CN103360243B - Preparation method of 1,3-diacyloxy dimethylmethane compound - Google Patents
Preparation method of 1,3-diacyloxy dimethylmethane compound Download PDFInfo
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- CN103360243B CN103360243B CN201210101410.6A CN201210101410A CN103360243B CN 103360243 B CN103360243 B CN 103360243B CN 201210101410 A CN201210101410 A CN 201210101410A CN 103360243 B CN103360243 B CN 103360243B
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Abstract
The invention relates to a preparation method of a 1,3-diacyloxy dimethylmethane compound in a general formula (I). The preparation method comprises the following steps of: in the presence of a catalyst containing anhydrous potassium carbonate, performing esterification on 1,3-propylene glycol compound with a general formula (II) and ester with a structural general formula RCOOR<5> to obtain the 1,3-diacyloxy dimethylmethane compound and an alcohol product with a general formula HOR<5>, wherein R<1> and R<2> are respectively selected from one of hydrogen atoms, methyl, ethyl and isopropyl; R<3> and R<4> are respectively selected from one of hydrogen atoms, linear chain C2-C8 alkyl, branch chain C3-C8 alkyl, C3-C6 naphthenic base, C4-C8 alkyl naphthenic base, C4-C8 naphthenic base alkyl and C7-C8 aralkyl; R is selected from one of linear chain C2-C17 aliphatic group, branch chain C3-C17 alkyl and C4-C8 alkyl naphthenic base; and R5 is selected from methyl or ethyl. According to the method, the environmental protection is facilitated, the yield of a product is increased, and the purity is high.
Description
Technical field
The present invention relates to the preparation method of contained internal electron donor 1,3-diol-lipid compound in the catalyst component for olefinic polymerization, be specifically related to the preparation method of 1,3-bis-acyloxy propane compound.
Background technology
In this area, as everyone knows, Ziegler-Natta catalyst is at least made up of two parts: the active ingredient (also claiming Primary Catalysts) containing transition metal and the organometallics (also claiming promotor) containing periodic system I A-IIIA race element.In Primary Catalysts, it is titanium or vanadium transistion metal compound that practical application obtains more, and this transistion metal compound generally forms ingredient of solid catalyst together with carrier magnesium chloride; In promotor, it is the halogenide of aluminum alkyls or aluminum alkyls that practical application obtains more.In some occasion, particularly when being used to propylene polymerization catalysis, usually add three components to control product degree of isotacticity and to improve polymerization activity etc.They are generally Lewis alkali, also claim electron donor compound.The electron donor added in Primary Catalysts preparation process is called as internal electron donor, and is called as external electron donor at the electron donor using Primary Catalysts to carry out joining olefin polymerization system with promotor in olefinic polyreaction process.
1 is disclosed in CN1436796A, CN1453298A and CN1580034A, 3-diol-lipid compound is as internal electron donor, it is disclosed that containing the substituent internal electron donor with 1,3-bis-acyloxy propane compound of having structure general formula (I)
In general structure (I),
R
1, R
2be selected from respectively following in one: hydrogen atom, methyl, ethyl and sec.-propyl; R
1, R
2group is same to each other or different to each other;
R
3, R
4be selected from respectively following in one: the C of hydrogen atom, straight chain
1-C
8the C of alkyl, side chain
3-C
8alkyl; R
3, R
4group is same to each other or different to each other;
R is selected from the C of straight chain
1-C
20the C of alkyl, side chain
3-C
20alkyl, C
3-C
20cycloalkyl, C
6-C
20aryl, C
7-C
20aralkyl, C
2-C
20alkylene in one.
CN1436796A and CN1453298A in an embodiment disclosed concrete internal electron donor compound is: 1,3-PD two laurate and 2,2-position alkyl substituents thereof, 1, ammediol dipropionate and 2,2-position alkyl substituents thereof, 1,3-PD diacrylate and 2,2-position alkyl substituents thereof, 2,4-pentanediol two laurate, 2,4-pentanediol dipropionate, 2,4-Diacrylate, 6-heptene-2,4-heptanediol two pivalate.
The preparation method of above-mentioned internal electron donor is also open in CN1436796A, CN1453298A and CN1580034A, uses corresponding glycol and excessive acyl chlorides and pyridine to react obtained respectively.But acyl chlorides has corrodibility, and facile hydrolysis becomes carboxylic acid and hydrogenchloride, is unfavorable for environment protection.This preparation method also produces at least equimolar by product pyridine hydrochloride and other impurity, and this adds difficulty to the abstraction and purification of principal product, thus causes principal product yield low, and purity is low.If obtain the product of higher degree, this patent documentation often adopts column chromatography method purifying, and this is unfavorable for scale operation.
In order to solve above-mentioned separation and purification problem, CN101665429A discloses a kind of quality optimization method of binary alcohol esters, under it is included in the existence of higher solvent, make dibasic alcohol and acyl chloride reaction, and add the good lower aliphatic alcohols of reactive behavior after the completion of reaction, itself and impurity are reacted, thus obtains binary alcohol esters compounds, but still to there is use in the method have corrosive acyl chlorides problem.
Summary of the invention
The object of the invention is, in order to overcome in prior art the shortcoming prepared and need to use acyl chlorides in 1,3-bis-acyloxy propane compound process, to provide a kind of without the need to using the preparation method of 1,3-bis-acyloxy propane compound of acyl chlorides.
