CN106496083A - Hydroxyl replacement prepares the method for sulfhydryl compound and sulfhydryl compound - Google Patents
Hydroxyl replacement prepares the method for sulfhydryl compound and sulfhydryl compound Download PDFInfo
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- CN106496083A CN106496083A CN201610908585.6A CN201610908585A CN106496083A CN 106496083 A CN106496083 A CN 106496083A CN 201610908585 A CN201610908585 A CN 201610908585A CN 106496083 A CN106496083 A CN 106496083A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/24—Thiols, sulfides, hydropolysulfides, or polysulfides having thio groups bound to carbon atoms of six-membered aromatic rings
- C07C321/26—Thiols
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
- C07C319/08—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups
- C07C319/10—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by replacement of hydroxy groups or etherified or esterified hydroxy groups by replacement of hydroxy groups or etherified or esterified hydroxy groups bound to carbon atoms of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C321/00—Thiols, sulfides, hydropolysulfides or polysulfides
- C07C321/12—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms
- C07C321/20—Sulfides, hydropolysulfides, or polysulfides having thio groups bound to acyclic carbon atoms of an unsaturated carbon skeleton containing rings
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Abstract
The invention provides a kind of hydroxyl replacement prepares method and the sulfhydryl compound of sulfhydryl compound.In the inventive method, with benzene or fused ring compound with phenolic hydroxyl group or benzyl hydroxyl substituent cheap and easy to get as raw material, and corresponding sulfhydryl compound is prepared with raw material reactions such as inorganic sulphides under catalytic condition, there is the simple and convenient low cost of preparation method, simultaneous reactions mild condition, reaction site selectivity are high, yield is high, last handling process is simple, the advantages of will not also bring pollution.
Description
Technical field
The present invention relates to sulfhydryl compound preparation field, prepares sulfhydryl compound in particular to a kind of hydroxyl replacement
Method and sulfhydryl compound.
Background technology
Sulfhydryl compound is the very important class raw material of industry and important medicine intermediate in chemical field,
Mainly include two big class of mercaptan and thiophenol.
Mercaptan is the class with sulfydryl (- SH) structure with the oxygen atom in sulphur atom replacement alcoholic extract hydroxyl group so as to be formed
Compound.Its property is similar with corresponding alcohol compound, has faintly acid and acidity is stronger than corresponding alcohol, easily two sulfur of oxidized generation
Compound.Mercaptan can be also used as antidote and the vulcanization of rubber promote as the intermediate of medicine, pesticide and herbicide
Agent etc..
Thiophenol is also a kind of important industrial chemicals and organic synthesis intermediate, can be widely applied to the conjunction of medicine and dyestuff
Into, additionally it is possible to as aluminium alloy slow releasing agent, complex analytical reagent, the reducing agent of sensitive material and polymerization inhibitor etc..
Further, since thiophenol has extremely smelly abnormal smells from the patient, thus can be used for coal gas leak detection.
For the synthesis of sulfhydryl compound has had more research in the prior art, for example, for mercaptan chemical combination
Thing, can with hydrogen sulfide and epoxide as raw material, and further pressurized, heated preparing mercaptan；It is also possible to adopt sulfur
Urea and halogenide are raw material, to prepare corresponding mercaptan compound；Likewise, can also be anti-by monoxone and sodium thiosulfate
Mercaptan should be prepared.Likewise, for thiol compounds, thiophenol can be prepared by benzene and chlorosulfonic acid reaction；Benzene can also be passed through
Phenol prepares p-mercaptophenol with sulfur monochloride reaction；It is also possible to pass through aniline diazotising, esterification and hydrolysis prepare
Thiophenol.
However, being not required to poisonous sulfuration in the preparation method of these existing sulfhydryl compounds as above
Hydrogen is raw material, exactly needs to use expensive or mordant sulfide or chloride as raw material；Meanwhile, in reaction
During, also need to prepare sulfhydryl compound through high temperature and multistep complex reaction in existing method, and past
Contact can produce a large amount of sulfide side products with murder by poisoning and abnormal flavour during the course of the reaction.This not only considerably increases chemical industry work
The synthesis difficulty of industry and chemical experiment and danger coefficient, while also improve the cost that production prepares synthesis.
In view of this, the special proposition present invention.
