CN104558053A - Salen-Fe-like complex, and preparation method and application thereof - Google Patents
Salen-Fe-like complex, and preparation method and application thereof Download PDFInfo
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- CN104558053A CN104558053A CN201510044672.7A CN201510044672A CN104558053A CN 104558053 A CN104558053 A CN 104558053A CN 201510044672 A CN201510044672 A CN 201510044672A CN 104558053 A CN104558053 A CN 104558053A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 238000010668 complexation reaction Methods 0.000 title 1
- 239000012989 trithiocarbonate Substances 0.000 claims abstract description 35
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 34
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- NGVCICDLVFASRT-UHFFFAOYSA-N C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.[Cl-].[NH4+] Chemical compound C1(=CC=CC=C1)P(C1=CC=CC=C1)C1=CC=CC=C1.[Cl-].[NH4+] NGVCICDLVFASRT-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 10
- RRIQVLZDOZPJTH-UHFFFAOYSA-N 3,5-di-tert-butyl-2-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=C(O)C(C(C)(C)C)=C1 RRIQVLZDOZPJTH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- QIJRTFXNRTXDIP-UHFFFAOYSA-N (1-carboxy-2-sulfanylethyl)azanium;chloride;hydrate Chemical compound O.Cl.SCC(N)C(O)=O QIJRTFXNRTXDIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- ICKWICRCANNIBI-UHFFFAOYSA-N 2,4-di-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C(C(C)(C)C)=C1 ICKWICRCANNIBI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229960001305 cysteine hydrochloride Drugs 0.000 claims abstract description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 38
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 101100494773 Caenorhabditis elegans ctl-2 gene Proteins 0.000 claims description 20
- 101100112369 Fasciola hepatica Cat-1 gene Proteins 0.000 claims description 20
- 101100005271 Neurospora crassa (strain ATCC 24698 / 74-OR23-1A / CBS 708.71 / DSM 1257 / FGSC 987) cat-1 gene Proteins 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 19
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 claims description 17
- 238000000967 suction filtration Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- 238000010025 steaming Methods 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEUMANXWQDHAJV-UHFFFAOYSA-N 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VEUMANXWQDHAJV-UHFFFAOYSA-N 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 230000015572 biosynthetic process Effects 0.000 claims description 13
- 238000000605 extraction Methods 0.000 claims description 10
- 239000013067 intermediate product Substances 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 239000008098 formaldehyde solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 239000012265 solid product Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 239000006193 liquid solution Substances 0.000 claims description 2
- CQRYARSYNCAZFO-UHFFFAOYSA-N o-hydroxybenzyl alcohol Natural products OCC1=CC=CC=C1O CQRYARSYNCAZFO-UHFFFAOYSA-N 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 125000004122 cyclic group Chemical group 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000012512 characterization method Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 6
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 150000004292 cyclic ethers Chemical class 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 241000237502 Ostreidae Species 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- HIZCIEIDIFGZSS-UHFFFAOYSA-N carbonotrithioic acid Chemical compound SC(S)=S HIZCIEIDIFGZSS-UHFFFAOYSA-N 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000004698 iron complex Chemical class 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 235000020636 oyster Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000005437 stratosphere Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/02—Iron compounds
- C07F15/025—Iron compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
- B01J2531/0252—Salen ligands or analogues, e.g. derived from ethylenediamine and salicylaldehyde
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
Abstract
The invention relates to a Salen-Fe-like complex, and a preparation method and application thereof. The structure of the complex is disclosed in the specification. The preparation method comprises the following steps: carrying out a two-step process on cysteine hydrochloride, 3,5-di-tert-butyl salicylaldehyde, 2,4-di-tert-butyl phenol and the like to synthesize a novel Salen-like ligand, and reacting the ligand with anhydrous ferric chloride to generate the Salen-Fe-like complex. The complex and bis triphenylphosphine ammonium chloride can be used as a catalyst to successfully generate cyclic trithiocarbonate; and the conversion rate of carbon bisulfide can reach 100%, the yield is 60%, and the catalytic efficiency is 9980 mol cyclic trithiocarbonate/mol catalyst.
