CN101186617B - Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis - Google Patents
Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis Download PDFInfo
- Publication number
- CN101186617B CN101186617B CN2007101708296A CN200710170829A CN101186617B CN 101186617 B CN101186617 B CN 101186617B CN 2007101708296 A CN2007101708296 A CN 2007101708296A CN 200710170829 A CN200710170829 A CN 200710170829A CN 101186617 B CN101186617 B CN 101186617B
- Authority
- CN
- China
- Prior art keywords
- rare earth
- alkyl
- mec
- archme
- ligand
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The invention relates to a new N-N-N tridentate ligand, a relative rare-earth complex and a relative application in the synthesis as poly-lactide acid or poly-caprolactone. The inventive ligand can be prepared from relative beta-diketone and amine via two-step condensation, while the rare-earth complex can be prepared from the ligand with rare-earth alkyl compound or aamino-compound. The complex can catalyze lactide to open ring and polymerize to obtain polymer polyester, and catalyze caprolactone to polymerize. The formula of the complex is represented as above, wherein Ln is rare-earth metal ion as Y, Nd, Sm, Sc or the like, R1 is alkane of C<SUB>1-10</SUB>, R2 is alkane of C<SUB>1-6</SUB>, R2 is chain or cyclic alkane of C<SUB>1-10</SUB>, and X is alkyl, amido or alkoxy bonded with rare-earth ion.
Description
Technical field:
The present invention relates to a class novel three-tooth nitrogen ligand and rare earth compounding thereof and the application in polylactide, poly-own lactones synthesize.
Technical background:
In the last few years, in many organic reactions and Polymer Synthesizing, rare earth metal complex had all shown the catalytic activity that it is good.The maximum class that this wherein studies is exactly a cyclopentadienyl rare-earth metal compound, but since this type of compound to synthesize relative cost higher, so people turn to attention the rare earth metal complex of synthetic lower-cost containing n-donor ligand gradually, and being formed with of rare earth-nitrogen key helps stable have high Electron Affinities, instable rare earth compound.In a series of containing n-donor ligands, the most potential is exactly beta diimine ligand, and this class part can be made by corresponding beta diketone and amine condensation.The solid of this type of part and electronic effect can be easily be regulated and control by the starting raw material of selecting, and they can be that pure σ key also can be combining of σ key and π key with the coordination mode of rare earth metal.Therefore in recent years, people have synthesized a large amount of beta diimine rare earth metal complexs, these some compounds have wherein shown good catalytic activity in polyreaction, the for example ring-opening polymerization of catalysis caprolactone or rac-Lactide, methyl methacrylate polymerization, the copolymerization of vinyl polymerization and cyclohexene oxide and carbonic acid gas.In these beta diimine rare earth metal complexs, two alkylates have highly active rare earth-carbon bond owing to it and merit attention especially.But because this type of pair alkyl beta diimine rare earth compounding reallocation, the dimerization of part takes place easily or eliminates reaction, so this compounds is synthetic very difficult, example is few.
People such as Warren E.Piers have reported two alkylates (Hayes, the P.G. of following several small ion radius metal Sc; Lee, L.W.M.; Knight, L.K.; Piers, W.E.; Parvez, M.; Elsegood, M.R.J.; Clegg, W.; MacDonald, R.Organometallics 2001,20, and 2533.).The complex structure formula is as follows:
R＝CH
3，
tBu
R’＝CH
3，CH
2CH
3，CH
2C
6H
5，CH
2 tBu，CH
2TMS
People such as Michael F.Lappert have reported two alkylates of a Ce, but that its usefulness is the big sterically hindered alkyl-CH of low activity (TMS)
2(Hitchcock, P.B.; Lappert, M.F.; Tian, S.J.Chem.Soc., Dalton Trans.1997,1945.).Complex structure is as follows:
R＝CH(TMS)
2
By introducing two symmetric nitrogenous side chains of giving body, Herbert W.Roesky etc. has designed and synthesized a tetradentate ligands, synthesized a series of solvent or the solvent-free rare-earth metal chloride of containing simultaneously, but it is very difficult during the synthesis of alkyl compound, they have only reported synthetic (Neculai, the D. of the two alkylates of beta diimine Tb; Roesky, H.W.; Neculai, A.M.; Magull, J.; Herbst-Irmer, R.; Walfort, B.; Stalke, D.Organometallics 2003,22, and 2279.).Complex structure is as follows:
R＝CH
2TMS
In recent years, when macromolecular material brings convenience to people's lives,, caused the serious environmental pollution problem after discarding because of its most of material does not possess biodegradable characteristic.At present the processing means of non-degradable goods are buried often and burned, do like this and can only alleviate environmental pollution.And the application of degradable high polymer material can fundamentally address this problem.Simultaneously, over nearly 20 years, increasing clinical needs have promoted the development of bio-medical material, the focus that the polymer materials of synthesized degradable has become current biomaterial research and used.The biodegradation type medical macromolecular materials mainly comprise polyester, poly-acid anhydrides, polyamino acid, poly-phosphorus cyanogen etc.Wherein aliphatic polyester is with its good biocompatibility, biological degradability, and advantages such as polymkeric substance and degraded product nontoxicity enjoy common people to pay close attention to.Aliphatic polyester generally prepares by ring-opening polymerization.
Summary of the invention:
The present invention is based on sterically hindered and dual consideration ligancy, designed and synthesized the two alkylates of a series of rare earths, aminocompound and alkoxy compound based on asymmetric beta diimine ligand to a metal-organic complex.
The object of the invention provides a class novel nitrogen-containing part and a rare earth metal complex thereof.
Another purpose of the present invention provides the synthetic method of synthetic above-mentioned part and title complex thereof.
The present invention also provide a kind of above-mentioned rare earth metal complex in polyester is synthetic application.
A class novel nitrogen-containing part and a rare earth metal complex thereof provided by the invention.
