CN116925146A - Preparation method of 1-butyl phosphoric acid cyclic anhydride - Google Patents

Preparation method of 1-butyl phosphoric acid cyclic anhydride Download PDF

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CN116925146A
CN116925146A CN202310902994.5A CN202310902994A CN116925146A CN 116925146 A CN116925146 A CN 116925146A CN 202310902994 A CN202310902994 A CN 202310902994A CN 116925146 A CN116925146 A CN 116925146A
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butyl
catalyst
tri
reaction
phosphite
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尹佑志
顾建超
李伟
朱文忠
李永锋
潘慧丽
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Lianhe Chemical Technology Taizhou Co ltd
Lianhua Angjian Pharmaceutical Taizhou Co ltd
Lianhe Chemical Technology Co Ltd
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Lianhe Chemical Technology Taizhou Co ltd
Lianhua Angjian Pharmaceutical Taizhou Co ltd
Lianhe Chemical Technology Co Ltd
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    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • C07F9/657181—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and, at least, one ring oxygen atom being part of a (thio)phosphonic acid derivative
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/141—Esters of phosphorous acids
    • C07F9/142—Esters of phosphorous acids with hydroxyalkyl compounds without further substituents on alkyl
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4006—Esters of acyclic acids which can have further substituents on alkyl
    • 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 System
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids RP(=O)(OH)2; Thiophosphonic acids, i.e. RP(=X)(XH)2 (X = S, Se)
    • C07F9/40—Esters thereof
    • C07F9/4071—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4075—Esters with hydroxyalkyl compounds
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Abstract

The invention relates to a preparation method of 1-butyl phosphoric acid cyclic anhydride. The invention specifically discloses a preparation method of 1-butyl phosphoric acid cyclic anhydride, which comprises the following steps: in the presence of a catalyst, a chlorinating agent and dibutyl 1-butyl phosphate are subjected to oligomerization reaction to obtain the 1-butyl phosphoric acid cyclic anhydride. The preparation method provided by the invention has the advantages of simplicity in operation, high productivity, simple equipment, good safety and low cost, and is more suitable for industrial production.

Description

Preparation method of 1-butyl phosphoric acid cyclic anhydride
Technical Field
The invention relates to a preparation method of 1-butyl phosphoric acid cyclic anhydride.
Background
1-butyl phosphoric acid cyclic anhydride is an important condensation reagent, and is gradually applied to dehydration and coupling reaction of acid and amine in the polypeptide synthesis process in organic synthesis due to high activity. Compared with the conventional condensation reagent, the method has the advantages of high reaction yield, low toxicity, convenient post-treatment and the like. Meanwhile, the lithium ion battery electrolyte can be used as a novel functional additive, and can effectively improve multiple electrochemical performances and use safety of the lithium ion battery. Has great market potential value.
At present, the synthesis methods for preparing 1-butyl phosphoric acid cyclic anhydride are few, and the synthesis methods for 1-propyl phosphoric acid cyclic anhydride which are similar compounds on the market mainly comprise the following steps:
patent CN200480019925.5 mentions a method of evaporating the product by dissolving propylphosphoric acid as a raw material in acetic anhydride to carry out reflux reaction for 2 hours, then evaporating acetic acid and acetic anhydride under reduced pressure, and then raising the external temperature and vacuum. However, the high purity of the propylphosphoric acid used in this method is not readily available and thus limits its industrial production.
In addition, patent CN201710270226 mentions that 1-propyl phosphoric acid and acetic anhydride are used as raw materials to prepare propyl pyrophosphoric acid, propyl phosphoric acid and thionyl chloride are used as raw materials to prepare propyl phosphoryl chloride, and propyl pyrophosphoric acid and propyl phosphoryl chloride are further reacted to synthesize cyclic propyl phosphoric anhydride. However, the method needs to obtain propyl phosphoric acid with higher content, and further needs to synthesize two intermediates and then a product, so that the method has a longer route and is not easy for industrial production.
Patent CN20131038775. X mentions that dimethyl propyl phosphate is added into an ionic liquid solvent by controlling the temperature to be 0-80 ℃, acetic anhydride is added within 1-3 hours at the same process temperature after dripping is finished, then the reaction liquid is obtained by heating and refluxing for 1-8 hours, and the ionic liquid solvent is distilled off the low-boiling component at normal pressure and then distilled under reduced pressure, so that the 1-propyl phosphoric acid cyclic anhydride is obtained. However, the method adopts acetic anhydride as a raw material for reaction, the reaction time is long, and ionic liquid is used, so that the cost is increased.