Description
Technical field
The present invention relates to the reaction of dithiocarbonic anhydride and epoxy cyclohexane, be specially kind Salen-Fe title complex and its preparation method and application.
Technical background
Dithiocarbonic anhydride (CS
2) be a kind of poisonous organosulfur compound, being extensively present in Sweet natural gas, coke oven device, gas maked coal, water-gas, refinery gas and Claus tail gases, also there is a small amount of dithiocarbonic anhydride in chemical fibre industry.Due to CS
2toxicity is large, high volatility and boiling point low, be easily dispersed in air in production and use procedure, serious pollution and harm caused to environment and human body.The dithiocarbonic anhydride of continuous discharge is easily oxidized to sulfurous gas in stratosphere, thus causes acid rain.Because dithiocarbonic anhydride is to the harm of environment, scientific worker is exploring the approach utilizing dithiocarbonic anhydride always.
The trithiocarbonate of ring-type, can as pesticide intermediate owing to having biological activity, and also open loop can form polymkeric substance, its synthetic method receives the concern of people always simultaneously.The method of having reported for work at present, document " Synthesis of cyclictrithiocarbonates from cyclic ethers and carbon disulfide catalyzed by titnaiumeom " (Tearlhedron, Vol 57, No.33,2007) the middle trithiocarbonate adopting titanium compound success catalysis cyclic ethers and dithiocarbonic anhydride to generate ring-type." Aconvenient method for the synthesis of cyclic trithiocarbonates on carbohydrate scaefflds " (Tetrahedron Let, Vol 44, No.2,2003) utilize carbohydrate to react as skeleton and trithiocarbonic acid sodium the trithiocarbonate etc. successfully generating ring-type.The method of the trithiocarbonate of the synthesis of cyclic of current bibliographical information, has by product more, and synthesis step is complicated, the shortcomings such as controllability is poor.
Summary of the invention
The object of this invention is to provide a kind of catalyzer for dithiocarbonic anhydride and epoxy cyclohexane coupled reaction, be specially a kind of Salen-Fe title complex, this title complex is, on the basis of Salen metal complexes, one of them carbon-to-nitrogen double bon is become carbon sulphur singly-bound, become the metal complexes with center of asymmetry, its preparation method is first with cysteine hydrochloride, 3, 5-di-tert-butyl salicylaldehyde and 2, the raw materials such as 4-DI-tert-butylphenol compounds are through the novel class Salen part of two step synthesis, and then to react with this part and Anhydrous Ferric Chloride and generate class Salen-Fe title complex, this catalyst preparing is convenient, technique is simple, controllability is good, environmental friendliness, inherit the good advantage of the metal complex catalyzed activity and selectivity of asymmetric Salen, overcome complex steps when synthesizing asymmetric Salen metal complexes, cost increases, the shortcomings such as severe reaction conditions.This title complex successfully can generate the trithiocarbonate of ring-type as catalyzer, and curing charcoal percent conversion can reach 100%, and productive rate is 60%, and catalytic efficiency is 9980mol ring-type trithiocarbonate/mol catalyzer.