Described containing n-donor ligand can be the intermediate of rare earth metal complex, and its structural formula is as follows:
The structural formula of described rare earth metal complex is as follows:
Wherein, R
1Be C
1-10Alkyl, R
2Be C
1-6Alkyl, n is the integer of 1-5, recommends
For
R
3Be C
1-10Chain-like alkyl or C
3-10Cyclic alkyl or two R
3Be connected to C
1-10Alkylidene group, X is and alkyl, amido or the alkoxyl group of rare earth ion Cheng Jian, described and alkyl, amido or alkoxyl group rare earth ion Cheng Jian can be alkyl, amido or the alkoxyl groups that replaces, described substituting group can be a silylation etc.The alkyl of described rare earth ion Cheng Jian, amido or alkoxyl group are recommended as C
1～C
30, further be recommended as C
1～C
10, CH for example
2Si (CH
3)
3Or N[Si (CH
3)
3]
2
Ln is a rare earth metal, and described rare earth metal is recommended as Y, Sc and all lanthanide series metals, further is recommended as Y, Nd, Sm, Sc, Lu or Dy.
Expression delocalized conjugated double bond, → expression coordinate bond.
Above-mentioned novel nitrogen-containing part of the present invention can directly be made by corresponding imines and diamine reactant, also can be made through twice condensation with different amine by corresponding beta diketone, and yield is at 50-95%.Finish by following reaction (2) or reaction (1), (2) specifically:
(1) by structural formula is
Beta diketone and arylamine
In mol ratio is 1: 0.2～3 o'clock, in the presence of 0.1%-3% molar equivalent tosic acid, in organic solvents such as toluene, benzene, methyl alcohol or ethanol, reacts 1～100h down at 0 ℃～110 ℃ and makes the monolateral substituted imine of intermediate
(2) then in organic solvents such as toluene, benzene, methyl alcohol or ethanol, the imines of above-mentioned (1) and 0.2～3 normal diamines
In the presence of 0.1%-3% molar equivalent tosic acid, react 1～100h down at 0 ℃～110 ℃ and make described novel nitrogen-containing part.
R wherein
1Be C
1-10Alkane, R
2Be C
1-6Alkane, n is the integer of 1-5.
Rare earth compounding of the present invention can be made by above-mentioned part and rare earth alkyl compound and aminocompound reaction; Perhaps part by after KH, NaH or the lithium alkylide deprotonation with LnCl
3After reaction obtains muriate, make with the MX reaction, yield is at 50-95% again.Can finish by following reaction specifically:
By above-mentioned part and LnX generated in-situ or that prepare
3In organic solvents such as hexane, toluene, benzene, ether or tetrahydrofuran (THF), react 0.1～20h down at-30 ℃～100 ℃ and make.
Wherein X is-CH
2TMS or-N (TMS)
2TMS represents Si (CH
3)
3
Can also at first form behind the lithium salts again and 0.2～3 normal LnCl by above-mentioned part in addition with KH, NaH or lithium alkylide deprotonation
3In organic solvents such as hexane, toluene, benzene, ether or tetrahydrofuran (THF), react 0.1～20h down at-30 ℃～100 ℃ and make muriate, this muriate and 0.2～3 normal MX reaction obtain product then.
Wherein M is Li, Na, K; X is-CH
2TMS ,-N (TMS)
2Or OR, R is C
1-10Alkane.
Synthetic novel nitrogen-containing rare earth metal complex of the present invention can be used as catalyzer, further recommend to be used for the polymerization of catalysis ester, especially recommend to be used for the ring-opening polymerization of catalysis rac-Lactide or own lactones, for example in organic solvents such as toluene, tetrahydrofuran (THF), methylene dichloride or hexane solution or under the solvent-free state, the ring-opening polymerization of catalysis rac-Lactide, own lactones efficiently under-20 ℃～160 ℃ conditions.
Embodiment
The present invention will be helped further to understand by following embodiment, but content of the present invention can not be limited.
Embodiment 1
With 8.20g 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone, 2.79g N, N-dimethyl-ethylenediamine and 50mg tosic acid are dissolved in the 30mL benzene, reflux is divided water reaction 24h, solvent removed in vacuo, underpressure distillation obtain 7.02g yellow oily three-tooth nitrogen ligand L1, productive rate 67%.With
1HNMR,
13CNMR, mass spectrum and elemental analysis the structure of part.Anal.Calcd.for?C
21H
35N
3：C，76.54；H，10.71；N，12.75.Found：C，76.65；H，10.86；N，12.76.
1H?NMR(300MHz，C
6D
6，25℃)：δ(ppm)11.04(br?s，1H，NH)，7.24-7.14(m，3H，Ar-H)，4.71(s，1H，MeC(N)CH)，3.20(sp，
3J
HH＝6.9Hz，2H，ArCHMe
2)，2.97(t，
3J
HH＝6.3Hz，2H，NCH
2)，2.18(t，
3J
HH＝6.3Hz，2H，NCH
2)，1.95(s，6H，NMe
2)，1.69(s，3H，MeC(NHAr))，1.66(s，3H，MeC(NCH
2CH
2NMe
2))，1.27(t，
3J
HH＝7.8Hz，12H，ArCHMe
2).
1H?NMR(300MHz，CDCl
3，25℃)：δ(ppm)10.83(br?s，1H，NH)，7.12-7.01(m，3H，Ar-H)，4.65(s，1H，MeC(N)CH)，3.33(q，2H，NCH
2)，2.88(sp，
3J
HH＝7.2Hz，2H，ArCHMe
2)，2.39(t，
3J
HH＝7.2Hz，2H，NCH
2)，2.21(s，6H，NMe
2)，2.02(s，3H，MeC(NHAr))，1.62(s，3H，MeC(NCH
2CH
2NMe
2))，1.16(d，
3J
HH＝6.9Hz，6H，ArCHMe
2)，1.12(d，
3J
HH＝6.6Hz，6H，ArCHMe
2).
