CN105085471B - A kind of 2- replaces the preparation method of -1,3- dithiane derivatives - Google Patents
A kind of 2- replaces the preparation method of -1,3- dithiane derivatives Download PDFInfo
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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
- C07D339/08—Six-membered rings
Abstract
The present invention provides a kind of 2- to replace -1, the preparation method of 3- dithiane derivatives, the following steps are included: by 1,3- dithiane (CAS:505-23-7) and 1,2- dichloroethanes (DCE) is added in reaction flask, N-chlorosuccinimide (NCS) is added under ice bath, chloro- 1, the 3- dithiane solution of 2- is made in 0.5~1h of stirring；Aldehydes or ketone compounds and lewis acid catalyst are added in the above solution, reaction is prepared into 2- and replaces -1,3- dithiane derivatives.The present invention with 1,3- dithiane solid and different types of aldehyde, ketone carbonyl class compound for raw material, with boron trifluoride ether, ferric trichloride, alchlor, ferrous chloride, one of nickel chloride is lewis acid catalyst, realizes that 2- replaces the preparation of -1,3- dithiane derivatives.Lewis acid catalyst used is cheap and easily-available, and dosage is few and pollution is small；Solid material used can be realized to experimenter's body protection and the purpose to reduce environmental pollution, and have reaction condition mild, high income, simple operation and other advantages to avoid the use of stench, 1, the 3- dimercaptopropane of strong volatility, toxicity.
Description
Technical field
The invention belongs to technical field of organic synthesis, more particularly to replace 1,3- dithiane derivatives preparation method.
Background technique
1,3- dithiane (1,3-dithiane) derivative is a kind of important organo-functional group reagent.1,3- dithiane is not
Can only be used to aldehyde, the synthesis of ketone and in organic synthesis as the protecting group of carbonyl, and can be used for multi-functional carbonylation
Object preparation is closed, complicated molecular skeleton and complicated molecule segment are constructed, to realize numerous target molecules, molecule of pharmaceutical and natural
The fully synthetic and preparation of product.Secondly, 1,3- dithiane may participate in numerous organic reaction researchs, such as: Linchpin reaction,
Brook rearrangement reaction, ARC (Anion Relay Chemistry) reaction and carbon lithiation etc..Usually replace 1,3- dithiane
The preparation method of derivative is that 1,3- dimercaptopropane is reacted with aldoketones and is synthetically prepared, but the stench and poison of 1,3- dimercaptopropane
Property, limit the application of this kind of reaction.Different reagents and method substitution 1,3- dimercaptopropane reagent have now been developed, but most of
Preparation method is complicated, needs multistep reaction synthesis, substitute valuableness and Atom economy difference etc..The chloro- 1,3- bis- of 2- is used herein
Thiophene alkane as mercaptan substitute, can a step be directly realized by 1, the 3- dithianeization reaction of aldehyde, ketone carbonyl.The chloro- 1,3- dithiane of 2-
Preparation is simple, and reaction condition is mild, high income, easy to operate, avoid stench, toxicity 1,3- dimercaptopropane use.This
Invention inexpensive catalyst is easy to get, and dosage is few and pollution-free, belongs to the side that green syt 2- replaces -1,3- dithiane derivatives
Method has significant application value and social effect.
Summary of the invention
The present invention provides a kind of preparation method of 2- substitution -1,3- dithiane derivatives, this method mild condition, and operates
Step is simple, has many advantages, such as to post-process and avoid environmental pollution.
The present invention provides the preparation methods that a kind of 2- replaces -1,3- dithiane derivatives, mainly comprise the steps that
A) 1,3- dithiane and DEC or DCM are added in reaction flask, ice bath, NCS is added, obtains 2- chlorine 1,3- dithiane
Solution；Aldehyde compound and catalyst are added in the above system, corresponding 2- is obtained after reaction and replaces -1,3- dithiane derivative
Object.
B) 1,3- dithiane and DEC or DCM are added in reaction flask, ice bath, NCS is added, obtains 2- chlorine 1,3- dithiane
Solution；Ketone compounds and catalyst are added in the above system, corresponding 2- is obtained after reaction and replaces -1,3- dithiane derivative
Object.
Preferably, the catalyst is boron trifluoride ether, ferric trichloride, and methanesulfonic acid is one or two kinds of in alchlor
Lewis acid.
Preferably, used solvent is 1,2- dichloroethanes and methylene chloride.
