JPH08134078A - Production of n,n-bis(trimethylsilyl)amine - Google Patents
Production of n,n-bis(trimethylsilyl)amineInfo
- Publication number
- JPH08134078A JPH08134078A JP6293948A JP29394894A JPH08134078A JP H08134078 A JPH08134078 A JP H08134078A JP 6293948 A JP6293948 A JP 6293948A JP 29394894 A JP29394894 A JP 29394894A JP H08134078 A JPH08134078 A JP H08134078A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- trimethylsilyl
- bis
- amine
- 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
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Natural products C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 title description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 10
- 239000005051 trimethylchlorosilane Substances 0.000 claims abstract description 10
- 239000011968 lewis acid catalyst Substances 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 6
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 7
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- -1 amino compound Chemical class 0.000 abstract description 31
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 abstract description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 6
- 125000003277 amino group Chemical group 0.000 abstract description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000008096 xylene Substances 0.000 abstract description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract description 2
- 239000000010 aprotic solvent Substances 0.000 abstract description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 36
- 238000001819 mass spectrum Methods 0.000 description 18
- 239000002585 base Substances 0.000 description 17
- 238000004949 mass spectrometry Methods 0.000 description 15
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 8
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 8
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 125000006239 protecting group Chemical group 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- PUGUQINMNYINPK-UHFFFAOYSA-N tert-butyl 4-(2-chloroacetyl)piperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(C(=O)CCl)CC1 PUGUQINMNYINPK-UHFFFAOYSA-N 0.000 description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- ANOUKFYBOAKOIR-UHFFFAOYSA-N 3,4-dimethoxyphenylethylamine Chemical compound COC1=CC=C(CCN)C=C1OC ANOUKFYBOAKOIR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000003747 Grignard reaction Methods 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- JKANAVGODYYCQF-UHFFFAOYSA-N prop-2-yn-1-amine Chemical compound NCC#C JKANAVGODYYCQF-UHFFFAOYSA-N 0.000 description 2
- 235000009518 sodium iodide Nutrition 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- NUORFFQMYGHTFG-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-n,n-bis(trimethylsilyl)ethanamine Chemical compound COC1=CC=C(CCN([Si](C)(C)C)[Si](C)(C)C)C=C1OC NUORFFQMYGHTFG-UHFFFAOYSA-N 0.000 description 1
- SRXFXCKTIGELTI-UHFFFAOYSA-N 2-(4-chlorophenyl)ethanamine Chemical compound NCCC1=CC=C(Cl)C=C1 SRXFXCKTIGELTI-UHFFFAOYSA-N 0.000 description 1
- LIOPDVCDDGVTLO-UHFFFAOYSA-N 2-(4-trimethylsilyloxyphenyl)ethanamine Chemical compound C[Si](C)(C)OC1=CC=C(CCN)C=C1 LIOPDVCDDGVTLO-UHFFFAOYSA-N 0.000 description 1
- HZHQSMMBJKLBCT-UHFFFAOYSA-N 2-amino-2-trimethylsilylacetonitrile Chemical compound C[Si](C)(C)C(N)C#N HZHQSMMBJKLBCT-UHFFFAOYSA-N 0.000 description 1
- SHUQHGWRROWAIC-UHFFFAOYSA-N 2-bromo-n,n-bis(trimethylsilyl)ethanamine Chemical compound C[Si](C)(C)N([Si](C)(C)C)CCBr SHUQHGWRROWAIC-UHFFFAOYSA-N 0.000 description 1
- IZQAUUVBKYXMET-UHFFFAOYSA-N 2-bromoethanamine Chemical compound NCCBr IZQAUUVBKYXMET-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- VKPPFDPXZWFDFA-UHFFFAOYSA-N 2-chloroethanamine Chemical compound NCCCl VKPPFDPXZWFDFA-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000006479 2-pyridyl methyl group Chemical group [H]C1=C([H])C([H])=C([H])C(=N1)C([H])([H])* 0.000 description 1
