JP2006160729A - New acetylene compound and method for producing the same - Google Patents
New acetylene compound and method for producing the same Download PDFInfo
- Publication number
- JP2006160729A JP2006160729A JP2005321373A JP2005321373A JP2006160729A JP 2006160729 A JP2006160729 A JP 2006160729A JP 2005321373 A JP2005321373 A JP 2005321373A JP 2005321373 A JP2005321373 A JP 2005321373A JP 2006160729 A JP2006160729 A JP 2006160729A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- acetylene
- carbon
- carbon atoms
- 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
- -1 acetylene compound Chemical class 0.000 title claims abstract description 39
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 150000003961 organosilicon compounds Chemical class 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910018557 Si O Inorganic materials 0.000 claims description 4
- 150000001721 carbon Chemical group 0.000 claims description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 3
- 238000006459 hydrosilylation reaction Methods 0.000 abstract description 3
- 239000002736 nonionic surfactant Substances 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 239000007818 Grignard reagent Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 4
- GGQYQDHVPNLDSQ-UHFFFAOYSA-N 3-methylpent-4-yne-1,3-diol Chemical compound C#CC(O)(C)CCO GGQYQDHVPNLDSQ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003377 silicon compounds Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SJBBXFLOLUTGCW-UHFFFAOYSA-N 1,3-bis(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=CC(C(F)(F)F)=C1 SJBBXFLOLUTGCW-UHFFFAOYSA-N 0.000 description 2
- 229910014033 C-OH Inorganic materials 0.000 description 2
- 229910014570 C—OH Inorganic materials 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910021419 crystalline silicon Inorganic materials 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 1
- XUDUTRMKKYUAKI-UHFFFAOYSA-N 3-[1-(1-phenylethyl)piperidin-4-yl]-1h-benzimidazol-2-one Chemical compound C1CC(N2C(NC3=CC=CC=C32)=O)CCN1C(C)C1=CC=CC=C1 XUDUTRMKKYUAKI-UHFFFAOYSA-N 0.000 description 1
- LVSQXDHWDCMMRJ-UHFFFAOYSA-N 4-hydroxybutan-2-one Chemical compound CC(=O)CCO LVSQXDHWDCMMRJ-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- VWWMOACCGFHMEV-UHFFFAOYSA-N dicarbide(2-) Chemical compound [C-]#[C-] VWWMOACCGFHMEV-UHFFFAOYSA-N 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- KDOWHHULNTXTNS-UHFFFAOYSA-N hex-3-yne-2,5-diol Chemical compound CC(O)C#CC(C)O KDOWHHULNTXTNS-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- BCNZYOJHNLTNEZ-UHFFFAOYSA-N tert-butyldimethylsilyl chloride Chemical compound CC(C)(C)[Si](C)(C)Cl BCNZYOJHNLTNEZ-UHFFFAOYSA-N 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Abstract
Description
本発明は、新規のアセチレン化合物およびその製造方法に関する。とくに蒸留による単離の困難な程に分子量の高いアセチレンアルコール類を提供するものである。 The present invention relates to a novel acetylene compound and a method for producing the same. In particular, the present invention provides acetylene alcohols having a molecular weight so high that isolation by distillation is difficult.
アセチレンアルコール類は、例えば「オルフィン」(日信化学工業株式会社の商品名)で3−メチル−1−ブチン−3−オール、3−メチル−1−ペンチン−3−オール 2,5−ジメチル−3−ヘキシン−2,5−ジオール等が、また「サーフィノール」(エアープロダクツ株式会社の商品名)で各種アセチレングリコール類が市販されている。
The acetylene alcohols are, for example, “Orphine” (trade name of Nissin Chemical Industry Co., Ltd.) 3-methyl-1-butyn-3-ol, 3-methyl-1-pentyn-3-
これらアセチレンアルコール類は化合物の中間体原料として用いられる他に、金属表面処理剤、低発泡性の濡れ剤、消泡剤、顔料分散剤などの非イオン系界面活性剤としての用途で、また遷移金属への高い配位能を利用したヒドロシリル化反応の制御剤として、工業的にも広く用いられているきわめて有用な化合物である(特許文献1〜3参照)。
These acetylene alcohols are used as intermediate raw materials for compounds, and are also used as nonionic surfactants such as metal surface treatment agents, low foaming wetting agents, antifoaming agents, and pigment dispersants. It is a very useful compound widely used industrially as a control agent for hydrosilylation reaction utilizing high coordination ability to metal (see
アセチレンアルコール類の製造は一般には、下記に示すようにケトン類にアセチリドを反応させることにより行われる。 In general, acetylene alcohols are produced by reacting ketones with acetylide as shown below.
