CN102702209B - Quaternary cationic quaternary ammnonium and preparation method thereof - Google Patents
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Abstract
The invention relates to a quaternary cationic quaternary ammnonium and a synthesis method thereof. According to the synthesis method, the target product is synthesized in one step from hexamethylenetetramine and organic halide serving as materials in the absence of solvent or corresponding solve, in the presence of corresponding catalysts, under certain temperature, pressure, atmosphere protection and stirring conditions. The synthesis method has the advantages of less synthesis steps, mild reaction conditions, simpleness and convenience in operation and no pollution; the obtained target product has the characteristics of high surface activity, strong sterilizing power, wide stem grafting, low toxicity, good stability and the like. The quaternary cationic quaternary ammnonium can be used in fields of daily chemical industry, food industry, textile, material and the like.
Description
Technical field
The present invention relates to a kind of four cation quaternary ammonium salts and preparation method thereof, particularly a kind of take vulkacit H as four cation quaternary ammonium salts of skeleton and preparation method thereof.
Technical background
Quaternary ammonium salt is one of widely used sterilant, and the bactericidal property of quaternary ammonium salt and its molecular structure closely related, the experimental results shows, but there is stronger absorption containing the quaternary ammonium salt of multiple Nitrenium ion to microorganism and kill ability (Garacia-Rsao A., et. al. A study of structure-activity relationships of quaternary ammonium salts. Anales de Quimica, Serie C:Quimica Organica y Bioquimica, 1981,77 (1): 12-18).Therefore, polycationic quaternary ammonium salt has become one of focus of current sterilant research and development, and the non-polymeric polycationic quaternary ammonium salt now containing Nitrenium ion number maximum is three cation quaternary ammonium salt.
Current three cation quaternary ammonium salt and preparation method thereof mainly contains following several:
In first method one: with bromododecane, 3 chloro-1-propyl alcohol, methylamine, Dodecyl Dimethyl Amine for raw material, three cation quaternary ammonium salt (Langmuir R. Zana is prepared by quaterisation, H.Levy, D. Papoutsi, G. Beinert. Micellization of two triquaternary ammonium surfactants in aqueous solution.Langmuir, 1995,11:3694-3698).This preparation method need divide four steps to carry out, and each step reaction conditions requires harsher, and low conversion rate, total cost is higher.
At first method two: with bromododecane, pentamethyl-diethylenetriamine for raw material, a series of single cation quaternary ammonium salt, dication quaternary ammonium salt, three cation quaternary ammonium salt (Kunio Esumi is prepared by quaterisation, Kazuhiro Taguma, Yoshifumi Koide. Aqueous properties of multichain quaternary cationic surfactants. Langmuir, 1996,12:4039-4041).This method can prepare different quaternary ammonium salts, but comparatively disperses due to electric charge positive and negative in its structure, make its surfactivity and bactericidal properties not so good.
In first method three: with bromo-octadecane, Tetramethyl Ethylene Diamine, 3-bromopropyl trimethylammonium bromide for raw material, octadecyl three cation quaternary ammonium salt (Shaodian Shen is prepared by quaterisation, Bozhi Tian, Chengzhou Yu, etc.Synthesis of highly ordered thermally stable cubic mesostructured zirconium oxphosphate templated by tri-headgroup quaternary ammonium surfactant. Chem.Mater, 2003,15:4046-4051).Though the method is novel, need carry out in two steps, product purity is not high, low conversion rate.
In first method four: with citric acid, higher aliphatic tertiary amine and epoxy haloalkane for raw material, prepare citrate tri-long-chain alkyl three quaternary cationics by one pot reaction, publication number CN 1778459A.2006-05-31).This method one step obtains three cation quaternary ammonium salt, but its product purity is lower, and acid-and base-resisting is poor, limits its application.
In first method five: with substituting group Soxylat A 25-7, epoxy alkyl chloride and pentamethyl-diethylenetriamine for raw material, a series of three Soxylat A 25-7 chain three cation quaternary ammonium salt (Xue Yongqiang are obtained, Zhang Junfeng, Tang Zhiping. polyoxyethylene chain three cation quaternary ammonium salt and synthetic method thereof. Chinese patent .CN 100415355C.2008-09-03).This method is carried out in two steps, and obtained three cation quaternary ammonium salt has good water-soluble and surfactivity, but the more difficult separation of its product, and overall yield is lower.