Technical scheme of the present invention is:
One kind Salen-Fe title complex, the structure of this title complex is as follows:
The preparation method of above-mentioned class Salen-Fe title complex, comprises the following steps
(1) synthesis of intermediate product (3,5-di-t-butyl saligenol) L1
2,4-DTBP is placed in three mouthfuls of round-bottomed flasks, anhydrous methanol dissolves, and adds sodium hydroxide, after stirring 20 ~ 40min, then adds formaldehyde solution at 25 ~ 35 DEG C, stirs 24 ~ 30h at finishing 25 ~ 35 DEG C; Being poured into by faint yellow for gained reaction solution is equipped with in the beaker of distilled water, adjusts between pH to 2 ~ 3 with concentrated hydrochloric acid; With dichloromethane extraction, saturated common salt water washing after merging, obtains faint yellow settled solution; Use anhydrous sodium sulfate drying again, suction filtration, revolve steaming and obtain faint yellow solid.Use sherwood oil recrystallization, dry, obtain white needle-like crystals, be intermediate product L1; Its material proportion is: mol ratio 2,4-di-tert-butyl: with sodium hydroxide=1:1.5, and every 0.15mol sodium hydroxide needs distilled water 200 ~ 300mL, and every 0.1mol2,4-DI-tert-butylphenol compounds needs formaldehyde solution to be 20 ~ 30ml;
(2) synthesis of intermediate product (2-brooethyl-4,6-bis--tert.-butyl phenol) L2
L1 is placed in three mouthfuls of round-bottomed flasks, CHCl
3dissolve, then drip PBr
3, reaction 2 ~ 3h, obtains milky white liquid, and mixed solution adding distil water washs, and stirs, uses CHCl
3extraction separatory, the anhydrous MgSO of gained organic phase
4drying, leaves standstill 4 ~ 8h; Suction filtration, revolves and steams to obtain oily liquid, and-10 DEG C ~-5 DEG C freezing Off-white solid, are intermediate product L2; Its material proportion is mol ratio: L2:PBr
3=1:2;
(3) class Salen ligand L ig
1h
2synthesis
3,5-di-tert-butyl salicylaldehyde and cysteine hydrochloride are placed in three mouthfuls of round-bottomed flasks, tetrahydrofuran (THF) dissolves, be heated to back flow reaction 1 ~ 2h; Suction filtration, obtains filtrate, revolves steaming, obtains yellow solid product; Above-mentioned yellow solid product and triethylamine are put into and dissolves with tetrahydrofuran (THF), be placed in three mouthfuls of round-bottomed flasks; Then drip the tetrahydrofuran solution containing intermediate product L2, drip reaction 3 ~ 4h at finishing 25 ~ 35 DEG C; Be precipitated liquid, suction filtration, obtain filtrate, revolve steaming, with the mixed solvent recrystallization of methyl alcohol/sherwood oil, obtain bright yellow solid Lig
1h
2;
Material proportion is: mol ratio 3,5-di-tert-butyl salicylaldehyde: cysteine hydrochloride=1:2, mol ratio triethylamine: L2=2:1; Mol ratio 3,5-di-tert-butyl salicylaldehyde: triethylamine=1:2;
(4) synthesis of class Salen-Fe title complex Cat1
Take class Salen ligand L ig
1h
2be put in a mouth bottle, under argon shield, methylene dichloride dissolves; Then the methanol solution containing Anhydrous Ferric Chloride and sodium acetate, anhydrous is dripped, 20 ~ 26h is stirred at 25 ~ 35 DEG C, obtain black liquor, revolve steaming, with dichloromethane extraction, saturated common salt water washing, obtain organic over anhydrous dried over sodium sulfate, leave standstill suction filtration, revolve steaming, vacuum drying oven is dry, obtains the Cat1 that black has metalluster; Material proportion is: mol ratio Lig
1h
2: Anhydrous Ferric Chloride=1:2, mol ratio Anhydrous Ferric Chloride: sodium acetate, anhydrous=1:1.5;
The application method of described class Salen-Fe title complex Cat1, the trithiocarbonate generating a kind of ring-type is reacted for dithiocarbonic anhydride and epoxy cyclohexane, Cat1 and bi triphenyl phosphine ammonium chloride (PPNCl) is comprised the steps: to put into three mouthfuls of round-bottomed flasks, the mol ratio of Cat1 and bi triphenyl phosphine ammonium chloride is 1:0.5 ~ 2, use argon gas pump drainage, then dithiocarbonic anhydride and epoxy cyclohexane is added successively, the mol ratio of dithiocarbonic anhydride and epoxy cyclohexane is 1:1 ~ 4, epoxy cyclohexane and Cat1 mol ratio are 50000:1, be between 90 ~ 130 DEG C in temperature of reaction, reaction times is 1 ~ 6h, obtain the trithiocarbonate of ring-type.
The concentration of the formaldehyde solution in described step (1) is 37 ~ 40%.
