CN101633611A - Method for synthesizing alpha-tetralone by gas solid phase reaction - Google Patents
Method for synthesizing alpha-tetralone by gas solid phase reaction Download PDFInfo
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- CN101633611A CN101633611A CN200910101675A CN200910101675A CN101633611A CN 101633611 A CN101633611 A CN 101633611A CN 200910101675 A CN200910101675 A CN 200910101675A CN 200910101675 A CN200910101675 A CN 200910101675A CN 101633611 A CN101633611 A CN 101633611A
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- tetralone
- butyrolactone
- gamma
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- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 33
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 12
- 238000003746 solid phase reaction Methods 0.000 title claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 64
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 239000002808 molecular sieve Substances 0.000 claims abstract description 20
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 5
- VGKDLMBJGBXTGI-SJCJKPOMSA-N sertraline Chemical compound C1([C@@H]2CC[C@@H](C3=CC=CC=C32)NC)=CC=C(Cl)C(Cl)=C1 VGKDLMBJGBXTGI-SJCJKPOMSA-N 0.000 claims description 25
- 229960002073 sertraline Drugs 0.000 claims description 25
- 239000007789 gas Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 238000002309 gasification Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 230000009466 transformation Effects 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000004587 chromatography analysis Methods 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims description 3
- 230000005494 condensation Effects 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 150000002500 ions Chemical group 0.000 claims description 2
- 238000000643 oven drying Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 230000005587 bubbling Effects 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 238000004939 coking Methods 0.000 claims 1
- 230000002779 inactivation Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002351 wastewater Substances 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000006213 oxygenation reaction Methods 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 22
- 239000002253 acid Substances 0.000 description 8
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 5
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WDQFELCEOPFLCZ-UHFFFAOYSA-N 1-(2-hydroxyethyl)pyrrolidin-2-one Chemical compound OCCN1CCCC1=O WDQFELCEOPFLCZ-UHFFFAOYSA-N 0.000 description 2
- NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- YEXIOUZEXADMJW-HHWOBMLOSA-N (8r,9s,13s,14s,17r)-17-ethynyl-17-hydroxy-13-methyl-1,2,4,6,7,8,9,11,12,14,15,16-dodecahydrocyclopenta[a]phenanthren-3-one;(8r,9s,13s,14s,17r)-17-ethynyl-3-methoxy-13-methyl-7,8,9,11,12,14,15,16-octahydro-6h-cyclopenta[a]phenanthren-17-ol Chemical compound C1CC(=O)CC2=C1[C@H]1CC[C@](C)([C@](CC3)(O)C#C)[C@@H]3[C@@H]1CC2.C1C[C@]2(C)[C@@](C#C)(O)CC[C@H]2[C@@H]2CCC3=CC(OC)=CC=C3[C@H]21 YEXIOUZEXADMJW-HHWOBMLOSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000001430 anti-depressive effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- DVECBJCOGJRVPX-UHFFFAOYSA-N butyryl chloride Chemical compound CCCC(Cl)=O DVECBJCOGJRVPX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- QABCGOSYZHCPGN-UHFFFAOYSA-N chloro(dimethyl)silicon Chemical compound C[Si](C)Cl QABCGOSYZHCPGN-UHFFFAOYSA-N 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003433 contraceptive agent Substances 0.000 description 1
- 230000002254 contraceptive effect Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention relates to a method for synthesizing alpha-tetralone by gas solid phase reaction. Benzene and gamma-butyrolactone are taken as raw materials; a molecular sieve is taken as a catalyst; the alpha-tetralone is continuously synthesized in a fixed bed reactor by the gas solid phase reaction; the reaction temperature is 210-300 DEG C; the reaction is carried out under the condition that the liquid space velocity is 1-6.0 h<-1>; the average conversion rate of gamma-butyrolactone is 25-79%; and the average mole yield of alpha-tetralone is 5-40%. The catalyst which is devitalized can be reproduced through oxygenation ignition to recover the catalyst performance. The method for synthesizing alpha-tetralone has the characteristics of avoiding the problems of not reusing the catalyst and discharging a great amount of acidic waste water. A serialization synthetic process is beneficial to automation production and production efficiency and enhances the production efficiency.
