CN100360543C - Method for preparing ammonium salts of cyclohexanpentol phosphate ester - Google Patents
Method for preparing ammonium salts of cyclohexanpentol phosphate ester Download PDFInfo
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- CN100360543C CN100360543C CNB2006100206813A CN200610020681A CN100360543C CN 100360543 C CN100360543 C CN 100360543C CN B2006100206813 A CNB2006100206813 A CN B2006100206813A CN 200610020681 A CN200610020681 A CN 200610020681A CN 100360543 C CN100360543 C CN 100360543C
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Abstract
The present invention discloses a preparation method for cyclohexanpentol phosphate ester ammonium salts. A compound of the cyclohexanpentol phosphate ester ammonium salts is shown in a general formula (I), wherein R1 is selected from amine whose carbon atomicity is 3 to 18; R2 and R3 are selected from-H, or-PO(OH)2 or PO(OH)2R', and R' is also selected from the amine whose carbon atomicity is 3 to 18. The preparation method of the compound comprises three main steps: the synthesis of cyclohexanpentol, the synthesis of cyclohexanpentol phosphate ester and the synthesis of the cyclohexanpentol phosphate ammonium salts. The present invention has the advantages of simple operation, low cost and little environmental pollution.
Description
Technical field
The present invention relates to a kind of preparation method of cyclopolyol phosphate amine salt compound.
Background technology
PAPE is the widely used compound of a class, can be used as fire retardant, water conditioner, tensio-active agent etc.Be mainly used in circulating water cooling systems such as refinery, chemical plant, fertilizer plant, Steel Plant, air-conditioning system and copper material interchanger, as the Scale inhibitors and the inhibiter of water treatment, be specially adapted to the serious circulating water system of process stream leakage and corrosion situation and the anti-incrustation corrosion inhibitor of oil-field flooding.
In addition, PAPE and amine substance all are the good buffer reagents of metal in the aqueous solution such as copper, tin, aluminium and aluminium alloy, zinc, steel.And be raw material synthetic PAPE class material with the carbohydrate, the similar natural phospholipid of its molecular structure, toxicity is low, stimulation is little, readily biodegradable, is surface of good promoting agent and inhibiter; The PAPE film strength that it forms in water is bigger, and the coalescent suffered resistance of milk sap liquid pearl is bigger, and the emulsion's stability of formation is better; And; its inhibition group number is moderate, makes that the inhibition group in the molecular structure can sequestering action more completely take place with the metallic surface, and because chelating and the synergy that precipitates two kinds of effects; can form than compact protective film in the metallic surface, corrosion mitigating effect is good.
Phosphate amine salt also is a class tensio-active agent commonly used, is widely used in fields such as makeup, leather, weaving.Commonly used as nonyl phenol ether phosphate amine salt, alkyl ether phosphate amine salt, alkyl phosphate amine salt etc.Also have as the plant-growth preparation as amino-ethyl formyl phosphate amine salt etc.
But still not about the report of PAPE amine salt, more there is not the report that waits about quercitol phosphate amine salt and preparation method thereof at present.
Summary of the invention
Purpose of the present invention just provides a kind of preparation method of quercitol phosphate amine salt.It has simple to operate, with low cost and advantage such as environmental pollution is little.
The technical solution adopted for the present invention to solve the technical problems is: a kind of preparation method of quercitol phosphate amine salt, and this quercitol phosphate amine salt is the compound by general formula (I) expression:
General formula (I)
Wherein, R
1Be selected from carbon atom number and be 3～18 amine;
R
2And R
3Be selected from-H or-PO (OH)
2, or-PO (OH)
2R '; Wherein, to be selected from carbon atom number be 3～18 amine to R '.