Content of the invention
The first object of the present invention is to provide a kind of method that hydroxyl replacement prepares sulfhydryl compound, described method
In, by carry the benzene or fused ring compound raw material of phenolic hydroxyl group or benzyl hydroxyl substituent, and under catalytic condition with inorganic sulfur
Compound is reacted, such that it is able to pass through to replace phenolic hydroxyl group or benzyl hydroxyl to prepare sulfhydryl compound, with reaction raw materials simple and easy to get,
The advantages of reaction condition is gentle, reactions steps are simple, yield is high and pollution is few.
Second object of the present invention is to provide a kind of sulfhydryl compound, and which is prepared by the method for the invention,
Have product purity high.
A kind of method that hydroxyl replacement prepares sulfhydryl compound, methods described comprise the steps：
Compound I, inorganic sulphide and catalyst are added after reacting in solvent, filter, solvent is evaporated off；Then purify
Acidifying, is filtered, washed and dried, obtains final product sulfhydryl compound；Reaction overall flow step is as shown in accompanying drawing Fig. 1.
Wherein, compound I structures are as follows：
Wherein, R1、R2、R3、R4、R5、R6It is independently selected from hydrogen, hydroxyl, alkyl and substituted hydrocarbon radical；
Wherein, adjacent R bases may be combined to form substituted or non-substituted second ring；Further, phase on second ring
Adjacent substituent group can be further combined with the 3rd ring of formation；
Condition is, at least one phenolic hydroxyl group or benzyl hydroxyl substituent in compound I.
Optionally, in the present invention, the compound I be at least one phenolic hydroxyl group or benzyl hydroxyl substituent substituted benzene,
Naphthalene, anthracene, luxuriant and rich with fragrance, pyrene or.
Optionally, in the present invention, the inorganic sulphide is in sodium sulfide, NaHS, Potassium monosulfide. or potassium bisulfide
The mixing inorganic sulphide of one or more.
Optionally, the present invention in, the catalyst be sodium bisulfate, disodium hydrogen phosphate or sodium dihydrogen phosphate in one kind or
Several mixing Inorganic acidic salt catalysts.
Optionally, in the present invention, the catalyst is ammonium hydrogen carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, carbonic acid
The mixed catalyst of one or more in hydrogen caesium, magnesium bicarbonate, calcium bicarbonate or bicarbonate zinc.
Optionally, in the present invention, the temperature of the reaction is 0～150 DEG C, and the time of reaction is 1～12h.
Optionally, in the present invention, the reaction temperature is 20～25 DEG C, and the time of reaction is 10～12h.
Optionally, in the present invention, the acidifying is to be acidified using hydrochloric acid.
Optionally, in the present invention, the concentration of hydrochloric acid used is 0.5～3mol/L.
Meanwhile, present invention also offers a kind of sulfhydryl compound obtained by the inventive method.
Compared with prior art, beneficial effects of the present invention are：
In the present invention, by with benzene or fused ring compound with phenolic hydroxyl group or benzyl hydroxyl substituent cheap and easy to get as original
Material, and under catalytic condition with inorganic sulphide reaction prepare corresponding sulfhydryl compound, with preparation method simple and convenient into
This is low, and simultaneous reactions mild condition, reaction site selectivity are high, products collection efficiency high-purity is good, and last handling process is simple, will not also
The advantages of bringing pollution.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described.
Fig. 1 is reaction process schematic diagram of the present invention.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.Unreceipted concrete in embodiment
Condition person, the condition that advises according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, are
The conventional products that commercially available purchase is obtained can be passed through.
In a preferred version of the present invention, in the compound I, R1、R2、R3、R4、R5、R6It is independently selected from
Hydrogen, hydroxyl, alkyl and substituted hydrocarbon radical；For example described alkyl can be the alkyl of C1-C12, the thiazolinyl of C1-C12, the alkynes of C1-C12
Base, the aryl of C6-C30；Or the alkyl can be the aryl base replacement alkane of the alkyl substituting aromatic base of C6-C30, C6-C30
Base, the alkenyl substituted aryl of C6-C30；The substituted hydrocarbon radical can be alkyl with the heteroatomic C1-C12 such as O, N, P, S,
The thiazolinyl of C1-C12, the alkynyl of C1-C12, the aryl of C6-C30；Or the substituted hydrocarbon radical can be miscellaneous with O, N, P, S etc.
The alkyl substituting aromatic base of the C6-C30 of atom, the aryl substituted alkyl of C6-C30.