Description
Technical field:
What the present invention relates to is a kind of method of synthetic α-Tetralone an intermediate of Sertraline, is raw material with benzene and gamma-butyrolactone, after gasification, under the solid molecular sieves catalyst action, synthesizes to continuous flow the method for α-Tetralone an intermediate of Sertraline.
Background technology:
α-Tetralone an intermediate of Sertraline (α-tetralone claims tetralone again) is a kind of xanchromatic liquid, is soluble in benzene and ethanol, is insoluble to chloroform, relative density 1.096 (25/4 ℃), fusing point 5-6 ℃, 255 ℃ of boiling points.Specific refractory power 1.5675-1.5695.
α-Tetralone an intermediate of Sertraline is a kind of important medicinal intermediates, be mainly used in the synthetic (petrochemical complex of products such as conovid,enavid E (a kind of contraceptive bian), antidepressive Sertraline and sterilant SevinCarbaryl, 2004, the 13 volumes the 1st phase P34; Japan ChemicalWeek, 2004,45 (2286)), also can be used as solvent, plastics tenderizer etc.
The synthetic method about α-Tetralone an intermediate of Sertraline of bibliographical information mainly contains following several at present:
(1) naphthane oxidation style.The catalyzer that can select for use and oxygenant have multiple, the method that is fit to large-scale commercial production is: use chromium acetate and 2-methyl-5-ethylpyridine composite catalyst, with the air is oxygenant, carry out the continuous liquid-phase oxidation of normal pressure, 130 ℃ of temperature of reaction, the mol ratio of naphthane and oxygen are 1: 0.6, residence time 60-70min, the naphthane per pass conversion can reach more than 20%, and it is about 90% to generate the selection rate of 1 α-Tetralone an intermediate of Sertraline, and main by product is a naphthane alcohol.Product can get 98% Tetralone an intermediate of Sertraline through vacuum fractionation.The shortcoming of this method is that transformation efficiency is on the low side.Some new catalyst system have appearred in recent years, patent as following discloses: CN101337872 (method of synthesizing tetralone by liquid-phase catalytic oxidation of tetralin), CN101177386 (a kind of method of preparing alpha-tetralin ketone by catalyzed oxidation tetrahydronaphthalene), CN101337186 (preparation of a kind of mesoporous A1203 and be used for catalyzed synthesizing alpha-Tetralone an intermediate of Sertraline)
(2) be that raw material is through multisteps such as acidylate, reduction, cyclization synthetic (R.Haworth Reaction) with benzene and Succinic anhydried.The shortcoming of this method is that processing step is many, and productive rate is low.Particularly acylation reaction needs to use aluminum trichloride (anhydrous) as catalyzer, and last handling process can produce a large amount of acid waste water, and is seriously polluted.
(3) γ-benzenebutanoic acid cyclisation method.γ-benzenebutanoic acid obtains α-Tetralone an intermediate of Sertraline 90 ℃ of cyclisation under phosphoric acid/phosphoric anhydride, Tripyrophosphoric acid, hydrofluoric acid or vitriol oil effect, yield is 75-86%.
(4) γ-benzene butyryl chloride cyclisation method.The dehydrochlorination cyclisation gets Tetralone an intermediate of Sertraline in the presence of aluminum trichloride (anhydrous) or anhydrous stannic chloride.
(5) benzene and 1, the 4-butyrolactone is synthetic (C.E.Olson under the effect of aluminum trichloride (anhydrous), A.R.Bader, Org.Synth., 1963,4,898), wherein as the mole dosage of the aluminum trichloride (anhydrous) of catalyzer generally be lactone 3-5 doubly, can't reclaim after the reaction, last handling process can produce a large amount of acid waste water.People such as Prakash (G.K.Surya Prakash, Ping Yan, Be í a
And George A.Olah, Catalysis Letters, 2003,87 (3-4) 109-112) once reported with the trifluoromethanesulfonic acid to be catalyzer benzene and 1, the reaction result of 4-butyrolactone, it is very low to find to generate α-Tetralone an intermediate of Sertraline yield.