In patent CN 111635434A, 1-propylphosphoric cyclic anhydride is prepared by reacting dimethyl 1-propylphosphate with thionyl chloride to form dichloride, and then reacting with two equivalents of dimethyl 1-propylphosphate. The method needs to be divided into two steps, is complicated, does not need to be added with a catalyst, needs to be cyclized at the high temperature of 250-300 ℃, has harsh reaction conditions, and is not beneficial to production and amplification.
Disclosure of Invention
The invention aims to overcome the defects that the existing 1-butyl phosphoric acid cyclic anhydride has long reaction steps, complex operation, difficult acquisition of raw materials, high cost, inapplicability to industrial production and the like in the preparation process, and provides a preparation method of the 1-butyl phosphoric acid cyclic anhydride. The preparation method provided by the invention has the advantages of simplicity in operation, high productivity, simple equipment, good safety and low cost, and is more suitable for industrial production.
The invention mainly solves the technical problems through the following technical scheme.
The invention discloses a preparation method of 1-butyl phosphoric acid cyclic anhydride, which comprises the following steps: in the presence of a catalyst, a chlorinating agent and 1-butyl dibutyl phosphate are subjected to oligomerization reaction as shown below to obtain 1-butyl phosphoric acid cyclic anhydride;
the catalyst is one or more of amide catalysts, quaternary ammonium salt catalysts, metal chlorides or metal oxides;
the chlorinating agent is one or more of thionyl chloride, oxalyl chloride and phosgene.
In the oligomerization reaction, the amide catalyst can be one or more of DMF, DMAC, DMAP, N, N-dimethylaniline and caprolactam acetone; the quaternary ammonium salt catalyst can be one or more of benzyl triethyl ammonium chloride (TEBA), tetrabutylammonium bromide (TBAB), tetrabutylammonium chloride, tetrabutylammonium bisulfate, trioctylmethyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride. The metal chloride may be one or more of magnesium chloride, lithium chloride, ferric chloride, calcium chloride and aluminum chloride. The metal oxide may be one or more of magnesium oxide, lithium oxide, iron oxide, calcium oxide and aluminum oxide.
In the oligomerization reaction, the catalyst may be one or more of DMF, DMAP, magnesium chloride, and tetrabutylammonium bromide (TBAB); preferably DMF and/or DMAP.
In the oligomerization reaction, the chlorinating agent is preferably thionyl chloride and/or oxalyl chloride.
In the oligomerization reaction, the mass ratio of the catalyst to the dibutyl 1-butylphosphate may be (0.01-0.1): 1, a step of; preferably (0.01-0.05): 1.
in the oligomerization reaction, the molar ratio of the chlorinating agent to the dibutyl 1-butyl phosphate may be (1.1-1.3): 1, a step of; preferably (1.1-1.2): 1.
in the oligomerization reaction, the reagents used in the oligomerization reaction are the dibutyl 1-butyl phosphate, the chlorinating reagent and the catalyst.
In the oligomerization reaction, the progress of the oligomerization reaction can be monitored using conventional testing methods in the art (e.g., TLC, HPLC, NMR or GC), typically with the starting materials disappearing or no longer reacting, or the product no longer increasing to the end of the reaction.
In the oligomerization, the temperature of the oligomerization may be 50 to 200 ℃, preferably 90 to 170 ℃.
The oligomerization reaction may further comprise the steps of:
(a) Mixing the catalyst with the dibutyl 1-butyl phosphate to obtain a mixture of the catalyst and the dibutyl 1-butyl phosphate;
(b) Adding the chlorinating agent to the mixture of step (a) to effect the indicated oligomerization reaction.
Preferably, the chlorinating agent is added dropwise.
Preferably, the chlorinating agent in step (b) may be added at a temperature of 90-140 ℃.
Preferably, the reaction temperature may be 110-170 ℃ after the completion of the addition of the chlorinating agent in step (b).
In the oligomerization reaction, 1-butyl dibutyl phosphate and a catalyst are mixed at the temperature of 90-140 ℃, a chlorinating reagent is added dropwise, and the temperature is raised to 110-170 ℃ after the completion of the oligomerization reaction.