Further, if there is thiazolinyl, alkynyl etc. in compound I with the substituent group for easily reacting active hydrogen, due to taking
The active hydrogen of Dai Jizhong is reacted so as to there is replacement phenomenon with inorganic sulphide equally under catalytic reaction condition, so as to affect mesh
The acquisition of mark product.Therefore, in the present invention, avoid as far as possible using with the compound that the groups such as thiazolinyl, alkynyl are substituent group
I.
Meanwhile, halogen substiuted will not occur with halogen F, Cl, Br for the compound I of substituent group during the course of the reaction；And I
There is I replacements in (iodine) substituted aryl compound under certain reaction condition, so as to affect the acquisition of target product.Therefore, originally
In invention, equally also to avoid as far as possible using the compound I with I as substituent group.
The present invention a preferred version in, the compound I be without thiazolinyl, alkynyl and I be substituent group
Aryl compound.
Meanwhile, in a preferred version of the present invention, in the compound I, the second ring can be the fragrance of C6-C12
Ring, second ring are condensed with the female ring phenyl ring of compound I；Further, formed by the substituent group carried on the second ring
3rd ring is Bicyclic-fused with.
In a preferred version of the present invention, the compound I is to take with one or more phenolic hydroxyl group or benzyl hydroxyl
The substituted benzene of Dai Ji, naphthalene, anthracene, phenanthrene, pyrene or；Further, the compound I can be with or without except phenol hydroxyl
The substituted benzene of other substituent groups outside base or benzyl hydroxyl, naphthalene, anthracene, phenanthrene, pyrene or.
For example, compound I can be substituted benzene with a phenolic hydroxyl group or benzyl hydroxyl, naphthalene, anthracene, phenanthrene, pyrene or；Or
Person, the compound I can be substituted benzene with two phenolic hydroxyl groups or benzyl hydroxyl, naphthalene, anthracene, phenanthrene, pyrene or；Or, described
Compound I can be substituted benzene with three phenolic hydroxyl groups or benzyl hydroxyl, naphthalene, anthracene, phenanthrene, pyrene or；Or, the compound I
Can be substituted benzene with a phenolic hydroxyl group and a Bian hydroxyl, naphthalene, anthracene, phenanthrene, pyrene or；Or, the compound I can be with
Be substituted benzene with two phenolic hydroxyl groups and a Bian hydroxyl, naphthalene, anthracene, phenanthrene, pyrene or；Or, the compound I can be band
Have the substituted benzene of a phenolic hydroxyl group and two Bian hydroxyls, naphthalene, anthracene, phenanthrene, pyrene or.
It is further preferred that the compound I can be, but it is not limited to：Phenol, catechol, resorcinol, to benzene two
Phenol；Benzyl alcohol, phthalyl alcohol, terephthalyl alcohol；1- naphthols, beta naphthal, 1,3- naphthalenediols, 1,6- naphthalenediols, 2,6- naphthalenes two
Phenol, 2,7- naphthalenediols；1- naphthalene methanol, 2- naphthalene methanol, Isosorbide-5-Nitrae-naphthalene dimethanol, 1,8- naphthalene dimethanols；1- anthrols, 2- anthrols, 1,8-
Oxanthranol；9- anthranols；2- pyrene phenol；1- pyrene methanol etc..
In the present invention, it is by reaction of the present invention, by the hydroxyl in the phenolic hydroxyl group in compound I and/or benzyl hydroxyl
Replaced, obtained corresponding sulfydryl salt compound, be further acidified to prepare corresponding sulfhydryl compound.
The present invention a preferred version in, the solvent be methanol, ethanol, dichloromethane, chloroform, propanol,
The mixed solvent of one or more in isopropanol.
In a preferred version of the present invention, the inorganic sulphide is sodium sulfide, NaHS, Potassium monosulfide. or sulfur hydrogen
Change the one kind in potassium.
In the present invention, using sodium sulfide, NaHS, Potassium monosulfide. or potassium bisulfide etc. as starting material inorganic sulfosalt, with original
Material is simple and easy to get, the advantages of cheap, while can also cost that further effective control is entirely reacted.
