CN86103456A - The synthetic method of phase transfer catalysts - Google Patents
The synthetic method of phase transfer catalysts Download PDFInfo
- Publication number
- CN86103456A CN86103456A CN198686103456A CN86103456A CN86103456A CN 86103456 A CN86103456 A CN 86103456A CN 198686103456 A CN198686103456 A CN 198686103456A CN 86103456 A CN86103456 A CN 86103456A CN 86103456 A CN86103456 A CN 86103456A
- Authority
- CN
- China
- Prior art keywords
- phase
- transfer catalyst
- synthetic method
- reaction
- iii
- 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.)
- Pending
Links
Abstract
Phase-transfer-catalyzed reactions is a kind of novel method of organic synthesis.The present invention reports the synthetic of the new phase-transfer catalyst of a class (figure) and uses.The above-claimed cpd I, II, III can be used for nucleophilic substitution reaction as phase-transfer catalyst, and is excellent to halogen atom replacement(metathesis)reaction catalytic effect.
Description
The invention belongs to the organic synthesis field.
Phase-transfer-catalyzed reactions is the novel method of a kind of organic synthesis of growing up 1960's.Because it has the production technique of simplification, reduces cost and reduce series of advantages such as pollution, therefore, phase-transfer-catalyzed reactions occupies very consequence in organic synthesis.
Realize the phase-transfer catalyst that phase-transfer-catalyzed reactions is commonly used, be divided into salt (quaternary ammonium salt, quaternary alkylphosphonium salt etc.) haply, macrocyclic polyether (total oxygen crown ether, cave ether etc.) and acyclic polyether three major types.In this three classes phase-transfer catalyst since cave ether and acyclic polyetherization synthesis step many, cost an arm and a leg, be very restricted in the use.Salt (quaternary ammonium salt, quaternary alkylphosphonium salt) though and the existing commodity selling of some total oxygen crown compound, and in preparative organic chemistry, use.The general effect of Dan phosphonium salt is not satisfactory, and it is still less that the total oxygen crown ether can obtain effective kind of using.
For overcoming the problem that above-mentioned cave ether, total oxygen crown ether etc. exist as phase-transfer catalyst, the comprehensive cave of the present invention ether has the tertiary amine structure type of nitrogen heteroatom, and the side chain that contains chain alkyl and alkyl oxide oxygen chain is to the fat-soluble characteristics that bigger improvement is arranged of works, design has been synthesized the N-that a class there is no report so far at home and abroad in the document and has been replaced benzo Azacrown ether containing compound, and structural formula is as follows:
I is N-(2 '-oxa-butyl)-1,4,7,13-four oxa-s-10-azepine-2,3-benzo ring 15-2-alkene; II is N-(5 '-oxa-heptyl)-1,4,7,13-four oxa-s-10-azepine-2,3-benzo ring 15-2-alkene; III is N-(2 ', 5 '-dioxaheptyl)-1,4,7,13-four oxa-s-10-azepine-2,3-benzo ring 15-2-alkene.
The synthetic method of above compound is simple, with low cost, safe in utilization, and catalytic efficiency is very high in phase-transfer-catalyzed reactions.
Main points: the N-that is not reported in a kind of document so far of this patent report replaces the synthetic method of benzo Azacrown ether containing chemical compounds I, II and III, and as phase-transfer catalyst, the application in nucleophilic substitution reaction.
The synthetic method that N-replaces the benzo Azacrown ether containing is as follows:
Parent 1,4,7,13-four oxa-s-10-azepine-
2,3-benzo ring 15-2-alkene synthetic, by 1,2 two (2 '-tolysulfonyl base oxethyl)-benzene (being called for short DTOS) and diethanolamine with etc. mol ratio, 50 °-55 ℃ of heating are reacted condensations in 7-10 hour and are got in strongly basic medium:
2.N-replace the synthetic method of benzo Azacrown ether containing compound, in acetonitrile, be condensing agent by parent and bromo alkyl oxide with the Anhydrous potassium carbonate, reflux, reacted through 12-15 hour:
n＝0，R＝C
4H
9（n）
n＝1，R＝CH
3
Phase-transfer catalyst I-III can be applicable to nucleophilic substitution reaction, and wherein the replacement(metathesis)reaction effect of the halogen atom of halogenated alkane is good.