すなわち、ある構造のアセチレンアルコールを製造するためには、前駆体であるケトン類を得なければならない。分子量の大きい複雑な構造のアセチレンアルコールを製造しようとした場合には上記方法は困難になると思われる。 That is, in order to produce acetylene alcohol having a certain structure, it is necessary to obtain ketones as precursors. If an attempt is made to produce an acetylene alcohol having a high molecular weight and a complicated structure, the above method will be difficult.
また、アセチレンアルコールとフロロアルキル基含有のクロロシラン類を反応させた物質は公知である(特許文献4参照)。しかし、該フッ素オルガノシリコーン化合物は、アルコール性水酸基を有しないので、制御剤として満足の行くものではない。 A substance obtained by reacting acetylene alcohol with a fluoroalkyl group-containing chlorosilane is known (see Patent Document 4). However, since the fluorine organosilicon compound does not have an alcoholic hydroxyl group, it is not satisfactory as a control agent.
本発明は、上記事情に鑑みなされたもので、比較的分子量の大きい複雑な構造のアセチレンアルコールを容易に製造する方法を提供するものである。 The present invention has been made in view of the above circumstances, and provides a method for easily producing acetylene alcohol having a relatively large molecular weight and a complicated structure.
本発明者らは、上記目的を達成するため検討を行った結果、下記一般式にて示されるシリル化されたアセチレン化合物を提供することにより、本発明を完成させた。 As a result of investigations to achieve the above object, the present inventors have completed the present invention by providing a silylated acetylene compound represented by the following general formula.
但し、R1は、ケイ素原子と結合する炭素原子が3級炭素である炭素数4〜10の1価炭化水素基、R2、R3は炭素数1〜4のアルキル基またはRf−Q−で示されるフロロアルキル基を含む1価の基であり、Rfは炭素数3〜100のパーフルオロアルキル基で、途中エーテル結合を含んでいてもよく、分岐していても良い。Qは炭素数2〜10の2価の基であって途中に窒素、酸素、イオウを含んでもよい。nは0または1である。
R 1 is a monovalent hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the silicon atom is a tertiary carbon, R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms or Rf-Q- And Rf is a perfluoroalkyl group having 3 to 100 carbon atoms and may contain an ether bond in the middle or may be branched. Q is a divalent group having 2 to 10 carbon atoms and may contain nitrogen, oxygen, or sulfur in the middle. n is 0 or 1.
下記一般式(A)にて示される有機ケイ素化合物と、 An organosilicon compound represented by the following general formula (A);
(但し、R1、R2及びR3は前記と同じ基、Xはハロゲン原子、nは0または1である。)下記のアセチレンアルコール(B)を反応させて、
(However, R 1 , R 2 and R 3 are the same groups as described above, X is a halogen atom, and n is 0 or 1.) The following acetylene alcohol (B) is reacted,
(A)のSi−Xと、(B)のいずれか一方または両方の水酸基とからSi−O結合を形成させることを特徴とするシリル化されたアセチレン化合物の製造方法。このとき1級炭素に結合した水酸基が優先的にハロゲン化ケイ素化合物と反応してSi−O結合を生じ、目的とするアセチレンアルコールを得ることができる。
A method for producing a silylated acetylene compound, wherein a Si—O bond is formed from Si—X of (A) and one or both of the hydroxyl groups of (B). At this time, the hydroxyl group bonded to the primary carbon preferentially reacts with the silicon halide compound to form a Si—O bond, and the target acetylene alcohol can be obtained.
本発明の新規の含フッ素アセチルアルコール化合物は、非イオン系界面活性剤、化合物の中間体、ポリマーのヒドロシリル化による硬化反応の制御剤としてきわめて有用である。 The novel fluorine-containing acetyl alcohol compound of the present invention is extremely useful as a nonionic surfactant, an intermediate of the compound, and a controller for a curing reaction by hydrosilylation of a polymer.
