CN102531929A - Compound containing N and O heteroatom, preparation and application thereof - Google Patents
Compound containing N and O heteroatom, preparation and application thereof Download PDFInfo
- Publication number
- CN102531929A CN102531929A CN2011104195077A CN201110419507A CN102531929A CN 102531929 A CN102531929 A CN 102531929A CN 2011104195077 A CN2011104195077 A CN 2011104195077A CN 201110419507 A CN201110419507 A CN 201110419507A CN 102531929 A CN102531929 A CN 102531929A
- Authority
- CN
- China
- Prior art keywords
- compound
- lithium
- general formula
- phenyl
- nitrogenous
- 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.)
- Granted
Links
- 0 Cc(cc1)cc(C*O)c1N(C)C Chemical compound Cc(cc1)cc(C*O)c1N(C)C 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a compound containing N and O heteroatom, and preparation and application of the compound. The compound has a structural formula (I) shown below, wherein R represents alkylene and Me is the abbreviation of methyl. The compound is used for preparing a zinc and aluminum compound, which is used as a catalyst for ring-opening polymerization of epsilon-caprolactone.
Description
Technical field
The present invention relates to a kind of nitrogenous, oxygen heteroatom compound and preparation and application, this compound is used to prepare zinc, aluminum compound, and this type of zinc, aluminum compound are used as the catalyzer of 6-caprolactone ring-opening polymerization.
Background technology
Polyester fat lactone is one type of important thermoplastic plastic, and important use is arranged in medical material.Particularly poly-epsilon-caprolactone with gather gamma-butyrolactone, can also be doped among many other plastics, to its carry out modification (X.Zhang, U.P.Wyss, D.Pichora, M.F.A.Goosen, J.Macromol.Sci.Pure Appl.Chem.A30 (1993) 933; R.G.Sinclair, J.Macromol.Sci.Pure Appl.Chem.A33 (1996) 585; A.Duda, A.Kowalski, S.Penczek, H.Uyama, S.Kobayashi.Macromolecules 35 (2002) 4266).(poly-epsilon-caprolactone (PCL) that the ring-opening polymerization of ε-CL) obtains is example to 6-caprolactone, and it has high-crystallinity (can reach 69%) and good thermostability, and decomposition temperature is up to 350 ℃.Simultaneously, poly-epsilon-caprolactone is easy to again decomposed by mikrobe or enzyme under field conditions (factors), finally generates carbonic acid gas and water.Its good biodegradable and good biocompatibility, can with material blend such as starch, process the macromolecular material of fully biodegradable.
Condensation polymerization method and ring-opening polymerization method are the main method of synthetic polylactone.But; The reaction of direct polycondensation method is a balanced reaction, and a spot of water of the later stage of polycondensation is difficult to remove fully, often obtains oligopolymer; So less employing (Xie Deliang; The ginger mark, Yang Changzheng. alcohol acid causes the research [J] of 6-caprolactone ring-opening polymerization. polymer journal, 2000 (5): 532-537).The ring-opening polymerization method can obtain HMW, low dispersed polymkeric substance, uses on the lactone ring opening polymerization method so present most of polyester synthetic research work all concentrates on.
In 1979, people such as Gschwend H W under study for action, at N, N; N ', under the existence of N '-Tetramethyl Ethylene Diamine, 4; N, amino adjacent benzene ring hydrogen is pulled out in N-trimethylaniline and n-Butyl Lithium reaction; With the UVNUL MS-40 reaction, being hydrolyzed at last obtains the amino alcohol part with separating again, but the kind of such amino alcohol part is less.And before the present invention, also not with 2,4, N, N-tetramethyl-aniline are the amino alcohol part of starting raw material preparation.
Summary of the invention
The object of the present invention is to provide a kind of nitrogenous, oxygen heteroatom compound and preparation and application.
Described nitrogenous, oxygen heteroatom compound of the present invention, shown in the following I of its general structure:
In the general formula I, R is an alkylidene group, and Me is the methyl abbreviation in the formula;
In the described general formula I shown in the following II of the general formula of alkylidene group R:
Among the general formula I I, R
1And R
2Be respectively hydrogen or alkyl or phenyl or substituted-phenyl or naphthyl or fused ring aryl;
Or in the described general formula I shown in the following III of general formula of alkylidene group R:
In the general formula III, n is 0 or 1 or 2 or 3 or 4.
