JPS60197694A - 2-substituted-1,3-butadiene derivative and its preparation - Google Patents
2-substituted-1,3-butadiene derivative and its preparationInfo
- Publication number
- JPS60197694A JPS60197694A JP59033733A JP3373384A JPS60197694A JP S60197694 A JPS60197694 A JP S60197694A JP 59033733 A JP59033733 A JP 59033733A JP 3373384 A JP3373384 A JP 3373384A JP S60197694 A JPS60197694 A JP S60197694A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- butadiene
- silyl
- substituted
- lower alkyl
- 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 2-substituted-1,3-butadiene Chemical class 0.000 title claims description 13
- 238000002360 preparation method Methods 0.000 title abstract description 3
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 25
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 24
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 150000004292 cyclic ethers Chemical group 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 13
- 150000002367 halogens Chemical class 0.000 abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- VTPSILBGBZHQJI-UHFFFAOYSA-N 1,4-dichlorobut-2-en-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(CCl)=CCCl VTPSILBGBZHQJI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract description 2
- HWCCZVRBWGLIGI-UHFFFAOYSA-N buta-1,3-dien-2-yl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C(=C)C=C HWCCZVRBWGLIGI-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 8
- BQIZQWJZCWVEGF-UHFFFAOYSA-N buta-1,3-dienylsilane Chemical compound [SiH3]C=CC=C BQIZQWJZCWVEGF-UHFFFAOYSA-N 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 6
- 238000005695 dehalogenation reaction Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 5
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 201000009841 cataract 21 multiple types Diseases 0.000 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- FJIHDNQJJPBXOD-UHFFFAOYSA-N buta-1,3-dien-2-yl(dimethoxymethyl)silane Chemical compound COC(OC)[SiH2]C(=C)C=C FJIHDNQJJPBXOD-UHFFFAOYSA-N 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 2
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical group ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RCHDLEVSZBOHOS-UHFFFAOYSA-N 1,4-dichlorobut-2-yne Chemical compound ClCC#CCCl RCHDLEVSZBOHOS-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-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
- WQRGDPLYFFKLCT-UHFFFAOYSA-N COC(OC)[SiH2]C(CCl)=CCCl Chemical compound COC(OC)[SiH2]C(CCl)=CCCl WQRGDPLYFFKLCT-UHFFFAOYSA-N 0.000 description 1
- 101150065749 Churc1 gene Proteins 0.000 description 1
- 241000219122 Cucurbita Species 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000234435 Lilium Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 102100038239 Protein Churchill Human genes 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- HVNLGTJPHUIWEO-UHFFFAOYSA-N buta-1,3-dien-2-yl(triethyl)silane Chemical compound CC[Si](CC)(CC)C(=C)C=C HVNLGTJPHUIWEO-UHFFFAOYSA-N 0.000 description 1
- IUKUREXRSPXMIE-UHFFFAOYSA-N buta-1,3-dienyl(trichloro)silane Chemical compound Cl[Si](Cl)(Cl)C=CC=C IUKUREXRSPXMIE-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000000382 dechlorinating effect Effects 0.000 description 1
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 description 1
- 230000002496 gastric effect Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 230000010412 perfusion Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は
構造式 〔■〕
H2C=C−CH=CH2[1)
(但シ、R’ 、 R2,R’ ハソレソレノ−tz
P y、低級アルキル基又は低級アルコキシ基を示す。[Detailed Description of the Invention] The present invention is based on the structural formula [■] H2C=C-CH=CH2[1] (However, R', R2,R'
P y represents a lower alkyl group or a lower alkoxy group.
但し、Bl 、 R2、BSが同時に低級アルキル基で
ある場合を除く・)
で表わされる新規2−1換−1,3−ブタジェン及びそ
の製造法に関する。However, the present invention relates to a novel 2-1-substituted-1,3-butadiene represented by the formula (excluding the case where Bl, R2, and BS are all lower alkyl groups) and a method for producing the same.
従来よ11.1.4−ジクロル−2−ブチントトリエチ
ルシランとを反応させて2−トリエチルシリ/L’−1
a4−ジクロル−2−ブテンを合成し、更にアルコール
中で脱塩素して2−トリエチルシリル−1,3−ブタジ
ェンとする方法は知られている〔テトラヘドロンレター
ズ(T*trah*dron Lstters)+36
巻、3323頁〕。しかしながら、この方法はハロゲン
及びアルコキシ基、更にアルコキシ基とアルキル基とを
同時に持つ化合物等、各種置換シリル基を有する化合物
の製造には適用できない欠点がある。Conventionally, 11.1.4-dichloro-2-butyntotriethylsilane is reacted to form 2-triethylsili/L'-1.
A method for synthesizing a4-dichloro-2-butene and further dechlorinating it in alcohol to produce 2-triethylsilyl-1,3-butadiene is known [Tetrahedron Letters (T*trah*dron Lstters) +36
Volume, page 3323]. However, this method has the disadvantage that it cannot be applied to the production of compounds having various substituted silyl groups, such as compounds having halogen and alkoxy groups, or compounds having both alkoxy and alkyl groups.
本発U者はこれらの欠点を改良し、2位のケイ素ニハロ
rンとアルコキシ基、アルコキシ基トアルキル基を同時
に有する2−置換−1,i−ブタジェンを得るため鋭意
研究を行った結果、新規化合物である前記構造式(1)
で表わされる2−置換−1,3−ブタジェンに到達した
。即ち、構造式(1)
%式%[11)
(但し、R’ 、 R2,R5はそれぞれ)・ログン、
低級アルキル基又は低級アルコキシ基を示す。但し、R
’ 、 R2,R5が同時に低級アルキル基である場冶
を除く。またXはハロゲンを示す。)
で表わされる2−@換−1,4−ジバロ・ゲ・ノー2−
ブテンを非アルコール性溶媒の存在下で脱ノhログンし
たシ、或いは、
構造式[1111
%式%[1111
(但し、A 、A 、A のいずれか1つは〕\ログン
、他は低級アルキル基又は低級アルコキシ基を示す。)
で表わされ不化合物を低級アルコールと反応させて、2
位のケイ素に結合しているノ・ログン原子を低級アルコ
キシ基で置換することにより前記構造式[11で示され
る化合物が得られると共に1この化合物がシランカップ
リング剤をけじめ、種々の用途に有効に使用されること
を知見し、本発明を完成するに至ったものである。The present inventor conducted intensive research to improve these drawbacks and obtain a 2-substituted-1,i-butadiene having silicon dihalone, an alkoxy group, and an alkoxy group at the same time at the 2-position, and as a result, a novel The compound 2-substituted-1,3-butadiene represented by the above structural formula (1) was arrived at. That is, Structural formula (1) %Formula%[11) (However, R', R2, R5 are respectively)・Rogon,
Indicates a lower alkyl group or a lower alkoxy group. However, R
', excludes cases where R2 and R5 are both lower alkyl groups. Moreover, X represents halogen. ) 2-@ exchange-1,4-jibaro ge no 2-
Butene is deoxygenated in the presence of a non-alcoholic solvent, or structural formula [1111 % formula % [1111 (however, any one of A , A , and A is]\rogon, and the others are lower alkyl or lower alkoxy group)
By reacting the uncompound represented by with lower alcohol, 2
By substituting the no-logon atom bonded to the silicon at position 1 with a lower alkoxy group, a compound represented by the above structural formula [11] can be obtained, and this compound is effective against silane coupling agents and is effective for various uses. The present invention has been completed based on the discovery that it can be used for
以下、本発明につき更に詳しく説明する。The present invention will be explained in more detail below.