13C?NMR(75MHz，CDCl
3，25℃)：δ(ppm)165.9(1C，MeC(NCH
2CH
2NMe
2))，155.3(1C，MeC(NHAr))，146.9(1C，C
ipso)，137.9(2C，C
ortho)，122.5(2C，C
meta)，122.3(1C，C
para)，93.1(1C，MeC(N)CH)，59.8(1C，NCH
2)，45.7(2C，NMe
2)，41.5(1C，NCH
2)，27.9(2C，ArCHMe
2)，23.8(2C，ArCHMe
2)，22.7(2C，ArCHMe
2)，21.5(1C，MeC(NHAr))，19.4(1C，MeC(NCH
2CH
2NMe
2)).EIMS?m/z329(M
+，1.30)，271(100)，58(48.53).
Embodiment 2
With 5.79g 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone, 2.59g N, N-diethyl ethylenediamine and 50mg tosic acid are dissolved in the 30mL toluene, reflux is divided water reaction 24h, solvent removed in vacuo, underpressure distillation obtain 4.51g yellow oily three-tooth nitrogen ligand L2, productive rate 56%.With
1HNMR,
13CNMR, mass spectrum and elemental analysis the structure of part.C
23H
39N
3The ultimate analysis data: calculated value C, 77.26; H, 10.99; N, 11.75. measured value: C, 77.45; H, 10.95; N, 11.64.
1H NMR (300MHz, C
6D
6, 25 ℃): δ (ppm) 10.95 (br s, 1H, NH), 7.23-7.13 (m, 3H, Ar-H), 4.72 (s, 1H, MeC (N) CH), 3.21 (sp,
3J
HH=6.9Hz, 2H, ArCHMe
2), 2.99 (q, 2H, NCH
2), 2.38 (t,
3J
HH=6.9Hz, 2H, NCH
2), 2.30 (q, 4H, N (CH
2CH
3)
2), 1.70 (s, 6H, MeC (NHAr) andMeC (NCH
2CH
2NEt
2)), 1.28 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 1.24 (d,
3J
HH=6.2Hz, 6H, ArCHMe
2), 0.83 (t,
3J
HH=6.9Hz, 6H, N (CH
2CH
3)
2).
1H NMR (300MHz, CDCl
3, 25 ℃): δ (ppm) 10.76 (br s, 1H, NH), 7.13-7.01 (m, 3H, Ar-H), 4.64 (s, 1H, MeC (N) CH), 3.30 (q, 2H, NCH
2), 2.88 (sp,
3J
HH=6.6Hz, 2H, ArCHMe
2), 2.52 (ov, m, 6H, NCH
2And N (CH
2CH
3)
2), 2.02 (s, 3H, MeC (NHAr)), 1.61 (s, 3H, MeC (NCH
2CH
2NEt
2)), 1.15 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 1.12 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 0.95 (t,
3J
HH=6.9Hz, 6H, N (CH
2CH
3)
2).
13C NMR (75MHz, CDCl
3, 25 ℃): δ (ppm) 165.9 (1C, MeC (NCH
2CH
2NEt
2)), 155.4 (1C, MeC (NHAr)), 147.1 (1C, C
Ipso), 137.9 (2C, C
Ortho), 122.6 (2C, C
Meta), 122.3 (1C, C
Para), 92.9 (1C, MeC (N) CH), 53.5 (1C, NCH
2), 47.3 (2C, N (CH
2CH
3)
2), 41.7 (1C, NCH
2), 27.9 (2C, ArCHMe
2), 23.8 (2C, ArCHMe
2), 22.8 (2C, ArCHMe
2), 21.6 (1C, MeC (NHAr)), 19.5 (1C, MeC (NCH
2CH
2NEt
2)), 11.7 (2C, N (CH
2CH
3)
2) .EIMS m/z 357 (M
+, 2.84), 271 (100), 86 (96.57).
Embodiment 3
With 5.01g 2-(2,6-diisopropyl benzene amido)-2-amylene-4-ketone, 2.47g N-(2-aminoethyl) piperidines and 50mg tosic acid be dissolved in the 25mL toluene, reflux is divided water reaction 24h, solvent removed in vacuo, underpressure distillation obtains 4.19g yellow oily three-tooth nitrogen ligand L3, productive rate 59%.With
1HNMR,
13CNMR, mass spectrum and elemental analysis the structure of part.C
24H
39N
3The ultimate analysis data: calculated value: C, 77.99; H, 10.64; N, 11.37. measured value: C, 78.01; H, 10.46; N, 10.93.
1H NMR (300MHz, C
6D
6, 25 ℃): δ (ppm) 11.01 (br s, 1H, NH), 7.24-7.16 (m, 3H, Ar-H), 4.71 (s, 1H, MeC (N) CH), 3.20 (sp,
3J
HH=6.9Hz, 2H, ArCHMe
2), 3.03 (t,
3J
HH=6.9Hz, 2H, NCH
2), 2.27 (t,
3J
HH=6.6Hz, 2H, NCH
2), 2.19 (m, 4H, N (CH
2CH
2)
2CH
2), 1.69 (s, 3H, MeC (NHAr)), 1.67 (s, 3H, MeC (NCH
2CH
2NC
5H
10)), 1.39 (m, 4H, N (CH
2CH
2)
2CH
2), 1.29 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 1.24 (d,
3J
HH=6.6Hz, 6H, ArCHMe
2), 1.17 (m, 2H, N (CH
2CH
2)
2CH
2).
1H NMR (300MHz, CDCl
3, 25 ℃): δ (ppm) 10.79 (br s, 1H, NH), 7.13-7.01 (m, 3H, Ar-H), 4.63 (s, 1H, MeC (N) CH), 3.35 (q, 2H, NCH
2), 2.87 (sp,
3J
HH=6.9Hz, 2H, ArCHMe
2), 2.40 (ov, m, 6H, NCH
2AndN (CH
2CH
2)
2CH
2), 2.01 (s, 3H, MeC (NHAr)), 1.61 (s, 3H, MeC (NCH
2CH
2NC
5H
10)), 1.50 (m, 4H, N (CH
2CH
2)
2CH
2), 1.37 (m, 2H, N (CH
2CH
2)
2CH
2), 1.15 (d,
3J
HH=6.6Hz, 6H, ArCHMe
2), 1.11 (d,
3J
HH=6.6Hz, 6H, ArCHMe
2).
