizes, and column chromatography obtains product.
Implement 40 in 10 milliliters of round-bottomed flasks, add 1,3-dithiane (0.250mmol), NCS (0.300mmol), add after 2 milliliters of DCE dissolve and react 0.5 ~ 1h in-10 DEG C.Add butyraldehyde-n (0.250mmol), iron trichloride (0.025mmol) after TLC monitoring question response is complete, continuation reaction 8h, TLC detection question response steams completely afterwards and desolventizes, and column chromatography obtains product.
Embodiment 44, in 10 milliliters of round-bottomed flasks, adds 1,3-dithiane (0.250mmol), NCS (0.300mmol), adds after 2 milliliters of DCE dissolve and reacts 0.5 ~ 1h in-10 DEG C.Add crotonic aldehyde (0.250mmol), iron trichloride (0.025mmol) after TLC monitoring question response is complete, continuation reaction 8h, TLC detection question response steams completely afterwards and desolventizes, and column chromatography obtains product.
Embodiment 2,4-39,41-43,45-48 is except the aldehyde difference used, and other reaction conditionss are all identical, are specially:
In 10 milliliters of round-bottomed flasks, add 1,3-dithiane (0.250mmol), NCS (0.300mmol), add after 2 milliliters of DCE dissolve and react 0.5 ~ 1h in-10 DEG C.Add aldehyde compound (0.200mmol), iron trichloride and/or boron trifluoride diethyl etherate (0.025mmol) after TLC monitoring question response is complete, continue reaction 0.5 ~ 18h, TLC detection question response steams completely afterwards and desolventizes, and column chromatography obtains product.
The product of chloro-1, the 3-dithiane of the aldehyde that all embodiments use, ketone and 2-, yield and temperature of reaction are as shown in the table:
The reaction product of table 1:1,3-dithiane and aldehydes
The reaction of table 1:1,3-dithiane and ketone
The product that all embodiments obtain all is proven by nuclear magnetic resonance map, specific as follows:
Embodiment 1 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.41-7.26 (m, 5H), 5.12 (s, 1H), 3.06-2.75 (m, 4H), 2.07-1.78 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 139.0,128.6,128.3,127.7,127.1,51.6,50.8,50.2,32.1,32.0,23.94.
Embodiment 2 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.53-6.96 (m, 4H), 5.20-5.00 (m, 1H), 3.07-2.75 (m, 4H), 2.36-2.22 (m, 3H), 2.10-1.79 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 137.82,135.91,129.02,127.25,50.81,31.76,24.77,20.91.
Embodiment 3 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.42-7.39 (m, 2H), 6.88-6.86 (m, 2H), 5.14 (s, 1H), 3.79 (s, 3H), 3.09-2.86 (m, 4H), 2.13-1.92 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 159.4,131.2,128.7,114.1,55.3,50.7,32.3,24.9.
Embodiment 4 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.76-7.34 (m, 4H), 5.13 (s, 1H), 3.09-2.87 (m, 4H), 2.18-1.88 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 138.0,131.9,129.4,122.11,50.0,31.8,24.8.
Embodiment 5 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.61-7.59 (m, 2H), 7.22-7.17 (m, 2H), 5.32 (s, 1H), 3.09-2.85 (m, 4H), 2.45 (m, 3H), 2.16-1.88 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 137.0,134.8,130.3,127.9,126.3,48.17,32.4,25.0,18.9.
Embodiment 6 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.76-7.16 (m, 4H), 5.56 (s, 1H), 3.20-2.93 (m, 4H), 2.23-1.94 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 138.0,132.6,129.8,127.9,122.7,50.4,30.0,24.8.
Embodiment 7 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.54-6.78 (m, 4H), 5.65 (s, 1H), 3.78 (s, 3H), 3.06-2.77 (m, 4H), 2.09-1.82 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 155.2,129.3,120.7,110.5,55.5,43.4,43.3,32.1,25.1.
Embodiment 8 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.52-7.15 (m, 3H), 5.47 (s, 1H), 3.03-2.77 (m, 4H), 2.07-1.78 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 135.1,134.7,131.6,129.9,131.6,128.1,46.6,36.8,28.4,21.4.
Embodiment 9 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.63-6.96 (m, 4H), 5.06 (s, 1H), 2.90 (m, J=15.9,14.5,1.2Hz, 4H), 2.14-1.65 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 137.48,133.87,129.01,128.70,50.33,31.8,24.7.