In existing disclosed document, three cation quaternary ammonium salt molecule is linearity molecular structure, and positive and negative electric charge comparatively disperses, and makes its surfactivity and bactericidal property excellent not.Positive and negative electric charge is comparatively concentrated, and four cation quaternary ammonium salts with stereo chemical structure have not been reported, and the performance that the polycationic quaternary ammonium salt of this structure has simultaneously that surfactivity is high, sterilizing power strong, good stability etc. is excellent.
Summary of the invention
The technical problem to be solved in the present invention is the quaternary ammonium salt of the polycation preparing a kind of charge concentration, to improve intensity and the intensity of positive and negative electric charge, makes it have excellent surfactivity, efficiently sterilizing ability and satisfactory stability, and provides
oneplant four cation quaternary ammonium salts and synthetic method thereof.
One four cation quaternary ammonium salt proposed by the invention, its general structure is as follows:
Wherein: R is the groups such as alkyl, benzyl, organosilicon radical or substituting group polyether chain, and X is halogen.
A kind of preparation method for above-mentioned four cation quaternary ammonium salts of the present invention, method described in it follows these steps to carry out:
With vulkacit H and Organohalogen compounds for raw material, during selective solvent reaction, Organohalogen compounds consumption be the 4-6 of vulkacit H amount of substance doubly, solvent load be the 3-8 of vulkacit H volume doubly; When selecting solvent-free reaction, Organohalogen compounds add-on is 6-8 times of vulkacit H volume; Under mixed catalyst catalysis, nitrogen atmosphere protection and agitation condition, synthesis under normal pressure temperature is 60 ~ 120 DEG C, and under pressurized conditions, temperature of reaction is 60 ~ 160 DEG C, reacts 10 ~ 48 hours; After reaction terminates, mixing solutions is cooled to room temperature, leaves standstill 12 ~ 24 hours, product sufficient crystallising is separated out; Then filter and obtain white solid; By washed with dichloromethane, be drying to obtain four described cation quaternary ammonium salts; Mother liquor after filtration is capable of circulation to be applied mechanically; Reusable edible after the methylene dichloride that washings after washing distills out, the residuum after distillation is a small amount of solvent, unreacted reactant and catalyzer can be applied mechanically in recirculation.
In technique scheme, technical characteristic additional described in it is: described solvent is the mixing of one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetonitrile and tetrahydrofuran (THF); Composition and the content thereof of described mixed catalyst are: quaternary ammonium salt is the 0-3% of vulkacit H quality, and iodide are the 1-3% of vulkacit H quality, and water is the 0-2% of vulkacit H quality; The washings of described washing is methylene dichloride.
A kind of four cation quaternary ammonium salts provided by the present invention and preparation method thereof, compared with prior art, there is following characteristics: the positive and negative electric charge of described four cation quaternary ammonium salt is comparatively concentrated, and there is high, the very strong bactericidal property of very high surfactivity and good stability; The features such as described synthetic method has that cheaper starting materials is easy to get, reactions steps is few, reaction conditions is gentleer, easy and simple to handle, productive rate is high, purity is high, mother liquor is capable of circulationly applied mechanically, non-environmental-pollution.
Embodiment
Below the specific embodiment of the present invention is made an explanation.
Implement a kind of four cation quaternary ammonium salts of the present invention, its general structure is as follows:
Wherein: R is the groups such as alkyl, benzyl, organosilicon radical or substituting group polyether chain, and X is halogen.