本発明に係る新規2−置換−1,3−ブタジェンは前記
構造式■で示されるもので、具体的には後述する2−〔
トリメトキシ〕シリルー1,3−ブタジェン、2−[メ
トキシジメチル〕シリルー1,3−ブタジエン、2−〔
ジメトキシメチル〕シリル−1,3−2タジエン、2−
[)リクロロ〕シリル−1,3−フタジエン、2−[ジ
メチルクロロ〕シリルー1,3−ブタジェン等を包含す
るものである。The novel 2-substituted-1,3-butadiene according to the present invention is represented by the above structural formula (2), and specifically, the 2-[
trimethoxy]silyl-1,3-butadiene, 2-[methoxydimethyl]silyl-1,3-butadiene, 2-[
dimethoxymethyl]silyl-1,3-2tadiene, 2-
These include [)lichloro]silyl-1,3-phtadiene, 2-[dimethylchloro]silyl-1,3-butadiene, and the like.
なお、これらの化合物の物性値は後述する通シである。The physical properties of these compounds are as described below.
本発明化合物の製造法は、例えばA式に示すように1,
4−ジハロゲノ−2−ブチンと少なくとも一つのハロゲ
ン原子を有するヒドロシラン類とを反応せしめ、出発原
料としての2位に少くとも一つのハロゲン置換シリル基
を有する1、4−ジハロゲノ−2−ブテン(構造式■)
を合成した後、本発明化合物を製造するものである。The method for producing the compound of the present invention includes, for example, 1, as shown in formula A,
4-dihalogeno-2-butyne is reacted with a hydrosilane having at least one halogen atom, and 1,4-dihalogeno-2-butene (structure: Expression ■)
After synthesizing, the compound of the present invention is produced.
■
〔但し、XけハOf7、k’ 、 A、’ 、 A’−
+7)少< ト4一つdハ*fン、残シは低級アルキル
基又はアルコキシ基である。〕
この場合、1,4−ジハロゲノ−2−ブテンとしては、
1,4−ジクロロ−2−ブテンが有効に用いられ、また
この反応は塩化白金酸をイソプロピルアルコール等の溶
剤に溶かしたものを触媒として用い、無溶媒で行なうこ
とが好ましい。■ [However, XkehaOf7,k', A,', A'-
+7) Less than 4, the remainder is a lower alkyl group or an alkoxy group. ] In this case, the 1,4-dihalogeno-2-butene is
1,4-dichloro-2-butene is effectively used, and this reaction is preferably carried out without a solvent using a solution of chloroplatinic acid in a solvent such as isopropyl alcohol as a catalyst.
なお、上記A式の反応に際して反応温度は室温を採用す
ることができる。In addition, room temperature can be adopted as the reaction temperature in the reaction of the above formula A.
この2位に少くとも一つのハロゲン置換シリル基を有す
る1、4−ジハロゲノ−2−ブテン紮出発原料として本
発明化合物を製造する方法はJ記反応弐Bに示すように
式Vの化合物を非アルコール性溶媒の存在下で脱ハロゲ
ンするものである。The method for producing the compound of the present invention using the 1,4-dihalogeno-2-butene ligation starting material having at least one halogen-substituted silyl group at the 2-position is as shown in Reaction 2B of Section J. Dehalogenation is performed in the presence of an alcoholic solvent.
この場合、反応式CK示すように前記構造式Iの化合物
(反応式C中においてこの化合物H2C=C−C)I=
CH2(は本発明化合物で、あ−る)を低級アルコール
と反応させるととKよシ、ハロゲン原子を低級アルコキ
シ基と置換した下記構造式■の化合物が得られる。In this case, as shown in the reaction formula CK, the compound of the structural formula I (in the reaction formula C, this compound H2C=C-C)I=
When CH2 (is a compound of the present invention) is reacted with a lower alcohol, a compound of the following structural formula (2) in which the halogen atom is replaced with a lower alkoxy group is obtained.
(構造式1) (構造式■)
(但し、A1 、 A2 、 Asのいずれか一つはハ
ロゲン、他は低級アルキル基又は低級アルコキシ基を示
し、R”、R”、n”のいずれか一つが低級アルコキシ
基であシ、他は低級アルキル基である。)なお、また構
造式■の化合物の製造法として下記反応式DK示すよう
に構造式Vの化合物を低級アルコールと反応させて、ハ
ロゲン原子を低級アルコキシ基と置換した構造式■の化
合物を製造した後、とれを非アルコール性溶媒の存在下
に脱ハロゲンを行なって前記構造式■を得るとともでき
る。(Structural formula 1) (Structural formula ■) (However, any one of A1, A2, and As represents a halogen, the others represent a lower alkyl group or a lower alkoxy group, and any one of R", R", and n" (1 is a lower alkoxy group, and the others are lower alkyl groups.) Furthermore, as a method for producing the compound of the structural formula (2), a compound of the structural formula V is reacted with a lower alcohol as shown in the reaction formula DK below, and the halogen After producing a compound of structural formula (1) in which an atom is substituted with a lower alkoxy group, the resulting compound is dehalogenated in the presence of a non-alcoholic solvent to obtain the above-mentioned structural formula (2).