Preferably, 2- according to claim 1 replaces -1,3- dithiane derivatives preparation method, it is characterised in that:
The aldehyde compound is the aromatic aldehyde and fatty aldehyde of different substituents, and the substituent group on the aromatic ring includes methoxyl group, methyl,
Ethyl, fluorine, chlorine, bromine, iodine, acetyl group, phenyl, hydrogen, cyano, nitro, cyano, sulfo group, phenolic hydroxyl group, one of fatty alkyl or
A variety of, the aromatic formaldehyde includes naphthaldehyde, benzaldehyde；The fatty aldehyde includes the saturated aldehyde of different carbon chain, unsaturated aldehyde.
Preferably, 2- according to claim 1 replaces -1,3- dithiane derivatives preparation method, it is characterised in that:
The structure of the ketone is as follows:
Wherein, R1, R2Including substituted-phenyl, substituted benzyl, substituted naphthyl, one of fatty alkyl or a variety of is described to take
For phenyl, substituted benzyl, the substituent group on substituted naphthyl includes methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, acetyl group, benzene
Base, hydrogen, cyano, nitro, phenolic hydroxyl group, sulfo group, one of fatty alkyl or a variety of；The fat alkanone includes different carbon chain
Saturated ketone, beta-unsaturated ketone.
Preferably, ratio of reagents used in the step a) is 1,3- dithiane: NCS: aldehyde=1:1.1:0.8.
Preferably, reagent molar ratio used in the step b) is 1,3- dithiane: NCS: ketone=1:1.1:0.8.
Preferably, reaction temperature is 0~100 degree Celsius in the step a) and step b).
Preferably, the reaction time is 0.5 hour to 18 hours in the step a) and step b).
Preferably, the reaction time of 1,3- dithiane and NCS are -1 hour 0.5 hour in the step a) and step b).
Specific embodiment
The following examples can make those skilled in the art that the present invention be more completely understood, but not limit in any way
The present invention.The raw materials used present invention is known compound, it is available on the market or can be used means known in the art and synthesize
It arrives.
Embodiment 1 is added 1,3- dithiane (0.250mmol), N- chlorosuccinimide in 10 milliliters of round-bottomed flasks
(0.300mmol) is added after 2 milliliters of 1,2- dichloroethanes dissolutions in -10 DEG C of 0.5~1h of reaction.TLC is monitored after complete reaction
It is added benzaldehyde (0.250mmol), ferric trichloride (0.025mmol), the reaction was continued 12h, TLC detection is evaporated off after complete reaction
Solvent, column chromatograph to obtain product.
Embodiment 3 is added 1,3- dithiane (0.250mmol), N- chlorosuccinimide in 10 milliliters of round-bottomed flasks
(0.300mmol) is added after 2 milliliters of 1,2- dichloroethanes dissolutions in -10 DEG C of 0.5~1h of reaction.TLC is monitored after complete reaction
It is added P-methoxybenzal-dehyde (0.250mmol), boron trifluoride ether (0.025mmol), the reaction was continued 4h, TLC is detected to anti-
Solvent is evaporated off after answering completely, column chromatographs to obtain product.
Implement 40 in 10 milliliters of round-bottomed flasks, is added 1,3- dithiane (0.250mmol), N- chlorosuccinimide
(0.300mmol) is added after 2 milliliters of 1,2- dichloroethanes dissolutions in -10 DEG C of 0.5~1h of reaction.TLC is monitored after complete reaction
It is added n-butanal (0.250mmol), ferric trichloride (0.025mmol), the reaction was continued 8h, TLC detection is evaporated off after complete reaction
Solvent, column chromatograph to obtain product.
Embodiment 44 is added 1,3- dithiane (0.250mmol), N- chlorosuccinimide in 10 milliliters of round-bottomed flasks
(0.300mmol) is added after 2 milliliters of 1,2- dichloroethanes dissolutions in -10 DEG C of 0.5~1h of reaction.TLC is monitored after complete reaction
It is added crotonaldehyde (0.250mmol), ferric trichloride (0.025mmol), the reaction was continued 8h, TLC detection is evaporated off after complete reaction
Solvent, column chromatograph to obtain product.
