CN103087102B - Preparation method for (tertiary buty imino group)-tri-(pyrrolidine) phosphine - Google Patents
Preparation method for (tertiary buty imino group)-tri-(pyrrolidine) phosphine Download PDFInfo
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- CN103087102B CN103087102B CN201310029759.8A CN201310029759A CN103087102B CN 103087102 B CN103087102 B CN 103087102B CN 201310029759 A CN201310029759 A CN 201310029759A CN 103087102 B CN103087102 B CN 103087102B
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- YVRLPOFVTKRWSU-UHFFFAOYSA-N CC(C)(C)N=P(Cl)Cl Chemical compound CC(C)(C)N=P(Cl)Cl YVRLPOFVTKRWSU-UHFFFAOYSA-N 0.000 description 1
- DOYIDCGGIWIMFW-MRXNPFEDSA-N CCCCNP(NC[C@H](C)CC)(N[IH](C)(C)C)N(C)CCC Chemical compound CCCCNP(NC[C@H](C)CC)(N[IH](C)(C)C)N(C)CCC DOYIDCGGIWIMFW-MRXNPFEDSA-N 0.000 description 1
Abstract
The invention relates to a preparation method for (tertiary buty imino group)-tri-(pyrrolidine) phosphine. The preparation method comprises the following steps of: (a), enabling a compound chloride-tri-(pyrrolidine) phosphine hexafluorophosphate in the formula (I) and tert-butylamine to carry out substitution reaction in an organic solvent to prepare an intermediate in the formula (II), wherein the temperature of the substitution reaction is 10 DEG C to 70 DEG C and the reaction time is 10 hours to 24 hours; (b), enabling the intermediate in the formula (II) prepared in the step (a) to react with sodium methoxide in methanol to obtain the compound (tertiary buty imino group)-tri-(pyrrolidine) phosphine in the formula (III). The preparation method disclosed by the invention is low in cost, simple in process, strong in operability, high in safety, short in production period and high in product purity, so the preparation method is applicable to industrial production; and the reaction route is shown in the specification.
Description
Technical field
The present invention relates to chemical preparation field, relate more specifically to the preparation method of one (tertbutylimido) three (tetramethyleneimine) phosphine.
Background technology
(tertbutylimido) three (tetramethyleneimine) phosphine is a kind of highly basic, and be the chemical reagent having very important application in organic synthesis, its structural formula is:
At present, the method preparing (tertbutylimido) three (tetramethyleneimine) phosphine generally has the following two kinds:
(the Chemische Berichte such as Schwesinger, 1994,127,2435-2454) disclose the method that one prepares (tertbutylimido) three (tetramethyleneimine) phosphine, the method (tertbutylimido) dichloride phosphine and Pyrrolidine is reacted within 2 hours, to obtain two (diisopropylaminoethyl) (2-cyanoethoxy) phosphine, but there are some shortcomings in the method, mainly raw material dichloro (2-cyanoethoxy) phosphine is a kind of acyl chlorides, unstable, perishable, and be difficult to buy, be therefore unfavorable for suitability for industrialized production.
(the Tetrahedron such as Ekaterina V, 2011,67,5382-5388) report the method for another preparation (tertbutylimido) three (tetramethyleneimine) phosphine, the method three (tetramethyleneimine) phosphines and tertiary butyl azide reaction is obtained two (diisopropylaminoethyl) (2-cyanoethoxy) phosphine for 40 hours.But the main drawback of the method is the raw material tertiary butyl, and nitrine is more dangerous, uses inconvenience, and be difficult to buy, reaction conditions is harsher in addition, and the time is long, is therefore unfavorable for suitability for industrialized production.
Summary of the invention
For overcoming the problems referred to above of the prior art, the invention provides the preparation method of one (tertbutylimido) three (tetramethyleneimine) phosphine, the method cycle is short, and feedstock property is stablized, and cost is low and operability good.