ここで、上記m−D式の反応において、脱ノ・ロダン反
応に用いる非アルコール性溶媒としては環状エーテルを
挙げることができ、具体的にはT)IF。Here, in the above m-D reaction, examples of the non-alcoholic solvent used in the deno-rhodan reaction include cyclic ethers, specifically T) IF.
ジオキサン等を使用することが好ましい。更に、脱ハロ
ゲン反応に際しては、亜鉛粉末等を使用すると反応が円
滑に進行する。との脱ノ・ロダン反応の温度は一り6℃
〜THFの沸点、時間は30分〜8時間、非アルコール
性溶媒の使用量は原料化合物1モルに対して3〜10モ
ルとすることが好ましいO
また、ノ・ロダン原子を低級アルコキシ基に置換する反
応においては、シリル基に結合したノ・口rンと低級ア
ルコールとを反応させるに際して塩基、例えばトリエチ
ルアミン等の有機脂肪族アミンを使用すると反応が円滑
に進行する。Preferably, dioxane or the like is used. Furthermore, in the dehalogenation reaction, the reaction proceeds smoothly if zinc powder or the like is used. The temperature of the deno-Rhodan reaction with is 6℃.
~The boiling point of THF and the time are preferably 30 minutes to 8 hours, and the amount of non-alcoholic solvent used is preferably 3 to 10 mol per 1 mol of the raw material compound.Also, the rhodane atom is replaced with a lower alkoxy group In this reaction, the reaction proceeds smoothly when a base, for example an organic aliphatic amine such as triethylamine, is used to react the silyl group-bonded group with the lower alcohol.
この場合、との胃換反応において、反応温度は一10℃
〜50℃、時間は30分〜2時間、低級アルコールの使
用量は原料化合物1モルに対して1.3〜1.5モル、
アミンの使用量は1.3〜1.5モルとすることが好ま
しく、また溶媒の使用量は2〜3モルとすることが好ま
しい。In this case, in the gastric perfusion reaction with
~50°C, time is 30 minutes to 2 hours, amount of lower alcohol used is 1.3 to 1.5 mol per 1 mol of raw material compound,
The amount of amine used is preferably 1.3 to 1.5 moles, and the amount of solvent used is preferably 2 to 3 moles.
なお、上記B−Dの方法を採用して本発明化合物を合成
する場合、その所用の工程における反応生成物を分離せ
ずにそのit次の工程の反応に使用することができる。Incidentally, when the compound of the present invention is synthesized by employing the above method BD, the reaction product in the required step can be used for the reaction in the next step without being separated.
上述した製造方法は脱ハロダン反応を利用しておシ、脱
ハロゲン反応は前記文献(テトラヘドロン、レターズ、
36巻、3323頁)記載の方法と異なり、非アルコー
ル性溶媒存在下で行うため、反応性ハロゲンを有する置
換シリル基を損なうこと々く、次の工程の反応に支障な
く使用することができるものである。The above-mentioned production method utilizes a dehalodanization reaction, and the dehalogenation reaction is described in the above-mentioned literature (Tetrahedron, Letters,
Unlike the method described in Vol. 36, p. 3323), it is carried out in the presence of a non-alcoholic solvent, so the substituted silyl group containing a reactive halogen is often damaged, and it can be used without any problem in the reaction of the next step. It is.
以上の説明から明らかな如く、2位に少くとも一つのハ
ロダン置換シリル基を有する1、4−ジクロル−2−ブ
テンと2位ニ少〈トモ一つのハロダン胃換シリルを有す
る1、3−ブタジェンのハロrンI換シリル基のハロゲ
ンの反応性を利用し、低級アルキル基、低級アルコキシ
基以外の各種置換基をシリル基に導入することは容易で
ある。As is clear from the above explanation, 1,4-dichloro-2-butene having at least one halodane-substituted silyl group at the 2-position and 1,3-butadiene having at least one halodane-substituted silyl group at the 2-position. It is easy to introduce various substituents other than lower alkyl groups and lower alkoxy groups into the silyl group by utilizing the reactivity of halogen in the halo-I-substituted silyl group.
以下、本発明の製造例を示す。Production examples of the present invention will be shown below.
〔製造例I−1〕
1.4−ジクロロ−2−〔トリクロロ〕シリルー2−ブ
テン
15mJ (0,153mot)の1,4−ジクロロ−
2−ブチン〔(1)式〕と13.6m’(0,16mo
j )のトリクロルシラン(bp:31〜32℃)との
混合溶液にH4F tcz6・6H20イソグロビルア
ルコール溶液(0,051/III )を0.15m(
10mmoL)加えて8時間加熱した。その後、直接蒸
留することによ、91.4−ジクロロ−2−()リクロ
ロ〕シリルー2−fテアc<2)式〕を37II得た。[Production Example I-1] 15 mJ (0,153 mot) of 1,4-dichloro-2-[trichloro]silyl-2-butene
2-butyne [formula (1)] and 13.6 m' (0,16 mo
0.15 m(
10 mmol) and heated for 8 hours. Thereafter, by direct distillation, 37II of 91.4-dichloro-2-()lichloro]silyl-2-ftheac<2) formula] was obtained.
収率:94%。Yield: 94%.
bp:’yo℃/1■Hg
’m(ccz4) :門標テトラメチルシラン64.2
3 (d 、 J+=7.5Hz 、 2H、CHCH
) 。bp:'yo℃/1■Hg'm (ccz4): Signpost Tetramethylsilane 64.2
3 (d, J+=7.5Hz, 2H, CHCH
).