以下、本発明につき更に詳しく説明する。上記一般式で示されるアセチレン化合物において、R1はケイ素原子と結合する炭素原子が3級炭素である炭素数4〜10の1価の炭化水素基である。このようなR1としては以下のような構造が挙げられる。 Hereinafter, the present invention will be described in more detail. In the acetylene compound represented by the above general formula, R 1 is a monovalent hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the silicon atom is a tertiary carbon. Examples of such R 1 include the following structures.
ここで、R1がケイ素原子と結合する炭素原子が3級炭素に限定するのは、上記に例示した3級炭素を含むアルキル基は嵩高い置換基であるので、このような置換基はSi−O結合を安定にする効果のあることが知られているためである。3級炭素を含むアルキル基が無い場合は、シリル化されたアセチレン化合物が不安定で、容易に加水分解するなど不都合の生じることがある。 Here, the carbon atom bonded to the silicon atom of R 1 is limited to the tertiary carbon because the alkyl group containing the tertiary carbon exemplified above is a bulky substituent. This is because it is known to have an effect of stabilizing the —O bond. In the absence of an alkyl group containing a tertiary carbon, the silylated acetylene compound is unstable and may cause inconvenience such as easy hydrolysis.
R2、R3はそれぞれ同一であっても異なっても良い炭素数1〜4のアルキル基またはRf−Q−で示されるフロロアルキル基を含む1価の基であり、Rfは炭素数3〜100のパーフルオロアルキル基で、途中エーテル結合を含んでいてもよく、分岐していても良い。 R 2 and R 3 may be the same or different and each is an alkyl group having 1 to 4 carbon atoms or a monovalent group containing a fluoroalkyl group represented by Rf-Q—, and Rf is 3 to 3 carbon atoms It is a 100 perfluoroalkyl group and may contain an ether bond in the middle or may be branched.
炭素数1〜4のアルキル基としては、具体的にはメチル基、エチル基、n−プロピル基、イソプロピル基、n−ブチル基、イソブチル基、t−ブチル基などが挙げられる。特に、メチル基が好ましい。 Specific examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. A methyl group is particularly preferable.
Rfの好ましい例としては、下記のものがあげられる。 Preferable examples of Rf include the following.
また、Qは炭素数1〜20の2価の有機基である。Qは炭素数1〜20の2価の有機基であれば特に制限されるものではないが、途中に酸素、窒素、カルボニル基などを介してもよく、例えば以下の構造が挙げられる。 Q is a divalent organic group having 1 to 20 carbon atoms. Q is not particularly limited as long as it is a divalent organic group having 1 to 20 carbon atoms, but may be intervened through oxygen, nitrogen, carbonyl group, etc., and examples thereof include the following structures.
−(CH2)p−
(但し、p=1〜10特に好ましくは2〜4)
−CH2−O−(CH2)q−
(但し、q=1〜9特に好ましくは2〜4)
− (CH 2 ) p −
(However, p = 1-10, particularly preferably 2-4)
-CH 2 -O- (CH 2) q -
(However, q = 1-9, particularly preferably 2-4)
本発明の上記した一般式で示されるセチレン化合物は、下記一般式にて示される有機ケイ素化合物(A)と、 The cetylene compound represented by the above general formula of the present invention is an organosilicon compound (A) represented by the following general formula:
(但し、R1、R2及びR3は前述の通り、Xはハロゲン原子)
(Wherein R 1 , R 2 and R 3 are as described above, X is a halogen atom)
下記のアセチレンアルコール(B) Acetylene alcohol (B) below
とを反応させると、(A)のSi−Xと(B)の1級炭素に結合した水酸基とからSi−O結合を形成させることにより製造される。
Is reacted with Si—X in (A) and a hydroxyl group bonded to the primary carbon in (B) to produce a Si—O bond.
(B)のアセチレンアルコール3−methyl−4−pentyne−1,3−diolは、4−hydroxy−2−butanoneにアセチレンのグリニャール試薬を反応させることにより製造することができる。また、J.Am.Chem.Soc.1980,102,6255−6259に記載された方法によっても製造することができる。これはふたつの水酸基を持ち、1つは一級炭素にもう1つは3級炭素に結合している。 The acetylene alcohol 3-methyl-4-pentyne-1,3-diol of (B) can be produced by reacting 4-hydroxy-2-butaneone with an acetylene Grignard reagent. In addition, in J. Am. Chem. Soc. 1980, 102, 6255-6259. It has two hydroxyl groups, one bonded to the primary carbon and the other to the tertiary carbon.