In the oligomerization reaction, after the oligomerization reaction is completed, a post-treatment can be further included, wherein the post-treatment is (reduced pressure) distillation (impurity removal); when the catalyst is a metal chloride or metal oxide, the post-treatment may also include filtration. Both the reduced pressure distillation and filtration can be referred to the methods of operation conventional in the art.
The preparation method of the 1-butyl phosphoric acid cyclic anhydride can also comprise the preparation method of the 1-butyl phosphoric acid dibutyl ester, the preparation method of the 1-butyl phosphoric acid dibutyl ester can be a method 1 or a method 2, and the method 1 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
wherein the mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.1): 1, a step of;
the catalyst is RBr, R is-C 1-6 An alkyl group;
the method 2 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
in the method 2, the catalyst is alkali metal bromide, alkaline earth metal bromide or iron bromide;
in the method 1, the reaction temperature may be 50-200 ℃; preferably 110-180 ℃; more preferably 140-160 ℃.
In the method 1, the mass ratio of the catalyst to the tri-n-butyl phosphite is preferably (0.01-0.05): 1, more preferably 0.03:1.
In the method 1, the reagents used for the substitution reaction are the tri-n-butyl phosphite and the RBr.
In the method 1, the progress of the substitution reaction can be monitored using conventional test methods in the art (e.g., TLC, HPLC, NMR or GC), typically with the starting material disappearing or no longer reacting, or the product no longer increasing to the end of the reaction.
In the method 1, after the tri-n-butyl phosphite and the catalyst react, the method further comprises post-treatment, wherein the post-treatment is distillation impurity removal. The distillation impurity removal can be carried out according to the conventional operation method in the field.
In the method 2, the catalyst is preferably alkali metal bromide, alkaline earth metal bromide, preferably alkali metal bromide.
In the method 2, the alkali metal bromide may be LiBr, naBr, KBr or CsBr; preferably NaBr, KBr or CsBr; the alkaline earth metal bromide may be CaBr 2 Or MgBr 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably CaBr 2 。
In the method 2, the mass ratio of the catalyst to the tri-n-butyl phosphite may be (0.01-0.1): 1, a step of; preferably (0.01-0.05): 1.
in the method 2, the reagents used for the substitution reaction are the tri-n-butyl phosphite and the catalyst.
In the method 2, the reaction temperature may be 50-200 ℃; preferably 110-180 ℃; more preferably 140-160 ℃.
In method 2, the progress of the substitution reaction can be monitored using methods conventional in the art (e.g., TLC, HPLC, NMR or GC), typically with the starting material disappearing or no longer reacting, or the product no longer increasing to the end of the reaction.
In the method 2, after the substitution reaction is completed, a post-treatment may be further included, and the post-treatment may be filtration. The filtration can be carried out by reference to methods conventional in the art.
The preparation method of the 1-butyl phosphoric acid cyclic anhydride can also comprise the preparation method of the tri-n-butyl phosphite, and the preparation method of the tri-n-butyl phosphite comprises the following steps: in the presence of alkali, carrying out transesterification reaction shown as the following on trialkyl phosphite shown as a formula A and n-butanol to obtain tri-n-butyl phosphite;
wherein the R is 1 、R 2 、R 3 Independently C 1-4 Alkyl of (a); and R is 1 、R 2 And R is 3 Not both n-butyl.
The alkali is one or more of inorganic alkali and organic alkali.
In the transesterification reaction, the inorganic base can be MOH or M 2 CO 3 Or M 3 PO 4 M is an alkali metal; preferably MOH or M 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably sodium hydroxide or potassium hydroxide.
In the transesterification reaction, the organic base may beOR M 'OR', R a 、R b 、R c R' is independently C 1-4 Alkyl, M' is an alkali metal; />Preferably triethylamine or DIPEA; m 'OR' is preferably one OR more of sodium methoxide, sodium ethoxide and potassium tert-butoxide.
In the transesterification, the base is preferably MOH,OR M 'OR'; more preferably sodium hydroxide and/or potassium hydroxide; such as sodium hydroxide.
In the preparation method of tri-n-butyl phosphite, the reagents used in the transesterification reaction are trialkyl phosphite shown in the formula A, n-butanol and the alkali.
In the transesterification reaction, the mass ratio of the base to the trialkyl phosphite represented by formula a may be (0.01-0.1): 1, a step of; preferably (0.01-0.05): 1.
in the transesterification reaction, the mass ratio of the trialkyl phosphite and n-butanol shown in formula a may be 1: (1.5-4); preferably 1: (2-3).
