JP6635257B2 - Method for producing nitrogen-containing silicon-containing compound having both amino and silyl groups - Google Patents
Method for producing nitrogen-containing silicon-containing compound having both amino and silyl groups Download PDFInfo
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- 239000002210 silicon-based material Substances 0.000 title claims description 42
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 title claims description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 title claims description 14
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 45
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 16
- 150000001993 dienes Chemical class 0.000 claims description 15
- 125000003277 amino group Chemical group 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 13
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 claims description 13
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 12
- 229910001882 dioxygen Inorganic materials 0.000 claims description 12
- 150000002940 palladium Chemical class 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 11
- 150000002430 hydrocarbons Chemical group 0.000 description 62
- -1 amide compound Chemical class 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- QENJZWZWAWWESF-UHFFFAOYSA-N tri-methylbenzoic acid Natural products CC1=CC(C)=C(C(O)=O)C=C1C QENJZWZWAWWESF-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 8
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 7
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 7
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 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 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 4
- FFFIRKXTFQCCKJ-UHFFFAOYSA-N 2,4,6-trimethylbenzoic acid Chemical compound CC1=CC(C)=C(C(O)=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 3
- UKSZBOKPHAQOMP-SVLSSHOZSA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 UKSZBOKPHAQOMP-SVLSSHOZSA-N 0.000 description 2
- FFFIRKXTFQCCKJ-UHFFFAOYSA-M 2,4,6-trimethylbenzoate Chemical compound CC1=CC(C)=C(C([O-])=O)C(C)=C1 FFFIRKXTFQCCKJ-UHFFFAOYSA-M 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 101150003085 Pdcl gene Proteins 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- NEXSMEBSBIABKL-UHFFFAOYSA-N hexamethyldisilane Chemical compound C[Si](C)(C)[Si](C)(C)C NEXSMEBSBIABKL-UHFFFAOYSA-N 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PBDBXAQKXCXZCJ-UHFFFAOYSA-L palladium(2+);2,2,2-trifluoroacetate Chemical compound [Pd+2].[O-]C(=O)C(F)(F)F.[O-]C(=O)C(F)(F)F PBDBXAQKXCXZCJ-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- GETTZEONDQJALK-UHFFFAOYSA-N (trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC=C1 GETTZEONDQJALK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910021605 Palladium(II) bromide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WXNOJTUTEXAZLD-UHFFFAOYSA-L benzonitrile;dichloropalladium Chemical compound Cl[Pd]Cl.N#CC1=CC=CC=C1.N#CC1=CC=CC=C1 WXNOJTUTEXAZLD-UHFFFAOYSA-L 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- WMKGGPCROCCUDY-PHEQNACWSA-N dibenzylideneacetone Chemical compound C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 WMKGGPCROCCUDY-PHEQNACWSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- QEWYKACRFQMRMB-UHFFFAOYSA-M fluoroacetate Chemical compound [O-]C(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-M 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007430 reference method Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000006884 silylation reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Description
本発明は、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物の製造方法に関し、より詳しくはパラジウム錯体等を利用した含窒素含ケイ素化合物の製造方法に関する。 The present invention relates to a method for producing a nitrogen-containing silicon-containing compound having both an amino group and a silyl group, and more particularly to a method for producing a nitrogen-containing silicon-containing compound using a palladium complex or the like.
アミノ基は、反応性に富んだ有用性の高い代表的な官能基であり、これを含む窒素化合物は、農薬、医薬品等の原料に利用される重要な化合物である。一方、シリル基は、官能基変換が容易で毒性が低いため、これを含んだ有機ケイ素化合物は、環境や安全性の観点から注目を集めている化合物である。
アミノ基とシリル基の両方を有する含窒素含ケイ素化合物は、半導体や機能性分子材料等の様々な分野への応用が期待されており、これを効率良く製造する技術が必要である。その方法としては、アミド化合物に対してリチウムジイソプロピルアミド(LDA)を反応させた後、ハロゲン化シランを反応させる方法が報告されている(例えば、非特許文献1参照。)。
An amino group is a highly reactive and highly useful representative functional group, and a nitrogen compound containing the amino group is an important compound used as a raw material for agricultural chemicals, pharmaceuticals, and the like. On the other hand, since silyl groups can be easily converted into functional groups and have low toxicity, organosilicon compounds containing them are attracting attention from the viewpoint of environment and safety.
A nitrogen-containing silicon-containing compound having both an amino group and a silyl group is expected to be applied to various fields such as a semiconductor and a functional molecular material, and a technique for efficiently producing the compound is required. As a method therefor, a method has been reported in which lithium diisopropylamide (LDA) is reacted with an amide compound and then reacted with a halogenated silane (for example, see Non-Patent Document 1).
本発明は、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物を効率良く製造することができる含窒素含ケイ素化合物の製造方法を提供することを目的とする。 An object of the present invention is to provide a method for producing a nitrogen-containing silicon-containing compound capable of efficiently producing a nitrogen-containing silicon-containing compound having both an amino group and a silyl group.
