CN103755678B - Preparation of cyclicpolybutylece terephthalate dimer - Google Patents
Preparation of cyclicpolybutylece terephthalate dimer Download PDFInfo
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- CN103755678B CN103755678B CN201410043632.6A CN201410043632A CN103755678B CN 103755678 B CN103755678 B CN 103755678B CN 201410043632 A CN201410043632 A CN 201410043632A CN 103755678 B CN103755678 B CN 103755678B
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- ester
- phthalic acid
- butyl
- benzyloxy
- acid
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical class OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 7
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 3
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 3
- -1 polybutylene terephthalate Polymers 0.000 claims description 107
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 39
- 239000002253 acid Substances 0.000 claims description 34
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 150000002148 esters Chemical class 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 150000005690 diesters Chemical class 0.000 claims description 20
- 238000006471 dimerization reaction Methods 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- CGCHCSJZVSGAIH-UHFFFAOYSA-N 4-trityloxybutan-1-ol Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(OCCCCO)C1=CC=CC=C1 CGCHCSJZVSGAIH-UHFFFAOYSA-N 0.000 claims description 10
- QWUWMCYKGHVNAV-UHFFFAOYSA-N 1,2-dihydrostilbene Chemical group C=1C=CC=CC=1CCC1=CC=CC=C1 QWUWMCYKGHVNAV-UHFFFAOYSA-N 0.000 claims description 9
- SXIFAEWFOJETOA-UHFFFAOYSA-N 4-hydroxy-butyl Chemical group [CH2]CCCO SXIFAEWFOJETOA-UHFFFAOYSA-N 0.000 claims description 9
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- TYROJDFHUXSBHC-UHFFFAOYSA-N 4-phenylmethoxybutan-1-ol Chemical compound OCCCCOCC1=CC=CC=C1 TYROJDFHUXSBHC-UHFFFAOYSA-N 0.000 claims description 8
- 230000000694 effects Effects 0.000 claims description 8
- 238000010189 synthetic method Methods 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- 238000007127 saponification reaction Methods 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 claims description 3
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 claims description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 3
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 229960004217 benzyl alcohol Drugs 0.000 claims description 3
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 3
- 229940073608 benzyl chloride Drugs 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- JBWKIWSBJXDJDT-UHFFFAOYSA-N triphenylmethyl chloride Chemical compound C=1C=CC=CC=1C(C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 JBWKIWSBJXDJDT-UHFFFAOYSA-N 0.000 claims description 3
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 2
- 230000005494 condensation Effects 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 3
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims 2
- 150000001412 amines Chemical class 0.000 claims 2
- 239000003153 chemical reaction reagent Substances 0.000 claims 2
- 239000011259 mixed solution Substances 0.000 claims 2
- WORJRXHJTUTINR-UHFFFAOYSA-N 1,4-dioxane;hydron;chloride Chemical compound Cl.C1COCCO1 WORJRXHJTUTINR-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims 1
- 239000012964 benzotriazole Substances 0.000 claims 1
- 230000032050 esterification Effects 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 6
- 239000004033 plastic Substances 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 238000001514 detection method Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 abstract 2
- 239000000539 dimer Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 16
- 239000007787 solid Substances 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 208000035126 Facies Diseases 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 8
- 239000000741 silica gel Substances 0.000 description 8
- 229910002027 silica gel Inorganic materials 0.000 description 8
- 229960001866 silicon dioxide Drugs 0.000 description 8
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920005565 cyclic polymer Polymers 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003550 marker Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
Abstract
The invention specifically discloses a preparation method of novel cyclicpolybutylece terephthalate (PBT) dimer, wherein paraphthaloyl chloride and 1,4-butanediol are used as the raw materials for oriented synthesis of the cyclicpolybutylece terephthalate dimer through a protection and deprotectionstrategy, and the method is used for contrast analysis and detection of cyclicpolybutylece terephthalate dimer impurities in a PBT plastic. The chemical structural formula of the cyclicpolybutylece terephthalate dimer is described in the specification.