In order to help to more clearly understand the structure of above-claimed cpd, illustrate below, what need stress is the compound that the present invention does not limit following these structures, Ph is the phenyl abbreviation in the formula:
Compound method nitrogenous, the oxygen heteroatom compound of the present invention is following, is made up of two-step reaction: under (1) nitrogen protection, between-78 ℃ to 80 ℃; In N, N, N '; N '-Tetramethyl Ethylene Diamine exists down; Compound V and lithium alkylide or phenyl lithium reaction 10 minutes to 8 hours obtain compound IV, directly are used for next step reaction without separating; (2) between-78 ℃ to 80 ℃; In organic solvent; What a last step obtained reacts 20 minutes after 6 hours without isolated compound IV and aldehydes or ketones, pours reaction solution in excessive formic acid or acetic acid or hydrochloric acid hydrolysis, obtains Novel Ligands I through separation and Extraction.
Reaction formula is following:
LiR
3Be lithium methide or lithium ethide or n-Butyl Lithium or tert-butyl lithium or phenyl lithium;
TMEDA is a N,N,N;
R is alkylidene group as previously mentioned;
Described organic solvent is normal hexane or THF or ether or benzene;
The mol ratio of described compound V and N,N,N is 1: 1.5;
The mol ratio of described compound V and lithium alkylide or phenyl lithium is 1: 1 to 1: 1.5;
The mol ratio of described compound IV and aldehydes or ketones is 1: 1 to 1: 1.1;
The separation and Extraction in the step of second in the compound method of described compound of Formula I specifically comprises following two steps: in excessive formic acid or acetic acid or hydrochloric acid hydrolysis is poured reaction solution in (1); Add hydrochloric acid to pH value less than 2; Add ether or ETHYLE ACETATE or methylene dichloride or trichloromethane again, tell water; (2) water hydro-oxidation sodium water solution to pH value then adds ether or ETHYLE ACETATE or methylene dichloride or trichloromethane greater than 8, tells organic phase, and drying is filtered, and obtains compound of Formula I with ETHYLE ACETATE or normal hexane recrystallization behind the desolventizing.
The purposes of compound of Formula I of the present invention is synthetic a series of zinc, aluminum compound.
The invention effect
For the preparation of a series of novel amino alcohol parts provides compound method.
Embodiment
Embodiment 1:
Part HL
1Synthetic
Under nitrogen protection, room temperature is to adding N, N, 2; 4-tetramethyl-aniline (7.47g, 50.0mmol) and N, N, N '; (8.81g in 200mlSchlenk bottle 76.0mmol), splashes into hexane solution (30.4ml, the 76.0mmol of n-Butyl Lithium to N '-Tetramethyl Ethylene Diamine; 2.84M), there is great amount of bubbles to produce immediately, solution becomes is muddy and by the colourless light red that becomes; React after 4 hours, (13.8g, anhydrous diethyl ether 75.0mmol) (40ml) solution react stirred overnight, and solution becomes yellow to wherein adding UVNUL MS-40.(12g, ether 200mmol) (30ml) solution are used the hydrochloric acid extraction 4 times of 50ml water and 5% then, merge water then under vigorous stirring, slowly to pour reaction solution into acetic acid; Water transfers to the pH value greater than 8 with 10% sodium hydroxide solution, and solution becomes is muddy, adds the methylene dichloride separatory, tells organic phase, and drying is filtered, and obtains white crystal 6.68g with ETHYLE ACETATE and normal hexane mixed solvent crystallization behind the desolventizing, and yield is 40%.Fusing point: 126-128 ℃.