Embodiment 10 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.40 (t, J=12.4Hz, 2H), 6.86 (d, J=8.6Hz, 2H), 5.30 (d, J=53.1Hz, 2H), 3.19-2.90 (m, 4H), 2.30-1.94 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 155.5,131.3,129.1,115.5,50.7,32.1,25.0.
Embodiment 11 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.13 (t, J=12.4Hz, 2H), 6.64 (d, J=8.6Hz, 2H), 5.20 (d, J=53.1Hz, 2H), 2.94-2.82 (m, 4H), 2.12-1.78 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 156.7,141.1,129.9,119.9,114.5,50.4,31.1,25.1.
Embodiment 12 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.48-6.94 (m, 4H), 5.08 (s, 1H), 3.01-2.54 (m, 5H), 2.07-1.63 (m, 2H), 1.29-0.96 (m, 6H). 13cNMR (75MHz, CDCl 3) δ 148.50,136.14,127.21,126.29,50.72,33.37,31.66,24.68,23.52.
Embodiment 13 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 7.00 (s, 1H), 6.33 (m, 2H), 5.16 (s, 1H), 3.75 (s, 6H), 2.95-2.83 (m, 4H), 2.13-1.79 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 161.0,140.0,106.7,99.4,56.6,51.9,31.7,24.8.
Embodiment 14 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.56-6.94 (m, 4H), 5,47 (s, 1H), 3.08-2.76 (m, 4H), 2,24-1.82 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 129.8,129.5,124.5,115.5,42.9,32.1,25.0.
Embodiment 15 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.72-7.09 (m, 4H), 5.26 (s, 1H), 2.97-2.78 (m, 4H), 2.23-1.74 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 139.7,132.0,129.9,126.9,123.7,51.4,32.3,25.1.
Embodiment 16 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.40-6.94 (m, 4H), 5.13 (d, J=1.6Hz, 1H), 2.99 (m, 4H), 2.34 (s, 3H), 2.30-1.44 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 138.9,138.4,135.2,129.9,129.2,128.5,124.74,51.5,32.1,30.9,28.8,27.2,25.1,21.3.
Embodiment 17 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.77-7.25 (m, 9H), 5.11 (s, 1H), 2.87-2.65 (m, 4H), 1.91-1.65 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 136.3,133.1,133.0,128.3,127.8,127.4,126.6,126.1,125.5,51.3,31.4,24.8.
Embodiment 18 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 6.76 (s, 1H), 6.40-6.38 (m, 2H), 5.27 (s, 1H), 3.41-3.27 (m, 6H), 2.65-2.21 (m, 4H), 1.78-1.46 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 153.5149.2,127.8,114.3,114.2,111.7,56.1,43.4,31.9,24.9.
Embodiment 19 product nuclear-magnetism, 1HNMR (300MHz, CDCl 3) δ 8.22-7.39 (m, 4H), 6.28-5.71 (m, 1H), 3.46-2.78 (m, 4H), 2.09 (d, J=26.0, t, 13.9Hz, 2H) .13CNMR (75MHz, CDCl 3) δ 147.4,133.2,130.4,128.8,124.4,45.65,31.9,24.7.
Embodiment 20 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 8.88-7.50 (m, 4H), 5.37 (s, 1H), 3.66-2.68 (m, 4H), 2.20 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 147.5,146.1,128.8,128.2,127.3,123.1,50.6,49.7,48.8,34.8,26.4.
Embodiment 21 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.67 (dd, J=34.4,33.5Hz, 2H), 7.57 (dd, J=12.6,4.5Hz, 2H), 5.37 (d, J=44.5Hz, 1H), 3.19-2.95 (m, 4H), 2.09-1.96 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 143.8,132.1,128.2,118.1,111.6,49.7,31.3,24.4.
Embodiment 22 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.45-7.50 (m, 2H), 6.94-7.00 (m, 2H), 5.60 (s, 1H), 3.19-2.95 (m, 4H), 2.09-1.96 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 163.8,160.5,135.8,129.5,129.4,115.3,115.0,49.8,32.0,24.5.
Embodiment 23 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.62 (d, J=7.9Hz, 2H), 7.55 (d, J=7.9Hz, 2H), 5.60 (s, 1H), 3.19-2.95 (m, 4H), 2.09-1.96 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 144.4,137.3,127.6,55.1,32.2,24.6.
Embodiment 24 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.62 (d, J=7.9Hz, 2H), 7.55 (d, J=7.9Hz, 2H), 5.60 (s, 1H), 3.19-2.95 (m, 4H), 2.09-1.96 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 144.9,128.3,125.4,55.3,32.0,24.5.
