CN103159628B - Preparation method of 1, 3-dibenzoyloxy group propane compound - Google Patents
Preparation method of 1, 3-dibenzoyloxy group propane compound Download PDFInfo
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- CN103159628B CN103159628B CN201110424997.XA CN201110424997A CN103159628B CN 103159628 B CN103159628 B CN 103159628B CN 201110424997 A CN201110424997 A CN 201110424997A CN 103159628 B CN103159628 B CN 103159628B
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- -1 propane compound Chemical class 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N dimethylmethane Natural products CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000001294 propane Substances 0.000 title abstract description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 60
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 30
- YPFDHNVEDLHUCE-UHFFFAOYSA-N Trimethylene glycol Natural products OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 13
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 11
- 125000003710 aryl alkyl group Chemical group 0.000 claims abstract description 5
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 86
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 82
- 238000000034 method Methods 0.000 claims description 44
- 229940035437 1,3-propanediol Drugs 0.000 claims description 23
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 16
- GTCCGKPBSJZVRZ-UHFFFAOYSA-N pentane-2,4-diol Chemical compound CC(O)CC(C)O GTCCGKPBSJZVRZ-UHFFFAOYSA-N 0.000 claims description 14
- SSEOOCRUUJYCKA-UHFFFAOYSA-N 3-benzoyloxypropyl benzoate Chemical class C=1C=CC=CC=1C(=O)OCCCOC(=O)C1=CC=CC=C1 SSEOOCRUUJYCKA-UHFFFAOYSA-N 0.000 claims description 13
- 238000007792 addition Methods 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 8
- JKKDDLAPNLMFHW-UHFFFAOYSA-N 4-benzoyloxypentan-2-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CC(C)OC(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-UHFFFAOYSA-N 0.000 claims description 8
- BQWORYKVVNTRAW-UHFFFAOYSA-N heptane-3,5-diol Chemical compound CCC(O)CC(O)CC BQWORYKVVNTRAW-UHFFFAOYSA-N 0.000 claims description 8
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical class C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000011541 reaction mixture Substances 0.000 claims description 6
- RDAWEBNAEYZNNL-UHFFFAOYSA-N 4-ethylheptane-3,5-diol Chemical compound CCC(O)C(CC)C(O)CC RDAWEBNAEYZNNL-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 239000008096 xylene Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 38
- 229940095102 methyl benzoate Drugs 0.000 description 19
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- ASFLIXVTLOHGHE-UHFFFAOYSA-N 5-benzoyloxyheptan-3-yl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(CC)CC(CC)OC(=O)C1=CC=CC=C1 ASFLIXVTLOHGHE-UHFFFAOYSA-N 0.000 description 7
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- RCRNVJYRWZUIKK-UHFFFAOYSA-N 1-hydroxypentyl benzoate Chemical compound CCCCC(O)OC(=O)C1=CC=CC=C1 RCRNVJYRWZUIKK-UHFFFAOYSA-N 0.000 description 3
- ZGHOZASFRNLRAS-UHFFFAOYSA-N 2-(3-methylbutyl)-2-propan-2-ylpropane-1,3-diol Chemical compound CC(C)CCC(CO)(CO)C(C)C ZGHOZASFRNLRAS-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- XOJVVFBFDXDTEG-UHFFFAOYSA-N pristane Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)C XOJVVFBFDXDTEG-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HVWZDMVPWXVEBP-UHFFFAOYSA-N 3-benzoyloxybutyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OC(C)CCOC(=O)C1=CC=CC=C1 HVWZDMVPWXVEBP-UHFFFAOYSA-N 0.000 description 2
- IKMRGDWUQUCQMN-UHFFFAOYSA-N 5-hydroxyheptan-3-yl benzoate Chemical compound C(C1=CC=CC=C1)(=O)OC(CC)CC(CC)O IKMRGDWUQUCQMN-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- GMIJLGFPOXCNBC-UHFFFAOYSA-N [2-(benzoyloxymethyl)-5-methyl-2-propan-2-ylhexyl] benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC(C(C)C)(CCC(C)C)COC(=O)C1=CC=CC=C1 GMIJLGFPOXCNBC-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UDEWPOVQBGFNGE-UHFFFAOYSA-N propyl benzoate Chemical compound CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 125000003258 trimethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- GTCCGKPBSJZVRZ-SYDPRGILSA-N (2s,4r)-pentane-2,4-diol Chemical compound C[C@@H](O)C[C@H](C)O GTCCGKPBSJZVRZ-SYDPRGILSA-N 0.000 description 1
- GTCCGKPBSJZVRZ-WHFBIAKZSA-N (2s,4s)-pentane-2,4-diol Chemical compound C[C@H](O)C[C@H](C)O GTCCGKPBSJZVRZ-WHFBIAKZSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- 0 *C(C(*)(*)C(*)OC(c1ccccc1)=O)OC(c1ccccc1)=O Chemical compound *C(C(*)(*)C(*)OC(c1ccccc1)=O)OC(c1ccccc1)=O 0.000 description 1
- TXBGWGCFHXRNPE-UHFFFAOYSA-N 1-hydroxybutyl benzoate Chemical compound CCCC(O)OC(=O)C1=CC=CC=C1 TXBGWGCFHXRNPE-UHFFFAOYSA-N 0.000 description 1
- SOWYHPBNCZZWRP-UHFFFAOYSA-N 1-hydroxypropyl benzoate Chemical compound CCC(O)OC(=O)C1=CC=CC=C1 SOWYHPBNCZZWRP-UHFFFAOYSA-N 0.000 description 1
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 1