Description
[technical field]
The invention belongs to the preparation of analysis examination criteria object of reference is and in particular to a kind of cyclic dimer p-phthalic acid fourth two
The synthetic method of alcohol ester (Cyclic PBT Dimer).
[background technology]
Polybutylene terephthalate (PBT) (Polybutylene terephthalate), also known as poly terephthalic acid four times
Methyl ester, abbreviation PBT, is the condensation polymer of p-phthalic acid and BDO.
Polybutylene terephthalate (PBT) (PBT) is a kind of thermoplastic polyester crystallinity engineering plastics of function admirable, just
Property and hardness high, heat stability is good, has excellent shock resistance, wearability is extremely excellent because coefficient of friction is low, dimensionally stable
Property is good, and hygroscopicity is less, and chemical resistance is good.Due to its excellent performance, PBT is widely used in electronic apparatus and accessory,
Auto parts and components, plant equipment and parts etc..
During the industrialization manufacture of polybutylene terephthalate (PBT) (PBT), can produce and there are different high polymerization degrees
With the polymer of macromolecule, linear polymer and the cyclic polymer of low polymerization degree and small-molecular-weight, such as ring can be produced simultaneously
Shape two polybutylene terephthalate (PBT) (c (TB) 2), ring-type three polybutylene terephthalate (PBT) (c (TB) 3), ring-type four are gathered
Mutual-phenenyl two acid bromide two alcohol ester (c (TB) 4), ring-type five polybutylene terephthalate (PBT) (c (TB) 5), ring-type six are gathered to benzene two
Formic acid butanediol ester (c (TB) 6), and bigger ring-type mutual-phenenyl two acid bromide two alcohol ester etc..Its structural formula is as follows：
Cyclic dimer mutual-phenenyl two acid bromide two alcohol ester (c (TB) 2)：
Ring-type three polybutylene terephthalate (PBT) (c (TB) 3)：
Ring-type four polybutylene terephthalate (PBT) (c (TB) 4)；
Ring-type five polybutylene terephthalate (PBT) (c (TB) 5)：
Ring-type six polybutylene terephthalate (PBT) (c (TB) 6)：
Although the linear polymer of low polymerization degree and small-molecular-weight and cyclic polymer content are seldom in PBT plastic,
It is a key factor of impact plastic quality, the especially higher cyclic dimer mutual-phenenyl two acid bromide two alcohol ester of content and ring-type
Three polybutylene terephthalate (PBT)s, thus cause extensive attention and the research of scientific and technological circle and industrial quarters.
Mainly the obtaining of low polymerization degree ring-type mutual-phenenyl two acid bromide two alcohol ester's marker currently used for PBT plastic research
The approach of obtaining is to be soaked after dissolution from PBT plastic using its dissolubility higher in organic solvent, is divided using high-pressure liquid phase method
From obtaining.The method yield is low, yield is few, expensive.
Quality analysiss detection and scientific research for PBT plastic provide cyclic dimer best in quality in a large number, affordable to benzene
Dioctyl phthalate butanediol ester marker, the present invention devises simplicity, quickly obtains a large amount of cyclic dimer p-phthalic acid fourths two
The method of alcohol ester, and using the synthetically prepared in a large number cyclic dimer mutual-phenenyl two acid bromide two alcohol ester of the method success.
[content of the invention]
It is an object of the invention to provide a kind of simply and effectively side of synthesis of cyclic two polybutylene terephthalate (PBT)
Method.
The synthetic route of cyclic dimer mutual-phenenyl two acid bromide two alcohol ester of the present invention is：
Concrete synthetic method is as follows：
(1) react 1：BDO and triphenylchloromethane react and obtain mono-protected BDO intermediate 4- tri-
Phenylmethoxy butanol 1.