The preparation method of this compound may further comprise the steps:
The first step: synthesizing cyclohexane 1 pentol.Get glucose, add an amount of methyl alcohol (add-on of methyl alcohol with glucose: methyl alcohol is about 1～4g: 1ml is advisable), add solvents tetrahydrofurane (THF) again, preparation is into about the glucose THF solution of 20～40g/100ml.Under whipped state, drip the vitriol oil that is about THF volume 1/8～1/12 amount, dropwise the back and continue to stir 2～4h; The NaOH aqueous solution with 30～50% is transferred pH value to 9～10 of reaction mixture, and the white solid that filtering is separated out steams and removes THF; With trichloromethane (CHCl
3) extract 2～3 times, combining extraction liquid adds an amount of K
2CO
3Dry; Steam and remove CHCl
3After, obtain dope, i.e. methyl glucoside; Can adopt column chromatography such as silica gel column chromatography to carry out purifies and separates, make eluent, the leacheate that obtains be removed desolvate, obtain the higher methyl glucoside of purity with trichloromethane.Add an amount of N in methyl glucoside, dinethylformamide (DMF) is made catalyzer as solvent with cesium fluoride (CsF), triethylbenzene ammonium chloride, 110-130 ℃ of following stirring and refluxing 3～5h, after treating that its reaction finishes, cooling obtains the intermediate product after the methyl glucoside open loop; Add CeCl again
3, add NaBH simultaneously
4Or LiBH
4Make solvent with ethanol or tetrahydrofuran (THF), stir 0.5～2h, after treating that it fully reacts, steaming desolventizes, the thick product of quercitol, can adopt column chromatography such as silica gel column chromatography to carry out purifies and separates again, make eluent with ethyl acetate, the leacheate that obtains is removed desolvate, obtain the higher quercitol of purity.
In order to improve productive rate, also can further optimize: at first in reaction solution (methyl glucoside), add an amount of DMF, make catalyzer, realize phase-transfer catalysis, obtain intermediate product with CsF and triethylbenzene ammonium chloride to its synthesis condition.The back is with HgCl
2Or Hg (OAc)
2Or Hg (NO2)
2Make catalyzer, add acetone and water (about 2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide act synergistically, and can improve the productive rate of intermediate product.In reaction solution, add CeCl then
3, add NaBH simultaneously
4Or LiBH
4, make solvent with ethanol or tetrahydrofuran (THF), stir 0.5～2h, treat that it fully reacts after, steaming desolventizes, and obtains the product quercitol; This product also can adopt column chromatography to carry out further purifies and separates, to obtain the higher quercitol of purity.
Second step: synthesizing cyclohexane 1 pentol phosphoric acid ester.With quercitol respectively with the phosphoric acid of different amounts and the mixture reaction of Vanadium Pentoxide in FLAKES, be heated to 90～150 ℃, the 4～6h that refluxes can obtain the quercitol phosphate product of different phosphatization degree.Adopt phosphoric acid and Vanadium Pentoxide in FLAKES to do raw material in this step, avoid using sulfuric acid to make catalyzer, Vanadium Pentoxide in FLAKES plays katalysis simultaneously, and the phosphoric acid ester productive rate can reach 90%.By the charging capacity ratio of adjustment phosphoric acid with Vanadium Pentoxide in FLAKES, and the method that adopts substep to add raw material, can make synthetic quercitol phosphate product comparatively single.
Used quercitol can adopt according to the prepared product quercitol of this preparation method the first step in this step; Also can adopt by the quercitol of buying gained on the market is raw material, directly carries out the synthetic of second step of this preparation method.
The 3rd step: synthesizing cyclohexane 1 pentol phosphate amine salt.With quercitol phosphoric acid ester and straight chain or contain the amine neutralization of side chain, can obtain quercitol phosphate amine salt product.By controlling kind that different reaction conditionss, raw material add scheme and amine, ratio etc., can obtain different quercitol phosphate amine salt products.
Character according to different amine salt, can adopt diverse ways to separate in the quercitol phosphate amine salt autoreaction liquid, one is according to the phase transition principle, reach after the threshold concentration assembling on the two-phase interface with polynary phosphate amine salt and to be separated after agglomerating, as the separation to quercitol phosphoric acid ester bay amine salt etc., its separation rate can reach 90%; It two (needs to add before the 3rd step neutralization reaction carrying out for adopting magnesium oxide to make precipitation agent, treat its reaction back filtering precipitation, again filtrate and amine are carried out neutralization reaction), the realization inorganic precipitation separates, as separation to quercitol phosphoric acid ester diisopropyl amine salt etc., after exploring the optimized Separation condition, its separation rate can reach 95%.