Implement a kind of preparation method for above-mentioned four cation quaternary ammonium salts of the present invention, be with vulkacit H and Organohalogen compounds for raw material, under solvent-free or coordinative solvent, corresponding catalyst and certain temperature, pressure, atmosphere protection and agitation condition, generate described four cation quaternary ammonium salts through quaterisation certain hour; Then through cooling, leave standstill, crystallization, filtration, washing and drying obtain described four cation quaternary ammonium salts.Its reaction formula is as follows:
In the preparation method of above-mentioned four cation quaternary ammonium salts, the haloalkane that Organohalogen compounds are 12-18 as selection carbonatoms can obtain four long-chain four cation quaternary ammonium salts with efficient sterilizing; Organohalogen compounds are as the four cationic quaternary ammonium bactericides selecting the Benzyl Chloride or derivatives thereof of the alkyl chain containing carbonatoms 12-18 can obtain high-efficiency low-toxicity more; Organohalogen compounds can obtain the four cationic silicones quaternary ammonium salt coupling agents with premium properties as selected γ-r-chloropropyl trimethoxyl silane and so on halogenated silanes; Organohalogen compounds have good aqueous solubility and surface-active four cation quaternary ammonium salt type surfactants as selected the halogenide of polyethers to obtain; Organohalogen compounds can obtain the quaternary ammonium salt of eight positively charged ions even more polycation containing the quaternary ammonium salt of halo group as selected.During selective solvent reaction, the mol ratio of quaternizing agent and vulkacit H is 4-6; When selecting solvent-free reaction, be using excessive reactant quaternizing agent as solvent, the add-on of its quaternizing agent is 6-8 times of added vulkacit H volume.
In the preparation method of above-mentioned four cation quaternary ammonium salts, described coordinative solvent is strong polar organic solvent, consider solvent separation after the reaction and recovery, the mixture of one or more in prioritizing selection methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetonitrile or tetrahydrofuran (THF); The add-on of solvent is 3-8 times of added vulkacit H volume.
In the preparation method of above-mentioned four cation quaternary ammonium salts, institute's spent mixed catalyst is the mixture of quaternary ammonium salt, iodide and water; The wherein preferred Tetrabutyl amonium bromide of quaternary ammonium salt, cetyl trimethylammonium bromide, dodecyl dimethyl benzyl ammonium chloride, the two common quaternary surfactant such as octadecyldimethyl ammonium, octadecyldimethyl hydroxyethyl ammonium nitrate of bromination; Wherein iodide are potassiumiodide, sodium iodide or quaternary ammonium iodide salt.Its consumption is respectively: quaternary ammonium salt is the 0-3% of vulkacit H quality, and iodide are the 1-3% of vulkacit H quality, and water is the 0-2% of vulkacit H quality.
In the preparation method of above-mentioned four cation quaternary ammonium salts, temperature of reaction is relevant with pressure; Under normal pressure, temperature of reaction is 60 ~ 120 DEG C; Under pressurized conditions, temperature of reaction is 60 ~ 160 DEG C, preferably 120 ~ 160 DEG C.
In the preparation method of above-mentioned four cation quaternary ammonium salts, in reaction process, nitrogen atmosphere is preferably selected to protect, to reduce the oxidation of raw material in reaction process.
In the preparation method of above-mentioned four cation quaternary ammonium salts, the reaction times is 10 ~ 48 hours.
In the preparation method of above-mentioned four cation quaternary ammonium salts, after reaction terminates, mixing solutions is cooled to room temperature, leaves standstill 12 ~ 24 hours, product sufficient crystallising is separated out; Then filter and obtain white solid; By washed with dichloromethane, be drying to obtain four described cation quaternary ammonium salts; Mother liquor after filtration is capable of circulation to be applied mechanically; Reusable edible after the methylene dichloride that washings after washing distills out, the residuum after distillation is a small amount of solvent, unreacted reactant and catalyzer can be applied mechanically in recirculation.
Below by specific embodiment, the specific embodiment of the present invention is further detailed.
Embodiment 1
Implement the preparation method of a kind of four cation quaternary ammonium salts of the present invention, for raw material is through obtained four cation quaternary ammonium salts of single step reaction with vulkacit H and Organohalogen compounds, compared with other preparation methods current, its feature is mainly that it is simple to operate, products collection efficiency and purity higher, cost is lower; In the four cation quaternary ammonium salt molecular structures prepared, positive and negative electric charge is comparatively concentrated and its intensity is comparatively large, has high, the very strong bactericidal property of very high surfactivity and stability preferably.
Concrete preparation method is as follows:
Select raw material to be: vulkacit H, bromododecane, methylene dichloride, Tetrabutyl amonium bromide and potassiumiodide, these raw materials are commercially available technical pure; Wherein select vulkacit H for raw material be due to its can provide there is three-dimensional arrangement and mutual alignment comparatively concentrate four three grades of nitrogen-atoms, have not been reported in other documents and patented technology.