Embodiment 2,4-39, other than the aldehyde used is different, other reaction conditions are all the same by 41-43,45-48, specifically:
In 10 milliliters of round-bottomed flasks, it is added 1,3- dithiane (0.250mmol), N- chlorosuccinimide
(0.300mmol) is added after 2 milliliters of 1,2- dichloroethanes dissolutions in -10 DEG C of 0.5~1h of reaction.TLC is monitored after complete reaction
It is added aldehyde compound (0.200mmol), ferric trichloride and/or boron trifluoride ether (0.025mmol), the reaction was continued 0.5~
Solvent is evaporated off in 18h, TLC detection after complete reaction, and column chromatographs to obtain product.
Product, yield and the reaction temperature of aldehyde used in all embodiments, ketone and the chloro- 1,3- dithiane of 2- such as following table institute
Show:
The reaction product of table 1:1,3- dithiane and aldehydes
Table 1:1,3- dithiane is reacted with ketone
All obtained products of embodiment are all proven by nuclear magnetic resonance map, specific as follows:
1 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.41-7.26(m,5H),5.12(s,1H),3.06-
2.75(m,4H),2.07-1.78(m,2H).13C NMR(75MHz,CDCl3)δ139.0,128.6,128.3,127.7,127.1,
51.6,50.8,50.2,32.1,32.0,23.94.
2 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.53-6.96(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).13C NMR(75MHz,CDCl3)δ137.82,
135.91,129.02,127.25,50.81,31.76,24.77,20.91.
3 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.42-7.39(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).13C NMR(75MHz,CDCl3)δ
159.4,131.2,128.7,114.1,55.3,50.7,32.3,24.9.
4 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.76-7.34(m,4H),5.13(s,1H),3.09-
2.87(m,4H),2.18-1.88(m,2H).13C NMR(75MHz,CDCl3)δ138.0,131.9,129.4,122.11,50.0,
31.8,24.8.
5 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.61-7.59(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).13C NMR(75MHz,CDCl3)δ
137.0,134.8,130.3,127.9,126.3,48.17,32.4,25.0,18.9.
6 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.76-7.16(m,4H),5.56(s,1H),3.20-
2.93(m,4H),2.23-1.94(m,2H).13C NMR(75MHz,CDCl3)δ138.0,132.6,129.8,127.9,122.7,
50.4,30.0,24.8.
7 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.54-6.78(m,4H),5.65(s,1H),3.78
(s,3H),3.06-2.77(m,4H),2.09-1.82(m,2H).13C NMR(75MHz,CDCl3)δ155.2,129.3,120.7,
110.5,55.5,43.4,43.3,32.1,25.1.
8 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.52-7.15(m,3H),5.47(s,1H),3.03-
2.77(m,4H),2.07-1.78(m,2H).13C NMR(75MHz,CDCl3)δ135.1,134.7,131.6,129.9,131.6,
128.1,46.6,36.8,28.4,21.4.
9 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.63-6.96(m,4H),5.06(s,1H),2.90
(m, J=15.9,14.5,1.2Hz, 4H), 2.14-1.65 (m, 2H)13C NMR(75MHz,CDCl3)δ137.48,133.87,
129.01,128.70,50.33,31.8,24.7.
10 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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)13C NMR(75MHz,
CDCl3)δ155.5,131.3,129.1,115.5,50.7,32.1,25.0.
11 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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)13C NMR(75MHz,
CDCl3)δ156.7,141.1,129.9,119.9,114.5,50.4,31.1,25.1.
12 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.48-6.94(m,4H),5.08(s,1H),3.01-
2.54(m,5H),2.07-1.63(m,2H),1.29-0.96(m,6H).13C NMR(75MHz,CDCl3)δ148.50,136.14,
127.21,126.29,50.72,33.37,31.66,24.68,23.52.
13 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ7.00(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).13C NMR(75MHz,CDCl3)δ161.0,140.0,
106.7,99.4,56.6,51.9,31.7,24.8.
14 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.56-6.94(m,4H),5,47(s,1H),3.08-
2.76(m,4H),2,24-1.82(m,2H).13C NMR(75MHz,CDCl3)δ129.8,129.5,124.5,115.5,42.9,
32.1,25.0.
15 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.72-7.09(m,4H),5.26(s,1H),2.97-
2.78(m,4H),2.23-1.74(m,2H).13C NMR(75MHz,CDCl3)δ139.7,132.0,129.9,126.9,123.7,
51.4,32.3,25.1.
16 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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).13C NMR(75MHz,CDCl3)δ138.9,138.4,
135.2,129.9,129.2,128.5,124.74,51.5,32.1,30.9,28.8,27.2,25.1,21.3.