Need liquid acid as catalyzer in the method for above-mentioned (2)-(5), catalyst levels is big and be difficult to repeat reclaim use, and product postprocessing needs a large amount of water to wash, and can't avoid the discharging of a large amount of acid waste waters.In addition, the raw material of method (1) (3) (4) is difficult to obtain, and application facet may be subjected to bigger restriction.
Comparatively speaking, employed raw material is benzene and gamma-butyrolactone in the method (5), and the both belongs to large industrial chemicals product, does not have the problem of starving usually.The reaction of the pass gamma-butyrolactone gas-solid phase of finding in the literature relates generally to the gas phase amination reaction of it and some aminated compoundss, as, synthetic N-hydroxyethyl-pyrrolidone (NHP) (the easy state guest etc. of gamma-butyrolactone and thanomin reaction, modified Y molecular sieve catalysis gamma-butyrolactone gas phase amination reaction, petrochemical complex, 2006,35 (8) .757-760).
Summary of the invention:
The objective of the invention is to develop a kind of environment amenable, method of preparing α-Tetralone an intermediate of Sertraline by benzene and gamma-butyrolactone, use novel catalyzing technology, avoid benzene and 1, the problem that 4-the butyrolactone synthetic a large amount of acid waste waters of discharging and catalyzer under the effect of aluminum trichloride (anhydrous) can't reclaim and regenerate and use, and the production serialization is carried out, enhance productivity greatly.
Solution of the present invention is to be catalyzer with acid solid molecular sieves, realizes benzene and gamma-butyrolactone in the F-C of gas-solid continuous flow condition mutually reaction in fixed-bed reactor, the synthetic target product α-Tetralone an intermediate of Sertraline that obtains.
The method of synthesizing alpha-tetralone by gas solid phase reaction provided by the invention is a raw material with benzene and gamma-butyrolactone, is catalyzer with the molecular sieve, synthesizing alpha-tetralone by gas solid phase reaction in fixed-bed reactor, and reaction equation is as follows:
Synthesis step is as follows:
(1) pack in fixed-bed reactor a kind of molecular sieve catalyst among a certain amount of H-Beta through ion exchange treatment, HZSM-5, the SAPO-11 is 400～600 ℃ of a certain steady temperatures, with the logical N of flow velocity 5～50ml/min
2Pre-treatment 1～5h reduces to temperature of reactor a certain steady temperature between 210～300 ℃ then;
(2) with the volume ratio of benzene and gamma-butyrolactone be 10～25: 1 mixed solution 210～300 ℃ of gasifications down, be 1～6h with the liquid air speed
-1With the benzene and the gamma-butyrolactone process catalyst layer of gasification, temperature of reaction is 210～300 ℃ of a certain steady temperatures;
(3) collect product in fixed-bed reactor outlet condensation,, determine the yield of the transformation efficiency and the α-Tetralone an intermediate of Sertraline of gamma-butyrolactone with the content of gamma-butyrolactone and α-Tetralone an intermediate of Sertraline in the gas chromatographic analysis product.
H-Beta of the present invention, HZSM-5, SAPO-11 molecular sieve catalyst ion exchange treatment method are according to molecular sieve/NH
4The Cl mass ratio is 10/12 ratio, molecular sieve is joined the NH of 1M
4In the Cl aqueous solution, in oil bath, reflux and stir 2h; Cooling back suction filtration, being washed with distilled water to does not have Cl in the filtrate
-Till checking out, the molecular sieve with ion-exchange spends the night at 110 ℃ of oven dryings again.Use the same method again with twice of sample ions exchange.With sample roasting 4h in 500 ℃ of retort furnaces, the cooling back is preserved standby at last.
Molecular sieve catalyst of the present invention catalyzer preferably is HZSM-5, and the Si/Al ratio among the HZSM-5 is 12～150: 1, and catalyst particle size is the 20-100 order.
The invention provides a kind of in fixed-bed reactor, with benzene and gamma-butyrolactone as raw material, the method for continuously synthetic α-Tetralone an intermediate of Sertraline under the molecular sieve catalytic effect.Beta, SAPO-11 and ZSM-5 with Hydrogen are catalyzer, and temperature of reaction is that 210～300 ℃, liquid air speed are 1～6.0h
-1, the average conversion of gamma-butyrolactone is 25～79%, the molar average yield of α-Tetralone an intermediate of Sertraline is 5～40%.Can be behind the catalyst deactivation by regenerating after the oxidation calcination, catalyst performance recovers.