First in the four-hole boiling flask of 250ml that thermometer, reflux condensing tube, dropping funnel and nitrogen protection device are housed; add the methanol solvate that 1.40 grams of volumes are about the vulkacit H of 13ml, 12.45 grams of bromododecanes, 0.02 gram of Tetrabutyl amonium bromide, 0.02 gram of potassiumiodide, 0.02 gram of water and 70ml; reflux temperature is heated under induction stirring; under nitrogen protection, continuously stirring back flow reaction 24 hours.Reaction times and temperature are general organic preparation condition, and without special conditions requirement, in above process, equipment used is common Preparation equipment, also without the need to operation in reactions steps.After reaction terminates, first cool the mixture after standing and reacting, filter after white solid product sufficient crystallising is separated out, obtain white solid product.Filtrate is capable of circulation herein applies mechanically, and the discharge that so there is no waste liquid decreases the pollution to environment simultaneously, and the product purity obtained so comparatively distillation method is high, and saves the energy, without the need to complex operations.Then the white solid product will obtained, with washed with dichloromethane 2-3 time, then obtain 11.55 grams of white solids through oven drying, be four cation quaternary ammonium salts that target product contains four dodecyl chains, product purity is more than 99%, yield 83.4%.Its chemical structural formula is as follows:
The quaternary ammonium salt productive rate that this method obtains comparatively additive method to prepare quaternary ammonium salt high, and purity is high.Reusable edible after the methylene dichloride that washings after washing distills out, the residuum after distillation is a small amount of solvent, unreacted reactant and catalyzer can be applied mechanically in recirculation, because this reducing the discharge of refuse and the pollution to environment, also saves cost simultaneously.This preparation process has only simply carried out single step reaction, comparatively saves labor cost and raw materials cost.With reference to the method for GB/T 5555-2003, the acid-and base-resisting of target product is measured, it is resistance to for result, soda acid grade is one-level.Under the aseptic condition of 50 DEG C, in 5 culture dish, pour agar solution into respectively, and require that it includes agar solution 15ml at the area of diameter 9cm; And then cool under room temperature, solidification; Respectively the Escherichia coli bacteria liquid of 105 of 5 parts of 0.2ml/ml is applied to the agar media surface of above-mentioned 5 culture dish; The sample getting 5 parts of 10mg is again placed in 5 culture dish respectively; Cultivate 48 hours at 36-37 DEG C; Measure and record the diameter of inhibition zone, result product is 31.30cm to colibacillary average antibacterial circle diameter.Therefore, four cation quaternary ammonium salts containing four dodecyl chains that this preparation process provides have stronger stability and bactericidal properties.
The preparation process of embodiment 2-8 is substantially the same manner as Example 1, and therefore following examples repeat no more its detailed preparation process, only its difference from Example 1 is explained.
Embodiment 2
Raw material is selected to be: Benzyl Chloride, vulkacit H, methylene dichloride, ethanol and tetrabutylammonium iodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, Benzyl Chloride is 6.33 grams, tetrabutylammonium iodide is 0.02 gram, alcohol solvent is 70ml, and temperature of reaction is the reflux temperature of ethanol, and the reaction times is 30 hours, and other are with the preparation process in embodiment 1.Finally obtain 6.58 grams of four cation quaternary ammonium salts containing four Benzyl Chlorides, yield 85.1%, yield is slightly high compared with the product yield of preparation in embodiment 1.Its chemical structural formula is as follows:
The methanol solvate polarity provided in the present embodiment is comparatively large, is conducive to the carrying out promoting reaction, improves productive rate, reduce energy consumption.What this preparation process provided also has stronger bactericidal properties and stability (be 37.20cm to colibacillary antibacterial circle diameter, acid and alkali-resistance grade is one-level) containing four cation quaternary ammonium salts of four Benzyl Chlorides.