R in the above-mentioned general formula (I)
1And R ' can be selected from primary octadecylamine, lauryl amine, propylamine, N-hydroxyl amber imines, Isopropylamine, normal hexyl Amine, Diisopropylamine, decamethylene diamine, butanediamine or hexanediamine etc.Further, the R in the general formula (I)
2And R
3It can be identical group.Further ,-PO (OH)
2R
1And R
2, R
3It can be identical group.
Compared with prior art, the invention has the beneficial effects as follows: the preparation method of (1) ring second of the present invention pentol phosphate amine salt is simple, easy handling.(2) raw material that is adopted is common is easy to get, with low cost.(4) refuse that produces in building-up process is few, and is less to the pollution of environment.
Description of drawings
Fig. 1 is the basic structure of quercitol phosphate amine salt of the present invention, i.e. general formula (I).
Fig. 2 is the process flow sheet of quercitol phosphate amine salt synthetic of the present invention.Wherein, R
4And R
5Can be the same or different, all can be selected from-H or-PO (OH)
2
Embodiment
The present invention is described in further detail below in conjunction with embodiment.
Embodiment 1
Method by present embodiment prepares quercitol phosphoric acid ester N-hydroxyl amber inferior amine salt, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add about 6g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 4h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 80ml, combining extraction liquid adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with Hg (NO
2)
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With LiBH
4Ethanolic soln, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: the quercitol that adds 0.05mol to there-necked flask, the phosphoric acid and an amount of Vanadium Pentoxide in FLAKES that add 0.05mol, heat 90～150 ℃, 4～6h refluxes, obtain monobasic phosphoric acid ester and other mixture of products of quercitol, this mixture is dissolved in the dehydrated alcohol, add appropriate MgO, filtration under diminished pressure behind stirring 20～40min, filtrate is the ethanol solution of quercitol phosphoric acid ester.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: adopt the dropping mode, in 0.001mol quercitol phosphoric acid ester ethanol solution, add 0.001mol N-hydroxyl amber imines ethanol solution, place and stir 30～60min on the magnetic stirring apparatus, keeping Heating temperature is 50～70 ℃, the control pH value, when treating pH ≈ 7, react complete substantially, promptly obtain the ethanol solution of quercitol phosphoric acid ester N-hydroxyl amber inferior amine salt, steaming desolventizes, and promptly obtains solid end product quercitol phosphoric acid ester N-hydroxyl amber inferior amine salt.
Embodiment 2
Method by present embodiment prepares three quercitol phosphoric acid ester N-hydroxyl amber inferior amine salts, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 5.72g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 3h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 70ml, combining extraction liquid adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with HgCl
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With NaBH
4THF solution, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: the quercitol that adds 0.05mol to there-necked flask, the phosphoric acid and an amount of Vanadium Pentoxide in FLAKES that add 0.15mol, heat 90～150 ℃, 4～6h refluxes, obtain ternary phosphoric acid ester and other mixture of products of quercitol, this mixture is dissolved in the dehydrated alcohol, add appropriate MgO, filtration under diminished pressure behind stirring 20～40min, filtrate is the ethanol solution of quercitol phosphoric acid ester.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: adopt the dropping mode, in 0.001mol quercitol phosphoric acid ester ethanol solution, add 0.001mol N-hydroxyl amber imines ethanol solution, place and stir 30～60min on the magnetic stirring apparatus, keeping Heating temperature is 50～70 ℃, the control pH value, when treating pH ≈ 7, after the basic end of reaction, the N-hydroxyl amber imines that adds 0.002mol again, with the dehydrated alcohol is solvent, in the time of 50～70 ℃, continue reaction 30～60min, treat pH value ≈ 10～11 o'clock, reaction finishes, and promptly obtains the ethanol solution of three quercitol phosphoric acid ester N-hydroxyl amber inferior amine salts, steaming desolventizes, and promptly obtains solid end product three quercitol phosphoric acid ester N-hydroxyl amber inferior amine salts.