17 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.77-7.25(m,9H),5.11(s,1H),2.87-
2.65(m,4H),1.91-1.65(m,2H).13C NMR(75MHz,CDCl3)δ136.3,133.1,133.0,128.3,127.8,
127.4,126.6,126.1,125.5,51.3,31.4,24.8.
18 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ6.76(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).13C NMR(75MHz,CDCl3)δ
153.5 149.2,127.8,114.3,114.2,111.7,56.1,43.4,31.9,24.9.
19 product nuclear-magnetism of embodiment, 1H NMR (300MHz, CDCl3)δ8.22-7.39(m,4H),6.28-5.71(m,
1H), 3.46-2.78 (m, 4H), 2.09 (d, J=26.0, t, 13.9Hz, 2H) .13C NMR (75MHz, CDCl3)δ147.4,
133.2,130.4,128.8,124.4,45.65,31.9,24.7.
20 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ8.88-7.50(m,4H),5.37(s,1H),3.66-
2.68(m,4H),2.20(m,2H).13C NMR(75MHz,CDCl3)δ147.5,146.1,128.8,128.2,127.3,
123.1,50.6,49.7,48.8,34.8,26.4.
21 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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)13C
NMR(75MHz,CDCl3)δ143.8,132.1,128.2,118.1,111.6,49.7,31.3,24.4.
22 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.45-7.50(m,2H),6.94-7.00(m,2H),
5.60(s,1H),3.19-2.95(m,4H),2.09-1.96(m,2H).13C NMR(75MHz,CDCl3)δ163.8,160.5,
135.8,129.5,129.4,115.3,115.0,49.8,32.0,24.5.
23 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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).13C NMR(75MHz,CDCl3)δ
144.4,137.3,127.6,55.1,32.2,24.6.
24 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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).13C NMR(75MHz,CDCl3)δ
144.9,128.3,125.4,55.3,32.0,24.5.
25 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.53(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).13C NMR(75MHz,
CDCl3)δ160.2,138.1,129.2,123.1,121.3,114.3,55.3,50.7,32.3,24.9.
26 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ7.52-7.26(m,3H),7.01-6.93(m,1H),
5.15(s,1H),2.96-2.67(m,4H),2.08-1.82(m,2H).13C NMR(75MHz,CDCl3)δ162.6,139.6,
130.4,125.4,116.1,50.2,32.1,24.9.
27 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ7.54-7.17(m,4H),5.14(s,1H),2.98-
2.66(m,4H),2.13-1.78(m,2H).13C NMR(75MHz,CDCl3)δ162.8,139.4,130.6,124.4,115.1,
50.6,32.2,25.2.
28 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ7.73(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).13C NMR(75MHz,CDCl3)δ
163.6,139.2,131.0,124.3,115.9,50.3,32.6,24.8.
29 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ8.60(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).13C NMR(75MHz,CDCl3)δ
149.4,138.6,133.5,122.6,50.4,32.4,24.8.
30 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ8.12(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).13C NMR(75MHz,CDCl3)δ149.2,
133.6,132.2,131.7,119.4,112.4,50.3,32.6,24.4.
31 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ8.07(d,1H),7.55-7.39(m,3H),5.13
(s,1H),2.92-2.64(m,4H),2.06-1.80(m,2H).13C NMR(75MHz,CDCl3)δ138.3,131.9,131.1,
130.2,125.4,124.3,123.6,53.2,33.1,25.4.
32 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.71-7.09(m,4H),5.42(s,1H),3.09-
2.88(m,4H),2.04-1.79(m,2H).13C NMR(75MHz,CDCl3)δ136.0,133.6,129.8,128.5,127.0,
47.2,32.0,24.9.
33 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.75-6.98(m,4H),5.34(s,1H),3.10-
2.83(m,4H),2.04-1.79(m,2H).13C NMR(75MHz,CDCl3)δ142.0,138.4,129.2,128.5,127.8,
97.7,56.4,32.0,24.9.
34 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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).13C NMR(75MHz,CDCl3)δ155.0,130.4,129.6,124.2,121.6,117.4,47.5,32.0,
24.6.
35 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.79-7.02(m,4H),5.42(s,1H),3.08-
2.80(m,4H),2.01-1.73(m,2H).13C NMR(75MHz,CDCl3)δ145.0,134.4,129.5,124.5,126.8,
99.7,56.6,32.4,24.8.
36 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.48-6.82(m,4H),4.97(s,1H),3.00-
2.72(m,4H),1.93-1.67(m,2H).13C NMR(75MHz,CDCl3)δ145.8,134.4,129.8,128.8,124.6,
120.6,109.7,53.6,31.4,24.5.