4.24(s、2H,CH2C)、6.66(t、J=
7.5H!、IH,CHCH2)〔製造例I−2〕
1.4−ジクロロ−2−〔トリメトキシ〕シリルー2−
ブテン
次に1.4−−/クロロー2−〔トリクロロ〕シリルー
2−ブテン〔(2)式)14.2g(55mmot)の
THF(14)溶液を一10℃に冷やし、CH,0H1
0I117!(55X3X1.5mmot)と(C,H
5)、N 34.5+117(55X3X1.5mmo
L)の混合溶液をゆりく少滴下した。その後室温で1時
間かきまぜ、乾燥エーテルを3017加えた。析出する
(C2H5)、N−HCtをF別し、溶媒を減圧下に留
去し、減圧蒸留によシ1,4−ジクロロ−2−〔トリメ
トキシ〕シリルー2−ブテン〔(3)式〕を10.81
I得た。4.24 (s, 2H, CH2C), 6.66 (t, J=
7.5H! , IH, CHCH2) [Production Example I-2] 1.4-dichloro-2-[trimethoxy]silyl-2-
Butene Next, a THF (14) solution of 14.2 g (55 mmot) of 1.4--/chloro-2-[trichloro]silyl-2-butene [formula (2)] was cooled to -10°C, CH,0H1
0I117! (55X3X1.5mmot) and (C,H
5), N 34.5+117 (55X3X1.5mmo
A mixed solution of L) was slowly added dropwise. The mixture was then stirred at room temperature for 1 hour, and 3017 g of dry ether was added. The precipitated (C2H5) and N-HCt were separated by F, the solvent was distilled off under reduced pressure, and 1,4-dichloro-2-[trimethoxy]silyl-2-butene [formula (3)] was distilled under reduced pressure. 10.81
I got it.
収率:80チe bp:ss〜90℃/1〜2■Hg’
HNMR(CC/!、4) :門標テトラメチルシラン
δ3.56(s、9H,C現0)、 4.08(s、2
H,C旦3C)4.15 (d 、 J=7.5d%t
2に、C旦、ctt )6.29(t、J−7,5Hz
、IH,CHCH2)〔製造例I−3〕
Zn粉末4.0II(41X1.5mmot)とTHF
15dをよくかtAtぜながら上記方法によシ得た1
、4ジクロロ−2−()リメトキシ〕シリルー2−ブテ
ン[(3)式] 101 (41mmot)を加えた〇
混合溶液を1時間加熱還流した後、室温まで冷却し、乾
燥ペンタン30ゴを加えて析出するZnCtz t F
別し、溶媒を減圧下留去し、波圧蒸留により2−〔トリ
メトキシ〕シリルー1.3−ブタゾエン[(4)式〕を
5.0d得た。Yield: 80 cm e bp: ss~90℃/1~2■Hg'
HNMR (CC/!, 4): Signature tetramethylsilane δ 3.56 (s, 9H, C current 0), 4.08 (s, 2
H, Cdan 3C) 4.15 (d, J=7.5d%t
2,Cdan,ctt)6.29(t,J-7,5Hz
, IH, CHCH2) [Production Example I-3] Zn powder 4.0II (41X1.5 mmot) and THF
1 obtained by the above method while carefully stirring 15d.
, 4dichloro-2-()rimethoxy]silyl-2-butene [formula (3)] 101 (41 mmot) was added. The mixed solution was heated under reflux for 1 hour, cooled to room temperature, and 30 grams of dry pentane was added. Precipitated ZnCtz t F
The solvent was removed under reduced pressure, and 5.0 d of 2-[trimethoxy]silyl-1,3-butazoene [formula (4)] was obtained by wave pressure distillation.
収率ニア0チ、bp:24℃/ 1 wax Hg’H
NMR(CCA4) :門標テトラメチルシランδ3.
49(1,9R,CH,O)、5.02(d、J=10
.8Hz、1)1゜C旦、CH)、 5.34(d、J
=17Hzt IH、C旦、CH)5.64(d 、
Jx3.3Hz 、 IH、CH2C’) 、 5.7
7 (d 、 J=3.3゜1に、C旦、C) # 6
.30(ad 、 J=10.8 、17 Hz 、
1)1.CHCH2)〔製造例■〕
2− () IJ クロロ〕シリルー1,3−ブタジェ
ンZn粉末6.91 (82X 1.3 mmoj)と
Tl(F 20dの混合物を一15℃に冷やし、よくか
きまぜな1Ec)1,4−ジクロロ−2−()リクロロ
〕シリルー2−ブテン〔(2)式) 21.31 (8
2mmoA)とT町1011L(の混合溶液をゆっくり
滴下した。その後−15℃で1時間かきまぜ、乾燥(ン
タン60−を加えた。析出するZnCtzをP別し、溶
媒を減圧下低温(−20℃)で留去することによシタ−
〔トリクロロ〕シリルー1,3−ブタジェン〔(5)式
〕を13I得た。Yield near 0chi, bp: 24℃/1 wax Hg'H
NMR (CCA4): Marked tetramethylsilane δ3.
49 (1,9R, CH, O), 5.02 (d, J=10
.. 8Hz, 1) 1°C Dan, CH), 5.34(d, J
=17Hzt IH, Cdan, CH) 5.64(d,
Jx3.3Hz, IH, CH2C'), 5.7
7 (d, J=3.3゜1, Cdan, C) #6
.. 30 (ad, J=10.8, 17 Hz,
1)1. CHCH2) [Production Example ■] 2- () IJ Chloro] Silyl-1,3-butadiene Zn powder 6.91 (82X 1.3 mmoj) and Tl (F20d) Cool the mixture to -15°C, stir well, and heat to 1Ec. )1,4-dichloro-2-()lichloro]silyl-2-butene [formula (2)) 21.31 (8
A mixed solution of 2mmoA) and T-cho 1011L (was slowly added dropwise.Then, the mixture was stirred at -15°C for 1 hour and dried (Ntan 60- was added. ) by distilling it off.
[Trichloro]silyl-1,3-butadiene [formula (5)] was obtained as 13I.
収率:85%。Yield: 85%.
’HNMR(C(’t4) :門標テトラメチルシ2ン
δ5−30 (dy J=i o、a Hz t I
K−cq、CH) I5.56 (d 、 J=17.
3■z e IHe c、至42cu)e 6.04(
s p2HeC旦2c )、6.40(dd、J=10
.3.17.3H篇eIHeC旦、CH2)〔製造例■
〕
2− () +7メトキシ〕シリル−1,3−プメジエ
ン2− () IJ クロロ〕シリルー1.3−1タジ
エン[(5)式]8.7.9(粗生成物46 mmoL
)とTHFIO−の混合溶液を一10℃に冷却しよく
かきまぜながらCHsOH8,3Ill (46X 3
X 1.5 mmoA)、(C2Hs)3N28.9
11j(46X 3 X 1.5 mmot)の混合溶
液をゆっくり滴下した。その後室温で30分間か!!ま
ぜ、(C2H5)20 V 30 at加えた。析出す
る(C2H5)−・HClt−7p別し、俗媒を減圧下
留去し、減圧蒸留によ!62−In)リメトキシ〕シリ
ルー1,3−ブタジェン〔(4)式)6.1#t−得た
。 収率ニア5−bp及び”)L’NMRは製造例Ii
3の場合と同様でありた。'HNMR(C('t4): Signpost tetramethylcine δ5-30 (dy J=io, a Hz t I
K-cq, CH) I5.56 (d, J=17.
