JPH04134089A - Production of phosphazene compound - Google Patents
Production of phosphazene compoundInfo
- Publication number
- JPH04134089A JPH04134089A JP2255947A JP25594790A JPH04134089A JP H04134089 A JPH04134089 A JP H04134089A JP 2255947 A JP2255947 A JP 2255947A JP 25594790 A JP25594790 A JP 25594790A JP H04134089 A JPH04134089 A JP H04134089A
- Authority
- JP
- Japan
- Prior art keywords
- compound
- formula
- azide
- phosphazene
- group
- 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
- -1 phosphazene compound Chemical class 0.000 title claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003937 drug carrier Substances 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical group 0.000 abstract description 6
- 239000012567 medical material Substances 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 5
- 239000002904 solvent Substances 0.000 abstract description 5
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 abstract description 4
- 229930195733 hydrocarbon Natural products 0.000 abstract description 4
- SEDZOYHHAIAQIW-UHFFFAOYSA-N trimethylsilyl azide Chemical compound C[Si](C)(C)N=[N+]=[N-] SEDZOYHHAIAQIW-UHFFFAOYSA-N 0.000 abstract description 4
- RLMOMHNXIWBGTF-UHFFFAOYSA-N diaminophosphinoamine Chemical compound NP(N)N RLMOMHNXIWBGTF-UHFFFAOYSA-N 0.000 abstract description 3
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000034 method Methods 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 8
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 8
- 125000003277 amino group Chemical group 0.000 description 7
- 239000007858 starting material Substances 0.000 description 7
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 150000001540 azides Chemical class 0.000 description 4
- 125000000962 organic group Chemical group 0.000 description 4
- 125000004437 phosphorous atom Chemical group 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 238000005580 one pot reaction Methods 0.000 description 3
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229920002627 poly(phosphazenes) Polymers 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 125000003342 alkenyl group Chemical group 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 238000006068 polycondensation reaction Methods 0.000 description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VPJNXYDJNYCAGY-UHFFFAOYSA-N 1-azido-2,3-dimethylbenzene Chemical compound CC1=CC=CC(N=[N+]=[N-])=C1C VPJNXYDJNYCAGY-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZHPIBTRBRKNTPI-UHFFFAOYSA-N C(CC)[Si](C)(C)N=[N+]=[N-] Chemical compound C(CC)[Si](C)(C)N=[N+]=[N-] ZHPIBTRBRKNTPI-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- YFDVPJXDRWGVRO-UHFFFAOYSA-N N-diaminophosphanylmethanamine Chemical compound CNP(N)N YFDVPJXDRWGVRO-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- QTBUYFOMOYNJIN-UHFFFAOYSA-N azido(benzhydryl)silane Chemical compound C=1C=CC=CC=1C([SiH2]N=[N+]=[N-])C1=CC=CC=C1 QTBUYFOMOYNJIN-UHFFFAOYSA-N 0.000 description 1
- MEGROZMJHSAQKL-UHFFFAOYSA-N azido(triethyl)silane Chemical compound CC[Si](CC)(CC)N=[N+]=[N-] MEGROZMJHSAQKL-UHFFFAOYSA-N 0.000 description 1
