CN110437114A - A method of synthesizing asymmetric cyanoalkyl disulfide - Google Patents
A method of synthesizing asymmetric cyanoalkyl disulfide Download PDFInfo
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- CN110437114A CN110437114A CN201910723485.XA CN201910723485A CN110437114A CN 110437114 A CN110437114 A CN 110437114A CN 201910723485 A CN201910723485 A CN 201910723485A CN 110437114 A CN110437114 A CN 110437114A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/22—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of hydropolysulfides or polysulfides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
The present invention relates to a kind of methods for synthesizing asymmetric cyanoalkyl disulfide, do sulphur source with thiocarbamide and alkyl Bunte salt, alkyl halide is as raw material, neopelex is as auxiliary reagent, sodium carbonate is reacted in water as alkali, obtains asymmetric cyanoalkyl disulfide compound.Present method avoids using the mercaptan with penetrating odor to be sulphur source, achieve the purpose that environmentally protective, simultaneous reactions are easy to operate, and reaction condition is mild, are suitble to large-scale production.
Description
Technical field
The present invention relates to a kind of synthetic methods of asymmetric cyanoalkyl disulfide.
Background technique
In in the past few decades, sulfur chemistry obtains sizable concern.Sulfur-containing compound is widely used in pharmacy, agricultural
And the every field such as chemistry.In addition, organosulfur compound also has significant impact in Material Field, for example, sulphur atom pair
The physically and electrically sublist face of some materials suffers from very strong active force.Have in natural products, especially marine natural products
The presence of sulfur-containing compound.The metabolite of marine organisms has very big science researching value, can be with by the research to them
Filter out effective molecule of pharmaceutical.For example, a kind of thio diketopiperazine compound of natural products for having unique texture
(Epidithiodiketopiperazine, ETP) shows the advantageous activity of poliomyelitis virus.Therefore building is not right
The method of disulfide bond is claimed to have very big reference value for synthesizing biologically active sulphur compound.
The synthetic method of symmetrical disulfide has much at present, but these methods are not particularly suited for the conjunction of unsymmetrical disulfide
At.Unsymmetrical disulfide can substantially be prepared by three kinds of modes: (1) two kinds of different mercaptan are in oxidant such as I2、H2O2、DDQ、
Coupling reaction occurs in the presence of DMSO, DEAD etc. to obtain；(2) mercaptan or thiol derivative and sulfinyl derivative or other
Compound with easy leaving group passes through SN2 reactions obtain；Such as 5, the 5- dimethyl -2- thio -1,3,2- of the researchs such as Wit
Dialkyl disulfides ether, diaryldisulfide, virtue can be obtained in dioxaphosphorinane -2- disulfonyl radical derivative and corresponding thiol reaction
Base-alkyl disulfide and asymmetric L-cysteine and l-cysteine disulfide, yield are generally all very high.Hunter etc. is used
Benzotriazole obtains ideal result as leaving group one pot process unsymmetrical disulfide.1- chlorine is used in experiment
For benzotriazole as oxidising agent, the reagent is economical and practical and environmentally friendly, can convert mercaptan effectively as corresponding N-
Sulfinyl derivative, then the derivative and another thiol reaction obtain unsymmetrical disulfide.(3) different thioethers are in transition
Exchange reaction occurs under metal catalytic to obtain.
However, still there are some defects and deficiencies for these methods:
(1) it is related to highly toxic reagent, such as Br in reaction2, SOCl2, S2Cl2And SO2Cl2Or some harshnesses
PH condition.
(2) reaction uses mercaptan as sulphur source mostly, and mercaptan is that a kind of environment is unfriendly and have larger penetrating odor
Reagent, certain genotoxic potential can be caused to the body of people, is not easy to large-scale production.
(3) organic solvent more or less has certain toxicity, and expensive, and certain pollution is caused to environment.