Embodiment 25 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.53 (m, 1H), 7.34 (s, 1H), 7.23-6.97 (m, 2H), 5.13 (s, 1H), 3.79 (s, 3H), 2.93-2.80 (m, 4H), 2.14-1.82 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 160.2,138.1,129.2,123.1,121.3,114.3,55.3,50.7,32.3,24.9.
Embodiment 26 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 7.52-7.26 (m, 3H), 7.01-6.93 (m, 1H), 5.15 (s, 1H), 2.96-2.67 (m, 4H), 2.08-1.82 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 162.6,139.6,130.4,125.4,116.1,50.2,32.1,24.9.
Embodiment 27 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 7.54-7.17 (m, 4H), 5.14 (s, 1H), 2.98-2.66 (m, 4H), 2.13-1.78 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 162.8,139.4,130.6,124.4,115.1,50.6,32.2,25.2.
Embodiment 28 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 7.73 (s, 1H) 7.54-7.23 (m, 2H), 7.03-6.90 (m, 1H), 5.14 (s, 1H), 3.14-2.69 (m, 4H), 1.87-1.76 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 163.6,139.2,131.0,124.3,115.9,50.3,32.6,24.8.
Embodiment 29 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 8.60 (s, 1H), 8.08-7.97 (m, 1H), 7.63-7.56 (m, 2H), 5.12 (s, 1H), 2.96-2.67 (m, 4H), 2.08-1.82 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 149.4,138.6,133.5,122.6,50.4,32.4,24.8.
Embodiment 30 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 8.12 (d, 1H), 7.94 (m, 1H), 7.52-7.41 (m, 2H), 5.12 (s, 1H), 3.10-2.69 (m, 4H), 2.03-1.76 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 149.2,133.6,132.2,131.7,119.4,112.4,50.3,32.6,24.4.
Embodiment 31 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 8.07 (d, 1H), 7.55-7.39 (m, 3H), 5.13 (s, 1H), 2.92-2.64 (m, 4H), 2.06-1.80 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 138.3,131.9,131.1,130.2,125.4,124.3,123.6,53.2,33.1,25.4.
Embodiment 32 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.71-7.09 (m, 4H), 5.42 (s, 1H), 3.09-2.88 (m, 4H), 2.04-1.79 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 136.0,133.6,129.8,128.5,127.0,47.2,32.0,24.9.
Embodiment 33 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.75-6.98 (m, 4H), 5.34 (s, 1H), 3.10-2.83 (m, 4H), 2.04-1.79 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 142.0,138.4,129.2,128.5,127.8,97.7,56.4,32.0,24.9.
Embodiment 34 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.24 (d, J=8.0Hz, 2H), (6.95 d, J=8.0Hz, 1H), (6.81 d, J=8.0Hz, 1H), 5.12 (s, 1H), 4.88 (s, 1H), 2.45-2.83 (m, 4H), (1.97-2.19 m, 2H). 13cNMR (75MHz, CDCl 3) δ 155.0,130.4,129.6,124.2,121.6,117.4,47.5,32.0,24.6.
Embodiment 35 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.79-7.02 (m, 4H), 5.42 (s, 1H), 3.08-2.80 (m, 4H), 2.01-1.73 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 145.0,134.4,129.5,124.5,126.8,99.7,56.6,32.4,24.8.
Embodiment 36 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.48-6.82 (m, 4H), 4.97 (s, 1H), 3.00-2.72 (m, 4H), 1.93-1.67 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 145.8,134.4,129.8,128.8,124.6,120.6,109.7,53.6,31.4,24.5.
Embodiment 37 product nuclear-magnetism, NMR (300MHz, CDCl 3) δ 5.21 (t, 1H), 3.13-3.04 (m, 4H), 2.21-2.04 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 176.2,38.9,25.4,24.5.
Embodiment 38 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 3.92 (t, 1H), 2.86 (m, 4H), 2.08 (m, 2H), 1.83 (m, 2H), 1.04 (t, 3H). 13cNMR (75MHz, CDCl 3) δ 49.2,30.6,28.9,26.1,11.6.
Embodiment 39 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 3.99 (s, 1H), 2.88 (dd, J=7.9,3.0,4H), 2.10-2.05 (m, 1H), 1.85-1.75 (m, 1H), 1.11 (s, 9H). 13cNMR (75MHz, CDCl 3) δ 61.9,35.8,31.3,27.9,25.9
Embodiment 40 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 4.04 (t, 1H), 2.88 (m, 4H), 2.04 (m, 2H), 1.83 (m, 2H), 1.50 (m, 2H), 1.04 (t, 3H). 13cNMR (75MHz, CDCl 3) δ 47.4,37.8,30.6,26.5,19.0,13.3.