3■z e IHe c, to 42cu)e 6.04(
s p2HeCdan2c), 6.40 (dd, J=10
.. 3.17.3H editioneIHeCdan, CH2) [Manufacturing example■
] 2- () +7methoxy]silyl-1,3-pumediene 2- () IJ chloro]silyl-1.3-1 tadiene [formula (5)] 8.7.9 (crude product 46 mmoL
) and THFIO- was cooled to -10°C and mixed with CHsOH8,3Ill (46X 3Ill) while stirring well.
X 1.5 mmoA), (C2Hs)3N28.9
A mixed solution of 11j (46×3×1.5 mmot) was slowly added dropwise. Then let it sit at room temperature for 30 minutes! ! Mix and add (C2H5) 20 V 30 at. Separate the precipitated (C2H5)-.HClt-7p, distill off the common medium under reduced pressure, and perform vacuum distillation! 62-In)rimethoxy]silyl-1,3-butadiene [Formula (4)) 6.1#t- was obtained. Yield near 5-bp and ")L'NMR is Preparation Example Ii
It was the same as in case 3.
〔製造例■−1)
−2−ブテン
1.4−ジクロロ−2−ブチン〔(1)式〕11d(0
,11’6moL)とりaaジメチルシラン(bp35
℃)13、5 mA (0,,121moL )の混合
溶液に製造例夏−1と同様に調製した塩化白金酸のイソ
ゾロノ々ノール溶液0.05 m (4,−4m mo
L )を加えて30分間加熱還流し1.4−ジクロロ−
2−〔クロロジメチル〕シリルー2−ブテン〔(6)式
1231iFを得た。[Production Example ■-1] -2-Butene 1,4-dichloro-2-butyne [Formula (1)] 11d (0
, 11'6mol) and aa dimethylsilane (bp35
℃) 13,5 mA (0,,121 moL) of an isozolononol solution of chloroplatinic acid prepared in the same manner as in Production Example Summer-1 was added to a mixed solution of 0.05 m (4,4 mmol).
1.4-dichloro-
2-[chlorodimethyl]silyl-2-butene [(6) formula 1231iF was obtained.
収率:91%、bp:68℃/1瓢Hg’m(ccz4
) :門標ベンゼン
δ0.57 (m r 6H−CHs81 ) 、4.
11 (d −J==7.5Hz 、2)1eCH20
H) 、4.16 (s 、2 He CH2C) 、
6.19 (t * J=7.5 Hz 。Yield: 91%, bp: 68°C/1 gourd Hg'm (ccz4
): Signal benzene δ0.57 (m r 6H-CHs81 ), 4.
11 (d −J==7.5Hz, 2)1eCH20
H), 4.16 (s, 2 He CH2C),
6.19 (t*J=7.5 Hz.
I Ii t C型)I2)
〔製造例■−2〕
1.4−ジクロロ−2−〔クロロジメチル〕シリルー2
−ブテン〔(6)式)13.3F(61mmot)TH
F 10wtlSCM、OR3,7m(61X 1.5
mmoA)(C2H5)、N 12.7 ml (61
X 1.5 m1not)、乾燥エーテル39m7を用
い、製造例[2と同様に減圧蒸留に!、り1.4−ジク
ロロ−2−〔メトキシジメチル〕シリルー2−ブテン〔
(7)式)10.5#を得た。I Iit C type) I2) [Production example ■-2] 1.4-dichloro-2-[chlorodimethyl]silyl-2
-Butene [formula (6)) 13.3F (61 mmot) TH
F 10wtlSCM, OR3,7m (61X 1.5
mmoA) (C2H5), N 12.7 ml (61
x 1.5 m1not), dry ether 39m7, and vacuum distillation as in Production Example [2! , 1,4-dichloro-2-[methoxydimethyl]silyl-2-butene[
(7) formula) 10.5# was obtained.
収率:81チ、bpニア4℃/l■Hg’m(ccz4
) :門標ベンゼン
δ0.28(m 、6H,CH,Si )、 3.39
(1,3H,CH,O)4.11 (@= 2H#CH
2C) 、4.14 (d 、J=7.3 Hz、2H
1CH2CH) 、 6.09(t 、 J=7.3
Hz 、 IH,CuCl2)〔製造例■−3〕
2−〔メトキシジメチル〕シリル−1,3−ブタジェン
Zn粉末4.01 (41Xl、5mmot)とTHF
15mをよくかきまぜながら、1,4−ジクロロ−2−
〔メトキシジメチル〕シリルー2−ブテン((7)式〕
8.7g(41mmoA)を加えた。混合溶液を2時間
加熱還流した後、製造例1−3と同様にして2−〔メト
キシゾメチル〕シリルー1.3ブタジェン((8)式〕
4.4gを得た。Yield: 81 cm, bp near 4°C/l Hg'm (ccz4
): Signpost benzene δ0.28 (m, 6H, CH, Si), 3.39
(1,3H,CH,O)4.11 (@= 2H#CH
2C), 4.14 (d, J=7.3 Hz, 2H
1CH2CH), 6.09(t, J=7.3
Hz, IH, CuCl2) [Production Example ■-3] 2-[methoxydimethyl]silyl-1,3-butadiene Zn powder 4.01 (41Xl, 5mmot) and THF
While stirring well, add 1,4-dichloro-2-
[Methoxydimethyl]silyl-2-butene (formula (7))
8.7 g (41 mmoA) was added. After heating the mixed solution under reflux for 2 hours, 2-[methoxyzomethyl]silyl-1.3butadiene (formula (8)) was prepared in the same manner as in Production Example 1-3.
4.4g was obtained.
収率;76 % t bp : 30℃/10〜12
m Hg’ HNMR(C’ct4) :門標ベンゼン
δ0.20 (s 、6 Hp C先81 ) e 3
.34 (* −aHy C巨、o)5.01(d、J
=10Hz、IH,C旦、CH) 、 5.32 (d
、 J=17.3)h。Yield: 76% tbp: 30°C/10-12
m Hg' HNMR (C'ct4): Signpost benzene δ0.20 (s, 6 Hp C point 81) e 3
.. 34 (* -aHy C giant, o) 5.01 (d, J
=10Hz, IH, Cdan, CH), 5.32 (d
, J=17.3)h.
