WO2020244162A1 - 一种氯磷酸二苯酯的化学合成方法 - Google Patents
一种氯磷酸二苯酯的化学合成方法 Download PDFInfo
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- WO2020244162A1 WO2020244162A1 PCT/CN2019/119001 CN2019119001W WO2020244162A1 WO 2020244162 A1 WO2020244162 A1 WO 2020244162A1 CN 2019119001 W CN2019119001 W CN 2019119001W WO 2020244162 A1 WO2020244162 A1 WO 2020244162A1
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- Prior art keywords
- diphenyl
- diphenyl phosphate
- chemical synthesis
- chlorophosphate
- certain amount
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- 238000000034 method Methods 0.000 title claims abstract description 28
- BHIIGRBMZRSDRI-UHFFFAOYSA-N [chloro(phenoxy)phosphoryl]oxybenzene Chemical compound C=1C=CC=CC=1OP(=O)(Cl)OC1=CC=CC=C1 BHIIGRBMZRSDRI-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000003786 synthesis reaction Methods 0.000 title claims description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical class C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 bis(trichloromethyl)carbonate ester Chemical class 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 4
- FVOMJWZIGNBHOA-UHFFFAOYSA-M sodium;diphenyl phosphate Chemical compound [Na+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 FVOMJWZIGNBHOA-UHFFFAOYSA-M 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- AJZFEJQZIOIQSR-UHFFFAOYSA-M potassium;diphenyl phosphate Chemical compound [K+].C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 AJZFEJQZIOIQSR-UHFFFAOYSA-M 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract 3
- 238000011084 recovery Methods 0.000 claims abstract 2
- 238000005406 washing Methods 0.000 claims abstract 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 36
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 150000001412 amines Chemical class 0.000 claims description 11
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 claims description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 claims description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 claims description 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims description 2
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical compound CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- UINDYXSBHHUJGO-UHFFFAOYSA-N 1-chloro-2,3-diphenylbenzene Chemical compound C=1C=CC=CC=1C=1C(Cl)=CC=CC=1C1=CC=CC=C1 UINDYXSBHHUJGO-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004821 distillation Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 239000002910 solid waste Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 abstract 1
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- CXHHBNMLPJOKQD-UHFFFAOYSA-N methyl hydrogen carbonate Chemical compound COC(O)=O CXHHBNMLPJOKQD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229960001701 chloroform Drugs 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- DMJNNHOOLUXYBV-PQTSNVLCSA-N meropenem Chemical compound C=1([C@H](C)[C@@H]2[C@H](C(N2C=1C(O)=O)=O)[C@H](O)C)S[C@@H]1CN[C@H](C(=O)N(C)C)C1 DMJNNHOOLUXYBV-PQTSNVLCSA-N 0.000 description 1
- 229960002260 meropenem Drugs 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- NZMAJUHVSZBJHL-UHFFFAOYSA-N n,n-dibutylformamide Chemical compound CCCCN(C=O)CCCC NZMAJUHVSZBJHL-UHFFFAOYSA-N 0.000 description 1
- HHXMXAQDOUCLDN-RXMQYKEDSA-N penem Chemical compound S1C=CN2C(=O)C[C@H]21 HHXMXAQDOUCLDN-RXMQYKEDSA-N 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/08—Esters of oxyacids of phosphorus
- C07F9/09—Esters of phosphoric acids
- C07F9/14—Esters of phosphoric acids containing P(=O)-halide groups
- C07F9/1406—Esters of phosphoric acids containing P(=O)-halide groups containing the structure Hal-P(=O)-O-aryl
Definitions
- the invention relates to the technical field of chemical engineering, in particular to a chemical synthesis method of diphenyl chlorophosphate.
- Diphenyl chlorophosphate is an important intermediate used in the synthesis of penem drugs, phosphorus-containing flame retardants and liquid crystal materials, such as the production of drugs meropenem, and 4-biphenoxy diphenyl phosphate.
- the synthetic route is as follows:
- This process uses phosphorus oxychloride, which has serious corrosion to equipment, and a large amount of high-phosphorus wastewater is difficult to treat and serious pollution; at the same time, the process has many by-products, requires high-vacuum high-temperature distillation products, high energy consumption, and a large amount of distillation residue Solid waste.
- the method has problems such as high corrosion, high energy consumption, high pollution, low yield, high production cost and other problems that need to be solved urgently.
- the present invention relates to a chemical synthesis method of diphenyl chlorophosphate, which has the characteristics of simple process, mild production conditions, high yield, low cost, and few wastes.