Characteristics of the present invention are that catalyzer can't be reused the problem of amplification quantity acid waste water side by side in the F-C reaction production α-Tetralone an intermediate of Sertraline technology that can avoid traditional, the automatization that the synthesis technique of serialization of the present invention simultaneously helps producing, enhance productivity, have important prospects for commercial application.
Embodiment:
Embodiment 1
At internal diameter is 2.2g H-ZSM5 (Si/Al=150) (20-40 order) catalyzer of packing in the 280mm silica tube fixed-bed reactor for 8mm length, at 380 ℃ of logical N
2(20ml/min) handle 2h after, be cooled to 240 ℃ and keep constant temperature.Use the micro-sampling pump with constant flow velocity (2.75mL/h, LHSV=1.1h benzene and gamma-butyrolactone mixed solution (volume ratio 19/1)
-1) squeeze into vaporizing chamber (280 ℃), the gasification back is with N
2Enter beds, N
2Flow velocity 20ml/min.Reaction tubes is exported the product of condensation, collected once every 20 minutes, content (chromatographic column: 5%FFAP/AW DMCS (60-80 order)), calculate the transformation efficiency of butyrolactone and the yield of α-Tetralone an intermediate of Sertraline with gamma-butyrolactone and α-Tetralone an intermediate of Sertraline in the gas chromatographic analysis product.The average conversion of gamma-butyrolactone is 46.5%, and the molar average yield of α-Tetralone an intermediate of Sertraline is 29.6%.Related data is listed in the table 1 (1).
Embodiment 2～4
Under the identical condition of other conditions and embodiment 1, benzene and gamma-butyrolactone mixed solution (volume ratio 15/1), respectively with H-Beta (S/Al=12.5) and SAPO-11 molecular sieve as catalyzer, the result who reacts under different temperature of reaction, liquid air speed and reaction times condition lists in respectively in the table 1 (2～4).
Embodiment 5～8
Under the identical condition of other conditions and embodiment 1, benzene and gamma-butyrolactone mixed solution (volume ratio 25/1), respectively with different Si/Al than the H-ZSM5 of (50,25,19,12.5) as catalyzer, be that 240 ℃, liquid air speed are 1.1h in temperature of reaction
-12-4 hour result lists in respectively in the table 1 (5～8) with reaction.
Embodiment 9～12
Under the identical condition of other conditions and embodiment 1, with Si/Al than be 50 H-ZSM5 as catalyzer, change temperature of reaction (being respectively 210,220,240,260 ℃), the liquid air speed is 1.1h
-13-4 hour result lists in respectively in the table 1 (9～12) with reaction.
Embodiment 13～16
Under the identical condition of other conditions and embodiment 1, with Si/Al than be 50 H-ZSM5 as catalyzer, temperature of reaction is 240 ℃, changes the liquid air speed and (is respectively 1.0,1.5,2.0,5.5h
-1), react 3-4 hour result and list in respectively in the table 1 (13～16).