- BZISNWGGPWSXTK-UHFFFAOYSA-N 3-hydroxypropyl benzoate Chemical class OCCCOC(=O)C1=CC=CC=C1 BZISNWGGPWSXTK-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JKKDDLAPNLMFHW-GJZGRUSLSA-N [(2s,4s)-4-benzoyloxypentan-2-yl] benzoate Chemical compound O([C@@H](C)C[C@H](C)OC(=O)C=1C=CC=CC=1)C(=O)C1=CC=CC=C1 JKKDDLAPNLMFHW-GJZGRUSLSA-N 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000037048 polymerization activity Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010898 silica gel chromatography Methods 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of 1, 3-dibenzoyloxy group propane compound having the structure formula (I). The preparation method is characterized by comprising the following steps: reacting 1, 3-propylene glycol compound having the structure formula (II) with benzoate having the structure formula of PhCOOR<5> under the condition that catalyst anhydrous potassium carbonate exists, generating 1, 3-dibenzoyloxy group propane compound having the structure formula (I) and corresponding alcohol HOR<5>, wherein R<1> and R<2> are respectively chosen from any one of hydrogen atom, methyl and ethyl, R<3> and R<4> are respectively chosen from any one of hydrogen atom, line chain C1-C8 alkyl, branched chain C3-C8 alkyl, C3-C6 naphthenic base, C4-C8 alkyl naphthenic base, C4-C8 naphthenic base alkyl and C7-C8 aralkyl, and R<5> is methyl or ethyl. The preparation method is environmental friendly, the production yield is high, and the purity is high.
Description
Technical Field
The invention relates to a preparation method of an internal electron donor 1, 3-diol ester compound contained in a catalyst component for olefin polymerization, in particular to a preparation method of a1, 3-dibenzoyloxy propane compound.
Background
It is well known in the art that Ziegler-Natta catalysts consist of at least two parts: the active component containing transition metal, also called main catalyst, the transition metal compound which is obtained in practice is titanium and vanadium, and generally forms a solid catalyst component together with the carrier magnesium chloride; and organometallic compounds containing elements of groups I A-IIIA of the periodic system, also known as cocatalysts, predominantly aluminum alkyls or halides of aluminum alkyls. In some applications, particularly when used in propylene polymerization catalysis, a third component is often added to control product isotacticity and improve polymerization activity, among other things. They are usually Lewis bases, also known as electron donor compounds. The electron donor added during the preparation of the main catalyst is called an internal electron donor, and the electron donor added to the olefin polymerization system with the co-catalyst during the olefin polymerization reaction using the main catalyst is called an external electron donor.
CN1436796A, CN1453298A and CN1580034A disclose 1, 3-diol ester compounds as internal electron donors, wherein 1, 3-dibenzoyl group oxygen propane compounds containing substituent and having the following structural general formula (I) are excellent internal electron donors,
in the general structural formula (I),
R1、R2are respectively selected from one of the following: hydrogen atom, methyl group, ethyl group; r1、R2The radicals are identical or different from one another;
R3、R4selected from one of the following: hydrogen atom, straight chain C1-C8Alkyl, branched C3-C8An alkyl group; r3、R4The groups may be the same or different from each other.
Particularly preferred internal electron donor compounds of CN1436796A and CN1453298A are: 1, 3-propanediol dibenzoate and its 2-position 1 or 2 alkyl substituents, 2, 4-pentanediol dibenzoate and its 3-position 1 or 2 alkyl substituents, 3, 5-heptanediol dibenzoate and its 4-position 1 or 2 alkyl substituents.
WO2011131033a1 further discloses that meso-2, 4-pentanediol dibenzoate and its 1-or 2-alkyl substituents in the 3-position, meso-3, 5-heptanediol dibenzoate and its 1-or 2-alkyl substituents in the 4-position, are all more effective than their racemic stereoisomers as internal electron donors in olefin polymerization systems; increasing the meso content of the stereoisomer increases the performance of the internal electron donor.
The preparation methods of the above internal electron donors are also disclosed in CN1436796A, CN1453298A, CN1580034A and WO2011131033A1, and are prepared by reacting the corresponding diols with excessive benzoyl chloride and pyridine respectively. However, benzoyl chloride is corrosive and easily hydrolyzed to benzoic acid and hydrogen chloride, which is not environmentally friendly. The preparation method also produces pyridine hydrochloride and other impurities as by-products at least equimolar, which adds difficulty to the separation and purification of the main product, resulting in low yield and purity of the main product.
In order to solve the above separation and purification problems, CN101665429A discloses a method for optimizing the quality of glycol ester, which comprises reacting glycol with acyl chloride in the presence of a solvent with a higher boiling point, and adding a lower aliphatic alcohol with better reactivity after the reaction is finished, so as to react with impurities, thereby obtaining glycol ester compounds, but the method still has the problem of using benzoyl chloride with corrosiveness.