To achieve these goals, the invention provides that a kind of general structure is (I) 1, the preparation method of 3-bis-acyloxy propane compound, wherein, under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be 1,3-PD compounds and the general structure of (II) by general structure be RCOOR
5ester react, generate comprise general structure for 1, the 3-bis-acyloxy propane compound of (I) and corresponding general formula be HOR
5alcohol product;
Wherein,
R
1, R
2be selected from the one in hydrogen atom, methyl, ethyl and sec.-propyl respectively;
R
3, R
4be selected from the C of hydrogen atom, straight chain respectively
1-C
8the C of alkyl, side chain
3-C
8alkyl, C
3-C
6cycloalkyl, C
4-C
8alkyl-cycloalkyl, C
4-C
8cycloalkylalkyl and C
7-C
8one in aralkyl;
R is selected from the C of straight chain
2-C
17the C of aliphatic group, side chain
3-C
17alkyl and C
4-C
8one in cycloalkyl;
R
5for methyl or ethyl.
The preparation method of 1,3-bis-acyloxy propane compound provided by the invention, owing to being RCOOR with general structure
5ester substitute there is corrosive acyl chlorides as acylating agent, therefore, the method is conducive to environment protection.In addition, product and reactant and catalyzer easily separated, the product yield obtained is high, and purity is good, is suitable for large-scale commercial production.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
According to general structure of the present invention is (I) 1, the preparation method of 3-bis-acyloxy propane compound, wherein, under the method is included in the catalyzer existence containing Anhydrous potassium carbonate, be 1,3-PD compounds and the general structure of (II) by general structure be RCOOR
5ester react, generate comprise general structure for 1, the 3-bis-acyloxy propane compound of (I) and corresponding general formula be HOR
5alcohol product;
Wherein,
R
1, R
2be selected from the one in hydrogen atom, methyl, ethyl and sec.-propyl respectively;
R
3, R
4be selected from the C of hydrogen atom, straight chain respectively
1-C
8the C of alkyl, side chain
3-C
8alkyl, C
3-C
6cycloalkyl, C
4-C
8alkyl-cycloalkyl, C
4-C
8cycloalkylalkyl and C
7-C
8one in aralkyl;
R is selected from the C of straight chain
2-C
17the C of aliphatic group, side chain
3-C
17alkyl and C
4-C
8one in cycloalkylalkyl;
R
5for methyl or ethyl.
According to the present invention, although under the catalyzer containing Anhydrous potassium carbonate exists, be that 1,3-PD compounds and the general structure of (II) is RCOOR by general structure
5ester carry out reaction and can realize object of the present invention, be namely beneficial to environment protection, product and reactant and catalyzer easily separated, yield is high, and purity is good.But under preferable case, described general structure is the 1,3-PD compounds of (II) and general structure is RCOOR
5the ester transesterification reaction of carrying out carry out under distillation or rectifying condition, with in reaction process except the alcohol HOR that dereaction generates
5; Further preferred version is, adds alcohol HOR in reaction after 5-7 hour in reaction solution
5entrainer, and further by distillation or rectifying except dereaction generate alcohol HOR
5.This preferred version can further improve yield and the purity of the product that general structure is (I).
What steadily continue to enable above-mentioned preferred version carries out forward, reaction brings into use upper end " skimmer " of prolong to be housed as water distilling apparatus, described " skimmer " refers to that the Dean and Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end) of piston switch is arranged at bottom, after reaction 5-7 hour, the feed postition of entrainer is preferably to divide and joins for 5-7 time in reaction solution, the adjacent timed interval added for twice is 1.1-1.5 hour, relative to reaction start time 1 mole 1, ammediol compounds, each add-on of entrainer is 60-180mL.
The another kind of preferred mode applying entrainer is: water distilling apparatus or rectifier unit are brought into use in reaction, under distillation or rectifying condition after transesterification reaction 5-7 hour, entrainer Continuous Flow under distillation or rectifying condition is added in reaction solution, relative to reaction start time 1 mole 1, ammediol compounds, the flow acceleration of entrainer is 60-180mL/ hour, and it is 5-7 hour that stream adds the time.
It will be understood by those skilled in the art that gradation adds fashionable, when adding entrainer, can not lower the temperature to reaction solution, also the temperature of reaction solution can be cooled under the boiling point of entrainer, then add entrainer.Under the boiling point preferably reaction solution being cooled to entrainer in laboratory, the time of general cooling is no more than half an hour, preferred 0.1-0.5 hour; The Continuous Flow added-time, carry out between the boiling point of the azeotrope that the alcohol that reaction should generate at the boiling point of entrainer and entrainer and reaction is formed, flow acceleration can regulate according to the kind of speed of response, entrainer and consumption, and the mode that entrainer Continuous Flow under distillation or rectifying condition is added to reaction solution is applicable to scale operation.
In the present invention, entrainer is preferably the aromatic hydrocarbon solvent that boiling point is 80-145 DEG C, is more preferably one or more in p-Xylol, o-Xylol, m-xylene, toluene and benzene; More preferably toluene.
In the present invention, general structure is RCOOR
5the boiling point of ester be generally HOR higher than general formula
5the boiling point of alcohol, work as RCOOR
5with HOR
5boiling point close to time, general structure is the 1,3-PD compounds of (II) and general structure is RCOOR
5transesterification reaction preferably react under rectifying condition, reaction removes the alcohol HOR of generation simultaneously
5.