Embodiment 3
Method by present embodiment prepares quercitol phosphoric acid ester diisopropyl amine salt, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 5g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 3h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 2 times, use CHCl at every turn
3About 70ml adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride.In reaction solution, add then and be dissolved with CeCl
3With LiBH
4THF solution, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: the quercitol that adds 0.05mol to there-necked flask, the phosphoric acid and an amount of Vanadium Pentoxide in FLAKES that add 0.10mol, heat 90～150 ℃, 4～6h refluxes, obtain binary phosphoric acid ester and other mixture of products of quercitol, this mixture is dissolved in the dehydrated alcohol, add appropriate MgO, filtration under diminished pressure behind stirring 20～40min, filtrate is the ethanol solution of quercitol phosphoric acid ester.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: adopt the dropping mode, in 0.001mol quercitol phosphoric acid ester ethanol solution, add 0.001mol Diisopropylamine ethanol solution, place and stir 30～60min on the magnetic stirring apparatus, keeping Heating temperature is 50～70 ℃, and the control pH value is when treating pH ≈ 8, react complete substantially, promptly obtain the ethanol solution of quercitol phosphoric acid ester diisopropyl amine salt, steaming desolventizes, and promptly obtains solid end product quercitol phosphoric acid ester diisopropyl amine salt.
Embodiment 4
Method by present embodiment prepares three quercitol phosphoric acid ester diisopropyl amine salt, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 4g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 2h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 60ml adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with Hg (OAc)
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With NaBH
4Ethanolic soln, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: the quercitol that adds 0.05mol to there-necked flask, the phosphoric acid and an amount of Vanadium Pentoxide in FLAKES that add 0.15mol, heat 90～150 ℃, 4～6h refluxes, the ternary phosphoric acid ester of quercitol and other mixture of products are dissolved in this mixture in the dehydrated alcohol, add appropriate MgO, filtration under diminished pressure behind stirring 20～40min, filtrate is the ethanol solution of quercitol phosphoric acid ester.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: adopt the dropping mode, in 0.001mol quercitol phosphoric acid ester ethanol solution, add 0.001mol Diisopropylamine ethanol solution, place and stir 30～60min on the magnetic stirring apparatus, keeping Heating temperature is 50～70 ℃, the control pH value, treat pH ≈ 8, after the basic end of reaction, adding the Diisopropylamine of 0.002mol again, is solvent with the dehydrated alcohol, in the time of 50～70 ℃, continue reaction 30～60min, treat pH value ≈ 10～11 o'clock, reaction finishes, and promptly obtains the ethanol solution of three quercitol phosphoric acid ester diisopropyl amine salt, steaming desolventizes, and promptly obtains solid end product three quercitol phosphoric acid ester diisopropyl amine salt.
Embodiment 5
By with embodiment 1 and 3 in identical method prepare quercitol phosphoric acid ester normal hexyl Amine salt, the amine that difference adds when only being final step synthesizing cyclohexane 1 pentol phosphate amine salt is normal hexyl Amine, the amount ratio of quercitol phosphoric acid and normal hexyl Amine is about 1: 1.
Embodiment 6
By with embodiment 2 and 4 in identical method prepare three quercitol phosphoric acid ester normal hexyl Amine salt, the amine that difference adds when only being final step synthesizing cyclohexane 1 pentol phosphate amine salt is normal hexyl Amine, the amount ratio of quercitol phosphoric acid and normal hexyl Amine is about 1: 3.
Embodiment 7
Method by present embodiment prepares quercitol phosphoric acid ester bay amine salt, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 8g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 3h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 70ml adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with HgCl
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With NaBH
4Ethanolic soln, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: add the quercitol of 0.05mol to there-necked flask, add phosphoric acid and an amount of Vanadium Pentoxide in FLAKES of 0.05mol, heat 90～150 ℃, the 4～6h that refluxes obtains monobasic phosphoric acid ester and other mixture of products of quercitol.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: second mixture that make of step removed desolvate, be dissolved in an amount of dehydrated alcohol, add the lauryl amine ethanol solution, the add-on of lauryl amine is about 1: 1 with the molar weight ratio of quercitol phosphoric acid ester, is heated to 50～60 ℃, stirs 20～30min postcooling, add less water, produce phase transition behavior, separate out aggregation, this aggregation is quercitol phosphoric acid ester bay amine salt.