13C NMR (75MHz, CDCl
3, 25 ℃): δ (ppm) 165.9 (1C, MeC (NCH
2CH
2NC
5H
10)), 155.4 (1C, MeC (NHAr)), 147.0 (1C, C
Ipso), 138.0 (2C, C
Ortho), 122.6 (2C, C
Meta), 122.3 (1C, C
Para), 93.0 (1C, MeC (N) CH), 60.0 (1C, NCH
2), 54.9 (2C, N (CH
2CH
2)
2CH
2), 40.9 (1C, NCH
2), 28.0 (2C, ArCHMe
2), 25.8 (2C, N (CH
2CH
2)
2CH
2), 24.2 (1C, N (CH
2CH
2)
2CH
2), 23.8 (2C, ArCHMe
2), 22.8 (2C, ArCHMe
2), 21.6 (1C, MeC (NHAr)), 19.5 (1C, MeC (NCH
2CH
2NC
5H
10)) .EIMS m/z 369 (M
+, 1.37), 271 (100), 98 (87.3).
Embodiment 4
The anhydrous YCl of 450mg
3Be dissolved in the 5mL tetrahydrofuran (THF), stirring is spent the night, and removes the back of desolvating and adds 5mL normal hexane formation suspension.Under the room temperature, 640mg LiCH
2TMS is dissolved in the 15mL normal hexane, changes YCl then over to
3Suspension.Behind the 2h, the centrifuging precipitation, filtrate changing over to is dissolved with the 5mL hexane solution of 622mg ligand L 1.Behind the reaction 1h, when vacuum concentration remained the 5mL solvent extremely approximately ,-10 ℃ of following freezing 2h separated out yellow crystals L
1Y (CH
2TMS)
2448mg, productive rate 40%.With X-Ray,
1HNMR,
13CNMR and elemental analysis its structure.C
29H
56N
3Si
2The ultimate analysis data of Y: calculated value: C, 58.85; H, 9.54; N, 7.10. measured value: C, 58.64; H, 9.26; N, 7.05.
1H NMR (300MHz, C
6D
6, 25 ℃): δ (ppm) 7.17-7.13 (m, 3H, Ar-H), 4.88 (s, 1H, MeC (N) CH), 3.25 (sp,
3J
HH=6.6Hz, 2H, ArCHMe
2), 2.88 (t,
3J
HH=5.8Hz, 2H, NCH
2), 2.21 (t,
3J
HH=6.1Hz, 2H, NCH
2), 2.07 (s, 6H, NMe
2), 1.69 (s, 3H, MeC), 1.63 (s, 3H, MeC), 1.43 (d,
3J
HH=6.6Hz, 6H, ArCHMe
2), 1.16 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 0.22 (s, 18H, Y (CH
2TMS)
2) ,-0.67 (dd,
2J
HH=12Hz,
2J
YH=3Hz, 2H, CH
2TMS) ,-0.92 (dd,
2J
HH=12Hz,
2J
YH=3Hz, 2H, CH
2TMS).
13C NMR (75MHz, C
6D
6, 25 ℃): δ (ppm) 166.4 (1C, imine-C), 165.7 (1C, imine-C), 144.1 (1C), 142,7 (2C), 126.1 (1C), 124.5 (2C) (Ar-C), 98.0 (1C, MeC (N) CH), 58.0 (1C, NCH
2), 47.3 (1C, NCH
2), 44.9 (2C, NMe
2), 35.6 (d,
1J
YC=39.8Hz, 2C, CH
2TMS), 28.3 (2C, ArCHMe
2), 25.3 (2C, ArCHMe
2), 24.6 (2C, ArCHMe
2), 24.1 (1C, MeC), 23.3 (1C, MeC), 4.6 (6C, CH
2TMS).
Embodiment 5
The anhydrous LuCl of 510mg
3Be dissolved in the 5mL tetrahydrofuran (THF), stirring is spent the night, and removes the back of desolvating and adds 5mL normal hexane formation suspension.Under the room temperature, 503mg LiCH
2TMS is dissolved in the 15mL normal hexane, changes YCl then over to
3Suspension.Behind the 2h, the centrifuging precipitation, filtrate changing over to is dissolved with the 5mL hexane solution of 489mg ligand L 1.Behind the reaction 1h, when vacuum concentration remained the 5mL solvent extremely approximately ,-10 ℃ of following freezing 2h separated out pale yellow crystals L
1Lu (CH
2TMS)
2732mg, productive rate 73%.With X-Ray,
1HNMR,
13CNMR and elemental analysis its structure.C
29H
56N
3Si
2The ultimate analysis data of Lu: calculated value: C, 51.38; H, 8.33; N, 6.20. measured value: C, 51.18; H, 8.21; N, 6.14.
1H NMR (300MHz, C
6D
6, 25 ℃): δ (ppm) 7.17-7.15 (m, 3H, Ar-H), 4.86 (s, 1H, MeC (N) CH), 3.28 (sp,
3J
HH=6.6Hz, 2H, ArCHMe
2), 2.88 (t,
3J
HH=5.7Hz, 2H, NCH
2), 2.15 (t,
3J
HH=6Hz, 2H, NCH
2), 2.04 (s, 6H, NMe
2), 1.66 (s, 3H, MeC), 1.62 (s, 3H, MeC), 1.43 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 1.16 (d,
3J
HH=6.6Hz, 6H, ArCHMe
2), 0.21 (s, 18H, Y (CH
2TMS)
2) ,-0.88 (d,
2J
HH=12Hz, 2H, CH
2TMS) ,-1.08 (d,
2J
HH=12Hz, 2H, CH
2TMS).