IH#C旦、CH)、 5.43(d 、J=3Hg
tlH,CH2C) 。IH#Cdan, CH), 5.43(d, J=3Hg
tlH, CH2C).
5.69 (d F J =3 Hz 、I H、CH
2C) e 6−33 (d d e J=10117
.3 Hs p I H−CuCl2 )〔製造例■〕
2−〔ジメチルクロロ〕シリルー1.3−プタジエ/Z
n粉末2.41 (28Xl、3mmot)とTHF
4 WLlの混合物を0℃に冷やしよくかきまぜな力I
ら1,4−シクロロー2−〔クロロゾメチル〕シリル−
2−フチy((6)式)6.111 (28mmoA
)とTI(F 3−の混合溶液をゆり〈シ滴下した。そ
の後θ℃で5時間よくかきまぜ、乾燥ペンタン15mj
を加えて析出するZ nCA2をテ別し、溶媒を減圧下
低温(−20℃)で留去し、bulb to bulb
蒸貿によシ2−〔ジメチルクロロ〕シリルー1,3−プ
タゾエン〔(9)式)3.1Nを得た。5.69 (d F J =3 Hz, I H, CH
2C) e 6-33 (d d e J=10117
.. 3 Hs p I H-CuCl2) [Production Example ■] 2-[dimethylchloro]silyl-1,3-putadiene/Z
n powder 2.41 (28Xl, 3mmot) and THF
4 Cool the mixture of WLl to 0℃ and stir well.
1,4-cyclo2-[chlorozomethyl]silyl-
2-edge y (formula (6)) 6.111 (28mmoA
) and TI (F3-) were added dropwise to a lily pad.Then, the solution was stirred well at θ℃ for 5 hours, and 15 mj of dry pentane was added.
The ZnCA2 precipitated by the addition of
3.1N of 2-[dimethylchloro]silyl-1,3-putazoene [formula (9)] was obtained by steam trade.
収率:685b、bp:57℃/ 1 vgs Hg’
HNMR(CCA4) :門標ベンゼンδ0.57(s
、6H,CM、81)、5.10(d、J=10.8H
z、IH。Yield: 685b, bp: 57°C/1 vgs Hg'
HNMR (CCA4): Signal benzene δ0.57 (s
, 6H, CM, 81), 5.10 (d, J = 10.8H
z, IH.
CH3OK) 、 5.32(d 、 J=17.5H
z 、 18.CH2C■)。CH3OK), 5.32(d, J=17.5H
z, 18. CH2C■).
5.61(d、J=2.5Hz、IH,CK、C)#
5.80(d、J=2.51(!。5.61 (d, J=2.5Hz, IH, CK, C) #
5.80(d, J=2.51(!.
IH,CH2C) 、 6.37(dd 、J=10.
8.17.5Hz 、IH,CuCl2)〔製造例■〕
2−〔エトキシジメチル〕シリル−1,3−ブタジェン
2−〔ジメチルクロロ〕シリルー1,3−シタジエン〔
(9)式〕0゜8811 (6mmoL ) THF
5m、C2H50H0,53ml (6X 1.5 m
mot)、(C2H,)、Nt、3mJ(6X1.5m
mot)、(c2H5)2o 10 mを用い、製造例
■と同様に処理し、更にシリカダルカラムクロマトグラ
フィー(ペンタンのみ使用)により、2−〔エトキシジ
メチル〕シリル−1,3−ブタジェン〔(11式10.
8Iiを得た。収率:86%’HNMR(CC/!、4
) :門標ベンゼン60.23(@、6H,C旦、81
)#1.14(t、J=6.8Hz、3H#CM3CI
(2)、3.58(q、2H,C旦、CH,) 、 5
.01 (d 、 J=10.3Hz、IH,C旦、C
H)。IH, CH2C), 6.37 (dd, J=10.
8.17.5Hz, IH, CuCl2) [Production Example ■] 2-[Ethoxydimethyl]silyl-1,3-butadiene 2-[Dimethylchloro]silyl-1,3-citadiene [
(9) Formula] 0°8811 (6mmol) THF
5m, C2H50H0,53ml (6X 1.5m
mot), (C2H,), Nt, 3mJ (6X1.5m
2-[ethoxydimethyl]silyl-1,3-butadiene [(11 Formula 10.
8Ii was obtained. Yield: 86%'HNMR (CC/!, 4
): Signpost benzene 60.23 (@, 6H, Cdan, 81
)#1.14(t, J=6.8Hz, 3H#CM3CI
(2), 3.58 (q, 2H, Cdan, CH,), 5
.. 01 (d, J=10.3Hz, IH, Cdan, C
H).
5.33 (d p J =17−3 Hz−I H−
CH3OK) −5−42(d −J =3 Hz 。5.33 (d p J =17-3 Hz-I H-
CH3OK) -5-42 (d-J = 3 Hz.
11(* CH2C) −5−67(d a J==3
Hz −IH−C旦、C)。11(*CH2C) -5-67(d a J==3
Hz-IH-Cdan, C).
s、aa(aa、J=xo:a*17.anz 、IH
,CuCl2)〔製造例■−1〕
1.4−シI * o −2−ff> C(1)式)I
Qmj(0,106mot)とジクaaメチルシラy(
bp41℃) ”11.5m (0,11mot)と製
造例1−1と同様に調製した塩化白金酸のイソグロノ4
ノール溶液0.05 ′Ill (4,8mmot%)
を加えて1時間加熱還流し、1.4−ジクロロ−2−〔
ジクロロメチル〕シリルー2−fテン〔α9式〕22I
を得た。s, aa(aa, J=xo:a*17.anz, IH
, CuCl2) [Production Example ■-1] 1.4-C I * o -2-ff> C (1) Formula) I
Qmj (0,106mot) and diku aa methylsilay (
bp41°C)”11.5m (0.11mot) and isoglono-4 of chloroplatinic acid prepared in the same manner as Production Example 1-1.
Nol solution 0.05'Ill (4.8 mmot%)
was added and heated under reflux for 1 hour to give 1,4-dichloro-2-[
dichloromethyl] silyl-2-f-tene [α9 formula] 22I
I got it.
収率:87チ# bp:57℃/ 1 wm Hg’H
Nla(ccz4) :門標テトラメチルシランδ0.