(A)のハロゲン化ケイ素化合物は、1つ置換基と3つのハロゲンを有するケイ素化合物に嵩高いアルキル基のグリニャール試薬、(例えばt-ブチルグリニャール試薬)を反応させることにより製造することができる。この方法により1つ置換基と2つのハロゲンおよび嵩高い置換基を有するケイ素化合物を得ることができる。さらに置換基を導入して一つのハロゲンと3つの置換基を有するケイ素化合物を得る場合は、引き続きn-ブチルグリニャール試薬などの比較的立体障害の少ない試薬を選択的条件にて反応させることもできる。 The silicon halide compound (A) can be produced by reacting a silicon compound having one substituent and three halogens with a bulky alkyl group Grignard reagent (for example, a t-butyl Grignard reagent). By this method, a silicon compound having one substituent, two halogens and a bulky substituent can be obtained. Further, when a silicon compound having one halogen and three substituents is obtained by introducing a substituent, a reagent with relatively little steric hindrance such as an n-butyl Grignard reagent can be subsequently reacted under selective conditions. .
(A)の有機ケイ素化合物はより具体的には次のものがあげられる。 Specific examples of the organosilicon compound (A) include the following.
(但し、Rfは前述の通り、t−Buはターシャリブチル基である。)
(However, Rf is a tertiary butyl group as described above.)
[製造方法]
本発明のアセチレン化合物の製造は、(B)のアセチレンアルコールおよび受酸剤を混合しておき、そこに(A)の有機ケイ素化合物を投入することにより行われる。受酸剤としては、トリエチルアミン、ピリジン、尿素、1,4−ジアザビシクロ〔2.2.2〕オクタン(DABCO)、1,8−ジアザビシクロ〔5.4.7〕−7−ウンデセン(DBU)、イミダゾールなどがよい。
[Production method]
The production of the acetylene compound of the present invention is carried out by mixing the acetylene alcohol (B) and the acid acceptor and introducing the organosilicon compound (A) therein. Examples of the acid acceptor include triethylamine, pyridine, urea, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.7] -7-undecene (DBU), and imidazole. Etc.
反応時に溶媒を使用することもできる。溶媒としてはトルエン、キシレン、ヘキサン、オクタン、イソオクタン、1,3−ビストリフロロメチルベンゼン、DMF、N−メチルピロリドンなどが好適である。 A solvent can also be used during the reaction. As the solvent, toluene, xylene, hexane, octane, isooctane, 1,3-bistrifluoromethylbenzene, DMF, N-methylpyrrolidone and the like are suitable.
使用量は、(A)におけるn=1の場合(1官能の場合)には、有機ケイ素化合物(A)1モルあたりアセチレンアルコール(B)1〜2モル、受酸剤1〜3モルを使用する。反応温度は20〜50℃、反応時間は1〜40時間でよい。反応終了後、水洗を繰り返して有機相を取り出し、適当な方法を用いて精製することにより、目的とするアセチレンアルコールを得ることができる。 When n = 1 in (A) (monofunctional), the amount used is 1 to 2 moles of acetylene alcohol (B) and 1 to 3 moles of acid acceptor per mole of organosilicon compound (A). To do. The reaction temperature may be 20 to 50 ° C., and the reaction time may be 1 to 40 hours. After completion of the reaction, washing with water is repeated to take out the organic phase, and purification is performed using an appropriate method, whereby the target acetylene alcohol can be obtained.
また、(A)におけるn=0の場合(2官能の場合)には、有機ケイ素化合物(A)1モルあたりアセチレンアルコール(B)2〜4モル、受酸剤2〜4モルを使用する。反応温度は20〜50℃、反応時間は1〜20時間でよい。反応終了後、水洗を繰り返して有機相を取り出し、適当な方法を用いて精製することにより、目的とするアセチレンアルコールを得ることができる。 Further, when n = 0 in (A) (in the case of bifunctionality), 2 to 4 mol of acetylene alcohol (B) and 2 to 4 mol of acid acceptor are used per 1 mol of the organosilicon compound (A). The reaction temperature may be 20 to 50 ° C., and the reaction time may be 1 to 20 hours. After completion of the reaction, washing with water is repeated to take out the organic phase, and purification is performed using an appropriate method, whereby the target acetylene alcohol can be obtained.