本発明者らは、上記の課題を解決すべく鋭意検討を重ねた結果、パラジウム錯体やパラジウム塩と酸素ガスの存在下で、ジエンに対し、アミンとジシランが共に付加して、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物が効率良く生成することを見出し、本発明を完成させた。 The present inventors have conducted intensive studies to solve the above problems, and as a result, in the presence of a palladium complex or a palladium salt and oxygen gas, an amine and a disilane are both added to a diene to form an amino group and a silyl group. The present inventors have found that a nitrogen-containing silicon-containing compound having both groups is efficiently produced, and have completed the present invention.
即ち、本発明は以下の通りである。
<1> アミノ基とシリル基の両方を有する含窒素含ケイ素化合物の製造方法であって、
パラジウム錯体及び/又はパラジウム塩、並びに酸素ガスの存在下、下記式(A)で表されるジエンと下記式(B)で表されるアミンと下記式(C)で表されるジシランを反応させて前記含窒素含ケイ素化合物を生成する反応工程(以下、「反応工程」と略す場合がある。)を含むことを特徴とする、含窒素含ケイ素化合物の製造方法。
<2> 下記式(D−1)又は(D−2)で表される含窒素含ケイ素化合物又はその塩。
<1> A method for producing a nitrogen-containing silicon-containing compound having both an amino group and a silyl group,
A diene represented by the following formula (A) is reacted with an amine represented by the following formula (B) and a disilane represented by the following formula (C) in the presence of a palladium complex and / or a palladium salt and oxygen gas. A process for producing the nitrogen-containing silicon-containing compound (hereinafter, may be abbreviated as “reaction step” in some cases).
<2> A nitrogen-containing silicon-containing compound represented by the following formula (D-1) or (D-2) or a salt thereof.
本発明によれば、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物を効率良く製造することができる。 According to the present invention, a nitrogen-containing silicon-containing compound having both an amino group and a silyl group can be efficiently produced.
本発明の詳細を説明するに当たり、具体例を挙げて説明するが、本発明の趣旨を逸脱しない限り以下の内容に限定されるものではなく、適宜変更して実施することができる。 In describing the details of the present invention, specific examples will be described. However, the present invention is not limited to the following contents without departing from the spirit of the present invention, and can be appropriately modified and implemented.
<含窒素含ケイ素化合物の製造方法>
本発明の一態様である含窒素含ケイ素化合物の製造方法(以下、「本発明の製造方法」と略す場合がある。)は、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物の製造方法であり、パラジウム錯体及び/又はパラジウム塩、並びに酸素ガスの存在下、下記式(A)で表されるジエンと下記式(B)で表されるアミンと下記式(C)で表されるジ
シランを反応させて前記含窒素含ケイ素化合物を生成する反応工程(以下、「反応工程」と略す場合がある。)を含むことを特徴とする。
本発明者らは、パラジウム錯体やパラジウム塩と酸素ガスの存在下で、ジエンに対し、アミンとジシランが共に付加して、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物が効率良く生成することを見出したのである。かかる反応のメカニズムは、十分に解明されていないが、例えば酢酸パラジウム、2,3−ジメチル−1,3−ブタジエン、N−メチルアニリン、及びヘキサメチルジシランを利用した場合、下記式で表される触媒サイクルによって反応が進行するものと考えられる。本発明の製造方法は、ジエンに対するアミンとジシランの付加を比較的穏和な条件下で一段階で行うことができ、多段階の反応を必要とする従来法に比べて、アミノ基とシリル基の両方を有する含窒素含ケイ素化合物を非常に効率良く製造することができるのである。また、ジシランを利用してシリル化を行うため、ハロゲン化シラン等を用いた場合に比べて、安全性の観点からも優れていると言える。
以下、「式(A)で表されるジエン」、「式(B)で表されるアミン」、「式(C)で表されるジシラン」、「パラジウム錯体」、「パラジウム塩」等について詳細に説明する。
<Method for producing nitrogen-containing silicon-containing compound>
The method for producing a nitrogen-containing silicon-containing compound according to one embodiment of the present invention (hereinafter, may be abbreviated as “the production method of the present invention”) is a method for producing a nitrogen-containing silicon-containing compound having both an amino group and a silyl group. A diene represented by the following formula (A), an amine represented by the following formula (B) and a formula represented by the following formula (C) in the presence of a palladium complex and / or a palladium salt and oxygen gas. It is characterized by including a reaction step of producing the nitrogen-containing silicon-containing compound by reacting disilane (hereinafter, may be abbreviated as “reaction step”).
The present inventors have found that, in the presence of a palladium complex or a palladium salt and oxygen gas, an amine and a disilane are both added to a diene to efficiently produce a nitrogen-containing silicon-containing compound having both an amino group and a silyl group. We found that we did. Although the mechanism of such a reaction has not been sufficiently elucidated, for example, when palladium acetate, 2,3-dimethyl-1,3-butadiene, N-methylaniline, and hexamethyldisilane are used, the reaction is represented by the following formula. It is considered that the reaction proceeds by the catalytic cycle. In the production method of the present invention, the addition of an amine and a disilane to a diene can be performed in a single step under relatively mild conditions, and the amino group and the silyl group can be compared with a conventional method requiring a multistep reaction. The nitrogen-containing silicon-containing compound having both of them can be produced very efficiently. In addition, since silylation is performed using disilane, it can be said that it is superior from the viewpoint of safety as compared with the case where halogenated silane or the like is used.
Hereinafter, “diene represented by formula (A)”, “amine represented by formula (B)”, “disilane represented by formula (C)”, “palladium complex”, “palladium salt” and the like are described in detail. Will be described.
(式(A)で表されるジエン)
式(A)で表されるジエン(以下、「ジエン」と略す場合がある。)の具体的種類は、特に限定されず、製造目的である含窒素含ケイ素化合物に応じて適宜選択されるべきである。
式(A)中、R1はそれぞれ独立して水素原子又は炭素数1〜20の炭化水素基を表しているが、「炭化水素基」とは、直鎖状の飽和炭化水素基に限られず、炭素−炭素不飽和結合、分岐構造、環状構造のそれぞれを有していてもよいことを意味する。また、2つのR1が共に炭化水素基である場合、2つの炭化水素基が連結して環状構造を形成していてもよいが、その環状構造の炭素数は20以下となるものとする。
R1が炭化水素基である場合の炭素数は、通常20以下、好ましくは15以下、より好ましくは10以下である。
R1としては、水素原子、メチル基(−CH3,−Me)、エチル基(−C2H5,−Et)、n−プロピル基(−nC3H7,−nPr)、i−プロピル基(−iC3H7,−iPr)、n−ブチル基(−nC4H9,−nBu)、t−ブチル基(−tC4H9,−tBu)、n−ペンチル基(−nC5H11)、n−ヘキシル基(−nC6H13,−nHex)、シクロヘキシル基(−cC6H11,−Cy)、フェニル基(−C6H5,−Ph)等が挙げられる。この中でも、メチル基、エチル基等が特に好ましい。
ジエンとしては、下記式で表されるものが挙げられる。
The specific type of the diene represented by the formula (A) (hereinafter sometimes abbreviated as “diene”) is not particularly limited and should be appropriately selected depending on the nitrogen-containing silicon-containing compound to be produced. It is.
In the formula (A), R 1 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, but the “hydrocarbon group” is not limited to a linear saturated hydrocarbon group. , A carbon-carbon unsaturated bond, a branched structure, or a cyclic structure. When both R 1 are hydrocarbon groups, the two hydrocarbon groups may be linked to form a cyclic structure, but the cyclic structure has 20 or less carbon atoms.
When R 1 is a hydrocarbon group, the number of carbon atoms is usually 20 or less, preferably 15 or less, more preferably 10 or less.
As R 1, a hydrogen atom, a methyl group (-CH 3, -Me), ethyl (-C 2 H 5, -Et) , n- propyl (- n C 3 H 7, - n Pr), i - propyl (- i C 3 H 7, - i Pr), n- butyl (- n C 4 H 9, - n Bu), t- butyl (- t C 4 H 9, - t Bu), n- pentyl (- n C 5 H 11) , n- hexyl group (- n C 6 H 13, - n Hex), cyclohexyl (- c C 6 H 11, -Cy), phenyl group (-C 6 H 5, -Ph), and the like. Among them, a methyl group, an ethyl group and the like are particularly preferable.
Examples of the diene include those represented by the following formula.
(式(B)で表されるアミン)
式(B)で表されるアミン(以下、「アミン」と略す場合がある。)の具体的種類は、特に限定されず、製造目的である含窒素含ケイ素化合物に応じて適宜選択されるべきである。
式(B)中、R2は炭素数1〜20の炭化水素基を、R3は水素原子又は炭素数1〜20の炭化水素基を表しているが、「炭化水素基」は、R1の場合と同義である。また、R3が炭化水素基である場合、R2とR3の炭化水素基が連結して環状構造を形成していてもよいが、その環状構造の炭素数は20以下となるものとする。
R2の炭化水素基の炭素数は、通常20以下、好ましくは15以下、より好ましくは10以下である。
R2としては、メチル基(−CH3,−Me)、エチル基(−C2H5,−Et)、n−プロピル基(−nC3H7,−nPr)、i−プロピル基(−iC3H7,−iPr)、n−ブチル基(−nC4H9,−nBu)、t−ブチル基(−tC4H9,−tBu)、n−ペンチル基(−nC5H11)、n−ヘキシル基(−nC6H13,−nHex)、シクロヘキシル基(−cC6H11,−Cy)、フェニル基(−C6H5,−Ph)等が挙げられる。この中でも、フェニル基等が特に好ましい。
R3が炭化水素基である場合の炭素数は、通常20以下、好ましくは15以下、より好ましくは10以下である。
R3としては、水素原子、メチル基(−CH3,−Me)、エチル基(−C2H5,−Et)、n−プロピル基(−nC3H7,−nPr)、i−プロピル基(−iC3H7,−iPr)、n−ブチル基(−nC4H9,−nBu)、t−ブチル基(−tC4H9,−tBu)、n−ペンチル基(−nC5H11)、n−ヘキシル基(−nC6H13,−nHex)、シクロヘキシル基(−cC6H11,−Cy)、フェニル基(−C6H5,−Ph)等が挙げられる。この中でも、メチル基、エチル基等が特に好ましい。
アミンとしては、下記式で表されるものが挙げられる。
The specific type of the amine represented by the formula (B) (hereinafter sometimes abbreviated as “amine”) is not particularly limited, and should be appropriately selected depending on the nitrogen-containing silicon-containing compound to be produced. It is.
Wherein (B), R 2 is a hydrocarbon group having 1 to 20 carbon atoms, but R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, the "hydrocarbon group", R 1 Is synonymous with Further, when R 3 is a hydrocarbon group, the hydrocarbon groups of R 2 and R 3 may be linked to form a cyclic structure, but the cyclic structure has 20 or less carbon atoms. .
The carbon number of the hydrocarbon group of R 2 is usually 20 or less, preferably 15 or less, more preferably 10 or less.
The R 2, a methyl group (-CH 3, -Me), ethyl (-C 2 H 5, -Et) , n- propyl (- n C 3 H 7, - n Pr), i- propyl (- i C 3 H 7, - i Pr), n- butyl (- n C 4 H 9, - n Bu), t- butyl (- t C 4 H 9, - t Bu), n- pentyl group (- n C 5 H 11) , n- hexyl group (- n C 6 H 13, - n Hex), cyclohexyl (- c C 6 H 11, -Cy),
When R 3 is a hydrocarbon group, the number of carbon atoms is usually 20 or less, preferably 15 or less, more preferably 10 or less.
R 3 represents a hydrogen atom, a methyl group (—CH 3 , —Me), an ethyl group (—C 2 H 5 , —Et), an n-propyl group ( —n C 3 H 7 , —n Pr), i - propyl (- i C 3 H 7, - i Pr), n- butyl (- n C 4 H 9, - n Bu), t- butyl (- t C 4 H 9, - t Bu), n- pentyl (- n C 5 H 11) , n- hexyl group (- n C 6 H 13, - n Hex), cyclohexyl (- c C 6 H 11, -Cy), phenyl group (-C 6 H 5, -Ph), and the like. Among them, a methyl group, an ethyl group and the like are particularly preferable.
Examples of the amine include those represented by the following formula.
アミンの使用量(仕込量)は、ジエンに対して物質量換算で、通常0.1倍以上であり、通常20倍以下、好ましくは10倍以下、より好ましくは3倍以下である。上記範囲内であると、より効率良く含窒素含ケイ素化合物を製造することができる。 The used amount (prepared amount) of the amine is usually 0.1 times or more, usually 20 times or less, preferably 10 times or less, more preferably 3 times or less, in terms of the amount of a diene. Within the above range, the nitrogen-containing silicon-containing compound can be produced more efficiently.
(式(C)で表されるジシラン)
式(C)で表されるジシラン(以下、「ジシラン」と略す場合がある。)の具体的種類は、特に限定されず、製造目的である含窒素含ケイ素化合物に応じて適宜選択されるべきである。
式(C)中、R4はそれぞれ独立して炭素数1〜20の炭化水素基を表しているが、「炭化水素基」は、R1の場合と同義である。
R4の炭化水素基の炭素数は、通常20以下、好ましくは15以下、より好ましくは10以下である。
R4としては、メチル基(−CH3,−Me)、エチル基(−C2H5,−Et)、n−プロピル基(−nC3H7,−nPr)、i−プロピル基(−iC3H7,−iPr)、n−ブチル基(−nC4H9,−nBu)、t−ブチル基(−tC4H9,−tBu)、n−ペンチル基(−nC5H11)、n−ヘキシル基(−nC6H13,−nHex)、シクロヘキシル基(−cC6H11,−Cy)、フェニル基(−C6H5,−Ph)等が挙げられる。この中でも、メチル基、エチル基等が特に好ましい。
ジシランとしては、下記式で表されるものが挙げられる。
The specific type of the disilane represented by the formula (C) (hereinafter sometimes abbreviated as “disilane”) is not particularly limited, and should be appropriately selected according to the nitrogen-containing silicon-containing compound to be produced. It is.
In the formula (C), R 4 each independently represents a hydrocarbon group having 1 to 20 carbon atoms, and “hydrocarbon group” has the same meaning as that of R 1 .
The carbon number of the hydrocarbon group of R 4 is usually 20 or less, preferably 15 or less, more preferably 10 or less.
The R 4, a methyl group (-CH 3, -Me), ethyl (-C 2 H 5, -Et) , n- propyl (- n C 3 H 7, - n Pr), i- propyl (- i C 3 H 7, - i Pr), n- butyl (- n C 4 H 9, - n Bu), t- butyl (- t C 4 H 9, - t Bu), n- pentyl group (- n C 5 H 11) , n- hexyl group (- n C 6 H 13, - n Hex), cyclohexyl (- c C 6 H 11, -Cy),
Examples of the disilane include those represented by the following formula.
ジシランの使用量(仕込量)は、ジエンに対して物質量換算で、通常0.1倍以上であり、通常20倍以下、好ましくは10倍以下、より好ましくは3倍以下である。上記範囲内であると、より効率良く含窒素含ケイ素化合物を製造することができる。 The amount of disilane used (prepared amount) is usually 0.1 times or more, usually 20 times or less, preferably 10 times or less, more preferably 3 times or less with respect to the diene. Within the above range, the nitrogen-containing silicon-containing compound can be produced more efficiently.
(パラジウム錯体・パラジウム塩)
パラジウム錯体及びパラジウム塩(以下、「パラジウム錯体等」と略す場合がある。)におけるパラジウムの酸化数、配位子若しくは対イオンの具体的種類等は特に限定されず、目的に応じて適宜選択することができる。
パラジウムの酸化数は、通常0、+1、+2、+4、+6であるが、+2であることが好ましい。
配位子若しくは対イオン、又はこれらになり得る化合物としては、酢酸、2,4,6−トリメチル安息香酸(TMBA)、トリフルオロ酢酸(TFA)、ベンゾニトリル(PhCN)、ジベンジリデンアセトン(dba)、アセチルアセトン(acac)、トリフェニルホスフィン(PPh3)、塩化物アニオン(Cl−)、臭化物アニオン(Br−)等が挙げられる。
なお、反応工程において、パラジウム錯体等を反応器に直接投入するほか、パラジウム元素を含む前駆体と配位子若しくは対イオンとなり得る化合物を添加剤として投入して、反応器内で目的のパラジウム錯体等を形成させてもよい。例えば、酢酸パラジウム(II)と2,4,6−トリメチル安息香酸(TMBA)を反応させることによって、2,4,6−トリメチル安息香酸パラジウム(II)(Pd(TMBA)2)を形成することが挙げられる。
パラジウム元素を含んだ前駆体の種類としては、塩化パラジウム(II)(PdCl2)、臭化パラジウム(II)(PdBr2)、酢酸パラジウム(II)(Pd(CH3CO2)2)、トリフルオロ酢酸パラジウム(II)(Pd(CF3CO2)2)等が挙げられる。
パラジウム錯体等としては、酢酸パラジウム(II)(Pd(OAc)2)、2,4,6−トリメチル安息香酸パラジウム(II)(Pd(TMBA)2)、トリフルオロ酢酸パラジウム(II)(Pd(TFA)2)、ビス(ベンゾニトリル)ジクロロパラジウム(II)(PdCl2(PhCN)2)、ビス(ジベンジリデンアセトン)パラジウム(0)(Pd(dba)2)、アセチルアセトンパラジウム(II)(Pd(acac)2)等が挙げられる。上記のものであると、より効率良く含窒素含ケイ素化合物を製造することができる。
(Palladium complex / palladium salt)
The oxidation number of palladium in the palladium complex and the palladium salt (hereinafter sometimes abbreviated as “palladium complex or the like”), the specific type of the ligand or the counter ion, and the like are not particularly limited, and are appropriately selected depending on the purpose. be able to.
The oxidation number of palladium is usually 0, +1, +2, +4, +6, but is preferably +2.
Examples of the ligand or counter ion or a compound that can be these include acetic acid, 2,4,6-trimethylbenzoic acid (TMBA), trifluoroacetic acid (TFA), benzonitrile (PhCN), dibenzylideneacetone (dba) Acetylacetone (acac), triphenylphosphine (PPh 3 ), chloride anion (Cl − ), bromide anion (Br − ) and the like.
In the reaction step, a palladium complex or the like is directly charged into the reactor, and a precursor containing a palladium element and a compound that can be a ligand or a counter ion are charged as additives, and the target palladium complex is charged in the reactor. Etc. may be formed. For example, forming palladium (II) 2,4,6-trimethylbenzoate (Pd (TMBA) 2 ) by reacting palladium (II) acetate with 2,4,6-trimethylbenzoic acid (TMBA) Is mentioned.
Examples of the type of the precursor containing a palladium element include palladium (II) chloride (PdCl 2 ), palladium (II) bromide (PdBr 2 ), palladium (II) acetate (Pd (CH 3 CO 2 ) 2 ), Palladium (II) fluoroacetate (Pd (CF 3 CO 2 ) 2 ) and the like.
Examples of the palladium complex and the like include palladium (II) acetate (Pd (OAc) 2 ), palladium (II) 2,4,6-trimethylbenzoate (Pd (TMBA) 2 ), palladium (II) trifluoroacetate (Pd ( TFA) 2 ), bis (benzonitrile) dichloropalladium (II) (PdCl 2 (PhCN) 2 ), bis (dibenzylideneacetone) palladium (0) (Pd (dba) 2 ), acetylacetone palladium (II) (Pd ( acac) 2 ) and the like. With the above, a nitrogen-containing silicon-containing compound can be produced more efficiently.
パラジウム錯体等の使用量(仕込量)は、ジエンに対して物質量換算で、通常0.0001倍以上、好ましくは0.001倍以上、より好ましくは0.01倍以上であり、通常1倍以下、好ましくは0.5倍以下、より好ましくは0.2倍以下である。上記範囲内であると、より効率良く含窒素含ケイ素化合物を製造することができる。 The amount of palladium complex or the like used (the amount charged) is usually 0.0001 times or more, preferably 0.001 times or more, more preferably 0.01 times or more, and usually 1 time, in terms of the amount of the diene. Or less, preferably 0.5 times or less, more preferably 0.2 times or less. Within the above range, the nitrogen-containing silicon-containing compound can be produced more efficiently.
(酸素ガス)
反応工程は、酸素ガスの存在下で行われることを特徴とするが、反応器内の気相の成分
(雰囲気ガス)としては、純酸素ガス、空気等が挙げられる。
酸素ガスの分圧としては、通常0.01atm以上、好ましくは0.05atm以上、より好ましくは0.1atm以上であり、通常10atm以下、好ましくは5atm以下、より好ましくは2atm以下である。
(Oxygen gas)
The reaction step is performed in the presence of oxygen gas. The gas phase components (atmosphere gas) in the reactor include pure oxygen gas and air.
The partial pressure of the oxygen gas is generally at least 0.01 atm, preferably at least 0.05 atm, more preferably at least 0.1 atm, usually at most 10 atm, preferably at most 5 atm, more preferably at most 2 atm.
(溶媒)
反応工程は、通常溶媒を使用することが好ましい。また、溶媒の種類は特に限定されず、目的に応じて適宜選択することができるが、具体的にはヘキサン、ベンゼン、トルエン等の炭化水素系溶媒;ジエチルエーテル、テトラヒドロフラン(THF)等のエーテル系溶媒;ジメチルアセトアミド(DMA)、N,N−ジメチルホルムアミド(DMF)、N−メチルピロリドン(NMP)等の非プロトン性極性溶媒等が挙げられる。この中でもN,N−ジメチルホルムアミド(DMF)が特に好ましい。
上記のものであると、より効率良く含窒素含ケイ素化合物を製造することができる。
(solvent)
In the reaction step, it is usually preferable to use a solvent. The type of the solvent is not particularly limited and can be appropriately selected depending on the purpose. Specifically, hydrocarbon solvents such as hexane, benzene, and toluene; ether solvents such as diethyl ether and tetrahydrofuran (THF) Solvent: aprotic polar solvents such as dimethylacetamide (DMA), N, N-dimethylformamide (DMF), and N-methylpyrrolidone (NMP). Among them, N, N-dimethylformamide (DMF) is particularly preferred.
With the above, a nitrogen-containing silicon-containing compound can be produced more efficiently.
(反応条件)
反応工程の反応温度は、通常25℃以上、好ましくは40℃以上、より好ましくは60℃以上であり、通常200℃以下、好ましくは150℃以下、より好ましくは100℃以下である。
反応工程の反応時間は、通常1時間以上、好ましくは3時間以上、より好ましくは6時間以上であり、通常120時間以下、好ましくは96時間以下、より好ましくは72時間以下である。
上記範囲内であると、より効率良く含窒素含ケイ素化合物を製造することができる。
(Reaction conditions)
The reaction temperature in the reaction step is usually 25 ° C. or higher, preferably 40 ° C. or higher, more preferably 60 ° C. or higher, and is usually 200 ° C. or lower, preferably 150 ° C. or lower, more preferably 100 ° C. or lower.
The reaction time of the reaction step is usually 1 hour or more, preferably 3 hours or more, more preferably 6 hours or more, and is usually 120 hours or less, preferably 96 hours or less, more preferably 72 hours or less.
Within the above range, the nitrogen-containing silicon-containing compound can be produced more efficiently.
本発明の製造方法によって製造される含窒素含ケイ素化合物は、アミノ基とシリル基の両方を有する化合物であれば、具体的種類は特に限定されないが、下記式(D−1)又は(D−2)で表される含窒素含ケイ素化合物であることが特に好ましい。
<含窒素含ケイ素化合物又はその塩>
本発明の製造方法によって式(D−1)又は(D−2)で表される含窒素含ケイ素化合物を製造することができることを前述したが、下記式(D−1)又は(D−2)で表される含窒素含ケイ素化合物及びその塩も本発明の一態様である。
なお、R1、R2、R3、R4については、<含窒素含ケイ素化合物の製造方法>において説明したものと同義である。
また、「その塩」とは、式(D−1)又は(D−2)で表される含窒素含ケイ素化合物とイオン等によって形成される塩を意味し、塩を形成するためのイオンの種類は特に限定されないが。塩酸塩、硝酸塩、硫酸塩、酢酸塩等が挙げられる。
<Nitrogen-containing silicon-containing compound or salt thereof>
Although it has been described above that the nitrogen-containing silicon-containing compound represented by the formula (D-1) or (D-2) can be produced by the production method of the present invention, the following formula (D-1) or (D-2) The nitrogen-containing silicon-containing compound represented by the formula (1) and a salt thereof are also an embodiment of the present invention.
Note that R 1 , R 2 , R 3 , and R 4 have the same meanings as those described in <Method for producing nitrogen-containing silicon-containing compound>.
Further, “the salt” means a salt formed by a nitrogen-containing silicon-containing compound represented by the formula (D-1) or (D-2) and an ion or the like. The type is not particularly limited. Hydrochloride, nitrate, sulfate, acetate and the like.
以下に実施例及び比較例を挙げて本発明をさらに具体的に説明するが、本発明の趣旨を逸脱しない限り適宜変更することができる。従って、本発明の範囲は以下に示す具体例により限定的に解釈されるべきものではない。 Hereinafter, the present invention will be described more specifically with reference to Examples and Comparative Examples. However, the present invention can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples described below.
<実施例1>
撹拌子を投入した30mLナスフラスコに、酢酸パラジウム(0.10mmol,0.02245g)、2,4,6−トリメチル安息香酸(TMBA)(0.20mmol,0.03284g)を入れ、アルゴンガスを吹き込んでセプタムを取り付けた。N,N−ジメチルホルムアミド(DMF)2mLをアルゴン置換したシリンジを用いて加え、その後、TMBAと酢酸パラジウムを完全に反応させるために、ナスフラスコをスターラ―を用いて20分撹拌した。撹拌後、ヘキサメチルジシラン(0.20mL,1mmol)、2,3−ジメチル−1,3−ブタジエン(0.565mL,5mmol)、N−メチルアニリン(0.108mL,1mmol)の順にアルゴン置換したシリンジを用いて加えた。環流管の上部に二方コック、さらに酸素ガスを入れたバルーンを取り付けて、系中を酸素雰囲気下にし、オイルバスで60℃(反応温度)に加熱して、撹拌しながら16時間(反応時間)反応させた。反応終了後、還流管内部を洗うようにクエンチ溶媒として、アセトン(10mL)を加えた。
内部基準法(内部基準物質:デカン)により基質の転化率、並びに生成物等の収率を算出(結果を表1に示す。)するとともに、NMR、GC−MS等で分析して生成物の定性を行った。結果、下記式で表される含窒素含ケイ素化合物が生成していることを確認した。また、生成物の収率はアミンを基準として算出した。
(s,3H)2.00(s,3H)3.71(s,3H)3.07 (s, 2H) 6.65-6.75(m,3H)7.20-7.25
(m,2H).
13C NMR(100MHz,CDCl3,23℃): δ0.26,16.36,20.62,26.10,37.49
,55.16,113.06,116.69,123.42,129.69,130.10,151.29.
GC−MS(EI)m/z(relative intencity) 261(5)[M+],155(9),120(8),107(56),77(7) HRMS(EI)calcd for C16H27NSi 261.1913 Found 261.1904
<Example 1>
Palladium acetate (0.10 mmol, 0.02245 g) and 2,4,6-trimethylbenzoic acid (TMBA) (0.20 mmol, 0.03284 g) were charged into a 30 mL eggplant flask charged with a stirrer, and argon gas was blown therein. Attach the septum. 2 mL of N, N-dimethylformamide (DMF) was added using a syringe purged with argon, and then the eggplant flask was stirred using a stirrer for 20 minutes to completely react TMBA and palladium acetate. After stirring, a syringe substituted with argon in the order of hexamethyldisilane (0.20 mL, 1 mmol), 2,3-dimethyl-1,3-butadiene (0.565 mL, 5 mmol), and N-methylaniline (0.108 mL, 1 mmol). Was added. Attach a two-way cock and a balloon containing oxygen gas to the upper part of the reflux pipe, put the system in an oxygen atmosphere, heat to 60 ° C (reaction temperature) in an oil bath, and stir for 16 hours (reaction time). ) Reacted. After completion of the reaction, acetone (10 mL) was added as a quench solvent so as to wash the inside of the reflux tube.
The conversion rate of the substrate and the yield of the product and the like were calculated by the internal reference method (internal reference substance: decane) (the results are shown in Table 1), and the product was analyzed by NMR, GC-MS and the like. Qualitative. As a result, it was confirmed that a nitrogen-containing silicon-containing compound represented by the following formula was formed. The product yield was calculated based on the amine.
(S, 3H) 2.00 (s, 3H) 3.71 (s, 3H) 3.07 (s, 2H) 6.65-6.75 (m, 3H) 7.20-7.25
(M, 2H).
13 C NMR (100 MHz, CDCl 3 , 23 ° C.): δ 0.26, 16.36, 20.62, 26.10, 37.49
, 55.16, 113.06, 116.69, 123.42, 129.69, 130.10, 151.29.
GC-MS (EI) m / z (relative intensity) 261 (5) [M + ], 155 (9), 120 (8), 107 (56), 77 (7) HRMS (EI) calcd for C 16 H 27 NSi 261.1913 Found 261.1904
<実施例2>
酢酸パラジウムをトリフルオロ酢酸パラジウム(Pd(TFA)2)に変更した以外、実施例1と同様の方法により反応を行った。結果を表1に示す。
<Example 2>
The reaction was carried out in the same manner as in Example 1, except that palladium acetate was changed to palladium trifluoroacetate (Pd (TFA) 2 ). Table 1 shows the results.
<実施例3>
酢酸パラジウムをビス(ジベンジリデンアセトン)パラジウム(Pd(dba)2)に変更した以外、実施例1と同様の方法により反応を行った。結果を表1に示す。
<Example 3>
The reaction was carried out in the same manner as in Example 1, except that palladium acetate was changed to bis (dibenzylideneacetone) palladium (Pd (dba) 2 ). Table 1 shows the results.
<比較例1>
バルーン内のガスを酸素ガスからアルゴンガスに変更した以外、実施例1と同様の方法により反応を行った。結果を表2に示す。
<Comparative Example 1>
The reaction was carried out in the same manner as in Example 1, except that the gas in the balloon was changed from oxygen gas to argon gas. Table 2 shows the results.
<実施例4>
バルーン内のガスを酸素ガスから空気に変更した以外、実施例1と同様の方法により反応を行った。結果を表2に示す。
<Example 4>
The reaction was carried out in the same manner as in Example 1, except that the gas in the balloon was changed from oxygen gas to air. Table 2 shows the results.
<実施例5>
TMBAを入れなかった以外、実施例1と同様の方法により反応を行った。結果を表3に示す。
<Example 5>
The reaction was carried out in the same manner as in Example 1, except that TMBA was not added. Table 3 shows the results.
<実施例6>
TMBAをアセチルアセトン(acac)に変更した以外、実施例1と同様の方法により反応を行った。結果を表3に示す。
<Example 6>
The reaction was carried out in the same manner as in Example 1, except that acetylacetone (acac) was used instead of TMBA. Table 3 shows the results.
<実施例7>
TMBAをトリフェニルホスフィン(PPh3)に変更した以外、実施例1と同様の方法により反応を行った。結果を表3に示す。
<Example 7>
The reaction was carried out in the same manner as in Example 1, except that TMBA was changed to triphenylphosphine (PPh 3 ). Table 3 shows the results.
<実施例8>
DMFをジメチルアセトアミド(DMA)に変更した以外、実施例1と同様の方法により反応を行った。結果を表4に示す。
<Example 8>
The reaction was carried out in the same manner as in Example 1, except that DMF was changed to dimethylacetamide (DMA). Table 4 shows the results.
<実施例9>
DMFをα,α,α−トリフルオロトルエン(TFT)に変更した以外、実施例1と同様の方法により反応を行った。結果を表4に示す。
<Example 9>
The reaction was carried out in the same manner as in Example 1, except that DMF was changed to α, α, α-trifluorotoluene (TFT). Table 4 shows the results.
<実施例10>
DMFをN−メチルピロリドン(NMP)に変更した以外、実施例1と同様の方法により反応を行った。結果を表4に示す。
<Example 10>
The reaction was carried out in the same manner as in Example 1, except that DMF was changed to N-methylpyrrolidone (NMP). Table 4 shows the results.
<実施例11>
反応温度を60℃から40℃に変更した以外、実施例1と同様の方法により反応を行った。結果を表5に示す。
<Example 11>
The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed from 60 ° C to 40 ° C. Table 5 shows the results.
<実施例12>
反応温度を60℃から70℃に変更した以外、実施例1と同様の方法により反応を行った。結果を表5に示す。
<Example 12>
The reaction was carried out in the same manner as in Example 1, except that the reaction temperature was changed from 60 ° C to 70 ° C. Table 5 shows the results.
<実施例13>
実施例1と同様の方法により反応を行い、反応開始1時間後、2時間後、4時間後、6時間後、8時間後、24時間後、48時間後の下記式で表される含窒素含ケイ素化合物のそれぞれ収率を算出した。含窒素含ケイ素化合物の収率と反応時間の関係を表したグラフを図1に示す。
The reaction was carried out in the same manner as in Example 1, and 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 24 hours, and 48 hours after the start of the reaction, the nitrogen-containing compound represented by the following formula: The yield of each of the silicon-containing compounds was calculated. FIG. 1 is a graph showing the relationship between the yield of the nitrogen-containing silicon-containing compound and the reaction time.
本発明の製造方法によって製造される含窒素含ケイ素化合物は、例えば有機合成における出発原料として利用することができる。 The nitrogen-containing silicon-containing compound produced by the production method of the present invention can be used, for example, as a starting material in organic synthesis.
Claims (2)
パラジウム錯体及び/又はパラジウム塩、並びに酸素ガスの存在下、下記式(A)で表されるジエンと下記式(B)で表されるアミンと下記式(C)で表されるジシランを反応させて前記含窒素含ケイ素化合物を生成する反応工程(以下、「反応工程」と略す場合がある。)を含むことを特徴とする、含窒素含ケイ素化合物の製造方法。
A diene represented by the following formula (A) is reacted with an amine represented by the following formula (B) and a disilane represented by the following formula (C) in the presence of a palladium complex and / or a palladium salt and oxygen gas. A process for producing the nitrogen-containing silicon-containing compound (hereinafter, may be abbreviated as “reaction step” in some cases).
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