Thiocarbamide and sodium thiosulfate are a kind of basic chemical raw materials, cheap to be easily obtained, and are a kind of ideal sulphur
Alcohol replacement reagent.Recently, Firouzabadi etc. has studied the reaction that thiocarbamide synthesizes symmetrical disulfide, but unsymmetrical disulfide
There is no further explore for reaction.Jiang Xuefeng seminar has also carried out corresponding research to asymmetric aryl alkyl disulfide, adopts
It uses sodium thiosulfate as sulphur source, target product is obtained by redox method, but this method is only applicable to aryl class
The synthesis of thioether, and the solvent used is that dioxanes has certain toxicity.Although there are many method of current sulfide synthesis,
Develop it is a kind of more effective, to more environment-friendly C-S construction method or essential.
Summary of the invention
For the defect more than solving, the present invention is using thiocarbamide and alkyl Bunte salt as sulphur source, alkyl halide conduct
Raw material, water explore the method for efficient, green an asymmetric cyanoalkyl disulfide of synthesis as reaction dissolvent.
The method reaction equation that the present invention synthesizes asymmetric cyanoalkyl disulfide is as follows:
Wherein: X is I or Br；R1It is normal-butyl or n-hexyl；R2It is n-hexyl, n-heptyl, isopentyl, normal-butyl, positive penta
Base, isobutyl group, cyclohexyl or cyclopenta；
Steps are as follows for asymmetric two sulphur synthetic method of cyanoalkyl:
Alkyl Bunte salt, thiocarbamide, sodium carbonate, neopelex SDBS, alkyl halide are sequentially added in reaction flask
Hydrocarbon and water are reacted, wherein alkyl Bunte salt, thiocarbamide, sodium carbonate, neopelex and halogenated alkane mole
Than being 1~1.25: 1.2~1.5: 1.2~1.5: 0.032~0.375: 1；Then anti-in 50~100 DEG C of heating under nitrogen protection
It answers, heating time is 3~7 hours；After solution is cooled to room temperature, 5mL water is added, gained mixture is extracted with ethyl acetate 3
It is secondary, 15mL/ times, merge organic phase, 2~5g anhydrous magnesium sulfate is dry, filter paper filtering, 80~100mmHg vacuum decompression, heating 40
~50 DEG C are concentrated to get crude product；Gained crude product is purified through 200~300 mesh silica gel column chromatographies, with 200~500mL petroleum ether/acetic acid
Ethyl ester quality proportioning is 20: 1 as eluent, obtains asymmetric cyanoalkyl disulfide.
Beneficial effects of the present invention:
(1) in asymmetric cyanoalkyl disulfide synthesis process, sulfiding reagent is alkyl Bunte salt and thiocarbamide, price
It is cheap, it is easily obtained, avoids using the mercaptan with genotoxic potential and penetrating odor, be suitble to large-scale industrial production；
(2) reaction does not need strong acid perhaps basic conditions does not need additional reducing agent or oxidant yet, is not necessarily to transition
Metal catalytic, economical and practical, reaction condition is relatively mild；
(3) solvent system of the selection based on water is avoided and is more toxic and expensive using some, to environment meeting
The organic solvent centainly polluted is caused, it is environmentally friendly, meet green chemical concept, and post-process simple, experimental implementation simplicity.
Detailed description of the invention
Fig. 1 4- (hexyl disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (hexyl disulfide group) butyronitrile1H NMR (300MHz, CD3OD) figure, b are 4- (hexyl disulfide group) fourth
Nitrile13C NMR (75MHz, CD3OD) figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 2 4- (heptyl disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (heptyl disulfide group) butyronitrile1H NMR figure, b are 4- (heptyl disulfide group) butyronitrile13C NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 3 4- (isopentyl disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (isopentyl disulfide group) butyronitrile1H NMR figure, b are 4- (isopentyl disulfide group) butyronitrile13C
NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 4 4- (butyl disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (butyl disulfide group) butyronitrile1H NMR figure, b are 4- (butyl disulfide group) butyronitrile13C NMR figure.