Embodiment 3
Raw material is selected to be: 2-ethylmercury chloride benzyl, vulkacit H, Virahol, methylene dichloride, cetyl trimethylammonium bromide and sodium iodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, 2-ethylmercury chloride benzyl is 7.73 grams, cetyl trimethylammonium bromide 0.02 gram, sodium iodide are 0.02 gram, isopropanol solvent is 70ml, temperature of reaction is the reflux temperature of Virahol, reaction times is 26 hours, and other are with the preparation process in embodiment 1.Finally obtain 6.89 grams of four cation quaternary ammonium salts containing four 2-ethylmercury chloride benzyls, yield 84.7%.Its chemical structural formula is as follows:
The isopropanol solvent boiling point provided in the present embodiment is higher, is conducive to the carrying out promoting reaction, improves productive rate, reduce energy consumption.What this preparation process provided also has stronger bactericidal properties and stability (be 38.65cm to colibacillary antibacterial circle diameter, acid and alkali-resistance grade is one-level) containing four cation quaternary ammonium salts of four 2-ethylmercury chloride benzyls.
Embodiment 4
Raw material is selected to be: γ-r-chloropropyl trimethoxyl silane, vulkacit H, n-propyl alcohol, methylene dichloride, dodecyl dimethyl benzyl ammonium chloride and potassiumiodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, γ-r-chloropropyl trimethoxyl silane is 10.00 grams, dodecyl dimethyl benzyl ammonium chloride is 0.02 gram, potassiumiodide is 0.02 gram, water is 0.01 gram, n-propyl alcohol solvent is 70ml, temperature of reaction is the reflux temperature of n-propyl alcohol, reaction times is 35 hours, and other are with the preparation process in embodiment 1.Finally obtain 9.51 grams of four cation quaternary ammonium salts containing four Benzyl Chlorides, yield 83.7%.Its chemical structural formula is as follows:
The n-propyl alcohol solvent boiling point provided in the present embodiment is higher, is conducive to the carrying out promoting reaction, improves productive rate, reduce energy consumption.What this preparation process provided also has stronger bactericidal properties (be 35.40cm to colibacillary antibacterial circle diameter) containing four cation quaternary ammonium salts of four organosilicon radicals, in addition this four cationic silicones quaternary ammonium salt is due to containing organic functional silicon group, can be widely used in other field.
Embodiment 5
Raw material is selected to be: the two octadecyldimethyl ammonium of propylene oxide base alkylpolyoxyethylene (EO=5), vulkacit H, acetonitrile, dilute hydrochloric acid, methylene dichloride, bromination and potassiumiodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, propylene oxide base alkylpolyoxyethylene (EO=5) is 11.75 grams, dilute hydrochloric acid is 5ml, the two octadecyldimethyl ammonium of bromination is 0.02 gram, potassiumiodide is 0.02 gram, water is 0.02 gram, acetonitrile solvent is 70ml, temperature of reaction is the reflux temperature of acetonitrile, reaction times is 40 hours, and other are with the preparation process in embodiment 1.Finally obtain 8.92 grams of four cation quaternary ammonium salts containing four substituting group Soxylat A 25-7 chains, yield 82.6%.Its chemical structural formula is as follows:
The acetonitrile solvent polarity provided in the present embodiment is comparatively large, is conducive to the carrying out promoting reaction, improves productive rate, reduce energy consumption.What this preparation process provided has excellent surfactivity containing four substituting group Soxylat A 25-7 chain four cation quaternary ammonium salts (its concentration is 1 × 10
-4the surface tension of the aqueous solution of g/ml is reduced to 4.50 × 10
-3n/m).
Embodiment 6
Raw material is selected to be: γ-r-chloropropyl trimethoxyl silane, vulkacit H, tetrahydrofuran (THF), methylene dichloride, octadecyldimethyl hydroxyethyl ammonium nitrate and potassiumiodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, γ-r-chloropropyl trimethoxyl silane is 10.00 grams, octadecyldimethyl hydroxyethyl ammonium nitrate is 0.02 gram, potassiumiodide is 0.02 gram, tetrahydrofuran solvent is 70ml, under pressurized conditions, temperature of reaction is 160 DEG C, reaction times is 10 hours, and other are with the preparation process in embodiment 1.Finally obtain 9.97 gram of four cationic silicones quaternary ammonium salt, yield 87.7%.The structure of the four cationic silicones quaternary ammonium salts that this preparation process provides is with four cationic silicones quaternary ammonium salts in embodiment 4.
