CN106674100A - Preparation method of tri[2-(N-oxide-pyridine-2-sulfenyl)ethyl]amine - Google Patents
Preparation method of tri[2-(N-oxide-pyridine-2-sulfenyl)ethyl]amine Download PDFInfo
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- CN106674100A CN106674100A CN201611199509.9A CN201611199509A CN106674100A CN 106674100 A CN106674100 A CN 106674100A CN 201611199509 A CN201611199509 A CN 201611199509A CN 106674100 A CN106674100 A CN 106674100A
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- amine
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- sulfenyls
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/89—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to the ring nitrogen atom
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- Chemical & Material Sciences (AREA)
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- Pyridine Compounds (AREA)
Abstract
The invention discloses a preparation method of tri[2-(N-oxide-pyridine-2-sulfenyl)ethyl]amine, namely taking a path for synthesizing the tri[2-(N-oxide-pyridine-2-sulfenyl)ethyl]amine through the interaction of 2-chloropyridine-N-oxide and tri(2-mercapto ethyl)amine. The oxygen on the N- reinforces the electrophilicity of alpha-position carbon on a pyridine ring, the alkaline media reinforces nucleophilicity of mercaptan negative ion, the reactivity of two reactant is sufficiently utilized, the cheap and excess 2-chloropyridine-N-oxide can be recycled, so that the preparation method disclosed by the invention is high in yield and less in material consumption.
Description
Technical field
The invention belongs to marine anti-pollution technical field, and in particular to three [2- (N- oxide-pyridin base -2- sulfenyls) of one kind
Ethyl] amine preparation method, mainly for the production of the anti-fouling agent in marine antifouling coating, prevent marine organisms cultivation netting gear,
Adhere on the surfaces of marine facility such as naval vessel, offshore oil and gas platform, harbour, bridge pier, seawater pipeline and grow.
Background technology
Attachment and growth of the marine organisms on marine facility surface is referred to as marine biofouling, marine biofouling have plus
Normally using for big ship resistance, blocking pipeline and cultivation netting gear, impact acoustic instrument and other offshore set-ups, increases
The burden of offshore oil and natural gas extraction platform, accelerates the serious harms such as metal erosion, so as to cause ocean military activity, sea
Ocean transport, industry and aquaculture production etc. produce massive losses.According to statistics, it is annual by marine biofouling in worldwide
The loss for causing is about 50,000,000,000 dollars.Marine biofouling problem, governs the mankind to the development and utilization of marine resources, and
Bring huge economic loss.Therefore, to the research of marine anti-pollution problem it is the neck such as sea transport, ocean engineering and sea fishery
Important topic in domain.
At present, method economic, simple and effective in marine anti-pollution technology be marine facility external coating contain it is antifouling
The antifouling paint of agent.And most important in the research and development of antifouling paint product is exactly to select suitable anti-fouling agent.
Traditional antifouling paint species is a lot, and wherein mineral-type mainly includes Red copper oxide, mercury oxide, zinc chloride etc., has
Machine class mainly includes machine tin compound (such as TBT), organochlorine compound (such as DDT).Wherein organo-tin compound is
Using main marine antifoulant for many years, its anti-fouling effect was up to more than 5 years, but research later finds that organotin is to ocean
Ecological environment is impacted.At present, International Maritime Organization has prohibited application of the organotin in marine antifouling coating.Now
80% marine antifouling coating is all as anti-fouling agent using Red copper oxide.The consumption of Red copper oxide accounts for nonvolatile component in coating
30-60%, but because Red copper oxide is stronger than great, hydrophilic, sedimentation is easily produced, in being discharged into water body, to antifouling paint
Using impacting.Meanwhile, excessive Red copper oxide is discharged in water body, heavy metal in water accumulation is easily caused, with potential
Contaminative, therefore, International Maritime Organization will start to limit the use of Red copper oxide in 2012.It can be seen that, develop new nontoxic
Or low toxicity anti-fouling agent is extremely urgent.
The copper of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine, zinc, the coordination compound of silver are fine sea anti-fouling agents,
Their medium effective concentrations to Phaeodactylum are respectively 13.2 μ g/L, 58.9 μ g/L, 6.31 μ g/L for (EC50).Triethyl group
On the precursor structure of amine, the pyrithione of bonding is more stable in anti-dirty Tu layers to be difficult to dissociate pyrithione, favourable Yu Haiyang
Environment.It is a kind of anti-fouling agent of promising high-efficiency low-toxicity.Three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine, because of it
There are three pyrithione units on precursor structure, its own also there are good other fungus and mildew resistance purposes.