In a preferred scheme of the present invention, the catalyst is sodium bisulfate, disodium hydrogen phosphate or biphosphate
A kind of acid salt catalyst in sodium；Or in the present invention, the catalyst is ammonium hydrogen carbonate, lithium bicarbonate, sodium bicarbonate, carbon
A kind of bicarbonate catalyst in potassium hydrogen phthalate, caesium bicarbonate, magnesium bicarbonate, calcium bicarbonate or bicarbonate zinc；It is furthermore preferred that
In the present invention, the catalyst is the one kind in sodium bicarbonate and potassium bicarbonate.
In the present invention, by selection and adjustment to used catalyst, and from acid salt or bicarbonate as catalysis
Agent, so that reaction just efficiently can be carried out in a mild condition, while reaction cost effectively can also be reduced, and has
Effect suppresses the generation of the toxic by-products sulfide such as hydrogen sulfide.
In a preferred version of the present invention, the temperature of the reaction is 0～150 DEG C, and the time of reaction is 1～24h.
Specifically, reaction of the present invention can react 1～2h under reflux conditions；Or, in the present invention, the reaction can be in room
10～12h is reacted under the conditions of 20～25 DEG C of temperature.And under both reaction conditions, identical sulfhydryl compound product can be accessed
Thing, and obtain close yield.
The present invention a preferred version in, described purification be by after revolving gained solid mixture elder generation recrystallization then
Column chromatography, and corresponding sodium salt is obtained, then it is acidified, last filtration washing dries purification to obtain product sulfhydryl compound.
In a preferred version of the present invention, the purification is column chromatography purification.
In a preferred version of the present invention, the concentration of the hydrochloric acid can be, but be not limited to 1,1.5,2 or
2.5mol/L.
Further, the method for the invention entirety preparation flow step is as follows：
(1) by compound I；The mixing of one or more in sodium sulfide, NaHS, Potassium monosulfide. or potassium bisulfide is inorganic
Sulfide；The mixing Inorganic acidic salt catalyst of one or more in sodium bisulfate, disodium hydrogen phosphate or sodium dihydrogen phosphate, or
Person's ammonium hydrogen carbonate, lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, caesium bicarbonate, magnesium bicarbonate, calcium bicarbonate or bicarbonate zinc
In the mixed catalyst of one or more；Add in solvent, and 1～12h is reacted under the conditions of 0～150 DEG C；
(2) reacted mixed system is cooled to after room temperature and is filtered, filtrate revolving removes solvent, then by gained solid
Mixture recrystallization, obtains sulfhydryl compound sodium salt；Then, the salt of appropriate 1mol/L is added in gained sulfhydryl compound sodium salt
Acid is acidified, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtains final product target sulfhydryl compound.
Embodiment 1
(1) in 150ml flasks, 1mmol phenol, 1.2mmolNa are added2S and 0.1g catalyst n aHCO3, and add
50ml ethanol, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product sulfydryl benzene sodium salt；Then, in gained sulfydryl benzene sodium salt the hydrochloric acid of appropriate 1mol/L is added to carry out acid
Change, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtain final product target sulfydryl benzene, and yield is 85%,
Purity ＞ 99%.
Embodiment 2
(1) in 150ml flasks, 1mmol hydroquinone, 2.5mmolNa are added2S and 0.2g catalyst n aHCO3, and
50ml methanol is added, is uniformly mixed；Then, at ambient temperature, react 12h；
(2) by reacted mixed system, filter, filtrate revolving removes solvent, and by gained solid mixture recrystallization,
Obtain final product thioresorcin sodium salt；Then, in gained thioresorcin sodium salt the hydrochloric acid of appropriate 1mol/L is added to be acidified, and by acid
After after change, system is filtered, washed and dried, then column chromatography purification, obtains final product target to thioresorcin, and yield is 70%, purity ＞
99%.
Embodiment 3
(1) in 150ml flasks, 1mmol naphthols, 1.2mmolNa are added2S and 0.1g catalyst KHCO3, and add
50ml ethanol, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product mercaptonaphthalene sodium salt；Then, in gained sulfydryl benzene sodium salt the hydrochloric acid of appropriate 1mol/L is added to carry out acid
Change, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtain final product target mercaptonaphthalene, and yield is 85%,
Purity ＞ 99%.
Embodiment 4
(1) in 150ml flasks, 1mmol phenol, 1.2mmolNaHS and 0.1g catalyst LiHCO are added3, and add
50ml ethanol, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product sulfydryl benzene sodium salt；Then, in gained sulfydryl benzene sodium salt the hydrochloric acid of appropriate 1mol/L is added to carry out acid
Change, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtain final product target sulfydryl benzene, and yield is 80%,
Purity ＞ 99%.
