CN104370951B - A kind of aluminium trimethide title complex of four tooth nitrogen oxygen parts and application thereof - Google Patents
A kind of aluminium trimethide title complex of four tooth nitrogen oxygen parts and application thereof Download PDFInfo
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- CN104370951B CN104370951B CN201410609375.8A CN201410609375A CN104370951B CN 104370951 B CN104370951 B CN 104370951B CN 201410609375 A CN201410609375 A CN 201410609375A CN 104370951 B CN104370951 B CN 104370951B
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- OLBVUFHMDRJKTK-UHFFFAOYSA-N [N].[O] Chemical group [N].[O] OLBVUFHMDRJKTK-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000004411 aluminium Substances 0.000 title claims abstract description 22
- JJTUDXZGHPGLLC-UHFFFAOYSA-N lactide Chemical group CC1OC(=O)C(C)OC1=O JJTUDXZGHPGLLC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 18
- 239000001257 hydrogen Substances 0.000 claims abstract description 18
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 12
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims abstract description 8
- 229910052736 halogen Chemical group 0.000 claims abstract description 7
- 150000002367 halogens Chemical group 0.000 claims abstract description 7
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 13
- 229910052794 bromium Inorganic materials 0.000 claims description 13
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 11
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 52
- 238000002360 preparation method Methods 0.000 abstract description 19
- 239000000126 substance Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 42
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 36
- 239000000047 product Substances 0.000 description 31
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000002994 raw material Substances 0.000 description 21
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 20
- 235000010210 aluminium Nutrition 0.000 description 20
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 19
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 238000005406 washing Methods 0.000 description 18
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 14
- 239000011261 inert gas Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 239000003708 ampul Substances 0.000 description 9
- 235000019445 benzyl alcohol Nutrition 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 229920000747 poly(lactic acid) Polymers 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 9
- 150000003938 benzyl alcohols Chemical class 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 238000001953 recrystallisation Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000012043 crude product Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- -1 phenyl aldehyde Chemical class 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 125000001153 fluoro group Chemical group F* 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical group OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- XMPPQSXGHPYSJO-UHFFFAOYSA-N n,n'-dimethyl-n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1N(C)CCN(C)C1=CC=CC=C1 XMPPQSXGHPYSJO-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- ZWDVQMVZZYIAHO-UHFFFAOYSA-N 2-fluorobenzaldehyde Chemical compound FC1=CC=CC=C1C=O ZWDVQMVZZYIAHO-UHFFFAOYSA-N 0.000 description 1
- 208000010392 Bone Fractures Diseases 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010792 warming Methods 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
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/06—Aluminium compounds
- C07F5/061—Aluminium compounds with C-aluminium linkage
- C07F5/066—Aluminium compounds with C-aluminium linkage compounds with Al linked to an element other than Al, C, H or halogen (this includes Al-cyanide linkage)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
- C08G63/08—Lactones or lactides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
- C08G63/82—Preparation processes characterised by the catalyst used
- C08G63/823—Preparation processes characterised by the catalyst used for the preparation of polylactones or polylactides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Toxicology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of aluminium trimethide title complex and application thereof of four tooth nitrogen oxygen parts, title complex has as shown in the formula the structural formula shown in I, and in formula, R is hydrogen or halogen.Title complex of the present invention can N, N, O, O quad-tree index, and structure is special, and preparation method is simple, excellent performance.Title complex of the present invention can as the catalyzer of rac-Lactide ring-opening polymerization, catalytic activity is high, speed of reaction is very fast, three-dimensional arrangement and the molecular weight of polymkeric substance can be regulated and controled, the product obtaining different molecular weight that can be controlled, the molecular weight of obtained polymkeric substance can from 2 thousand to ten seven ten thousand, and selectivity is wide, has good market outlook.
Description
Technical field
The present invention relates to aluminium trimethide title complex of a kind of four tooth nitrogen oxygen parts and preparation method thereof, also relate to the application of this aluminum complex as the catalyzer of the ring-opening polymerization of rac-Lactide.
Background technology
The biodegradated polymer materals such as polylactide had both had the feature of conventional polymer material, do not pollute the environment after a procedure again, and medically also have been widely used, as the aspects such as medicine controlled releasing, surgical sutures, bone fracture internal fixation material are studied widely.
The structure of polylactide material and molecular weight have a great impact its purposes, such as, as propping material, require high molecular and high mechanical strength, and as medicinal film material, then tackling medicine has permeability.Can molecular weight distribution be controlled by controllable polymerization method, obtain the polymkeric substance of narrow molecular weight distribution and measurable molecular weight.Now, the catalyzer major part for polylactide synthesis is metal complexes, by can regulate and control the stereoselectivity of catalyzer to the adjustment of part, obtains the polymkeric substance that three-dimensional regularity is high, can better play its machinery, physics and degradation property.Therefore, in order to obtain the more and better polymkeric substance that we need, just need the catalyzer developing different performance to improve three-dimensional regularity and the molecular weight of polymkeric substance.Because metallic aluminium catalyzer has excellent catalytic effect, there is good stereoselectivity, find the focus that suitable Al catalysts is research all the time.
Summary of the invention
The invention provides a kind of aluminium trimethide title complex of four tooth nitrogen oxygen parts, this complex structure is special, excellent performance, can as the catalyzer of rac-Lactide ring-opening polymerization, and catalytic activity is high.Stereoselectivity is good.
Present invention also offers the application of aluminium trimethide title complex as the catalyzer of rac-Lactide ring-opening polymerization of this four teeth nitrogen oxygen part.
Technical solution of the present invention is as follows:
A kind of four tooth nitrogen oxygen parts, have as shown in the formula the structural formula shown in II, in formula, R is hydrogen or halogen;
。
In above-mentioned four tooth nitrogen oxygen parts, halogen is preferably fluorine or bromine.
The preparation method of above-mentioned four tooth nitrogen oxygen parts, comprise the following steps: by raw material A (N, N '-dimethyl-N, N '-diphenyl ethylene diamine) be dissolved in anhydrous diethyl ether, slowly n-Butyl Lithium is dripped at 0 DEG C, slowly be raised to room temperature reaction 12 hours, cool to 0 DEG C after reaction, slowly drip the phenyl aldehyde of phenyl aldehyde or replacement, be raised to room temperature, react 12 hours, then add water stopped reaction, separatory collects organic phase, obtains thick product, thick product, through recrystallizing methanol, obtains four tooth nitrogen oxygen parts (formula II).
Reaction formula is as follows:
In above-mentioned preparation method, the consumption of the phenyl aldehyde of n-Butyl Lithium, phenyl aldehyde or replacement is 2 times of molar weights of raw material A.
Above-mentioned part and aluminium trimethide react, and can form the aluminium trimethide title complex of four tooth nitrogen oxygen parts, it has as shown in the formula the structural formula shown in I, and in formula, R is hydrogen or halogen;
In the aluminium trimethide title complex of above-mentioned four tooth nitrogen oxygen parts, halogen is preferably fluorine or bromine.
The preparation method of the aluminium trimethide title complex of above-mentioned four tooth nitrogen oxygen parts, comprise the following steps: with four tooth nitrogen oxygen parts shown in formula II for part, part is joined in organic solvent, at-20 ~ 0 DEG C, add the trimethyl aluminium of equimolar amount, after adding, reaction solution is risen to room temperature naturally, be then warming up to 80 DEG C of reaction 12h, solvent is pumped after having reacted, obtain thick product, thick product recrystallization, obtains the aluminium trimethide title complex (formula I) of four tooth nitrogen oxygen parts.Reaction formula is as follows:
In above-mentioned preparation method, react and carry out under protection of inert gas.
In above-mentioned preparation method, described organic solvent is the saturated alkane of C5 ~ C10 or aromatic hydrocarbon or haloalkane organic solvent, is preferably toluene, tetrahydrofuran (THF) or chloroform.
In above-mentioned preparation method, consumption of organic solvent should be 5 ~ 20 times of reaction raw materials total mass.
In above-mentioned preparation method, recrystallization solvent for use is normal hexane.
The aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part can be used as the catalyzer of rac-Lactide ring-opening polymerization, when the aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part is used as the catalyzer of rac-Lactide ring-opening polymerization, speed of reaction is very fast, and can obtain the lactone of molecular weight within the scope of 2000-170000 according to demand, molecular weight controllability is high.When substituent R in title complex is hydrogen, title complex is high as catalyst activity, the time used when catalyzing and synthesizing the polyester of same molecular amount is short, substituent R is that fluorine takes second place, substituent R is that the bromine time used is the longest, this shows sterically hinderedly have certain influence to catalyst activity, and along with sterically hindered increase, the activity of catalyzer decreases.Catalyzer of the present invention also has good stereoselectivity, and experiment shows, when R is fluorine, stereoselectivity is best, and bromine takes second place, and hydrogen is minimum, and this illustrates that the stereoselectivity of substituent electron attraction more powerful catalyst is higher.
During with the aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part for catalyzer; the preparation method of polylactide comprises the following steps: catalyzer, organic solvent, alcohol promotor and rac-Lactide are mixed; polymerization ring-opening reaction is carried out under anhydrous and oxygen-free and protection of inert gas; after reaction, reactant is processed, obtain polylactide.
In above-mentioned preparation method, add cold methanol purifying polylactide after the process carried out reactant refers to reaction, obtain the polylactide after purifying.
In above-mentioned preparation method, alcohol promotor is benzylalcohol or Virahol.
In above-mentioned preparation method, described rac-Lactide is levorotatory lactide or rac-lactide.
In above-mentioned preparation method, the mol ratio of rac-Lactide and catalyzer is 30 ~ 2000:1, preferred 500-1000:1; The mol ratio of alcohol promotor and catalyzer is 1 ~ 4:1.
In above-mentioned preparation method, polymeric reaction temperature is 20 ~ 120 DEG C, is preferably 20-70 DEG C; Time is 3-24 hour, and preferably 6 is little of 15 hours.
In above-mentioned preparation method, reacting organic solvent used is toluene, chloroform or tetrahydrofuran (THF), preferred toluene.
In above-mentioned preparation method, cause the polymerization of rac-Lactide using the aluminium trimethide title complex of the present invention four tooth nitrogen oxygen part as catalyzer, thus obtain a series of polylactide.The molecular weight Mn of the final gained polylactide of the present invention is between 2000 ~ 170000, by regulating the reaction conditions amount ratio etc. of cocatalyst (lactide monomer and the catalyzer also), can obtain the polymkeric substance of different molecular weight ranges, and molecular weight distribution is narrow.
The invention provides a kind of aluminium trimethide title complex of four tooth nitrogen oxygen parts, this title complex can N, N, O, O quad-tree index, and structure is special, and preparation method is simple, excellent performance.Title complex of the present invention can as the catalyzer of rac-Lactide ring-opening polymerization, catalytic activity is high, speed of reaction is very fast, three-dimensional arrangement and the molecular weight of polymkeric substance can be regulated and controled, the product obtaining different molecular weight that can be controlled, the molecular weight of obtained polymkeric substance can from 2 thousand to ten seven ten thousand, and selectivity is wide, has good market outlook.
Accompanying drawing explanation
Fig. 1 is the crystal schematic diagram of the novel four tooth nitrogen oxygen parts of the present invention, and wherein R is hydrogen.
Embodiment
Further illustrate the present invention below by specific embodiment, but the present invention is not limited to this, concrete protection domain see claim.
The present invention's raw material A used can prepare voluntarily by method disclosed in prior art, and following embodiment raw material A used adopts document " EmilFr hlich; DarstellungvonN, N '-Dialkyl-methylendiaryl-diaminenundHomologen, ChemischeBerichte; Vol.40; (1907); P.764 " disclosed in, method obtains; step is: by 1; the methylphenylamine of 2-ethylene dibromide and its 2 moles of times amount reacts 12 hours under 100 DEG C of conditions; obtain purple mixture; mixture obtains white solid through pillar layer separation (petrol ether/ethyl acetate=10/1); be raw material A, productive rate 81wt%.
prepare four tooth nitrogen oxygen parts
According to following route synthesizing new four tooth nitrogen oxygen part, the following formula II of structural formula of gained part, simply exemplifies the preparation process of several part below.Preferred part R is hydrogen, fluorine, bromine.
embodiment 1
Ligand structure formula used as above formula II, wherein R is hydrogen, and reaction process is: be dissolved in 30mL anhydrous diethyl ether, 0 by raw material A (N, N '-dimethyl-N, N '-diphenyl ethylene diamine) (8.30g, 34.6mmol)
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drips the phenyl aldehyde (7.34g, 69.2mmol) of raw material A twice molar weight, is raised to room temperature and reacts 12 hours later, add water stopped reaction after reaction, and separatory collects organic phase, obtains thick product, obtains straight product 10.52g through recrystallizing methanol, productive rate 67%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 79.69; H, 7.18; N, 6.24%.