The result of benzene and gamma-butyrolactone reaction under table 1. different catalysts and the differential responses condition
| Embodiment | Catalyzer | Temperature of reaction/℃ | ??LHSV ??/h -1 | Reaction times/h | Average conversion/% | Average yield/% |
| ??1 | ??HZSM-5(Si/Al＝150) | ??240 | ??1.1 | ??3 | ??46.5 | ??29.6 |
| ??2 | ??H-Beta(Si/Al＝12.5) | ??300 | ??3.4 | ??2 | ??37.5 | ??4.9 |
| ??3 | ??SAPO-11 | ??300 | ??3.5 | ??1 | ??37.0 | ??8.4 |
| ??4 | ??SAPO-11 | ??240 | ??1.3 | ??2 | ??39.3 | ??26.7 |
| ??5 | ??HZSM-5(Si/Al＝50) | ??240 | ??1.1 | ??4 | ??78.9 | ??38.6 |
| ??6 | ??HZSM-5(Si/Al＝25) | ??240 | ??1.2 | ??2 | ??44.5 | ??15.4 |
| ??7 | ??HZSM-5(Si/Al＝19) | ??240 | ??1.1 | ??2 | ??61.4 | ??9.9 |
| ??8 | ??HZSM-5(Si/Al＝12.5) | ??240 | ??1.5 | ??3 | ??43.5 | ??6.4 |
| ??9 | ??HZSM-5(Si/Al＝50) | ??210 | ??1.0 | ??3 | ??29.0 | ??18.6 |
| ??10 | ??HZSM-5(Si/Al＝50) | ??220 | ??1.0 | ??3 | ??31.8 | ??20.4 |
| ??11 | ??HZSM-5(Si/Al＝50) | ??240 | ??1.5 | ??3 | ??62.1 | ??33.3 |
| ??12 | ??HZSM-5(Si/Al＝50) | ??260 | ??1.5 | ??3 | ??72.9 | ??35.9 |
| ??13 | ??HZSM-5(Si/Al＝50) | ??240 | ??1.0 | ??4 | ??46.1 | ??27.0 |
| ??14 | ??HZSM-5(Si/Al＝50) | ??240 | ??1.5 | ??4 | ??36.8 | ??22.9 |
| ??15 | ??HZSM-5(Si/Al＝50) | ??240 | ??2.0 | ??4 | ??25.4 | ??19.4 |
| ??16 | ??HZSM-5(Si/Al＝50) | ??260 | ??5.5 | ??3 | ??35.8 | ??28.9 |
Embodiment 17
Catalyzer after embodiment 5 used is 420 ℃ in temperature, and calcination 4h regeneration under the online condition of oxygen flow 20mL/min is reacted the regenerated catalyzer under the identical condition of embodiment 5, and the result of reaction is as shown in table 2.
Reaction result is used in the regeneration of table 2HZSM5 (Si/Al=50)
| The regeneration access times | Average conversion/% | Average yield/% |
| ??1 | ??66.1 | ??42.2 |
| ??2 | ??52.7 | ??37.3 |
| ??3 | ??49.0 | ??36.6 |
| ??4 | ??62.1 | ??39.8 |
| ??5 | ??51.9 | ??37.5 |
Embodiment 18
Catalyzer after embodiment 8 used is 500 ℃ in temperature, and calcination 4h regeneration under the online condition of air flow quantity 20mL/min is reacted the regenerated catalyzer under the identical condition of embodiment 8, and the result who reacts 2 hours is as shown in table 3.
Reaction result is used in the regeneration of table 3.HZSM5 (Si/Al=12.5)
| The regeneration access times | ??LHSV/h -1 | Average conversion/% | Average yield/% |
| ??1 | ??2.4 | ??18.8 | ??5.5 |
| ??2 | ??2.5 | ??20.5 | ??6.7 |
| ??3 | ??3.1 | ??18.1 | ??7.5 |
| ??4 | ??3.3 | ??16.0 | ??6.8 |
| ??5 | ??32 | ??15.6 | ??9.1 |
| ??6 | ??2.3 | ??16.5 | ??8.8 |
| ??7 | ??3.6 | ??12.3 | ??7.0 |
| ??8 | ??4.3 | ??10.5 | ??6.5 |
Claims (4)
1, a kind of method of synthesizing alpha-tetralone by gas solid phase reaction is characterized in that: with benzene and gamma-butyrolactone is raw material, is catalyzer with the hydrogen type molecular sieve, the synthetic continuously α-Tetralone an intermediate of Sertraline of gas-solid phase reaction in fixed-bed reactor, and reaction equation is as follows:
Synthesis step is as follows:
(1) pack in fixed-bed reactor a kind of hydrogen type molecular sieve catalyzer among a certain amount of H-Beta through ion exchange treatment, HZSM-5, the SAPO-11 400～600 ℃ of a certain steady temperatures, is the N of 5～50ml/min with through-flow speed
2Pre-treatment 1～5h reduces to temperature of reactor a certain steady temperature between 210～300 ℃ then;
(2) with the volume ratio of benzene and gamma-butyrolactone being 10～25: 1 mixed solution, 210～300 ℃ of gasifications down, is 1～6h with the liquid air speed
-1With the benzene and the gamma-butyrolactone process catalyst layer of gasification, temperature of reaction is 210～300 ℃ of a certain steady temperatures;
(3) collect product in fixed-bed reactor outlet condensation,, determine the yield of the transformation efficiency and the α-Tetralone an intermediate of Sertraline of gamma-butyrolactone with the content of gamma-butyrolactone and α-Tetralone an intermediate of Sertraline in the gas chromatographic analysis product.