Disclosure of Invention
The invention aims to overcome the defects of using benzoyl chloride in the prior art and provide a novel preparation method of a1, 3-dibenzoyloxy propane compound.
In order to achieve the above object, the present invention provides a process for producing a1, 3-dibenzoyloxypropane compound of the general structural formula (I), which comprises reacting a1, 3-propanediol compound of the general structural formula (II) with a1, 3-propanediol compound of the general structural formula PhCOOR in the presence of a catalyst containing anhydrous potassium carbonate5The benzoate is reacted to generate 1, 3-dibenzoyl oxypropane compounds with the structural general formula (I) and corresponding alcohol HOR5The product of (a);
wherein,
R1、R2one selected from hydrogen atom, methyl and ethyl;
R3、R4are respectively selected from hydrogen atoms and straight chain C1～C8Alkyl, branched C3～C8Alkyl radical, C3～C6Cycloalkyl radical, C4～C8Alkyl cycloalkyl radical, C4～C8Cycloalkylalkyl and C7～C8One of aralkyl groups;
R5is methyl or ethyl.
According to the preparation method of the 1, 3-dibenzoyloxy propane compound, methyl benzoate or ethyl benzoate is used for replacing corrosive benzoyl chloride as an acylating agent, so that the environmental protection is facilitated, and the preparation method is suitable for large-scale industrial production; the product is easy to separate from the reactant and the catalyst, and has high yield and good purity. The method of the invention can be widely applied to industrial production.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The invention provides a preparation method of a1, 3-dibenzoyloxy propane compound with a general formula (I), which is characterized by comprising the following steps of reacting a1, 3-propanediol compound with a general formula (II) with PhCOOR in the presence of a catalyst containing anhydrous potassium carbonate5The benzoate is reacted to generate 1, 3-dibenzoyl oxypropane compounds with the structural general formula (I) and corresponding alcohol HOR5The product of (a);
wherein,
R1、R2one selected from hydrogen atom, methyl and ethyl;
R3、R4are respectively selected from hydrogen atoms and straight chain C1～C8Alkyl, branched C3～C8Alkyl radical, C3～C6Cycloalkyl radical, C4～C8Alkyl cycloalkyl radical, C4～C8Cycloalkylalkyl and C7～C8One of aralkyl groups;
R5is methyl or ethyl.
According to the invention, 1, 3-propanediol compounds of the general formula (II) are reacted with PhCOOR in the presence of a catalyst comprising anhydrous potassium carbonate5The benzoate is reacted to generate 1, 3-dibenzoyl oxypropane compounds with the structural general formula (I) and corresponding alcohol HOR5The product of (a); wherein R is1、R2One selected from hydrogen atom, methyl and ethyl; r3、R4Are respectively selected from hydrogen atoms and straight chain C1～C8Alkyl, branched C3～C8Alkyl radical, C3～C6Cycloalkyl radical, C4～ C8Alkyl cycloalkyl radical, C4～C8Cycloalkylalkyl and C7～C8One of aralkyl groups; r5The invention can be realized by methyl or ethyl, which is beneficial to environmental protection, and the product is easy to separate from reactants and catalyst, and has high yield and good purity. Preferably, however, the transesterification reaction comprises carrying out the reaction under distillation or rectification conditions with simultaneous removal of the alcohol HOR formed5(ii) a Further preferably, the alcohol HOR is added to the reaction mixture after the reaction for 5 to 7 hours5Further removing alcohol HOR generated by the reaction by distillation or rectification5. The preferred scheme can further improve the yield and purity of the product with the structural general formula (I).
In the present invention, in order to allow the above-mentioned preferable embodiment to proceed smoothly and continuously, the reaction is started using a "dispenser" equipped with a condenser at the upper end as a distillation apparatus, the "dispenser" being a Dean and Stark apparatus with a stopcock at the lower end, and after 5 to 7 hours of the reaction, the entrainer is preferably added to the reaction solution in 5 to 7 times, the time interval between two consecutive additions is 1.1 to 1.5 hours, and the amount of the entrainer added per time is 60 to 180mL relative to 1 mole of the 1, 3-propanediol compound at the start of the reaction.
Or alternatively, the entrainer is added in such a manner that after the transesterification reaction for 5 to 7 hours under distillation or rectification conditions using a distillation apparatus or a rectification apparatus at the beginning of the reaction, the entrainer is continuously fed to the reaction solution under distillation or rectification conditions at a feeding rate of 60 to 180 mL/hour and a feeding time of 5 to 7 hours with respect to 1 mole of the 1, 3-propanediol compound at the beginning of the reaction.
It will be understood by those skilled in the art that, in the case of the split addition, the temperature may be lowered without adding the entrainer, or the temperature of the reaction solution may be cooled to below the boiling point of the entrainer, and the entrainer is added, and the temperature is preferably lowered to below the boiling point of the entrainer in a laboratory, and the time required for the temperature lowering is generally not more than half an hour, preferably 0.1 to 0.5 hours; when the continuous flow is carried out, the reaction temperature should be controlled between the boiling point of the entrainer and the boiling point of an azeotrope formed by the entrainer and the alcohol generated by the reaction, the flow heating speed can be adjusted according to the reaction speed, the type and the dosage of the entrainer, and the mode of continuously feeding the entrainer to the reaction liquid under the distillation or rectification condition is suitable for large-scale production.