13C NMR (75MHz, C
6D
6, 25 ℃): δ (ppm) 166.8 (1C, imine-C), 166.5 (1C, imine-C), 145.3 (1C), 142.7 (2C), 126.0 (1C), 124.4 (2C) (Ar-C), 98.6 (1C, MeC (N) CH), 57.7 (1C, NCH
2), 47.4 (1C, NCH
2), 45.0 (2C, NMe
2), 43.0 (2C, CH
2TMS), 28.2 (2C, ArCHMe
2), 25.3 (2C, ArCHMe
2), 24.8 (2C, ArCHMe
2), 24.5 (1C, MeC), 23.3 (1C, MeC), 4.8 (6C, CH
2TMS).
Embodiment 6
The anhydrous SmCl of 478mg
3Be dissolved in the 5mL tetrahydrofuran (THF), stirring is spent the night, and removes the back of desolvating and adds 5mL normal hexane formation suspension.Under the room temperature, 517mg LiCH
2TMS is dissolved in the 15mL normal hexane, changes SmCl then over to
3Suspension.Behind the 2h, the centrifuging precipitation, filtrate changing over to is dissolved with the 5mL hexane solution of 502mg ligand L 1.Behind the reaction 1h, when vacuum concentration remained the 5mL solvent extremely approximately ,-10 ℃ of following freezing 2h separated out yellow crystals L
1Sm (CH
2TMS)
2486mg, productive rate 49%.With X-Ray and elemental analysis its structure.C
29H
56N
3Si
2The ultimate analysis data of Sm: calculated value: C, 53.32; H, 8.64; N, 6.43. measured value: C, 52.71; H, 8.41; N, this complex compound of 6.66. is a paramagnetic compound.
Embodiment 7
The anhydrous NdCl of 537mg
3Be dissolved in the 10mL tetrahydrofuran (THF), stirring is spent the night.Under the room temperature, 595mg LiCH
2TMS is dissolved in the 10mL tetrahydrofuran (THF), changes NdCl then over to
3Suspension.Behind the 10min, solution becomes sapphirine.Behind the reaction 2h, the 5mL tetrahydrofuran solution that ice bath will be dissolved with 578mg ligand L 1 down adds.After continuing reaction 2h, vacuum is removed reaction solvent, adds the 30mL n-hexane extraction, and when extraction liquid was concentrated into about 5mL solvent ,-10 ℃ were descended freezing 2h, separate out blue-greenish colour crystal L
1Nd (CH
2TMS)
2374mg, productive rate 33%.With X-Ray and elemental analysis its structure.C
29H
56N
3Si
2The ultimate analysis data of Nd: calculated value: C, 53.82; H, 8.72; N, 6.49. measured value: C, 52.98; H, 7.94; N, this complex compound of 6.36. is a paramagnetic compound.
Embodiment 8
The anhydrous YCl of 286mg
3Be dissolved in the 5mL tetrahydrofuran (THF), stirring is spent the night, and removes the back of desolvating and adds 5mL normal hexane formation suspension.Under the room temperature, 406mg LiCH
2TMS is dissolved in the 15mL normal hexane, changes YCl then over to
3Suspension.Behind the 2h, the centrifuging precipitation, filtrate changing over to is dissolved with the 5mL hexane solution of 428mg ligand L 2.Behind the reaction 1h, when vacuum concentration remained the 5mL solvent extremely approximately ,-10 ℃ of following freezing 2h separated out yellow solid L
2Y (CH
2TMS)
2319mg, productive rate 43%.With
1HNMR,
13CNMR and elemental analysis its structure.C
31H
60N
3Si
2The ultimate analysis data of Y: calculated value: C, 60.06; H, 9.76; N, 6.78. measured value: C, 59.17; H, 9.53; N, 7.01.
1H NMR (300MHz, C
6D
6, 25 ℃): δ (ppm) 7.17-7.14 (m, 3H, Ar-H), 4.90 (s, 1H, MeC (N) CH), 3.29 (sp,
3J
HH=6.9Hz, 2H, ArCHMe
2), 2.93 (t,
3J
HH=5.7Hz, 2H, NCH
2), 2.83 (sextet, 2H, N (CH
2CH
3)
2), 2.51-2.42 (overlapped, m, 4H, N (CH
2CH
3)
2And NCH
2), 1.69 (s, 3H, MeC), 1.64 (s, 3H, MeC), 1.44 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 1.16 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 0.78 (t,
3J
HH=7.1Hz, 6H, N (CH
2CH
3)
2), 0.19 (s, 18H, Y (CH
2TMS)
2) ,-0.62 (dd,
2J
HH=12Hz,
2J
YH=3Hz, 2H, CH
2TMS) ,-0.84 (dd,
2J
HH=12Hz,
2J
YH=3Hz, 2H, CH
2TMS).
13C NMR (75MHz, C
6D
6, 25 ℃): δ (ppm) 165.9 (1C, imine-C), 165.8 (1C, imine-C), 145.1 (1C), 142.7 (2C), 126.0 (1C), 124.4 (2C) (Ar-C), 98.0 (1C, MeC (N) CH), 49.9 (1C, NCH
2), 46.7 (1C, NCH
2), 44.3 (2C, N (CH
2CH
3)
2), 36.0 (d,
1J
YC=38.3Hz, 2C, CH
2TMS), 28.2 (2C, ArCHMe
2), 25.4 (2C, ArCHMe
2), 24.8 (2C, ArCHMe
2), 24.3 (1C, MeC), 22.9 (1C, MeC), 8.4 (2C, N (CH
2CH
3)
2), 4.5 (6C, CH
2TMS).
Embodiment 9
The anhydrous YCl of 230mg
3Be dissolved in the 5mL tetrahydrofuran (THF), stirring is spent the night, and removes the back of desolvating and adds 5mL normal hexane formation suspension.Under the room temperature, 327mg LiCH
2TMS is dissolved in the 15mL normal hexane, changes YCl then over to
3Suspension.Behind the 2h, the centrifuging precipitation, filtrate changing over to is dissolved with the 5mL hexane solution of 369mg ligand L 3.Behind the reaction 1h, when vacuum concentration remained the 5mL solvent extremely approximately ,-10 ℃ of following freezing 2h separated out pale yellow crystals L
3Y (CH
2TMS)
2240mg, productive rate 38%.With X-Ray,
1HNMR,
13CNMR and elemental analysis its structure.C
32H
60N
3Si
2The ultimate analysis data of Y: calculated value: C, 60.82; H, 9.57; N, 6.65. measured value: C, 61.79; H, 9.82; N, 6.66.