In the transesterification reaction, the reaction temperature may be 50 to 120 ℃, preferably 50 to 110 ℃, more preferably 70 to 90 ℃.
In the transesterification reaction, the progress of the transesterification reaction can be monitored by conventional test methods in the art (e.g., TLC, HPLC, NMR or GC), typically with the disappearance of the starting material or no longer reacting as the endpoint of the reaction.
In the transesterification, after the transesterification is finished, the method can further comprise post-treatment, wherein the post-treatment is reduced pressure distillation for removing impurities. The distillation impurity removal can be carried out according to the conventional operation method in the field.
The invention also discloses a preparation method of the dibutyl 1-butyl phosphate, which is a method 1 or a method 2, wherein the method 1 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
wherein the mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.1): 1, a step of;
the catalyst is RBr, R is-C 1-6 An alkyl group;
the method 2 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
in the method 2, the catalyst is alkali metal bromide, alkaline earth metal bromide or iron bromide;
in the preparation method of the dibutyl 1-butyl phosphate, the reaction conditions of the method 1 and the method 2 are defined as above.
The preparation method of the dibutyl 1-butyl phosphate can also comprise the preparation method of the tributyl phosphite, and the preparation method of the tributyl phosphite is described in any scheme.
The invention also discloses a preparation method of tri-n-butyl phosphite, which comprises the following steps: in the presence of alkali, carrying out transesterification reaction shown as the following on trialkyl phosphite shown as a formula A and n-butanol to obtain tri-n-butyl phosphite;
wherein the R is 1 、R 2 、R 3 Independently C 1-4 Alkyl of (a); and R is 1 、R 2 And R is 3 Not both n-butyl.
In the preparation method of tri-n-butyl phosphite, the reaction conditions of the transesterification are defined as above.
The invention also discloses a preparation method of the 1-butyl phosphoric acid cyclic anhydride, which comprises the following steps:
(1) In the presence of alkali, carrying out transesterification reaction on trialkyl phosphite shown in a formula A and n-butanol as shown below to obtain tri-n-butyl phosphite;
wherein the R is 1 、R 2 、R 3 Independently C 1-4 Alkyl of (a); and R is 1 、R 2 And R is 3 Not both n-butyl;
(2) Adopting a method 1 or a method 2 to obtain 1-butyl dibutyl phosphate;
the method 1 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
wherein the mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.1): 1, a step of;
the catalyst is RBr, R is-C 1-6 An alkyl group;
the method 2 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
in the method 2, the catalyst is alkali metal bromide, alkaline earth metal bromide or iron bromide;
(3) In the presence of a catalyst, carrying out oligomerization reaction on a chlorinating reagent and 1-butyl dibutyl phosphate as shown below to obtain 1-butyl phosphoric acid cyclic anhydride;
the catalyst is one or more of amide catalysts, quaternary ammonium salt catalysts, metal chlorides or metal oxides.
Terminology
The term "alkyl" refers to a compound having a specified number of carbon atoms (e.g., C 1-6 ，C 1-4 ) Straight or branched, saturated monovalent hydrocarbon radicals. Alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl and the like.
In the preparation method of the 1-butyl phosphoric acid cyclic anhydride, the definition of each reaction condition is as described above.
The above preferred conditions can be arbitrarily combined on the basis of not deviating from the common knowledge in the art, and thus, each preferred embodiment of the present invention can be obtained.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: 1. the reaction raw materials are simple and easy to obtain, and the steps are very concise; 2. the conditions are mild, the equipment requirements are low, and the large-scale production is easy; 3. the amount of the three wastes is less, and the method is green and environment-friendly.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1: preparation of intermediate 1 (tri-n-butyl phosphite)
Weighing trimethyl phosphite (500 g,4.03 mol), sodium hydroxide solid (5 g, 1%w/w) and n-butanol (1000 g, 200%w/w) into a 3L reaction bottle, heating to 70-80 ℃, reacting for 24 hours, and after the reaction, decompressing and distilling excess n-butanol to obtain an intermediate 1 (tri-n-butyl phosphite), wherein the GC purity is 97%, the yield is 95%, and EI [ M+H ]] + ＝251。
Referring to the conditions of example 1, intermediate 1 (tri-n-butyl phosphite) was prepared using different bases, and the purity and yield of the obtained intermediate 1 are shown in table 1 below:
TABLE 1
Remarks: "-" indicates that no yield was measured, only a sample was taken during the reaction, and the purity of the product was measured by GC without stopping the reaction.