1HNMR(400MHz,CDCl
3)
δ7.36–7.29(m,8H,Ar–
H),7.27–7.22(m,4H,Ar–
H),7.20–7.16(m,2H,Ar–
H),7.15–7.09(m,2H,Ar–
H),7.06(dd,
J=7.7,1.5Hz,2H,Ar–
H),6.02(s,2H,ArCHO
H),5.98(s,2H,ArC
HOH),2.98(s,4H,NC
H 2),2.48(s,6H,C
H 3).
13CNMR(100MHz,CDCl
3)
δ150.49,144.08,139.35,129.54,128.43,128.14,126.98,126.77,125.62,122.40,74.00,54.98,44.64.
As can be seen from above characterization result, it is the part of hydrogen that products obtained therefrom is R in formula II.
The crystal schematic diagram of products obtained therefrom as shown in Figure 1.
embodiment 2
Ligand structure formula used as above formula II, wherein R is fluorine, and reaction process is: raw material A (7.60g, 31.6mmol) be dissolved in 30mL anhydrous diethyl ether, 0
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drips the o fluorobenzaldehyde (7.82g, 63.2mmol) of raw material A 2 times of molar weights, is raised to room temperature and reacts 12 hours later, add water stopped reaction after reaction, and separatory collects organic phase, obtains thick product, obtains straight product 12.03g through recrystallizing methanol, productive rate 78%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 73.79; H, 6.25; N, 5.81%.
1HNMR(400MHz,CDCl
3)
δ7.59(t,
J=7.6Hz,2H,Ar–
H),7.30–7.24(m,4H,Ar–
H),7.17(t,
J=8.0Hz,3H,Ar–
H),7.08(dd,
J=9.2,4.0Hz,2H,Ar–
H),7.04–6.98(m,3H,Ar–
H),6.91(d,
J=7.7Hz,2H,Ar–
H),6.49(s,2H,ArC
HOH),6.23(s,2H,ArCHO
H)3.18(s,4H,NC
H 2),2.72(s,6H,C
H 3).
13CNMR(100MHz,CDCl
3)
δ161.24,158.79,138.78,130.57,128.80,128.66,128.40,125.90,124.17,122.24,115.17,114.95,67.33,55.12,44.91.
As can be seen from above characterization result, it is the part of fluorine that products obtained therefrom is R in formula II.
embodiment 3
Ligand structure formula used as above formula II, wherein R is bromine, and reaction process is: raw material A (6.50g, 27.0mmol) be dissolved in 30mL anhydrous diethyl ether, 0
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drips the o-bromobenzaldehye (9.91g, 54.0mmol) of raw material A 2 times of molar weights, is raised to room temperature and reacts 12 hours later, add water stopped reaction after reaction, and separatory collects organic phase, obtains thick product, obtains straight product 6.92g through recrystallizing methanol, productive rate 42%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 59.12; H, 4.87; N, 4.65%.
1HNMR(400MHz,CDCl
3)
δ7.66(dd,
J=7.7,1.3Hz,2H,Ar–
H),7.53(d,
J=1.1Hz,2H,Ar–
H),7.36(t,
J=7.7Hz,2H,Ar–
H),7.28(d,
J=3.3Hz,2H,Ar–
H),7.22–7.13(m,2H,Ar–
H),7.01(d,
J=4.5Hz,2H,Ar–
H),6.67(d,
J=7.6Hz,2H,Ar–
H),6.45(br,2H,ArCHO
H)6.33(s,2H,ArC
H),3.22(s,4H,NC
H 2),2.82(s,6H,C
H 3).