Embodiment 5
(1) in 150ml flasks, 1mmol hydroquinone, 2.5mmolNaHS and 0.2g catalyst LiHCO are added3, and
50ml ethanol is added, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtain final product thioresorcin sodium salt；Then, the hydrochloric acid of appropriate 1mol/L is added in gained thioresorcin sodium salt
It is acidified, and after system after acidifying is filtered, washed and dried, then column chromatography purification, is obtained final product target to thioresorcin, produced
Rate is 73%, purity ＞ 99%.
Embodiment 6
(1) in 150ml flasks, 1mmol naphthols, 1.2mmolNaHS and 0.1g catalyst n aHCO are added3, and add
50ml chloroforms, are uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product mercaptonaphthalene sodium salt；Then, in gained mercaptonaphthalene sodium salt the hydrochloric acid of appropriate 1mol/L is added to carry out acid
Change, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtain final product target mercaptonaphthalene, and yield is 85%,
Purity ＞ 99%.
Embodiment 7
(1) in 150ml flasks, 1mmol benzyl alcohol, 1.2mmolNa are added2S and 0.1g catalyst n aHCO3, and plus
Enter 50ml ethanol, be uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product thiopurine methyltransferase benzene sodium salt；Then, in gained thiopurine methyltransferase benzene sodium salt the hydrochloric acid of appropriate 1mol/L is added to enter
Row acidifying, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtains final product target thiopurine methyltransferase benzene, and yield is
85%, purity ＞ 99%.
Embodiment 8
(1) in 150ml flasks, 1mmol naphthalene methanol, 1.2mmolNa are added2S and 0.1g catalyst n aHCO3, and plus
Enter 50ml ethanol, be uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product thiopurine methyltransferase naphthalene sodium salt；Then, in gained thiopurine methyltransferase naphthalene sodium salt the hydrochloric acid of appropriate 1mol/L is added to enter
Row acidifying, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtains final product target thiopurine methyltransferase naphthalene, and yield is
75%, purity ＞ 99%.
Embodiment 9
(1) in 150ml flasks, 1mmol1- anthrols, 1.2mmolNa are added2S and 0.1g catalyst Z n (HCO3)2, and
50ml ethanol is added, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product sulfydryl anthracene sodium salt；Then, in gained sulfydryl anthracene sodium salt the hydrochloric acid of appropriate 1mol/L is added to carry out acid
Change, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtains final product target 1- sulfydryl anthracene, and yield is
65%, purity ＞ 99%.
Embodiment 10
(1) in 150ml flasks, 1mmol2- pyrene phenol, 2.5mmolNaHS and 0.1g catalyst Ca (HCO are added3)2, and
50ml ethanol is added, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product thiopurine methyltransferase pyrene sodium salt；Then, in gained thiopurine methyltransferase pyrene sodium salt the hydrochloric acid of appropriate 1mol/L is added to enter
Row acidifying, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtains final product target 2- sulfydryl pyrene, and yield is
60%, purity ＞ 99%.
Embodiment 11
(1) in 150ml flasks, 1mmol1- pyrene methanol, 2.5mmolNaHS and 1mmolNaHSO are added4, and add
50ml ethanol, is uniformly mixed；Then, under reflux conditions, react 2h；
(2) reacted mixed system is cooled to after room temperature, is filtered, filtrate revolving removes solvent, and by gained solid
Mixture recrystallization, obtains final product thiopurine methyltransferase pyrene sodium salt；Then, in gained thiopurine methyltransferase pyrene sodium salt the hydrochloric acid of appropriate 1mol/L is added to enter
Row acidifying, and after system after acidifying is filtered, washed and dried, then column chromatography purification, obtains final product target 1- thiopurine methyltransferase pyrene, yield
For 60%, purity ＞ 99%.
The inventive method raw material is simple and easy to get, while can just can be preparing product in high yield under gentle reaction condition
Thing sulfhydryl compound, while will not also produce the toxic by-product such as hydrogen sulfide, is a kind of green, environmental protection, safety, and is suitable for
In the aromatic with phenolic hydroxyl group and/or benzyl hydroxyl substituent of different structure preparing corresponding sulfhydryl compound.