Patent 2012101771411 discloses a kind of anti-fouling agent antifouling for marine facility and preparation method thereof, and this is special
Profit is disclosed in the ethanol solution of sodium hydroxide, and sodium pyrithione and three (2- chloroethyls) amine hydrochlorates react, and prepare three (2-
(N- oxide-pyridin base -2- sulfenyls) ethyl) amine.Its preparation method is as follows：
In existing preparation method, the carbon-chlorine key on (2- chloroethyls) amine alkyl is stable, and chlorine is difficult to leave away, its parent
It is electrically bad, so its synthetic yield not high (yield is 67.2% or so).Two raw material equimolars feed intake, and unreacted
It is complete.Two raw materials are intended to reclaim during post processing, and difficulty is big, loss is big, easily forms pollution.The new preparation of such medicament is developed for this
Method is necessary.
The content of the invention
In order to overcome the shortcomings of described in background technology, the invention provides a kind of three [2- (N- oxide-pyridin base -2- sulfur
Base) ethyl] amine preparation method, the method interacted conjunction using 2- chloropyridine-N- oxides and three (2- mercaptoethyls) amine
Into three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine, the upper oxides of N- enhance the electrophilicity of α positions carbon on pyridine ring,
Alkaline medium strengthens mercaptan anionic amphiphilic nuclearity, and two reactant reaction activity are fully utilized, cheap excessive 2- chloropyridine-N-
Oxide is recyclable, makes this preparation method yield high, and material consumption is few.
The technical solution adopted for the present invention to solve the technical problems is：
A kind of preparation method of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine, three described [2- (N- oxidations
Thing-pyridine radicals -2- sulfenyls) ethyl] amine is using excessive 2- chloropyridine-N- oxides and three (2- mercaptoethyls) amine phase interactions
With preparing, the equation of its reaction is as follows：
Preferably, described method is comprised the following steps：
(1) preparing raw material：Prepare three (2- mercaptoethyls) amine and 2- chloropyridine-N- oxides：
(2) fully reaction is heated：Three (2- mercaptoethyls) amine, Feldalat NM are added in the absolute methanol solution containing Feldalat NM
Alkaline environment is provided, after reaction a period of time, 2- chloropyridine-N- oxides is added, is heated to reflux, thin layer chromatography tracking reaction is complete
Journey, and and determination reaction end qualitative to product, stopped reaction；
(3) product that step (2) is obtained is cooled down, is filtered, reduced pressure on a rotary evaporator, heating is steamed low boiling
Solvent；
(4) the height boiling residue obtained to step (3), adds acid solution to stir and adjusts pH, ethyl acetate extraction
Take three times, organic faciess are dried with anhydrous sodium sulfate, go solvent to obtain light yellow liquid using decompression on Rotary Evaporators afterwards
Body crude product；
(5) crude product obtained to step (4) purification on column chromatography, obtains eluant, and eluant is in Rotary Evaporators
Upper decompression and solvent recovery, that is, obtain light yellow oil three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine.
Preferably, in step (2), three (2- mercaptoethyls) amine post-reacted times of addition be 15-25 minutes, thin layer chromatography
The support plate for adopting is GF254 lamellaes, and the developing solvent that thin layer chromatography is adopted includes methanol, chloroform, wherein V (methanol)：V (chlorine
It is imitative)=1：6.
Preferably, in step (2), described dehydrated alcohol consumption is 40-60ml, and described Feldalat NM consumption is 0.045-
0.065mol, described three (2- mercaptoethyls) amine consumptions are 0.03-0.08mol, described 2- chloropyridine-N- oxides and three
The mol ratio of (2- mercaptoethyls) amine is 2.1-4:1.
Preferably, in step (2), described 2- chloropyridine-N- oxides are with the mol ratio of three (2- mercaptoethyls) amine
3:1。
Preferably, the acid solution used in step (4) is hydrochloric acid, and the scope for adjusting pH value is 3-4.