- CUCDHIYTCSBMGZ-UHFFFAOYSA-N azido(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(N=[N+]=[N-])C1=CC=CC=C1 CUCDHIYTCSBMGZ-UHFFFAOYSA-N 0.000 description 1
- PJCCYXZYFYFZHB-UHFFFAOYSA-N azido(tripropyl)silane Chemical compound CCC[Si](CCC)(CCC)N=[N+]=[N-] PJCCYXZYFYFZHB-UHFFFAOYSA-N 0.000 description 1
- KAVMYSIPAJXDOK-UHFFFAOYSA-N azido-dimethyl-propan-2-ylsilane Chemical compound CC(C)[Si](C)(C)N=[N+]=[N-] KAVMYSIPAJXDOK-UHFFFAOYSA-N 0.000 description 1
- XOSCNMJNJPIXSS-UHFFFAOYSA-N azido-tert-butyl-dimethylsilane Chemical compound CC(C)(C)[Si](C)(C)N=[N+]=[N-] XOSCNMJNJPIXSS-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- XROJHNIYTPDFCQ-UHFFFAOYSA-N n-[bis(dimethylamino)-trimethylsilylimino-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(N(C)C)(N(C)C)=N[Si](C)(C)C XROJHNIYTPDFCQ-UHFFFAOYSA-N 0.000 description 1
- LIXGZTMJRCYCFX-UHFFFAOYSA-N n-bis(n-phenylanilino)phosphanyl-n-phenylaniline Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)P(N(C=1C=CC=CC=1)C=1C=CC=CC=1)N(C=1C=CC=CC=1)C1=CC=CC=C1 LIXGZTMJRCYCFX-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
Description
【発明の詳細な説明】
産業上の１加分国
本発明は、分離膜、薬物用担体、医療用材料等として有
用なアミノ基を含むホスファゼンポリマーを合成する際
の原料又は合成中間体として好適なホスファゼン化合物
の製造方法に関する。Detailed Description of the Invention The present invention is suitable as a raw material or synthetic intermediate for synthesizing phosphazene polymers containing amino groups useful as separation membranes, drug carriers, medical materials, etc. The present invention relates to a method for producing a phosphazene compound.
従来の技術及び発明が解決しようとする課題ポリオルガ
ノホスファゼンはＰ＝Ｎ構造を有する高分子物質であり
、燐原子に結合する有機基の種類によって様々な特性を
付与することができ、高機能材料として種々の用途が期
待されている。Prior Art and Problems to be Solved by the Invention Polyorganophosphazene is a polymer substance with a P=N structure, and can be given various properties depending on the type of organic group bonded to the phosphorus atom, making it a highly functional material. It is expected to have a variety of uses.
中でも燐原子にアミノ基が結合したホスファゼンポリマ
ーは、酸素選択透過性、生体適合性等の特性に優れ、分
離膜、薬物用担体、医療用材料等の機能材料として期待
される。Among them, phosphazene polymers in which an amino group is bonded to a phosphorus atom have excellent properties such as oxygen selective permeability and biocompatibility, and are expected to be used as functional materials for separation membranes, drug carriers, medical materials, etc.
ここで、従来、ポリホスファゼンを製造する方法として
は、ヘキサクロルシクロトリホスファゼンを開環重合さ
せてポリジクロロホスファゼンとした後、この化合物中
の塩素原子を種々の有機基で置換する方法が知られてい
る（米国特許第３．３７０，０２０号）。また、重縮合
反応によるポリホスファゼンの製造方法として、Ｎ−（
ジクロロホスホリル）トリクロロホスファゼンを重縮合
する方法（特表昭６２−５０１１４．４号公報）も提案
されている。Here, conventional methods for producing polyphosphazene include ring-opening polymerization of hexachlorocyclotriphosphazene to produce polydichlorophosphazene, and then substituting the chlorine atom in this compound with various organic groups. (U.S. Pat. No. 3,370,020). In addition, as a method for producing polyphosphazene by polycondensation reaction, N-(
A method of polycondensing dichlorophosphoryl)trichlorophosphazene (Japanese Patent Application Publication No. 1982-50114.4) has also been proposed.