37 product nuclear-magnetism of embodiment, NMR (300MHz, CDCl3)δ5.21(t,1H),3.13-3.04(m,4H),2.21-
2.04(m,2H).13C NMR(75MHz,CDCl3)δ176.2,38.9,25.4,24.5.
38 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ3.92(t,1H),2.86(m,4H),2.08(m,
2H),1.83(m,2H),1.04(t,3H).13C NMR(75MHz,CDCl3)δ49.2,30.6,28.9,26.1,11.6.
39 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3) 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).13C NMR(75MHz,CDCl3)δ61.9,35.8,
31.3,27.9,25.9
40 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ4.04(t,1H),2.88(m,4H),2.04(m,
2H),1.83(m,2H),1.50(m,2H),1.04(t,3H).13C NMR(75MHz,CDCl3)δ47.4,37.8,30.6,26.5,
19.0,13.3.
41 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ3.84(t,1H),2.92(m,4H),1.92(m,
3H),1.67(m,4H),1.50(m,4H),1.24(t,2H).13C NMR(75MHz,CDCl3)δ52.3,41.4,31.0,29.4,
26.5,26.0,25.3.
42 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ4.47(m,2H),2.86(m,8H),2.14-1.76
(m,4H),1.22(m,6H).13C NMR(75MHz,CDCl3)δ59.1,43.1,31.4,26.2,22.5.
43 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ7.41-7.39(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).13C NMR(75MHz,CDCl3)δ
136.1,133.4,128.6,128.1,126.6,126.0,47.7,30.2,25.2
44 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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).13C NMR(75MHz,CDCl3)δ54.57,
45.31,44.08,29.94,29.49,25.75,25.19.
45 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ4.04(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).13C NMR(75MHz,CDCl3)δ47.4,35.3,30.5,28.2,26.0,22.3.13.9.
46 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ4.00(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).13C NMR(75MHz,CDCl3)δ44.4,
35.8,32.0,30.7,26.7,26.0,22.6.13.9.
47 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ4.02(t,1H),2.87(m,4H),2.14(m,
2H),1.85(m,2H),1.54-1.32(m,8H),0.91(t,3H).13C NMR(75MHz,CDCl3)δ44.5,35.7,32.1,
30.8,28.0,26.7,26.0,22.6,13.9.
48 product nuclear-magnetism of embodiment1H NMR(300MHz,CDCl3)δ4.01(t,1H),2.86(m,4H),2.13(m,2H),
1.84(m,2H),1.56-1.31(m,10H),0.90(t,3H).13C NMR(75MHz,CDCl3)δ44.6,35.7,32.2,
30.7,28.1,27.6,26.6,26.1,22.5,13.9.
49 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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)13C NMR(75MHz,
CDCl3)δ195.31,136.37,133.32,128.54,43.73,41.71,30.14,25.14.
50 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ8.09-7.20(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)13C NMR
(75MHz,CDCl3)δ194.92,144.19,133.94,129.21,43.55,42.06,30.15,25.27,21.54.
51 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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)13C
NMR(75MHz,CDCl3)δ194.09,139.68,134.58,129.75,129.40,128.98,128.78,127.81,
43.60,41.75,30.05,25.02.
52 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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)13C
NMR(75MHz,CDCl3)δ194.26,134.94,132.06,131.61,129.66,129.28,128.46,43.56,
41.43,30.02,24.99.
58 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3)δ8.05-7.09(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)13C NMR(75MHz,CDCl3)δ194.69,143.61,133.25,131.77,128.38,
127.47,126.42,52.34,47.96,47.88,31.07,30.53,28.43,25.34,25.06.
64 product nuclear-magnetism of embodiment,1H NMR(300MHz,CDCl3) 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=7.1 Hz, 2H), 1.92 (d, J=56.3 Hz,
2H), 0.98 (t, J=7.2 Hz, 3H)13C NMR(75 MHz,CDCl3)δ207.37,134.40,128.50,128.44,
127.90,61.65,47.53,36.53,29.68,29.45,25.24,7.44,7.21.
Claims (7)
1. a kind of 2- replaces the preparation method of -1,3- dithiane derivatives, mainly comprise the steps that
A) by 1,3- dithiane and 1,2- dichloroethanes (DCE) is added in reaction flask, and N-chlorosuccinimide is added under ice bath
(NCS), 2- chlorine 1,3- dithiane solution is made after stirring 0.5~1h；Aldehyde compound and Louis are added in the above system
Acid catalyst, stirring are prepared corresponding 2- and replace -1,3- dithiane compound after reaction:
Wherein, the aldehyde compound is the aromatic aldehyde of different substituents and the fatty aldehyde of different carbon chain, on the aromatic rings
Substituent group is respectively methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, acetyl group, phenyl, hydrogen, cyano, one of nitro or more
Kind, the fatty aldehyde is the saturated aldehyde of different carbon chain, unsaturated aldehyde；
B) 1,3- dithiane and DCE are added in reaction flask, NCS is added, 2- chlorine 1,3- dithiane solution is made；In above-mentioned system
Middle addition ketone compounds and lewis acid catalyst, stirring are prepared corresponding 2- and -1,3- dithiane are replaced to spread out after reaction
Biology:
Wherein, R1, R2Respectively substituted-phenyl, substituted benzyl, substituted naphthyl, one of fatty alkyl or a variety of, the substitution
Phenyl, substituted benzyl, the substituent group on substituted naphthyl, respectively methoxyl group, methyl, ethyl, fluorine, chlorine, bromine, iodine, acetyl group, benzene
Base, hydrogen, cyano, one of nitro or a variety of；The fat alkanone is the saturated ketone of different carbon chain, beta-unsaturated ketone.
2. 2- according to claim 1 replaces -1,3- dithiane derivatives preparation method, it is characterised in that: lewis acid
Catalyst is boron trifluoride ether, ferric trichloride, alchlor, ferrous chloride, one of nickel chloride.
3. 2- according to claim 1 replaces -1,3- dithiane derivatives preparation method, it is characterised in that: the step
A) reagent molar ratio used in is 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 characterised in that: the step
B) reagent molar ratio used in is 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 characterised in that: the step
A) reaction temperature of aldehyde and the chloro- 1,3- dithiane of 2- is 0~100 DEG C in.
6. 2- according to claim 1 replaces -1,3- dithiane derivatives preparation method, it is characterised in that: the step
B) reaction temperature of ketone and the chloro- 1,3- dithiane of 2- is 0~100 DEG C in.
7. 2- replaces -1,3- dithiane derivatives preparation method according to claim 1, it is characterised in that: the step a)
It is 0.5 hour to 18 hours with the reaction time in step b).
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Citations (5)
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|---|---|---|---|---|
| US3965157A (en) * | 1973-12-17 | 1976-06-22 | Lilly Industries, Ltd. | Preparation of α-acetoxy aldehydes and ketones |
| US4089876A (en) * | 1976-07-23 | 1978-05-16 | Ortho Pharmaceutical Corporation | Method for reacting 2-aromatic substituted 1,3-dithianes with α,.beta. |
| JPS63297376A (en) * | 1987-05-28 | 1988-12-05 | Nitto Kasei Kk | Production of 1,3-dithiane derivative |
| CN1068569A (en) * | 1991-07-18 | 1993-02-03 | 弗·哈夫曼-拉罗切有限公司 | Dithiane |
| DE10150063C2 (en) * | 2001-10-10 | 2003-08-14 | Degussa | Process for the multi-stage production of alpha-lipoic acid, new 1,3-dithiane and their use |
-
2014
- 2014-05-16 CN CN201410206794.7A patent/CN105085471B/en not_active Expired - Fee Related
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|---|---|---|---|---|
| US3965157A (en) * | 1973-12-17 | 1976-06-22 | Lilly Industries, Ltd. | Preparation of α-acetoxy aldehydes and ketones |
| US4089876A (en) * | 1976-07-23 | 1978-05-16 | Ortho Pharmaceutical Corporation | Method for reacting 2-aromatic substituted 1,3-dithianes with α,.beta. |
| JPS63297376A (en) * | 1987-05-28 | 1988-12-05 | Nitto Kasei Kk | Production of 1,3-dithiane derivative |
| CN1068569A (en) * | 1991-07-18 | 1993-02-03 | 弗·哈夫曼-拉罗切有限公司 | Dithiane |
| DE10150063C2 (en) * | 2001-10-10 | 2003-08-14 | Degussa | Process for the multi-stage production of alpha-lipoic acid, new 1,3-dithiane and their use |
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| 羰基极性转换中间体— 1 , 3-二噻烷在有机合成中的应用;胡艾希，曾昭琼;《化学试剂》;19871231;第11卷(第6期);351-357 |
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