Although having illustrate and described the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes and modification can be made in the case of spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (10)
1. a kind of method that hydroxyl replacement prepares sulfhydryl compound, it is characterised in that methods described comprises the steps：
Compound I, inorganic sulphide and catalyst are added after reacting in solvent, filter, solvent is evaporated off；Then purified acid
Change, purification after filtration, washing are dry obtains final product sulfhydryl compound；
Compound I structures are as follows：
Wherein, R1、R2、R3、R4、R5、R6It is independently selected from hydrogen, hydroxyl, alkyl or substituted hydrocarbon radical；
Wherein, adjacent R bases may be combined to form substituted or non-substituted second ring；Further, adjacent on second ring
Substituent group can be further combined with the 3rd ring of formation；
Condition is, at least one phenolic hydroxyl group or benzyl hydroxyl substituent in compound I.
2. method according to claim 1, it is characterised in that the compound I is at least one phenolic hydroxyl group or benzyl hydroxyl
The substituted benzene of base substituent group, naphthalene, anthracene, luxuriant and rich with fragrance, pyrene waits aromatic ring.
3. method according to claim 1, it is characterised in that the inorganic sulphide is sodium sulfide, NaHS, sulfuration
The mixing inorganic sulphide of one or more in potassium or potassium bisulfide.
4. method according to claim 1, it is characterised in that the catalyst is sodium bisulfate, disodium hydrogen phosphate or phosphorus
The mixing Inorganic acidic salt catalyst of one or more in acid dihydride sodium.
5. method according to claim 1, it is characterised in that the catalyst is ammonium hydrogen carbonate, lithium bicarbonate, bicarbonate
The mixed catalyst of one or more in sodium, potassium bicarbonate, caesium bicarbonate, magnesium bicarbonate, calcium bicarbonate or bicarbonate zinc.
6. method according to claim 1, it is characterised in that the temperature of the reaction is 0～150 DEG C, the time of reaction
For 1～12h.
7. method according to claim 1, it is characterised in that the temperature of the reaction is 20～25 DEG C, the response time is
10～12h.
8. method according to claim 1, it is characterised in that the acidifying is to be acidified using hydrochloric acid.
9. method according to claim 8, it is characterised in that the concentration of hydrochloric acid used is 0.5～3mol/L.
10. sulfhydryl compound obtained in method according to any one of claim 1-9.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820062A (en) * | 1954-08-11 | 1958-01-14 | Pure Oil Co | Preparation of organic thiols |
| US4740623A (en) * | 1987-01-30 | 1988-04-26 | Stauffer Chemical Company | Method for preparation of benzyl mercaptan |
| US5733836A (en) * | 1996-03-22 | 1998-03-31 | Phillips Petroleum Company | Compositions comprising inorganic oxide and process for producing mercaptans |
| CN1261552A (en) * | 1998-12-01 | 2000-08-02 | 埃勒夫阿托化学有限公司 | Catalyst for preparing thio-alcohol using zircomiumoxide as base |
| EP3034490A1 (en) * | 2014-12-19 | 2016-06-22 | Evonik Degussa GmbH | Process for the preparation of alkyl mercaptans |
-
2016
- 2016-10-18 CN CN201610908585.6A patent/CN106496083A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2820062A (en) * | 1954-08-11 | 1958-01-14 | Pure Oil Co | Preparation of organic thiols |
| US4740623A (en) * | 1987-01-30 | 1988-04-26 | Stauffer Chemical Company | Method for preparation of benzyl mercaptan |
| US5733836A (en) * | 1996-03-22 | 1998-03-31 | Phillips Petroleum Company | Compositions comprising inorganic oxide and process for producing mercaptans |
| CN1261552A (en) * | 1998-12-01 | 2000-08-02 | 埃勒夫阿托化学有限公司 | Catalyst for preparing thio-alcohol using zircomiumoxide as base |
| EP3034490A1 (en) * | 2014-12-19 | 2016-06-22 | Evonik Degussa GmbH | Process for the preparation of alkyl mercaptans |
Non-Patent Citations (2)
| Title |
|---|
| JANETTE HOUK 等: "Structure-Reactivity Relations for Thiol-Disulfide Interchange", 《J.AM.CHEM.SOC.》 * |
| 熊飞: "巯基化合物的合成", 《南京理工大学硕士学位论文》 * |
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