(2) 2 are reacted：BDO and benzyl chloride react and obtain mono-protected BDO intermediate 4- benzyloxy fourth
Alcohol 2.
(3) 3 are reacted：Paraphthaloyl chloride and intermediate 4- benzyloxy butanol 2 reaction obtain double (the 4- benzyloxy of p-phthalic acid
Base butyl) ester 3.
(4) 4 are reacted：The saponification under the effect of a certain amount of potassium hydroxide of double (the 4- benzyloxy butyl) ester 3 of p-phthalic acid obtains
To p-phthalic acid list (4- benzyloxy butyl) ester 4.
(5) 5 are reacted：It is right that p-phthalic acid list (4- benzyloxy butyl) ester 4 and 4- triphenylmethoxy butanol 1 reaction obtain
Phthalic acid 1- (4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5.
(6) 6 are reacted：P-phthalic acid 1- (4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5 is molten with acid
Liquid process is sloughed trityl group and is obtained p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6.
(7) 7 are reacted：Paraphthaloyl chloride and benzylalcohol react and obtain intermediate p-phthalic acid dibenzyl ester 7.
(8) 8 are reacted：P-phthalic acid dibenzyl ester 7 saponification under the effect of a certain amount of potassium hydroxide obtains p-phthalic acid
Single benzyl ester 8.
(9) 9 are reacted：P-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6 and p-phthalic acid list
Benzyl ester 8 reaction obtains the linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 of dibenzyl protection.
(10) 10 are reacted：The linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 of dibenzyl protection sloughs benzyl through catalytic hydrogenation
Blocking group generates linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10.
(11) linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10 cyclization under condensing agent auxiliary generates cyclic dimer to benzene two
Formic acid butanediol ester 11.
The present invention is easy to get using on market, low-cost p-phthalic acid, butanediol are raw material, using chemosynthesis
Method is successfully prepared cyclic dimer mutual-phenenyl two acid bromide two alcohol ester, and easy and simple to handle, yield is higher, cost is relatively low.
Intermediate of the present invention and product all confirm through 1HNMR.
The present invention can synthesize large batch of cyclic dimer mutual-phenenyl two acid bromide two alcohol ester, and so that production scale is become can
Energy.
[specific embodiment]
The preparation of intermediate 4- triphenylmethoxy butanol (1)：
Reaction equation is：
BDO (100g, 1.11mol), triphenylchloromethane (61.87g, 0.22mol) and triethylamine (66.67g,
Dichloromethane solution (600mL) 0.66mol) is stirred overnight at room temperature.Add water, organic faciess separate and wash (200mL × 3) with water, satisfy
With Sal washing, after anhydrous sodium sulfate drying, boil off solvent, excess silica gel column separating purification, ethyl acetate/petroleum ether mixes
Liquid drip washing, obtains 4- triphenylmethoxy butanol 1, yellow oil 63.9g, yield 86.7%.
The preparation of intermediate 4- benzyloxy butanol (2)：
Reaction equation is：
BDO (28.5g, 0.32mol) is dissolved in anhydrous dimethyl formamide (50mL), under stirring in ice bath
Above-mentioned solution is added drop-wise in sodium hydride (6.3g, 0.158mol) anhydrous dimethyl formamide (50mL) suspension, ice bath relays
Continuous stirring half an hour, then Deca benzyl chloride (10g, 0.079mol).Mixed liquor is stirred overnight at room temperature.Add water and ethyl acetate,
Separate organic faciess, wash with water (200mL × 3), saturated common salt is washed, and boils off solvent, excess silica gel after anhydrous sodium sulfate drying
Column separating purification, ethyl acetate/petroleum ether mixed liquor drip washing, obtain 4- benzyloxy butanol 2, light yellow oil 11.2g, yield
79%.