In the invention, the entrainer is preferably an aromatic hydrocarbon solvent with a boiling point of 80-145 ℃, and is more preferably one or more of dimethylbenzene, methylbenzene and benzene; further preferred is toluene.
In the present invention, the amount of the reactant is preferably one having the general structural formula PhCOOR5The number of moles of the benzoate is at least 2 times of that of the 1, 3-propanediol compound with the structural general formula (II); more preferably, the 1, 3-propanediol compound of the general formula (II) and the compound of the general formula PhCOOR5The molar ratio of the benzoate is 1: 2-10; more preferably, the 1, 3-propanediol compound of the general formula (II) and the compound of the general formula PhCOOR5The molar ratio of the benzoate is 1: 2-5. It will be appreciated by those skilled in the art that as the molar amount of benzoate is increased, the reaction rate is increased, the yield is increased,but also affects the separation of the product.
In the present invention, the catalyst containing anhydrous potassium carbonate is preferably anhydrous potassium carbonate. The amount of the anhydrous potassium carbonate is preferably that the mol ratio of the 1, 3-propanediol compound with the general structural formula (II) to the anhydrous potassium carbonate is 1: 0.001-0.5; more preferably, the molar ratio of the 1, 3-propanediol compound with the general structural formula (II) to the anhydrous potassium carbonate is 1: 0.01-0.4. It will be appreciated by those skilled in the art that as the amount of catalyst is increased, the reaction rate increases, but product separation is also affected.
In the present invention, the reaction temperature is preferably 65 to 160 ℃ and more preferably 65 to 120 ℃. In practical operation, a conventional glass flask is used as a reactor and heated in a water bath or an oil bath, and when the temperature of the water bath or the oil bath is 100-160 ℃, preferably 150-160 ℃, the reaction temperature can be controlled to be 65-120 ℃. The temperature of the water or oil bath may be provided by various methods known in the art, for example 100 ℃ may be provided by heating with a steam or oil bath, and the temperature range of 100 ℃ and 160 ℃ may be provided by heating with a pressurized steam or oil bath.
It will be appreciated by those skilled in the art that, in order to obtain 1, 3-dibenzoyloxypropane compounds of the general structural formula (I) in higher purity, the process according to the invention preferably further comprises, after termination of the reaction, separating the 1, 3-dibenzoyloxypropane compounds of the general structural formula (I) from the mixture obtained after the reaction. A process for separating 1, 3-dibenzoyloxypropane compounds of the general formula (I) from the mixture obtained after the reaction, which comprises reacting a mixture of the general formula HOR5Alcohol of (2), catalyst containing anhydrous potassium carbonate, unreacted structural formula of PhCOOR5The benzoic acid ester of (A) and the 1, 3-propanediol compound of the general formula (II), and a small amount of the intermediate 1-benzoyloxy-3-hydroxypropane compound are removed from the reaction mixture by various methods which are conceivable by those skilled in the art, and in the present invention, the method of removing is preferably a method of distilling or rectifying the productThe general formula of the structure generated by the reaction is HOR5Removing the alcohol from the reaction mixture, removing the catalyst containing anhydrous potassium carbonate from the reaction mixture by filtration, centrifugation or extraction, and distilling under reduced pressure or rectifying under reduced pressure to obtain the final product5And 1, 3-propanediol compounds with the structural general formula (II) and a small amount of intermediate 1-benzoyloxy-3-hydroxypropane compounds are removed from the mixture obtained by the reaction.
In the present invention, R3、R4Are each preferably selected from hydrogen atoms, straight-chain C1-C5Alkyl and branched C3-C5One of alkyl groups; r5Preferably methyl. The 1, 3-propanediol compound of the general structural formula (II) is preferably one selected from 1, 3-propanediol, 2, 4-pentanediol, 3, 5-heptanediol, 4-ethyl-3, 5-heptanediol, 2-isopropyl-2-isoamyl-1, 3-propanediol and 1, 3-butanediol; further preferably one selected from 2, 4-pentanediol, 3, 5-heptanediol, and 4-ethyl-3, 5-heptanediol; still more preferred is 2, 4-pentanediol.
In the present invention, when the 1, 3-propanediol compound of the general structural formula (II) is 2, 4-pentanediol, the process of the present invention preferably further comprises allowing the 2, 4-dibenzoyloxypentane obtained by the reaction to stand at 15 to 30 ℃ for 10 to 14 hours to obtain crystals, and removing the obtained crystals. The method of removing the crystals may employ various methods commonly used in the art, such as filtration. The obtained crystals are crystals of racemic dl-2, 4-dibenzoyloxypentane compounds, and the proportion of meso-2, 4-dibenzoyloxypentane is increased by removing the crystals of racemic dl-2, 4-dibenzoyloxypentane compounds, which is beneficial to improving the performance of polypropylene catalysts.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that, in the above embodiments, the various technical features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations of the features described in the present invention are not described again.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Examples
The following examples further illustrate the invention but are not intended to limit the invention thereto. Examples the "dispenser" refers to a Dean and Stark apparatus with a stopcock at the lower end of the Dean and Stark apparatus.