13CNMR(100MHz,CDCl
3)
δ150.85，141.74,138.73,132.46,129.38,128.82,128.79,128.16,127.57,125.76,123.26,122.00,71.56,54.99,44.60.
As can be seen from above characterization result, it is the part of bromine that products obtained therefrom is R in formula II.
prepare the aluminium trimethide title complex of four tooth nitrogen oxygen parts
The aluminium trimethide title complex of nitrogen oxygen coordination reacts by part (formula II) and trimethyl aluminium the title complex generated, the structural formula of its part is as shown in the formula II, the following formula I of complex structure formula, illustrates to the catalyzer that different ligands obtains below, and preferred part R is hydrogen, fluorine, bromine.
embodiment 4
Part used is part prepared by embodiment 1, R is hydrogen, and reaction process is: under nitrogen atmosphere, by part (0.52g, 1.1mmol) be dissolved in 10mL toluene, at 0 DEG C, add the trimethyl aluminium of equimolar amount, be slowly raised to room temperature, be heated to 80 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 0.49g, productive rate 91%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 75.63; H, 6.79; N, 5.74%.
1HNMR(400MHz,CDCl
3)
δ7.42(d,J=7.9Hz,4H,Ph–
H),7.35(d,J=5.7Hz,8H,Ph–
H),7.28(s,2H,Ph–
H),7.19(m,2H,Ph–
H),7.18(m,2H,Ph–
H),5.00(s,2H,PhC
HO),4.07(t,J=6.5Hz,4H,NC
H 2),2.35(s,6H,C
H 3),–1.22(s,3H,Al–C
H 3).
13CNMR(101MHz,CDCl
3)
δ151.06,132.89,131.30,130.06,129.62,129.10,128.37,125.36,120.05,118.20,53.33,40.71,21.54,–9.11.
As can be seen from above characterization result, it is the title complex of hydrogen that products obtained therefrom is R in formula I.
embodiment 5
Part used is part prepared by embodiment 2, R is fluorine, and reaction process is: under nitrogen atmosphere, by part (0.71g, 1.40mmoL) be dissolved in 15mL tetrahydrofuran (THF), at-20 DEG C, add equimolar amount trimethyl aluminium, be slowly raised to room temperature, be heated to 80 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 0.65g, productive rate 87%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 70.51; H, 5.97; N, 5.41%.
1HNMR(400MHz,CDCl
3,293K):
δ7.89(d,
J=2.9Hz,2H,Ar–
H),7.82(d,
J=2.8Hz,2H,Ph–
H),7.64–7.56(m,4H,Ph–
H),7.43–7.38(m,8H,Ph–
H),7.24(m,2H,PhC
HO),3.15(s,2H,NC
H 2),3.03(s,2H,NC
H 2),2.45(s,6H,C
H 3),–1.19(s,6H,AlC
H 3).
13CNMR(101MHz,CDCl
3,293K):
δ198.97,154.91,142.45,141.26140.54,138.52,137.08,135.17,127.01,122.41,121.71,118.33,53.50,45.22,12.35,–9.10.
As can be seen from above characterization result, it is the title complex of fluorine that products obtained therefrom is R in formula I.
embodiment 6
Part used is part prepared by embodiment 3, R is bromine, and reaction process is: under nitrogen atmosphere, by part (0.93g, 1.50mmoL) be dissolved in 15mL tetrahydrofuran (THF), at 0 DEG C, add equimolar amount trimethyl aluminium, be slowly raised to room temperature, be heated to 50 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product 0.80g, productive rate 81%.
Characterize products obtained therefrom, result is as follows:
Results of elemental analyses: C, 57.32; H, 4.84; N, 4.39%.
1HNMR(400MHz,CDCl
3)
δ7.77(d,
J=7.6Hz,2H,Ph–
H),7.54(d,
J=7.0Hz,2H,Ph–
H),7.48–7.38(m,5H,Ph–
H),7.27(d,
J=7.8Hz,7H,Ph–
H),6.99–6.92(m,2H,PhC
HO),2.90(s,2H,NC
H 2),2.51(s,2H,NC
H 2),2.38(s,6H,C
H 3),–1.21(s,3H,Al–C
H 3).