In the present invention, the amount of reactant is preferably, and general structure is RCOOR
5at least 2 times of the mole number of ester to be general structure the be mole number of the 1,3-PD compounds of (II); Be more preferably, general structure is the 1,3-PD compounds of (II) and general structure is RCOOR
5the mol ratio of ester be 1: 2-10; More preferably, general structure is the 1,3-PD compounds of (II) and general structure is RCOOR
5the mol ratio of ester be 1: 2.5-4.It will be understood by those skilled in the art that along with general formula is RCOOR
5ester mole dosage increase, although speed of response accelerate, yield improve, also affect product separation.
The kind of the present invention to the catalyzer containing Anhydrous potassium carbonate is not particularly limited, as long as just can realize goal of the invention containing Anhydrous potassium carbonate in catalyzer.Preferably, in described catalyzer, with the total amount of catalytic active component, the content of Anhydrous potassium carbonate is not less than 50 % by weight, and more preferably described catalyzer is that Anhydrous potassium carbonate itself or Anhydrous potassium carbonate load are forming loaded catalyst (namely catalytic active component is Anhydrous potassium carbonate) on inorganic refractory metal oxide carrier.When described catalyzer be Anhydrous potassium carbonate load at the loaded catalyst that inorganic refractory metal oxide carrier is formed time, with the gross weight of this catalyzer for benchmark, the content of described Anhydrous potassium carbonate is 10-30%.In the present invention, described inorganic refractory metal oxide carrier can be aluminum oxide, the one in molecular sieve and zirconium white.
It will be understood by those skilled in the art that the consumption along with catalyzer increases, although speed of response is accelerated, also affect product separation.Amid all these factors, in the present invention, when described catalyzer adopt Anhydrous potassium carbonate catalyzer or and the loaded catalyst of Anhydrous potassium carbonate load on inorganic refractory metal oxide carrier time, preferred structure general formula is the 1,3-PD compounds of (II) and the mol ratio of Anhydrous potassium carbonate is 1: 0.001-0.5; Be more preferably, general structure is the 1,3-PD compounds of (II) and the mol ratio of Anhydrous potassium carbonate is 1: 0.01-0.2.The amount of above-mentioned Anhydrous potassium carbonate, with the gauge of Anhydrous potassium carbonate actual in catalyzer, does not comprise the amount of carrier.
In the present invention, the temperature of reaction is 65-160 DEG C.In actually operating, the temperature of reaction solution is along with the lower boiling by-product alcohol HOR removing dereaction generation in reaction process
5(the boiling point bp65 DEG C of such as methyl alcohol) and increase.In laboratory, adopt conventional glass flask as reactor, usually with water-bath or the oil bath thermal source as heating.When the temperature of water-bath or oil bath is 100-170 DEG C, and reactant is carboxylate methyl ester, when entrainer is toluene, reacting liquid temperature can be made to control 65-160 DEG C of scope.In the industrial production, control thermal source needed for temperature of reaction to be provided by the various known method in this area, such as 100 DEG C provide by water vapor bath or oil bath heating, and the temperature range of 100-170 DEG C provides by pressured steam bath or oil bath heating.
What those skilled in the art should understand that is, in order to obtain that the higher general structure of purity is (I) 1,3-bis-acyloxy propane compound, the inventive method preferably also comprises after termination of the reaction, by general structure be (I) 1,3-bis-acyloxy propane compound from reaction after gained mixture separate.Be the method that 1, the 3-bis-acyloxy propane compound of (I) is separated from the rear gained mixture of reaction by general structure, comprising the general structure in reaction gained mixture is HOR
5alcohol, the catalyzer comprising Anhydrous potassium carbonate, unreacted general structure be RCOOR
5ester and general structure be the 1,3-PD compounds of (II), and a small amount of intermediate product 1-acyloxy-3-hydroxy propane compounds, removes from reaction gained mixture.The present invention to the aforesaid method that partial reaction thing, reaction intermediate and catalyzer are removed from reaction gained mixture without particular requirement, can adopt those skilled in the art the thinkable various method removing other impurity from reaction mixture, preferably first by distillation or rectifying method by reaction generate general structure be HOR
5alcohol remove from reaction gained mixture, again by filtering, the catalyzer comprising Anhydrous potassium carbonate removes by the method for centrifugation or extraction from reaction gained mixture, finally by the method for underpressure distillation or rectification under vacuum, be RCOOR by unreacted general structure
5ester and general structure be the 1,3-PD compounds of (II), and a small amount of intermediate product 1-acyloxy-3-hydroxy propane compounds, removes from reaction gained mixture.