Example 1
This example serves to illustrate the preparation of 2, 4-dibenzoyloxypentane provided by the present invention.
20g (0.192mol) of 2, 4-pentanediol (American chemical Abstract CA accession No. [625-69-4]), 104.6g (0.754mol) of methyl benzoate, and 5.31g (0.038mol) of anhydrous potassium carbonate were charged into a 250mL round bottom flask equipped with a condenser, a liquid separator, and a stirrer, the oil bath in the contact reaction flask was heated to 160 ℃ and the alcohol produced during the reaction was distilled off to the liquid separator, toluene was added to the reaction flask after 5 hours of reaction, 5 times in total were added, the time interval between two consecutive additions was 1.5 hours, 12mL was added each time, toluene was added after 1 hour of reaction and toluene and azeotrope were distilled off from the reaction flask simultaneously, and the next toluene was added after the reaction solution was cooled for about 30 minutes. After the reaction, the mixture in the reaction flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was subjected to vacuum distillation at 263Pa at 84 ℃ to remove unreacted methyl benzoate, 2, 4-pentanediol and pentanediol monobenzoate, to obtain 55.5g of 2, 4-dibenzoyloxypentane in a yield of 92.6%, which was analyzed by gas chromatography-mass spectrometry (GC-MS) to have a purity of 100% (among them, meso form 43% and racemic form 57%). The results are shown in Table 1.
MS(EI，m/z)：227(M-85)+，207(M-105)+，190(M-122)+，148(M-164)+，123，122，105，85，77。
1H NMR(CDCl3/TMS，300MHZ)(ppm)：1.399～1.420(d，6H，2CHCH3，J＝6.3Hz)，1.883～1.931&2.313～2.360(m，43％×2H，mesomeric CHCH2CH，J＝6.3Hz)，2.076～2.118(t，57％×2H，racemic CHCH2CH，J＝6.3Hz)，5.287～5.371(m，2H，CH3CHCH2CHCH3，J＝6.3Hz)，7.344～7.424(m，4H，2C6H5)，7.481～7.529(m，2H，2C6H5)，7.961～8.041(m，4H，2C6H5)。
Example 2
This example is intended to illustrate the preparation of 2, 4-dibenzoyloxypentane and the isolation of dl-2, 4-dibenzoyloxypentane as racemate provided by the present invention and to further confirm the analytical test results of example 1.
A250 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 24g (0.23mol) of 2, 4-pentanediol (American chemical Abstract CA accession No. [625-69-4]), 62.6g (0.46mol) of methyl benzoate and 6.4g (0.046mol) of anhydrous potassium carbonate, the oil bath in the contact reaction flask was heated to 150 ℃ and the resultant alcohol was distilled off to the liquid separator and removed at the same time as the reaction, after 6 hours of reaction, toluene was added to the reaction flask for a total of 6 additions, the time interval between two consecutive additions was 1.1 hours, 18mL was added each, after 1 hour of each addition of toluene and at the same time toluene and azeotrope were distilled out of the reaction flask, and after the reaction was cooled for about 6 minutes, the next toluene was added. After the reaction was complete, the flask was cooled. Anhydrous potassium carbonate was removed by filtration, and unreacted methyl benzoate, 2, 4-pentanediol and pentanediol monobenzoate were removed by distillation under reduced pressure to give 66.2g of 2, 4-dibenzoyloxypentane in a yield of 92%, which was analyzed by gas chromatography-mass spectrometry (GC-MS) and had a purity of 100%. After the liquid product was left at 25 ℃ for 12 hours, crystals of a part of racemic dl-2, 4-dibenzoyloxypentane compound were precipitated, and the separated crystals were subjected to mass spectrometry and nuclear magnetic resonance hydrogen spectrometry, with the following results.
MS(EI，m/z)：227(M-85)+，207(M-105)+，190(M-122)+，148(M-164)+，123，122，105，85，77。
1H NMR(CDCl3/TMS，300MHZ)(ppm)：1.398～1.419(d，6H，2CHCH3， J＝6.3Hz)，2.075～2.118(t，2H，CHCH2CH，J＝6.3Hz)，5.264～5.369(m，2H，CH3CHCH2CHCH3，J＝6.3Hz)，7.345～7.396(m，4H，2C6H5)，7.483～7.532(m，2H，2C6H5)，7.960～7.992(m，4H，2C6H5)。
Example 3
This example serves to illustrate the process for the preparation of 1, 3-dibenzoyloxybutane provided by the present invention.
A250 mL round bottom flask with a condenser, a liquid separator and a stirrer is added with 18g (0.2mol) of 1, 3-butanediol, 136g (1mol) of methyl benzoate and 0.276g (0.002mol) of anhydrous potassium carbonate, an oil bath in a contact reaction bottle is heated to 150 ℃, generated alcohol is distilled to the liquid separator and removed by a distillation method during the reaction, after 7 hours of reaction, toluene is added into the reaction liquid, the total amount of the toluene is added for 7 times, the time interval between two adjacent times of addition is 1.25 hours, 15mL of the azeotrope is added, after each time of toluene addition, the reaction is carried out for 1 hour, the toluene and the azeotrope are distilled out of the reaction bottle, and after the reaction liquid is cooled for about 15 minutes, the next time of toluene is added. After the reaction was completed, the mixture in the reaction flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was distilled at 81 ℃ under 287.6Pa to remove unreacted methyl benzoate, 1, 3-butanediol and butanediol monobenzoate, to give 54.2g of 1, 3-dibenzoyloxybutane, yield 91%, and purity 99.7% by gas chromatography. The results are shown in Table 1.