Beneficial effect of the present invention is:
The present invention is a kind of for dithiocarbonic anhydride (CS
2) catalyzer that reacts with epoxy cyclohexane (CHO), be specially a kind Salen-Fe title complex Cat1, this catalyst preparation step is simple, condition is easy to control, with low cost, and the metal ion of use is iron ion, biocompatibility is better, and heavy metal free pollutes; This reaction does not need solvent, the mol ratio that can be just 1:1, dithiocarbonic anhydride and epoxy cyclohexane at Cat1 and bi triphenyl phosphine ammonium chloride mol ratio is 1:2, temperature of reaction 120 DEG C, reaction times 4h catalysis dithiocarbonic anhydride and epoxy cyclohexane react, obtaining product is a kind of ring-type trithiocarbonate, curing charcoal percent conversion can reach 100%, productive rate is 60%, and catalytic efficiency is 9980mol ring-type trithiocarbonate/mol catalyzer.This is a kind of novel method of trithiocarbonate of synthesis of cyclic, compared with the synthetic method of bibliographical information, have easy to operate, step is simple, selectivity good, with low cost, advantages of environment protection.
Accompanying drawing explanation
Fig. 1 is the class Salen ligand L ig in embodiment 1
1h
2's
1hNMR spectrogram;
Fig. 2 is the class Salen ligand L ig in embodiment 1
1h
2infrared spectrum;
Fig. 3 is the uv atlas of the class Salen-Fe title complex Cat1 in embodiment 2;
Fig. 4 is the infrared spectrum of the ring-type trithiocarbonate in embodiment 3;
Fig. 5 is ring-type trithiocarbonate in embodiment 3
1hNMR spectrogram;
Fig. 6 is ring-type trithiocarbonate in embodiment 3
13cNMR spectrogram
Embodiment
The synthetic route of class Salen part and iron complex thereof is as follows:
Concrete synthesis step is as follows:
Embodiment 1
The first step, by 0.1mol 2,4-DI-tert-butylphenol compounds is placed in three mouthfuls of round-bottomed flasks, anhydrous methanol dissolves (quantity of methyl alcohol is for dissolving), add 0.15mol sodium hydroxide, add 25ml formaldehyde solution (concentration is 37% ~ 40% (massfraction)) after stirring at room temperature 30min, finish stirring at room temperature 26h.Pour in the beaker filling 250ml distilled water by faint yellow for gained reaction solution, solution turbid also has large yellow particle to form, and adjusts between pH to 2 ~ 3 with concentrated hydrochloric acid (concentration is 37.5%).With dichloromethane extraction, saturated common salt water washing after merging, on a small quantity repeatedly, obtains faint yellow settled solution.With anhydrous sodium sulfate drying, suction filtration, revolve steaming and obtain faint yellow solid.Use sherwood oil recrystallization, dry, obtain white needle-like crystals and be L1.
Second step, is placed in three mouthfuls of round-bottomed flasks, CHCl by 48mmol L1
3dissolve (CHCl
3amount is for dissolving), then slowly drip 96mmol PBr
3, 15min drips off, and reacts 2.5h, obtain milky white liquid under room temperature, and mixed solution adds appropriate distilled water wash and (ensures without white cigarette, quencher PBr
3), stir, use CHCl
3extraction separatory, upper strata is water layer, lower organic layer.Merge extraction, the anhydrous MgSO of organic phase
4drying, leaves standstill 6h.Suction filtration, revolves and steams to obtain oyster white oily liquid, and freezing (-8 DEG C) obtain Off-white solid, are L2.
3rd step, is placed in three mouthfuls of round-bottomed flasks by 80mmol 3,5-di-tert-butyl salicylaldehyde and 160mmol cysteine hydrochloride, and tetrahydrofuran (THF) dissolves, and is heated to back flow reaction 2h.Obtain turbid solution, suction filtration, obtains filtrate, revolves steaming, obtains yellow solid product (mixture).Above-mentioned gained yellow solid product and 160mmol triethylamine being put into there-necked flask, dissolving (tetrahydrofuran (THF) amount is for dissolving) with tetrahydrofuran (THF).Slow dropping is dissolved with the tetrahydrofuran solution (amount of tetrahydrofuran (THF) is dissolved) of 80mmol L2, and 30min drips off, and drips complete room temperature reaction 4h.Be precipitated liquid, suction filtration, obtain filtrate, revolve steaming, be the mixed solvent recrystallization of 10:1 by methyl alcohol/sherwood oil volume ratio, obtain bright yellow solid-class Salen ligand L ig
1h
2.