Embodiment 41 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 3.84 (t, 1H), 2.92 (m, 4H), 1.92 (m, 3H), 1.67 (m, 4H), 1.50 (m, 4H), 1.24 (t, 2H). 13cNMR (75MHz, CDCl 3) δ 52.3,41.4,31.0,29.4,26.5,26.0,25.3.
Embodiment 42 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 4.47 (m, 2H), 2.86 (m, 8H), 2.14-1.76 (m, 4H), 1.22 (m, 6H). 13cNMR (75MHz, CDCl 3) δ 59.1,43.1,31.4,26.2,22.5.
Embodiment 43 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.41-7.39 (m, 2H), 7.35-7.31 (m, 2H), 7.28-7.26 (m, 1H), 6.77 (d, J=15.7,1H), 6.27 (dd, J=15.7,7.7,1H), 4.82 (dd, J=7.7,0.7,1H), 2.99-2.88 (m, 4H), 2.16-2.12 (m, 1H), 1.93-1.89 (m, 1H). 13cNMR (75MHz, CDCl 3) δ 136.1,133.4,128.6,128.1,126.6,126.0,47.7,30.2,25.2
Embodiment 44 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 4.20 (m, J=14.5,11.1,6.2Hz, 2H), 2.98-2.64 (m, 4H), 2.13-1.70 (m, 3H), 1.61-1.32 (m, 3H). 13cNMR (75MHz, CDCl 3) δ 54.57,45.31,44.08,29.94,29.49,25.75,25.19.
Embodiment 45 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 4.04 (t, 1H), 2.91-2.80 (m, 4H), 2.13-2.10 (m, 1H), 1.89-1.86 (m, 1H), 1.84-1.72 (m, 2H), 1.51-1.45 (m, 2H), 1.36-1.29 (m, 2H), 0.90 (t, 3H). 13cNMR (75MHz, CDCl 3) δ 47.4,35.3,30.5,28.2,26.0,22.3.13.9.
Embodiment 46 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 4.00 (t, 1H), 2.85 (m, 4H), 2.13 (m, 2H), 1.83 (m, 2H), 1.53 (m, 2H), 1.33 (m, 4H), 0.87 (t, 3H). 13cNMR (75MHz, CDCl 3) δ 44.4,35.8,32.0,30.7,26.7,26.0,22.6.13.9.
Embodiment 47 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 4.02 (t, 1H), 2.87 (m, 4H), 2.14 (m, 2H), 1.85 (m, 2H), 1.54-1.32 (m, 8H), 0.91 (t, 3H). 13cNMR (75MHz, CDCl 3) δ 44.5,35.7,32.1,30.8,28.0,26.7,26.0,22.6,13.9.
Embodiment 48 product nuclear-magnetism 1hNMR (300MHz, CDCl 3) δ 4.01 (t, 1H), 2.86 (m, 4H), 2.13 (m, 2H), 1.84 (m, 2H), 1.56-1.31 (m, 10H), 0.90 (t, 3H). 13cNMR (75MHz, CDCl 3) δ 44.6,35.7,32.2,30.7,28.1,27.6,26.6,26.1,22.5,13.9.
Embodiment 49 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 8.03-7.26 (m, 5H), 4.61 (t, J=6.7Hz, 1H), 3.28 (dd, J=6.8,0.9Hz, 2H), 3.04-2.60 (m, 4H), 2.19-1.67 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 195.31,136.37,133.32,128.54,43.73,41.71,30.14,25.14.
Embodiment 50 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 8.09-7.20 (m, 4H), 4.94-4.59 (m, 1H), 3.41 (dt, J=6.9,2.0Hz, 2H), 3.18-2.75 (m, 4H), 2.48 (s, 3H), 2.32-1.84 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 194.92,144.19,133.94,129.21,43.55,42.06,30.15,25.27,21.54.
Embodiment 51 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 8.11-7.35 (m, 4H), 4.67 (t, J=6.8Hz, 1H), 3.31 (t, J=15.5Hz, 2H), 2.91 (ddd, J=17.5,14.3,8.6Hz, 4H), 2.21-1.84 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 194.09,139.68,134.58,129.75,129.40,128.98,128.78,127.81,43.60,41.75,30.05,25.02.