Example 2: preparation of intermediate 1 (tri-n-butyl phosphite)
Tripropyl phosphite (500 g,2.40 mol), potassium hydroxide solid (10 g, 2%w/w) and n-butanol (1500 g, 300%w/w) are weighed into a 3L reaction bottle, heated to 80-90 ℃, reacted for 48 hours, after the reaction is finished, excess n-butanol is distilled off under reduced pressure, thus obtaining intermediate 1 (tri-n-butyl phosphite) with GC purity of 95%, yield of 93% and EI [ M+1 ]] + ＝251。
Example 3: preparation of intermediate 2 (dibutyl 1-butylphosphate)
Weighing intermediate 1 (tributyl phosphite) (500 g,2.00 mol), sodium bromide solid (10 g, 2%w/w), putting into a 1L reaction bottle, heating to 140 ℃, reacting for 48h, cooling to 20-30 ℃ after the reaction is finished, filtering to obtain intermediate 2 (dibutyl 1-butylphosphate) with GC purity of 97%, yield of 99%, EI [ M+1 ]] + ＝251。
Referring to the conditions of example 3, intermediate 2 (dibutyl 1-butylphosphate) was prepared using different catalysts, and the purity and yield of intermediate 2 obtained are shown in table 2 below:
TABLE 2
Example 4: preparation of intermediate 2 (dibutyl 1-butylphosphate)
Weighing intermediate 1 (tributyl phosphite) (500 g,2.00 mol), bromoethane (25 g, 5%w/w), putting into a 1L autoclave, sealing and heating to 160 ℃, reacting for 24 hours, distilling at 60 ℃ until no liquid is extracted after the reaction is finished, cooling the residual liquid to 20-30 ℃ to obtain intermediate 2 (1-butyl dibutyl phosphate) with GC purity of 94%, yield of 100%, EI [ M+1 ]] + ＝251。
Referring to the conditions of example 4, intermediate 2 (dibutyl 1-butylphosphate) was prepared using different catalysts, and the purity and yield of intermediate 2 obtained are shown in table 3 below:
TABLE 3 Table 3
Example 5: preparation of 1-butyl phosphoric acid cyclic anhydride
1-butyl dibutyl phosphate (600 g,2.40 mol) and calcium chloride (6 g,1% w/w) are weighed and put into a 1L reaction bottle, the temperature is raised to 110-120 ℃, thionyl chloride (399 g,2.88mol,1.2 eq) is added dropwise, after the dropwise addition, the temperature is kept at 110-120 ℃ for 24 hours, residual chlorobutane is distilled off under reduced pressure, the temperature is reduced, and the filtration is carried out, thereby obtaining 273.6g of 1-butyl phosphoric acid cyclic anhydride, the phosphorus spectrum purity is 96.7%, the yield is 95%, and the 1-butyl phosphoric acid cyclic anhydride is obtained by comparing with a standard (purchased in market). 1 P NMR(243MHz,Chloroform-d)δ19.47–12.15(m)，EI[M] + ＝360。
Referring to the conditions of example 5, 1-butyl phosphoric acid cyclic anhydride was prepared using different chlorinating agents, and the purity and yield of the obtained 1-butyl phosphoric acid cyclic anhydride are shown in table 4 below:
TABLE 4 Table 4
Referring to the conditions of example 5, 1-butyl phosphoric acid cyclic anhydride was prepared using different catalysts, and the purity and yield of the obtained 1-butyl phosphoric acid cyclic anhydride are shown in Table 5 below:
TABLE 5
Example 6: preparation of 1-butyl phosphoric acid cyclic anhydride
1-butyl dibutyl phosphate (600 g,2.40 mol) and DMF (12 g, 2%w/w) are weighed and put into a 1L reaction bottle, the temperature is raised to 110-120 ℃, thionyl chloride (311 g,2.64mol,1.1 eq) is added dropwise, the temperature is raised to 130-150 ℃ after the dropwise addition, the temperature is kept for 12 hours, residual chlorobutane is distilled off under reduced pressure, 270.7g of 1-butyl phosphoric acid cyclic anhydride is obtained, the phosphorus spectrum purity is 100%, the yield is 94%, and the phosphorus spectrum is compared with a standard (commercial) to determine 1-butyl phosphoric acid cyclic anhydride, EI [ M ]] + ＝360。

Claims (10)

1. The preparation method of the 1-butyl phosphoric acid cyclic anhydride is characterized by comprising the following steps of: in the presence of a catalyst, a chlorinating agent and 1-butyl dibutyl phosphate are subjected to oligomerization reaction as shown below to obtain 1-butyl phosphoric acid cyclic anhydride;
the catalyst is one or more of amide catalysts, quaternary ammonium salt catalysts, metal chlorides or metal oxides;
the chlorinating agent is one or more of thionyl chloride, oxalyl chloride and phosgene.