1H NMR(CDCl3/TMS，300MHZ)(ppm)：1.433～1.454(d，3H，CHCH3，J＝6.3Hz)，2.130～2.236(m，2H，CH2CH2CH)，4.418～4.517(m，2H，OCH2CH2CHCH3)，5.263～5.368(m，1H，OCH2CH2CHCH3)，7.366～7.430(m，4H，2C6H5)，7.497～7.551(m，2H，2C6H5)，7.994～8.047(m，4H，2C6H5)。
Example 4
This example serves to illustrate the preparation of 3, 5-dibenzoyloxyheptane provided by the present invention.
A250 mL round bottom flask equipped with a condenser, a liquid separator and a stirrer was charged with 12.7g (0.1mol) of 3, 5-heptanediol having a gas chromatography content of 95% (see example 12 of CN1453298A reference for the preparation method), 39.3g (0.29mol) of methyl benzoate and 5.53g (0.04mol) of anhydrous potassium carbonate, the oil bath in the contact reaction flask was heated to 145 ℃ and the resultant alcohol was distilled off to the liquid separator and removed by distillation while reacting, after 6 hours of reaction, toluene was added to the reaction solution for 6 times in total, the time interval between two consecutive additions was 1.1 hours, 18mL was added each time, after each addition of toluene, the reaction was carried out for 1 hour while distilling toluene and azeotrope out of the reaction flask, and after the reaction solution was cooled for about 6 minutes, the next toluene was added. After completion of the reaction, the mixture in the reaction flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was distilled at 86 ℃ under 315Pa to remove unreacted methyl benzoate and 3, 5-heptanediol, whereby 28.4g of 3, 5-dibenzoyloxyheptane was obtained with a yield of 92%, and a purity of 96% by gas chromatography (in this case, meso form was 64% and racemic body was 32%). The results are shown in Table 1.
MS(EI，m/z)：235(M-105)+，218(M-122)+，189，122，113，106，105，96，77。
1H NMR(CDCl3/TMS，300MHZ)(ppm)：0.930～0.991(d，6H，2CH2CH3，J＝6.3Hz)，1.720～1.803(m，4H，CH3CH2CHCH2CHCH2CH3)，2.007～2.237(m，2H，64％mesomeric，32％racemic CH3CH2CHCH2CHCH2CH3)，5.192～5.250(m，2H，CH3CH2CHCH2CHCH2CH3)，7.322～7.466(m，4H，2C6H5)，7.491～7.553(m，2H，2C6H5)，7.942～8.034(m，4H，2C6H5)。
Example 5
This example serves to illustrate the process for the preparation of 1, 3-dibenzoyloxypropane provided by the present invention.
15.2g (0.2mol) of 1, 3-propanediol, 54.4g (0.4mol) of methyl benzoate and 5.5g (0.04mol) of anhydrous potassium carbonate are added into a 250mL round bottom flask with a condenser, a liquid distributor and a stirrer, an oil bath in a contact reaction bottle is heated to 120 ℃, generated alcohol is distilled to the liquid distributor and removed by a distillation method at the same time of reaction, after 6 hours of reaction, toluene is added into the reaction liquid, the total amount is added for 6 times, the time interval between two adjacent times is 1.1 hour, 18mL is added, after each time of toluene addition, the reaction is carried out for 1 hour, toluene and azeotrope are distilled out of the reaction bottle, and after the reaction liquid is cooled for about 6 minutes, the next time of toluene is added. After the reaction was completed, the mixture in the reaction flask was cooled and filtered to remove anhydrous potassium carbonate, and the filtrate was distilled at 87 ℃ under 330Pa to remove unreacted methyl benzoate, 1, 3-propanediol and propanediol monobenzoate, to obtain 50g of 1, 3-dibenzoyloxypropane in 88% yield and 99.8% purity by gas chromatography. The results are shown in Table 1.
MS(EI，m/z)：227(M-57)+，179(M-105)+，162(M-122)+，134(M-150)+，123，122，105，77。
1H NMR(CDCl3/TMS，300MHZ)(ppm)：2.221～2.304(m，2H，CH2CH2CH2，J＝6.3Hz)，4.489～4.531(t，4H，CH2CH2CH2)，7.389～7.441(m，4H，2C6H5)，7.520～7.574(m，2H，2C6H5)，8.022～8.054(m，4H，2C6H5)。
Example 6
This example illustrates the preparation of 2-isopropyl-2-isoamyl-1, 3-dibenzoyloxypropane according to the present invention.