Embodiment 8
Method by present embodiment prepares two quercitol lauryl amine phosphoric acid ester N-hydroxyl amber inferior amine salts, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 7g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 3h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 70ml adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with HgCl
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With NaBH
4Ethanolic soln, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: add the quercitol of 0.05mol to there-necked flask, add phosphoric acid and an amount of Vanadium Pentoxide in FLAKES of 0.15mol, heat 90～150 ℃, the 4～6h that refluxes obtains ternary phosphoric acid ester and other mixture of products of quercitol.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: second mixture that make of step removed desolvate, be dissolved in an amount of dehydrated alcohol, add the lauryl amine ethanol solution, the add-on of lauryl amine is about 1: 1 with the molar weight ratio of quercitol phosphoric acid ester, be heated to 50～60 ℃, stir 20～30min postcooling, add less water, produce phase transition behavior, the aggregation of this process is quercitol phosphoric acid ester bay amine salt.About 0.001mol is dissolved in an amount of ethanol-cyclohexane solution with this quercitol phosphoric acid ester bay amine salt, again to the ethanol solution that wherein adds about 0.002mol N-hydroxyl amber imines, make it in the time of 50～70 ℃, to continue reaction 30～60min, treat pH value ≈ 10～11 o'clock, react completely, get precipitate, be end product two quercitol lauryl amine phosphoric acid ester N-hydroxyl amber inferior amine salts.
Embodiment 9
Method by present embodiment prepares two quercitol primary octadecylamine phosphoric acid ester N-hydroxyl amber inferior amine salts, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 7g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 3h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 80ml adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with Hg (OAc)
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With LiBH
4THF solution, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: add the quercitol of 0.05mol to there-necked flask, add phosphoric acid and an amount of Vanadium Pentoxide in FLAKES of 0.15mol, heat 90～150 ℃, the 4～6h that refluxes obtains ternary phosphoric acid ester and other mixture of products of quercitol.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: second mixture that make of step removed desolvate, be dissolved in an amount of dehydrated alcohol, add the primary octadecylamine ethanol solution, the add-on of primary octadecylamine is about 1: 1 with the molar weight ratio of quercitol phosphoric acid ester, be heated to 50～60 ℃, stir 20～30min postcooling, add less water, produce phase transition behavior, the aggregation of this process is quercitol phosphoric acid ester primary octadecylamine salt.About 0.001mol is dissolved in an amount of ethanol-cyclohexane solution with this quercitol phosphoric acid ester primary octadecylamine salt, again to the ethanol solution that wherein adds about 0.002mol N-hydroxyl amber imines, place and stir 30～60min on the magnetic stirring apparatus, keeping Heating temperature is 50～70 ℃, the control pH value when treating pH ≈ 7, reacts completely, get precipitate, be end product two quercitol primary octadecylamine phosphoric acid ester N-hydroxyl amber inferior amine salts.
Embodiment 10
Method by present embodiment prepares two quercitol primary octadecylamine phosphoric acid ester diisopropyl amine salt, may further comprise the steps:
(1), synthesizing cyclohexane 1 pentol: in there-necked flask, add 5.72g glucose, 2ml methyl alcohol, 20ml THF; Under whipped state, drip the 2ml vitriol oil, drip Bi Jixu stir about 3h,, steam and remove THF with pH value to 9～10 that the 40%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out; Use CHCl
3Extract 3 times, use CHCl at every turn
3About 70ml adds an amount of K
2CO
3Carry out drying; Steam then and remove CHCl
3, adopt silica gel column chromatography to separate residuum, with CHCl
3As eluent, the leacheate that obtains removed desolvate, obtain dope, i.e. methyl glucoside.In methyl glucoside, add 30mlDMF, make catalyzer, realize phase-transfer catalysis, obtain the intermediate product after the methyl glucoside open loop with The addition of C sF and triethylbenzene ammonium chloride; The back is with Hg (NO
2)
2Make catalyzer, add acetone and water (2: 1) and make solvent, and add an amount of thiocarbamide, mercury and thiocarbamide synergy are to improve the productive rate of intermediate product.In reaction solution, add then and be dissolved with CeCl
3With LiBH
4Ethanolic soln, treat that it fully reacts after, steaming desolventizes, and can obtain the thick product of quercitol, separates through silica gel column chromatography again, can obtain the higher quercitol of purity.