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 5 4- (diamyl disulfide base) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (diamyl disulfide base) butyronitrile1HNMR figure-, b are 4- (diamyl disulfide base) butyronitrile13CNMR figure.
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 6 4- (isobutyl group disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (isobutyl group disulfide group) butyronitrile1H NMR figure, b are 4- (isobutyl group disulfide group) butyronitrile13C
NMR figure.
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 7 4- (sec-butyl disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (sec-butyl disulfide group) butyronitrile1H NMR figure, b are 4- (sec-butyl disulfide group) butyronitrile13C
NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 8 4- (cyclohexyl disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (cyclohexyl disulfide group) butyronitrile1H NMR figure, b are 4- (cyclohexyl disulfide group) butyronitrile13C
NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Fig. 9 4- (cyclopenta disulfide group) butyronitrile1H NMR、13C NMR figure
In figure: a is 4- (cyclopenta disulfide group) butyronitrile1H NMR figure, b are 4- (cyclopenta disulfide group) butyronitrile13C
NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Figure 10 4- (isopentyl disulfide group) own nitrile1H NMR、13C NMR figure
In figure: a is 4- (isopentyl disulfide group) own nitrile1H NMR figure, b are 4- (isopentyl disulfide group) own nitrile13C
NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Figure 11 4- (diamyl disulfide base) own nitrile1H NMR、13C NMR figure
In figure: a is 4- (diamyl disulfide base) own nitrile1H NMR figure, b are 4- (diamyl disulfide base) own nitrile13C NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Figure 12 4- (hexyl disulfide group) own nitrile1H NMR、13C NMR figure
In figure: a is 4- (hexyl disulfide group) own nitrile1H NMR figure, b are 4- (hexyl disulfide group) own nitrile13C NMR figure；
Ordinate is that ordinate is peak intensity, unit ppm；Abscissa is chemical shift, unit ppm.
Specific embodiment
Embodiment 1
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 83%；1H NMR (300MHz, CD3OD) δ 2.75 (t, J=7.1Hz, 2H),
2.68 (t, J=7.4Hz, 2H), 2.55 (t, J=7.2Hz, 2H), 2.07-1.95 (m, 2H), 1.72-1.60 (m, 2H), 1.44-
1.24 (m, 6H), 0.92-0.84 (m, 3H)13C NMR (75MHz, CD3OD) 120.8 δ, 39.8,37.7,32.9,30.5,
29.5,26.2,23.9,16.3,14.7..
Embodiment 2
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 1- iodohexane (169mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 89%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 3
The preparation of 4- (heptyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 1- heptyl bromide (142mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (heptyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 76%；1H NMR (300MHz, CD3OD) δ 2.76 (t, J=7.0Hz, 2H),
2.69 (t, J=7.3Hz, 2H), 2.55 (t, J=7.1Hz, 2H), 2.07-1.95 (m, 2H), 1.73-1.59 (m, 2H), 1.44-
1.22 (m, 8H), 0.94-0.83 (m, 3H)13C NMR (75MHz, CD3OD) 120.5 δ, 39.5,37.4,32.9,30.2,
30.0,29.5,25.9,23.7,16.1,14.4.
Embodiment 4
The preparation of 4- (isopentyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), the bromo- 3- methybutane of 1- (120mg, 0.8mmol,
1equiv.) with water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL is added
Water, mixture are extracted with ethyl acetate (15mL × 3), merge organic phase, and 4g anhydrous magnesium sulfate is dry, and filter paper filtering, vacuum subtracts
It presses (vacuum degree 95mmHg, 48 DEG C of heating temperature) to remove solvent, 4- (isopentyl disulfide group) fourth is obtained after column chromatography for separation
Nitrile (eluant, eluent polarity: petrol ether/ethyl acetate 20: 1).Yield: 87%；1H NMR (300MHz, CDCl3) δ 2.77 (t, J=
6.9Hz, 2H), 2.69 (t, J=7.8Hz, 2H), 2.51 (t, J=7.3Hz, 2H), 2.13-2.02 (m, 2H), 1.72-1.62
(m, 1H), 1.55 (q, J=7.3Hz, 2H), 0.91 (d, J=6.1Hz, 6H)13C NMR (75MHz, CDCl3) δ 118.6,
37.9,36.6,36.1,26.9,24.2,22.0,15.4.