- XPQIPUZPSLAZDV-UHFFFAOYSA-N 2-pyridylethylamine Chemical compound NCCC1=CC=CC=N1 XPQIPUZPSLAZDV-UHFFFAOYSA-N 0.000 description 1
- LSSLIYHUUYSCLC-UHFFFAOYSA-N 2-trimethylsilyloxyethanamine Chemical compound C[Si](C)(C)OCCN LSSLIYHUUYSCLC-UHFFFAOYSA-N 0.000 description 1
- NCITYJREKCYVGX-UHFFFAOYSA-N 3-bromo-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound C[Si](C)(C)N([Si](C)(C)C)CCCBr NCITYJREKCYVGX-UHFFFAOYSA-N 0.000 description 1
- ZTGQZSKPSJUEBU-UHFFFAOYSA-N 3-bromopropan-1-amine Chemical compound NCCCBr ZTGQZSKPSJUEBU-UHFFFAOYSA-N 0.000 description 1
- YFLJAXYLNOMKKU-UHFFFAOYSA-N 3-chloro-n,n-bis(trimethylsilyl)propan-1-amine Chemical compound C[Si](C)(C)N([Si](C)(C)C)CCCCl YFLJAXYLNOMKKU-UHFFFAOYSA-N 0.000 description 1
- BZFKSWOGZQMOMO-UHFFFAOYSA-N 3-chloropropan-1-amine Chemical compound NCCCCl BZFKSWOGZQMOMO-UHFFFAOYSA-N 0.000 description 1
- TZFFUFIGAAJZAJ-UHFFFAOYSA-N C[Si](C)(C)C1=C(C=CC=N1)CN Chemical compound C[Si](C)(C)C1=C(C=CC=N1)CN TZFFUFIGAAJZAJ-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 1
- DFNYGALUNNFWKJ-UHFFFAOYSA-N aminoacetonitrile Chemical compound NCC#N DFNYGALUNNFWKJ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000005161 aryl oxy carbonyl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 1
- YBWBKYMQYUTNMI-UHFFFAOYSA-N ethyl 2-[bis(trimethylsilyl)amino]acetate Chemical compound CCOC(=O)CN([Si](C)(C)C)[Si](C)(C)C YBWBKYMQYUTNMI-UHFFFAOYSA-N 0.000 description 1
- NTNZTEQNFHNYBC-UHFFFAOYSA-N ethyl 2-aminoacetate Chemical compound CCOC(=O)CN NTNZTEQNFHNYBC-UHFFFAOYSA-N 0.000 description 1
- VFIQTPDNEIHMCP-UHFFFAOYSA-N ethyl 3-[bis(trimethylsilyl)amino]propanoate Chemical compound CCOC(=O)CCN([Si](C)(C)C)[Si](C)(C)C VFIQTPDNEIHMCP-UHFFFAOYSA-N 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 1
- CVNCFZIIZGNVFD-UHFFFAOYSA-N n,n-bis(trimethylsilyl)prop-2-en-1-amine Chemical compound C[Si](C)(C)N([Si](C)(C)C)CC=C CVNCFZIIZGNVFD-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 125000006678 phenoxycarbonyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- OTYNBGDFCPCPOU-UHFFFAOYSA-N phosphane sulfane Chemical compound S.P[H] OTYNBGDFCPCPOU-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HDOUGSFASVGDCS-UHFFFAOYSA-N pyridin-3-ylmethanamine Chemical compound NCC1=CC=CN=C1 HDOUGSFASVGDCS-UHFFFAOYSA-N 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- GSQBIOQCECCMOQ-UHFFFAOYSA-N β-alanine ethyl ester Chemical compound CCOC(=O)CCN GSQBIOQCECCMOQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、アミノ基を有する化合
物のグリニヤール反応などの有機金属試薬を用いた反応
において、活性基となるアミノ基を保護する方法として
有用であるＮ，Ｎ−ビス（トリメチルシリル）アミンの
製造方法に関する。FIELD OF THE INVENTION The present invention is useful as a method for protecting an amino group to be an active group in a reaction using an organometallic reagent such as a Grignard reaction of a compound having an amino group. It relates to a method for producing trimethylsilyl) amine.
【０００２】[0002]
【従来の技術】アミノ化合物のＮ，Ｎ−ビストリメチル
シリル化反応としては、トリエチルアミンの存在下、触
媒量の四塩化チタン、ヨウ化ナトリウムなどを用いて、
アミノ化合物とトリメチルクロロシランとを反応させる
方法［ＰｈｏｓｐｈｏｒｕｓＳｕｌｆｕｒ ａｎｄ Ｓ
ｉｌｉｃｏｎｅ、６８巻、２５−３５頁、１９９２年］
が知られている。2. Description of the Related Art As an N, N-bistrimethylsilylation reaction of an amino compound, a catalytic amount of titanium tetrachloride, sodium iodide or the like is used in the presence of triethylamine.
Method for reacting amino compound with trimethylchlorosilane [Phosphorus Sulfur and S
ilicone, 68, 25-35, 1992]
It has been known.
【０００３】しかしながら、この方法は、沸点の低い塩
化メチレンや取扱いにくいアセトニトリルを溶媒として
使用し、毒性の高い四塩化チタンや高価なヨウ化ナトリ
ウムを触媒として使用するものであり、工業的にＮ，Ｎ
−ビス（トリメチルシリル）アミンを製造する方法であ
るとは言いがたい。However, this method uses methylene chloride having a low boiling point or acetonitrile which is difficult to handle as a solvent, and titanium tetrachloride having high toxicity or expensive sodium iodide as a catalyst. N
-It is hard to say that this is a method for producing bis (trimethylsilyl) amine.