以下、実施例及び比較例を示し、本発明を具体的に説明するが、本発明は下記の実施例に制限されるものではない。 EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not restrict | limited to the following Example.
[実施例1]
3−メチル−3,5−ジヒドロキシ−ペンチン5.00g (0.0439mol)、t−ブチルジメチルクロロシラン 6.58g (0.0439mol)、 イミダゾール7.50g (0.110 mol)、 ジメチルホルムアミド 10.0g を反応器に仕込み、室温にて20時間攪拌を行った。反応終了後、ジエチルエ−テル30gを添加、水50gで3回水洗、その後70℃/5mmHgにてストリップをして7.2gの生成物を得た。この生成物をNMRにて分析したところ下記の構造であることが確認された。
[Example 1]
3-methyl-3,5-dihydroxy-pentyne 5.00 g (0.0439 mol), t-butyldimethylchlorosilane 6.58 g (0.0439 mol), imidazole 7.50 g (0.110 mol), dimethylformamide 10.0 g Was stirred at room temperature for 20 hours. After completion of the reaction, 30 g of diethyl ether was added, washed with 50 g of water three times, and then stripped at 70 ° C./5 mmHg to obtain 7.2 g of product. The product was analyzed by NMR and confirmed to have the following structure.
この化合物の1H NMRスペクトルを図1に示す。結果は以下の通りであった。
1H NMRスペクトル(CDCl3)
δ0.05(Si−CH 2, 6H, d)
δ0.84((CH 3)3C−Si, 9H, s)
δ1.43(CH 3−C−OH,3H, s)
δ1.63(−OCH2CH 2−, 1H, m)
δ1.90(−OCH2CH 2−, 1H, m) δ2.38(−C≡CH, 1H, s)
δ3.83(−OCH 2CH2−, 1H, m)
δ4.18(−OCH 2CH2−, 1H, m)
δ4.66(−OH, 1H, s)
The 1 H NMR spectrum of this compound is shown in FIG. The results were as follows.
1 H NMR spectrum (CDCl 3 )
δ0.05 (Si—C H 2 , 6H, d)
δ 0.84 ((C H 3 ) 3 C-Si, 9H, s)
δ1.43 (C H 3 —C—OH, 3H, s)
δ1.63 (-OCH 2 C H 2 - , 1H, m)
δ1.90 (-OCH 2 C H 2 - , 1H, m) δ2.38 (-C≡C H, 1H, s)
δ 3.83 (—OC H 2 CH 2 —, 1H, m)
δ 4.18 (—OC H 2 CH 2 —, 1H, m)
δ4.66 (-O H, 1H, s )
また、この化合物のIRスペクトルを図2に示す。結果は以下の通りであった。
赤外吸収スペクトル
3478cm−1 (−OH)
3315cm−1 (−C≡CH)
The IR spectrum of this compound is shown in FIG. The results were as follows.
Infrared absorption spectrum 3478 cm −1 (—OH)
3315 cm −1 (—C≡CH)
[実施例2]
3−メチル−3,5−ジヒドロキシ−ペンチン5.0g、トリエチルアミン3.2g、1,3−ビストリフロロメチルベンゼン20g、および下記構造の有機ケイ素化合物10g、
[Example 2]
3-methyl-3,5-dihydroxy-pentyne 5.0 g, triethylamine 3.2 g, 1,3-bistrifluoromethylbenzene 20 g, and 10 g of an organosilicon compound having the following structure,
を反応器に仕込み、室温にて15時間攪拌を行った。反応終了後、反応混合物を水に投入して有機相を取り出し、さらに水洗を3回繰り返した。回収した有機相に少量の無水硫酸ナトリウムを加え、ろ過したのち、100℃/5mmHgにてストリップして溶媒を取り除いた。このようにして11.3gの生成物を得た。この物質をNMRにて分析したところ、主な生成物は下記(C)の構造であり、少量の副生成物として(D)が含まれているものであった。
Was stirred at room temperature for 15 hours. After completion of the reaction, the reaction mixture was poured into water, the organic phase was taken out, and further washed with water three times. A small amount of anhydrous sodium sulfate was added to the collected organic phase, filtered, and then stripped at 100 ° C./5 mmHg to remove the solvent. In this way 11.3 g of product was obtained. When this substance was analyzed by NMR, the main product had the following structure (C), and (D) was contained as a small amount of by-products.