In the present invention, R
3, R
4the preferred C from hydrogen atom, straight chain respectively
1-C
5the C of alkyl and side chain
3-C
5one in alkyl; R is preferably from the C of straight chain
3-C
17aliphatic group; R
5be preferably methyl.General structure is that the 1,3-PD compounds of (II) is more preferably from 1,3-PD, 2,2-dimethyl-1, ammediol, 2,4-pentanediols, 3,5-heptanediols, 4-ethyl-3,5-heptanediol, 2-sec.-propyl-2-isopentyl-1, ammediol, 1,3 butylene glycol and 2,2, one in 4-trimethylammonium-1,3-pentanediol; Preferred one in 2，2-dimethyl-1，3-propanediol, 2,4-pentanediols and 1,3 butylene glycol further; Further be preferably 2,4-pentanediol.It will be understood by those skilled in the art that 2,4-pentanediol has multiple steric isomer owing to there is chiral centre in 2,4-pentanediol.In the present invention, described 2,4-pentanediols are one or more steric isomers in meso 2,4-pentanediol, racemize 2,4-pentanediol, left-handed 2,4-pentanediols and dextrorotation 2,4-pentanediol.In the present invention, under a kind of preferable case, described 2,4-pentanediols are a kind of steric isomer in meso 2,4-pentanediol, racemize 2,4-pentanediol, left-handed 2,4-pentanediols and dextrorotation 2,4-pentanediol.Under another kind of preferable case, described 2,4-pentanediols 2, the 4-pentanediols that to be U.S. chemical abstract CA registration number be [625-69-4].2, the 4-pentanediols being [625-69-4] when selection U.S. chemical abstract CA registration number are reactant, are RCOOR with general structure
5ester reaction, resulting structures general formula be in 1, the 3-bis-acyloxy propane compound product of (I) contain meso and racemic stereoisomers.
The present invention is further illustrated for following embodiment, but therefore do not limit the present invention." skimmer " described in embodiment refers to that the Dean and Stark apparatus (Dean and Stark apparatus with a stopcock at the lower end) of piston switch is arranged at bottom
Embodiment 1
This embodiment is for illustration of the preparation method of 2,4-bis-pungent acyloxy pentanes provided by the invention.
10.4g (0.1mol) 2 is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator, 4-pentanediol (U.S. chemical abstract CA registration number is the commercially available reagent of [625-69-4]), 47.47g (0.3mol) n-caprylic acid methyl esters, 2.76g (0.02mol) Anhydrous potassium carbonate, adopt oil bath heating round-bottomed flask.Oil bath is heated to 160 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 5 hours, in round-bottomed flask, add toluene, front and back add 5 times altogether, the adjacent timed interval added for twice is 1.5 hours, add 12mL, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 30 minutes more at every turn.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, then by filtrate 500Pa, at 50 DEG C underpressure distillation remove unreacted n-caprylic acid methyl esters and other impurity, obtain 2,4-bis-pungent acyloxy pentane 34.9g.The yield of the pungent acyloxy pentane of 2,4-bis-is 98%, analyzes, purity 100% (wherein, mesomeride 44%, racemic modification 56%) through gas chromatography-mass spectrography (GC-MS).The results are shown in Table 1.Carry out mass spectrum, infrared spectra and hydrogen nuclear magnetic resonance spectrum analysis, result is as follows.
MS(EI，m/z)：214(M-142)
.+，213(M-143)
+，183，171，169，155，145，141，128，127，125，109，85，69，57，43，41。
IR(cm
-1)：2957，2929，2857，1736，1458，1378，1254，1174，1143，1102，1037，1003，962，725。
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.901(t，6H，2CH
3(CH
2)
5CH
2COO)，1.207～1.278&1.500～1.700(m，26H，2CH
3(CH
2)
5CH
2COO；CH
3CHCH
2CHCH
3)，1.500～1.700&1.934～2.029(m，44％×2H，mesomeric CHCH
2CH)，1.729～1.774(dd，56％×2H，racemicCHCH
2CH，J＝6.3Hz)，2.246～2.311(m，4H，2CH
3(CH
2)
5CH
2COO)，4.926～5.007(m，2H，CH
3CHCH
2CHCH
3)。
Embodiment 2
This embodiment is for illustration of the preparation method of 1,3-bis-pungent acyloxy butane provided by the invention.
18g (0.2mol) 1 is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator, 3-butyleneglycol, 94.9g (0.6mol) n-caprylic acid methyl esters, 5.53g (0.04mol) Anhydrous potassium carbonate, adopt oil bath heating round-bottomed flask.Oil bath is heated to 143 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, in round-bottomed flask, add toluene, front and back add toluene 6 times altogether, the adjacent timed interval adding toluene for twice is 1.1 hours, add 18mL, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 6 minutes more at every turn.After reaction terminates, round-bottomed flask is cooled.Cross and filter Anhydrous potassium carbonate, then filtrate is distilled the unreacted n-caprylic acid methyl esters of removing and other impurity under 271Pa at 72 DEG C, obtain 1,3-bis-pungent acyloxy butane 63.4g.The yield of 1,3-bis-pungent acyloxy butane 63.4g is 93%, analyzes, purity 97% through gas chromatography-mass spectrography (GC-MS).The results are shown in Table 1.Carry out mass spectrum and hydrogen nuclear magnetic resonance spectrum analysis, result is as follows.
MS(EI，m/z)：217(M-125)
+，215(M-127)
+，214(M-128)
.+，200(M-142).
+，199(M-143)
+，171，145，128，127，125，114，57，43。
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.857～0.902(t，6H，2CH
3(CH
2)
5CH
2COO，J＝6.8Hz)，1.240～1.291(m，20H，2CH
3(CH
2)
5CH
2COO，J＝6.8Hz)，1.558～1.633(m，3H，COOCH
2CH
2CHCH
3)，1.833～1.918(m，2H，COOCH
2CH
2CHCH
3)，2.246～2.311(m，4H，2CH
3(CH
2)
5CH
2COO)，4.081～4.126(m，2H，COOCH
2CH
2CHCH
3)，4.961～5.067(m，H，COOCH
2CH
2CHCH
3)。
Embodiment 3
This embodiment is for illustration of the preparation method of 1,3-bis-hexylyloxy butane provided by the invention.