- the present invention provides the following technical solutions:
- a method for synthesizing diphenyl chlorophosphate which is characterized in that it comprises the following steps:
- a certain amount of organic amine as a catalyst a certain amount of one or two of diphenyl phosphate or diphenyl phosphate salt is mixed in any ratio with a certain amount of bis(trichloromethyl) carbonate Reacting in an organic solvent for 1-10 hours, the reaction temperature is 0-60°C, and the diphenyl phosphate salt is any one of diphenyl phosphate sodium salt or diphenyl phosphate potassium salt;
- step 2) After the reaction in the above step 1) is completed, the product is cooled and washed with water, dried, and the solvent is recovered under normal pressure or reduced pressure, and the insoluble matter is removed by cooling and filtering to obtain diphenyl chlorophosphate.
- M sodium or potassium
- Said step 1) A certain amount of one or two of diphenyl phosphate or diphenyl phosphate salt is mixed in any ratio and reacted with a certain amount of bis(trichloromethyl) carbonate in an organic solvent 3-6h.
- step 2 The product described in step 2) is cooled to below 10°C, washed with water, dried, and recovered at normal pressure or reduced pressure, and filtered to remove insolubles to obtain diphenyl chlorophosphate.
- the quantity ratio of the diphenyl phosphate (or diphenyl phosphate salt): bis(trichloromethyl) carbonate: organic amine catalyst is 1:0.35-1.0:0.01-1.5.
- the amount ratio of the diphenyl phosphate (or diphenyl phosphate salt): bis(trichloromethyl) carbonate: organic amine catalyst is 1:0.35-0.5:0.1-0.5.
- the organic amine catalyst is one of the following or a mixture of more than one in any ratio: triethylamine, diisopropylethylamine, pyridine, morpholine, imidazole, 2-methylimidazole, tetramethylguanidine, tetramethyl Urea, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dibutylformamide, N-methylpyrrole, N-methyltetrahydropyrrole.
- the organic amine catalyst is N,N-dimethylformamide.
- the organic solvent is one or more of the following mixtures in any ratio: benzene, toluene, xylene, chlorobenzene, dichlorobenzene, n-hexane, cyclohexane, diisopropyl ether, dibutyl ether, tetrahydrofuran , Ethyl Acetate, Dichloromethane, Trichloromethane or Dichloroethane.
- the organic solvent is methylene chloride.
- the amount of the organic solvent is 3-8 times the mass of diphenyl phosphate or diphenyl phosphate salt. The amount of materials below this amount does not react sufficiently, and the amount above this amount will increase the cost and decrease the reaction efficiency.