しかし、ヘキサクロルシクロトリホスファゼンを開環重
合させる方法においては、ポリマー収率が６０％前後に
なると架橋反応が起こってゲル化してしまうため、重合
反応をポリマー収率が５０％程度となった時点で停止さ
せなければならず、また重合後ポリマー中の塩素原子を
種々の有機基で置換するのに手間がかかり、得られるポ
リマーが極めて高価なものになってしまう。更に、上記
置換反応においても完全に塩素原子を置換させるのは困
難であり、微量の残存塩素がポリマーの性能に影響を与
える場合があるという問題を有する。However, in the method of ring-opening polymerization of hexachlorocyclotriphosphazene, when the polymer yield reaches around 60%, a crosslinking reaction occurs and gelation occurs, so the polymerization reaction is stopped when the polymer yield reaches around 50%. Furthermore, it takes time and effort to replace the chlorine atoms in the polymer with various organic groups after polymerization, and the resulting polymer becomes extremely expensive. Furthermore, even in the above substitution reaction, it is difficult to completely replace chlorine atoms, and there is a problem that trace amounts of residual chlorine may affect the performance of the polymer.
また、Ｎ−（ジクロロホスホリル）トリクロロホスファ
ゼンを重縮合させる方法においては、ポリマー収率に関
しては改善されるものの残存塩素に関する問題点は解消
されていない。Further, in the method of polycondensing N-(dichlorophosphoryl)trichlorophosphazene, although the polymer yield is improved, the problem regarding residual chlorine is not solved.
このため、残存塩素の問題を生じることのないポリホス
ファゼンの製造方法として、ホスファゼン単量体である
Ｎ−１リメチルシリルホスフアゼンを重縮合させる方法
も提案されている（米国特許第４，４１２，０５３号）
。Therefore, as a method for producing polyphosphazene that does not cause the problem of residual chlorine, a method has been proposed in which N-1-limethylsilylphosphazene, which is a phosphazene monomer, is polycondensed (U.S. Pat. No. 4,412 , No. 053)
.
しかし、この製造方法においては、ポリマー収率及び残
存塩素の問題は改善し得るものの、重合原料の単量体で
あるホスファゼン化合物の製造工程が非常に複雑である
という問題点を有する。即ち、この方法においては、重
合原料のホスファゼン単量体であるＮ−トリメチルシリ
ルホスファゼンの製造は、ヘキサメチルシラザンをリチ
ウム塩とした後、三塩化リンを反応させてジシリルアミ
ノジクロロホスフィンとし、次いでこれにグリニヤール
試薬を作用させて塩素原子を有機基で置換し、次いで臭
素酸化してＰ−ブロモ−Ｎ−）−リメチルシリルオルガ
ノホスファゼンとし、更にこれをトリ・フルオロエトキ
シ化するという５段階もの反応工程からなる複雑な方法
によって行なわれており、工業的製法としては実用性に
欠けるものである。However, although this production method can improve the polymer yield and residual chlorine problems, it has a problem in that the process for producing the phosphazene compound, which is a monomer of the polymerization raw material, is extremely complicated. That is, in this method, N-trimethylsilylphosphazene, which is a phosphazene monomer as a polymerization raw material, is produced by converting hexamethylsilazane into a lithium salt, reacting it with phosphorus trichloride to form disilylaminodichlorophosphine, and then converting this into a lithium salt. This is a five-step reaction in which a Grignard reagent is applied to replace the chlorine atom with an organic group, followed by bromine oxidation to produce P-bromo-N-)-limethylsilylorganophosphazene, which is then trifluoroethoxylated. It is carried out by a complicated method consisting of steps, and it lacks practicality as an industrial manufacturing method.
本発明は、上記事情に鑑みなされたもので、ポリホスフ
ァゼン、更に詳しくは、分離膜、薬物用担体、医療用材
料等として有用なアミノ基を含むホスファゼンポリマー
に残存塩素の問題を生じることなく、しかも効率よく誘
導することができるホスファゼン化合物を容易に製造す
る方法を提供することを目的とする。The present invention has been made in view of the above circumstances, and more specifically, the present invention has been made in view of the above-mentioned circumstances. Moreover, it is an object of the present invention to provide a method for easily producing a phosphazene compound that can be efficiently induced.