The technical solution used in the present invention is: a kind of preparation method of (tertbutylimido) three (tetramethyleneimine) phosphine, comprises the following steps:
A () makes formula (1) compound phosphofluoric acid chlorination three (tetramethyleneimine) phosphine and TERTIARY BUTYL AMINE in organic solvent substitution reaction occur, the temperature of described substitution reaction is 10 DEG C ~ 70 DEG C, and the reaction times is 10-24 hour, obtained formula (2) intermediate;
B formula (2) intermediate obtained in step (a) reacts with sodium methylate by () in methyl alcohol, obtained formula (3) compound (tertbutylimido) three (tetramethyleneimine) phosphine,
Preferably, in step (a)., the temperature of substitution reaction is 30-50 DEG C.
More preferably, in step (a)., the temperature of substitution reaction is 40 DEG C.
Further, in step (a)., organic solvent is aprotic solvent.
Further, in step (a)., this non-protonic solvent is selected from methylene dichloride or tetrahydrofuran (THF) or chloroform or toluene, in use, re-uses after solvent is carried out drying.Herein, other similar organic solvents can also be used.
Preferably, in step (a)., the molar feed ratio of TERTIARY BUTYL AMINE and phosphofluoric acid chlorination three (tetramethyleneimine) phosphine is 3: 1, and react with this molar feed ratio, productive rate is higher, but the present invention is not limited to this.
Preferably, in step (b), the time of reaction is 2 hours.
Further, the preparation method of (tertbutylimido) provided by the present invention three (tetramethyleneimine) phosphine, specifically comprise the following steps: phosphofluoric acid chlorination three (tetramethyleneimine) phosphine is dissolved in dry methylene dichloride or tetrahydrofuran solvent, add TERTIARY BUTYL AMINE and obtain reaction system, make described reaction system back flow reaction 18 hours at 40 DEG C; Solvent evaporated, adds methyl alcohol and sodium methylate, back flow reaction 2 hours, suction filtration, evaporate to dryness obtains (tertbutylimido) three (tetramethyleneimine) phosphine.Reaction with this understanding, can obtain higher yield, but does not invent and be not limited to this.
Compared with prior art, the present invention has following advantages: the preparation method that the invention provides one (tertbutylimido) three (tetramethyleneimine) phosphine, substitution reaction is there is in organic solvent in it by making phosphofluoric acid chlorination three (tetramethyleneimine) phosphine and TERTIARY BUTYL AMINE, obtain intermediate product, then this intermediate product is obtained by reacting (tertbutylimido) three (tetramethyleneimine) phosphine again in methyl alcohol with sodium methylate.The method has the following advantages:
1, feedstock property is stablized, and easily buys;
2, reaction conditions is gentle, reaction time short (only needing 10-24 hour);
3, technique is simple, workable, security is good, is suitable for suitability for industrialized production.
Embodiment
In order to more clearly understand technology contents of the present invention, below in conjunction with specific embodiment, the present invention is described in further detail.
embodiment 1
6g phosphofluoric acid chlorination three (tetramethyleneimine) phosphine is added in there-necked flask, and 20ml methylene dichloride, be stirred to and dissolve completely, then add 4.4ml TERTIARY BUTYL AMINE, temperature is maintained 10 DEG C, react 18 hours; Solvent evaporated, adds 5ml methyl alcohol, 0.76g sodium methylate, continues reaction 2 hours, and cooling, suction filtration desalination, adds 20ml methylene dichloride, suction filtration desalination, and evaporate to dryness obtains colorless gel shape material 2.5g.Molar yield 56.3%.
31P-NMR(C
6D
6，400MHz)：δ＝8.87ppm。
embodiment 2
6g phosphofluoric acid chlorination three (tetramethyleneimine) phosphine is added in there-necked flask, and 20ml methylene dichloride, be stirred to and dissolve completely, then add 4.4ml TERTIARY BUTYL AMINE, back flow reaction 20 hours at 40 DEG C; Solvent evaporated, adds 5ml methyl alcohol, 0.76g sodium methylate, continues reaction 2 hours, and cooling, suction filtration desalination, adds 20ml methylene dichloride, suction filtration desalination, and evaporate to dryness obtains colorless gel shape material 3.1g.Molar yield 69.8%.