96 (m −3He CHs81 ) −4,19(
d −J=7.5Hz −2HeCH20H)、4.2
4(1,2H,C旦2C) −6,49(t 、J==
7.5Hz 。Yield: 87chi# bp: 57℃/1 wm Hg'H
Nla (ccz4): marker tetramethylsilane δ0.
96 (m −3He CHs81 ) −4,19(
d-J=7.5Hz-2HeCH20H), 4.2
4(1,2H,Cdan2C) -6,49(t, J==
7.5Hz.
IH,C匹H,)
〔製造例■−2〕
1.4−ジクロロ−2−〔ジクロロメチル〕シリルー2
−ブテン((111式) 11.51 (48mmot
)、THF 10 mu、CH,OH5,9td (4
8X 2 X 1.5mmot)(C2H5)3N 2
0 ”ll(48X 2 X 1.5 m moL )
、(C2H5)2030+/を用い、製造例1−2と同
様に減圧蒸留によ、91.4−ジクロロ−2−〔ジメト
キシメチル〕シリルー2−ブテン〔(2)式)8.8F
を得た。IH, C animals H,) [Production example ■-2] 1.4-dichloro-2-[dichloromethyl]silyru 2
-butene ((formula 111) 11.51 (48 mmot
), THF 10 mu, CH,OH5,9td (4
8X 2 X 1.5mmot) (C2H5)3N2
0”ll (48 x 2 x 1.5 mmol)
, (C2H5)2030+/ and distilled under reduced pressure in the same manner as in Production Example 1-2 to obtain 91.4-dichloro-2-[dimethoxymethyl]silyl-2-butene [formula (2)) 8.8F
I got it.
収率:80%、bp:63℃/ l wm HglHN
MR(CC64):門標テトラメチルシランδ0.24
(s 、3 H= C旦s 8 l ) e 3−4
8 (s 、e He C先O)。Yield: 80%, bp: 63°C/l wm HglHN
MR (CC64): Signpost tetramethylsilane δ0.24
(s, 3 H= Cdans 8 l) e 3-4
8 (s, e He C ahead O).
4.10(4,2H,C旦、C) 、 4.14 (d
e J=7.5■Z 、 2m(、C旦、CH)6.
19 (t p J==7.5FIz t I H−C
HCH2)〔製造例■−3〕
2−〔ジメトキシメチル〕シリル−1,3−ブタジェン
Zn粉末3.51 (35X1.5mmot)とTl(
F 15 mjをよくかきまぜながら、1.4−ジクロ
ロ−2−〔ジメトキシメチル〕シリルー2−ブテン〔(
6)式〕8.0g(35mmot)t−加えた。混合溶
液を2時間加熱還流した後製造例ト3と同様にして2−
〔ジメトキシメチル〕シリル−1,3−ブタジェン〔(
2)式)3.9#t−得た。4.10 (4,2H,Cdan,C), 4.14 (d
e J=7.5■Z, 2m(,Cdan,CH)6.
19 (t p J==7.5 FIz t I H-C
HCH2) [Production Example ■-3] 2-[dimethoxymethyl]silyl-1,3-butadiene Zn powder 3.51 (35X1.5 mmot) and Tl (
While stirring F 15 mj well, add 1,4-dichloro-2-[dimethoxymethyl]silyl-2-butene [(
6) Formula] 8.0 g (35 mmot) was added. After heating the mixed solution under reflux for 2 hours, 2-
[dimethoxymethyl]silyl-1,3-butadiene [(
2) Formula) 3.9#t-obtained.
収率ニア1チ、bp:31℃/ 7 m Hg’HNM
R(CCA4) :門標テトツメチルシラン80.17
(1,3H,CH381)#3.42(膠、6H,C先
O)。Yield near 1cm, bp: 31℃/7m Hg'HNM
R (CCA4): Signpost Tetotsumethylsilane 80.17
(1,3H, CH381) #3.42 (glue, 6H, C tip O).
5−00 (d 、J=10.3flz # I Ha
CH2CH) −5,33(d v J =17−8
Hz−IH,C旦1CH)、5.58(d、J=3.8
11Zt IH,CH,C)。5-00 (d, J=10.3flz # I Ha
CH2CH) −5,33(d v J =17−8
Hz-IH, C Dan 1CH), 5.58 (d, J=3.8
11Zt IH, CH, C).
5.73(d ?J=3.8112.IH,CH,C)
、6.32(dd 、J=lQ、3゜17.8Hz 、
IH、CHCH2)なお、上記製造例の表を下記に示
す;と共に反応式も併せ示す。5.73 (d?J=3.8112.IH, CH, C)
, 6.32 (dd, J=lQ, 3°17.8Hz,
IH, CHCH2) A table of the above production examples is shown below; the reaction formula is also shown.
・3
し し
手続補正書(自発)
昭和60年4月2−6日(a
特許庁長官 志 賀 学 殿
」事件の表示
昭和59年特許願第33733号
、発明の名称
2−置換−1,3−ブタジェン誘導体及びその製造法、
補正をする者
事件との関係 特許出願人
住 所 神奈川県茅ケ崎市赤松町7の2の1の402氏
名 佐藤史衛
、代理人 〒104
住 所 東京都中央区銀座3丁目10番9号、補正の対
象
明細書の「特許請求の範囲」の欄及び
「発明の詳細な説明」の欄。・3 Written amendment (voluntary) April 2-6, 1985 (a. Manabu Shiga, Commissioner of the Patent Office) 1985 Patent Application No. 33733, Title of Invention 2-Replacement-1, 3-butadiene derivative and method for producing the same,
Relationship with the case of the person making the amendment Patent Applicant Address 402-7-2-1 Akamatsucho, Chigasaki City, Kanagawa Prefecture Name Fumie Sato, Agent 104 Address 3-10-9 Ginza, Chuo-ku, Tokyo; The "Claims" column and the "Detailed Description of the Invention" column of the specification to be amended.
6、補正の内容 (1)特許請求の範囲を別紙の通り訂正する。6. Contents of correction (1) Amend the scope of claims as shown in the attached sheet.
(2)明細書第4頁第5行目乃至第6行目及び同第5頁
最終行乃至第6頁第1行目に「それぞれハロゲン・・・
・・・低級アルコキシ基を示す0但し・」とあるのを[
いずれもハロゲン、低級アルキル基゛及び低級アルコキ
シ基より成る群から選ばれる一種を示し、R1、R2、
R3は互いに同じであっても異なっていてもよいが、」
と訂正する。(2) In the 5th line to 6th line of page 4 of the specification, and from the last line of page 5 to the 1st line of page 6 of the specification, ``Respectively halogen...''