Embodiment 5
The preparation of 4- (butyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 1- bromobutane (108mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (butyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 75%；1H NMR (300MHz, CDCl3) δ 2.76 (t, J=5.9Hz, 2H),
2.51 (t, J=7.0Hz, 2H), 2.13-2.02 (m, 2H), 1.76-1.65 (m, 1H), 1.58-1.47 (m, 1H), 1.34-1.23
(m, 4H), 0.98 (t, J=7.4Hz, 3H)13C NMR (75MHz, CDCl3) δ 119.2,48.1,37.3,29.0,24.7,
20.3,15.9,11.7.
Embodiment 6
The preparation of 4- (diamyl disulfide base) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 1- bromo pentane silane (120mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (diamyl disulfide base) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 73%；1H NMR (300MHz, CDCl3) δ 2.77 (t, J=6.8Hz, 2H),
2.68 (t, J=7.4Hz, 2H), 2.51 (t, J=7.0Hz, 2H), 2.14-2.02 (m, 2H), 1.73-1.58 (m, 2H), 1.42-
1.28 (m, 4H), 0.94-0.86 (m, 3H)13C NMR (75MHz, CDCl3) δ 119.2,39.0,36.7,30.8,29.0,
24.7,22.4,15.9,14.1.
Embodiment 7
The preparation of 4- (isobutyl group disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), the bromo- 2- methylpropane of 1- (120mg, 0.8mmol,
1equiv.) with water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL is added
Water, mixture are extracted with ethyl acetate (15mL × 3), merge organic phase, and 4g anhydrous magnesium sulfate is dry, and filter paper filtering, vacuum subtracts
It presses (vacuum degree 95mmHg, 48 DEG C of heating temperature) to remove solvent, 4- (isobutyl group disulfide group) fourth is obtained after column chromatography for separation
Nitrile (eluant, eluent polarity: petrol ether/ethyl acetate 20: 1).Yield: 11%；1H NMR (300MHz, CDCl3) δ 2.77 (t, J=
6.5Hz, 2H), 2.60 (d, J=5.9Hz, 2H), 2.52 (t, J=6.8Hz, 2H), 2.14-2.03 (m, 2H), 1.99-1.87
(m, 1H), 1.00 (d, J=6.1Hz, 6H)13C NMR (75MHz, CDCl3) δ 119.2,48.6,36.4,28.4,24.7,
21.9 15.9.
Embodiment 8
The preparation of 4- (sec-butyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 2- bromobutane (108mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (sec-butyl disulfide group) butyronitrile (eluant, eluent is obtained after column chromatography for separation
Polarity: petrol ether/ethyl acetate 20: 1).Yield: 20%；1H NMR (300MHz, CDCl3) δ 2.81-2.70 (m, 3H), 2.51
(t, J=7.1Hz, 2H), 2.14-2.01 (m, 2H), 1.77-1.65 (m, 1H), 1.61-1.47 (m, 1H), 1.31 (d, J=
6.7Hz, 3H), 0.98 (t, J=8.3Hz, 3H)13C NMR (75MHz, CDCl3) δ 119.2,48.1,37.3,29.0,24.7,
20.3,15.9,11.7.
Embodiment 9
The preparation of 4- (cyclohexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), bromine hexamethylene (130mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (cyclohexyl disulfide group) butyronitrile (eluant, eluent is obtained after column chromatography for separation
Polarity: petrol ether/ethyl acetate 20: 1).Yield: 12%；1H NMR (300MHz, CDCl3) δ 2.76 (t, J=6.9Hz, 2H),
2.51 (t, J=6.9Hz, 2H), 2.13-1.97 (m, 3H), 1.84-1.57 (m, 4H), 1.45-1.22 (m, 5H), 0.96 (t, J
=7.2Hz, 1H)13C NMR (75MHz, CDCl3) δ 119.2,49.6,37.6,33.0,26.2,25.7,24.7,15.9.