Adding 37.6g (0.2mol) of 2-isopropyl-2-isoamyl-1, 3-propanediol, 54.4g (0.4mol) of methyl benzoate and 2.76g (0.02mol) of anhydrous potassium carbonate into a 250mL three-necked flask with a condenser, a liquid separator, a dropping funnel and a stirrer, heating an oil bath of a contact reaction flask to 150 ℃, evaporating generated alcohol to the liquid separator and removing the alcohol by a distillation method during the reaction, continuously feeding toluene into a reaction liquid after the reaction is carried out for 6 hours, controlling the feeding speed to be 12-18 mL/hour, distilling the toluene and azeotrope out of the reaction flask during the feeding, stopping the feeding after the feeding is carried out for 6 hours, cooling and filtering the mixture in the reaction flask to remove the anhydrous potassium carbonate, distilling the filtrate at the reduced pressure of 223Pa at the temperature of 80 ℃ to remove unreacted methyl benzoate and 2-isopropyl-2-isoamyl-1, 3-propanediol to obtain 70.5gg of 2-isopropyl-2-isoamyl-1, 3-dibenzoyloxy propane with 89 percent of yield. The results are shown in Table 1.
Electrospray mass spectrometry (ESI): 419.23 and formula C25H32O4The ion peak mass numbers of the compound M + Na are consistent.
IR(cm-1)：3064，2958，2870，1720，1602，1585，1468，1451，1386，1314， 1270，1112，1070，1026，710。
1H NMR(CDCl3/TMS，300MHZ)(ppm)：0.869～0.891(d，6H，CH3CHCH3，J＝6.6Hz)，1.040～1.063(d，6H，CH3CHCH3，J＝6.9Hz)，1.248～1.606(m，5H，CH2CH2CH)，2.014～2.107(m，1H，CH3CHCH3)，4.357～4.447(m，4H，2CH2O)，7.378～7.429(m，4H，2C6H5)，7.511～7.565(m，2H，2C6H5)，7.984～7.995(m，4H，2C6H5)。
Example 7
1, 3-Benzoyloxypropane was prepared by the method of example 5 except that ethyl benzoate was used instead of methyl benzoate to give 15.1g of 1, 3-benzoyloxypropane in 53% yield and 90% purity by gas chromatography. The results are shown in Table 1.
Example 8
3, 5-Dibenzoyloxyheptane was prepared according to the method of example 4, except that toluene was not added during the reaction, the mixture in the reaction flask was cooled and filtered to remove anhydrous potassium carbonate after the reaction was completed, and the filtrate was distilled at 330MPa at 86 ℃ to remove unreacted methyl benzoate and 3, 5-heptanediol, to obtain a mixture containing 3, 5-dibenzoyloxyheptane, which was analyzed by GC-MS: purity of 3, 5-dibenzoyloxy heptane 82% (wherein, meso-form 55%, racemic form 27%); the purity of the intermediate 3-hydroxy-5-benzoyloxyheptane was 14%. The results are shown in Table 1.
Example 9
This example serves to illustrate that the crystal isolated in example 2 is the racemate of 2, 4-dibenzoyloxypentane.
A1, 3-dibenzoyloxypropane compound was prepared according to the procedure of example 2 except that 0.5g (4.8mmol) of (2S, 4S) - (+) -2, 4-pentanediol, 1.31g (9.6mmol) of methyl benzoate, 0.133g (0.96mmol) of anhydrous potassium carbonate was charged in a 25mL round-bottomed flask, and after the reaction was completed, unreacted methyl benzoate, 2, 4-pentanediol, and pentanediol monobenzoate were not removed by distillation but purified by silica gel column chromatography to give 1.24g of (2S, 4S) -2, 4-dibenzoyloxypentane in a yield of 83% and a purity of 94% by gas chromatography-mass spectrometry (GC-MS). The results are shown in Table 1.
MS(EI，m/z)：227(M-85)+，207(M-105)+，190(M-122)+，148(M-164) +，123，122，105，85，77。
IR(cm-1)：1719，1601，1584，1452，1382，1349，1315，1280，1145，1105。
1H NMR(CDCl3/TMS，300MHZ)(ppm)：1.399～1.419(d，6H，2CHCH3)，2.077～2.119(t，2H，CHCH2CH，J＝6.3Hz)，5.263～5.368(m，2H，CH3CHCH2CHCH3)，7.345～7.398(m，4H，2C6H5)，7.481～7.535(m，2H，2C6H5)，7.959～7.992(m，4H，2C6H5)。
TABLE 1
| Yield (%) | Purity (%) | |
| Example 1 | 92.6 | 100 |
| Example 2 | 92 | 100 |
| Example 3 | 91 | 99.7 |
| Example 4 | 92 | 96 |
| Example 5 | 88 | 99.8 |
| Example 6 | 89 | - |
| Example 7 | 53 | 90 |
| Example 8 | 100 | 82 |
| Example 9 | 83 | 94 |
Note: example 6 the product obtained was large in molecular weight and gas phase analysis could not be performed, so purity was not indicated; since the residual amount of the intermediate 3-hydroxy-5-benzoyloxyheptane in example 8 was large, the yield was expressed as the conversion of 3, 5-heptanediol, and the yields in other examples were calculated as the percentage of the actual yield to the theoretical yield.
As can be seen from Table 1, the 1, 3-dibenzoyloxypropane compounds prepared by the method have high yield and high purity, and the method avoids using corrosive benzoyl chloride as an acylating agent, thereby being beneficial to environmental protection.