この化合物の1H NMRスペクトルを図3に示す。結果は以下の通りであった。
1H NMRスペクトル(CDCl3)
δ0.82(Si−CH 2, 2H, s)
δ0.99((CH 3)3C−Si, 9H, s)
δ1.53(CH 3−C−OH,6H, s)
δ1.80(−OCH2− CH 2− CH2, 2H, m)
δ1.80(−OCH2CH 2−, 2H, m)
δ2.06(−OCH2CH 2−, 2H, m) δ2.47(−C≡CH, 2H, m)
δ3.56(−OCH 2− CH2− CH2, 2H, m)
δ3.98(CF−CH2−O, 2H, d)
δ4.15(−OCH 2CH2−, 2H, m)
δ4.25(−OH, 2H, m)
δ4.43(−OCH 2CH2−, 2H, m)
The 1 H NMR spectrum of this compound is shown in FIG. The results were as follows.
1 H NMR spectrum (CDCl 3 )
δ 0.82 (Si—C H 2 , 2H, s)
δ0.99 ((C H 3 ) 3 C-Si, 9H, s)
δ 1.53 (C H 3 —C—OH, 6H, s)
δ1.80 (-OCH 2 - C H 2 -
δ1.80 (-OCH 2 C H 2 - , 2H, m)
δ2.06 (-OCH 2 C H 2 - , 2H, m) δ2.47 (-C≡C H, 2H, m)
δ3.56 (—OC H 2 —CH 2 —CH 2 , 2H, m)
δ 3.98 (CF—CH 2 —O, 2H, d)
δ 4.15 (—OC H 2 CH 2 —, 2H, m)
δ4.25 (-O H, 2H, m )
δ 4.43 (—OC H 2 CH 2 —, 2H, m)
また、この化合物のIRスペクトルを図4に示す。結果は以下の通りであった。
赤外吸収スペクトル
3478cm−1 (−OH)
3315cm−1 (−C≡CH)
1300〜1000cm−1 (C−F)
The IR spectrum of this compound is shown in FIG. The results were as follows.
Infrared absorption spectrum 3478 cm −1 (—OH)
3315 cm −1 (—C≡CH)
1300-1000cm -1 (C-F)
以上の結果から、得られた化合物の生成物(C)の構造を持つことを確認した。 From the above results, it was confirmed that the product had the structure of the product (C).
副生成物(D)の構造 Structure of by-product (D)
Claims (2)
(但し、R1は、ケイ素原子と結合する炭素原子が3級炭素である炭素数4〜10の1価炭化水素基、R2、R3は炭素数1〜4のアルキル基またはRf−Q−で示されるフロロアルキル基を含む1価の基であり、Rfは炭素数3〜100のパーフルオロアルキル基で、途中エーテル結合を含んでいてもよく、分岐していても良い。Qは炭素数2〜10の2価の基であって途中に窒素、酸素、イオウを含んでもよい。nは0または1である。) An acetylene compound represented by the following general formula.
(However, R 1 is a monovalent hydrocarbon group having 4 to 10 carbon atoms in which the carbon atom bonded to the silicon atom is a tertiary carbon, R 2 and R 3 are alkyl groups having 1 to 4 carbon atoms, or Rf-Q. -Is a monovalent group containing a fluoroalkyl group represented by-, Rf is a perfluoroalkyl group having 3 to 100 carbon atoms, may contain an ether bond, or may be branched, Q is carbon. (It is a divalent group of 2 to 10 and may contain nitrogen, oxygen and sulfur in the middle. N is 0 or 1.)
(但し、R1、R2及びR3は前記と同じ基、Xはハロゲン原子、nは0または1である。)
下記のアセチレンアルコール(B)を反応させて、
(A)のSi−Xと、(B)のいずれか一方または両方の水酸基とからSi−O結合を形成させることを特徴とするシリル化されたアセチレン化合物の製造方法。 An organosilicon compound represented by the following general formula (A);
(However, R 1 , R 2 and R 3 are the same groups as described above, X is a halogen atom, and n is 0 or 1.)
The following acetylene alcohol (B) is reacted,
A method for producing a silylated acetylene compound, wherein a Si—O bond is formed from Si—X of (A) and one or both of the hydroxyl groups of (B).