13CNMR(101MHz,CDCl
3)
δ198.19,151.06,137.91,132.89,131.30,129.91,129.10,128.37,125.36,122.68,120.05,118.20,53.33,40.71,21.54,–9.11.
As can be seen from above characterization result, it is the title complex of bromine that products obtained therefrom is R in formula I.
embodiment 7
Part used is part prepared by embodiment 1, R is hydrogen, and reaction process is: under nitrogen atmosphere, by part (0.52g, 1.1mmol) be dissolved in 10mL hexane, at 5 DEG C, add the trimethyl aluminium of 1.2 times of molar weights, be slowly raised to room temperature, be heated to 100 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product, productive rate 82%.
embodiment 8
Part used is part prepared by embodiment 2, R is fluorine, and reaction process is: under nitrogen atmosphere, by part (0.71g, 1.40mmoL) be dissolved in 15mL tetracol phenixin, at-20 DEG C, add 1.2 times of molar weight trimethyl aluminiums, be slowly raised to room temperature, be heated to 60 DEG C of reactions 12 hours, except desolventizing, crude product hexane recrystallization, obtains straight product, productive rate 71%.
the application of aluminum complex
embodiment 9
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 40mL tetrahydrofuran (THF), 50 μm of ol benzylalcohols and the 50mmol that 25 μm of olR are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react stopped reaction after 12 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 7.06 grams, molecular weight 6.6 ten thousand, molecular weight distribution is 1.13, stereoselectivity (Pr=0.70), yield 98%.
embodiment 10
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 40mL tetrahydrofuran (THF), 50 μm of ol benzylalcohols and the 50mmol that 25 μm of olR are fluorine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react stopped reaction after 13 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain product, molecular weight 6.7 ten thousand, molecular weight distribution is 1.11, stereoselectivity (Pr=0.76), yield 98%.
embodiment 11
React under anhydrous and oxygen-free and protection of inert gas; first adding the rac-lactide of catalyzer, 40mL tetrahydrofuran (THF), 50 μm of ol benzylalcohols and the 50mmol that 25 μm of olR are bromine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react stopped reaction after 16 hours, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain product, molecular weight 6.6 ten thousand, molecular weight distribution is 1.12, stereoselectivity (Pr=0.72), yield 97%.
embodiment 12
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 30mL tetrahydrofuran (THF), 50 μm of ol Virahols and the 42mmol that 25 μm of olR are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 50 are placed in
oreact 14 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 5.81 grams, molecular weight 8.5 ten thousand, molecular weight distribution is 1.11, stereoselectivity (Pr=0.64), yield 96%.
embodiment 13
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 15mL toluene, 75 μm of ol benzylalcohols and the 10mmol that 25 μm of olR are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 120 are placed in
oreact 13 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 1.40 grams, molecular weight 6.8 ten thousand, molecular weight distribution is 1.09, yield 97%.
embodiment 14
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 10mL toluene, 35 μm of ol benzylalcohols and the 4mmol that 35 μm of olR are fluorine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react 18 hours stopped reaction, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 0.56 gram, molecular weight 8.9 ten thousand, molecular weight distribution is 1.10, stereoselectivity (Pr=0.74) yield 97%.
embodiment 15
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the rac-lactide of catalyzer, 10mL toluene, 200 μm of ol benzylalcohols and the 3mmol that 100 μm of olR are bromine by order in the ampulla after the baking of high pure nitrogen gas washing, then 20 are placed in
oin the environment of C, react 24 hours stopped reaction, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 0.42 gram, molecular weight 0.7 ten thousand, molecular weight distribution is 1.13, stereoselectivity (Pr=0.72), yield 96%.
embodiment 16
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 30mL tetrahydrofuran (THF), 100 μm of ol benzylalcohols and the 25mmol that 25 μm of olR are hydrogen by order in the ampulla after the baking of high pure nitrogen gas washing, then 50 are placed in
oreact 16 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 3.53 grams, molecular weight 10.9 ten thousand, molecular weight distribution is 1.08, yield 98%.
