CN104892418A - Synthesis method of citric acid tributyl citrate - Google Patents
Synthesis method of citric acid tributyl citrate Download PDFInfo
- Publication number
- CN104892418A CN104892418A CN201510291963.6A CN201510291963A CN104892418A CN 104892418 A CN104892418 A CN 104892418A CN 201510291963 A CN201510291963 A CN 201510291963A CN 104892418 A CN104892418 A CN 104892418A
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- China
- Prior art keywords
- citric acid
- tributyl citrate
- product
- acid
- propyl carbinol
- Prior art date
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- RAGVGXLZTQDOKB-UHFFFAOYSA-N 2-hydroxypropane-1,2,3-tricarboxylic acid;tributyl 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC RAGVGXLZTQDOKB-UHFFFAOYSA-N 0.000 title abstract 4
- 238000001308 synthesis method Methods 0.000 title abstract 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 61
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 241000289690 Xenarthra Species 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000004821 distillation Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 8
- DOOTYTYQINUNNV-UHFFFAOYSA-N Triethyl citrate Chemical compound CCOC(=O)CC(O)(C(=O)OCC)CC(=O)OCC DOOTYTYQINUNNV-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- 239000001069 triethyl citrate Substances 0.000 claims description 7
- VMYFZRTXGLUXMZ-UHFFFAOYSA-N triethyl citrate Natural products CCOC(=O)C(O)(C(=O)OCC)C(=O)OCC VMYFZRTXGLUXMZ-UHFFFAOYSA-N 0.000 claims description 7
- 235000013769 triethyl citrate Nutrition 0.000 claims description 7
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 4
- 150000007530 organic bases Chemical class 0.000 claims description 4
- 238000010189 synthetic method Methods 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000007670 refining Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims 1
- 239000012299 nitrogen atmosphere Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 21
- 239000012153 distilled water Substances 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- -1 tetrafluoroborate Chemical compound 0.000 abstract description 9
- 238000003756 stirring Methods 0.000 abstract description 8
- 238000005886 esterification reaction Methods 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract 1
- 230000006837 decompression Effects 0.000 abstract 1
- 239000007857 degradation product Substances 0.000 abstract 1
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002253 acid Substances 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 12
- 239000004902 Softening Agent Substances 0.000 description 9
- 150000002148 esters Chemical class 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910001385 heavy metal Inorganic materials 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012044 organic layer Substances 0.000 description 6
- 230000032050 esterification Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- QZCLKYGREBVARF-UHFFFAOYSA-N Acetyl tributyl citrate Chemical compound CCCCOC(=O)CC(C(=O)OCCCC)(OC(C)=O)CC(=O)OCCCC QZCLKYGREBVARF-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 3
- 235000014113 dietary fatty acids Nutrition 0.000 description 3
- 229930195729 fatty acid Natural products 0.000 description 3
- 150000004665 fatty acids Chemical class 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 2
- 244000248349 Citrus limon Species 0.000 description 2
- 235000005979 Citrus limon Nutrition 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 2
- 208000027418 Wounds and injury Diseases 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000011964 heteropoly acid Substances 0.000 description 2
- 208000014674 injury Diseases 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 2
- WEAPVABOECTMGR-UHFFFAOYSA-N triethyl 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound CCOC(=O)CC(C(=O)OCC)(OC(C)=O)CC(=O)OCC WEAPVABOECTMGR-UHFFFAOYSA-N 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229940074391 gallic acid Drugs 0.000 description 1
- 235000004515 gallic acid Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-M hydrogensulfate Chemical compound OS([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- VXWSFRMTBJZULV-UHFFFAOYSA-H iron(3+) sulfate hydrate Chemical compound O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VXWSFRMTBJZULV-UHFFFAOYSA-H 0.000 description 1
- 230000006651 lactation Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 201000007270 liver cancer Diseases 0.000 description 1
- 208000014018 liver neoplasm Diseases 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 1
- 125000005498 phthalate group Chemical group 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of citric acid tributyl citrate. The synthesis method comprises the following steps of stirring and reacting at the room temperature to obtain a product citric acid tributyl citrate by utilizing a condensing agent o-benzotriazole-N, N, N', N'-tetramethyluronium tetrafluoroborate (abbreviated as TATU) by means of esterification reaction of citric acid and n-butyl alcohol, removing the condensing agent and degradation products thereof by utilizing a distilled water washing reaction system, washing a product by virtue of a hydrochloric acid solution with pH value of 1 to remove organic alkali in the product, and removing residual hydrochloric acid in the product by virtue of distilled water washing. The high-purity citric acid tributyl citrate is obtained in a distilling manner under the decompression situation.