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2005321373A JP4471384B2 (en) | 2004-11-09 | 2005-11-04 | Novel acetylene compound and process for producing the same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2004324877 | 2004-11-09 | ||
JP2005321373A JP4471384B2 (en) | 2004-11-09 | 2005-11-04 | Novel acetylene compound and process for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2006160729A true JP2006160729A (en) | 2006-06-22 |
JP4471384B2 JP4471384B2 (en) | 2010-06-02 |
Family
ID=36663143
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005321373A Active JP4471384B2 (en) | 2004-11-09 | 2005-11-04 | Novel acetylene compound and process for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP4471384B2 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009037975A (en) * | 2007-08-03 | 2009-02-19 | Honda Motor Co Ltd | Seal composition for fuel cell, seal for fuel cell, fuel cell with the seal, and its manufacturing method |
JP2021042131A (en) * | 2019-09-06 | 2021-03-18 | 信越化学工業株式会社 | Alkynyl group-containing cyclic organopolysiloxane and hydrosilylation reaction control agent |
-
2005
- 2005-11-04 JP JP2005321373A patent/JP4471384B2/en active Active
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2009037975A (en) * | 2007-08-03 | 2009-02-19 | Honda Motor Co Ltd | Seal composition for fuel cell, seal for fuel cell, fuel cell with the seal, and its manufacturing method |
JP2021042131A (en) * | 2019-09-06 | 2021-03-18 | 信越化学工業株式会社 | Alkynyl group-containing cyclic organopolysiloxane and hydrosilylation reaction control agent |
JP7126999B2 (en) | 2019-09-06 | 2022-08-29 | 信越化学工業株式会社 | Alkynyl group-containing cyclic organopolysiloxane and hydrosilylation reaction control agent |
Also Published As
Publication number | Publication date |
---|---|
JP4471384B2 (en) | 2010-06-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6959864B2 (en) | Fluorine compound | |
JPH03197484A (en) | Production of hydrogensiloxane | |
JP5115729B2 (en) | Organosilicon compound containing acetoacetate group protected with trialkylsilyl group and process for producing the same | |
JP6096531B2 (en) | Fluorine-containing alkoxysilane compound, coating agent, and water-repellent film | |
JP4471384B2 (en) | Novel acetylene compound and process for producing the same | |
EP1604968B1 (en) | Acetylene alcohols having a fluoroalkyl group and methods for preparing the same | |
US7067688B2 (en) | Acetylene alcohol and method for preparing the same | |
KR101780102B1 (en) | Process for preparing (meth)acrylamido-functional silanes by the reaction of aminoalkyl alkoxysilanes with acrylic acid anhydride | |
KR100994637B1 (en) | Process for preparing organosilicon compound | |
JP4310639B2 (en) | Process for producing organosilicon compound containing β-ketoester structure | |
JP5699990B2 (en) | Method for producing organoxysilane compound having piperazinyl group and piperazine compound | |
JP2016040233A (en) | Bicyclo amino organoxysilane compound and method for producing the same | |
JP6665437B2 (en) | Method for producing tertiary alkyl silane and tertiary alkyl alkoxy silane | |
JP4275417B2 (en) | Method for producing alkoxysilane compound | |
KR100945557B1 (en) | Method of preparing Perfluoro-alkyl modified alkylalkoxysilane | |
JP3210850B2 (en) | Preparation of fluoroalkylalkoxysilane | |
JP5942868B2 (en) | Method for producing sulfide group-containing organosilicon compound | |
JP2012006844A (en) | Production method of alkoxyhydrosilane | |
US7847116B2 (en) | Method of manufacturing an aminoaryl-containing organosilicon compound and method of manufacturing an intermediate product of the aforementioned compound | |
JPH06287305A (en) | Preparation of (meth) acrylic-functional organosilicon compound | |
JP2022171026A (en) | Method of producing hydroxyalkylsilane compound | |
JP2007091601A (en) | New silane compound having fluorosulfonyl group | |
JP2019218279A (en) | Method for producing organosilicon compound, method for producing amino aryl group-containing organosilicon compound and organosilicon compound | |
JP2005306783A (en) | Method for producing yellow sulfide chain-containing organosilicon compound | |
JP2005330196A (en) | Fluorine-containing acetylene alcohols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20071025 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20091027 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20091124 |
|
RD02 | Notification of acceptance of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: A7422 Effective date: 20091124 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20091216 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20100203 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100225 |
|
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100301 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130312 Year of fee payment: 3 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 4471384 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20160312 Year of fee payment: 6 |