CN102199172A - Method for preparing 1-substituted phosphorus dichloride - Google Patents
Method for preparing 1-substituted phosphorus dichloride Download PDFInfo
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- CN102199172A CN102199172A CN2010101312483A CN201010131248A CN102199172A CN 102199172 A CN102199172 A CN 102199172A CN 2010101312483 A CN2010101312483 A CN 2010101312483A CN 201010131248 A CN201010131248 A CN 201010131248A CN 102199172 A CN102199172 A CN 102199172A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a method for preparing 1-substituted phosphorus dichloride, which comprises the following steps of: 1) mixing raw materials of dialkyl phosphate and thionyl chloride with a catalytic dose of catalyst, wherein the molar ratio of the dialkyl phosphate to the chlorination reagent is 1:1-1:40; 2) after the materials in the step (1) are completely added, reacting until the dialkyl phosphate is fully reacted so as to obtain phosphonous dichloride compounds; and 3) evaporating out unreacted chlorination reagent or the chlorination reagent and an inert solvent under normal pressure, recovering, and rectifying under reduced pressure to obtain the product shown as a formula II. The initial raw materials are readily available, the reaction conditions are mild and easily controlled, the catalyst can be recyclable inorganic salt or alkali, the unreacted chlorination reagent also can be recycled, the cost is low, and the method is suitable for industrialization; and the obtained product has high purity and stable quality.
Description
Technical field
The invention belongs to medicine intermediate and relevant technical field of catalytic chemistry, relate to the improvement preparation method that 1-replaces inferior phosphinylidyne dichloro compounds formula (II).1-by formula (I) replaces the phosphorous acid diester under catalyst specifically, directly obtains formula (II) from the ester chloride.
Background technology
Acyl chloride reaction often uses chlorination reagents such as sulfur oxychloride, phosphorus pentachloride, phosphorus oxychloride, phosphorus trichloride; chloride for phosphorons acid compound is very difficult; can use the so strong acylating reagent temperature of reaction height of phosphorus pentachloride and phosphorus oxychloride, equipment corrosion is strong, and environmental pollution is big.Replace two acyl chloride reactions of phosphorous acid two ester compounds for 1-, do not add catalyst if 1-replaces phosphorous acid two ester compounds, only using sulfur oxychloride to carry out acyl chloride reaction can't pair acyl chlorides product, and can only obtain single acyl chlorides product.Having bibliographical information 1-to replace phosphorous acid two ester compounds at present can be under DMF or other nitrogenous organic reagent catalysis, use sulfur oxychloride can obtain 1-at a lower temperature and replace phosphorous acid diacid chloride [Phosphorus Sulfur and Scilicon 1990Vol.47,465-470].In addition, also have bibliographical information to replace the thiophosphorous acid diester from alkyl, through obtaining alkyl and replace inferior phosphinylidyne dichloro again with under the catalysis of chloride reagent at pyridine after the over cure oxygen exchange, the thiophosphite preparation difficulty of this method, and experience sulphur oxygen exchange process, this process is that reversible reaction is very big to the reaction yield influence, makes the impurity [Phosphorus Sulfur and Scilicon 2002 Vol.177,1093-1099] that contains sulphur phosphorus thing in the product.
1-replaces inferior phosphinylidyne dichloro compounds and is used for the medicine intermediate purposes, to its specification of quality strictness, organic reagent catalysis such as use DMF will be introduced organic impurity in product, reduce product colour, the present invention adopts sulfur oxychloride as gentle chlorination reagent, and preparation 1-replaces inferior phosphinylidyne dichloro compounds under acids, bases, amino acid or saline catalyst effect, and this novel method is cheap, the recyclable utilization of catalyzer, environment friendly and pollution-free, reaction conditions temperature.
Summary of the invention
The purpose of this invention is to provide the novel method that 1-replaces the preparation of phosphorous acid diacid chloride compounds, adopt gentle chlorination reagent under the effect of catalyzer, 1-to be replaced the phosphorous acid diester and transform its pair of generation chloro thing, having solved gentle chlorination reagent can only replace 1-the phosphorous acid diester and change into its monochloro for thing, the problem of two chloro things be can't generate and strong chlorination reagent temperature of reaction height, equipment corrosion is strong, product yield is low shortcoming adopted.
The technical solution used in the present invention:
Replace the phosphorous acid diester with 1-and under katalysis, can obtain 1-replacement phosphorous acid acyl dichloro with the sulfur oxychloride reaction.