Description
Technical field
The present invention relates to a kind of preparation method of tributyl citrate, belong to the field of chemical synthesis.
Background technology
Softening agent is that one is added in macromolecular material, can improve its plasticity-, processibility, swelling property or flexible additive.It is widely used in durable in a large number and in the plastics of easy-formation, as in toy for children, material of construction, trolley part and the medicine equipment such as plasma bags and transfusion device.Commercial softening agent has kind more than 500 at present, mainly contain epoxidation class, polyester, the many esters of gallic acid of benzene, di-fatty acid esters class, citric acid ester type, and in the softening agent of numerous kind, especially based on the softening agent of phthalate structure, its consumption accounts for about 80% of whole softening agent industry.
Along with to the further investigation of fluidizer, people find that the softening agent facing phthalic acid ester class formation has injury to human body, especially to being in the children of etap, the pregnant woman of lactation has larger injury.More there are some researches show that such softening agent of absorption that is long-term, high dosage can increase the incidence of liver cancer, deformity.Therefore the research and apply of the softening agent of new green environment protection becomes the emphasis direction in this field.
Citric acid ester plasticizer is ratified as toy for children, sanitary product, field of food by states such as America and Europes.At present, main on the market citric acid ester plasticizer mainly comprises following several: triethyl citrate (TEC), tributyl citrate (TBC), citric acid three (2-ethyl) ethyl ester (TOC), acetyl triethyl citrate (ATEC), tributyl acetylcitrate (ATBC), acetyl tributyl citrate three (2-ethyl) own ester (ATOC).
Citrate fluidizer is that origin comes from natural citric acid and corresponding pure generation esterification obtains.The topmost characteristic of citrate is easy to biological degradation, low to the toxicity of animal, is a kind of environmentally friendly softening agent.Quality product depends on synthetic technology, is exactly the quality of its catalyzer specifically.Mainly contain following several catalyzer at present:
Sulfuric acid and its esters: sulfuric acid, sodiuim bisulfate, ferric sulfate hydrate ammonium, sal enixum, titanium sulfate etc.;
Sulphonic acids: thionamic acid, p-methyl benzenesulfonic acid, naphthene sulfonic acid etc.;
Muriate: iron trichloride, aluminum chloride, tin tetrachloride etc.;
Heteropolyacid: heteropolyacid is of a great variety, report many have phospho-wolframic acid and silicotungstic acid;
Solid super-strong acid: reporting many has SO
2- 4/ ZrO
2, SO
2- 4/ TiO
2, SO
2- 4/ TiO
2-Fe
2o
3deng;
Catalyst-loaded: the macropore strong acid resin that has of report supports tin tetrachloride, Activated Carbon Supported iron trichloride, activated carbon supported phospho-wolframic acid etc.;
Patent CN102503824A(CN201110350388) disclose a kind of technique of long chain acylation citric acid ester.An acidic catalyst that this patent uses is sulfonic acid type organic acid or mineral acid, at 60 DEG C ~ 100 DEG C, react 0.5 ~ 3.5h, i.e. obtained corresponding crude product, then obtains citrate finished product through decolorizing and refining.
Patent CN101830203(CN201010100456) disclose a kind of with citric acid and fatty alcohol for raw material; with Phenylsulfonic acid or thionamic acid for catalyzer, when reflux through esterification and acetylize, in and, washing, drying, the purge process such as distillation synthesized citric acid ester type compound.
Patent CN103172514A(201310072388.1) provide a kind of preparation method of fatty acid lemon acid ester.The method for reactant with fatty acid chloride and citric acid, is made acid binding agent with the sodium carbonate of 1.5 times of citric acid molar weights, is reacted 4-12h and prepare fatty acid lemon acid ester at 25 DEG C-75 DEG C.
Patent CN103180286A describes the trialkyl ester and acidylate trialkyl ester that manufacture carboxylic acid, and the method for the improvement of the trialkyl carboxylicesters of epoxidised trialkyl ester and acidylate.React in this patent by Lewis Acid metal trifluoro sulfonate catalyzer to the step of the esterification and acidylate that manufacture the design of acidylate trialkyl ester.