1HNMR:(400MHz,CDCl
3,δin ppm):1.23(d,9H,C(CH
3)
3),1.26(d,9H,C(CH
3)
3),1.30(d,9H,C(CH
3)
3),1.42(d,9H,C(CH
3)
3),2.73(s，2H，CH
2),3.64(s,2H,CH
2),3.83(s,2H,CH
2),6.95(d,2H,Ar),7.26～7.43(m,2H,Ar),8.32(s,1H,CH＝N)。Class Salen ligand L ig
1h
2's
1hNMR spectrogram, infrared spectrum are shown in accompanying drawing 1,2, illustrate and obtain target product.
Embodiment 2
Take the class Salen part 0.5mmol Lig obtained in example 1
1h
2be put in a mouth bottle, with argon gas pump drainage three times, and under argon shield; add methylene chloride and make it dissolve, then drip the methanol solution containing 1mmol Anhydrous Ferric Chloride and 1.5mmol sodium acetate, anhydrous, stirred at ambient temperature 24h; obtain black liquor, revolve steaming, with dichloromethane extraction; saturated common salt water washing; obtain organic over anhydrous dried over sodium sulfate, leave standstill suction filtration, revolve steaming, vacuum drying oven is dry; obtain the class Salen-Fe title complex Cat1 that black has metalluster, productive rate is 63%.Infrared (υ in cm
-1): 2959,1610,1539,1458,1385,1255,1180,1096,878,803,669,551,484.Ultimate analysis: C 63.90% (63.94%), H 7.92%, (7.88%), O 5.24% (5.32%), N 2.27% (2.34%), S 5.28 (5.33%), Cl 5.83% (5.90%).Title complex Cat1 uv atlas is shown in accompanying drawing 3, illustrates and obtains target product.
Embodiment 3
0.5 μm of ol bi triphenyl phosphine ammonium chloride (PPNCl) is put into three mouthfuls of round-bottomed flasks, with argon gas pump drainage three times, then add 0.0125mol dithiocarbonic anhydride and 0.025mol epoxy cyclohexane successively, namely the mol ratio of dithiocarbonic anhydride and epoxy cyclohexane is 1:2.120 DEG C, reaction 4h, pours into gained reaction solution and fills in the beaker of methyl alcohol, obtain precipitated liquid, suction filtration, obtain precipitation, with methanol wash, vacuum-drying, obtain product 0.13g.
1hNMR:(400MHz, CDCl
3, δ in ppm): 1.43 ~ 1.52 (m, 2H, CH
2), 1.67 ~ 1.77 (m, 2H, CH
2), 1.91 ~ 2.00 (m, 2H, CH
2), 2.20 ~ 2.23 (m, 2H, CH
2)), 4.05 ~ 4.13 (m, H, CHS), infrared spectrum, nucleus magnetic hydrogen spectrum figure, the nuclear-magnetism carbon spectrogram of product, are shown in accompanying drawing 4,5,6 respectively, and these characterize and illustrate that products are ring-type trithiocarbonate.
Embodiment 4
The 0.5 μm of ol class Salen-Fe title complex Cat1 obtained by embodiment 2 replaces 0.5 μm of ol bi triphenyl phosphine ammonium chloride in embodiment 3, and other operations are with example 3, and obtain 0.14g ring-type trithiocarbonate, the characterization data of gained material is with embodiment 3.
Embodiment 5
0.5 μm of ol Cat1 and the 0.25 μm of ol bi triphenyl phosphine ammonium chloride obtained by embodiment 2 replaces 0.5 μm of ol bi triphenyl phosphine ammonium chloride in embodiment 3, other operations are with example 3, obtain 0.64g ring-type trithiocarbonate, the characterization data of gained material is with embodiment 3.
Embodiment 6
0.5 μm of ol Cat1 and the 0.5 μm of ol bi triphenyl phosphine ammonium chloride obtained by embodiment 2 replaces 0.5 μm of ol bi triphenyl phosphine ammonium chloride in embodiment 3, other operations are with example 3, obtain 0.95g ring-type trithiocarbonate, the characterization data of gained material is with embodiment 3.
Embodiment 7
0.5 μm of ol Cat1 and the 1 μm of ol bi triphenyl phosphine ammonium chloride obtained by embodiment 2 replaces 0.5 μm of ol bi triphenyl phosphine ammonium chloride in embodiment 3, other operations are with example 3, obtain 0.81g ring-type trithiocarbonate, the characterization data of gained material is with embodiment 3.
Embodiment 8
In embodiment 6 120 DEG C are become 90 DEG C, and other operate same embodiment 6 simultaneously, obtain 0.30g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 9
In embodiment 8 90 DEG C are become 100 DEG C, and other operate same embodiment 8 simultaneously, obtain 0.82g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 10
In embodiment 9 100 DEG C are become 130 DEG C, and other operate same embodiment 9 simultaneously, obtain 0.43g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 11
4h in embodiment 6 is become 1h, and other operate same embodiment 6 simultaneously, obtain 0.17g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 12
1h in embodiment 11 is become 2h, and other operate same embodiment 11 simultaneously, obtain 0.76g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 13
2h in embodiment 12 is become 6h, and other operate same embodiment 12 simultaneously, obtain 0.74g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 14
The molar weight of dithiocarbonic anhydride in embodiment 6 changed, make the mol ratio of dithiocarbonic anhydride and epoxy cyclohexane become 1:4 from 1:2, other operate same embodiment 6 simultaneously, obtain 0.36g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
Embodiment 15
The molar weight of dithiocarbonic anhydride in embodiment 14 changed, make the mol ratio of dithiocarbonic anhydride and epoxy cyclohexane become 1:1 from 1:4, other operate same embodiment 14 simultaneously, obtain 0.71g ring-type trithiocarbonate, and the characterization data of gained material is with embodiment 3.
In sum, be used alone Salen-Fe or bi triphenyl phosphine ammonium chloride bad as the catalytic effect of catalyzer, as embodiment 3,4, catalytic efficiency is respectively 1471mol ring-type trithiocarbonate/molCat1,1366mol ring-type trithiocarbonate/mol bi triphenyl phosphine ammonium chloride, and catalytic efficiency can improve greatly when they are used at the same time, can up to 9980mol ring-type trithiocarbonate/mol catalyzer.
Claims (4)
1. a kind Salen-Fe title complex, the structure that it is characterized by this title complex is as follows:
2. the preparation method of class Salen-Fe title complex as claimed in claim 1, is characterized by and comprise the following steps:
(1) synthesis of intermediate product (3,5-di-t-butyl saligenol) L1
2,4-DTBP is placed in three mouthfuls of round-bottomed flasks, anhydrous methanol dissolves, and adds sodium hydroxide, after stirring 20 ~ 40min, then adds formaldehyde solution at 25 ~ 35 DEG C, stirs 24 ~ 30h at finishing 25 ~ 35 DEG C; Being poured into by faint yellow for gained reaction solution is equipped with in the beaker of distilled water, adjusts between pH to 2 ~ 3 with concentrated hydrochloric acid; With dichloromethane extraction, saturated common salt water washing after merging, obtains faint yellow settled solution; Use anhydrous sodium sulfate drying again, suction filtration, revolve steaming and obtain faint yellow solid.Use sherwood oil recrystallization, dry, obtain white needle-like crystals, be intermediate product L1; Its material proportion is: mol ratio 2,4-di-tert-butyl: with sodium hydroxide=1:1.5, and every 0.15mol sodium hydroxide needs distilled water 200 ~ 300mL, and every 0.1mol2,4-DI-tert-butylphenol compounds needs formaldehyde solution to be 20 ~ 30ml;
(2) synthesis of intermediate product (2-brooethyl-4,6-bis--tert.-butyl phenol) L2
L1 is placed in three mouthfuls of round-bottomed flasks, CHCl
3dissolve, then drip PBr
3, reaction 2 ~ 3h, obtains milky white liquid, and mixed solution adding distil water washs, and stirs, uses CHCl
3extraction separatory, the anhydrous MgSO of gained organic phase