18g (0.2mol) 1 is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator, 3-butyleneglycol, 78g (0.6mol) methyl hexyl, 5.53g (0.04mol) Anhydrous potassium carbonate, adopt oil bath heating round-bottomed flask.Oil bath is heated to 143 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 7 hours, in reaction solution, add toluene, front and back add toluene 7 times altogether, the adjacent timed interval adding toluene for twice is 1.25 hours, add toluene 15mL, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 15 minutes more at every turn.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, then filtrate is distilled the unreacted methyl hexyl of removing and other impurity under 271Pa at 69 DEG C, obtain 1,3-bis-hexylyloxy butane 54.3g.The yield of 1,3-bis-hexylyloxy butane is 95%, analyzes, purity 96% through gas chromatography-mass spectrography (GC-MS).The results are shown in Table 1.Carry out mass spectrum and hydrogen nuclear magnetic resonance spectrum analysis, result is as follows.
MS(EI，m/z)：187(M-99)
+，186(M-100)
.+，172(M-114)
.+，171(M-115)
+，143，141，127，117，114，99，71，55，43，41。
Electrospray ionization mass spectrum (ESI): 309.23 with molecular formula C
16h
30o
4the quasi-molecular ions total mass number of compound M+Na is consistent.
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.873～0.919(t，6H，2CH
3(CH
2)
3CH
2COO，J＝6.9Hz)，1.242～1.315(m，12H，2CH
3(CH
2)
3CH
2COO)，1.592～1.642(m，3H，COOCH
2CH
2CHCH
3)，1.854～1.900(m，2H，COOCH
2CH
2CHCH
3)，2.247～2.313(m，4H，2CH
3(CH
2)
3CH
2COO)，4.082～4.127(m，2H，COOCH
2CH
2CHCH
3)，4.983～5.047(m，H，COOCH
2CH
2CHCH
3)。
Embodiment 4
This embodiment is for illustration of the preparation method of 1,3-diamyl acyloxy butane provided by the invention.
18g (0.2mol) 1 is added in the 250mL round-bottomed flask of band condenser, skimmer, agitator, 3-butyleneglycol, 69.7g (0.6mol) positive methyl valerate, 5.53g (0.04mol) Anhydrous potassium carbonate, adopt oil bath heating round-bottomed flask.Oil bath is heated to 145 DEG C, react under 0.1MPa, by distillating method the alcohol of generation steamed to skimmer in reaction simultaneously and remove, react after 6 hours, in reaction solution, add toluene, front and back add toluene 6 times altogether, the adjacent timed interval adding toluene for twice is 1.1 hours, add 18mL, react 1 hour after adding toluene at every turn and toluene and azeotrope distilled out round-bottomed flask simultaneously, question response liquid cooling but adds toluene next time after about 6 minutes more at every turn.By the mixture cold filtration removing Anhydrous potassium carbonate in round-bottomed flask after reaction terminates, then filtrate is distilled at 150Pa and 81 DEG C the unreacted positive methyl valerate of removing and other impurity, obtain 1,3-diamyl acyloxy butane 47g.The yield of 1,3-diamyl acyloxy butane is 91%, analyzes, purity 95% through gas chromatography-mass spectrography (GC-MS).The results are shown in Table 1.Carry out mass spectrum and hydrogen nuclear magnetic resonance spectrum analysis, result is as follows.
MS(EI，m/z)：172(M-86)
.+，158(M-100)
.+，157(M-101)，129，127，114，103，85，71，57，55，43，41。
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.86～0.940(t，6H，2CH
3(CH
2)
2CH
2COO，J＝6.8Hz)，1.241～1.262(d，3H，COOCH
2CH
2CHCH
3，J＝6.3Hz)，1.281～1.404 & 1.559～1.651(m，8H，2 CH
3(CH
2)
2CH
2COO)，1.834～1.919(m，2H，COOCH
2CH
2CHCH
3)，2.254～2.336(m，4H，2CH
3(CH
2)
2CH
2COO)，4.082～4.128(m，2H，COOCH
2CH
2CHCH
3)，4.982～5.046(m，H，COOCH
2CH
2CHCH
3)。
Embodiment 5
This embodiment is for illustration of the preparation method of 1,3-bis-butyryl acyloxy butane provided by the invention.
1 is prepared according to the method for embodiment 4,3-bis-butyryl acyloxy butane, unlike, substitute the positive methyl valerate of 69.7g (0.6mol) with 61.2g (0.6mol) methyl butyl, react after 6 hours, do not add toluene, directly unreacted methyl butyl is distilled, obtain 1,3-bis-butyryl acyloxy butane 45.7g, analyze through gas chromatography-mass spectrography (GC-MS), purity 85%.The results are shown in Table 1.Carry out mass spectroscopy, result is as follows.
MS(EI，m/z)：159(M-71)
+，158(M-72)
.+，143(M-87)
+，142(M-88).