- the present invention has the beneficial effect of using diphenyl phosphate (or diphenyl phosphate salt) and bis(trichloromethyl) carbonate as raw materials to synthesize diphenyl chlorophosphate under the catalysis of organic amines.
- This solution replaces the existing synthesis method using phenol and phosphorus oxychloride as raw materials.
- the technical solution used in this application has simple process routes, mild reaction conditions, and low energy consumption for post-processing It does not require high vacuum and high temperature distillation, has the advantages of low production cost, high product yield and quality, and at the same time avoids the problem of large amounts of phosphorus-containing wastewater and solid waste.
- the synthesis method of diphenyl chlorophosphate has greater advantages The economic value and environmental protection value.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
Abstract
本发明涉及一种氯磷酸二苯酯的合成方法,包括以下步骤:以一定量的有机胺为催化剂,将一定量的磷酸二苯酯或磷酸二苯酯盐中的一种或者两种以任意比例混合后与一定量的二(三氯甲基)碳酸酯在有机溶剂中反应1-10h,所述反应温度为 0-60℃,且所述磷酸二苯酯盐为磷酸二苯酯钠盐或磷酸二苯酯钾盐中的任一种;待上述步骤1)中反应结束后,将生成物降温水洗、干燥、常压或减压回收溶剂,降温过滤除去不溶物制得氯磷酸二苯酯。本发明的有益效果是工艺路线简单,反应条件温和,后处理能耗小,无须高真空、高温蒸馏,生产成本低,产品收率和质量都较高的优点,且同时避免了产生大量含磷废水和固废的问题。
Description
本发明涉及化工技术领域,尤其涉及一种氯磷酸二苯酯的化学合成方法。
氯磷酸二苯酯是用于合成培南类药物、含磷阻燃剂和液晶材料的重要中间体,如用它生产药物美罗培南,以及4-联苯氧基磷酸二苯酯等。
在本发明给出之前,现有技术中氯磷酸二苯酯的化学合成方法多以三氯氧磷和苯酚为原料,在路易斯酸催化下合成。
合成路线如下:
如:化学研究2012,23(6)提出的用0.8g无水三氯化铝和15.3g三氯氧磷升温至60℃,向反应体系中滴加10ml二氯乙烷和18.8g苯酚的混合液,滴加控温70℃以下,滴毕升温至70℃,保温反应15小时,滴加适量水,过滤,滤液先常压蒸除低沸点物,再减压蒸馏,收集140~160℃/3mmHg馏分。
该工艺方法使用了三氯氧磷,对设备腐蚀严重,大量高磷废水很难处理,污染严重;同时该工艺副产物较多,需要高真空高温蒸馏产品,能耗高、蒸馏残余物产生大量固废。该方法存在高腐蚀、高能耗、高污染等问题,收率低,生产成本高等问题急需解决。
针对现有技术的不足,本发明涉及一种氯磷酸二苯酯的化学合成方法,该方法具备工艺简单、生产条件温和、高收率、低成本、三废少的特点。
为实现上述目的,本发明提供如下技术方案:
一种氯磷酸二苯酯的合成方法,其特征在于,包括以下步骤:
1)以一定量的有机胺为催化剂,将一定量的磷酸二苯酯或磷酸二苯酯盐中的一种或者两种以任意比例混合后与一定量的二(三氯甲基)碳酸酯在有机溶剂中反应1-10h,所述的反应温度为 0-60℃,且所述磷酸二苯酯盐为磷酸二苯酯钠盐或磷酸二苯酯钾盐中的任一种;
2)待上述步骤1)中反应结束后,将生成物降温水洗、干燥、常压或减压回收溶剂,降温过滤除去不溶物制得氯磷酸二苯酯。
其反应方程式如下:
或
其中,M=钠或钾
所述的步骤1)将一定量的磷酸二苯酯或磷酸二苯酯盐中的一种或者两种以任意比例混合后与一定量的二(三氯甲基)碳酸酯在有机溶剂中反应3-6h。
所述的步骤2)中所述的生成物降温至10℃以下进行水洗、干燥、常压或减压回收溶剂,降温过滤除去不溶物制得氯磷酸二苯酯。
所述的磷酸二苯酯(或磷酸二苯酯盐):二(三氯甲基)碳酸酯:有机胺催化剂的物质的量比为1:0.35-1.0:0.01-1.5。
所述的磷酸二苯酯(或磷酸二苯酯盐):二(三氯甲基)碳酸酯:有机胺催化剂的物质的量比为1:0.35-0.5:0.1-0.5。
所述的有机胺催化剂为下列之一或一种以上任意比例混合物:三乙胺、二异丙基乙胺、吡啶、吗啉、咪唑、2-甲基咪唑、四甲基胍、四甲基脲、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二丁基甲酰胺、N-甲基吡咯、N-甲基四氢吡咯。
所述的有机胺催化剂为N,N-二甲基甲酰胺。
所述的有机溶剂为下列之一或一种以上任意比例混合物:苯、甲苯、二甲苯、氯苯、二氯苯、正己烷、环己烷、二异丙基醚、二丁基醚、四氢呋喃、乙酸乙酯、二氯甲烷、三氯甲烷或二氯乙烷。
所述的有机溶剂为二氯甲烷。
所述的有机溶剂用量为磷酸二苯酯或磷酸二苯酯盐质量的3-8倍,低于此用量物料反应不充分,高于此用量会造成成本增加,反应效率下降。