を重ねた結果、下記一般式（Ｉ）
Ｔ？’
Ｒ゛
（但し、式中Ｒ１，Ｒ２，Ｒ３は互いに同−或いは異種
の無置換又は置換−価炭化水素基を示す）で表わされる
オルガノシリルアジド化合物と、下記一般式（ＩＩ）
（但し、式中Ｒ４〜Ｒ９は水素原子もしくは互いに同−
或いは異種の無置換又は置換−価炭化水素基を示す）
で表わされる亜リン酸トリアミド化合物とを反応させる
ことにより、単に加熱撹拌するだけで容易に１段階反応
で効率よく下記一般式（ＩＩＩ）＝６一
（但し、式中Ｒ１〜Ｒ９は前記と同様の意味を示す）
で表わされるＮ−シリル−ホスファゼン化合物を合成し
得ること、そしてＮ−シリル−ホスファゼン化合物を重
縮合することにより、分離膜、薬物用担体、医療用材料
等として有用な燐原子にアミノ基が結合したホスファゼ
ンポリマーを残留塩素の問題を全く生じることなく、製
造し得ることを見い出し、本発明を完成したものである
。As a result of overlapping, the following general formula (I) T? 'R'' (wherein R1, R2, R3 represent the same or different unsubstituted or substituted hydrocarbon groups) and the following general formula (II) (however, In the formula, R4 to R9 are hydrogen atoms or the same as each other.
or a different type of unsubstituted or substituted-valent hydrocarbon group), the following general formula (III) can be easily and efficiently produced by a one-step reaction simply by heating and stirring. =61 (wherein R1 to R9 have the same meanings as above) It is possible to synthesize the N-silyl-phosphazene compound represented by We have completed the present invention by discovering that phosphazene polymers in which amino groups are bonded to phosphorus atoms, which are useful as membranes, drug carriers, medical materials, etc., can be produced without any problem of residual chlorine.
従って、本発明は、一般式（Ｉ）で表わされるオルガノ
シリルアジド化合物と一般式（ＩＩ）で表わされる亜リ
ン酸トリアミド化合物とを反応させて、一般式（ＩＩＩ
）で表わされるＮ−シリル−ホスファゼン化合物を得る
ことを特徴とするホスファゼン化合物の製造方法を提供
する。Therefore, in the present invention, the organosilylazide compound represented by the general formula (I) and the phosphorous acid triamide compound represented by the general formula (II) are reacted, and the organosilylazide compound represented by the general formula (III) is
) provides a method for producing a phosphazene compound, which is characterized by obtaining an N-silyl-phosphazene compound represented by:
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明のオルガノホスファゼンの製造方法において、そ
の第１の出発原料であるオルガノシリルアジド化合物は
、上述したように下記一般式（Ｉ）％式％
ここで、上記式（Ｉ）中Ｒ１，Ｒ２，Ｒ３は、上記した
ように互いに同−或いは異種の無置換又は置換−価炭化
水素基であり、好ましくは炭素数１〜１０、特に１〜６
のものである。具体的にはメチル基、エチル基、プロピ
ル基、ブチル基等のアルキル基、ビニル基、アリル基等
のアルケニル基、シクロプロピル基、シクロペンチル基
、シクロヘキシル基等のシクロアルキル基、フェニル基
等のアリール基、ベンジル基等のアラルキル基、更にこ
れらの基の水素原子の一部又は全部をハロゲン原子で置
換したものなどが挙げられる。In the method for producing organophosphazene of the present invention, the organosilyl azide compound which is the first starting material has the following general formula (I) % formula % Here, in the above formula (I), R1, R2, As mentioned above, R3 is the same or different unsubstituted or substituted hydrocarbon group, preferably having 1 to 10 carbon atoms, especially 1 to 6 carbon atoms.
belongs to. Specifically, alkyl groups such as methyl group, ethyl group, propyl group, butyl group, alkenyl groups such as vinyl group and allyl group, cycloalkyl groups such as cyclopropyl group, cyclopentyl group, and cyclohexyl group, and aryl groups such as phenyl group. and aralkyl groups such as benzyl groups, as well as those in which some or all of the hydrogen atoms of these groups are replaced with halogen atoms.