embodiment 17
All operations all carries out under anhydrous and oxygen-free and protection of inert gas.First, adding the levorotatory lactide of catalyzer, 20mL toluene, 15 μm of ol benzylalcohols and the 8mmol that 15 μm of olR are hydrogen group by order in the ampulla after the baking of high pure nitrogen gas washing, then 70 are placed in
oreact 19 hours stopped reaction in the oil bath of C, with cold methanol precipitation, washing several, ambient temperature in vacuum is dry, and obtain 1.11 grams, molecular weight 16.5 ten thousand, molecular weight distribution is 1.12, yield 96%.
comparative example 1
Raw material A (8.30g, 34.6mmol) is dissolved in 30mL anhydrous diethyl ether, 0
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drip the benzophenone (69.2mmol) of raw material A twice molar weight, be raised to room temperature and react 12 hours later, water stopped reaction is added after reaction, obtain the compound being insoluble in usual vehicle, DMF and DMSO is difficult to dissolve, and the unknown compound obtained can only be dissolved in acid, cannot carry out necessary sign to it.
comparative example 2
Raw material A (8.30g, 34.6mmol) is dissolved in 30mL anhydrous diethyl ether, 0
oc slowly drips the n-Butyl Lithium of raw material A twice molar weight, is slowly raised to room temperature reaction after 12 hours, cools to 0
oc, slowly drip the dry acetone (69.2mmol) of raw material A twice molar weight, be raised to room temperature and react 12 hours later, add water stopped reaction after reaction, the compound productive rate obtained is very low (lower than 5%), does not have using value.
Claims (3)
1. an aluminium trimethide title complex for four tooth nitrogen oxygen parts, it is characterized in that: have as shown in the formula the structural formula shown in I, in formula, R is hydrogen or halogen;
。
2. the aluminium trimethide title complex of four tooth nitrogen oxygen parts according to claim 1, is characterized in that: halogen is fluorine or bromine.
3. the aluminium trimethide title complex of four tooth nitrogen oxygen parts described in claim 1 or 2 is as the application of the catalyzer of rac-Lactide ring-opening polymerization.
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| CN108503661B (en) * | 2017-12-12 | 2020-09-08 | 济南大学 | Asymmetric aluminum complex containing o-phenylenediamine group, and preparation method and application thereof |
| CN108084218B (en) * | 2017-12-12 | 2020-08-21 | 济南大学 | Chiral asymmetric aluminum complex containing salicylaldehyde group and preparation method and application thereof |
| CN107973815B (en) * | 2017-12-12 | 2020-09-04 | 泰山医学院 | Asymmetric aluminum complex containing acetylacetone derivative, and preparation method and application thereof |
| CN108084411B (en) * | 2017-12-12 | 2020-12-01 | 济南大学 | Method for catalyzing glycolide polymerization by using chiral aluminum complex containing acetylacetone derivative |
| CN107973906B (en) * | 2017-12-12 | 2020-09-04 | 济南大学 | Method for catalyzing lactide polymerization by using tetradentate nitrogen-oxygen coordinated aluminum compound |
| CN107973814B (en) * | 2017-12-12 | 2020-09-08 | 济南大学 | Tetradentate nitrogen-oxygen coordinated aluminum compound and preparation method and application thereof |
| CN108569993B (en) * | 2017-12-12 | 2020-10-09 | 济南大学 | Tetradentate nitrogen-oxygen symmetric ligand containing chiral cyclohexanediamine and preparation method and application thereof |
| CN108003183B (en) * | 2017-12-12 | 2021-03-02 | 济南大学 | Method for catalyzing caprolactone polymerization by using tetradentate nitrogen-oxygen coordinated aluminum compound |
| CN108239102B (en) * | 2017-12-12 | 2020-09-08 | 济南大学 | Aluminum complex containing salicylaldehyde group and preparation method and application thereof |
| CN108570066B (en) * | 2017-12-12 | 2020-10-09 | 济南大学 | Aluminum compound containing chiral cyclohexanediamine and preparation method and application thereof |
| CN108570144B (en) * | 2017-12-12 | 2020-10-09 | 济南大学 | Method for catalyzing caprolactone polymerization by using aluminum compound containing chiral cyclohexanediamine |
| CN108503812B (en) * | 2017-12-12 | 2020-09-08 | 济南大学 | Method for catalyzing caprolactone polymerization by using asymmetric aluminum complex containing o-phenylenediamine group |
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