31P-NMR(C
6D
6，400MHz)：δ＝8.87ppm。
embodiment 3
In there-necked flask, add 6g phosphofluoric acid chlorination three (tetramethyleneimine) phosphine and 20ml tetrahydrofuran (THF), be stirred to and dissolve completely, then add 4.4ml TERTIARY BUTYL AMINE.Back flow reaction 17 hours at 65 DEG C.Solvent evaporated, adds 5ml methyl alcohol, 0.76g sodium methylate, continues reaction 2 hours, and cooling, suction filtration desalination, adds 20ml tetrahydrofuran (THF), suction filtration desalination, and evaporate to dryness obtains colorless gel shape material 2.7g.Molar yield 60.8%.
31P-NMR(C
6D
6，400MHz)：δ＝8.87ppm。
In sum, the synthetic method of (tertbutylimido) of the present invention three (tetramethyleneimine) phosphine is applicable to suitability for industrialized production, the standard in industrial production aspect can be met, and product purity and Environmental compatibility can be improved, improve operability, security and productive rate.
Above specific embodiment of the present invention is illustrated; but protection content of the present invention is not only limited to above embodiment; in art of the present invention, the usual knowledge of a GPRS, just can carry out diversified change within the scope of its technology main idea.
Claims (3)
1. the preparation method of a kind (tertbutylimido) three (tetramethyleneimine) phosphine, it is characterized in that, the method is: in there-necked flask, add 6g phosphofluoric acid chlorination three (tetramethyleneimine) phosphine, with 20ml methylene dichloride, be stirred to and dissolve completely, add 4.4ml TERTIARY BUTYL AMINE again, temperature is maintained 10 DEG C, react 18 hours; Solvent evaporated, adds 5ml methyl alcohol, 0.76g sodium methylate, continues reaction 2 hours, cooling, and suction filtration desalination, adds 20ml methylene dichloride, suction filtration desalination, and evaporate to dryness obtains colorless gel shape material 2.5g, molar yield 56.3%,
31p-NMR (C
6d
6, 400MHz): δ=8.87ppm,
2. the preparation method of a kind (tertbutylimido) three (tetramethyleneimine) phosphine, it is characterized in that, the method is: in there-necked flask, add 6g phosphofluoric acid chlorination three (tetramethyleneimine) phosphine, with 20ml methylene dichloride, be stirred to and dissolve completely, add 4.4ml TERTIARY BUTYL AMINE again, back flow reaction 20 hours at 40 DEG C; Solvent evaporated, adds 5ml methyl alcohol, 0.76g sodium methylate, continues reaction 2 hours, cooling, and suction filtration desalination, adds 20ml methylene dichloride, suction filtration desalination, and evaporate to dryness obtains colorless gel shape material 3.1g, molar yield 69.8%,
31p-NMR (C
6d
6, 400MHz): δ=8.87ppm,
3. the preparation method of a kind (tertbutylimido) three (tetramethyleneimine) phosphine, it is characterized in that, the method is: in there-necked flask, add 6g phosphofluoric acid chlorination three (tetramethyleneimine) phosphine and 20ml tetrahydrofuran (THF), be stirred to and dissolve completely, add 4.4ml TERTIARY BUTYL AMINE again, back flow reaction 17 hours at 65 DEG C; Solvent evaporated, adds 5ml methyl alcohol, 0.76g sodium methylate, continues reaction 2 hours, cooling, and suction filtration desalination, adds 20ml tetrahydrofuran (THF), suction filtration desalination, and evaporate to dryness obtains colorless gel shape material 2.7g, molar yield 60.8%,
31p-NMR (C
6d
6, 400MHz): δ=8.87ppm,
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Non-Patent Citations (3)
| Title |
|---|
| 1,3-Dimethyl-2-(3-nitro-1,2,4-triazol-1-yl)-2-pyrrolidin-1-yl-1,3,2-diazaphospholidinium hexafluorophosphate (MNTP): a powerful condensing reagent for phosphate and phosphonate esters;Natsuhisa Oka, et al.;《Tetrahedron》;20060228;第62卷;3667-3673 * |
| Design and Synthesis of Monomeric and Polymer-Bound Triaminoiminophosphorane Bases of Broadly Varied Steric Demand.《Chem. Ber.》.1994,第127卷2435-2454. * |
| Reinhard Schwesinger, et al..Novel, Very Strong, Uncharged Auxiliary Bases * |
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