このようなオルガノシリルアジド化合物としては、トリ
メチルシリルアジド、トリエチルシリルアジド、トリプ
ロピルシリルアジド、ジメチルプロピルシリルアジド、
ジメチルイソプロピルシリルアジド、ｔ−ブチルジメチ
ルシリルアジド、ジメチルオクチルシリルアジド、ジメ
チルオクタデシルシリルアジド、トリフェニルシリルア
ジド、ジメチルフェニルアジド、ベンジルジメチルフェ
ニルアジド、ジフェニルメチルシリルアジド、トリベン
ジルシリルアジド等が挙げられるが、特にトリメチルシ
リルアジドが好適である。なお、第１出発原料のオルガ
ノシリルアジド化合物は、これらに限定されるものでは
なく、上記一般式（Ｉ）で表わされるものであればいず
れのものでも使用可能である。Such organosilylazide compounds include trimethylsilyl azide, triethylsilyl azide, tripropylsilyl azide, dimethylpropylsilyl azide,
Examples include dimethylisopropylsilyl azide, t-butyldimethylsilyl azide, dimethyloctylsilyl azide, dimethyloctadecylsilyl azide, triphenylsilyl azide, dimethylphenyl azide, benzyldimethylphenyl azide, diphenylmethylsilyl azide, tribenzylsilyl azide, etc. , particularly trimethylsilyl azide. Note that the organosilylazide compound as the first starting material is not limited to these, and any compound represented by the above general formula (I) can be used.
一方、本発明製造方法の第２の出発原料である亜リン酸
トリアミド化合物は、下記一般式（ＩＩ）で表わされる
ものである。On the other hand, the phosphorous triamide compound, which is the second starting material for the production method of the present invention, is represented by the following general formula (II).
ここで、上記式（ＩＩ）中Ｒ４〜Ｒ９は水素原子或いは
アルキル基、アルケニル基、シクロアルキル基、アリー
ル基、アラルキル基などの無置換又は置換−価炭化水素
基であり、好ましくは炭素数１〜２０、特に１〜６のも
のである。Here, R4 to R9 in the above formula (II) are hydrogen atoms or unsubstituted or substituted-valent hydrocarbon groups such as alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and preferably have 1 carbon number. ~20, especially those from 1 to 6.
このような亜リン酸トリアミド化合物としては、亜リン
酸トリアミド、Ｎ−メチル亜リン酸トリアミド、Ｎ、Ｎ
’−ジメチル亜リン酸トリアミド、Ｎ、Ｎ、Ｎ’、Ｎ”
−テトラメチル亜リン酸トリアミド、ヘキサメチル亜リ
ン酸１−リアミド、ヘキサエチル亜リン酸トリアミド、
Ｎ、Ｎ’、Ｎ”−トリフェニル亜リン酸トリアミド、ヘ
キサフェニル亜リン酸トリアミド等を例示することがで
きるが、この第２出発原料の亜リン酸トリアミド化合物
は、これらに限定されるものではなく、上記（ＩＩ）式
で示されるものであればいずれのものも使用可能である
。Such phosphorous triamide compounds include phosphorous triamide, N-methyl phosphorous triamide, N,N
'-Dimethylphosphite triamide, N, N, N', N"
-tetramethylphosphite triamide, hexamethylphosphite 1-lyamide, hexaethylphosphite triamide,
Examples include N,N',N"-triphenyl phosphite triamide, hexaphenyl phosphite triamide, etc., but the phosphite triamide compound as the second starting material is not limited to these. However, any compound represented by the above formula (II) can be used.
本発明のホスファゼン化合物の製造方法は、上記第１出
発原料のオルガノシリルアジド化合物と第２出発原料の
亜リン酸トリアミド化合物とを反応させるもので、これ
により下記一般式（Ｉｌｌ）（但し、式中Ｒ１〜Ｒ９は
前記と同様の意味を示す）
で示されるＮ−シリル−ホスファゼン化合物が一段階反
応で得られる。The method for producing a phosphazene compound of the present invention involves reacting the organosilyl azide compound as the first starting material with the phosphorous triamide compound as the second starting material, whereby the following general formula (Ill) (however, the formula The N-silyl-phosphazene compound represented by (wherein R1 to R9 have the same meanings as above) is obtained by a one-step reaction.
ここで、上記反応において、亜すン酸トリアミド化合物
は、オルガノシリルアジド化合物１モルに対して０．８
〜１．２モルの範囲で用いることができるが、本質的に
は両者を等モルずつ用いることが好ましい。Here, in the above reaction, the amount of the sulfite triamide compound is 0.8 per mole of the organosilylazide compound.
Although it can be used in a range of 1.2 to 1.2 moles, it is essentially preferable to use equal moles of both.
この反応は無溶媒下に行なっても、適宜溶媒を用いて行
なってもよい。この場合、反応溶媒としては、ジエチル
エーテル、テトラヒドロフラン、ジオキサン、ベンゼン
、トルエン、キシレン、ジメチルホルムアミド、ジメチ
ルアセトアミド、Ｎ−メチルピロリドン、ヘキサメチル
ホスファミド等が好適に用いられる。また、反応条件は
室温から２００ °Ｃまでの温度において、３０分〜１
０時間反応させる条件が好適に採用される。This reaction may be carried out without a solvent or may be carried out using an appropriate solvent. In this case, diethyl ether, tetrahydrofuran, dioxane, benzene, toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, hexamethylphosphamide, etc. are preferably used as the reaction solvent. The reaction conditions were from room temperature to 200 °C for 30 minutes to 1 hour.
Conditions for reacting for 0 hours are preferably employed.
なお、反応の進行状況は、経時的に２１００ｃｍ−’付
近のアジドの赤外線吸収スペクトルの強度を追跡するこ
とによって容易に検知することができる。Note that the progress of the reaction can be easily detected by tracking the intensity of the infrared absorption spectrum of azide around 2100 cm-' over time.
即ち、上記反応を赤外線吸収スペクトルの強度を追跡す
ることによってモニターすると、２１０ＯＣＩＴｌ付近
のアジドの吸収が反応の進行に伴なって次第に減少し、
消失するので、このアジドの赤外線吸収の減少及び消失
を検知することにより、反応の進行状況及び終了を知る
ことができるものである。That is, when the above reaction was monitored by tracking the intensity of the infrared absorption spectrum, the absorption of azide near 210OCITl gradually decreased as the reaction progressed.
The progress and completion of the reaction can be determined by detecting the decrease in infrared absorption and disappearance of the azide.
本発明の製造方法により得られる上記式（ＩＩＩ）のホ
スファゼン化合物は、そのまま又はフェノキシ基、２，
２．２−１−リフルオロエトキシ基、トシル基等のより
脱離し易い脱離基を導入して１５０〜３００°Ｃの温度
で加熱する等の簡易な方法により重縮合し、効率よく分
離膜、薬物用担体、医療用材料等の機能材料として好適
な塩素原子を全く含まないアミノ基含有ホスファゼンポ
リマーを生成する。この場合、本発明の製造方法により
重合原料のホスファゼン化合物を得る際、第２出発原料
の亜すン酸トリアミド化合物の官能基Ｒ４〜Ｒ９を適宜
選定することにより、得られるホスファゼン化合物の燐
原子に結合するアミノ基の置換基を種々選択することが
でき、この化合物を上記のように重合することにより所
望の構造のホスファゼンポリマーを得ることができる。The phosphazene compound of the above formula (III) obtained by the production method of the present invention can be used as it is or with a phenoxy group, 2,
2.2-2-Efficient separation membranes can be formed by polycondensation using a simple method such as introducing a leaving group that is easier to leave, such as a 1-lifluoroethoxy group or a tosyl group, and heating at a temperature of 150 to 300°C. This method produces an amino group-containing phosphazene polymer that does not contain any chlorine atoms and is suitable as a functional material for drug carriers, medical materials, and the like. In this case, when obtaining the phosphazene compound as a polymerization raw material by the production method of the present invention, by appropriately selecting the functional groups R4 to R9 of the sulfite triamide compound as the second starting material, the phosphorus atom of the obtained phosphazene compound can be Various substituents for the amino group to be bonded can be selected, and a phosphazene polymer having a desired structure can be obtained by polymerizing this compound as described above.
芳凱匁Ｕ
本発明のホスファゼン化合物の製造方法によれば、簡易
な操作で分離膜、薬物用担体、医療用材料等の機能材料
として好適なアミノ基含有ホスファゼンポリマーに残留
塩素の問題を全く生じることなく誘導することができる
アミノ基を含有するホスファゼン化合物を１段階反応で
簡単かつ確実に得ることがとできる。According to the method for producing a phosphazene compound of the present invention, there is no problem of residual chlorine in the amino group-containing phosphazene polymer, which is suitable as a functional material for separation membranes, drug carriers, medical materials, etc., with a simple operation. A phosphazene compound containing an amino group that can be derived without derivatization can be easily and reliably obtained in a one-step reaction.
以下、実施例を示し、本発明を具体的に説明するが、本
発明は下記実施例に制限されるものではない。EXAMPLES Hereinafter, the present invention will be specifically explained with reference to Examples, but the present invention is not limited to the following Examples.
〔実施例１〕
ヘキサメチル亜リン酸トリアミド１６．３ｇを３ Ｑ
ｎ＋Ｑのトルエンに溶解し、これに１〜リメチルシリＪ
レアシト１１．５ｇを２０１１１９の１〜ルエンにｉ容
解した溶液に加えて撹拌下に加熱還流し、両者を反応さ
せた。この場合、反応混合物の赤外線吸収スペクトルを
経時的に測定してトリメチルシリルアジドのアジド基に
よる２１４０ｃｍ−１の吸収強度の変化を観測し、この
吸収強度が十分に減少した時点を反応終了点とした。こ
の反応は初めの３０分間に激しい発泡が見られ、約３時
間でアジド基に起因する２１４０ｃｍ−’の吸収は殆ん
ど消失した。[Example 1] 16.3 g of hexamethylphosphite triamide was added to 3 Q
Dissolve n+Q in toluene and add 1 to
A solution of 11.5 g of 201119 dissolved in toluene was added to the solution and heated to reflux with stirring to cause the two to react. In this case, the infrared absorption spectrum of the reaction mixture was measured over time to observe the change in the absorption intensity at 2140 cm-1 due to the azide group of trimethylsilyl azide, and the point at which this absorption intensity decreased sufficiently was defined as the end point of the reaction. In this reaction, intense foaming was observed during the first 30 minutes, and the absorption at 2140 cm-' due to the azide group almost disappeared in about 3 hours.
反応終了後、減圧下に溶媒を留去してから減圧蒸留する
ことにより、沸点６５℃７２ｍｍ）ＩｇのＰトリス（ジ
メチルアミノ）−Ｎ−トリメチルシリルホスファゼン１
５．１ｇを得た。After the reaction is completed, the solvent is distilled off under reduced pressure and then distilled under reduced pressure to obtain Ptris(dimethylamino)-N-trimethylsilylphosphazene 1 of Ig (boiling point: 65°C, 72mm).
5.1 g was obtained.
〔実施例２〕
亜リン酸トリアミド化合物としてヘキサエチル亜リン酸
トリアミド２４．７ｇを用いた以外は実施例１と同様に
して沸点８２〜８５°（：、 ／ １ ｎｕｎＨｇのＰ
−１−リス（ジエチルアミノ）−Ｎ−トリメチルシリル
−ホスファゼン２１．７ｇを得た。[Example 2] The same procedure as in Example 1 was carried out except that 24.7 g of hexaethyl phosphite triamide was used as the phosphite triamide compound.