1H NMR (300MHz, C
6D
6, 25 ℃): δ (ppm) 7.18-7.14 (m, 3H, Ar-H), 4.91 (s, 1H, MeC (N) CH), 3.29 (sp,
3J
HH=6.9Hz, 2H, ArCHMe
2), 3.16 (m, 2H, N (CH
2CH
2)
2CH
2), 2.94 (t,
3J
HH=5.8Hz, 2H, NCH
2), 2.49 (t,
3J
HH=5.6Hz, 2H, NCH
2), 2.10 (m, 2H ,-N (CH
2CH
2)
2CH
2), 1.69 (s, 3H, MeC), 1.65 (s, 3H, MeC), 1.44 (d,
3J
HH=7.2Hz, 6H, ArCHMe
2), 1.25 (m, 6H, N (CH
2CH
2)
2CH
2And N (CH
2CH
2)
2CH
2), 1.17 (d,
3J
HH=6.9Hz, 6H, ArCHMe
2), 0.20 (s, 18H, Y (CH
2TMS)
2) ,-0.55 (dd,
2J
HH=12Hz,
2J
YH=3Hz, 2H, CH
2TMS) ,-0.81 (dd,
2J
HH=12Hz,
2J
YH=3Hz, 2H, CH
2TMS).
13C NMR (75MHz, C
6D
6, 25 ℃): δ (ppm) 165.9 (1C, imine-C), 165.6 (1C, imine-C), 145.0 (1C), 142.6 (2C), 126.0 (1C), 124.4 (2C) (Ar-C), 98.1 (1C, MeC (N) CH), 52.3 (1C, N (CH
2CH
2)
2CH
2), 52.0 (1C, NCH
2), 46.2 (1C, NCH
2), 36.5 (d,
1J
YC=40.5Hz, 2C, CH
2TMS), 28.2 (2C, ArCHMe
2), 25.4 (2C, ArCHMe
2), 24.7 (2C, ArCHMe
2), 24.2 (1C, MeC), 23.9 (1C, MeC), 22.7 (2C, N (CH
2CH
2)
2CH
2), 21.8 (2C, N (CH
2CH
2)
2CH
2), 4.5 (6C, CH
2TMS).
Embodiment 10
The anhydrous YCl of 286mg
3Be dissolved in the 10mL tetrahydrofuran (THF), stirring is spent the night.Under the room temperature, 862mg KN (TMS)
2Be dissolved in the 10mL tetrahydrofuran (THF), change YCl then over to
3Suspension.Behind the reaction 2h, the 5mL tetrahydrofuran solution that ice bath will be dissolved with 395mg ligand L 1 down adds.After continuing reaction 2h, vacuum is removed reaction solvent, adds the extraction of 30mL toluene, and when extraction liquid was concentrated into about 5mL solvent, freezing 24h under-30 ℃ separated out light yellow solid L
1Y (N (TMS)
2)
2405mg, productive rate 46%.With
1HNMR has characterized its structure.
1H?NMR(300MHz，C
6D
6，25℃)：δ(ppm)7.19-7.11(m，3H，Ar-H)，4.65(s，1H，MeC(N)CH)，3.14(sp，
3J
HH＝6.6Hz，2H，ArCHMe
2)，2.92(q，2H，NCH
2)，2.13(t，
3J
HH＝6.3Hz，2H，NCH
2)，1.90(s，6H，NMe
2)，1.63(s，3H，MeC)，1.61(s，3H，MeC)，1.21(t，
3J
HH＝7.2Hz，12H，ArCHMe
2)，0.25(s，36H，Y(N(TMS)
2)
2).
Embodiment 11
659mg ligand L 1 is dissolved in the 25mL hexane ,-30 ℃ of n-BuLi hexane solutions that add down 1.5mL 1.6M, after rise to stirred overnight at room temperature after, centrifuging adds the 20mL tetrahydrofuran (THF) after the solid hexane wash 3 times, ice bath adds anhydrous DyCl down
3538mg reacts centrifugal after two hours, and when changeing the clear liquid vacuum concentration to about 5mL solvent ,-10 ℃ times freezing 2h separate out crystal L
1DyCl
2584mg, productive rate 52%.C
21H
34N
3Cl
2The ultimate analysis data of Dy: calculated value: C, 44.89; H, 6.10; N, 7.48. measured value: C, 44.99; H, 6.12; N, 7.42.
Embodiment 12
562mg L
1DyCl
2Be dissolved in the 25mL tetrahydrofuran (THF), ice bath adds 196mg KO down
iPr, stirring reaction is centrifugal after two hours, and when changeing the clear liquid vacuum concentration to about 5mL solvent ,-20 ℃ times freezing 2h separate out crystal L
1Dy (O
iPr)
2293mg, wherein
iPr represents sec.-propyl, productive rate 48%.C
27H
48N
3O
2The ultimate analysis data of Dy: calculated value: C, 53.23; H, 7.94; N, 6.90. measured value: C, 53.27; H, 7.82; N, 6.81.
Embodiment 13
Take by weighing the 0.548g rac-Lactide in the glove box and be dissolved in 5.5g toluene, take by weighing catalyzer L
1Y (CH
2TMS)
211.3mg be dissolved in 1.25g toluene wiring solution-forming.Under the room temperature, the 0.5g catalyst solution is added monomer solution, stir 40min, the methyl alcohol that contains 5%HCl with 2mL goes out its essence.Be poured into the sedimentation of 20mL methanol solution then, precipitation small amount of methanol washing 3 times is filtered, and obtains white polymer.Vacuum is evacuated to weight, gets polylactide 0.545g, transformation efficiency 99%.