Experiment embodiment:
Example (one), 1,4,7,13-four oxa-s-10-azepine-2,3-benzo ring 15-2-alkene synthetic:
4.25 gram (40mmol) diethanolamine; 1.6 gram (70mmol) sodium Metal 99.5 is dissolved in the 120ml trimethyl carbinol; be heated to 50 °～55 ℃; stir and drip 15.3 gram (30mmol) 1 down; 2-two (2 '-tolysulfonyl base oxethyl)-benzene is dissolved in the solution of 100ml dioxane; after dripping in three hours; continue reaction 4 hours, be chilled to room temperature, filter; wash with chloroform; merging filtrate and chloroformic solution, evaporate to dryness, the solid that obtains; with acetone-sherwood oil (60 °～90 ℃ (volume ratio 1: 2) recrystallizations; obtain white plates crystallization 3.0 grams, yield 40%, mp are 148 °～149 ℃.
Example (two), N-replaces the synthetic of benzo Azacrown ether containing chemical compounds I:
1.07 gram (4mmol) 1,4,7,13-four oxa-s-10-azepine-2,3,-benzo ring 15-2-alkene is dissolved in the 50ml acetonitrile, add 2.0 gram levigated Anhydrous potassium carbonates and 0.69 gram (5mmol) 2-oxa-n-butyl bromide, stir heating reflux reaction 12 hours, be chilled to room temperature, filter, wash merging filtrate and chloroformic solution, evaporate to dryness with minimum of chloroform, solids mixes with weight ratio with the neutral alumina dry method at 1: 10, with sherwood oil (60 °～90 ℃) extraction heat 16 hours, pressure reducing and steaming petroleum ether obtained colourless viscous liquid, through ultimate analysis, IR,
1HNMR and
13CNMR and MS are determined as I, yield 66%.
According to last method, also can synthesize and obtain compound ii (n=O, R=-C
4H
9) and III (n=1, R=-CH
3).Yield 48～50%.
Example (three) as phase-transfer catalyst, is applied to prepare the method for iodate alkane in nucleophilic substitution reaction.
Reaction formula:
The 1ml-bromooctane is dissolved in the toluene, adds 2 gram sodium iodides and 50mg phase-transfer catalyst I (be about 1-bromooctane amount 2%), stirs, and is heated to 50 °～60 ℃, reaction half an hour.Borrow gas chromatograph to follow the tracks of and detect 1-bromooctane yield～100%.
The reaction biology is removed Sodium Bromide after filtration, and pressure reducing and steaming toluene obtains 1-iodo-octane.
Effect: the effect of phase-transfer catalyst in prepare the 1-iodo-octane reaction by the 1-bromooctane that this class is new, with at present known to the result that reported on the document compare, yield and side chain cryptand ether compound (IV) and dicyclohexyl 18-hat-6(V) quite, and the reaction times II is shorter than IV, V.No matter yield and reaction times all are better than other phase-transfer catalysts (quaternary ammonium salt, quaternary alkylphosphonium salt), and its result relatively sees the following form:
HDTBP: bromination hexadecyl tributyl;
HTBPC: chlorination hexadecyl tributyl;
Document:
①J.C.S.Chem.Commun;393.1975
②J.C.S.Chem.Commun;879.1974
③Tetrahedron????Lett，1381，1976
④Synthesis，472，1976
Claims (4)
1, the phase-transfer catalyst that a class is new-N-replaces the synthetic method of benzo Azacrown ether containing.It is characterized in that this method makes 1 earlier; 2-two (2 '-tolysulfonyl base oxethyl)-benzene (being called for short DTOS) and diethanolamine condensation in strongly basic medium obtain parent 1; 4; 7; 13-four oxa-s-10-azepine-2,3-benzo ring 15-2-alkene is then with the bromo alkyl oxide; in acetonitrile, be that the condensing agent reaction makes phase-transfer catalyst I-III with the Anhydrous potassium carbonate.
Ⅰ：n=0，R=CH
3
Ⅱ：n=0，R=C
4H
9(n)
Ⅲ：n=1，R=CH
3
2, require the synthetic method of 1 described phase-transfer catalyst according to patent, it is characterized in that the synthetic method of parent is, reactant consumption mol ratio: DTOS: diethanolamine is 1: 1.0～1.3; Strongly basic medium is sodium tert-butoxide/trimethyl carbinol-dioxane; Heating temperature: 50 °～55 ℃; Reaction times: 7-10 hour.Products therefrom is through washing volume ratio 1: 2, acetone-sherwood oil (60 °～90 ℃) recrystallization with chloroform.
3, require the synthetic method of 1 described phase-transfer catalyst according to patent, it is characterized in that the preparation method of phase-transfer catalyst I-III is: reactant consumption mol ratio: parent: the bromination alkyl oxide is 1: 1.0～1.2; Condensing agent is an Anhydrous potassium carbonate; In acetonitrile reflux 12-15 hour.Be chilled to room temperature after reaction finishes and filter, with chloroform washing, merging filtrate and chloroformic solution, evaporate to dryness, gained solids and neutral alumina dry mixed, weight ratio are 1: 8.0～10.0, with sherwood oil (60 °～90 ℃) extraction heat 16～20 hours, pressure reducing and steaming petroleum ether promptly obtained product.