2,, it is characterized in that the ion exchange treatment method of described molecular sieve catalyst, according to molecular sieve/NH according to the method for right 1 described synthesizing alpha-tetralone by gas solid phase reaction
4The Cl mass ratio is 10/12 ratio, molecular sieve is joined the NH of 1M
4In the Cl aqueous solution, in oil bath, reflux and stir 2h; Cooling back suction filtration, being washed with distilled water to does not have Cl in the filtrate
-Till checking out, the molecular sieve with ion-exchange spends the night at 110 ℃ of oven dryings again; Use the same method again with twice of sample ions exchange; With sample roasting 4h in 500 ℃ of retort furnaces, the cooling back is preserved standby at last.
3, according to the method for right 1 described synthesizing alpha-tetralone by gas solid phase reaction, it is characterized in that the Si/Al ratio among the described molecular sieve catalyst HZSM-5 is 12～150: 1, catalyst particle size is the 20-100 order.
4, according to the method for right 1 described synthesizing alpha-tetralone by gas solid phase reaction, it is characterized in that reacting catalyzer behind the inactivation by online bubbling air or oxygen, under 400～550 ℃ of temperature condition, the coking carbon deposit of burn off catalyst surface makes catalyst regeneration.
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Cited By (5)
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| CN102584556A (en) * | 2011-12-19 | 2012-07-18 | 浙江大学 | Method for synthesizing Alpha-tetralone through 4-phenylbutyric acid in catalytic way |
| CN105017154A (en) * | 2015-07-07 | 2015-11-04 | 丽水市南明化工有限公司 | Preparation method of 3-bromo-1,3,4,5-tetrahydro-2H-1-benzazepine-2-keto |
| CN110283058A (en) * | 2019-07-04 | 2019-09-27 | 海门华祥医药科技有限公司 | The novel method for synthesizing of 1-tetralone |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| DE2814129A1 (en) * | 1978-04-01 | 1979-10-11 | Hoechst Ag | Alpha-tetralone cpds. prodn. - by reacting aromatic hydrocarbon cpds. e.g. benzene with gamma-lactone cpds. e.g. gamma-butyrolactone in hydrogen fluoride |
| US7115782B2 (en) * | 2002-06-03 | 2006-10-03 | Showa Denko K.K. | Process for producing aromatic compounds by Friedel-Crafts reaction |
| JP4243683B2 (en) * | 2003-10-02 | 2009-03-25 | 独立行政法人産業技術総合研究所 | Method for producing 1-tetralone |
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| CN102584556A (en) * | 2011-12-19 | 2012-07-18 | 浙江大学 | Method for synthesizing Alpha-tetralone through 4-phenylbutyric acid in catalytic way |
| CN105017154A (en) * | 2015-07-07 | 2015-11-04 | 丽水市南明化工有限公司 | Preparation method of 3-bromo-1,3,4,5-tetrahydro-2H-1-benzazepine-2-keto |
| CN110283058A (en) * | 2019-07-04 | 2019-09-27 | 海门华祥医药科技有限公司 | The novel method for synthesizing of 1-tetralone |
| CN112409145A (en) * | 2020-11-13 | 2021-02-26 | 杭州新拜思生物医药有限公司 | Preparation method of 1-tetralone |
| CN112409145B (en) * | 2020-11-13 | 2023-03-28 | 杭州新拜思生物医药有限公司 | Preparation method of 1-tetralone |
| CN114166979A (en) * | 2021-12-09 | 2022-03-11 | 四川阿格瑞新材料有限公司 | Method for measuring content of 1-tetralone |
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