Embodiment 52 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.78 (dd, J=63.7,8.6Hz, 4H), 4.74 (t, J=6.9Hz, 1H), 3.38 (dd, J=15.1,6.1Hz, 2H), 3.08-2.81 (m, 4H), 2.21-1.88 (m, 2H). 13cNMR (75MHz, CDCl 3) δ 194.26,134.94,132.06,131.61,129.66,129.28,128.46,43.56,41.43,30.02,24.99.
Embodiment 58 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 8.05-7.09 (m, 4H), 5.01 (s, 1H), 3.20-2.85 (m, 4H), 2.85-2.60 (m, 2H), 2.35 (dd, J=13.0,4.0Hz, 1H), 2.23-1.92 (m, 2H), 1.75 (dd, J=25.7,12.6Hz, 1H). 13cNMR (75MHz, CDCl 3) δ 194.69,143.61,133.25,131.77,128.38,127.47,126.42,52.34,47.96,47.88,31.07,30.53,28.43,25.34,25.06.
Embodiment 64 product nuclear-magnetism, 1hNMR (300MHz, CDCl 3) δ 7.29 (s, 5H), 4.74 (d, J=11.2Hz, 1H), 4.02 (d, J=11.3Hz, 1H), 3.02-2.66 (m, 4H), (2.48 d, J=7.1Hz, 2H), (1.92 d, J=56.3Hz, 2H), 0.98 (t, J=7.2Hz, 3H). 13cNMR (75MHz, CDCl 3) δ 207.37,134.40,128.50,128.44,127.90,61.65,47.53,36.53,29.68,29.45,25.24,7.44,7.21.

Claims (9)

1. the preparation method of 2-replacement-1, a 3-dithiane derivatives, mainly comprises the following steps:
A) by 1,3-dithiane and 1,2-ethylene dichloride (DCE) or methylene dichloride (DCM) add in reaction flask, add N-chlorosuccinimide (NCS) under ice bath, obtained 2-chlorine 1,3-dithiane solution after stirring 0.5 ~ 1h; In above-mentioned system, add aldehyde compound and lewis acid catalyst, stir, prepare corresponding 2-after reaction and replace-1,3-dithiane compound.
B) by 1,3-dithiane and DCE or DCM add in reaction flask, add NCS, obtained 2-chlorine 1,3-dithiane solution; In above-mentioned system, add ketone compounds and catalyzer, stir, prepare corresponding 2-after reaction and replace-1,3-dithiane derivatives.
。
2. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: catalyzer is boron trifluoride diethyl etherate, iron trichloride, methylsulfonic acid, aluminum chloride, ferrous chloride, one or several Lewis acids in nickelous chloride.
3. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: described step a) in ratio of reagents used be 1,3-dithiane: NCS: aldehyde=1:1.1:0.8.
4. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: described step b) in reagent molar ratio used be 1,3-dithiane: NCS: ketone=1:1.1:0.8.
5. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: described aldehyde compound is the aromatic aldehyde of different substituents and the alkanoic of different carbon chain, and the substituting group on described phenyl ring comprises methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, ethanoyl, phenyl, hydrogen, cyano group, nitro, cyano group, sulfo group, phenolic hydroxyl group, one or more in fatty alkyl, described aromatic aldehyde comprises naphthaldehyde, phenyl aldehyde; Described alkanoic comprises the saturated aldehyde of different carbon chain, unsaturated aldehyde.
6. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: the structure of described ketone is as follows:
Wherein, R 1, R 2comprise substituted-phenyl, substituted benzyl, substituted naphthyl, one or more in fatty alkyl, described substituted-phenyl, substituted benzyl, the substituting group on substituted naphthyl, comprises methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, ethanoyl, phenyl, hydrogen, cyano group, nitro, phenolic hydroxyl group, sulfo group, one or more in fatty alkyl; Described aliphatic ketone comprises the saturated ketone of different carbon chain, beta-unsaturated ketone.
7. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: described step a) in the temperature of reaction of aldehyde and chloro-1, the 3-dithiane of 2-be 0 ~ 100 DEG C.
8. 2-according to claim 1 replaces-1,3-dithiane derivatives preparation method, it is characterized in that: described step b) in the temperature of reaction of ketone and chloro-1, the 3-dithiane of 2-be 0 ~ 100 DEG C.
9. 2-replaces-1,3-dithiane derivatives preparation method according to claim 1, it is characterized in that: in described step, the reaction times is 0.5 little of 18 hours.
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