与现有技术相比,本发明的有益效果是:以磷酸二苯酯(或磷酸二苯酯盐)和二(三氯甲基)碳酸酯为原料,在有机胺催化下合成氯磷酸二苯酯,本方案替代了现有的以苯酚和三氯氧磷为原料的合成方法,同现有方案相比,本申请中使用的技术方案具有工艺路线简单,反应条件温和,后处理能耗小,无须高真空、高温蒸馏,生产成本低,产品收率和质量都较高的优点,且同时避免了产生大量含磷废水和固废的问题,该氯磷酸二苯酯的合成方法具有较大的经济价值和环保价值。
下面对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明一部分实施例,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1
在装有温度计、回流冷凝管和机械搅拌的500ml四口反应瓶中投入120g二氯甲烷、7.3g的N,N-二甲基甲酰胺,搅拌控温10℃以下,投入28g二(三氯甲基)碳酸酯,流加入50g磷酸二苯酯和120g二氯甲烷的溶液,加毕,反应3小时,检测反应结束后,控温10℃以下,缓慢加入水20g,搅拌分液,有机相用无水硫酸钠干燥;过滤除去干燥剂,滤液常压蒸除二氯甲烷,降温至0℃,过滤除去不溶物,得氯磷酸二苯酯48.9g,GC检测纯度99.2%,收率90.3%。
实施例2
在装有温度计、回流冷凝管和机械搅拌的500ml四口反应瓶中投入120g二氯甲烷、3.6g的N,N-二甲基甲酰胺,搅拌控温10℃以下,投入28g二(三氯甲基)碳酸酯,流加入50g磷酸二苯酯和120g二氯甲烷的溶液,加毕,反应3小时,检测反应结束后,控温10℃以下,缓慢加入水20g,搅拌分液,有机相用无水硫酸钠干燥;过滤除去干燥剂,滤液常压蒸除二氯甲烷,降温至0℃,过滤除去不溶物,得氯磷酸二苯酯47.2g,GC检测纯度98.1%,收率86.2%。
实施例3
在装有温度计、回流冷凝管和机械搅拌的500ml四口反应瓶中投入330g二氯甲烷、7.3g的N,N-二甲基甲酰胺,搅拌控温10℃以下,投入28g二(三氯甲基)碳酸酯,分批加入55g磷酸二苯酯钠盐,加毕,反应5小时,检测反应结束后,控温10℃以下,缓慢加入水20g,搅拌分液,有机相用无水硫酸钠干燥;过滤除去干燥剂,滤液常压蒸除二氯甲烷,降温至0℃,过滤除去不溶物,得氯磷酸二苯酯47.5g,GC检测纯度99.3%,收率87.8%。
还需要说明的是,术语“包括”、“包含”或者其任何其他变体意在涵盖非排他性的包含,从而使得包括一系列要素的过程、方法、商品或者设备不仅包括那些要素,而且还包括没有明确列出的其他要素,或者是还包括为这种过程、方法、商品或者设备所固有的要素。在没有更多限制的情况下,由语句“包括一个……”限定的要素,并不排除在包括要素的过程、方法、商品或者设备中还存在另外的相同要素。
尽管参照前述实施例对本发明进行了详细的说明,对于本领域的技术人员来说,其依然可以对前述各实施例所记载的技术方案进行修改,或者对其中部分技术特征进行等同替换,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (10)
- 一种氯磷酸二苯酯的合成方法,其特征在于,包括以下步骤:1)以一定量的有机胺为催化剂,将一定量的磷酸二苯酯或磷酸二苯酯盐中的一种或者两种以任意比例混合后与一定量的二(三氯甲基)碳酸酯在有机溶剂中反应1-10h,所述的反应温度为 0-60℃,且所述磷酸二苯酯盐为磷酸二苯酯钠盐或磷酸二苯酯钾盐中的任一种;2)待上述步骤1)中反应结束后,将生成物降温水洗、干燥、常压或减压回收溶剂,降温过滤除去不溶物制得氯磷酸二苯酯。
- 如权利要求1所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的步骤1)将一定量的磷酸二苯酯或磷酸二苯酯盐中的一种或者两种以任意比例混合后与一定量的二(三氯甲基)碳酸酯在有机溶剂中反应3-6h。
- 如权力要求1所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的步骤2)中所述的生成物降温至10℃以下进行水洗、干燥、常压或减压回收溶剂,降温过滤除去不溶物制得氯磷酸二苯酯。
- 如权利要求1所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的磷酸二苯酯(或磷酸二苯酯盐):二(三氯甲基)碳酸酯:有机胺催化剂的物质的量比为1:0.35-1.0:0.01-1.5。
- 如权利要求4所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的磷酸二苯酯(或磷酸二苯酯盐):二(三氯甲基)碳酸酯:有机胺催化剂的物质的量比为1:0.35-0.5:0.1-0.5。
- 如权利要求1所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的有机胺催化剂为下列之一或一种以上任意比例混合物:三乙胺、二异丙基乙胺、吡啶、吗啉、咪唑、2-甲基咪唑、四甲基胍、四甲基脲、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N,N-二丁基甲酰胺、N-甲基吡咯、N-甲基四氢吡咯。
- 如权利要求6所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的有机胺催化剂为N,N-二甲基甲酰胺。
- 如权利要求1所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的有机溶剂为下列之一或一种以上任意比例混合物:苯、甲苯、二甲苯、氯苯、二氯苯、正己烷、环己烷、二异丙基醚、二丁基醚、四氢呋喃、乙酸乙酯、二氯甲烷、三氯甲烷或二氯乙烷。
- 如权利要求8所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的有机溶剂为二氯甲烷。
- 如权利要求1-9中任一项中所述的一种氯磷酸二苯酯的化学合成方法,其特征在于所述的有机溶剂用量为磷酸二苯酯或磷酸二苯酯盐质量的3-8倍。
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