【０００４】[0004]
【発明が解決しようとする課題】本発明は、取扱いが容
易で安全な材料を用いて工業的にＮ，Ｎ−ビス（トリメ
チルシリル）アミンを製造する新規な方法を提供する点
にある。An object of the present invention is to provide a novel method for industrially producing N, N-bis (trimethylsilyl) amine using a material which is easy to handle and safe.
【０００５】[0005]
【課題を解決するための手段】本発明者らは前述の課題
を解決すべく鋭意検討を重ねた結果、アミノ化合物とト
リメチルクロロシランとを第三級アミンの存在下、ルイ
ス酸触媒を用いて反応することにより、Ｎ，Ｎ−ビス
（トリメチルシリル）アミンを製造する方法を見いだ
し、本発明を完成したものである。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, reacted an amino compound and trimethylchlorosilane in the presence of a tertiary amine using a Lewis acid catalyst. By doing so, a method for producing N, N-bis (trimethylsilyl) amine was found, and the present invention was completed.
【０００６】すなわち、本発明は、一般式（Ｉ）That is, the present invention has the general formula (I)
【化３】Ｒ−ＮＨ2 （Ｉ） （式中、Ｒは、アルキル基、アルケニル基、アルキニル
基、アラルキル基、又はピリジルアルキル基を表し、こ
れらはいずれも置換基を有することもある。）で示され
るアミノ化合物［以下、アミノ化合物（Ｉ）と称す］と
トリメチルクロロシランとを第三級アミンの存在下、ル
イス酸触媒を用いて反応させることを特徴とする一般式
（II）Embedded image R—NH 2 (I) (In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or a pyridylalkyl group, each of which may have a substituent.) A general formula (II) characterized by reacting an amino compound represented by the formula [hereinafter referred to as an amino compound (I)] with trimethylchlorosilane in the presence of a tertiary amine using a Lewis acid catalyst.
【化４】 （式中、Ｒは前記と同一を表す。）で示されるＮ，Ｎ−
ビス（トリメチルシリル）アミンの製造方法である。[Chemical 4] (In the formula, R represents the same as the above.) N, N-
It is a method for producing bis (trimethylsilyl) amine.
【０００７】本発明において、アルキル基とは、メチル
基、エチル基、プロピル基、ｎ−ブチル基、ｎ−ヘキシ
ル基、ノニル基、オクタデシル基などを、アルケニル基
とは、アリル基、イソプロペニル基、２−ブテニル基な
どを、アルキニル基とは、プロパギル基、２−ブチニル
基などを、アラルキル基とは、ベンジル基、フェネチル
基などのアリールアルキル基、また、低級アルキル基で
置換されたアリールアルキル基を、ピリジルアルキル基
とは、２−ピリジルメチル基、２−ピリジルエチル基、
３−ピリジルメチル基、４−ピリジルメチル基、４−ピ
リジルエチル基などを意味する。In the present invention, the alkyl group means a methyl group, an ethyl group, a propyl group, an n-butyl group, an n-hexyl group, a nonyl group, an octadecyl group and the like, and the alkenyl group means an allyl group and an isopropenyl group. , A 2-butenyl group, an alkynyl group, a propargyl group, a 2-butynyl group, an aralkyl group, an arylalkyl group such as a benzyl group and a phenethyl group, and an arylalkyl group substituted with a lower alkyl group. The group is a pyridylalkyl group, 2-pyridylmethyl group, 2-pyridylethyl group,
It means a 3-pyridylmethyl group, a 4-pyridylmethyl group, a 4-pyridylethyl group and the like.
【０００８】また、置換基とは、ハロゲン原子、シアノ
基、ニトロ基、エステル基、又は保護基を有することも
あるヒドロキシ基を意味する。なお、エステル基とは、
メトキシカルボニル基、エトキシカルボニル基などのア
ルコキシカルボニル基、フェノキシカルボニル基などの
アリールオキシカルボニル基が、保護基を有するヒドロ
キシ基とは、メトキシ基、エトキシ基、ベンジル基など
のエーテル系保護基を有するヒドロキシ基、トリメチル
シロキシ基、トリエチルシロキシ基、ｔ−ブチルジメチ
ルシロキシ基、ｔ−ブチルジフェニルシロキシ基などの
シリル系保護基を有するヒドロキシ基が例示される。The substituent means a halogen atom, a cyano group, a nitro group, an ester group, or a hydroxy group which may have a protecting group. The ester group means
A hydroxy group having a protective group such as an alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group, or an aryloxycarbonyl group such as a phenoxycarbonyl group is a hydroxy group having an ether type protecting group such as a methoxy group, an ethoxy group or a benzyl group. Examples thereof include a hydroxy group having a silyl protecting group such as a group, a trimethylsiloxy group, a triethylsiloxy group, a t-butyldimethylsiloxy group, and a t-butyldiphenylsiloxy group.
【０００９】本発明では、アミノ化合物（Ｉ）とトリメ
チルクロロシランとを第三級アミンの存在下、ルイス酸
触媒を用いて反応させることにより目的物のＮ，Ｎ−ビ
ス（トリメチルシリル）アミンを得るものであるが、こ
の場合のアミノ化合物（Ｉ）とトリメチルクロロシラン
の使用割合は、アミノ化合物（Ｉ）に対してトリメチル
クロロシランが２倍モルと化学量論的に使用することが
経済上好ましい。In the present invention, the amino compound (I) is reacted with trimethylchlorosilane in the presence of a tertiary amine using a Lewis acid catalyst to obtain the desired N, N-bis (trimethylsilyl) amine. However, in this case, it is economically preferable to use a stoichiometric ratio of trimethylchlorosilane to the amino compound (I) in an amount of 2 times the molar ratio of the amino compound (I) and trimethylchlorosilane.
【００１０】第三級アミンとしては、トリエチルアミ
ン、トリブチルアミン、ジイソプロピルエチルアミン、
ジメチルアニリン、ピリジン、Ｎ−メチルピペリジンな
どが挙げられるが、好ましくはトリエチルアミン、ピリ
ジンである。As the tertiary amine, triethylamine, tributylamine, diisopropylethylamine,
Examples thereof include dimethylaniline, pyridine, and N-methylpiperidine, but triethylamine and pyridine are preferable.
【００１１】第三級アミンの使用量は、アミノ化合物
（Ｉ）に対して２倍モル以上あればよいが、好ましくは
２〜３倍モルである。The amount of the tertiary amine used may be 2 times or more the molar amount of the amino compound (I), but is preferably 2 to 3 times the molar amount.
【００１２】触媒として使用するルイス酸は、例えば、
塩化アルミニウム、臭化アルミニウム、塩化第二鉄、塩
化第二スズ、塩化亜鉛などが挙げられるが、好ましくは
塩化アルミニウムである。ルイス酸触媒の使用量は特に
限定されないが、アミノ化合物（Ｉ）１００重量部に対
して１〜２５重量部の範囲が好ましい。The Lewis acid used as a catalyst is, for example,
Aluminum chloride, aluminum bromide, ferric chloride, stannic chloride, zinc chloride and the like can be mentioned, but aluminum chloride is preferable. The amount of the Lewis acid catalyst used is not particularly limited, but is preferably in the range of 1 to 25 parts by weight based on 100 parts by weight of the amino compound (I).
【００１３】無溶媒でも本発明の反応は進行するが、溶
媒を使用する際は、非プロトン性溶媒を使用する。例え
ば、トルエン、キシレンなどの芳香族炭化水素類、ヘキ
サン、ヘプタンなどの脂肪族炭化水素類、シクロヘキサ
ンなどの脂環式炭化水素類などが挙げられるが、好まし
くはトルエン、キシレンである。The reaction of the present invention proceeds even without solvent, but when a solvent is used, an aprotic solvent is used. Examples thereof include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane and heptane, and alicyclic hydrocarbons such as cyclohexane, with preference given to toluene and xylene.
【００１４】反応温度は特に限定されないが、通常は２
０〜１１０℃の範囲で行われる。反応は室温下で十分に
進行し、通常２０時間以内に終了する。The reaction temperature is not particularly limited, but is usually 2
It is performed in the range of 0 to 110 ° C. The reaction proceeds sufficiently at room temperature and is usually completed within 20 hours.
【００１５】[0015]
【実施例】以下、実施例を挙げて本発明を更に説明する
が、本発明はこれに限定されるものではない。The present invention will be further described below with reference to examples, but the present invention is not limited thereto.
【００１６】実施例１ 撹拌機、冷却管、温度計、滴下ロートを備えた５０ｍｌ
の四つ口反応フラスコに、トルエン５ｍｌ、ルイス酸触
媒としての塩化アルミニウム０．０６ｇ（０．５ミリモ
ル）、第三級アミンとしてのトリエチルアミン２．４ｇ
（２４．２ミリモル）、トリメチルクロロシラン２．４
ｇ（２２ミリモル）を仕込んだ。室温下、アミノ化合物
としてのアリルアミン０．６ｇ（１０ミリモル）を滴下
した後、終夜撹拌した。反応混合物に１０％水酸化ナト
リウム水溶液を滴下した後、活性白土０．１ｇを混合物
中に加えてろ過した。有機層を無水硫酸マグネシウムで
乾燥した後、ろ過し、減圧濃縮した。残渣を質量分析計
により分析した結果、Ｎ，Ｎ−ビス（トリメチルシリ
ル）アリルアミン（本化合物の構造式は下記に示すとお
りである）であることを確認した。 マススペクトル ｍ／ｅ：２０１（Ｍ+），１８６，１
７４，１１４，７３（ｂａｓｅ）Example 1 50 ml equipped with a stirrer, cooling tube, thermometer, dropping funnel
5 ml of toluene, 0.06 g (0.5 mmol) of aluminum chloride as a Lewis acid catalyst, and 2.4 g of triethylamine as a tertiary amine in a four-neck reaction flask.
(24.2 mmol), trimethylchlorosilane 2.4
g (22 mmol) was charged. 0.6 g (10 mmol) of allylamine as an amino compound was added dropwise at room temperature, and the mixture was stirred overnight. After 10% aqueous sodium hydroxide solution was added dropwise to the reaction mixture, 0.1 g of activated clay was added to the mixture and the mixture was filtered. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. As a result of mass spectrometric analysis of the residue, it was confirmed to be N, N-bis (trimethylsilyl) allylamine (the structural formula of the present compound is as shown below). Mass spectrum m / e: 201 (M + ), 186, 1
74, 114, 73 (base)
【００１７】実施例２ アリルアミンの代わりにプロパギルアミン１０ミリモル
を使用して実施例１と同様の操作を行い、質量分析計に
より分析した結果、Ｎ，Ｎ−ビス（トリメチルシリル）
プロパギルアミン（本化合物の構造式は下記に示すとお
りである）であることを確認した。 マススペクトル ｍ／ｅ：１９９（Ｍ+），１８４，８
６，７３（ｂａｓｅ）Example 2 The same operation as in Example 1 was carried out using 10 mmol of propargylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl).
It was confirmed that this was propargylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 199 (M + ), 184, 8
6,73 (base)
【００１８】実施例３ アリルアミンの代わりに２−クロロエチルアミン１０ミ
リモルを使用して実施例１と同様の操作を行い、質量分
析計により分析した結果、Ｎ，Ｎ−ビス（トリメチルシ
リル）−２−クロロエチルアミン（本化合物の構造式は
下記に示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：２２３（Ｍ+），１７４，１
００，８６，７３（ｂａｓｅ）Example 3 The same operation as in Example 1 was carried out using 10 mmol of 2-chloroethylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl) -2-chloro. It was confirmed to be ethylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 223 (M + ), 174, 1
00,86,73 (base)
【００１９】実施例４ アリルアミンの代わりに２−ブロモエチルアミン１０ミ
リモル、塩化アルミニウムの代わりに臭化アルミニウム
０．５ミリモルを使用して実施例１と同様の操作を行
い、質量分析計により分析した結果、Ｎ，Ｎ−ビス（ト
リメチルシリル）−２−ブロモエチルアミン（本化合物
の構造式は下記に示すとおりである）であることを確認
した。 マススペクトル ｍ／ｅ：２６８（Ｍ+），１７４，１
００，８６，７３（ｂａｓｅ）Example 4 The same operation as in Example 1 was carried out using 10 mmol of 2-bromoethylamine instead of allylamine and 0.5 mmol of aluminum bromide instead of aluminum chloride, and the result was analyzed by mass spectrometry. , N, N-bis (trimethylsilyl) -2-bromoethylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 268 (M + ), 174, 1
00,86,73 (base)
【００２０】実施例５ アリルアミンの代わりに３−クロロプロピルアミン１０
ミリモルを使用して実施例１と同様の操作を行い、質量
分析計により分析した結果、Ｎ，Ｎ−ビス（トリメチル
シリル）−３−クロロプロピルアミン（本化合物の構造
式は下記に示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：２３７（Ｍ+），１９４，１
７４，８６，７３（ｂａｓｅ）Example 5 3-chloropropylamine 10 instead of allylamine
The same operation as in Example 1 was performed using millimoles, and as a result of analysis by a mass spectrometer, N, N-bis (trimethylsilyl) -3-chloropropylamine (the structural formula of this compound is as shown below) ) Was confirmed. Mass spectrum m / e: 237 (M + ), 194, 1
74, 86, 73 (base)
【００２１】実施例６ アリルアミンの代わりに３−ブロモプロピルアミン１０
ミリモル、塩化アルミニウムの代わりに臭化アルミニウ
ム０．５ミリモルを使用して実施例１と同様の操作を行
い、質量分析計により分析した結果、Ｎ，Ｎ−ビス（ト
リメチルシリル）−３−ブロモプロピルアミン（本化合
物の構造式は下記に示すとおりである）であることを確
認した。 マススペクトル ｍ／ｅ：２８１（Ｍ+−１），２４
１，１７５，８６（ｂａｓｅ），７３Example 6 3-Bromopropylamine 10 instead of allylamine
Mmol and 0.5 mmol of aluminum bromide in place of aluminum chloride, the same operation as in Example 1 was carried out, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl) -3-bromopropylamine. (The structural formula of this compound is as shown below). Mass spectrum m / e: 281 (M + -1), 24
1,175,86 (base), 73
【００２２】実施例７ アリルアミンの代わりに２−（トリメチルシロキシ）エ
チルアミン１０ミリモルを使用して実施例１と同様の操
作を行い、質量分析計により分析した結果、Ｎ，Ｎ−ビ
ス（トリメチルシリル）−２−（トリメチルシロキシ）
エチルアミン（本化合物の構造式は下記に示すとおりで
ある）であることを確認した。 マススペクトル ｍ／ｅ：２７７（Ｍ+），２６２，１
７４，８６，７３（ｂａｓｅ）Example 7 The same operation as in Example 1 was carried out using 10 mmol of 2- (trimethylsiloxy) ethylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl)-. 2- (trimethylsiloxy)
It was confirmed to be ethylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 277 (M + ), 262, 1
74, 86, 73 (base)
【００２３】実施例８ アリルアミンの代わりに１−ヘキシルアミン１０ミリモ
ルを使用して実施例１と同様の操作を行い、質量分析計
により分析した結果、Ｎ，Ｎ−ビス（トリメチルシリ
ル）−１−ヘキシルアミン（本化合物の構造式は下記に
示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：２４５（Ｍ+），２３０，１
７４（ｂａｓｅ），７３Example 8 The same operation as in Example 1 was carried out using 10 mmol of 1-hexylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl) -1-hexyl. It was confirmed to be amine (the structural formula of this compound is as shown below). Mass spectrum m / e: 245 (M + ), 230, 1
74 (base), 73
【００２４】実施例９ アリルアミンの代わりに１−ノニルアミン１０ミリモル
を使用して実施例１と同様の操作を行い、質量分析計に
より分析した結果、Ｎ，Ｎ−ビス（トリメチルシリル）
−１−ノニルアミン（本化合物の構造式は下記に示すと
おりである）であることを確認した。 マススペクトル ｍ／ｅ：２８７（Ｍ+），２７２，１
９８，１７４（ｂａｓｅ），７３Example 9 The same operation as in Example 1 was carried out using 10 mmol of 1-nonylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl).
It was confirmed to be -1-nonylamine (the structural formula of the compound is as shown below). Mass spectrum m / e: 287 (M + ), 272, 1
98, 174 (base), 73
【００２５】実施例１０ アリルアミンの代わりに１−オクタデシルアミン１０ミ
リモルを使用して実施例１と同様の操作を行い、質量分
析計により分析した結果、Ｎ，Ｎ−ビス（トリメチルシ
リル）−１−オクタデシルアミン（本化合物の構造式は
下記に示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：４１３（Ｍ+），３９８，１
７４（ｂａｓｅ），７３Example 10 The same operation as in Example 1 was carried out using 10 mmol of 1-octadecylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl) -1-octadecyl. It was confirmed to be amine (the structural formula of this compound is as shown below). Mass spectrum m / e: 413 (M + ), 398, 1
74 (base), 73
【００２６】実施例１１ アリルアミンの代わりにグリシンエチルエステル１０ミ
リモルを使用して実施例１と同様の操作を行い、質量分
析計により分析した結果、Ｎ，Ｎ−ビス（トリメチルシ
リル）グリシンエチルエステル（本化合物の構造式は下
記に示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：２４７（Ｍ+），２３２，１
７４，１４７，７３（ｂａｓｅ）Example 11 The same operation as in Example 1 was carried out using 10 mmol of glycine ethyl ester instead of allylamine, and the result of mass spectrometric analysis revealed that N, N-bis (trimethylsilyl) glycine ethyl ester The structural formula of the compound is as shown below). Mass spectrum m / e: 247 (M + ), 232, 1
74, 147, 73 (base)
【００２７】実施例１２ アリルアミンの代わりにβ−アラニンエチルエステル１
０ミリモルを使用して実施例１と同様の操作を行い、質
量分析計により分析した結果、Ｎ，Ｎ−ビス（トリメチ
ルシリル）−β−アラニンエチルエステル（本化合物の
構造式は下記に示すとおりである）であることを確認し
た。 マススペクトル ｍ／ｅ：２６１（Ｍ+），２４６，１
７４，１４７，７３（ｂａｓｅ）Example 12 β-alanine ethyl ester 1 instead of allylamine
The same operation as in Example 1 was performed using 0 mmol, and as a result of analysis by a mass spectrometer, N, N-bis (trimethylsilyl) -β-alanine ethyl ester (the structural formula of this compound is as shown below) Yes). Mass spectrum m / e: 261 (M + ), 246, 1
74, 147, 73 (base)
【００２８】実施例１３ アリルアミンの代わりにアミノアセトニトリル１０ミリ
モルを使用して実施例１と同様の操作を行い、質量分析
計により分析した結果、Ｎ，Ｎ−ビス（トリメチルシリ
ル）アミノアセトニトリル（本化合物の構造式は下記に
示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：２００（Ｍ+），１８５，８
６（ｂａｓｅ），７３Example 13 The same operation as in Example 1 was carried out using 10 mmol of aminoacetonitrile instead of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl) aminoacetonitrile (of this compound). The structural formula is as shown below). Mass spectrum m / e: 200 (M + ), 185, 8
6 (base), 73
【００２９】実施例１４ アリルアミンの代わりに２−［４−（トリメチルシロキ
シ）フェニル］エチルアミン１０ミリモルを使用して実
施例１と同様の操作を行い、質量分析計により分析した
結果、Ｎ，Ｎ−ビス（トリメチルシリル）−２−［４−
（トリメチルシロキシ）フェニル］エチルアミン（本化
合物の構造式は下記に示すとおりである）であることを
確認した。 マススペクトル ｍ／ｅ：３５３（Ｍ+），３３８，１
７４，８６，７３（ｂａｓｅ）Example 14 The same operation as in Example 1 was carried out using 10 mmol of 2- [4- (trimethylsiloxy) phenyl] ethylamine instead of allylamine, and the result of mass spectrometric analysis was N, N-. Bis (trimethylsilyl) -2- [4-
It was confirmed that the compound was (trimethylsiloxy) phenyl] ethylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 353 (M + ), 338, 1
74, 86, 73 (base)
【００３０】実施例１５ アリルアミンの代わりに２−（４−クロロフェニル）エ
チルアミン１０ミリモルを使用して実施例１と同様の操
作を行い、質量分析計により分析した結果、Ｎ，Ｎ−ビ
ス（トリメチルシリル）−２−（４−クロロフェニル）
エチルアミン（本化合物の構造式は下記に示すとおりで
ある）であることを確認した。 マススペクトル ｍ／ｅ：２９９（Ｍ+），２８４，１
７４，８６，７３（ｂａｓｅ）Example 15 The same operation as in Example 1 was carried out using 10 mmol of 2- (4-chlorophenyl) ethylamine in place of allylamine, and the result of mass spectrometric analysis was N, N-bis (trimethylsilyl). -2- (4-chlorophenyl)
It was confirmed to be ethylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 299 (M + ), 284, 1
74, 86, 73 (base)
【００３１】実施例１６ アリルアミンの代わりに２−（３，４−ジメトキシフェ
ニル）エチルアミン１０ミリモルを使用して実施例１と
同様の操作を行い、質量分析計により分析した結果、
Ｎ，Ｎ−ビス（トリメチルシリル）−２−（３，４−ジ
メトキシフェニル）エチルアミン（本化合物の構造式は
下記に示すとおりである）であることを確認した。 マススペクトル ｍ／ｅ：３２５（Ｍ+），１７４（ｂ
ａｓｅ），１５１，８６，７３Example 16 The procedure of Example 1 was repeated using 10 mmol of 2- (3,4-dimethoxyphenyl) ethylamine instead of allylamine, and the result of mass spectrometric analysis was as follows:
It was confirmed that the compound was N, N-bis (trimethylsilyl) -2- (3,4-dimethoxyphenyl) ethylamine (the structural formula of this compound is as shown below). Mass spectrum m / e: 325 (M + ), 174 (b
as)), 151, 86, 73
【００３２】実施例１７ アリルアミンの代わりに３−（アミノメチル）ピリジン
１０ミリモルを使用して実施例１と同様の操作を行い、
質量分析計により分析した結果、Ｎ，Ｎ−ビス（トリメ
チルシリル）−３−（アミノメチル）ピリジン（本化合
物の構造式は下記に示すとおりである）であることを確
認した。 マススペクトル ｍ／ｅ：２５２（Ｍ+），２３７，１
６３，１３６，７３（ｂａｓｅ）Example 17 The same operation as in Example 1 was carried out using 10 mmol of 3- (aminomethyl) pyridine instead of allylamine.
As a result of analysis by a mass spectrometer, it was confirmed to be N, N-bis (trimethylsilyl) -3- (aminomethyl) pyridine (the structural formula of this compound is as shown below). Mass spectrum m / e: 252 (M + ), 237, 1
63, 136, 73 (base)
【００３３】実施例１８ アリルアミンの代わりに２−（２−アミノエチル）ピリ
ジン１０ミリモルを使用して実施例１と同様の操作を行
い、質量分析計により分析した結果、Ｎ，Ｎ−ビス（ト
リメチルシリル）−２−（２−アミノエチル）ピリジン
（本化合物の構造式は下記に示すとおりである）である
ことを確認した。 マススペクトル ｍ／ｅ：２６６（Ｍ+），２５１，１
７４（ｂａｓｅ），８６，７３Example 18 The same operation as in Example 1 was carried out using 10 mmol of 2- (2-aminoethyl) pyridine instead of allylamine, and the result of mass spectrometry analysis was N, N-bis (trimethylsilyl). ) -2- (2-Aminoethyl) pyridine (the structural formula of this compound is as shown below). Mass spectrum m / e: 266 (M + ), 251,1
74 (base), 86, 73
【化５】 Embedded image
【化６】 [Chemical 6]
【化７】 [Chemical 7]
【００３４】以下に本発明の実施態様を列挙する。 １． 一般式（Ｉ）The embodiments of the present invention will be listed below. 1. General formula (I)
【化８】Ｒ−ＮＨ2 （Ｉ） （式中、Ｒは、アルキル基、アルケニル基、アルキニル
基、アラルキル基、又はピリジルアルキル基を表し、こ
れらはいずれも置換基を有することもある。）で示され
るアミノ化合物とトリメチルクロロシランとを第三級ア
ミンの存在下、ルイス酸触媒を用いて反応させることを
特徴とする一般式（II）Embedded image R—NH 2 (I) (In the formula, R represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or a pyridylalkyl group, each of which may have a substituent.) A general formula (II) characterized by reacting an amino compound represented by with trimethylchlorosilane with a Lewis acid catalyst in the presence of a tertiary amine.
【化９】 （式中、Ｒは前記と同一を表す。）で示されるＮ，Ｎ−
ビス（トリメチルシリル）アミンの製造方法。 ２．前記第三級アミンをアミノ化合物（Ｉ）に対して２
倍モル以上使用する前項１記載のＮ，Ｎ−ビス（トリメ
チルシリル）アミンの製造方法。 ３．前記ルイス酸触媒をアミノ化合物（Ｉ）１００重量
部当り１〜２５重量部使用する前項１または２記載の
Ｎ，Ｎ−ビス（トリメチルシリル）アミンの製造方法。[Chemical 9] (In the formula, R represents the same as the above.) N, N-
Process for producing bis (trimethylsilyl) amine. 2. The tertiary amine is added to the amino compound (I) in an amount of 2
The method for producing N, N-bis (trimethylsilyl) amine according to the above item 1, which is used in an amount of at least 2 times the molar amount. 3. 3. The method for producing N, N-bis (trimethylsilyl) amine according to 1 or 2 above, wherein 1 to 25 parts by weight of the Lewis acid catalyst is used per 100 parts by weight of the amino compound (I).
【００３５】[0035]
【発明の効果】本発明によれば、アミノ基を有する化合
物のグリニヤール反応などの有機金属試薬を用いた反応
において活性基となるアミノ基を保護した化合物として
有用なＮ，Ｎ−ビス（トリメチルシリル）アミンを、取
扱いが容易で、安全な材料を用いて工業的に製造するこ
とができる。INDUSTRIAL APPLICABILITY According to the present invention, N, N-bis (trimethylsilyl) which is useful as a compound in which an amino group serving as an active group is protected in a reaction using an organometallic reagent such as a Grignard reaction of a compound having an amino group. Amines can be industrially produced using materials that are easy to handle and safe.
Claims (1)
基、アラルキル基、又はピリジルアルキル基を表し、こ
れらはいずれも置換基を有することもある。）で示され
るアミノ化合物とトリメチルクロロシランとを第三級ア
ミンの存在下、ルイス酸触媒を用いて反応させることを
特徴とする一般式（II） 【化２】 （式中、Ｒは前記と同一を表す。）で示されるＮ，Ｎ−
ビス（トリメチルシリル）アミンの製造方法。1. A compound represented by the general formula (I): R—NH 2 (I) (wherein R represents an alkyl group, an alkenyl group, an alkynyl group, an aralkyl group, or a pyridylalkyl group, any of which is May have a substituent) and trimethylchlorosilane are reacted with a Lewis acid catalyst in the presence of a tertiary amine to give a compound of the general formula (II) (In the formula, R represents the same as the above.) N, N-
Process for producing bis (trimethylsilyl) amine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29394894A JP3507962B2 (en) | 1994-11-02 | 1994-11-02 | Method for producing N, N-bis (trimethylsilyl) amine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29394894A JP3507962B2 (en) | 1994-11-02 | 1994-11-02 | Method for producing N, N-bis (trimethylsilyl) amine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08134078A true JPH08134078A (en) | 1996-05-28 |
| JP3507962B2 JP3507962B2 (en) | 2004-03-15 |
Family
ID=17801255
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29394894A Expired - Fee Related JP3507962B2 (en) | 1994-11-02 | 1994-11-02 | Method for producing N, N-bis (trimethylsilyl) amine |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3507962B2 (en) |
Cited By (9)
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| JP2009137858A (en) * | 2007-12-05 | 2009-06-25 | Shin Etsu Chem Co Ltd | Method for silylating amino group |
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1994
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| JP2016128518A (en) * | 2014-12-04 | 2016-07-14 | 信越化学工業株式会社 | Method for producing polyalkylene glycol derivative having amino group at end |
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| WO2018163517A1 (en) * | 2017-03-10 | 2018-09-13 | Jnc株式会社 | Method for producing dialkylaminosilane |
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| JP3507962B2 (en) | 2004-03-15 |
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