4drying, leaves standstill 4 ~ 8h; Suction filtration, revolves and steams to obtain oily liquid, and-10 DEG C ~-5 DEG C freezing Off-white solid, are intermediate product L2; Its material proportion is mol ratio: L2:PBr
3=1:2;
(3) class Salen ligand L ig
1h
2synthesis
3,5-di-tert-butyl salicylaldehyde and cysteine hydrochloride are placed in three mouthfuls of round-bottomed flasks, tetrahydrofuran (THF) dissolves, be heated to back flow reaction 1 ~ 2h; Suction filtration, obtains filtrate, revolves steaming, obtains yellow solid product; Above-mentioned yellow solid product and triethylamine are put into and dissolves with tetrahydrofuran (THF), be placed in three mouthfuls of round-bottomed flasks; Then drip the tetrahydrofuran solution containing intermediate product L2, drip reaction 3 ~ 4h at finishing 25 ~ 35 DEG C; Be precipitated liquid, suction filtration, obtain filtrate, revolve steaming, with the mixed solvent recrystallization of methyl alcohol/sherwood oil, obtain bright yellow solid Lig
1h
2;
Material proportion is: mol ratio 3,5-di-tert-butyl salicylaldehyde: cysteine hydrochloride=1:2, mol ratio triethylamine: L2=2:1; Mol ratio 3,5-di-tert-butyl salicylaldehyde: triethylamine=1:2;
(4) synthesis of class Salen-Fe title complex Cat1
Take class Salen ligand L ig
1h
2be put in a mouth bottle, under argon shield, methylene dichloride dissolves; Then the methanol solution containing Anhydrous Ferric Chloride and sodium acetate, anhydrous is dripped, 20 ~ 26h is stirred at 25 ~ 35 DEG C, obtain black liquor, revolve steaming, with dichloromethane extraction, saturated common salt water washing, obtain organic over anhydrous dried over sodium sulfate, leave standstill suction filtration, revolve steaming, vacuum drying oven is dry, obtains the Cat1 that black has metalluster; Material proportion is: mol ratio Lig
1h
2: Anhydrous Ferric Chloride=1:2, mol ratio Anhydrous Ferric Chloride: sodium acetate, anhydrous=1:1.5.
3. the preparation method of class Salen-Fe title complex as claimed in claim 2, the concentration that it is characterized by the formaldehyde solution in described step (1) is 37 ~ 40%.
4. the application method of class Salen-Fe title complex as claimed in claim 1, its special this is characterized as and reacts for dithiocarbonic anhydride and epoxy cyclohexane the trithiocarbonate generating a kind of ring-type, Cat1 and bi triphenyl phosphine ammonium chloride (PPNCl) is comprised the steps: to put into three mouthfuls of round-bottomed flasks, the mol ratio of Cat1 and bi triphenyl phosphine ammonium chloride is 1:0.5 ~ 2, use argon gas pump drainage, then dithiocarbonic anhydride and epoxy cyclohexane is added successively, the mol ratio of dithiocarbonic anhydride and epoxy cyclohexane is 1:1 ~ 4, epoxy cyclohexane and Cat1 mol ratio are 50000:1, be between 90 ~ 130 DEG C in temperature of reaction, reaction times is 1 ~ 6h, obtain the trithiocarbonate of ring-type.
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| CN108069894A (en) * | 2016-11-11 | 2018-05-25 | 天津工业大学 | A kind of new Salen ligands synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde and preparation method thereof |
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| AYELLET STOPPER ET AL.: "Ring-Opening Polymerization of Lactide with Zr Complexes of {ONSO} Ligands: From Heterotactically Inclined to Isotactically Inclined Poly(lactic acid)", 《MACROMOLECULES》 * |
| DONALD J. DARENSBOURG ET AL.: "Investigations into the coupling of cyclohexene oxide and carbon disulfide catalyzed by (salen)CrCl. Selectivity for the production of copolymers vs. cyclic thiocarbonates", 《DALTON TRANSACTIONS》 * |
| KOJI NAKANO ET AL.: "Alternating Copolymerization of Cyclohexene Oxide with Carbon Dioxide Catalyzed by (salalen)CrCl Complexes", 《MACROMOLECULES》 * |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108069894A (en) * | 2016-11-11 | 2018-05-25 | 天津工业大学 | A kind of new Salen ligands synthesized by 1,2- cyclohexanediamine with pyridine-2-formaldehyde and preparation method thereof |
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