+，115，114，99，89，71，43，41。
Embodiment 6
This embodiment is for illustration of the preparation method of 1,3 butylene glycol dioleate provided by the invention.
1 is prepared according to the method for embodiment 2,3-butyleneglycol dioleate, unlike, with 9g (0.1mol) 1,3-butyleneglycol, 88.8g (0.3mol) Witconol 2301,2.76g (0.02mol) Anhydrous potassium carbonate react, obtain 1,3 butylene glycol dioleate 55.5g, yield 90%.
Embodiment 7
This embodiment is for illustration of the preparation method of 2,4-bis-butyryl acyloxy pentanes provided by the invention.
2,4-bis-butyryl acyloxy pentane is prepared according to the method for embodiment 1, unlike, substitute 47.47g (0.3mol) n-caprylic acid methyl esters with 30.64g (0.3mol) methyl butyl, obtain two butyryl acyloxy pentane 13.5g, yield 57%.Analyze through gas chromatography-mass spectrography (GC-MS), purity 98% (wherein, mesomeride 40%, racemic modification 58%).The results are shown in Table 1.Carry out mass spectroscopy, result is as follows.
MS(EI，m/z)：159(M-85)
+，157(M-87)
+，141，128(M-116).
+，115，113，89，85，71，69，43，41。
Embodiment 8
This embodiment is for illustration of the preparation method of the pungent acyloxy propane of 2-sec.-propyl-2-isopentyl-1,3-bis-provided by the invention.
2-sec.-propyl-2-isopentyl-1 is prepared according to the method for embodiment 1, the pungent acyloxy propane of 3-bis-, unlike, substitute 2 with 11.3g (0.06mol) 2-sec.-propyl-2-isopentyl-1,3-PD, 4-pentanediol, obtain the pungent acyloxy propane 25.3g of 2-sec.-propyl-2-isopentyl-1,3-bis-, yield 96%, analyze through gas chromatography-mass spectrography (GC-MS), purity 98%.The results are shown in Table 1.Carry out mass spectrum and hydrogen nuclear magnetic resonance spectrum analysis, result is as follows.
MS(EI，m/z)：397(M-43)
+，396(M-44)
.+，297(M-143)
+，282(M-158).
+，252，169，152，140，137，127，110，109，97，85，83，57，69，57，55，44，43，41。
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.886～0.932(m，18H，2CH
3CHCH
3，2CH
3(CH
2)
5CH
2COO)，1.100～1.288(m，20H，2CH
3(CH
2)
5CH
2COO)，1.416～1.460(m，1H，CH
2CH
2CH)，1.583～1.631(m，4H，CH
2CH
2CH)，1.787～1.856(m，1H，CH
3CHCH
3)，2.263～2.313(t，4H，2CH
3(CH
2)
5CH
2COO，J＝7.5Hz)，3.977～4.058(m，4H，2CH
2O)。
Embodiment 9
This embodiment is for illustration of the preparation method of the pungent acyloxy propane of 2,2-dimethyl-1,3-bis-provided by the invention.
The pungent acyloxy propane of 2,2-dimethyl-1,3-bis-is prepared according to the method for embodiment 1, unlike, with 10.4g (0.1mol) 2,2-dimethyl-1, ammediol substitutes 2,4-pentanediol, substitutes 47.47g (0.3mol) n-caprylic acid methyl esters with 63.3g (0.4mol) n-caprylic acid methyl esters, obtain 2, the pungent acyloxy propane 32.3g of 2-dimethyl-1,3-bis-, yield 91%, analyze through gas chromatography-mass spectrography (GC-MS), purity 100%.The results are shown in Table 1.Carry out mass spectrum, infrared spectra and hydrogen nuclear magnetic resonance spectrum analysis, result is as follows.
MS(EI，m/z)：231(M-125)
+，213(M-143)
+，199，188，170，168，147，141，129，128，127，109，98，85，83，69，57，43，41。
IR(cm
-1)：2957，2929，2857，1741，1467，1379，1252，1162，1106，1005，938，725。
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.857～0.902(t，6H，2CH
3(CH
2)
5CH
2COO)，0.964(s，6H，(CH
3)
2C(CH
2O)
2)，1.282～1.301(m，16H，2CH
3(CH
2)
4CH
2CH
2COO)，1.595～1.643(m，4H，2 CH
3(CH
2)
4CH
2CH
2COO)，2.286～2.337(t，4H，2CH
3(CH
2)
4CH
2CH
2COO)，3.881(s，4H，(CH
3)
2C(CH
2O)
2)。
Embodiment 10
This embodiment is for illustration of the preparation method of the pungent acyloxy propane of 2,2-dimethyl-1,3-bis-provided by the invention.
The pungent acyloxy propane of 2,2-dimethyl-1,3-bis-is prepared according to the method for embodiment 1, unlike, with 10.4g (0.1mol) 2,2-dimethyl-1, ammediol substitutes 2,4-pentanediol, substitutes 47.47g (0.3mol) n-caprylic acid methyl esters with 39.56g (0.25mol) n-caprylic acid methyl esters, obtains being mainly 2,2-dimethyl-1, the product 29.60g of the pungent acyloxy propane of 3-bis-, analyzes through gas chromatography-mass spectrography (GC-MS), purity 71%.The results are shown in Table 1.
Embodiment 11
This embodiment is for illustration of the preparation method of the pungent acyloxy propane of 2,2-dimethyl-1,3-bis-provided by the invention.