1H?NMR(600MHz，293K，CDCl
3)：δ(ppm)3.70(s，2H，ArCH
2C)，2.04(s，3H，ArCH
3)，2.74(s，6H，NMe
2)，6.92-7.42(m，13H，ArH)，8.61(s，1H，OH)。ESl-MS?m/z(％)：332.4(100)[M+H]
+。IR(KBr，cm
-1)：3053.5(br，s)，2831.2(s)，1473.1(s)，699.9(m)。
Embodiment 2:
Part HL
2Synthetic
Under nitrogen protection, room temperature is to adding N, N, 2; 4-tetramethyl-aniline (9.95g, 66.0mmol) and N, N, N '; (9.68g in 200mlSchlenk bottle 84.0mmol), splashes into hexane solution (33.6ml, the 84.0mmol of n-Butyl Lithium to N '-Tetramethyl Ethylene Diamine; 2.5M), there is great amount of bubbles to produce immediately, solution becomes is muddy and by the colourless light red that becomes; React after 4 hours, (10.1g, the solution of anhydrous diethyl ether 84.0mmol) (40ml) react stirred overnight, and solution becomes yellow to wherein splashing into methyl phenyl ketone.(12g, ether 200mmol) (30ml) solution are used the hydrochloric acid extraction 4 times of 50ml water and 5% then, merge water then under vigorous stirring, slowly to pour reaction solution into acetic acid; Greater than 8, solution becomes is muddy with 10% sodium hydroxide solution key to pH value for water, adds methylene dichloride, tells organic phase, and drying is filtered, and gets white crystal 3.72g with re-crystallizing in ethyl acetate behind the desolventizing, and yield is 30%.Fusing point: 84-85 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)3.08(d，
2J
H-H＝14.1Hz，1H，ArCH
2C)，3.22(d，
2J
H-H＝14.1Hz，1H，ArCH
2C)，2.20(s，3H，ArCH
3)，1.46(s，3H，CCH
3)，2.69(s，6H，NMe
2)，6.72-7.51(m，8H，ArH)，7.94(s，1H，OH)。ESI-MS?m/z(％)：270.4(100)[M+H]
+。IR(KBr，cm
-1)：3183.3(br，s)，2966.6(s)，1509.9(s)，705.8(m)。
Embodiment 3:
Part HL
3Synthetic
Under nitrogen protection, room temperature is to adding N, N, and 2,4-tetramethyl-aniline (14.92g, 100mmol) and N,N,N (14.53g, 1.2 * 10
2Mmol) in the 200mlSchlenk bottle, splash into hexane solution (50.0ml, 1.2 * 10 of n-Butyl Lithium
2Mmol 2.5M), has great amount of bubbles to produce immediately, and solution becomes is muddy and by the colourless light red that becomes; React after 4 hours, to wherein splashing into α-acetonaphthone (21.3g, 1.2 * 10
2Mmol) solution of anhydrous diethyl ether (40ml), the reaction stirred overnight, solution becomes yellow.(12g, ether 200mmol) (30ml) solution are used the hydrochloric acid extraction 4 times of 50ml water and 5% then, merge water then under vigorous stirring, slowly to pour reaction solution into acetic acid; Water transfers to the pH value greater than 8 with 10% sodium hydroxide solution, and solution becomes is muddy, adds methylene dichloride, tells organic phase, and drying is filtered, and with getting white crystal 5.72g with the normal hexane recrystallization, yield is 31% behind the desolventizing.Fusing point: 113-115 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)3.40(d，
2J
H-H＝14.3Hz，1H，ArCH
2C)，3.74(d，
2J
H-H＝14.3Hz，1H，ArCH
2C)，2.13(s，3H，ArCH
3)，1.72(s，3H，CCH
3)，2.72(s，6H，NMe
2)，6.74-7.88(m，10H，ArH)，8.11(s，1H，OH)。ESI-MS?m/z(％)：320.4(100)[M+H]
+。IR(KBr，cm
-1)：3201.2(br，s)，2978.0(s)，1506.0(s)，1115.3(s)，782.2(m)。
Embodiment 4:
Part HL
4Synthetic
Under nitrogen protection, room temperature is to adding N, N, and 2,4-tetramethyl-aniline (14.92g, 100mmol) and N,N,N (14.53g, 1.2 * 10
2Mmol) in the 200mlSchlenk bottle, splash into hexane solution (50.0ml, 1.2 * 10 of n-Butyl Lithium
2Mmol 2.5M), has great amount of bubbles to produce immediately, and solution becomes is muddy and by the colourless light red that becomes; React after 4 hours, (12.3g, the solution of 1.2 * 102mmol) anhydrous diethyl ether (40ml) react stirred overnight, and solution becomes yellow to wherein splashing into pimelinketone.(12g 200mmol) is dissolved in the solution of 30ml ether, uses the hydrochloric acid extraction 4 times of 50ml water and 5% then, merges water then under vigorous stirring, slowly to pour reaction solution into acetic acid; Water transfers to the pH value greater than 8 with 10% sodium hydroxide solution, and solution becomes is muddy, adds methylene dichloride, tells organic phase, and drying is filtered, and gets white crystal 3.73g with re-crystallizing in ethyl acetate behind the desolventizing, and yield is 35%.Fusing point: 71-72 ℃.
1H?NMR(400MHz，293K，CDCl
3)：δ(ppm)2.87(q，2H，ArCH
2C)，2.28(s，3H，ArCH
3)，2.66(s，6H，NMe
2)，1.46(m，10H，-(CH
2)
5-)，6.88-7.01(m，3H，ArH)，6.88(s，1H，OH)。ESI-MS?m/z(％)：248.4(100)[M+H]
+。IR(KBr，cm
-1)：3159.2(br，s)，2933.9(s)，1500.4(m)，817.3(m)。
Claims (5)
1. nitrogenous, oxygen heteroatom compound is characterized in that: shown in the following general formula I of its general structure:
In the general formula I, R is an alkylidene group, and Me is the methyl abbreviation.
2. nitrogenous, oxygen heteroatom compound as claimed in claim 1 is characterized in that: the general formula of alkylidene group R is shown in II or the III in the general formula I;
General formula I I:
Among the general formula I I, R
1And R
2Be respectively hydrogen, alkyl, phenyl, substituted-phenyl, naphthyl or fused ring aryl; Or R
1And R
2Be methyl, ethyl or phenyl; Or R
1Be methyl, R
2Be phenyl or Alpha-Naphthyl;
Or general formula III:
In the general formula III, n is 0,1,2,3 or 4.
3. the compound method of nitrogenous, an oxygen heteroatom compound as claimed in claim 1 is characterized in that:
Constitute by two-step reaction:
(1) under the nitrogen protection, between-78 ℃ to 80 ℃, in N, N; N ', N '-Tetramethyl Ethylene Diamine exist down, compound V and lithium alkylide or phenyl lithium reaction 10 minutes to 8 hours; The compound IV that obtains directly is used for next step reaction without separating, wherein compound V and N, N; N ', the mol ratio of N '-Tetramethyl Ethylene Diamine is 1: 1.5, the mol ratio of compound V and lithium alkylide or phenyl lithium is 1: 1 to 1: 1.5;
(2) between-78 ℃ to 80 ℃, in organic solvent, with a last step obtain react 20 minutes after 6 hours without isolated compound IV and aldehydes or ketones; Pour reaction solution in excessive formic acid, acetic acid or hydrochloric acid hydrolysis, add hydrochloric acid to pH value, then add ether, ETHYLE ACETATE, methylene dichloride or trichloromethane, tell water less than 2; Water hydro-oxidation sodium water solution to pH value adds ether, ETHYLE ACETATE, methylene dichloride or trichloromethane again greater than 8, tells organic phase, and drying is filtered, and obtains formula I part with ETHYLE ACETATE or normal hexane recrystallization behind the desolventizing; Wherein the mol ratio of compound IV and aldehydes or ketones is 1: 1 to 1: 1.1;
Shown in VI:
Formula VI
Wherein, LiR
3Be lithium alkylide or phenyl lithium, R is an alkylidene group;
Said organic solvent is normal hexane, THF, ether or benzene.
4. the compound method of nitrogenous, oxygen heteroatom part as claimed in claim 3, it is characterized in that: described lithium alkylide is lithium methide or lithium ethide or n-Butyl Lithium or tert-butyl lithium.