1-is replaced in the mixed system that the phosphorous acid diester joins sulfur oxychloride or sulfur oxychloride and inert solvent, adding catalyzer reacts and obtains 1-and replace inferior phosphinylidyne dichloro, elder generation's normal pressure steams unreacted sulfur oxychloride and other inert solvent that may contain, and rectification under vacuum obtains product again.
Specific operation process:
1) with the catalyst mix of raw material phosphonic acids dialkyl ester and sulfur oxychloride and catalytic amount;
2) material in the step (1) add finish after, reaction reacts completely until phosphonic acids dialkyl ester, generates the phosphonyl dichloride compounds;
3) first normal pressure steams unreacted chlorination reagent or chlorination reagent and inert solvent, reclaims usefulness again, and rectification under vacuum obtains formula II product again.
The reaction formula of described method is as follows,
In the formula, R is methyl, ethyl, n-propyl, sec.-propyl, allyl group, cyclopropyl, normal-butyl, isobutyl-, cyclobutyl, 2-methyl-2-allyl group, n-pentyl, 2-methyl butyl, n-hexyl, cyclohexyl, phenyl, 4-aminomethyl phenyl, 3-aminomethyl phenyl, 2-aminomethyl phenyl, 4-ethylphenyl, 4-chloro-phenyl-or 2-chloro-phenyl-;
In the formula, R ' and R " can be identical, also can be different, they are respectively methyl, ethyl, n-propyl, sec.-propyl, allyl group, normal-butyl, isobutyl-, 2-methyl-2-allyl group, n-hexyl, cyclohexyl, cyclopentyl or 2-methyl hexyl; R and R ' or R " can be identical, also can be different.
Described catalyzer comprises can one or more acids, bases, amino acid or saline catalyst;
Wherein acid catalyst is, one or more in sulfuric acid, hydrochloric acid, phosphoric acid, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, monocalcium phosphate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, secondary calcium phosphate, formic acid, acetate, propionic acid, butyric acid, isopropylformic acid, phenylformic acid, toluylic acid, Citric Acid, tartrate, oxalic acid, the Phenylsulfonic acid;
Basic catalyst is one or more in sodium methylate, sodium ethylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium tert.-butoxide, sodium hydroxide, potassium hydroxide, tripropyl amine, triethylamine, dimethylamine, methylamine, pyridine, N-picoline, 2-picoline, 3-picoline, 4-picoline, 2-chloro-3-picoline, the 2-chloro-4-picoline;
The amino acids catalyzer is: one or more in Serine, network propylhomoserin, methionine(Met), Xie Ansuan, Methionin, Isoleucine, leucine, phenylamino acid, tryptophane, Threonine, the N-trifluoromethoxy-L-Methionin;
Saline catalyst is: one or more in hydrofluoric acid pyridine, pyridine hydrochloride, pyridine benzene sulfonate, Potassium monofluoride, Repone K, cesium fluoride, sodium-chlor, Potassium Bromide, Sodium Bromide, magnesium chloride, calcium chloride, iron trichloride, iron protochloride, zinc chloride, titanium tetrachloride, ruthenium chloride, tri-phenyl-phosphorus bromide, the triphenyl phosphorus chloride;
Above-mentioned an acidic catalyst can mix use with saline catalyst, and alkali catalyst can use with saline catalyst and amino acids catalyst mix, forms the catalyzer of mixed type;
Can use the catalyzer of same type more than a kind or a kind or mixed type in the same reaction process.
Can add or not add inert solvent in the described step (1); Be that described reaction is made solvent with sulfur oxychloride or mixed with inert solvent with sulfur oxychloride and makes solvent;
Wherein inert solvent is, one or more in trichloromethane, methylene dichloride, ether, propyl ether, n-butyl ether, dithiocarbonic anhydride, tetracol phenixin, sherwood oil, methyl tertiary butyl ether, methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF), pentamethylene, hexanaphthene, normal hexane, normal heptane, hexanodioic acid dme, dimethyl sulfoxide (DMSO), the phenyl ether.
The mol ratio of phosphonic acids dialkyl ester and described chlorination reagent is preferably 1: 1-1: 40; The mol ratio of phosphonic acids dialkyl ester and catalyzer is preferably 1000: 1-1: 1; Described reaction Heating temperature is within 30-200 ℃ of scope, and the time is between 5-20 hour; Described reaction can be finished in the reflux process.