2 are prepared according to the method for embodiment 1, 2-dimethyl-1, the pungent acyloxy propane of 3-bis-, unlike, with 8.32g (0.08mol) 2, 2-dimethyl-1, ammediol substitutes 10.4g (0.1mol) 2, 4-pentanediol, 47.47g (0.3mol) n-caprylic acid methyl esters is substituted with 50.63g (0.32mol) n-caprylic acid methyl esters, 2.76g (0.02mol) Anhydrous potassium carbonate is substituted with 1.11g (0.008mol) Anhydrous potassium carbonate, oil bath is heated to 152 DEG C, 12mL toluene is substituted with 15mL dimethylbenzene (Beijing Chemical Plant's commercially available reagent), obtain 2, 2-dimethyl-1, 3-bis-pungent acyloxy propane 26.16g, yield 92%, analyze through gas chromatography-mass spectrography (GC-MS), purity 99%.The results are shown in Table 1.
Embodiment 12
This embodiment is for illustration of the preparation method of the pungent acyloxy pentane of 2,2,4-trimethylammonium-1,3-bis-provided by the invention.
2 are prepared according to the method for embodiment 9, 2, 4 trimethylammoniums-1, the pungent acyloxy pentane of 3-bis-, unlike, with 8.77g (0.06mol) 2, 2, 4-trimethylammonium-1, 3-pentanediol substitutes 10.4g (0.1mol) 2, 2-dimethyl-1, ammediol, 63.3g (0.4mol) n-caprylic acid methyl esters is substituted with 37.97g (0.24mol) n-caprylic acid methyl esters, 2.76g (0.02mol) Anhydrous potassium carbonate is substituted with 1.66g (0.012mol) Anhydrous potassium carbonate, obtain 2, 2, 4 trimethylammoniums-1, 3-bis-pungent acyloxy pentane 21.6g, yield 90%, analyze through gas chromatography-mass spectrography (GC-MS), purity 100%.The results are shown in Table 1.Carry out mass spectrum, Infrared spectroscopy, result is as follows.
MS(EI，m/z)：271(M-127)
+，229，211，170，145，129，128，127，112，111，99，98，97，84，83，71，69，67，57，43，41，29。
IR(cm
-1)：2959，2929，2857，1739，1467，1378，1251，1166，1107，1011，725。
1H NMR(CDCl
3/TMS，300MHZ)(δppm)：0.875～0.980(m，18H，2CH
3(CH
2)
5CH
2COO；(CH
3)
2C(CH
2O)；(CH
3)
2CHCHO)，1.282～1.306(m，16H，2CH
3(CH
2)
4CH
2CH
2COO)，1.598～1.662(m，4H，2CH
3(CH
2)
4CH
2CH
2COO)，1.996～2.052(m，1H，(CH
3)
2CHCHO)，2.289～2.356(t，4H，2CH
3(CH
2)
4CH
2CH
2COO)，3.772～3.912(dd，2H，(CH
3)
2C(CH
2O))，4.770～4.781(d，1H，(CH
3)
2CHCHO)。
Embodiment 13
The method of the pungent acyloxy pentane of catalyst preparing 2,4-bis-of this embodiment and Anhydrous potassium carbonate salic for illustration of employing provided by the invention.
(1) preparation of Anhydrous potassium carbonate load catalyzer on alumina
By stand-by for neutral alumina roasting 4 hours at 550 DEG C.By Anhydrous potassium carbonate 105 DEG C of air dry oven inner dryings 3 hours, get the dried Anhydrous potassium carbonate of 6g and be dissolved in 40mL deionized water, add the neutral alumina after the aforementioned roasting of 24g after fully dissolving, fully stir, static 24 hours, obtain the mixture of aluminum oxide and Anhydrous potassium carbonate.Salic and mixture that is Anhydrous potassium carbonate are put into furnace pot evaporating water, then air dry oven is put at 105 DEG C dry 24 hours, to be placed in retort furnace at 600 DEG C roasting again 5 hours, to obtain the catalyst fines 28.89g of Anhydrous potassium carbonate load on neutral alumina.
The preparation of the pungent acyloxy pentane of (2) 2,4-bis-
Band condenser, skimmer, nitrogen ingress pipe, agitator 100mL there-necked flask in add 3g (0.0288mol) 2,4-pentanediol (U.S. chemical abstract CA registration number be the commercially available reagent of [625-69-4]), 18.23g (0.115mol) n-caprylic acid methyl esters, the present embodiment step (1) obtain the catalyst fines 0.8g (Anhydrous potassium carbonate be about 0.0012mol) of Anhydrous potassium carbonate load on neutral alumina.Adopt oil bath heating there-necked flask, oil bath is heated to 160 DEG C, reacts under 0.1MPa, simultaneously lead to nitrogen to there-necked flask in reaction, and by distillating method the alcohol of generation steamed to skimmer and remove, react 20 hours.By the catalyzer of mixture cold filtration removing Anhydrous potassium carbonate load on neutral alumina in there-necked flask after reaction terminates, again by filtrate 300Pa, at 75 DEG C underpressure distillation remove unreacted n-caprylic acid methyl esters and other impurity, obtain 2,4-bis-pungent acyloxy pentane 9.8g.The yield of the pungent acyloxy pentane of 2,4-bis-is 95%, analyzes, purity 100% (wherein, mesomeride 43%, racemic modification 57%) through gas chromatography-mass spectrography (GC-MS).The results are shown in Table 1.