(2), synthesizing cyclohexane 1 pentol phosphoric acid ester: add the quercitol of 0.05mol to there-necked flask, add phosphoric acid and an amount of Vanadium Pentoxide in FLAKES of 0.15mol, heat 90～150 ℃, the 4～6h that refluxes obtains ternary phosphoric acid ester and other mixture of products of quercitol.
(3), synthesizing cyclohexane 1 pentol phosphate amine salt: second mixture that make of step removed desolvate, be dissolved in an amount of dehydrated alcohol, add the lauryl amine ethanol solution, the add-on of lauryl amine is about 1: 1 with the molar weight ratio of quercitol phosphoric acid ester, be heated to 50～60 ℃, stir 20～30min postcooling, add less water, produce phase transition behavior, the aggregation of this process is quercitol phosphoric acid ester bay amine salt.About 0.001mol is dissolved in an amount of ethanol-cyclohexane solution with this quercitol phosphoric acid ester bay amine salt, again to the ethanol solution that wherein adds about 0.002mol Diisopropylamine, place and stir 30～60min on the magnetic stirring apparatus, keeping Heating temperature is 50～70 ℃, the control pH value when treating pH ≈ 7, reacts completely, get precipitate, be end product two quercitol primary octadecylamine phosphoric acid ester diisopropyl amine salt.
With same method, the different phosphoric acid add-on of control in second step of concrete preparation process, and in the 3rd step, add different amines, can also obtain a series of different quercitol phosphate amine salts.As:
Two quercitol phosphoric acid ester N-hydroxyl amber inferior amine salts, two quercitol phosphoric acid ester diisopropyl amine salt, quercitol phosphoric acid ester propylamine salt, two quercitol phosphoric acid ester propylamine salt, three quercitol phosphoric acid ester propylamine salt, quercitol phosphoric acid ester primary octadecylamine salt, two quercitol phosphoric acid ester primary octadecylamine salt, three quercitol phosphoric acid ester primary octadecylamine salt, quercitol phosphoric acid ester isopropyl amine salt, three quercitol phosphoric acid ester isopropyl amine salts, quercitol phosphoric acid ester decamethylene diamine salt, three quercitol phosphoric acid ester decamethylene diamine salt, quercitol phosphoric acid ester butanediamine salt, three quercitol phosphoric acid ester butanediamine salt, quercitol phosphoric acid ester hexanediamine salt, three quercitol phosphoric acid ester hexanediamine salt or the like.
Claims (9)
1. the preparation method of a quercitol phosphate amine salt, this quercitol phosphate amine salt is the compound by general formula (I) expression:
Wherein, R
1Be selected from carbon atom number and be 3～18 amine;
R
2And R
3Be selected from-H or-PO (OH)
2, or-PO (OH)
2R '; Wherein, to be selected from carbon atom number be 3～18 amine to R ';
The preparation method of this compound may further comprise the steps:
The first step: synthesizing cyclohexane 1 pentol: get glucose, add an amount of methyl alcohol, add solvents tetrahydrofurane again, be mixed with the glucose tetrahydrofuran solution of 20～40g/100ml; Drip the vitriol oil under whipped state, the add-on of the vitriol oil is 1/8～1/12 of a tetrahydrofuran solution volume, dropwises the back and continues to stir 2～4h; With pH value to 9～10 that 30～50%NaOH aqueous solution is transferred reaction mixture, the white solid that filtering is separated out, steam and remove tetrahydrofuran (THF); With chloroform extraction 2～3 times, combining extraction liquid adds an amount of K
2CO
3Dry; Steam except that behind the trichloromethane, obtain dope, i.e. methyl glucoside; Add an amount of N in methyl glucoside, dinethylformamide is made catalyzer as solvent with cesium fluoride, triethylbenzene ammonium chloride, 110-130 ℃ of following stirring and refluxing 3～5h, after treating that its reaction finishes, cooling obtains the intermediate product after the methyl glucoside open loop; Add CeCl again
3, add NaBH simultaneously
4Or LiBH
4, make solvent with ethanol or tetrahydrofuran (THF), stir 0.5～2h, treat that it fully reacts after, steaming desolventizes, products therefrom is quercitol;
Second step: synthesizing cyclohexane 1 pentol phosphoric acid ester: with quercitol respectively with the phosphoric acid of different amounts and the mixture reaction of Vanadium Pentoxide in FLAKES, be heated to 90～150 ℃, the 4～6h that refluxes can obtain the quercitol phosphate product of different phosphatization degree;
The 3rd step: synthesizing cyclohexane 1 pentol phosphate amine salt: quercitol phosphoric acid ester and straight chain or the amine that contains side chain are neutralized, can obtain quercitol phosphate amine salt product.