Embodiment 7
Raw material is selected to be: Benzyl Chloride (not only making solvent but also do quaternizing agent), methylene dichloride, vulkacit H and potassiumiodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, Benzyl Chloride is 20.50 grams, potassiumiodide is 0.02 gram, and temperature of reaction 85 DEG C, the reaction times is 25 hours, and other are with the preparation process in embodiment 1.Finally obtain 7.50 grams of four cation quaternary ammonium salts containing four Benzyl Chlorides, yield 88.5%, yield is slightly high compared with the product yield of preparation in embodiment 1; The solvent-free reaction preparation method provided in the present embodiment, is conducive to the carrying out promoting reaction, improves productive rate, reduce energy consumption.The structure of the four cationic silicones quaternary ammonium salts that this preparation process provides is with four cationic silicones quaternary ammonium salts in embodiment 1.
Embodiment 8
Raw material is selected to be: 3-bromopropyl trimethylammonium bromide, vulkacit H, methanol/ethanol mixed solvent (methanol/ethanol volume ratio is 3:7), methylene dichloride, Tetrabutyl amonium bromide and potassiumiodide, these raw materials are commercially available technical pure.
In preparation process, vulkacit H is 1.40 grams, 3-bromopropyl trimethylammonium bromide is 13.70 grams, Tetrabutyl amonium bromide is 0.02 gram, potassiumiodide is 0.02 gram, methanol/ethanol mixed solvent is 70ml, temperature of reaction is the reflux temperature of mixed solvent, reaction times is 25 hours, and other are with the preparation process in embodiment 1.Finally obtain 12.60 gram of eight cation quaternary ammonium salt, yield 89.4%.Its chemical structural formula is as follows:
The mixed solvent polarity provided in the present embodiment is comparatively large, is conducive to the carrying out promoting reaction, improves productive rate, reduce energy consumption.Eight cation quaternary ammonium salts that this preparation process provides also have stronger bactericidal properties and stability (be 39.70cm to colibacillary antibacterial circle diameter, acid and alkali-resistance grade is one-level).
Claims (3)
1. four cation quaternary ammonium salts, its general structure is as follows:
Wherein: R is benzyl, organosilicon radical or substituting group polyether chain group;
Described organosilicon radical is :-CH
2cH
2cH
2si (OCH
3)
3; Described substituting group polyether chain group is-CH
2cH (OH) CH
2(C
2h
4o)
5oC
12h
25, X is Cl simultaneously
-.
2. a preparation method for four cation quaternary ammonium salts according to claim 1, described in it, method is as follows:
With vulkacit H and Organohalogen compounds for raw material, react having under solvent or condition of no solvent, when selecting there is solvent reaction, Organohalogen compounds consumption be the 4-6 of vulkacit H amount of substance doubly, solvent load be the 3-8 of vulkacit H volume doubly; When selecting solvent-free reaction, Organohalogen compounds add-on is 6-8 times of vulkacit H volume; Under mixed catalyst catalysis, nitrogen atmosphere protection and agitation condition, react 10 ~ 48 hours, reaction is divided into synthesis under normal pressure or compressive reaction, during synthesis under normal pressure, temperature of reaction is 60 ~ 120 DEG C, during compressive reaction, temperature of reaction is 60 ~ 160 DEG C, after completion of the reaction, through cooling standing, crystallization, filtration, washing and drying, four cation quaternary ammonium salts are obtained;
Composition and the content thereof of described mixed catalyst are: the quaternary ammonium salt of the 0-3% of vulkacit H quality, the iodide of the 1-3% of vulkacit H quality, the water of the 0-2% of vulkacit H quality; Described iodide are potassiumiodide, sodium iodide or quaternary ammonium iodide salt
Described Organohalogen compounds are Benzyl Chloride or γ-r-chloropropyl trimethoxyl silane;
Described solvent is the mixing of one or more in methyl alcohol, ethanol, n-propyl alcohol, Virahol, acetonitrile and tetrahydrofuran (THF).
3. preparation method as claimed in claim 2, the washings washed described in it is methylene dichloride.
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