2. The method of preparation of claim 1, wherein the method of preparation meets one or more of the following conditions:
(1) The amide catalyst is one or more of DMF, DMAC, DMAP, N, N-dimethylaniline and caprolactam acetone;
(2) The quaternary ammonium salt catalyst is one or more of benzyl triethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetrabutyl ammonium bisulfate, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride;
(3) The metal chloride is one or more of magnesium chloride, lithium chloride, ferric chloride, calcium chloride and aluminum chloride;
(4) The metal oxide is one or more of magnesium oxide, lithium oxide, ferric oxide, calcium oxide and aluminum oxide;
(5) The chlorinating reagent is thionyl chloride and/or oxalyl chloride;
(6) The mass ratio of the catalyst to the dibutyl 1-butyl phosphate is (0.01-0.1): 1, a step of; preferably (0.01-0.05): 1, a step of;
(7) The molar ratio of the chlorinating agent to the dibutyl 1-butyl phosphate is (1.1-1.3): 1, a step of; preferably (1.1-1.2): 1, a step of;
(8) The oligomerization temperature is 50-200deg.C, preferably 90-170deg.C.
3. The method of preparation of claim 2, wherein the method of preparation meets one or more of the following conditions:
(1) The catalyst is one or more of DMF, DMAP, magnesium chloride and tetrabutylammonium bromide; preferably DMF and/or DMAP;
(2) The reagent used in the oligomerization reaction is the dibutyl 1-butyl phosphate, the chlorinating reagent and the catalyst;
(3) The oligomerization reaction further comprises the steps of:
(a) Mixing the catalyst with the dibutyl 1-butyl phosphate to obtain a mixture of the catalyst and the dibutyl 1-butyl phosphate;
(b) Adding the chlorinating agent to the mixture of step (a) to effect the oligomerization reaction shown;
preferably, the chlorinating agent is added dropwise;
and/or, the adding temperature of the chlorinating agent in the step (b) is 90-140 ℃;
and/or, after the chlorinating agent is added in the step (b), the reaction temperature is 110-170 ℃;
(4) After the oligomerization reaction is completed, further comprising post-treatment, wherein the post-treatment is distillation; when the catalyst is a metal chloride or metal oxide, the post-treatment further comprises filtration.
4. The process according to any one of claims 1 to 3, wherein the process for producing 1-butyl phosphoric acid cyclic anhydride further comprises a process for producing dibutyl 1-phosphate, wherein the process for producing dibutyl 1-phosphate is process 1 or process 2,
the method 1 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
wherein the mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.1): 1, a step of;
the catalyst is RBr, R is-C 1-6 An alkyl group;
the method 2 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
in the method 2, the catalyst is alkali metal bromide, alkaline earth metal bromide or iron bromide;
5. the method according to claim 4, wherein,
the method 1 satisfies one or more of the following conditions:
(1) The reaction temperature is 50-200 ℃; preferably 110-180 ℃; more preferably 140-160 ℃;
(2) The mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.05): 1, preferably 0.03:1;
(3) The reagents used in the substitution reaction are the tri-n-butyl phosphite and the RBr;
(4) After the reaction of the tri-n-butyl phosphite and the catalyst is completed, the method further comprises post-treatment, wherein the post-treatment is distillation impurity removal;
the method 2 satisfies one or more of the following conditions:
(1) The catalyst is alkali metal bromide and alkaline earth metal bromide; alkali metal bromides are preferred;
wherein the alkali metal bromide may be LiBr, naBr, KBr or CsBr; preferably NaBr, KBr or CsBr;
the alkaline earth metal bromide may be CaBr 2 Or MgBr 2 The method comprises the steps of carrying out a first treatment on the surface of the Preferably CaBr 2 ；
(2) The mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.1): 1, a step of; preferably (0.01-0.05): 1, a step of;
(3) The reagents used in the substitution reaction are the tri-n-butyl phosphite and the catalyst;
(4) The reaction temperature is 50-200 ℃; preferably 110-180 ℃; more preferably 140-160 ℃;
(5) After the substitution reaction is completed, the method further comprises post-treatment, wherein the post-treatment is filtration.