Embodiment 14
Take by weighing the 1.552g caprolactone in the glove box and be dissolved in 5.5g toluene, take by weighing catalyzer L
3Y (CH
2TMS)
24mg is dissolved in 0.5g toluene wiring solution-forming.Under the room temperature, in the toluene solution adding monomer with catalyzer, behind the stirring 20min, the methyl alcohol that contains 5%HCl with 2mL goes out its essence.Be poured into the sedimentation of 20mL methanol solution then, precipitation small amount of methanol washing 3 times is filtered, and obtains white polymer.Vacuum is evacuated to weight, gets polycaprolactone 1.518g, transformation efficiency 98%.
The result such as the following table of the ring-opening polymerization of the own lactones of part catalysis, rac-Lactide:
The catalytic rac-Lactide ring-opening polymerization of table 1. rare earth metal complex result
a
| Catalyzer | Transformation efficiency | Active b | M w | M w/M n |
| ?4?5?6?7 | 99％ 97％ 95％ 92％ | 107 105 103 99 | 144?200 227?800 154?400 117?600 | 1.19 1.32 1.29 1.23 |
| 8 9 10 | 98％ 99％ 99％ | 106 107 107 | 147?200 137?700 273?700 | 1.13 1.22 1.31 |
aPolymerizing condition: catalyzer/monomer=1/500 (mol/mol); Solvent is a 6g toluene; Temperature is 26 ℃; Polymerization time 40min.
bKg?polymer/mol·Ln·h。
The catalytic own lactones ring-opening polymerization result of table 2. rare earth metal complex
a
| Catalyzer | Transformation efficiency | Active b | M w | M w/M n |
| 4 5 6 7 8 9 10 | 89％ 95％ 85％ 89％ 97％ 98％ 97％ | 610 618 575 610 664 671 664 | 23?700 46?900 28?700 29?400 62?500 67?800 54?300 | 1.37 1.35 1.35 1.35 1.39 1.34 1.35 |
aPolymerizing condition: catalyzer/monomer=1/2000 (mol/mol); Solvent is a 6g toluene; Temperature is 26 ℃; Polymerization time 20min.
bKg?polymer/mol·Ln·h。
The structure of ligand L 1-L3 is as follows:
L1：R＝Me；
L2：R＝Et；
L3：R-R＝-(CH
2)
5
The structure of catalyzer 4-10 is as follows:
Claims (13)
1. the rare earth compounding of a class three-tooth nitrogen ligand is characterized in that structural formula is as follows:
In the said structure formula, Ln is a rare earth ion, R
1Be C
1-10Alkyl, R
2Be C
1-6Alkyl, n is 1-5, R
3Be C
1-10Chain-like alkyl or C
3-10Cyclic alkyl or two R
3Be connected to C
1-10Alkylidene group, X is the C with rare earth ion Cheng Jian
1-6Alkyl, [three (C
1～C
30Alkyl)] C of silica-based replacement
1-6Alkyl, two (C
1-8Alkyl) amido, two [three (C
1-8Alkyl) silica-based] amido or C
1-4Alkoxyl group,
Expression delocalized conjugated double bond, → expression coordinate bond.
2. the rare earth compounding of three-tooth nitrogen ligand as claimed in claim 1 is characterized in that structural formula is as follows:
3. the rare earth compounding of three-tooth nitrogen ligand as claimed in claim 1 is characterized in that described X is CH
2Si (CH
3)
3Or N[Si (CH
3)
3]
2
4. the rare earth compounding of three-tooth nitrogen ligand as claimed in claim 1 is characterized in that described rare earth metal is Y, Sc or lanthanide series metal.
5. the rare earth compounding of three-tooth nitrogen ligand as claimed in claim 1 is characterized in that described rare earth metal is Y, Nd, Sm, Sc, Lu or Dy.
6. the part of a class three-tooth nitrogen ligand rare earth compounding as claimed in claim 1 is characterized in that structural formula is as follows:
In the said structure formula, R
1, R
2And R
3According to claim 1.
7. the preparation method of rare earth compounding as claimed in claim 1 is characterized in that in organic solvent, under-30 ℃～100 ℃, by part and rare earth alkyl compound or aminocompound LnX
3Reaction 0.1～20h makes, wherein part and LnX
3Mol ratio be 1: 0.2～3; After perhaps part forms salt by KH, NaH or lithium alkylide deprotonation, again with the LnCl of 0.2～3 molar equivalent
3In organic solvent, after-30 ℃～100 ℃ reaction 0.1～20h obtains muriate down, make with the MX reaction again, wherein part, LnCl
3, MX and KH, NaH or lithium alkylide mol ratio be 1: (0.2～3): (0.2～3): (0.2～3);
Described ligand structure formula is as follows:
Wherein, R
1, R
2, n, R
3, Ln, X according to claim 1, M is Li, Na or K.
8. the described preparation method of claim 7 is characterized in that described organic solvent is hexane, toluene, benzene, ether or tetrahydrofuran (THF).
9. the described preparation method of claim 7 is characterized in that described part is synthetic by (2) two kinds of steps of following reaction (1):
(1) in organic solvent and under 0 ℃～110 ℃, is by structural formula
Beta diketone and arylamine
Its mol ratio is 1: 0.2～3, reacts 1～100h and make the monolateral substituted imine of intermediate in the presence of 0.1%-3% molar equivalent tosic acid
(2) in organic solvent, monolateral substituted imine
With 0.2～3 normal diamines
In the presence of 0.1%-3% molar equivalent tosic acid, react 1～100h down at 0 ℃～110 ℃ and make described part;
R wherein
1, R
2, R
3, n is as described in the claim 7.
10. the described preparation method of claim 9 is characterized in that described organic solvent is toluene, benzene, methyl alcohol or ethanol.
11. the purposes of each described rare earth compounding in the claim 1 to 5 is characterized in that the catalyzer as the ring-opening polymerization of catalyzing lactone.