Embodiment 10
The preparation of 4- (cyclopenta disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), bromine pentamethylene (130mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (cyclopenta disulfide group) butyronitrile (eluant, eluent is obtained after column chromatography for separation
Polarity: petrol ether/ethyl acetate 20: 1).Yield: 41%；1H NMR (300MHz, CDCl3) δ 3.32-3.22 (m, 1H), 2.79
(t, J=6.9Hz, 2H), 2.51 (t, J=7.1Hz, 2H), 2.14-2.03 (m, 2H), 2.03-1.90 (m, 2H), 1.79-1.53
(m, 6H)13C NMR (75MHz, CDCl3) δ 119.2,50.2,36.9,33.2,24.8,15.9.
Embodiment 11
The preparation of 4- (isopentyl disulfide group) own nitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyano hexyl sodium thiosulfate (231mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), the bromo- 3- methybutane of 1- (118mg, 0.8mmol,
1equiv.) and water, 80 DEG C of thermotonuses stir 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water is added, and mix
It closes object to be extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, and vacuum decompression is (true
Reciprocal of duty cycle is 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (isopentyl disulfide group) own nitrile is obtained after column chromatography for separation (to be washed
De- agent polarity: petrol ether/ethyl acetate 20: 1).Yield: 92%；1H NMR (300MHz, CDCl3) δ 2.73-2.63 (m, 4H),
2.36 (t, J=7.1Hz, 2H), 1.79-1.63 (m, 5H), 1.61-1.49 (m, 4H), 0.90 (d, J=6.6Hz, 6H)13C
NMR (75MHz, CDCl3) δ 119.3,38.0,38.0,36.9,36.8,28.0,27.2,26.9,26.9,24.8,24.7,
22.0 16.8.
Embodiment 12
The preparation of 4- (diamyl disulfide base) own nitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyano hexyl sodium thiosulfate (231mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 1- bromo pentane silane (120mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, own nitrile (the eluant, eluent pole 4- (diamyl disulfide base) is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 90%；1H NMR (300MHz, CDCl3) δ 2.67 (t, J=7.4Hz, 4H),
2.36 (t, J=7.1Hz, 2H), 1.80-1.62 (m, 6H), 1.61-1.50 (m, 2H), 1.41-1.24 (m, 4H), 0.94-0.84
(m, 3H)13C NMR (75MHz, CDCl3) δ 119.7,39.3,39.2,38.4,38.4,30.8,29.0,28.4,27.6,
25.2,25.2,22.4,17.2,14.1.
Embodiment 13
The preparation of 4- (hexyl disulfide group) own nitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyano hexyl sodium thiosulfate (231mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 100 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixing is added
Object is extracted with ethyl acetate (15mL × 3), merges organic phase, and 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum
Degree is 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) own nitrile (eluant, eluent is obtained after column chromatography for separation
Polarity: petrol ether/ethyl acetate 20: 1).Yield: 55%；1H NMR (300MHz, CDCl3) δ 2.67 (t, J=7.4Hz, 4H),
2.36 (t, J=7.1Hz, 2H), 1.78-1.63 (m, 6H), 1.61-1.52 (m, 2H), 1.44-1.23 (m, 6H), 0.92-0.84
(m, 3H)13C NMR (75MHz, CDCl3) δ 119.7,39.3,39.2,38.4,38.4,31.5,29.3,28.4,28.3,
27.6,25.2,25.2,22.7,17.2,14.2.
Embodiment 14
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), 1- bromo-n-hexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 3 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 73%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 15
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 50 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 64%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 16
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.50equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 70%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 17
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.50equiv.),
Neopelex (34.8mg, 0.1mmol, 0.125equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 78%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 18
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (203mg, 1mmol,
1.25equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.),
Neopelex (34.8mg, 0.1mmol, 0.375equiv.), l- bromohexane (132mg, 0.8mmol, 1equiv.)