5. the purposes of described nitrogenous, the oxygen heteroatom compound of a claim 1 is characterized by: itself and dialkyl group zinc and trialkylaluminium reaction, preparation zinc, aluminum compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110419507.7A CN102531929B (en) | 2011-12-15 | 2011-12-15 | Compound containing N and O heteroatom, preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110419507.7A CN102531929B (en) | 2011-12-15 | 2011-12-15 | Compound containing N and O heteroatom, preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102531929A true CN102531929A (en) | 2012-07-04 |
| CN102531929B CN102531929B (en) | 2014-10-15 |
Family
ID=46340113
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110419507.7A Active CN102531929B (en) | 2011-12-15 | 2011-12-15 | Compound containing N and O heteroatom, preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102531929B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387283B (en) * | 2014-11-04 | 2016-06-08 | 济南大学 | A kind of four tooth nitrogen oxygen part and application thereof |
-
2011
- 2011-12-15 CN CN201110419507.7A patent/CN102531929B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| WALTER FUHRER ET AL: "Ortho functionalization of aromatic amines: ortho lithiation of N-pivaloylanilines", 《J. ORG. CHEM.》 * |
| 硅桥联有机锂化合物的合成及结构测定: "硅桥联有机锂化合物的合成及结构测定", 《山西大学学报(自然科学版)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104387283B (en) * | 2014-11-04 | 2016-06-08 | 济南大学 | A kind of four tooth nitrogen oxygen part and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102531929B (en) | 2014-10-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7060697B2 (en) | Light-colored modified isocyanate mixture and its preparation method | |
| TW201002732A (en) | Preparation of novel phosphorus-containing biphenols and their derivatives | |
| CN100391945C (en) | S-(-)-indolyl-2-carboxylic acid synthesizing method | |
| CN101381389B (en) | Chemical synthesis method of 5,7-diene steroids compounds | |
| CN101880294B (en) | Novel phosphorus series bisphenols and manufacture method of derivatives thereof | |
| CN102531929B (en) | Compound containing N and O heteroatom, preparation and application thereof | |
| JP5815507B2 (en) | Process for purification of 1-methylpyrazole-4-carboxylic acid ester | |
| CN102070596B (en) | Preparation method for dihydrosafrole | |
| CN105254678A (en) | Preparation method for fire retardant high in phosphorus content | |
| CN102653525A (en) | Preparing bendamustine alkyl ester compounds, comprises reacting substituted 2-((2-hydroxy-ethyl)-phenyl-amino)-ethanol compounds with a mixture comprising carbonyl amine compounds and sulfonyl compounds, or diketo compounds | |
| US2146730A (en) | Metallic and hydroxy derivatives of dibenzofurane | |
| CN103951546B (en) | Novel synthetic process of thymol | |
| CN102516273B (en) | Compound containing zinc core as well as preparation method and application thereof | |
| KR100541786B1 (en) | A method for preparing alcohols by using (3-alkoxyphenyl)magnesium chlorides | |
| CN102786547A (en) | Process for synthesizing glyphosine | |
| KR102320689B1 (en) | Isocyanuric acid derivative having an alkoxyalkyl group and method for producing the same | |
| CN104987302B (en) | N, N diethyl formic acid 4 halogenated methyl 3,5 xylenol ester compounds and preparation method thereof | |
| CN102127061B (en) | One prepares improving one's methods of fluoro-3, the 4-dihydro-2 H-1-benzopyran-2-epoxy ethanes of 6- | |
| CN106432328B (en) | A kind of preparation method of Suo Feibuwei intermediate | |
| JP5273941B2 (en) | Process for producing polyhedral silsesquioxane | |
| JPH09227583A (en) | Production of n-phosphono-methyl-glycine | |
| CN102171201B (en) | Method for producing spirocyclic tetronic acid derivatives | |
| CN102516279A (en) | Compound containing aluminum core as well as preparation method and application thereof | |
| CN102796056B (en) | Peramivir intermediate and preparation method for analogue | |
| EP2468706A1 (en) | Process for the preparation of resveratrol |
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 |