In the described step (3), normal pressure steams the Heating temperature of unreacted chlorination reagent within 50-200 ℃ of scope; Rectification under vacuum obtains the Heating temperature of product within 50-200 ℃ of scope, and vacuum tightness is between 0.5-30mmHg
Major advantage of the present invention is as follows.The preparation method of phosphonyl dichloride compounds of the present invention compared with prior art, starting raw material is easy to get, reaction conditions is gentle and easy to control, the intact chlorination reagent of catalyzer and unreacted can recycling, and cost is lower, easily realizes industrialization, products obtained therefrom purity height, steady quality.
Embodiment
Replace two acyl chloride reactions of phosphorous acid two ester compounds for 1-, do not add catalyst if 1-replaces phosphorous acid two ester compounds, only using sulfur oxychloride to carry out acyl chloride reaction can't pair acyl chlorides product, and it can only obtain single acyl chlorides product.The present invention uses one or more different catalyzer, has realized that the use sulfur oxychloride does chlorination reagent and obtain 1-and replace the two acyl chloride compounds of inferior phosphorus.
Be described in detail specific embodiments of the invention below in conjunction with technical scheme.The following examples are only understood with increase and theme of the present invention are described, but not are intended to limit the invention to these embodiment.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 1:1-cyclopropyl
Having agitator, stopper, internal thermometer and condensing reflux pipe and be furnished with in the there-necked flask that the absorption of alkali lye tail gas is arranged, stir down 150g (1mol) 1-cyclopropyl dimethylphosphite is added dropwise in the 500g sulfur oxychloride, be warming up to 60 ℃ of reactions 2 hours, add an acidic catalyst 15.8g (0.1mol) Phenylsulfonic acid again and be warming up to 78 ℃ of reactions 5 hours, after finishing with unreacted sulfur oxychloride, and rectification under vacuum, collect 110 ℃ of cuts under-112 ℃ (8mmHg), get the inferior phosphinylidyne dichloro of 121g1-cyclopropyl, yield 76.5%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 2:1-cyclopropyl
Describe identically among operation and the embodiment 1, use the mixed catalyst of an acidic catalyst 5g secondary calcium phosphate and 10g oxalic acid to react, obtain 132g 1-cyclopropyl Asia phosphinylidyne dichloro, yield 83.4%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 3:1-benzyl
Having agitator, stopper, internal thermometer and condensing reflux pipe and be furnished with in the there-necked flask that the absorption of alkali lye tail gas is arranged, stir down the 1g magnesium chloride is added in the 500g sulfur oxychloride, be warming up to 60 ℃, under this temperature, 228g (1mol) 1-benzyl diethyl phosphite is splashed in the above-mentioned reaction system, reacted 4 hours, add the 5g Potassium monofluoride again, be warming up to back flow reaction about 8 hours, reacting the post chlorization sulfoxide that finishes steams, and rectification under vacuum, collect 147 ℃ of cuts under-148 ℃ (3mmHg), get the inferior phosphinylidyne dichloro of 100g 1-benzyl, yield 47.8%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 4:1-benzyl
Describe identically among operation and the embodiment 3, difference is, uses basic catalyst 15g triethylamine to react, 153.1g 1-benzyl Asia phosphinylidyne dichloro, yield 73.2%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 5:1-benzyl
Describe identically among operation and the embodiment 3, difference is, uses basic catalyst 10g triethylamine and saline catalyst 10g titanium tetrachloride to react, must 180.1g 1-benzyl Asia phosphinylidyne dichloro, and yield 86.1%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 6:1-butyl
Having agitator, stopper, internal thermometer and condensing reflux pipe and be furnished with in the there-necked flask that the absorption of alkali lye tail gas is arranged, under the stirring at room 194g (1mol) 1-butyl diethyl phosphite, 1g hydrofluoric acid pyridinium salt are added in the 800g sulfur oxychloride, be warming up to 50 ℃ of reactions 2 hours, be warming up to back flow reaction about 5 hours, after reaction finishes sulfur oxychloride is steamed, and rectification under vacuum, 60 ℃ of cuts under-61 ℃ (2mmHg) collected, get the inferior phosphinylidyne dichloro of 160g 1-butyl, yield 91.4%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 7:1-isobutyl-
Having agitator, stopper, internal thermometer and condensing reflux pipe and be furnished with in the there-necked flask that the absorption of alkali lye tail gas is arranged, under the stirring at room 222g (1mol) 1-isobutyl-diisopropyl phosphite, 1g Methionin and 1g Serine are added in 560g sulfur oxychloride and the 500g methyl iso-butyl ketone (MIBK), be warming up to back flow reaction about 16 hours, after finishing, reaction under the normal pressure sulfur oxychloride and methyl iso-butyl ketone (MIBK) are steamed, rectification under vacuum again, collect 67 ℃ of cuts under-69 ℃ (2mmHg), get the inferior phosphinylidyne dichloro of 145g1-isobutyl-, yield 83.1%.