Summary of the invention
The present invention uses citric acid and propyl carbinol to carry out esterification, employ a kind of condensing agent o-benzotriazole-N in the reaction, N, N', N'-tetramethyl-urea a tetrafluoro borate (is called for short: TATU), at room temperature stirring reaction obtains product tributyl citrate, then by distillation washing reaction system, removing condensing agent and its degraded product, by the organic bases in the hydrochloric acid soln washed product removing product of PH=1, remained by the hydrochloric acid in distilled water wash removing product.Distillation obtains highly purified triethyl citrate under reduced pressure.
advantage of the present invention:
The present invention's other method preparing triethyl citrate that compares possesses following advantage: productive rate is high, the reaction times is short, without the need to heating, without the need to while using strong acid to the corrosion of equipment less, follow-up treating processes is simply without the need to crossing column purification.In addition, obtain triethyl citrate for strong acid catalyst esterification, present method selectivity is good, obtains triethyl citrate purity higher, and the condensation of self can not occur, thus affects the quality of product.
Embodiment
Embodiment 1
By the propyl carbinol of the citric acid of 50.0g, TATU, 20.0g of 98.0g and the mixing of 39.5g triethylamine, the acetonitrile adding solvent 1.0L dissolves above-mentioned raw materials.The air nitrogen replacement of above-mentioned system 2 times, at room temperature stirs 1h.By reaction system, underpressure distillation is except desolventizing on a rotary evaporator, and with distilled water 1.0L cleaning product twice, separatory removes water layer.With the hydrochloric acid soln 1.0L cleaning product twice that PH is 1.Use the distilled water wash product twice of 1.0L again, collected organic layer.Tributyl citrate is obtained after the residual and moisture of propyl carbinol unnecessary in drying under reduced pressure removing product.The productive rate of product is 88%, moisture≤0.2%, heavy metal < 100,000/.
Embodiment 2
By the propyl carbinol of the citric acid of 50.0g, TATU, 25.0g of 98.0g and the mixing of 39.5g triethylamine, the acetonitrile adding solvent 1.0L dissolves above-mentioned raw materials.The air nitrogen replacement of above-mentioned system 2 times, at room temperature stirs 1h.By reaction system, underpressure distillation is except desolventizing on a rotary evaporator, and with distilled water 1.0L cleaning product twice, separatory removes water layer.With the hydrochloric acid soln 1.0L cleaning product twice that PH is 1.Use the distilled water wash product twice of 1.0L again, collected organic layer.Tributyl citrate is obtained after the residual and moisture of propyl carbinol unnecessary in drying under reduced pressure removing product.The productive rate of product is 92%, moisture≤0.2%, heavy metal < 100,000/.
Embodiment 3
By the propyl carbinol of the citric acid of 50.0g, TATU, 21.0g of 110.0g and the mixing of 39.5g triethylamine, the acetonitrile adding solvent 1.0L dissolves above-mentioned raw materials.The air nitrogen replacement of above-mentioned system 2 times, at room temperature stirs 1h.By reaction system, underpressure distillation is except desolventizing on a rotary evaporator, and with distilled water 1.0L cleaning product twice, separatory removes water layer.With the hydrochloric acid soln 1.0L cleaning product twice that PH is 1.Use the distilled water wash product twice of 1.0L again, collected organic layer.Tributyl citrate is obtained after the residual and moisture of propyl carbinol unnecessary in drying under reduced pressure removing product.The productive rate of product is 95%, moisture≤0.2%, heavy metal < 100,000/.
Embodiment 4
By the propyl carbinol of the citric acid of 50.0g, TATU, 21.0g of 155.0g and the mixing of 39.5g triethylamine, the acetonitrile adding solvent 1.0L dissolves above-mentioned raw materials.The air nitrogen replacement of above-mentioned system 2 times, at room temperature stirs 1h.By reaction system, underpressure distillation is except desolventizing on a rotary evaporator, and with distilled water 1.0L cleaning product twice, separatory removes water layer.With the hydrochloric acid soln 1.0L cleaning product twice that PH is 1.Use the distilled water wash product twice of 1.0L again, collected organic layer.Tributyl citrate is obtained after the residual and moisture of propyl carbinol unnecessary in drying under reduced pressure removing product.The productive rate of product is 99%, moisture≤0.2%, heavy metal < 100,000/.
Embodiment 5
By the propyl carbinol of the citric acid of 50.0g, TATU, 21.0g of 155.0g and the mixing of 26.3g triethylamine, the acetonitrile adding solvent 1.0L dissolves above-mentioned raw materials.The air nitrogen replacement of above-mentioned system 2 times, at room temperature stirs 1h.By reaction system, underpressure distillation is except desolventizing on a rotary evaporator, and with distilled water 1.0L cleaning product twice, separatory removes water layer.With the hydrochloric acid soln 1.0L cleaning product twice that PH is 1.Use the distilled water wash product twice of 1.0L again, collected organic layer.Tributyl citrate is obtained after the residual and moisture of propyl carbinol unnecessary in drying under reduced pressure removing product.The productive rate of product is 97%, moisture≤0.2%, heavy metal < 100,000/.