2. the preparation method of quercitol phosphate amine salt according to claim 1 is characterized in that: in the process of described the first step synthesizing cyclohexane 1 pentol, with chloroform extraction and use K
2CO
3The methyl glucoside that obtains after the drying can adopt column chromatography to carry out purifies and separates, the reaction after continuing again.
3. the preparation method of quercitol phosphate amine salt according to claim 2 is characterized in that: described column chromatography is a silica gel column chromatography, and makes eluent with trichloromethane, the leacheate that obtains is removed desolvate, and promptly gets the higher methyl glucoside of purity.
4. the preparation method of quercitol phosphate amine salt according to claim 1, it is characterized in that: in the process of described the first step synthesizing cyclohexane 1 pentol, in methyl glucoside, add an amount of N, dinethylformamide is as solvent, make catalyzer with cesium fluoride, triethylbenzene ammonium chloride, 110-130 ℃ of following stirring and refluxing 3～5h, treat that its reaction finishes after, again with HgCl
2Or Hg (OAc)
2Or Hg (NO
2)
2Make catalyzer, the adding volume ratio is that 2: 1 acetone-water is made solvent, and adds an amount of thiocarbamide; Treat that it fully reacts the back and add CeCl in reaction solution
3, add NaBH simultaneously
4Or LiBH
4, make solvent with ethanol or tetrahydrofuran (THF), stir 0.5～2h, treat that it fully reacts after, steaming desolventizes, and obtains quercitol.
5. the preparation method of quercitol phosphate amine salt according to claim 4 is characterized in that: resulting quercitol can adopt column chromatography to carry out further purifies and separates again.
6. the preparation method of quercitol phosphate amine salt according to claim 5 is characterized in that: described column chromatography is a silica gel column chromatography, and makes eluent with ethyl acetate, the leacheate that obtains is removed desolvate, and promptly gets the higher quercitol of purity.
7. the preparation method of quercitol phosphate amine salt according to claim 1 is characterized in that: R wherein
1And R ' is selected from primary octadecylamine, lauryl amine, propylamine, N-hydroxyl amber imines, Isopropylamine, normal hexyl Amine, Diisopropylamine, decamethylene diamine, butanediamine or hexanediamine.
8. the preparation method of quercitol phosphate amine salt according to claim 1 is characterized in that: R wherein
2And R
3It is identical group.
9. the preparation method of quercitol phosphate amine salt according to claim 1 is characterized in that: wherein-PO (OH)
2R
1And R
2, R
3It is identical group.
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| Cleophax,Jeannine, Verre-Sebrie, Catherine, Pipelier, Muriel,Prestat,Guillaume, Vass, Georges, Gero, Stephane D.Stereoselective synthesis of inositol mono-, bis-andtrisphosphate analogs from 6-deoxy-D-inositol precursors.. De Almeida, Mauro Vieira, Dubreuil, Didier,Cleophax,Jeannine, Verre-Sebrie, Catherine, Pipelier, Muriel,Prestat,Guillaume, Vass, Georges, Gero, Stephane D.Tetrahedron,Vol.55 No.23. 1999 * |
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