The preparation of double (the 4- benzyloxy butyl) ester (3) of intermediate p-phthalic acid：
Reaction equation is：
4- benzyloxy butanol 2 (57g, 0.32mol), triethylamine (12.64g, 0.32mol) is dissolved in anhydrous methylene chloride
(300mL), the anhydrous methylene chloride solution (100mL) of the lower Deca paraphthaloyl chloride (30.6g, 0.15mol) of ice bath cooling.Mixed
Close liquid to be stirred at room temperature 3 hours, add water, separate organic faciess saturated common salt water washing, solvent after anhydrous sodium sulfate drying, is evaporated off.
Excess silica gel column separating purification, methylene chloride/methanol mixed liquor drip washing, obtain double (the 4- benzyloxy butyl) ester of p-phthalic acid
(3), white solid, 59g, yield 82%.
The preparation of intermediate p-phthalic acid list (4- benzyloxy butyl) ester (4)：
Reaction equation is：
Double (the 4- benzyloxy butyl) ester 3 (30g, 0.061mol) of p-phthalic acid, potassium hydroxide (3.43g, 0.061mol),
The mixture of water (0.86g) tert-butyl alcohol (300mL) is stirred at reflux 4 hours.Reactant liquor is cooled to room temperature, filters, filter cake acetic acid
It is dried after ethyl ester washing.Solid adds in dichloromethane, plus 2N hydrochloric acid is adjusted to pH=2, and solid is completely dissolved.Separate organic faciess,
Wash with water, after anhydrous sodium sulfate drying, solvent is evaporated off, obtain p-phthalic acid list (4- benzyloxy butyl) ester (4), light yellow
Solid, 17g, yield 85%.
The preparation of intermediate p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester (5)：
Reaction equation is：
P-phthalic acid list (4- benzyloxy butyl) ester 4 (3.8g, 0.012mol) is added in 50mL thionyl chloride, drips
Plus anhydrous dimethyl formamide (1ml).Mixture is stirred at reflux and is completely dissolved until compound 4, and thionyl chloride is evaporated off, and excess is molten
In 20ml anhydrous methylene chloride, in ice bath stir under be added drop-wise to 4- triphenylmethoxy butanol 11 (4.23g, 0.013mol),
In the 100ml anhydrous methylene chloride solution of triethylamine (11.7g, 0.12mol).It is stirred at room temperature 1 hour, add water, separate organic faciess,
Saturated common salt water washing, is evaporated off solvent after anhydrous sodium sulfate drying.Excess silica gel column separating purification, ethyl acetate/petroleum ether
Mixed liquor drip washing, obtains p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5, and white is solid
Body, 4.8g, yield 64%.
The preparation of intermediate p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester (6)：
Reaction equation is：
By p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5 (30g, 0.047mol)
It is dissolved in 100mL dichloromethane, lower dichloromethane (200ml) solution that adds formic acid (30ml) is stirred at room temperature.Reaction is examined with TLC
Survey and disappear to raw material, add saturated sodium bicarbonate solution to alkalescence.Separate organic faciess, use saturated common salt water washing, anhydrous slufuric acid
Sodium is evaporated off solvent after being dried.Excess silica gel column separating purification, ethyl acetate/petroleum ether mixed liquor drip washing, obtain terephthaldehyde
Sour 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6, white solid, 13g, yield 71%.
The preparation of intermediate p-phthalic acid dibenzyl base ester (7)：
Reaction equation is：
Benzylalcohol (11.2g, 0.10mol), triethylamine (23.9g, 0.25mol) is dissolved in anhydrous methylene chloride (100mL), ice
The anhydrous methylene chloride solution (30mL) of the lower Deca paraphthaloyl chloride (10g, 0.05mol) of bath cooling.Mixed liquor stirs in room temperature
Mix 1 hour, add water, separate organic faciess saturated common salt water washing, solvent after anhydrous sodium sulfate drying, is evaporated off.Excess silicagel column
Isolate and purify, ethyl acetate/petroleum ether mixed liquor drip washing, obtain p-phthalic acid dibenzyl ester 7, white solid, 12g, yield
70%.