Table 1
* note: by the percentage calculation of actual output and theoretical yield
As can be seen from Table 1,1, the 3-bis-acyloxy propane compound yield adopting the inventive method obtained is higher, and purity is higher, and avoids use and have corrosive acyl chlorides as acylating agent, is conducive to environment protection.
The preparation method of 1,3-bis-acyloxy propane compound provided by the invention avoids use and has corrosive acyl chlorides as acylating agent, is conducive to environment protection, is suitable for large-scale commercial production; Product and reactant and catalyzer easily separated, yield is high, and purity is good.The inventive method can be widely used in industrial production.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. a general structure is (I's) 1, the preparation method of 3-bis-acyloxy propane compound, it is characterized in that, under described method is included in the catalyzer existence containing Anhydrous potassium carbonate, be 1,3-PD compounds and the general structure of (II) by general structure be RCOOR
5ester react, generate comprise general structure for 1, the 3-bis-acyloxy propane compound of (I) and corresponding general formula be HOR
5alcohol product;
Wherein,
R
1be selected from the one in hydrogen atom, methyl, ethyl and sec.-propyl; R
2be selected from the one in methyl, ethyl and sec.-propyl;
R
3, R
4be selected from the C of hydrogen atom, straight chain respectively
1-C
8the C of alkyl, side chain
3-C
8alkyl, C
3-C
6cycloalkyl, C
4-C
8alkyl-cycloalkyl, C
4-C
8cycloalkylalkyl and C
7-C
8one in aralkyl;
R is selected from the C of straight chain
2-C
17the C of aliphatic group, side chain
3-C
17alkyl and C
4-C
8one in cycloalkyl;
R
5for methyl.
2. method according to claim 1, wherein, described reaction is carried out under distillation or rectifying condition, to remove the alcohol HOR that dereaction generates in reaction process
5.
3. method according to claim 2, wherein, adds alcohol HOR in reaction after 5-7 hour in reaction solution
5entrainer, and further by distillation or rectifying except dereaction generate alcohol HOR
5.
4. method according to claim 3, wherein, described entrainer divides and joins for 5-7 time in reaction solution, the adjacent timed interval added for twice is 1.1-1.5 hour, the 1,3-PD compounds of 1 mole when starting relative to reaction, each add-on of entrainer is 60-180mL.
5. method according to claim 3, wherein, described entrainer Continuous Flow is added in reaction solution, and the 1,3-PD compounds of 1 mole when starting relative to reaction, flow acceleration is 60-180mL/ hour, and it is 5-7 hour that stream adds the time.
6. according to the method in claim 3-5 described in any one, wherein, described entrainer is one or more in p-Xylol, o-Xylol, m-xylene, toluene and benzene.
7. method according to claim 6, wherein, described entrainer is toluene.
8. the method according to claim 1,4 or 5, wherein, described general structure is RCOOR
5at least 2 times of the mole number of ester to be described general structure the be mole number of the 1,3-PD compounds of (II).
9. method according to claim 8, wherein, described general structure is the 1,3-PD compounds of (II) and described general structure is RCOOR
5the mol ratio of ester be 1:2-10.
10. method according to claim 9, wherein, described general structure is the 1,3-PD compounds of (II) and described general structure is RCOOR
5the mol ratio of ester be 1:2.5-4.
11. according to the method in claim 1-5 described in any one, and wherein, described catalyzer is Anhydrous potassium carbonate.
12. methods according to claim 11, wherein, described catalyzer be Anhydrous potassium carbonate load on inorganic refractory metal oxide carrier, and with the gross weight of this catalyzer for benchmark, the content of described Anhydrous potassium carbonate is 10-30%.
13. methods according to claim 10, wherein, described general structure is the 1,3-PD compounds of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.001-0.5.
14. methods according to claim 13, wherein, described general structure is the 1,3-PD compounds of (II) and the mol ratio of described Anhydrous potassium carbonate is 1:0.01-0.2.
15. according to the method in claim 1-5 described in any one, and wherein, the temperature of described reaction is 65-160 DEG C.
16. according to the method in claim 1-5 described in any one, and wherein, described method also comprises after termination of the reaction, is that 1, the 3-bis-acyloxy propane compound of (I) is separated from the mixture of the rear gained of reaction by general structure.
17. according to the method in claim 1-5 described in any one, wherein, and described R
3, R
4be selected from the C of hydrogen atom, straight chain respectively
1-C
5the C of alkyl and side chain
3-C
5one in alkyl; R is selected from the C of straight chain
3-C
17one in aliphatic group.
18. methods according to claim 14, wherein, described general structure is that the 1,3-PD compounds of (II) is selected from 2,4-pentanediol, 3,5-heptanediols, 4-ethyl-3,5-heptanediol, 1,3 butylene glycol and 2, one in 2,4-trimethylammonium-1,3-pentanediol.
19. methods according to claim 18, wherein, described general structure is the one that the 1,3-PD compounds of (II) is selected from 2,4-pentanediols and 1,3 butylene glycol.
20. methods according to claim 19, wherein, described general structure is the 1,3-PD compounds of (II) is 2,4-pentanediols.
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