With water (1mL), 80 DEG C of thermotonuses are stirred 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water, mixture is added
It is extracted with ethyl acetate (15mL × 3), merges organic phase, 4g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 72%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 19
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (162mg, 0.8mmol,
1equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.), ten
Dialkyl benzene sulfonic acids sodium (34.8mg, 0.1mmol, 0.125equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.) and
Water (1mL), 80 DEG C of thermotonuses stir 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water is added, and mixture is used
Ethyl acetate (15mL × 3) extracts, and merges organic phase, and 4g anhydrous magnesium sulfate is dry, filter paper filtering, and (vacuum degree is vacuum decompression
95mmHg, 48 DEG C of heating temperature) remove solvent, obtained after column chromatography for separation 4- (hexyl disulfide group) butyronitrile (eluant, eluent polarity:
Petrol ether/ethyl acetate 20: 1).Yield: 35%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
Embodiment 20
The preparation of 4- (hexyl disulfide group) butyronitrile
Equipped with magneton 10mL reaction flask in, sequentially add 4- cyanobutyl sodium thiosulfate (162mg, 0.8mmol,
1equiv.), thiocarbamide (73mg, 0.96mmol, 1.20equiv.), sodium carbonate (102mg, 0.96mmol, 1.20equiv.), ten
Dialkyl benzene sulfonic acids sodium (34.8mg, 0.1mmol, 0.032equiv.), hexyl bromide 1 bromohexane (132mg, 0.8mmol, 1equiv.) and
Water (1mL), 80 DEG C of thermotonuses stir 7 hours under nitrogen protection.The reaction is cooled to room temperatures, and 5mL water is added, and mixture is used
Ethyl acetate (15mL × 3) extracts, and merges organic phase, and 2~5g anhydrous magnesium sulfate is dry, filter paper filtering, vacuum decompression (vacuum degree
For 95mmHg, 48 DEG C of heating temperature) solvent is removed, 4- (hexyl disulfide group) butyronitrile (eluant, eluent pole is obtained after column chromatography for separation
Property: petrol ether/ethyl acetate 20: 1).Yield: 80%；1H NMR、13C NMR analysis data are same as
Embodiment 1.
The new asymmetric cyanoalkyl disulfide compound of the invention of table 1
Claims (1)
1. a kind of method for synthesizing asymmetric cyanoalkyl disulfide, it is characterised in that it is anti-to synthesize asymmetric cyanoalkyl disulfide
Answer formula as follows:
Wherein: X is I or Br；R1For normal-butyl or n-hexyl；R2For n-hexyl, n-heptyl, isopentyl, normal-butyl, n-pentyl, different
Butyl, cyclohexyl or cyclopenta；
Steps are as follows for asymmetric two sulphur synthetic method of cyanoalkyl:
Sequentially add alkyl Bunte salt, thiocarbamide, sodium carbonate, neopelex SDBS in reaction flask, halogenated alkane and
Water is reacted, wherein alkyl Bunte salt, thiocarbamide, sodium carbonate, neopelex and halogenated alkane molar ratio be 1
~1.25: 1.2~1.5: 1.2~1.5: 0.032~0.375: 1；Then it reacts, adds in 50~100 DEG C of heating under nitrogen protection
The hot time is 3~7 hours；After solution is cooled to room temperature, 5mL water is added, gained mixture is extracted with ethyl acetate 3 times,
15mL/ times, merging organic phase, 2~5g anhydrous magnesium sulfate is dry, filter paper filtering, 80~100mmHg vacuum decompression, heating 40~
50 DEG C are concentrated to get crude product；Gained crude product is purified through 200~300 mesh silica gel column chromatographies, with 200~500mL petroleum ether/acetic acid second
Ester quality proportioning is 20: 1 as eluent, obtains asymmetric cyanoalkyl disulfide.
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