The preparation of intermediate p-phthalic acid monobenzyl ester (8)：
Reaction equation is：
P-phthalic acid dibenzyl ester 7 (12.5g, 0.036mol), potassium hydroxide (2g, 0.036mol), the tertiary fourth of water (0.5g)
The mixture of alcohol (200mL) is stirred at reflux 4 hours.Reactant liquor is cooled to room temperature, filters, and filter cake is dry after being washed with ethyl acetate
Dry.Solid is dissolved in a small amount of water, plus 2N hydrochloric acid is adjusted to pH=2, separates out solid, filters, and cold water washs, and is dried, obtains to benzene two
Formic acid list benzyl ester (8), white solid, 7.4g, yield 84%.
The preparation of the linear dimerization mutual-phenenyl two acid bromide two alcohol ester (9) of intermediate dibenzyl protection：
Reaction equation is：
P-phthalic acid list benzyl ester 8 (11.1g, 0.043mol) is added in 20mL thionyl chloride, Deca anhydrous dimethyl
Base Methanamide (1ml).Mixture is stirred at reflux and is completely dissolved until compound 8, thionyl chloride is evaporated off, it is anhydrous that excess is dissolved in 20ml
In dichloromethane, under stirring in ice bath, it is added drop-wise to p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6
In the 300ml anhydrous methylene chloride solution of (15.7g, 0.039mol), triethylamine (39.7g, 0.39mol).It is stirred at room temperature 1 little
When, add water, separate organic faciess, saturated common salt water washing, solvent after anhydrous sodium sulfate drying, is evaporated off.Excess is pure with silica gel post separation
Change, methylene chloride/methanol mixed liquor drip washing, obtain the linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 of dibenzyl protection, white is solid
Body, 16g, yield 60%.
The preparation of intermediate linear dimerization mutual-phenenyl two acid bromide two alcohol ester (10)：
Reaction equation is：
The linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 that dibenzyl is protected is dissolved in 180mL ethanol and 90mL dichloromethane
In mixed liquor, add 1.6g Pd/C (10%).Reactor first uses nitrogen displacement three times, then with hydrogen exchange three times, under 40psi
Hydrogenated over night, kieselguhr filters, and methylene chloride/methanol is washed, and obtains linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10, and white is solid
Body, 10.2g, yield 88.4%.
The preparation of cyclic dimer mutual-phenenyl two acid bromide two alcohol ester (11),
Reaction equation is：
Under room temperature under nitrogen protection, by linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10 (8.8g, 0.019mol), EDCI
(7.36g, 0.038mol), HOBt (5.19g, 0.038mol), triethylamine (7.77g, 0.076mol) and DMAP
It is dissolved in 880mL anhydrous dimethyl formamide, be stirred overnight.TLC detection reaction disappears to raw material 10.Remove solvent under reduced pressure, remaining
Thing adds water mixing, ethyl acetate or dichloromethane extraction, and organic faciess use saturated common salt water washing after merging, and anhydrous sodium sulfate is dry
Dry, solvent is evaporated off.Excess silica gel column separating purification, ethyl acetate/petroleum ether mixed liquor drip washing, obtain target product ring-type two
Polybutylene terephthalate (PBT) 11, white solid, 3g, yield 35.5%.HPLC analysis result show its purity be 99% with
On.