Comparing example 5 with example 7, it can be seen that methyl benzoate is more advantageous than ethyl benzoate for the preparation of 1, 3-dibenzoyloxypropane; comparing example 4 with example 8, it can be seen that the addition of an aromatic hydrocarbon solvent during the reaction is more advantageous for the preparation of 3, 5-dibenzoyloxyheptane; as can be seen from a comparison of example 2 with example 9, after completion of the reaction and removal of anhydrous potassium carbonate by filtration, unreacted methyl benzoate can be efficiently removed by distillation under reduced pressure or rectification under reduced pressure,
The preparation method of the 1, 3-dibenzoyloxy propane compound provided by the invention avoids using corrosive benzoyl chloride as an acylating agent, is beneficial to environmental protection, and is suitable for large-scale industrial production; the product is easy to separate from the reactant and the catalyst, and has high yield and good purity. The method of the invention can be widely applied to industrial production.
Claims (21)
1. A preparation method of 1, 3-dibenzoyl oxypropane compounds with a structural general formula (I) is characterized by comprising the step of reacting 1, 3-propanediol compounds with a structural general formula PhCOOR in the presence of a catalyst containing anhydrous potassium carbonate5The benzoate is reacted to generate 1, 3-dibenzoyl oxypropane compounds with a structural general formula (I) and corresponding alcohol HOR5The product of (a);
wherein,
R1one selected from hydrogen atom, methyl group and ethyl group, R2One selected from methyl and ethyl;
R3、R4are respectively selected from hydrogen atoms and straight chain C1～C8Alkyl, branched C3～C8Alkyl radical, C3～C6Cycloalkyl radical, C4～C8Alkyl cycloalkyl radical, C4～C8Cycloalkylalkyl and C7～C8One of aralkyl groups;
R5is methyl.
2. The process as claimed in claim 1, wherein the reaction comprises carrying out under distillation or rectification conditions, with simultaneous removal of alcohol HOR formed by the reaction5。
3. The method according to claim 2, wherein the alcohol HOR is added to the reaction solution after the reaction for 5 to 7 hours5Further removing alcohol HOR generated by the reaction by distillation or rectification5。
4. A process according to claim 3, wherein the azeotropic agent is added to the reaction mixture in 5 to 7 portions, the time interval between two consecutive additions is 1.1 to 1.5 hours, and the amount of the azeotropic agent added per one portion is 60 to 180mL relative to 1 mole of the 1, 3-propanediol-based compound at the start of the reaction.
5. The process according to claim 3, wherein the azeotropic agent is continuously fed to the reaction mixture at a rate of 60 to 180 mL/hr and for a time of 5 to 7 hr, based on 1mol of the 1, 3-propanediol compound at the start of the reaction.
6. The process according to any one of claims 3-5, wherein the entrainer is one or more of xylene, toluene and benzene.
7. The process of claim 6, wherein the entrainer is toluene.
8. The method of any one of claims 1-5, wherein the general structural formula is PhCOOR5The number of moles of the benzoate is at least 2 times of that of the 1, 3-propanediol compound with the structural general formula (II).
9. The process of claim 8, wherein the 1, 3-propanediol compound of formula (II) and the compound of formula PhCOOR5The molar ratio of the benzoic acid ester is 1: 2-10.
10. The process of claim 9, wherein the 1, 3-propanediol compound of formula (ii) and the compound of formula PhCOOR5The molar ratio of the benzoic acid ester is 1: 2-5.
11. The process of any one of claims 1-5, wherein the catalyst is anhydrous potassium carbonate.
12. The method according to claim 11, wherein the molar ratio of the 1, 3-propanediol compound of general structural formula (ii) to the anhydrous potassium carbonate is 1: 0.001-0.5.
13. The method according to claim 12, wherein the molar ratio of the 1, 3-propanediol compound of general structural formula (ii) to the anhydrous potassium carbonate is 1: 0.01-0.4.
14. The process according to any one of claims 1 to 5, wherein the temperature of the reaction is 65 to 160 ℃.
15. The process according to claim 14, wherein the temperature of the reaction is 65-120 ℃.
16. The process according to any one of claims 1 to 5, further comprising, after the reaction has ended, separating the 1, 3-dibenzoyloxypropane compound of the general structural formula (I) from the mixture obtained after the reaction.
17. The method of any one of claims 1-5, wherein R is3、R4Are respectively selected from hydrogen atoms and straight chain C1-C5Alkyl and branched C3-C5One of the alkyl groups.
18. The method according to claim 17, wherein the 1, 3-propanediol compound of the general structural formula (ii) is selected from one of 2, 4-pentanediol, 3, 5-heptanediol, 4-ethyl-3, 5-heptanediol, and 1, 3-butanediol.
19. The method according to claim 18, wherein the 1, 3-propanediol compound of the general structural formula (ii) is selected from 2, 4-pentanediol, 3, 5-heptanediol, and 4-ethyl-3, 5-heptanediol.
20. The method according to claim 19, wherein the 1, 3-propanediol compound of formula (ii) is 2, 4-pentanediol.
21. The process of claim 20, further comprising allowing the 2, 4-dibenzoyloxypentane obtained from the reaction to stand at 15-30 ℃ for 10-14 hours to obtain crystals, and removing the obtained crystals.
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| 酯化反应中的化学催化方法研究进展;周开志 等;《兴义民族师范学院学报》;20100630(第1期);第120-124页 * |
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