The present invention is compared to the advantage of prior art：
(1) in the present invention, with the strong electrophilicity of 2- chloropyridine-N- oxides of the prior art inactive three are replaced
(2- chloroethyls) amine hydrochlorate, the chlorine quilt on 2- chloropyridine-N- oxides reinforcing pyridine ring in the electrophilicity and α positions carbon of α positions carbon
The activity of nucleophilic displacement of fluorine, with 2- chloropyridine-N- oxides as three [2- (N- oxide-pyridin base -2- sulfenyls) ethyls] of synthesis
The electrophilic type reaction raw materials of amine, using the chlorine on the electronic effect activation 2- positions of oxygen in pyridine ring nitrogen, increase its electrophilicity, reaction
Activity；
(2) in the present invention, with three (2- mercaptoethyls) amine, the negative son of the mercaptan formed under alkaline media is used as three [2- of synthesis
(N- oxide-pyridin base -2- sulfenyls) ethyl] amine nucleophilic form reaction raw materials, three (2- mercaptoethyls) amine are in alkaline media
Mercaptan anion state, has very strong nucleophilicity and reactivity so that 2- chloropyridine-N- oxides and three (2- mercaptoethyls)
The reactivity of amine is given full play to and utilization, more effectively synthesizes three (2- (N- oxide-pyridin base -2- sulfenyls) ethyls)
Amine, mentions yield；
(3) in the present invention, the low 2- chloropyridine-N- oxide Excess quantities of price pull reaction balance to move to right, and react residual
2- chloropyridines-N- oxides are principal goods matter in excess, favourable its recycling；
(4) in the present invention, the superposition of the respective reactivity of two new raw materials is taken full advantage of, is received so as to improve product
Rate, while 2- chloropyridine-N- oxides are more cheap than the sodium pyrithione described in background technology, can be excessive, this favourable reaction balance
Point is moved to right, the recyclable recycling of raw material in reaction residual；
(5) in the present invention, opposition thinking, favorable factor, condition etc. are fully excavated, utilized in the present invention, react this
Material consumption is few, and yield is high, post processing is easy, ambient pressure is little, global advantage is greatly brought into play.
Specific embodiment
Below in conjunction with embodiment, the present invention is further illustrated：
Embodiment 1
In tetra- mouthfuls of reaction bulbs of 250ml, 50ml absolute methanols, 0.055mol Feldalat NMs are added, obtain alcohol sodium solution, added new
Three (2- mercaptoethyls) the amine 0.05mol for preparing, after reacting 20 minutes, plus freshly prepd 2- chloropyridines-N- oxides
0.15mol.It is heated to reflux, thin layer chromatography tracks reaction whole process, and qualitative in time to product, quantitative and determination reaction end, stops
Only react.Cooled and filtered, on a rotary evaporator recovered under reduced pressure low-boiling-point substance.In height boiling residue plus containing salt aqueous acid
Stir evenly, adjust pH to 3, be extracted with ethyl acetate three times, organic faciess anhydrous sodium sulfate drying, decompression on Rotary Evaporators is gone molten
Agent obtains light yellow liquid crude product, and crude product purification on column chromatography, eluant obtains shallow in Rotary Evaporators decompression and solvent recovery
20.59 grams of yellow oil, yield is 86%.
Wherein, for GF254 lamellaes, the developing solvent that thin layer chromatography is adopted is V (methanol) to the carrier that thin layer chromatography is adopted：V
(chloroform)=1：6, thin layer chromatograph detection the diminishing of 2- chloropyridine-N- oxides, disappear and product point appearance with become big.Cause
Raw material and product have good color development and auxochrome, and thin layer chromatography is cheap, classical, easy to operate to make the production scene in the future
Quality supervision and Quality Control use.
Synthesize product with existing technology of preparing (patent 2012101771411), as mark product the RF values of product are determined.Together
Under a thin layer plate and chromatography condition, upper this method product is identical with the RF values for synthesizing product with existing technology of preparing, it was demonstrated that new
Synthesis is simple, actual effect.
Embodiment 2
In tetra- mouthfuls of reaction bulbs of 250ml, addition 40ml absolute methanols, 0.045mol potassium ethoxides obtain potassium alkoxide solution, add new
After three (2- mercaptoethyls) amine (0.03mol) for preparing react 15 minutes, the 2- chloropyridine-N- oxides of Deca 0.112mol,
With embodiment 1, products therefrom yield is 80.8% to other preparation process.
Embodiment 3
In tetra- mouthfuls of reaction bulbs of 250ml, addition 60ml absolute methanols, 0.065mol potassium ethoxides obtain potassium alkoxide solution, add new
After three (2- mercaptoethyls) amine (0.08mol) for preparing react 25 minutes, the 2- chloropyridine-N- oxides of Deca 0.175mol,
With embodiment 1, products therefrom yield is 82.5% to other preparation process.
Finally it should be noted that：Obviously, above-described embodiment is only intended to clearly illustrate example of the present invention, and not
Restriction to embodiment.For those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.And thus amplified
Among the obvious change for going out or variation are still in protection scope of the present invention.