6. The process according to claim 4, wherein the process for producing 1-butyl phosphoric acid cyclic anhydride further comprises a process for producing tri-n-butyl phosphite, which comprises the steps of:
in the presence of alkali, carrying out transesterification reaction shown as the following on trialkyl phosphite shown as a formula A and n-butanol to obtain tri-n-butyl phosphite;
wherein the R is 1 、R 2 、R 3 independently-C 1-4 Alkyl of (a); and R is 1 、R 2 And R is 3 Not both n-butyl.
7. The process of claim 6, wherein the process of preparing tri-n-butyl phosphite satisfies one or more of the following conditions:
(1) The reagents used in the transesterification reaction are the trialkyl phosphite shown in the formula A, n-butanol and the alkali;
(2) The alkali is one or more of inorganic alkali and organic alkali;
wherein the inorganic base can be MOH or M 2 CO 3 Or M 3 PO 4 M is an alkali metal; preferably MOH or M 2 CO 3 The method comprises the steps of carrying out a first treatment on the surface of the More preferably sodium hydroxide or potassium hydroxide;
the organic base may beOR M 'OR', R a 、R b 、R c And R' is independently C 1-4 Alkyl, M' is an alkali metal; />Preferably triethylamine or DIPEA; m 'OR' is preferably one OR more of sodium methoxide, sodium ethoxide and potassium tert-butoxide;
the base is preferably MOH,OR M 'OR'; more preferably sodium hydroxide and/or potassium hydroxide; such as sodium hydroxide;
(3) The mass ratio of the alkali to the trialkyl phosphite shown in the formula A is (0.01-0.1): 1, a step of; preferably (0.01-0.05): 1, a step of;
(4) The mass ratio of the trialkyl phosphite to the n-butanol shown in the formula A is 1: (1.5-4); preferably 1: (2-3);
(5) The reaction temperature is 50-120 ℃, preferably 50-110 ℃, more preferably 70-90 ℃;
(6) And after the transesterification reaction is finished, the method further comprises post-treatment, wherein the post-treatment is reduced pressure distillation for removing impurities.
8. A process for the preparation of dibutyl 1-butyl phosphate, characterized in that it is process 1 or process 2, said process 1 comprising the steps of: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
wherein the mass ratio of the catalyst to the tri-n-butyl phosphite is (0.01-0.1): 1, a step of;
the catalyst is RBr, R is-C 1-6 An alkyl group;
the method 2 comprises the following steps: performing substitution reaction on tri-n-butyl phosphite and a catalyst as shown below to obtain 1-butyl dibutyl phosphate;
in the method 2, the catalyst is alkali metal bromide, alkaline earth metal bromide or iron bromide;
9. the method of claim 8, wherein,
the reaction conditions of method 1 and method 2 are defined in claim 5;
and/or the preparation method of the 1-butyl dibutyl phosphate further comprises the preparation method of the tri-n-butyl phosphite, wherein the preparation method of the tri-n-butyl phosphite is as described in claim 6 or 7.
10. The preparation method of tri-n-butyl phosphite is characterized by comprising the following steps: in the presence of alkali, carrying out transesterification reaction shown as the following on trialkyl phosphite shown as a formula A and n-butanol to obtain tri-n-butyl phosphite;
wherein the R is 1 、R 2 、R 3 independently-C 1-4 Alkyl of (a); and R is 1 、R 2 And R is 3 Not both n-butyl;
preferably, the reaction conditions of the transesterification reaction are defined as in claim 7.
CN202310902994.5A 2023-07-21 2023-07-21 Preparation method of 1-butyl phosphoric acid cyclic anhydride Pending CN116925146A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115253339A (en) * 2022-07-21 2022-11-01 西安彩晶光电科技股份有限公司 Production device and process of 1-propylphosphoric cyclic anhydride

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115253339A (en) * 2022-07-21 2022-11-01 西安彩晶光电科技股份有限公司 Production device and process of 1-propylphosphoric cyclic anhydride
CN115253339B (en) * 2022-07-21 2024-04-12 西安彩晶光电科技股份有限公司 Production device and process of 1-propyl phosphoric acid cyclic anhydride

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