Claims (2)
1. a kind of method of synthesis of cyclic two polybutylene terephthalate (PBT), the method includes：
(1) BDO and triphenylchloromethane react and obtain mono-protected BDO intermediate 4- triphenylmethoxy
Butanol 1；
(2) BDO and benzyl chloride react and obtain mono-protected BDO intermediate 4- benzyloxy butanol 2；
(3) paraphthaloyl chloride and 4- benzyloxy butanol 2 reaction obtain double (the 4- benzyloxy butyl) ester 3 of p-phthalic acid；
(4) double (the 4- benzyloxy butyl) ester 3 of p-phthalic acid saponification under the effect of a certain amount of potassium hydroxide obtains terephthaldehyde
Single (the 4- benzyloxy butyl) ester 4 of acid；
(5) p-phthalic acid list (4- benzyloxy butyl) ester 4 and 4- triphenylmethoxy butanol 1 reaction obtain p-phthalic acid 1-
(4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5；
(6) p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5 is processed with acid solution and sloughs
Trityl group obtains p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6；
(7) paraphthaloyl chloride and benzylalcohol react and obtain intermediate p-phthalic acid dibenzyl ester 7；
(8) p-phthalic acid dibenzyl ester 7 saponification under the effect of a certain amount of potassium hydroxide obtains p-phthalic acid list benzyl ester 8；
(9) p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6 and p-phthalic acid list benzyl ester 8 are reacted
Linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 to dibenzyl protection；
(10) the linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 of dibenzyl protection sloughs benzyl protection group through catalytic hydrogenation and generates
Linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10；
(11) linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10 is sub- in condensing agent 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne two
Amine hydrochlorate auxiliary is lower to be esterified cyclization generation cyclic dimer mutual-phenenyl two acid bromide two alcohol ester 11.
2. method according to claim 1, including：
(1) double (4- benzyloxy butyl) ester 3 of p-phthalic acid, in the potassium hydroxide of monovalent in tertiary butanol and water mixed solution
The lower selectivity saponification of effect obtains the synthetic method of p-phthalic acid list (4- benzyloxy butyl) ester 4；
(2) p-phthalic acid list (4- benzyloxy butyl) ester 4 and 4- triphenylmethoxy butanol 1 reaction obtain p-phthalic acid 1-
(4- benzyloxy butyl) 4- (4- triphenylmethoxy butyl) diester 5, then uses dichloromethane solution, the hydrogen chloride of trifluoroacetic acid
Diethyl ether solution, the ethyl acetate solution of hydrogen chloride, the alcoholic solution of hydrogen chloride or hydrogen chloride dioxane solution process slough
Trityl group obtains the synthetic method of p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6；
(3) p-phthalic acid dibenzyl ester 7, in tertiary butanol and water mixed solution monovalent potassium hydroxide effect under selectivity
Saponification obtains the synthetic method of p-phthalic acid list benzyl ester 8；
(4) p-phthalic acid 1- (4- benzyloxy butyl) 4- (4- hydroxybutyl) diester 6 and p-phthalic acid list benzyl ester 8 are in condensation
Agent includes but is not limited to 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne diimmonium salt hydrochlorate (EDCI) and auxiliary reagent 1- hydroxyl
Base benzotriazole (HOBt) and the lower reaction of triethylamine effect obtain the linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 that dibenzyl is protected
Synthetic method；
(5) the linear dimerization mutual-phenenyl two acid bromide two alcohol ester 9 of dibenzyl protection, including but not limited under palladium/carbon catalytic hydrogenation
Slough the synthetic method that benzyl protection group generates linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10；
(6) linear dimerization mutual-phenenyl two acid bromide two alcohol ester 10 is sub- in condensing agent 1- ethyl-(3- dimethylaminopropyl) phosphinylidyne two
Amine hydrochlorate (EDCI) and auxiliary reagent I-hydroxybenzotriazole (HOBt) and triethylamine effect lower esterification cyclization generate ring-type
The synthetic method of two polybutylene terephthalate (PBT)s 11.
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| CN109293624A (en) * | 2018-09-21 | 2019-02-01 | 华东师范大学 | A kind of preparation method of cyclic dimer mutual-phenenyl two acid bromide two alcohol ester |
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| US5231161A (en) * | 1992-10-22 | 1993-07-27 | General Electric Company | Method for preparation of macrocyclic poly(alkylene dicarboxylate) oligomers from bis(hydroxyalkyl) dicarboxylates |
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