Claims (6)
1. the preparation method of one kind three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine, it is characterised in that described three
[2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine is using excessive 2- chloropyridine-N- oxides and three (2- sulfydryl second
Base) amine interact prepare, its reaction equation it is as follows：
2. the preparation method of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine of one kind as claimed in claim 1, its
It is characterised by, described method is comprised the following steps：(1) preparing raw material：Prepare three (2- mercaptoethyls) amine and 2- chloropyridine-N-
Oxide：(2) fully reaction is heated：Three (2- mercaptoethyls) amine, reaction one are added in the absolute methanol solution containing Feldalat NM
After the section time, 2- chloropyridine-N- oxides are added, be heated to reflux, thin layer chromatography tracking reaction is whole and qualitative and true to product
Determine reaction end, stopped reaction；
(3) product that step (2) is obtained is cooled down, is filtered, reduced pressure on a rotary evaporator, it is molten that heating is steamed low boiling
Agent；
(4) the height boiling residue obtained to step (3), adds acid solution to stir and adjusts pH, ethyl acetate extraction three
It is secondary, organic faciess are dried with anhydrous sodium sulfate, go solvent to obtain light yellow liquid using decompression on Rotary Evaporators afterwards thick
Product；
(5) crude product obtained to step (4) purification on column chromatography, obtains eluant, and eluant subtracts on a rotary evaporator
Pressure recycling design, that is, obtain light yellow oil three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine.
3. the preparation method of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine of one kind as claimed in claim 2, its
It is characterised by, in step (2), three (2- mercaptoethyls) amine post-reacted times of addition are 15-25 minutes, what thin layer chromatography was adopted
Support plate is GF254 lamellaes, and the developing solvent that thin layer chromatography is adopted includes methanol, chloroform, wherein V (methanol)：V (chloroform)=1：
6。
4. the preparation method of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine of one kind as claimed in claim 3, its
It is characterised by, in step (2), described dehydrated alcohol consumption is 40-60ml, and described Feldalat NM consumption is 0.045-
0.065mol, described three (2- mercaptoethyls) amine consumptions are 0.03-0.08mol, described 2- chloropyridine-N- oxides and three
The mol ratio of (2- mercaptoethyls) amine is 2.1-4:1.
5. the preparation method of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine of one kind as claimed in claim 4, its
It is characterised by, in step (2), described 2- chloropyridine-N- oxides and the mol ratio of three (2- mercaptoethyls) amine is 3:1.
6. the preparation method of three [2- (N- oxide-pyridin base -2- sulfenyls) ethyl] amine of one kind as claimed in claim 5, its
It is characterised by, the acid solution used in step (4) is hydrochloric acid, the scope for adjusting pH value is 3-4.
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| CN201611199509.9A CN106674100A (en) | 2016-12-22 | 2016-12-22 | Preparation method of tri[2-(N-oxide-pyridine-2-sulfenyl)ethyl]amine |
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| CN201611199509.9A CN106674100A (en) | 2016-12-22 | 2016-12-22 | Preparation method of tri[2-(N-oxide-pyridine-2-sulfenyl)ethyl]amine |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053544A1 (en) * | 2000-12-29 | 2002-07-11 | Darwin Discovery Ltd. | Pharmaceutical uses and synthesis of nicotinanilide-n-oxides |
| US6498254B1 (en) * | 2001-10-29 | 2002-12-24 | Uniroyal Chemical Company, Inc. | Antiretroviral compounds and compositions |
| WO2003037311A2 (en) * | 2001-10-29 | 2003-05-08 | Uniroyal Chemical Company, Inc. | Method for treating retroviral infections |
| CN102702821A (en) * | 2012-05-31 | 2012-10-03 | 上海海事大学 | Anti-fouling agent for fouling prevention of ocean facilities and preparation method thereof |
-
2016
- 2016-12-22 CN CN201611199509.9A patent/CN106674100A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2002053544A1 (en) * | 2000-12-29 | 2002-07-11 | Darwin Discovery Ltd. | Pharmaceutical uses and synthesis of nicotinanilide-n-oxides |
| US6498254B1 (en) * | 2001-10-29 | 2002-12-24 | Uniroyal Chemical Company, Inc. | Antiretroviral compounds and compositions |
| WO2003037311A2 (en) * | 2001-10-29 | 2003-05-08 | Uniroyal Chemical Company, Inc. | Method for treating retroviral infections |
| CN102702821A (en) * | 2012-05-31 | 2012-10-03 | 上海海事大学 | Anti-fouling agent for fouling prevention of ocean facilities and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| MATTHIAS NETTEKOVEN AND CHRISTIAN JENNY: "The Development of a Practical and Reliable Large-Scale Synthesis of 2,6-Diamino-4-bromopyridine", 《ORGANIC PROCESS RESEARCH & DEVELOPMENT》 * |
| 胡春 主编: "《有机化学（药学类专业通用）（第二版）》", 31 July 2013, 中国医药科技出版社 * |
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Application publication date: 20170517 |