4, require the prepared phase-transfer catalyst I-III of preparation method of 1～3 described phase-transfer catalyst according to patent, as the phase-transfer catalyst of nucleophilic substitution reaction, wherein excellent to halogen atom replacement(metathesis)reaction effect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198686103456A CN86103456A (en) | 1986-05-21 | 1986-05-21 | The synthetic method of phase transfer catalysts |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN198686103456A CN86103456A (en) | 1986-05-21 | 1986-05-21 | The synthetic method of phase transfer catalysts |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN86103456A true CN86103456A (en) | 1986-11-12 |
Family
ID=4802084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN198686103456A Pending CN86103456A (en) | 1986-05-21 | 1986-05-21 | The synthetic method of phase transfer catalysts |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN86103456A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7862632B2 (en) | 2006-12-12 | 2011-01-04 | East China University Of Science & Technology | Multi-burner gasification reactor for gasification of slurry or pulverized hydrocarbon feed materials and industry applications thereof |
| CN102167692A (en) * | 2011-03-03 | 2011-08-31 | 清华大学 | Synthesis method of alkyl-substituted benzocrown ether |
-
1986
- 1986-05-21 CN CN198686103456A patent/CN86103456A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7862632B2 (en) | 2006-12-12 | 2011-01-04 | East China University Of Science & Technology | Multi-burner gasification reactor for gasification of slurry or pulverized hydrocarbon feed materials and industry applications thereof |
| CN102167692A (en) * | 2011-03-03 | 2011-08-31 | 清华大学 | Synthesis method of alkyl-substituted benzocrown ether |
| CN102167692B (en) * | 2011-03-03 | 2014-01-01 | 清华大学 | Synthesis method of alkyl-substituted benzocrown ether |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Saa et al. | Palladium-catalyzed cross-coupling synthesis of hindered biaryls and terphenyls. Cocatalysis by copper (I) salts | |
| Dohle et al. | Copper-mediated cross-coupling of functionalized arylmagnesium reagents with functionalized alkyl and benzylic halides | |
| US6417357B1 (en) | Coupling reactions with palladium catalysts | |
| CN100569713C (en) | A kind of preparation method of biphenyl compound | |
| CN108774263B (en) | Synthesis method of allyl phosphine oxide compound | |
| CN109879731B (en) | Diaryl methane halogenated olefin derivative and preparation method thereof | |
| JPH06298731A (en) | Production of heterocyclic compound | |
| JP2004529956A (en) | Use of ionic compositions as replacement reagents, compositions comprising fluorinated reagents and methods of using the same | |
| CN115304518A (en) | Biocompatible zwitterionic compound and preparation method thereof | |
| CN86103456A (en) | The synthetic method of phase transfer catalysts | |
| CN110423217A (en) | A kind of preparation method of conjugated enynes compound | |
| Blum et al. | Kinetic resolution of racemic 2, 2′-bis (trifluoromethane-sulfonyloxy)-1, 1′-binaphthalene by chiral dimethylaluminum complexes and an achiral Pd catalyst, as well as by achiral dimethylaluminum reagents in the presence of a chiral Pd catalyst | |
| CN111170899B (en) | Synthesis method of N-diaryl methyl sulfonamide compound | |
| CN100569746C (en) | Two (perfluoroalkyl group sulfonyl) methane of aryl and metal-salt thereof, and preparation method thereof | |
| US4093667A (en) | Preparation of 4-n-hexylresorcinol | |
| CN101073779B (en) | Quaternary-ammonium poly-L-leucine catalyst, its production and use | |
| CN112321639A (en) | Preparation method of aryl diphenylphosphine derivative | |
| CN1296944A (en) | Process for producing malononitrile | |
| CN112876515B (en) | Triptycene carbene allyl palladium compound and application thereof | |
| Ochiai et al. | Synthesis and structure of 1-(diacetoxyiodo)-2, 4, 6-tri-tert-butylbenzene and its analogues | |
| CN109942361A (en) | A kind of preparation method and applications for the Sanya benzene-like compounds that aryl replaces | |
| CN110003062B (en) | N-phenyl-N-p-toluenesulfonyl difluoroacetamide and application thereof | |
| EP0350293B1 (en) | Process for preparing derivatives of 2'-deoxy-beta-cytidine and salts thereof | |
| CN114805017B (en) | Preparation method of 2-fluoro-1, 5-hexadiene compound | |
| JP2802706B2 (en) | Method for producing heterocyclic compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |