JPH03261789A - Production of silylamine - Google Patents
Production of silylamineInfo
- Publication number
- JPH03261789A JPH03261789A JP5814990A JP5814990A JPH03261789A JP H03261789 A JPH03261789 A JP H03261789A JP 5814990 A JP5814990 A JP 5814990A JP 5814990 A JP5814990 A JP 5814990A JP H03261789 A JPH03261789 A JP H03261789A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- halide
- expressed
- hydrosilane
- 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
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 title claims description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000004820 halides Chemical class 0.000 claims abstract description 12
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 10
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000003118 aryl group Chemical group 0.000 claims abstract description 7
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 7
- 125000000524 functional group Chemical group 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- -1 amine compound Chemical class 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 4
- 229910019891 RuCl3 Inorganic materials 0.000 abstract description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 abstract description 3
- 150000001298 alcohols Chemical class 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- RXZBMPWDPOLZGW-XMRMVWPWSA-N (E)-roxithromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=N/OCOCCOC)/[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 RXZBMPWDPOLZGW-XMRMVWPWSA-N 0.000 abstract 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 abstract 1
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 238000002955 isolation Methods 0.000 abstract 1
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 abstract 1
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WPWHSFAFEBZWBB-UHFFFAOYSA-N 1-butyl radical Chemical compound [CH2]CCC WPWHSFAFEBZWBB-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KZOWNALBTMILAP-JBMRGDGGSA-N ancitabine hydrochloride Chemical compound Cl.N=C1C=CN2[C@@H]3O[C@H](CO)[C@@H](O)[C@@H]3OC2=N1 KZOWNALBTMILAP-JBMRGDGGSA-N 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- UITYJPORVGLJRW-UHFFFAOYSA-N n-[tert-butyl(dimethyl)silyl]aniline Chemical compound CC(C)(C)[Si](C)(C)NC1=CC=CC=C1 UITYJPORVGLJRW-UHFFFAOYSA-N 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- ILMRJRBKQSSXGY-UHFFFAOYSA-N tert-butyl(dimethyl)silicon Chemical compound C[Si](C)C(C)(C)C ILMRJRBKQSSXGY-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Abstract
Description
【発明の詳細な説明】
産業上のｉｌｌ用分野
本発明はシリルアミンの製造方法に関する。更に詳しく
は、本発明は、一般式Ｒ’ Ｎ Ｈ＊で表されるアミン
化合物と、一般式）（ＳｉＲ”Ｒ３Ｒ’で表されるヒド
ロシランから一般式
ＲＩＮＨ３ｉＲ”Ｒ”Ｒ’で表されるシリルアミンを製
造する方法に関する（ただしＲ１、Ｒｔ。DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for producing silylamines. More specifically, the present invention relates to an amine compound represented by the general formula R'N H* and a silylamine represented by the general formula RINH3iR"R"R' from a hydrosilane represented by the general formula) (However, R1, Rt.
Ｈｓ％Ｒ′はアルキル基、アルケニル基またはアリール
基であって、Ｃ０ＯＨ，Ｃ１，０Ｈ１ＣＯＯＲなどの官
能基を含んでいても良い、）。Hs%R' is an alkyl group, an alkenyl group, or an aryl group, and may contain functional groups such as COOH, C1, 0H1COOR, etc.).
従来の技術
シリルアミンは、アミンの保護化合物またはアルコール
などのシリル化剤として多用されている。BACKGROUND OF THE INVENTION Silylamines are frequently used as protecting compounds for amines or silylating agents such as alcohols.
アミノシランの最も一般的な方法は、アミンとクロロシ
ランを反応させる方法であり、例えば、Ｊ、 Ａｔ Ｃ
ｈｅｗ、 Ｓｏｃ、＋ コ！、４．５６９９ （１９
５２’）に記載されている。The most common method for producing aminosilanes is to react amines with chlorosilanes, for example, J, AtC
hew, Soc, + Ko! , 4.5699 (19
52').
２ （ＣＨ３） ５ｓｉｃｌ ＋４ Ｒ’ＮＨｚ＝
２ Ｒ’ＮＨ３Ｃｌ ＋２ （ＣＨｓ） ５ｓｉＮＨ
Ｒ’但しＲｈはアルキル基である。2 (CH3) 5sicl +4 R'NHz=
2 R'NH3Cl +2 (CHs) 5siNH
R' However, Rh is an alkyl group.
しかしこの方法には■加水分解され易く不安定なりロロ
シランを用いる、■煩雑な分離操作を必要とする、■プ
ロセスの腐食がある、などの問題がある。一方、本発明
にかかるヒドロシランとアミンとの反応にかかわる報告
は極めて少なく、例えば、アルカリ金属の水素化物、Ｒ
ｈＣｌ （ＰＣＪｓ） ｓ−に雪（ＩｒＣ１ａ ） 、
ＷＯＣｌａ 、Ｃｏｔ（ＣＯ）＊、Ｒｈ４（ＣＯ）＋ｚ
、Ｐｄ／Ｃを触媒にもちいる方法が提案されている（Ｂ
ｕｌｌ、 Ｃｈｅｗ、 Ｓｏｃ、 Ｊｐｎ、、 ｇ、
２１１１ （１９８９）、；Ｚｈ、 ０ｂｓｈｃｈ、
Ｋｈｉｍ、、 ４５４ （１０）、 ２２５７ （
１９７８）、；Ｊ、 Ｏｒｇａｎｏｓ＋ｅｔ、 Ｃｈｅ
ｍ、４１＋ １４２ （１９７７）、； Ｈｅ１ｖ。However, this method has problems such as: (1) it uses rolosilane, which is easily hydrolyzed and unstable, (2) it requires complicated separation operations, and (2) there is corrosion in the process. On the other hand, there are very few reports regarding the reaction between hydrosilane and amine according to the present invention.
hCl (PCJs) s- to snow (IrC1a),
WOCla, Cot(CO)*, Rh4(CO)+z
, a method using Pd/C as a catalyst has been proposed (B
ull, Chew, Soc, Jpn,, g,
2111 (1989); Zh, 0bshch,
Khim, 454 (10), 2257 (
1978);J, Organos+et, Che
m, 41+142 (1977); He1v.
Ｃｈｉｎ、 ＾ｃｔａ、、、Ｌｌ （４）＋ １
４０８ （１９６６）、 ）。Chin, ^cta,,,Ll (4)+1
408 (1966), ).
しかしこれらの方法は目的とするシリルアミンの収率が
低く、未だ不十分である。However, these methods have low yields of the desired silylamine and are still insufficient.
発明が解決しようとする課題
本発明の目的は、ヒドロシランを原料とするシリルアミ
ンの工業的製造方法を提供することにある。Problems to be Solved by the Invention An object of the present invention is to provide an industrial method for producing silylamine using hydrosilane as a raw material.
課題を解決するための手段
本発明者らは、上記課題を達成するために鋭意検討した
結果、アミン化合物とヒドロシランとを特定の触媒の存
在下に反応させることによって収率良くシリルアミンが
生成することを見出し、本発明を完成させるに至った。Means for Solving the Problems As a result of intensive studies to achieve the above problems, the present inventors have discovered that silylamine can be produced in good yield by reacting an amine compound and hydrosilane in the presence of a specific catalyst. They discovered this and completed the present invention.
すなわち、本発明は、
一般式Ｒ’ＮＨｚ （ただしＲ’はアルキル基、アルケ
ニル基またはアリール基であって、Ｃ０ＯＨ，Ｃｊ！、
○Ｈ、ＣＯＯＲなどの官能基を含んでいても良い、）で
表されるアミン化合物と、一般式Ｈ３ｉＲ”Ｒ’Ｒ’
（ただしＲ１，Ｒ３、Ｒ４はアルキル基、アルケニル基
または了り−ル基であって、Ｃ０ＯＨ，Ｃｆ、ＯＨ、Ｃ
ＯＯＲなどの官能基を含んでいても良い、）で表される
ヒドロシランとを、Ｒｕおよび／またはＲｈのハロゲン
化物と一般式Ｐ （Ｒ’） ｚ （Ｒ’はアルキル基、
アルケニル基またはアリール基である。）で表されるホ
スフィンの存在下に反応させることを特徴とする一般式
Ｒ１ＮＨＳｉＲ２Ｒ’Ｒ’ｉ”表されるシリルアミンの
製造方法である。That is, the present invention is based on the general formula R'NHz (where R' is an alkyl group, an alkenyl group, or an aryl group, and C0OH, Cj!,
○An amine compound represented by (which may contain a functional group such as H or COOR) and the general formula H3iR"R'R'
(However, R1, R3, and R4 are an alkyl group, an alkenyl group, or an atomyl group, and are C0OH, Cf, OH, C
), which may contain a functional group such as OOR, and a halide of Ru and/or Rh with the general formula P (R') z (R' is an alkyl group,
It is an alkenyl group or an aryl group. ) is a method for producing a silylamine represented by the general formula R1NHSiR2R'R'i'', which is characterized by carrying out the reaction in the presence of a phosphine represented by the following formula.
本発明の反応式は以下のとおりである。The reaction formula of the present invention is as follows.
Ｒ’ＮＨ１＋Ｈ３ｉＲ冨Ｒ１Ｒ４ 以下、本発明を更に詳細に説明する。R’NH1+H3iRtomiR1R4 The present invention will be explained in more detail below.
本発明に用いられるアミン化合物として以下のものが例
示される。The following are exemplified as the amine compounds used in the present invention.
ＣＨ，ＮＨ，、Ｃ５ＨｙＮＨｚ 、 Ｃ５ＨｙＮＨｚ 、ｔ −Ｃ５ＨｙＮＨｚ 。CH, NH,, C5HyNHz, C5HyNHz, t-C5HyNHz.
ｎ −Ｃｓ Ｈｒ ｔ Ｎ Ｈｔ 、ＣＨｚ ＝ ＣＨ
−Ｎ Ｈｔ 、ＣＨｘ−ＣＨ−ＣＨｘＮＨｇ 、
本発明に用いられるヒドロシランとして以下のものが例
示される。n −Cs Hr t N Ht , CHz = CH
-NHt, CHx-CH-CHxNHg The following are exemplified as hydrosilanes used in the present invention.
ＨＳｉ（ＣＨｓｈ 、ＨＳｉ（Ｃｚ）ｉｓ）ｚ、ＨＳｉ
（Ｃ１Ｈｔ）ｓ 、ＨＳｉ（ｔ−Ｃ４Ｈ９）ｚ、ＨＳｉ
（ＣＨｚ）ｚ（ｔ−ＣａＨ，）、Ｈ５ｉ（ＣＲ２）（Ｃ
Ｈ＝ＣＨｚ）ｚ、Ｈ５ｉＣＣＨ＝ＣＨｔ）ｓ、
これら原料の仕込み組成比は特に限定されるものではな
く、反応様式によって任意に変化されうる。HSi(CHsh, HSi(Cz)is)z, HSi
(C1Ht)s, HSi(t-C4H9)z, HSi
(CHz)z(t-CaH,), H5i(CR2)(C
H=CHz)z, H5iCCH=CHt)s, The compositional ratio of these raw materials is not particularly limited and can be arbitrarily changed depending on the reaction mode.
好ましい仕込み組成比（アミン化合物／ヒドロシラン）
は０．５〜２（モル比）である。また、原料として必要
に応して各々２種類以上を同時に用いることができる。Preferred charging composition ratio (amine compound/hydrosilane)
is 0.5 to 2 (molar ratio). Moreover, two or more types of each can be used simultaneously as raw materials if necessary.
本発明において用いられるＲｕのハロゲン化物はＲｕ
Ｆ ｘ、ＲｕＣ１ｚ、ＲｕＢｒｘ、Ｒｕ１３などである
３本発明において用いられるＲｈのハロゲン化物はＲｈ
Ｆ３、Ｒｈ Ｃｌ ｓ、ＲｈＢｒｘ、Ｒｈｌ！などであ
る。これらの中でＲｕＣｌ３、ＲｈＣｌ、が特に好まし
い。The Ru halide used in the present invention is Ru
The three Rh halides used in the present invention, such as F x, RuC1z, RuBrx, and Ru13, are Rh
F3, RhCl s, RhBrx, Rhl! etc. Among these, RuCl3 and RhCl are particularly preferred.
本発明において用いられるホスフィンとして、Ｐ （Ｃ
Ｈｚ）ｚ 、Ｐ （ＣｚＨｓ）ｉ、Ｐ （ｔ−ＣａＨＪ
ｓ、 Ｐ （ｃｙｃｌｏ−Ｃ，Ｈ，）ｓ、Ｐ （ＣＨｚ
ＣＨ’ＣＨｚ）ｓ、
Ｐ （ＣＨ３）（Ｃ４Ｈ９）ｚ 、Ｐ （ＣｈＨ５）３
などが例示される。As the phosphine used in the present invention, P (C
Hz)z, P (CzHs)i, P (t-CaHJ
s, P (cyclo-C,H,)s, P (CHz
CH'CHz)s, P (CH3)(C4H9)z, P (ChH5)3
Examples include.
本発明においてＲｕのハロゲン化物またはＲｈのハロゲ
ン化物をそれぞれ２１１類以上用いることができ・る。In the present invention, 211 or more Ru halides or Rh halides can be used.
ホスフィンも同様に２種類以上用いることができる。Similarly, two or more types of phosphine can be used.
これらの触媒の使用量は原料のヒドロシランに対して０
．００１〜ｌＯ倍モル、好ましくは０．０１〜０．５倍
モルである。Ｒｕのハロゲン化物またはＲｈのハロゲン
化物に対するホスフィンの使用量は０．０１〜１００倍
モル、好ましくは０．１〜１０倍モルである。これらの
範囲を越えて多く用いることは副生酸物も多くなりかつ
経済的でない。これらの範囲より少ないと触媒作用が不
充分でシリルア多ンの収率が低い。The amount of these catalysts used is 0 based on the raw material hydrosilane.
．． 001 to 10 times the mole, preferably 0.01 to 0.5 times the mole. The amount of phosphine used is 0.01 to 100 times the mole of Ru halide or Rh halide, preferably 0.1 to 10 times mole. Using more than these ranges results in a large amount of by-product acids and is not economical. If the amount is less than these ranges, the catalytic action will be insufficient and the yield of silylapolymer will be low.
反応様式に特に朝駆はなく、液相、気相のいずれでも行
いうる。液相で行う場合には溶媒としてベンゼン、トル
エン、キシレン、ヘプタン、ヘキサン、エーテル、テト
ラヒドロフラン、ジオキサンなどの炭化水素が用いられ
る。There is no particular reaction mode, and the reaction can be carried out in either liquid phase or gas phase. When conducting in a liquid phase, hydrocarbons such as benzene, toluene, xylene, heptane, hexane, ether, tetrahydrofuran, and dioxane are used as solvents.
反応温度は０〜３００℃、好ましくは５０〜２００℃の
範囲である。The reaction temperature ranges from 0 to 300°C, preferably from 50 to 200°C.
反応後通常蒸留によって生成物を分離する。After the reaction, the product is usually separated by distillation.
実施例 以下の実施例により本発明を具体的に説明する。Example The present invention will be specifically explained by the following examples.
実施例１
５０−ステンレス製オートクレーブにヘンシルアミン（
３，１）＋５ｏｌ） 、ｔ−ブチルジメチルシラン （
３，：３−ｍｏｌ） 、 ＲｕＣｌ３ （０，１ｍｍ
ｏｌ） 、Ｐ （ｔ−Ｃ４ＨＪｓ （０，３ｍｓ＋
ｏｌ） 、ベンゼン（３，Ｏｍｍｏｌ）を入れ、Ａｒ下
で１２０°Ｃにて６時間反応させた０反応生成物は減圧
蒸留により単離し、 ’Ｈ−ＮＭＲ，”Ｃ−ＮＭＲｌＩ
Ｒ。Example 1 50-Hensylamine (
3,1)+5ol), t-butyldimethylsilane (
3,:3-mol), RuCl3 (0,1 mm
ol), P (t-C4HJs (0,3ms+
ol), benzene (3, Ommol) and reacted at 120 °C for 6 hours under Ar. The reaction product was isolated by vacuum distillation, 'H-NMR, "C-NMRlI
R.
ＱＣ−ＭＳにより同定を行い、ＧＣにより定量した。Identification was performed by QC-MS and quantification was performed by GC.
ベンジルアミンの転化率は９３モル％で、主生成物はＮ
−（ｔ−ブチルジメチルシリル）ベンジルアミン
（ＣｉＨｓＣＨｚＮＨＳｉ（ＣＨｓ）ｚ （ｔ−Ｃ４
Ｈ９））（収率８４モル％）であった。The conversion rate of benzylamine was 93 mol%, and the main product was N.
-(t-butyldimethylsilyl)benzylamine (CiHsCHzNHSi(CHs)z (t-C4
H9)) (yield 84 mol%).
この場合副生酸物としてジベンジルアミンが認められた
。In this case, dibenzylamine was observed as a by-product acid.
実施例２〜５
実施例１においてＲｕＣ１１／ Ｐ （ｔ−ＣａＨｑ）
ｓＲｕＣＩｓ ／Ｐ （ＣｔＨＪｓ 、ＲｕＣ１ｚ
／ Ｐ （ｃｙｃｌｏ−ＣａＨ＋＋）３、ＲｈＣ
ｌ３ ／Ｐ （ｔ−ｃａＨ＊）ｉ 、ＲｈＣｌ１
／Ｐ （ＣｌＨ５）３を用いた以外は実施例１と同様
番こ実験を行った。Examples 2 to 5 In Example 1, RuC11/P (t-CaHq)
sRuCIs /P (CtHJs, RuC1z
/P (cyclo-CaH++)3, RhC
l3 /P (t-caH*)i, RhCl1
An experiment was conducted in the same manner as in Example 1 except that /P (ClH5)3 was used.
結果を第１表に示す。The results are shown in Table 1.
比較例１〜５
実施例１においてＲｕＣ１１／ Ｐ （ｔ−ＣｎＨｑ）
３のかわりにそれぞれ
ＲｕＣ１：＋、ＲｕＣ１ｚ ＣＰ （Ｃ４Ｈ６）ｌ ）
、ＲｈＣｘｚ、ＲｈＣｌ （Ｐ （Ｃ，Ｈ５）３ ）３
、Ｃｏｔ（Ｃｏ）ｓを用いた以外は実施例１と同様に実
験を行った。Comparative Examples 1 to 5 RuC11/P (t-CnHq) in Example 1
RuC1:+, RuC1z CP (C4H6)l ) instead of 3, respectively.
, RhCxz, RhCl(P(C,H5)3)3
, Cot(Co)s was used, but the experiment was conducted in the same manner as in Example 1.
結果を第１表に示す。いずれの場合も実施例よりも収率
は低かった。The results are shown in Table 1. In both cases, the yield was lower than in the examples.
実施例６〜７
実施例１においてベンジルアもンのかわりにオクチルア
ミンまたはアニリンを用いた以外は実施例１と同様に実
験を行った。Examples 6-7 Experiments were conducted in the same manner as in Example 1 except that octylamine or aniline was used instead of benzylamine.
ジメチルシリル）オクチルアミン
（ＣｓＨ＋ｔＮＨＳｉ（ＣＨｓ）ｚ （ｔ−ＣａＨｑ
））およびＮ−（ｔ−ブチルジメチルシリル） フェニ
ルアミン
（ＣａＨｓＮＨ３ｉ（ＣＨｓ）ｚ （ｔ−Ｃ４ＨＪ）
で、収率はそれぞれ７６モル％、８０モル％であった。dimethylsilyl)octylamine (CsH+tNHSi(CHs)z (t-CaHq
)) and N-(t-butyldimethylsilyl) phenylamine (CaHsNH3i(CHs)z (t-C4HJ)
The yields were 76 mol% and 80 mol%, respectively.
第
表
＊ｌ Ｂｕ ：ｎ−Ｃ４Ｈ９、Ｅｔ：ＣｚＨｓ、Ｃｙ
：ｃｙｃｌｏ −Ｃ＆ＨＩＩ、Ｐｈ：Ｃ１Ｈｓ
＊２ ベンジルアミンの転化率
＊３ Ｎ −（ｔ−ｊ’チｎｔジメチルシリル）ベン
ジルアミンの収率発明の効果
本発明はヒドロシランとアミン化合物からシリルアミン
を製造する新規な方法である。本発明によれば目的とす
るシリルアミンが高収率で得られる。この場合副生酸物
が少なくシリルアミンの単離が容易である。Table *l Bu: n-C4H9, Et: CzHs, Cy
: cyclo -C&HII, Ph:C1Hs *2 Conversion rate of benzylamine *3 Yield of N -(t-j'nt dimethylsilyl)benzylamine Effect of the invention The present invention is a novel method for producing silylamine from hydrosilane and an amine compound. This is a great method. According to the present invention, the desired silylamine can be obtained in high yield. In this case, it is easy to isolate the silylamine with few by-product acids.
Claims (3)
基、アルケニル基またはアリール基であって、 ＣＯＯＨ、Ｃｌ、ＯＨ、ＣＯＯＲなどの官能基を含んで
いても良い。）で表されるアミン化合物と、一般式ＨＳ
ｉＲ＾２Ｒ＾３Ｒ＾４（ただしＲ＾２、Ｒ＾３、Ｒ＾４
はアルキル基、アルケニル基またはアリール基であって
、ＣＯＯＨ、Ｃｌ、ＯＨ、ＣＯＯＲなどの官能基を含ん
でいても良い。）で表されるヒドロシランとを、Ｒｕお
よび／またはＲｈのハロゲン化物と一般式Ｐ（Ｒ＾５）
＿３（Ｒ＾５はアルキル基、アルケニル基またはアリー
ル基である。）で表されるホスフィンの存在下に反応さ
せることを特徴とする一般式Ｒ＾１ＮＨＳｉＲ＾２Ｒ＾
３Ｒ＾４で表されるシリルアミンの製造方法。(1) An amine represented by the general formula R^1NH_2 (where R^1 is an alkyl group, alkenyl group, or aryl group, and may contain a functional group such as COOH, Cl, OH, COOR, etc.) Compound and general formula HS
iR^2R^3R^4 (However, R^2, R^3, R^4
is an alkyl group, an alkenyl group, or an aryl group, and may contain a functional group such as COOH, Cl, OH, or COOR. ), Ru and/or Rh halide and general formula P(R^5)
_3 (R^5 is an alkyl group, alkenyl group or aryl group.) General formula R^1NHSiR^2R^ characterized by being reacted in the presence of a phosphine represented by
A method for producing silylamine represented by 3R^4.
１に記載の方法。(2) The method according to claim 1, wherein the Ru halide is a Ru chloride.
１に記載の方法。(3) The method according to claim 1, wherein the Rh halide is a Rh chloride.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5814990A JPH03261789A (en) | 1990-03-12 | 1990-03-12 | Production of silylamine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5814990A JPH03261789A (en) | 1990-03-12 | 1990-03-12 | Production of silylamine |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH03261789A true JPH03261789A (en) | 1991-11-21 |
Family
ID=13075936
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5814990A Pending JPH03261789A (en) | 1990-03-12 | 1990-03-12 | Production of silylamine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH03261789A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731556A (en) * | 2012-06-08 | 2012-10-17 | 新亚强硅化学江苏有限公司 | Process for preparing tetramethyldivinyldisilazane by conversion of divinyl tetramethyl disiloxane |
-
1990
- 1990-03-12 JP JP5814990A patent/JPH03261789A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102731556A (en) * | 2012-06-08 | 2012-10-17 | 新亚强硅化学江苏有限公司 | Process for preparing tetramethyldivinyldisilazane by conversion of divinyl tetramethyl disiloxane |
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