Synthesizing of the inferior phosphinylidyne dichloro of embodiment 8:1-butyl
Having agitator, stopper, internal thermometer and condensing reflux pipe also are furnished with in the there-necked flask that the absorption of alkali lye tail gas is arranged, under the stirring at room with 258.1g (1mol) 1-butyl phosphorous acid diphenyl ester, 10g sodium-chlor adds in the 800g sulfur oxychloride, be warming up to 60 ℃ of reactions 3 hours, add in 5g magnesium chloride and the 300g tetrahydrofuran (THF) after being cooled to 30 ℃, be warming up to back flow reaction about 8 hours, after finishing, reaction under the normal pressure sulfur oxychloride and tetrahydrofuran (THF) are steamed, rectification under vacuum again, collect 60 ℃ of cuts under-61 ℃ (2mmHg), get the inferior phosphinylidyne dichloro of 120g 1-butyl, yield 68.5%.
Claims (9)
1. a 1-replaces the preparation method of inferior phosphinylidyne dichloro, and it is characterized in that: this method may further comprise the steps:
1) with the catalyst mix of raw material phosphonic acids dialkyl ester and sulfur oxychloride and catalytic amount;
2) material in the step (1) add finish after, reaction reacts completely until phosphonic acids dialkyl ester, generates the phosphonyl dichloride compounds;
3) first normal pressure steams unreacted chlorination reagent or chlorination reagent and inert solvent, reclaims usefulness again, and rectification under vacuum obtains formula II product again.
2. according to the method for claim 1, it is characterized in that:
The reaction formula of described method is as follows,
In the formula, R is methyl, ethyl, n-propyl, sec.-propyl, allyl group, cyclopropyl, normal-butyl, isobutyl-, cyclobutyl, 2-methyl-2-allyl group, n-pentyl, 2-methyl butyl, n-hexyl, cyclohexyl, phenyl, 4-aminomethyl phenyl, 3-aminomethyl phenyl, 2-aminomethyl phenyl, 4-ethylphenyl, 4-chloro-phenyl-or 2-chloro-phenyl-;
In the formula, R ' and R " can be identical, also can be different, they are respectively methyl, ethyl, n-propyl, sec.-propyl, allyl group, normal-butyl, isobutyl-, 2-methyl-2-allyl group, n-hexyl, cyclohexyl, cyclopentyl or 2-methyl hexyl; R and R ' or R " can be identical, also can be different.
3. according to the method for claim 1, it is characterized in that:
Described catalyzer comprises can one or more acids, bases, amino acid or saline catalyst;
Wherein acid catalyst is, one or more in sulfuric acid, hydrochloric acid, phosphoric acid, SODIUM PHOSPHATE, MONOBASIC, potassium primary phosphate, monocalcium phosphate, Sodium phosphate dibasic, dipotassium hydrogen phosphate, secondary calcium phosphate, formic acid, acetate, propionic acid, butyric acid, isopropylformic acid, phenylformic acid, toluylic acid, Citric Acid, tartrate, oxalic acid, the Phenylsulfonic acid;
Basic catalyst is one or more in sodium methylate, sodium ethylate, sodium tert-butoxide, potassium methylate, potassium ethylate, potassium tert.-butoxide, sodium hydroxide, potassium hydroxide, tripropyl amine, triethylamine, dimethylamine, methylamine, pyridine, N-picoline, 2-picoline, 3-picoline, 4-picoline, 2-chloro-3-picoline, the 2-chloro-4-picoline;
The amino acids catalyzer is: one or more in Serine, network propylhomoserin, methionine(Met), Xie Ansuan, Methionin, Isoleucine, leucine, phenylamino acid, tryptophane, Threonine, the N-trifluoromethoxy-L-Methionin;
Saline catalyst is: one or more in hydrofluoric acid pyridine, pyridine hydrochloride, pyridine benzene sulfonate, Potassium monofluoride, Repone K, cesium fluoride, sodium-chlor, Potassium Bromide, Sodium Bromide, magnesium chloride, calcium chloride, iron trichloride, iron protochloride, zinc chloride, titanium tetrachloride, ruthenium chloride, tri-phenyl-phosphorus bromide, the triphenyl phosphorus chloride;
Above-mentioned an acidic catalyst can use with saline catalyst and amino acids catalyst mix, alkali catalyst can use with saline catalyst and amino acids catalyst mix, above-mentioned saline catalyst can use with the amino acids catalyst mix, forms the catalyzer of mixed type;
Can use the catalyzer of same type more than a kind or a kind or mixed type in the same reaction process.