21.7 g of -1-lis(diethylamino)-N-trimethylsilyl-phosphazene was obtained.
〔実施例３〕
亜リン酸トリアミド化合物としてヘキサフェニル亜リン
酸トリアミド３０．７ｇを用いた以外は実施例１と同様
にして反応捲行なった後、溶媒等を減圧下に留去してＰ
−１−リス（ジフェニルアミノ）−Ｎ−１−リスチル
シリルーホスファゼン２６．６ｇを得た。[Example 3] The reaction was carried out in the same manner as in Example 1 except that 30.7 g of hexaphenyl phosphorous triamide was used as the phosphorous triamide compound, and then the solvent etc. were distilled off under reduced pressure to obtain P.
26.6 g of -1-lith(diphenylamino)-N-1-listylsilylphosphazene was obtained.
出願人 信越化学工業 株式会社 代理人 弁理士 小 島 隆 司Applicant: Shin-Etsu Chemical Co., Ltd. Agent: Patent Attorney Takashi Kojima
Claims (1)
は異種の無置換又は置換一価炭化水素基を示す）で表わ
されるオルガノシリルアジド化合物と、下記一般式（I
I） ▲数式、化学式、表等があります▼・・・（II） （但し、式中Ｒ＾４〜Ｒ＾９は水素原子もしくは互いに
同一或いは異種の無置換又は置換一価炭化水素基を示す
） で表わされる亜リン酸トリアミド化合物とを反応させる
ことにより、下記一般式（III） ▲数式、化学式、表等があります▼・・・（III） （但し、式中Ｒ＾１〜Ｒ＾９は前記と同様の意味を示す
） で表わされるＮ−シリル−ホスファゼン化合物を得るこ
とを特徴とするホスファゼン化合物の製造方法。[Claims] 1. The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(I) (However, in the formula, R^1, R^2, R^3 are the same as each other or An organosilyl azide compound represented by the following general formula (I
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(II) (However, in the formula, R^4 to R^9 represent hydrogen atoms or unsubstituted or substituted monovalent hydrocarbon groups that are the same or different from each other. ) By reacting with the phosphorous triamide compound represented by the following general formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼... (III) (However, R^1 to R^9 in the formula has the same meaning as above) A method for producing a phosphazene compound, which comprises obtaining an N-silyl-phosphazene compound represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255947A JPH04134089A (en) | 1990-09-26 | 1990-09-26 | Production of phosphazene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2255947A JPH04134089A (en) | 1990-09-26 | 1990-09-26 | Production of phosphazene compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04134089A true JPH04134089A (en) | 1992-05-07 |
Family
ID=17285792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2255947A Pending JPH04134089A (en) | 1990-09-26 | 1990-09-26 | Production of phosphazene compound |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04134089A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008513593A (en) * | 2004-09-23 | 2008-05-01 | イギリス国 | New energy polyphosphazene |
| WO2015052859A1 (en) * | 2013-10-10 | 2015-04-16 | 信越化学工業株式会社 | Room temperature curing resin composition |
-
1990
- 1990-09-26 JP JP2255947A patent/JPH04134089A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008513593A (en) * | 2004-09-23 | 2008-05-01 | イギリス国 | New energy polyphosphazene |
| WO2015052859A1 (en) * | 2013-10-10 | 2015-04-16 | 信越化学工業株式会社 | Room temperature curing resin composition |
| US9434817B2 (en) | 2013-10-10 | 2016-09-06 | Shin-Etsu Chemical Co., Ltd. | Room-temperature-curable resin composition |
| JPWO2015052859A1 (en) * | 2013-10-10 | 2017-03-09 | 信越化学工業株式会社 | Room temperature curable resin composition |
| EP3056546A4 (en) * | 2013-10-10 | 2017-06-21 | Shin-Etsu Chemical Co., Ltd. | Room temperature curing resin composition |
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