Embodiment 6
By the propyl carbinol of the citric acid of 50.0g, TATU, 21.0g of 155.0g and the mixing of 50.4g DIPEA, the acetonitrile adding solvent 1.0L dissolves above-mentioned raw materials.The air nitrogen replacement of above-mentioned system 2 times, at room temperature stirs 1h.By reaction system, underpressure distillation is except desolventizing on a rotary evaporator, and with distilled water 1.0L cleaning product twice, separatory removes water layer.With the hydrochloric acid soln 1.0L cleaning product twice that PH is 1.Use the distilled water wash product twice of 1.0L again, collected organic layer.Tributyl citrate is obtained after the residual and moisture of propyl carbinol unnecessary in drying under reduced pressure removing product.The productive rate of product is 99%, moisture≤0.2%, heavy metal < 100,000/.
Claims (3)
1. the synthetic method of a tributyl citrate, it is characterized in that: use citric acid and propyl carbinol by condensing agent o-benzotriazole-N, N, N', N'-tetramethyl-urea a tetrafluoro borate (TATU) and organic bases at room temperature and stirred under nitrogen atmosphere, are obtaining tributyl citrate by refining; Molar ratio between described citric acid and propyl carbinol is 1:1 to 1:1.3; Molar ratio between the usage quantity of described condensing agent TATU and citric acid is 1:1 to 1:1.5; Molar ratio between described organic bases and citric acid is 1:1.5 to 1:2.0; The dilute hydrochloric acid that described treating process comprises washing, pH is 1 is washed, is washed three steps, then obtains triethyl citrate finished product by underpressure distillation removing excess of solvent and propyl carbinol.
2. according to the synthetic method of claim 1 tributyl citrate, it is characterized in that: at room temperature condensation reaction time is at 0.5-1.5h.
3. according to the synthetic method of claim 1 tributyl citrate, it is characterized in that: organic bases is one in triethylamine, DIPEA or combination.
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|---|---|---|---|
| CN201510291963.6A CN104892418A (en) | 2015-06-02 | 2015-06-02 | Synthesis method of citric acid tributyl citrate |
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|---|---|---|---|
| CN201510291963.6A CN104892418A (en) | 2015-06-02 | 2015-06-02 | Synthesis method of citric acid tributyl citrate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384630A (en) * | 2015-11-17 | 2016-03-09 | 湖南尔康制药股份有限公司 | Triethylene glycol citrate and preparation method thereof |
| CN105384636A (en) * | 2015-11-17 | 2016-03-09 | 湖南尔康制药股份有限公司 | Preparation method of citrate |
| WO2017085745A1 (en) | 2015-11-17 | 2017-05-26 | Council Of Scientific & Industrial Research | An auto-catalyzed process for the synthesis of tributyl citrate (tbc) |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105384630A (en) * | 2015-11-17 | 2016-03-09 | 湖南尔康制药股份有限公司 | Triethylene glycol citrate and preparation method thereof |
| CN105384636A (en) * | 2015-11-17 | 2016-03-09 | 湖南尔康制药股份有限公司 | Preparation method of citrate |
| WO2017085745A1 (en) | 2015-11-17 | 2017-05-26 | Council Of Scientific & Industrial Research | An auto-catalyzed process for the synthesis of tributyl citrate (tbc) |
| CN105384630B (en) * | 2015-11-17 | 2017-07-07 | 湖南尔康制药股份有限公司 | Hexylene glycol ester of citric acid three and preparation method thereof |
| US10604472B2 (en) | 2015-11-17 | 2020-03-31 | Council Of Scientific & Industrial Research | Auto-catalyzed process for the synthesis of tributyl citrate (TBC) |
| CN108892613A (en) * | 2018-07-11 | 2018-11-27 | 广东轻工职业技术学院 | A kind of method of the modified H-ZMS-5 type Zeolite synthesis tri-n-butyl citrate of acid |
| CN108892613B (en) * | 2018-07-11 | 2021-02-19 | 广东轻工职业技术学院 | Method for synthesizing tri-n-butyl citrate by acid-modified H-ZMS-5 molecular sieve |
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