4. according to the method for claim 3, it is characterized in that:
Described when the C of R chain length is 1-3, one or more in one or more in the preferred acidic catalyzer or an acidic catalyst mix use with in the saline catalyst one or more; The C chain length of R is 〉=4 o'clock, and one or more in one or more in one or more in the preferred alkali catalyst or the alkali catalyst and the amino acids catalyzer mix use.
5. according to the method for claim 1, it is characterized in that: can add or not add inert solvent in the described step (1); Be that described reaction is made solvent with sulfur oxychloride or mixed with inert solvent with sulfur oxychloride and makes solvent;
Wherein inert solvent is, one or more in trichloromethane, methylene dichloride, ether, propyl ether, n-butyl ether, dithiocarbonic anhydride, tetracol phenixin, sherwood oil, methyl tertiary butyl ether, methyl iso-butyl ketone (MIBK), tetrahydrofuran (THF), pentamethylene, hexanaphthene, normal hexane, normal heptane, hexanodioic acid dme, dimethyl sulfoxide (DMSO), the phenyl ether.
6. according to the method for claim 1, it is characterized in that: the mol ratio of phosphonic acids dialkyl ester and described chlorination reagent is 1: 1-1: 40; The mol ratio of phosphonic acids dialkyl ester and catalyzer is 1000: 1-1: 1.
7. according to the method for claim 1, it is characterized in that: described reaction Heating temperature is within 30-200 ℃ of scope, and the time is between 5-20 hour.
8. according to the method for claim 1, it is characterized in that: described being reflected in the reflux process finished.
9. according to the method for claim 1, it is characterized in that: in the described step (3), normal pressure steams the Heating temperature of unreacted chlorination reagent within 50-200 ℃ of scope; Rectification under vacuum obtains the Heating temperature of product within 50-200 ℃ of scope, and vacuum tightness is between 0.5-30mmHg.
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CN111635434A (en) * | 2020-07-20 | 2020-09-08 | 苏州昊帆生物股份有限公司 | Synthesis method of 1-propylphosphoric cyclic anhydride |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1287489A (en) * | 1998-01-09 | 2001-03-14 | 吉尔特药品公司 | Lipase inhibiting polymers |
JP2004043312A (en) * | 2002-07-04 | 2004-02-12 | Teijin Chem Ltd | Method for producing cyclic phosphonate |
-
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Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1287489A (en) * | 1998-01-09 | 2001-03-14 | 吉尔特药品公司 | Lipase inhibiting polymers |
JP2004043312A (en) * | 2002-07-04 | 2004-02-12 | Teijin Chem Ltd | Method for producing cyclic phosphonate |
Non-Patent Citations (4)
Title |
---|
《 J. Org. Chem.》 19981231 D. E. Bergstrom, et al. Synthesis and Characterization of a New Fluorine Substituted Nonionic Dinucleoside Phosphonate Analogue, P -Deoxy-P - (difluoromethyl) t hymidylyl( 3'->5') t hymidine 第3953-3958页 1-9 第53卷, * |
D. E. BERGSTROM, ET AL.: "Synthesis and Characterization of a New Fluorine Substituted Nonionic Dinucleoside Phosphonate Analogue, P -Deoxy-P - (difluoromethyl) t hymidylyl( 3’→5’) t hymidine", 《 J. ORG. CHEM.》 * |
IRENE G. BOUTSELIS, ET AL.: "Synthesis and Cell-Based Activity of a Potent and Selective Protein Tyrosine Phosphatase 1B Inhibitor Prodrug, Irene G. Boutselis", 《 J. MED. CHEM.》 * |
YU-TING HSUA, ET AL.: "Evaluation of Organophosphorus Chemicals-Degrading Enzymes:A Comparison of Escherichia coli and Human Cytosolic Aminopeptidase P", 《CHEMISTRY & BIODIVERSITY》 * |
Cited By (2)
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CN111635434A (en) * | 2020-07-20 | 2020-09-08 | 苏州昊帆生物股份有限公司 | Synthesis method of 1-propylphosphoric cyclic anhydride |
CN111635434B (en) * | 2020-07-20 | 2023-04-07 | 苏州昊帆生物股份有限公司 | Synthesis method of 1-propylphosphoric cyclic anhydride |
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