12. the purposes of each described rare earth compounding in the claim 1 to 5 is characterized in that the catalyzer as the ring-opening polymerization of catalysis rac-Lactide, own lactones.
13. the purposes of the described rare earth compounding of claim 11 is characterized in that in toluene, tetrahydrofuran (THF), methylene dichloride or hexane solution or under the solvent-free state, the ring-opening polymerization of catalysis rac-Lactide or own lactones under-20 ℃～160 ℃ conditions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101708296A CN101186617B (en) | 2007-11-23 | 2007-11-23 | Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007101708296A CN101186617B (en) | 2007-11-23 | 2007-11-23 | Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101186617A CN101186617A (en) | 2008-05-28 |
| CN101186617B true CN101186617B (en) | 2010-12-22 |
Family
ID=39479265
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007101708296A Expired - Fee Related CN101186617B (en) | 2007-11-23 | 2007-11-23 | Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101186617B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101492390B (en) * | 2009-03-06 | 2012-08-29 | 中国科学院上海有机化学研究所 | Novel three-tooth nitrogen ligand and rare earth metal complex |
| CN101555317B (en) * | 2009-05-22 | 2011-05-11 | 中国科学院上海有机化学研究所 | Azotic lateral chain beta diimine ligand metallic catalyst and application thereof in polyester synthesis |
| CN104140435B (en) * | 2013-05-08 | 2017-07-28 | 中国石油化工股份有限公司 | The preparation method of rare earth compounding and preparation method thereof and catalyst and its application and rare-earth isoprene rubber |
| CN114106308B (en) * | 2020-08-31 | 2023-07-21 | 中国石油化工股份有限公司 | Catalyst composition and application thereof, polylactide and preparation method thereof |
| CN113680389B (en) * | 2021-08-20 | 2023-09-05 | 安徽师范大学 | Multidentate beta-diimine ligand rare earth metal catalyst and preparation method and application thereof |
-
2007
- 2007-11-23 CN CN2007101708296A patent/CN101186617B/en not_active Expired - Fee Related
Non-Patent Citations (3)
| Title |
|---|
| Daniela V. Vitanova et al..Rare earth metal complexes based on b-diketiminatoandnovel linked bis(b-diketiminato) ligands: Synthesis,structuralcharacterization and catalytic application inepoxide/CO2-polymerization.Journal of Organometallic Chemistry690.2005,6905182-5197. * |
| Daniela V. Vitanova et al..Synthesis and structural characterisation of novel linked bis(b-diketiminato) rare earth metal complexes.Dalton Trans..2005,1565-1566. * |
| DanielaV.Vitanovaetal..Rareearthmetalcomplexesbasedonb-diketiminatoandnovellinkedbis(b-diketiminato)ligands:Synthesis structuralcharacterization and catalytic application inepoxide/CO2-polymerization.Journal of Organometallic Chemistry690.2005 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101186617A (en) | 2008-05-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Han et al. | Influence of Schiff base and lanthanide metals on the synthesis, stability, and reactivity of monoamido lanthanide complexes bearing two Schiff bases | |
| CN101186617B (en) | Nitrogen-containing ligand rare earth catalyst and application thereof in polyester synthesis | |
| Feher et al. | New polyhedral oligosilsesquioxanes via the catalytic hydrogenation of aryl-containing silsesquioxanes | |
| Okuda | Cationic rare-earth metal hydrides | |
| Kisanga et al. | Synthesis of new proazaphosphatranes and their application in organic synthesis | |
| CN101492390B (en) | Novel three-tooth nitrogen ligand and rare earth metal complex | |
| Cheng et al. | Cationic terminal hydrido rare earth complexes bearing an amidinate ancillary ligand | |
| Guo et al. | Potassium complexes containing bidentate pyrrole ligands: synthesis, structures, and catalytic activity for the cyclotrimerization of isocyanates | |
| JPH03112995A (en) | Iridium complex and method of its preparation and use | |
| Li et al. | Reaction of 1-(dimethylsilyl)-2-silylbenzene with platinum (0) phosphine complex: Isolation and characterization of the Si3–PtIV–H complex | |
| Schmidt et al. | Zinc Carbodiimide Cluster Complexes: Synthesis, X-ray Crystal Structures, and Reaction Mechanism | |
| CN104557874A (en) | Quinoline amido indolyl zinc, magnesium and calcium compound as well as preparation method and application thereof | |
| JP2011122145A5 (en) | ||
| Bai et al. | An alkyl-ended ansa-bis (amidine) and solvent-influenced complexation modes of its group IV metal derivatives | |
| Yuan et al. | Reactions of Boratabenzene Yttrium Complexes with KN (SiMe3) 2: Salt Elimination and π-Ligand Displacement | |
| Jende et al. | Yttrium half-sandwich complexes bearing the 2-(N, N-dimethylamino) ethyl-tetramethylcyclopentadienyl ligand | |
| CN101555317B (en) | Azotic lateral chain beta diimine ligand metallic catalyst and application thereof in polyester synthesis | |
| George et al. | Metal-metal bonded organometallic complexes. III. Ligand derivatives of. eta. 5-cyclopentadienyltricarbonyl tungsten (I) bonded to group 4 elements | |
| CN108912010A (en) | A kind of schiff bases manganese compound, preparation method and its application | |
| CN101508704B (en) | Organic bismuth ion compound containing bridge nitrogen atom ligand, preparation and uses thereof | |
| Eisenmann et al. | Syntheses and X‐Ray Structures of Zinc Amidinate Complexes | |
| CN101302230A (en) | Synthesis and application of carbon bridged diketone monoimino aluminum complex | |
| CN101544672B (en) | Organic antimony compound bearing a nitrogen-bridged ligand and its preparation and application | |
| JP3086803B1 (en) | Triazacyclononane compounds with chiral substituents and their metal complexes | |
| CN103254247A (en) | Preparation of p phenylenediamine group bridged tetra aryloxy bimetallic rare earth amide and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20101222 Termination date: 20151123 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |