JP6846738B2 - Method for producing an organosilicon compound having a cyclic alkyl group - Google Patents
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- JP6846738B2 JP6846738B2 JP2017010665A JP2017010665A JP6846738B2 JP 6846738 B2 JP6846738 B2 JP 6846738B2 JP 2017010665 A JP2017010665 A JP 2017010665A JP 2017010665 A JP2017010665 A JP 2017010665A JP 6846738 B2 JP6846738 B2 JP 6846738B2
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- 150000003961 organosilicon compounds Chemical class 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000006165 cyclic alkyl group Chemical group 0.000 title description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 51
- -1 trimethylsiloxy group Chemical group 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000010948 rhodium Substances 0.000 claims description 21
- 150000001925 cycloalkenes Chemical class 0.000 claims description 15
- 229910052703 rhodium Inorganic materials 0.000 claims description 15
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 6
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 150000002430 hydrocarbons Chemical group 0.000 description 32
- 125000005843 halogen group Chemical group 0.000 description 21
- 125000001309 chloro group Chemical group Cl* 0.000 description 13
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 12
- 238000006459 hydrosilylation reaction Methods 0.000 description 12
- 125000001246 bromo group Chemical group Br* 0.000 description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 10
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 9
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 8
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 7
- 125000004430 oxygen atom Chemical group O* 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- 125000001153 fluoro group Chemical group F* 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 125000002947 alkylene group Chemical group 0.000 description 5
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 125000005389 trialkylsiloxy group Chemical group 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 239000003054 catalyst Substances 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
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 125000002346 iodo group Chemical group I* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 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 3
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000006606 n-butoxy group Chemical group 0.000 description 2
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 description 1
- 239000004912 1,5-cyclooctadiene Substances 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 1
- 125000001340 2-chloroethyl group Chemical group [H]C([H])(Cl)C([H])([H])* 0.000 description 1
- 0 CCCC1=CC*C1 Chemical compound CCCC1=CC*C1 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 125000003935 n-pentoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 description 1
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、環状アルキル基を有する有機ケイ素化合物の製造方法に関し、より詳しくはロジウム錯体を触媒として利用した環状アルキル基を有する有機ケイ素化合物の製造方法に関する。 The present invention relates to a method for producing an organosilicon compound having a cyclic alkyl group, and more particularly to a method for producing an organosilicon compound having a cyclic alkyl group using a rhodium complex as a catalyst.
ヒドロシリル化反応は、ケイ素原子上にアルキル基を導入する優れた手法であり、白金触媒をはじめとする様々な触媒が開発されている。環状オレフィンを基質に用いるとケイ素原子上に環状アルキル基を導入することができる。歪みのために反応性が高いノルボルネンや電子求引基と共役したα，β−不飽和カルボニル化合物などの環状基質を用いた例は多いものの、シクロヘキセン等の単純な環状オレフィンを用いた例は比較的少ない。さらに、ケイ素原子上にアルコキシ基を有するヒドロシランを用いた環状オレフィンのヒドロシリル化となると、前例は限られているのが現状である（特許文献１及び非特許文献１参照）。白金触媒を用いる特許文献１では水銀灯照射が必要であり、ロジウム錯体を用いる非特許文献１では、芳香環と共役した環状オレフィンを用いた例は示されているが、非共役環状オレフィンの例は示されていない。 The hydrosilylation reaction is an excellent method for introducing an alkyl group onto a silicon atom, and various catalysts such as a platinum catalyst have been developed. When a cyclic olefin is used as a substrate, a cyclic alkyl group can be introduced on the silicon atom. Although there are many examples of using cyclic substrates such as norbornene, which is highly reactive due to strain, and α, β-unsaturated carbonyl compounds conjugated with electron attracting groups, examples of using simple cyclic olefins such as cyclohexene are compared. There are few targets. Further, when it comes to hydrosilylation of a cyclic olefin using a hydrosilane having an alkoxy group on a silicon atom, there are currently limited precedents (see Patent Document 1 and Non-Patent Document 1). Patent Document 1 using a platinum catalyst requires irradiation with a mercury lamp, and Non-Patent Document 1 using a rhodium complex shows an example using a cyclic olefin conjugated with an aromatic ring, but an example of a non-conjugated cyclic olefin is shown. Not shown.
本発明は、有機ケイ素化合物、特に環状アルキル基を有する有機ケイ素化合物を効率よく製造することができる有機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 an organosilicon compound capable of efficiently producing an organosilicon compound, particularly an organosilicon compound having a cyclic alkyl group.
本発明者らは、前記課題を解決すべく鋭意検討を重ねた結果、フェニル−ビス（オキサゾリン）配位子を有する特定のロジウム錯体の存在下でシクロアルケンのヒドロシリル化反応が効率よく進行し、環状アルキル基を有する有機ケイ素化合物を製造することができることを見出し、本発明を完成させた。
即ち、本発明は以下の通りである。
As a result of diligent studies to solve the above problems, the present inventors have efficiently proceeded with the hydrosilylation reaction of cycloalkene in the presence of a specific rhodium complex having a phenyl-bis (oxazoline) ligand. The present invention has been completed by finding that an organosilicon compound having a cyclic alkyl group can be produced.
That is, the present invention is as follows.
＜１＞ 下記式（Ｉ）で表されるロジウム錯体の存在下、下記式（Ａ）で表されるシクロアルケンと下記式（Ｂ）で表されるヒドロシランを反応させて有機ケイ素化合物を生成する反応工程を含むことを特徴とする有機ケイ素化合物の製造方法。
（式（Ｉ）中、Ｒはそれぞれ独立して炭素原子数１〜２０の炭化水素基を、Ｒ’はそれぞれ独立してハロゲン原子を含んでいてもよい炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のアルコキシ基、炭素原子数０〜２０のアミノ基、ニトロ基、又はハロゲン原子を、Ｘはそれぞれ独立してハロゲン原子、又は炭素原子数１〜１０のアシロキシ基を、ｍはそれぞれ独立して０〜４の整数を、ｎは０〜３の整数を表す。）
（式（Ａ）中、Ｒ１は炭素−炭素不飽和結合を含んでいてもよい炭素原子数１〜１０の直鎖状のアルキレン基を、Ｒ２はそれぞれ独立して酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素原子数１〜２０の炭化水素基、又はハロゲン原子を、ｉは０〜（Ｒ１の炭素原子数＋２）の間の整数を表す。）
（式（Ｂ）中、Ｒ３はそれぞれ独立して水素原子、炭素原子数１〜２０のアルコキシ基、炭素原子数１〜２０の炭化水素基、又は炭素原子数１〜２０のトリアルキルシロキシ基を表す。）
＜２＞ 前記反応工程において、銀塩が添加される、＜１＞に記載の有機ケイ素化合物の製造方法。
<1> In the presence of a rhodium complex represented by the following formula (I), an organosilicon compound is produced by reacting a cycloalkene represented by the following formula (A) with a hydrosilane represented by the following formula (B). A method for producing an organosilicon compound, which comprises a reaction step.
(In the formula (I), R is a hydrocarbon group having 1 to 20 carbon atoms independently, and R'is a hydrocarbon group having 1 to 20 carbon atoms which may independently contain a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, a nitro group, or a halogen atom, and X independently having a halogen atom or an acyloxy group having 1 to 10 carbon atoms. m represents an integer of 0 to 4 independently, and n represents an integer of 0 to 3).
(In the formula (A), R 1 is a linear alkylene group having 1 to 10 carbon atoms which may contain a carbon-carbon unsaturated bond, and R 2 is independently composed of an oxygen atom and a halogen atom, respectively. A hydrocarbon group having 1 to 20 carbon atoms or a halogen atom which may contain at least one atom selected from the group, i is an integer between 0 and (the number of carbon atoms in R 1 + 2). Represents.)
(In the formula (B), R 3 is independently a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a trialkylsiloxy group having 1 to 20 carbon atoms. Represents.)
<2> The method for producing an organosilicon compound according to <1>, wherein a silver salt is added in the reaction step.
本発明によれば、環状アルキル基を有する有機ケイ素化合物を効率よく製造することが
できる。
According to the present invention, an organosilicon compound having a cyclic alkyl 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 explaining the details of the present invention, specific examples will be given, but the present invention is not limited to the following contents as long as it does not deviate from the gist of the present invention, and can be appropriately modified and carried out.
＜有機ケイ素化合物の製造方法＞
本発明の一態様である有機ケイ素化合物の製造方法は、下記式（Ｉ）で表されるロジウム錯体の存在下、下記式（Ａ）で表されるシクロアルケンと下記式（Ｂ）で表されるヒドロシランを反応させて有機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。
（式（Ｉ）中、Ｒはそれぞれ独立して炭素原子数１〜２０の炭化水素基を、Ｒ’はそれぞれ独立してハロゲン原子を含んでいてもよい炭素原子数１〜２０の炭化水素基、炭素原子数１〜２０のアルコキシ基、炭素原子数０〜２０のアミノ基、ニトロ基、又はハロゲン原子を、Ｘはそれぞれ独立してハロゲン原子、又は炭素原子数１〜１０のアシロキシ基を、ｍはそれぞれ独立して０〜４の整数を、ｎは０〜３の整数を表す。）
（式（Ａ）中、Ｒ１は炭素−炭素不飽和結合を含んでいてもよい炭素原子数１〜１０の直鎖状のアルキレン基を、Ｒ２はそれぞれ独立して酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素原子数１〜２０の炭化水素基、又はハロゲン原子を、ｉは０〜（Ｒ１の炭素原子数＋２）の間の整数を表す。）
（式（Ｂ）中、Ｒ３はそれぞれ独立して水素原子、炭素原子数１〜２０のアルコキシ基、炭素原子数１〜２０の炭化水素基、又は炭素原子数１〜２０のトリアルキルシロキシ基を表す。）
本発明者らは、環状アルキル基を有する有機ケイ素化合物の製造方法を求め鋭意検討を重ねた結果、フェニル−ビス（オキサゾリン）配位子を有するロジウム錯体、即ち式（Ｉ）で表されるロジウム錯体の存在下で、式（Ａ）で表されるシクロアルケンのヒドロシリル化反応が効率よく進行し、環状アルキル基を有する有機ケイ素化合物が製造できることを見出した。
なお、「有機ケイ素化合物」とは、炭素−ケイ素結合（Ｃ−Ｓｉ）を少なくとも１つ有する有機化合物を意味するものとし、「式（Ａ）で表されるシクロアルケン」と「式（Ｂ）で表されるヒドロシラン」の反応によって生成し得る化合物を意味する。
以下、「反応工程」等について詳細に説明する。
<Manufacturing method of organosilicon compound>
The method for producing an organosilicon compound, which is one aspect of the present invention, is represented by a cycloalkene represented by the following formula (A) and a following formula (B) in the presence of a rhodium complex represented by the following formula (I). It is characterized by including a reaction step (hereinafter, may be abbreviated as "reaction step") for reacting the hydrosilane to produce an organosilicon compound.
(In the formula (I), R is a hydrocarbon group having 1 to 20 carbon atoms independently, and R'is a hydrocarbon group having 1 to 20 carbon atoms which may independently contain a halogen atom. , An alkoxy group having 1 to 20 carbon atoms, an amino group having 0 to 20 carbon atoms, a nitro group, or a halogen atom, and X independently having a halogen atom or an acyloxy group having 1 to 10 carbon atoms. m represents an integer of 0 to 4 independently, and n represents an integer of 0 to 3).
(In the formula (A), R 1 is a linear alkylene group having 1 to 10 carbon atoms which may contain a carbon-carbon unsaturated bond, and R 2 is independently composed of an oxygen atom and a halogen atom, respectively. A hydrocarbon group having 1 to 20 carbon atoms or a halogen atom which may contain at least one atom selected from the group, i is an integer between 0 and (the number of carbon atoms in R 1 + 2). Represents.)
(In the formula (B), R 3 is independently a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a trialkylsiloxy group having 1 to 20 carbon atoms. Represents.)
As a result of diligent studies on a method for producing an organosilicon compound having a cyclic alkyl group, the present inventors have conducted a diligent study, and as a result, a rhodium complex having a phenyl-bis (oxazoline) ligand, that is, a rhodium represented by the formula (I). It has been found that the hydrosilylation reaction of the cycloalkene represented by the formula (A) proceeds efficiently in the presence of the complex, and an organosilicon compound having a cyclic alkyl group can be produced.
The "organosilicon compound" shall mean an organic compound having at least one carbon-silicon bond (C-Si), and "cycloalkene represented by the formula (A)" and "formula (B)). It means a compound that can be produced by the reaction of "hydrosilane represented by".
Hereinafter, the “reaction step” and the like will be described in detail.
反応工程は、「式（Ｉ）で表されるロジウム錯体」の存在下、「式（Ａ）で表されるシクロアルケン」と「式（Ｂ）で表されるヒドロシラン」を反応させて有機ケイ素化合物を生成する工程であるが、「式（Ｉ）で表されるロジウム錯体」、「式（Ａ）で表されるシクロアルケン」、及び「式（Ｂ）で表されるヒドロシラン」の具体的種類は、製造目的である有機ケイ素化合物に応じて適宜選択されるべきである。以下、「式（Ｉ）で表されるロジウム錯体」、「式（Ａ）で表されるシクロアルケン」、及び「式（Ｂ）で表されるヒドロシラン」について具体例を挙げて説明する。
式（Ｉ）中のＲは、それぞれ独立して「炭素原子数１〜２０の炭化水素基」を表しているが、「炭化水素基」は、分岐構造、環状構造のそれぞれを有していてもよく、飽和炭化水素基、芳香族炭化水素基等の何れであってもよいものとする。
Ｒが炭化水素基である場合の炭素原子数は、好ましくは１２以下、より好ましくは１０以下、さらに好ましくは８以下であり、Ｒが芳香族炭化水素基である場合の炭素原子数は、通常６以上である。
Ｒ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、ｉ−プロピル基、フェニル基が特に好ましい。
式（Ｉ）中のＲ’は、それぞれ独立して「ハロゲン原子を含んでいてもよい炭素原子数１〜２０の炭化水素基」、「炭素原子数１〜２０のアルコキシ基」、「炭素原子数０〜２０のアミノ基」、「ニトロ基」、又は「ハロゲン原子」を表しているが、「炭化水素基」は、Ｒの場合と同義である。また、「ハロゲン原子を含んでいてもよい」とは、炭化水素基の水素原子がハロゲン原子に置換されていてもよいことを意味する。さらに、「炭素原
子数０」のアミノ基とは、第１級アミノ基（−ＮＨ２）を意味する。
Ｒ’に含まれる官能基としては、フルオロ基（−Ｆ）、クロロ基（−Ｃｌ）、ブロモ基（−Ｂｒ）、ヨード基（−Ｉ）等が挙げられる。
Ｒ’が炭化水素基である場合の炭素原子数は、好ましくは１２以下、より好ましくは１０以下、さらに好ましくは８以下であり、Ｒ’が芳香族炭化水素基である場合の炭素原子数は、通常６以上である。
Ｒ’としては、メチル基（−ＣＨ３，−Ｍｅ）、トリフルオロメチル基（−ＣＦ３）、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）、メトキシ基（−ＯＣＨ３，−ＯＭｅ）、エトキシ基（−ＯＣ２Ｈ５，−ＯＥｔ）、ｎ−プロポキシ基（−ＯｎＣ３Ｈ７，−ＯｎＰｒ）、ｉ−プロポキシ基（−ＯｉＣ３Ｈ７，−ＯｉＰｒ）、ｎ−ブトキシ基（−ＯｎＣ４Ｈ９，−ＯｎＢｕ）、ｔ−ブトキシ基（−ＯｔＣ４Ｈ９，−ＯｔＢｕ）、ｎ−ペントキシ基（−ＯｎＣ５Ｈ１１）、ｎ−ヘキソキシ基（−ＯｎＣ６Ｈ１３，−ＯｎＨｅｘ）、フェノキシ基（−ＯＣ６Ｈ５，−ＯＰｈ）、ジメチルアミノ基（−Ｎ（ＣＨ３）２，−ＮＭｅ２）、ニトロ基（−ＮＯ２）、フッ素原子（フルオロ基，−Ｆ）、塩素原子（クロロ基，−Ｃｌ）、臭素原子（ブロモ基，−Ｂｒ）、ヨウ素原子（ヨード基，−Ｉ）等が挙げられる。この中でも、メチル基、ｔ−ブチル基が特に好ましい。
式（Ｉ）中のＸは、それぞれ独立して「ハロゲン原子」、又は「炭素原子数１〜１０のアシロキシ基」を表しているが、「アシロキシ基」とは、−ＯＣ（＝Ｏ）Ｒ”で表される構造を意味し、「アシロキシ基」の「炭化水素基（Ｒ”）」もＲの場合と同義である。
Ｘがアシロキシ基である場合のアシロキシ基の炭化水素基の炭素原子数は、好ましくは８以下、より好ましくは６以下、さらに好ましくは４以下であり、アシロキシ基の炭化水素基が芳香族炭化水素基である場合の炭素原子数は、通常６以上である。
Ｘとしては、クロロ基（−Ｃｌ）、ブロモ基（−Ｂｒ）、ヨード基（−Ｉ）、アセトキシ基（−ＯＣ（＝Ｏ）ＣＨ３，−ＯＡｃ）等が挙げられる。この中でも、クロロ基、アセトキシ基が特に好ましい。
式（Ｉ）中のｍは、それぞれ独立して０〜４の整数を、ｎは０〜３の整数を表しているが、ｍは１が好ましく、ｎは０又は１が好ましい
式（Ｉ）で表されるロジウム錯体としては、下記式で表される化合物が挙げられる。下記式で表される化合物であると、より効率よくヒドロシリル化反応が進行する。
なお、「式（Ｉ）で表されるロジウム錯体」は、例えばＨ．Ｎｉｓｈｉｙａｍａ ｅｔ
ａｌ．，Ｐｕｒｅ ａｎｄ Ａｐｐｌｉｅｄ Ｃｈｅｍｉｓｔｒｙ ８０，７４３−７４９．等に記載の方法で調製することができる。
In the reaction step, in the presence of the "lodium complex represented by the formula (I)", the "cycloalkene represented by the formula (A)" and the "hydrosilane represented by the formula (B)" are reacted to form an organosilicon. Regarding the step of producing a compound, specific examples of "a rhodium complex represented by the formula (I)", "a cycloalkene represented by the formula (A)", and "a hydrosilane represented by the formula (B)". The type should be appropriately selected depending on the organosilicon compound intended for production. Hereinafter, "a rhodium complex represented by the formula (I)", "a cycloalkene represented by the formula (A)", and "a hydrosilane represented by the formula (B)" will be described with reference to specific examples.
R in the formula (I) independently represents a "hydrocarbon group having 1 to 20 carbon atoms", but the "hydrocarbon group" has a branched structure and a cyclic structure, respectively. It may be any of a saturated hydrocarbon group, an aromatic hydrocarbon group and the like.
The number of carbon atoms when R is a hydrocarbon group is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, and the number of carbon atoms when R is an aromatic hydrocarbon group is usually 12 or less. 6 or more.
R includes methyl group (-CH 3 , -Me), ethyl group (-C 2 H 5 , -Et), n-propyl group ( -n C 3 H 7 , -n Pr), and i-propyl group (-n Cr). -I C 3 H 7 , -i Pr), n- butyl group ( -n C 4 H 9 , -n Bu), t- butyl group ( -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), phenyl group (-C 6 H 5, - Ph) and the like. Of these, i-propyl group and phenyl group are particularly preferable.
R'in the formula (I) is independently "a hydrocarbon group having 1 to 20 carbon atoms which may contain a halogen atom", "an alkoxy group having 1 to 20 carbon atoms", and "a carbon atom". Although it represents an "amino group of several to 20", a "nitro group", or a "halogen atom", the "hydrocarbon group" is synonymous with the case of R. Further, "may contain a halogen atom" means that the hydrogen atom of the hydrocarbon group may be substituted with a halogen atom. Further, the amino group having "0 carbon atoms" means a primary amino group (-NH 2).
Examples of the functional group contained in R'include a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br), an iodine group (-I) and the like.
When R'is a hydrocarbon group, the number of carbon atoms is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, and when R'is an aromatic hydrocarbon group, the number of carbon atoms is , Usually 6 or more.
As R', methyl group (-CH 3 , -Me), trifluoromethyl group (-CF 3 ), ethyl group (-C 2 H 5 , -Et), 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 group ( -n C 5 H 11 ), n-hexyl group ( -n C 6 H 13 , -n Hex), cyclohexyl group ( -c C 6 H 11 , -Cy) , a phenyl group (-C 6 H 5, -Ph) , a methoxy group (-OCH 3, -OMe), ethoxy group (-OC 2 H 5, -OEt) , n- propoxy group (-O n C 3 H 7 , -O n Pr), i- propoxy group (-O i C 3 H 7, -O i Pr), n- butoxy group (-O n C 4 H 9, -O n Bu), t- butoxy group ( -O t C 4 H 9, -O t Bu), n- pentoxy group (-O n C 5 H 11) , n- hexoxy (-O n C 6 H 13, -O n Hex), a phenoxy group ( -OC 6 H 5 , -OPh), dimethylamino group (-N (CH 3 ) 2 , -NMe 2 ), nitro group (-NO 2 ), fluorine atom (fluoro group, -F), chlorine atom (chloro group) , -Cl), bromine atom (bromo group, -Br), iodine atom (iodo group, -I) and the like. Of these, a methyl group and a t-butyl group are particularly preferable.
Each of the Xs in the formula (I) independently represents a "halogen atom" or an "acyloxy group having 1 to 10 carbon atoms", and the "acyloxy group" is -OC (= O) R. It means the structure represented by "", and the "hydrocarbon group (R") "of the" acyloxy group "is also synonymous with the case of R.
When X is an asyloxy group, the number of carbon atoms of the hydrocarbon group of the asyloxy group is preferably 8 or less, more preferably 6 or less, still more preferably 4 or less, and the hydrocarbon group of the asyloxy group is an aromatic hydrocarbon. When it is a group, the number of carbon atoms is usually 6 or more.
Examples of X include a chloro group (-Cl), a bromo group (-Br), an iodine group (-I), an acetoxy group (-OC (= O) CH 3 , -OAc) and the like. Of these, a chloro group and an acetoxy group are particularly preferable.
M in the formula (I) independently represents an integer of 0 to 4, n represents an integer of 0 to 3, but m is preferably 1 and n is preferably 0 or 1. Examples of the rhodium complex represented by (2) include a compound represented by the following formula. When the compound is represented by the following formula, the hydrosilylation reaction proceeds more efficiently.
The "rhodium complex represented by the formula (I)" is, for example, H.I. Nishiyama et
al. , Pure and Applied Chemistry 80, 743-749. Etc. can be prepared by the method described in the above.
反応工程における「式（Ｉ）で表されるロジウム錯体」の使用量（仕込量）は、後述する「式（Ｂ）で表されるヒドロシラン」に対して物質量換算で、通常０．００１倍以上、
好ましくは０．０１倍以上、より好ましくは０．０４倍以上であり、通常０．２倍以下、好ましくは０．１倍以下、より好ましくは０．０６倍以下である。前記範囲内であると、より効率良くヒドロシリル化が進行する。
The amount (charged amount) of the "rhodium complex represented by the formula (I)" used in the reaction step is usually 0.001 times the amount of the "hydrosilane represented by the formula (B)" described later in terms of substance amount. that's all,
It is preferably 0.01 times or more, more preferably 0.04 times or more, usually 0.2 times or less, preferably 0.1 times or less, and more preferably 0.06 times or less. Within the above range, hydrosilylation proceeds more efficiently.
式（Ａ）中のＲ１は、「炭素−炭素不飽和結合を含んでいてもよい炭素原子数１〜１０の直鎖状のアルキレン基」を表しているが、「炭素−炭素不飽和結合を含んでいてもよい」とは、「アルキレン基」内の炭素−炭素単結合が、炭素−炭素二重結合及び／又は炭素−炭素三重結合に置き換わっていてもよいことを意味する。
Ｒ１の炭素原子数は、好ましくは８以下、より好ましくは７以下、さらに好ましくは６以下である。
Ｒ１としては、メチレン基（−ＣＨ２−）、エチレン基（−ＣＨ２ＣＨ２−）、ｎ−プロピレン基（−ＣＨ２ＣＨ２ＣＨ２−）、ｎ−ブチレン基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ２−）、ブト−２−エン−１，４−ジイル基（−ＣＨ２ＣＨ＝ＣＨＣＨ２−）、ｎ−ペンチレン基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２−）、ペント−２−エン−１，５−ジイル基（−ＣＨ２ＣＨ＝ＣＨＣＨ２ＣＨ２−）、ｎ−ヘキシレン基（−ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２ＣＨ２−）、ヘキサ−３−エン−１，６−ジイル基（−ＣＨ２ＣＨ２ＣＨ＝ＣＨＣＨ２ＣＨ２−）等が挙げられる。
式（Ａ）中のＲ２は、それぞれ独立して「酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素原子数１〜２０の炭化水素基」、又は「ハロゲン原子」を表しているが、「炭化水素基」は、Ｒの場合と同義である。また、「酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい」とは、炭化水素基の水素原子が酸素原子、ハロゲン原子等を含む１価の官能基で置換されていてもよいほか、炭化水素基の炭素骨格内部の炭素原子が酸素原子を含む２価以上の官能基（連結基）で置換されていてもよいことを意味する。
Ｒ２に含まれる官能基としては、エーテル基（オキサ基，−Ｏ−）、フルオロ基（−Ｆ）、クロロ基（−Ｃｌ）、ブロモ基（−Ｂｒ）、ヨード基（−Ｉ）等が挙げられる。
Ｒ２が炭化水素基である場合の炭素原子数は、好ましくは１２以下、より好ましくは１０以下、さらに好ましくは８以下であり、Ｒ’が芳香族炭化水素基である場合の炭素原子数は、通常６以上である。
Ｒ２としては、メチル基（−ＣＨ３，−Ｍｅ）、フルオロメチル基（−ＣＨ２Ｆ）、トリフルオロメチル基（−ＣＦ３）、メトキシメチル基（−ＣＨ２ＯＣＨ３）エチル基（−Ｃ２Ｈ５，−Ｅｔ）、２−クロロエチル基（−ＣＨ２ＣＨ２Ｃｌ）、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）、フッ素原子（フルオロ基，−Ｆ）、塩素原子（クロロ基，−Ｃｌ）、臭素原子（ブロモ基，−Ｂｒ）、ヨウ素原子（ヨード基，−Ｉ）等が挙げられる。この中でも、メチル基、ｔ−ブチル基が特に好ましい。
式（Ａ）中のｉは、「０〜（Ｒ１の炭素原子数＋２）の間の整数」を表しているが、例
えばＲ１が炭素原子数３のｎ−プロピレン基である場合、式（Ａ）で表されるシクロアルケンの環状構造は五員環のシクロペンテンとなり、ｉは０〜５となる。
式（Ａ）で表されるシクロアルケンとしては、下記式で表される化合物が挙げられる。下記式で表される化合物であると、より効率よくヒドロシリル化反応が進行する。
R 1 in the formula (A) represents "a linear alkylene group having 1 to 10 carbon atoms which may contain a carbon-carbon unsaturated bond", but is a "carbon-carbon unsaturated bond". "May contain" means that the carbon-carbon single bond in the "alkylene group" may be replaced by a carbon-carbon double bond and / or a carbon-carbon triple bond.
The number of carbon atoms of R 1 is preferably 8 or less, more preferably 7 or less, still more preferably 6 or less.
R 1 includes methylene group (-CH 2- ), ethylene group (-CH 2 CH 2- ), n-propylene group (-CH 2 CH 2 CH 2- ), n-butylene group (-CH 2 CH 2-). CH 2 CH 2 -), but-2-ene-1,4-diyl group (-CH 2 CH = CHCH 2 - ), n- pentylene (-CH 2 CH 2 CH 2 CH 2 CH 2 -), pent -2-en-1,5-diyl group (-CH 2 CH = CH CH 2 CH 2- ), n-hexylene group (-CH 2 CH 2 CH 2 CH 2 CH 2 CH 2- ), hexa-3-ene -1,6-diyl group (-CH 2 CH 2 CH = CH CH 2 CH 2- ) and the like can be mentioned.
R 2 in the formula (A) is independently "a hydrocarbon group having 1 to 20 carbon atoms which may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom". Alternatively, it represents a "halogen atom", but the "hydrocarbon group" is synonymous with the case of R. Further, "may contain at least one atom selected from the group consisting of an oxygen atom and a halogen atom" means that the hydrogen atom of the hydrocarbon group is a monovalent functional group containing an oxygen atom, a halogen atom and the like. In addition to being substituted with, it means that the carbon atom inside the carbon skeleton of the hydrocarbon group may be substituted with a divalent or higher functional group (linking group) containing an oxygen atom.
Examples of the functional group contained in R 2 include an ether group (oxa group, -O-), a fluoro group (-F), a chloro group (-Cl), a bromo group (-Br), an iodo group (-I) and the like. Can be mentioned.
When R 2 is a hydrocarbon group, the number of carbon atoms is preferably 12 or less, more preferably 10 or less, still more preferably 8 or less, and when R'is an aromatic hydrocarbon group, the number of carbon atoms is , Usually 6 or more.
R 2 includes methyl group (-CH 3 , -Me), fluoromethyl group (-CH 2 F), trifluoromethyl group (-CF 3 ), methoxymethyl group (-CH 2 OCH 3 ) ethyl group (-CH 2 OCH 3) ethyl group (-CH 2 OCH 3). C 2 H 5 , -Et), 2-chloroethyl group (-CH 2 CH 2 Cl), n-propyl group ( -n C 3 H 7 , -n Pr), i-propyl group ( -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 group ( -c C 6 H 11 , -Cy), phenyl group (-C 6 H 5 , -Ph), fluorine atom (-C 6 H 5, -Ph) Fluoro group, −F), chlorine atom (chloro group, −Cl), bromine atom (bromo group, −Br), iodine atom (iodo group, −I) and the like can be mentioned. Of these, a methyl group and a t-butyl group are particularly preferable.
I in the formula (A) represents "an integer between 0 and (the number of carbon atoms of R 1 + 2)". For example, when R 1 is an n-propylene group having 3 carbon atoms, the formula is The cyclic structure of the cycloalkene represented by (A) is a five-membered ring cyclopentene, and i is 0 to 5.
Examples of the cycloalkene represented by the formula (A) include compounds represented by the following formula. When the compound is represented by the following formula, the hydrosilylation reaction proceeds more efficiently.
反応工程における「式（Ａ）で表されるシクロアルケン」の使用量（仕込量）は、後述する「式（Ｂ）で表されるヒドロシラン」に対して物質量換算で、通常１倍以上、好ましくは５倍以上、より好ましくは１０倍以上であり、通常１００倍以下、好ましくは５０倍以下、より好ましくは３０倍以下である。前記範囲内であると、より効率良くヒドロシリル化が進行する。 The amount (charged amount) of the "cycloalkene represented by the formula (A)" used in the reaction step is usually 1 times or more in terms of the amount of substance of the "hydrosilane represented by the formula (B)" described later. It is preferably 5 times or more, more preferably 10 times or more, usually 100 times or less, preferably 50 times or less, and more preferably 30 times or less. Within the above range, hydrosilylation proceeds more efficiently.
式（Ｂ）中のＲ３は、それぞれ独立して「水素原子」、「炭素原子数１〜２０のアルコキシ基」、「炭素原子数１〜２０の炭化水素基」、又は「炭素原子数１〜２０のトリアルキルシロキシ基」を表しているが、「炭化水素基」はＲの場合と同義である。「トリアルキルシロキシ基」とは、−ＯＳｉＲ”３で表される構造を意味し、「アルキル基」は「アリール基」を含むものとする。
Ｒ３がアルコキシ基、炭化水素基、又はトリアルキルシロキシ基である場合の炭化水素基の炭素原子数は、好ましくは１２以下、より好ましくは１０以下、さらに好ましくは８
以下であり、炭化水素基が芳香族炭化水素基である場合の炭素原子数は、通常６以上である。
Ｒ３としては、水素原子、メトキシ基（−ＯＣＨ３，−ＯＭｅ）、エトキシ基（−ＯＣ２Ｈ５，−ＯＥｔ）、ｎ−プロポキシ基（−ＯｎＣ３Ｈ７，−ＯｎＰｒ）、ｉ−プロポキシ基（−ＯｉＣ３Ｈ７，−ＯｉＰｒ）、ｎ−ブトキシ基（−ＯｎＣ４Ｈ９，−ＯｎＢｕ）、ｔ−ブトキシ基（−ＯｔＣ４Ｈ９，−ＯｔＢｕ）、フェノキシ基（−ＯＣ６Ｈ５，−ＯＰｈ）、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）、トリメチルシロキシ基（−ＯＳｉ（ＣＨ３）３，−ＯＳｉＭｅ３）等が挙げられる。この中でも、メトキシ基、メチル基、フェニル基、トリメチルシロキシ基が特に好ましい。
式（Ｂ）で表されるヒドロシランとしては、下記式で表される化合物が挙げられる。下記式で表される化合物であると、より効率よくヒドロシリル化反応が進行する。
R 3 in the formula (B) is independently a "hydrogen atom", an "alkoxy group having 1 to 20 carbon atoms", a "hydrocarbon group having 1 to 20 carbon atoms", or a "carbon atom number 1". It represents "~ 20 trialkylsiloxy groups", but "hydrocarbon groups" is synonymous with the case of R. The "trialkylsiloxy group" means a structure represented by -OSiR "3 , and the" alkyl group "includes an" aryl group ".
When R 3 is an alkoxy group, a hydrocarbon group, or a trialkylsiloxy group, the number of carbon atoms of the hydrocarbon group is preferably 12 or less, more preferably 10 or less, still more preferably 8.
When the hydrocarbon group is an aromatic hydrocarbon group, the number of carbon atoms is usually 6 or more.
As R 3, a hydrogen atom, a methoxy group (-OCH 3, -OMe), ethoxy group (-OC 2 H 5, -OEt) , n- propoxy group (-O n C 3 H 7, -O n Pr) , i- propoxy group (-O i C 3 H 7, -O i Pr), n- butoxy group (-O n C 4 H 9, -O n Bu), t- butoxy (-O t C 4 H 9, -O t Bu), phenoxy group (-OC 6 H 5, -OPh) , methyl group (-CH 3, -Me), ethyl (-C 2 H 5, -Et) , n- propyl ( -N C 3 H 7 , -n Pr), i-propyl group ( -i C 3 H 7 , -i Pr), n- butyl group ( -n C 4 H 9 , -n Bu), t-butyl group ( -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 group ( -c C 6) H 11 , -Cy), phenyl group (-C 6 H 5 , -Ph), trimethylsiloxy group (-OSi (CH 3 ) 3 , -OSiMe 3 ) and the like. Of these, a methoxy group, a methyl group, a phenyl group and a trimethylsiloxy group are particularly preferable.
Examples of the hydrosilane represented by the formula (B) include compounds represented by the following formula. When the compound is represented by the following formula, the hydrosilylation reaction proceeds more efficiently.
反応工程は、その他については特に限定されないが、銀塩が添加されることが好ましい。なお、「銀塩」とは、銀イオン（Ａｇ＋）と陰イオンによって形成される塩を意味する。「銀塩」は、反応工程において「式（Ｉ）で表されるロジウム錯体」の陰イオン交換剤として作用するものと考えられる。
銀塩としては、テトラフルオロホウ酸銀（Ｉ）（ＡｇＢＦ４）、酢酸銀（Ｉ）（ＡｇＯＡｃ）、トリフルオロ酢酸銀（ＡｇＯＣＯＣＦ３）等が挙げられる。
The reaction step is not particularly limited in other respects, but it is preferable that a silver salt is added. The "silver salt" means a salt formed by silver ions (Ag +) and anions. The "silver salt" is considered to act as an anion exchanger of the "rhodium complex represented by the formula (I)" in the reaction step.
Examples of the silver salt include silver tetrafluoroborate (I) (AgBF 4 ), silver acetate (I) (AgOAc), silver trifluoroacetate (AgOCOCF 3 ) and the like.
反応工程における「銀塩」の使用量（添加量）は、「式（Ｂ）で表されるヒドロシラン」に対して物質量換算で、通常０．００１倍以上、好ましくは０．０１倍以上、より好ましくは０．０４倍以上であり、通常０．２倍以下、好ましくは０．１倍以下、より好ましくは０．０６倍以下である。前記範囲内であると、より効率良くヒドロシリル化が進行する。
反応工程における「銀塩」の使用量（添加量）は、「式（Ｉ）で表されるロジウム錯体」に対して物質量換算で、通常０．０１倍以上、好ましくは０．１倍以上、より好ましくは０．５倍以上であり、通常１００倍以下、好ましくは１０倍以下、より好ましくは５倍以下である。前記範囲内であると、より効率良くヒドロシリル化が進行する。
The amount (addition amount) of the "silver salt" used in the reaction step is usually 0.001 times or more, preferably 0.01 times or more, in terms of the amount of substance of the "hydrosilane represented by the formula (B)". It is more preferably 0.04 times or more, usually 0.2 times or less, preferably 0.1 times or less, and more preferably 0.06 times or less. Within the above range, hydrosilylation proceeds more efficiently.
The amount (addition amount) of "silver salt" used in the reaction step is usually 0.01 times or more, preferably 0.1 times or more in terms of substance amount with respect to the "rhodium complex represented by the formula (I)". , More preferably 0.5 times or more, usually 100 times or less, preferably 10 times or less, more preferably 5 times or less. Within the above range, hydrosilylation proceeds more efficiently.
反応工程は、溶媒を使用しても、無溶媒であってもよい。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等が挙げられる。 The reaction step may be solvent-free or solvent-free. The type of solvent is not particularly limited and may be appropriately selected depending on the intended purpose, and specific examples thereof include hydrocarbon solvents such as hexane, benzene and toluene.
反応工程の反応温度は、通常０℃以上、好ましくは１５℃以上であり、通常１００℃以下、好ましくは６０℃以下である。
反応工程の反応時間は、通常３時間以上、好ましくは１０時間以上であり、通常４８時間以下、好ましくは３６時間以下である。
反応工程は、窒素、アルゴン等の不活性雰囲気下で行うことが好ましい。
前記範囲内であると、より効率良くヒドロシリル化が進行する。
The reaction temperature in the reaction step is usually 0 ° C. or higher, preferably 15 ° C. or higher, and usually 100 ° C. or lower, preferably 60 ° C. or lower.
The reaction time of the reaction step is usually 3 hours or more, preferably 10 hours or more, usually 48 hours or less, preferably 36 hours or less.
The reaction step is preferably carried out in an inert atmosphere such as nitrogen or argon.
Within the above range, hydrosilylation proceeds more efficiently.
反応工程によって生成する有機ケイ素化合物の具体的種類は、特に限定されず、製造目的に応じて適宜選択することができるが、下記式（Ｃ−１）又は（Ｃ−２）で表される化合物が挙げられる。
（式（Ｃ−１）及び（Ｃ−２）中、Ｒ１は炭素−炭素不飽和結合を含んでいてもよい炭素原子数１〜１０の直鎖状のアルキレン基を、Ｒ２はそれぞれ独立して酸素原子及びハロゲン原子からなる群より選択される少なくとも１種の原子を含んでいてもよい炭素原子数１〜２０の炭化水素基、又はハロゲン原子を、ｉは０〜（Ｒ１の炭素原子数＋２）の間の整数を、Ｒ３はそれぞれ独立して水素原子、炭素原子数１〜２０のアルコキシ基、炭素原子数１〜２０の炭化水素基、又は炭素原子数１〜２０のトリアルキルシロキシ基を表す。）
なお、Ｒ１、Ｒ２、Ｒ３は、「式（Ａ）で表されるシクロアルケン」及び「式（Ｂ）で表されるヒドロシラン」で挙げたものと同様のものが挙げられる。
また、「式（Ａ）で表されるシクロアルケン」が、２以上の炭素−炭素不飽和結合を有する化合物である場合、有機ケイ素化合物は、少なくとも１つの炭素−炭素不飽和結合がヒドロシリル化されていればよく、例えば「式（Ａ）で表されるシクロアルケン」が、１，５−シクロオクタジエンである場合、有機ケイ素化合物としては下記式で表される化合物が挙げられる。
(In formulas (C-1) and (C-2), R 1 is a linear alkylene group having 1 to 10 carbon atoms which may contain a carbon-carbon unsaturated bond, and R 2 is independent of each other. to an oxygen atom and at least one also contain atoms optionally having 1 to 20 carbon atoms of a hydrocarbon group selected from the group consisting of halogen atom, or a halogen atom, i is the carbon of 0 to (R 1 An integer between the number of atoms + 2), R 3 is an independent hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, a hydrocarbon group having 1 to 20 carbon atoms, or a trie having 1 to 20 carbon atoms. Represents an alkylsiloxy group.)
Examples of R 1 , R 2 , and R 3 are the same as those listed in "Cycloalkene represented by the formula (A)" and "Hydrosilane represented by the formula (B)".
When the "cycloalkene represented by the formula (A)" is a compound having two or more carbon-carbon unsaturated bonds, at least one carbon-carbon unsaturated bond is hydrosilylated in the organosilicon compound. For example, when the "cycloalkene represented by the formula (A)" is 1,5-cyclooctadiene, the organosilicon compound includes a compound represented by the following formula.
以下に実施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 in more detail with reference to examples, but the present invention can be appropriately modified without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as limited by the specific examples shown below.
＜実施例１、２＞
下記式で表されるＲｈ（Ｐｈｅｂｏｘ−ｉＰｒ）Ｃｌ２ＯＨ２（４．９ｍｇ，０．０１０ｍｍｏｌ）（Ｐｈｅｂｏｘ＝２，６−ｂｉｓ（２−ｏｘｙａｚｏｌｙｌｉｎｙｌ）ｐｈｅｎｙｌ）のシクロヘキセン溶液（０．５ｍＬ）に、表１に記載のヒドロシラン（表１に記載の量）を加えた。５０℃で１２時間撹拌した後、ペンタデカン（４２．５ｍｇ，５５．２μＬ，０．２０ｍｍｏｌ）を加え、ＧＣ（ガスクロマトグラフィー）を測定することにより各生成物の収率を決定した。結果、実施例１（ｎ＝１）の生成物が収率３５％で、実施例２（ｎ＝０）の生成物が収率２２％で得られた。
<Examples 1 and 2>
In a cyclohexene solution (0.5 mL) of Rh (Phebox-i Pr) Cl 2 OH 2 (4.9 mg, 0.010 mmol) (Phebox = 2,6-bis (2-oxolylinyl) phenyl) represented by the following formula. , The hydrosilanes listed in Table 1 (the amounts listed in Table 1) were added. After stirring at 50 ° C. for 12 hours, pentadecane (42.5 mg, 55.2 μL, 0.20 mmol) was added, and the yield of each product was determined by measuring GC (gas chromatography). As a result, the product of Example 1 (n = 1) was obtained in a yield of 35%, and the product of Example 2 (n = 0) was obtained in a yield of 22%.
＜実施例３〜６＞
下記式で表されるＲｈ（Ｐｈｅｂｏｘ−ｉＰｒ）Ｃｌ２ＯＨ２（表２に記載の量）と表２に記載の銀塩（表２に記載の量）のＴＨＦ懸濁液（実施例３：２ｍＬ、実施例４：１．５ｍＬ、実施例５、６：１ｍＬ）を１時間撹拌した。その後、溶媒を減圧留去し、シクロヘキセン（表２に記載の量）、表２に記載のヒドロシラン（表２に記載の量）を加え、５０℃で１２時間撹拌した。この溶液にペンタデカン（実施例３：８５．０ｍｇ，１１０μＬ，０．４０ｍｍｏｌ、実施例４、５、６：４２．５ｍｇ，５５．２μＬ，０．２０ｍｍｏｌ）を加え、ＧＣを測定することにより、各生成物の収率を決定した。結果、実施例３（ｎ＝１、Ｘ＝ＢＦ４）の生成物が収率５８％で、実施例４（ｎ＝１、Ｘ＝ＯＡｃ）の生成物が収率５５％で、実施例５（ｎ＝０、Ｘ＝ＢＦ４）の生成物が収率４４％で、実施例
６（ｎ＝０、Ｘ＝ＯＡｃ）の生成物が収率６２％で得られた。
<Examples 3 to 6>
THF suspension of Rh (Phebox-i Pr) Cl 2 OH 2 (amount shown in Table 2) and silver salt (amount shown in Table 2) represented by the following formula (Example 3). : 2 mL, Example 4: 1.5 mL, Example 5, 6: 1 mL) was stirred for 1 hour. Then, the solvent was distilled off under reduced pressure, cyclohexene (amount shown in Table 2) and hydrosilane (amount shown in Table 2) were added, and the mixture was stirred at 50 ° C. for 12 hours. Pentadecane (Example 3: 85.0 mg, 110 μL, 0.40 mmol, Examples 4, 5, 6: 42.5 mg, 55.2 μL, 0.20 mmol) was added to this solution, and GC was measured. The yield of the product was determined. As a result, the product of Example 3 (n = 1, X = BF 4 ) had a yield of 58%, and the product of Example 4 (n = 1, X = OAc) had a yield of 55%, and Example 5 The product of (n = 0, X = BF 4 ) was obtained in a yield of 44%, and the product of Example 6 (n = 0, X = OAc) was obtained in a yield of 62%.
＜実施例７、８＞
下記式で表されるＲｈ（Ｐｈｅｂｏｘ−ｉＰｒ）（ＯＡｃ）２ＯＨ２（５．４ｍｇ，０．０１０ｍｍｏｌ）のシクロヘキセン溶液（０．５ｍＬ）に、表３に記載のヒドロシラン（表３に記載の量）を加えた。５０℃で１２時間撹拌した後、ペンタデカン（４２．５ｍｇ，５５．２μＬ，０．２０ｍｍｏｌ）を加え、ＧＣを測定することにより各生成物の収率を決定した。結果、実施例７（ｎ＝１）の生成物が収率５９％で、実施例８（ｎ＝０）の生成物が収率７３％で得られた。
<Examples 7 and 8>
Rh (Phebox-i Pr) (OAc) 2 OH 2 (5.4 mg, 0.010 mmol) represented by the following formula in a cyclohexene solution (0.5 mL) and hydrosilanes shown in Table 3 (shown in Table 3). Amount) was added. After stirring at 50 ° C. for 12 hours, pentadecane (42.5 mg, 55.2 μL, 0.20 mmol) was added, and the GC was measured to determine the yield of each product. As a result, the product of Example 7 (n = 1) was obtained in a yield of 59%, and the product of Example 8 (n = 0) was obtained in a yield of 73%.
＜実施例９、１０＞
下記式で表されるＲｈ（Ｐｈｅｂｏｘ−Ｐｈ）（ＯＡｃ）２ＯＨ２（６．１ｍｇ，０．０１０ｍｍｏｌ）のシクロヘキセン溶液（０．５ｍＬ）に、表４に記載のヒドロシラン（表４に記載の量）を加えた。５０℃で１２時間撹拌した後、ペンタデカン（４２．５ｍｇ，５５．２μＬ，０．２０ｍｍｏｌ）を加え、ＧＣを測定することにより各生成物の収率を決定した。結果、実施例９（ｎ＝１）の生成物が収率５７％で、実施例１０（ｎ＝０）の生成物が収率６７％で得られた。
<Examples 9 and 10>
Hydrosilane (amount shown in Table 4) shown in Table 4 in a cyclohexene solution (0.5 mL) of Rh (Phebox-Ph) (OAc) 2 OH 2 (6.1 mg, 0.010 mmol) represented by the following formula. ) Was added. After stirring at 50 ° C. for 12 hours, pentadecane (42.5 mg, 55.2 μL, 0.20 mmol) was added, and the GC was measured to determine the yield of each product. As a result, the product of Example 9 (n = 1) was obtained in a yield of 57%, and the product of Example 10 (n = 0) was obtained in a yield of 67%.
＜実施例１１、１２＞
下記式で表されるＲｈ（Ｐｈｅｂｏｘ−ｉＰｒ）（ＯＡｃ）２ＯＨ２（５．４ｍｇ，０．０１０ｍｍｏｌ）のシクロヘキセン溶液（０．５ｍＬ）に、表５に記載のヒドロシラン（表５に記載の量）を加えた。２５℃で１２時間撹拌した後、ペンタデカン（４２．５ｍｇ，５５．２μＬ，０．２０ｍｍｏｌ）を加え、ＧＣを測定することにより各生成物の収率を決定した。結果、実施例１１（ｎ＝１）の生成物が収率６５％で、実施例１２（ｎ＝０）の生成物が収率７２％で得られた。
<Examples 11 and 12>
Rh (Phebox-i Pr) (OAc) 2 OH 2 (5.4 mg, 0.010 mmol) represented by the following formula in a cyclohexene solution (0.5 mL) and hydrosilanes shown in Table 5 (shown in Table 5). Amount) was added. After stirring at 25 ° C. for 12 hours, pentadecane (42.5 mg, 55.2 μL, 0.20 mmol) was added, and the GC was measured to determine the yield of each product. As a result, the product of Example 11 (n = 1) was obtained in a yield of 65%, and the product of Example 12 (n = 0) was obtained in a yield of 72%.
＜実施例１３＞
下記式で表されるＲｈ（Ｐｈｅｂｏｘ−ｉＰｒ）（ＯＡｃ）２ＯＨ２（５．４ｍｇ，０．０１０ｍｍｏｌ）のシクロペンテン溶液（０．５ｍＬ）に、表６に記載のヒドロシラン（表６に記載の量）を加え、２５°Cで１２時間撹拌した。この反応溶液にＰｈＳｉＭｅ３（３０．１ｍｇ，３４．６μＬ，０．２０ｍｍｏｌ）を加えた後、この溶液０．３ｍＬにＣｒ（ａｃａｃ）３（２０ｍｇ）(ａｃａｃ＝アセチルアセトナート)を加え、２９ＳｉＮＭＲを測定することにより生成物の収率を決定した。実施例１３（ｎ＝１）の生成物が収率９１％で得られた。
<Example 13>
The hydrosilanes shown in Table 6 (shown in Table 6) were added to a cyclopentene solution (0.5 mL) of Rh (Phebox-i Pr) (OAc) 2 OH 2 (5.4 mg, 0.010 mmol) represented by the following formula. Amount) was added, and the mixture was stirred at 25 ° C. for 12 hours. After adding PhSiMe 3 (30.1 mg, 34.6 μL, 0.20 mmol) to this reaction solution, Cr (acac) 3 (20 mg) (acac = acetylacetoneate) was added to 0.3 mL of this solution, and 29 SiNMR was added. The yield of the product was determined by measuring. The product of Example 13 (n = 1) was obtained in a yield of 91%.
本発明の製造方法によって提供される有機ケイ素化合物は、シリコーンポリマーや機能性シロキサン化合物等の原料として有用である。 The organosilicon compound provided by the production method of the present invention is useful as a raw material for a silicone polymer, a functional siloxane compound, and the like.
Claims (1)
（式（Ｉ）中、Ｒはそれぞれ独立して炭素原子数１〜８の炭化水素基を、Ｘはそれぞれ独立して炭素原子数１〜４のアシロキシ基を、ｍはそれぞれ独立して０〜４の整数を表す。）
（式（Ｂ）中、Ｒ３はそれぞれ独立してメトキシ基、メチル基、フェニル基、又はトリメチルシロキシ基を表す。）
（式（Ｃ’−１）〜（Ｃ’−５）中、Ｒ ３ はそれぞれ式（Ｂ）のＲ ３ と同一である。） Cycloalkene selected from the compounds represented by the following formulas (A'-1) to (A'-5) and hydrosilane represented by the following formula (B) in the presence of the rhodium complex represented by the following formula (I). A method for producing an organosilicon compound, which comprises a reaction step of producing an organosilicon compound selected from the compounds represented by the following formulas (C'-1) to (C'-5) by reacting the above.
(In formula (I), the hydrocarbon group of R are each independently carbon atoms. 1 to 8, X is independently a carbon atom number 1-4 acyloxy group, m is independently 0 Table vinegar to 4 integer.)
(In formula (B), R 3 independently represents a methoxy group, a methyl group, a phenyl group, or a trimethylsiloxy group .)
(In formulas (C'-1) to (C'-5), R 3 is the same as R 3 in formula (B), respectively .)
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