...indicates a lower alkoxy group, but..." is replaced with [
Each represents one selected from the group consisting of halogen, lower alkyl group and lower alkoxy group, R1, R2,
R3 may be the same or different from each other, but
I am corrected.
(3)同第6頁第9行目、同第10頁下から第11行目
、及び同第10頁下から第9行目1こrb)ずれか」と
あるのを[少なくとも」と訂正する。(3) "At least" on page 6, line 9, page 10, line 11 from the bottom, and page 10, line 9 from the bottom, corrected to "at least" do.
(4)同第11頁の[D式]の括弧中[但し、R11、
LRI 、 R3/ のいずれか一つ」とあるのを「但
し、R11、R27、R81の少なくとも一つ」と訂正
する。(4) In the parentheses of [Formula D] on page 11 [However, R11,
The phrase "any one of LRI, R3/" is corrected to "However, at least one of R11, R27, and R81."
(5)同第12頁第4行目「更に、」を削除する。(5) Delete "Furthermore," in the fourth line of page 12.
(6)同第12頁第5行目乃至第6行目「亜鉛粉末等を
使用すると反応が円滑に進行する。」とあるのを「脱ハ
ロゲン反応剤として亜鉛粉末等を使用すればよい、更に
、亜鉛塩等を添加すると脱ハロゲン反応はより円滑に進
行する。」と訂正する。(6) On page 12, lines 5 and 6, the statement "The reaction proceeds smoothly when zinc powder, etc. is used" is replaced with "Zinc powder, etc. may be used as a dehalogenation reagent." Furthermore, if a zinc salt or the like is added, the dehalogenation reaction will proceed more smoothly.''
以上
特許請求の範囲
[1,構造式[1]
%式%[11
(但し、 R1,R”、 R”はいずれもハロゲン、低
級アルキル基及び低級アルコキシ基より成る群から選ば
れる一種を示し、RL、 R1,R3は互いに同じであ
っても異なっていてもよいが、R1,R2,R”が同時
に低級アルキル基である場合を除く。)
で表わされる2−置換−1,3−ブタジェン。Claims [1, Structural formula [1] % Formula % [11 (However, R1, R'', R'' all represent one selected from the group consisting of halogen, lower alkyl group, and lower alkoxy group, 2-substituted-1,3-butadiene represented by RL, R1, and R3 may be the same or different, except when R1, R2, and R'' are all lower alkyl groups.
2、構造式[11]
%式%[[]
(但し、R1,R”、 R”はいずれもハロゲン、低級
アルキル基及び低級アルコキシ基より成る群から選ばれ
る一種を示し、R1,Ra、 R3は互いに同じであっ
ても異なっていてもよいが、R1,Rm、 R1が同時
に低級アルキル基である場合を除く、またXはハロゲン
を示す、)で表わされる2−置換−1,4−ジハロゲノ
−2−ブテンを非アルコール性溶媒の存在下で脱ハロゲ
ンすることを特徴とする構造式[1]%式%
(但し、R1,Rm、 Raは前記と同じ意味を表わす
。)で示される2−置換−1,3−ブタジェンの製造法
。2. Structural formula [11] % Formula % [[] (However, R1, R", R" all represent one selected from the group consisting of halogen, lower alkyl group, and lower alkoxy group, and R1, Ra, R3 may be the same or different from each other, except when R1, Rm, and R1 are all lower alkyl groups, and X represents a halogen. -2-Butene is dehalogenated in the presence of a non-alcoholic solvent, and is represented by the structural formula [1]% (wherein, R1, Rm, and Ra have the same meanings as above). -Production method of substituted-1,3-butadiene.
3、非アルコール性溶媒が環状エーテルである特許請求
の範囲第2項′記載の2−置換−1゜3−ブタジェンの
製造法。3. The method for producing 2-substituted-1°3-butadiene according to claim 2', wherein the non-alcoholic solvent is a cyclic ether.
4、構造式[ml
I
HC=C−CH=CH[m]
2
(但し、A1. AN、 AMの少なくとも一つはハロ
ゲン、他は低級アルキル基又は低級アルコキシ基を示す
。)
で表わされる化合物を低級アルコールと反応させて、2
位のケイ素に結合しているハロゲン原子を低級アルコキ
シ基で置換することを特徴とする構造式[IV]
HC=C−CH=CH[IV]
2
(但し、R” 、R” 、R”の少なくとも一つが低級
アルコキシ基であり、他は低級アルキル基である)で表
わされる2−置換−1,3−ブタジェンの製造法。4. Compound represented by the structural formula [ml I HC=C-CH=CH[m] 2 (However, A1. At least one of AN and AM is a halogen, and the others represent a lower alkyl group or a lower alkoxy group.) By reacting with lower alcohol, 2
Structural formula [IV] HC=C-CH=CH[IV] 2 (However, R", R", R" A method for producing 2-substituted-1,3-butadiene, at least one of which is a lower alkoxy group and the others are lower alkyl groups.
5、構造式[1[]で表わされる化合物と低級アルコー
ルとを塩基の存在下に反応させる特許請求の範囲第4項
記載の2−置換−1,3−ブタジェンの製造法。5. A method for producing 2-substituted-1,3-butadiene according to claim 4, which comprises reacting a compound represented by the structural formula [1[] with a lower alcohol in the presence of a base.
Claims (1)
級アルキル基又は低級アルコキシ基を示す。但し、Rl
r *21 R3が同時に低級アルキル基である場合を
除く。) で表わされる2−置換−1,3−ブタジェン。 2、構造式 [11〕 X−CH2−C= CM−CH2・X [II:1(但
し、R’ l R2,R’はそれぞれハロダン、低級ア
ルキル基又は低級アルコキシ基を示す。但し、R’ e
R21R3が同時に低級アルキル基である場合 □を
除く。またXはハロダンを示す。) で表わされる2−置換−1,4−ジハロゲノ−2−プテ
ンを非アルコール性溶媒の存在下で脱ハロゲンすること
を特徴とする構造式m H2C=C−CH=CH2 (但し、R’ e H2CR”?を前記と同じ意味を表
す。)で示される2−置換−1,3−ブタジェンの製造
法。 3、非アルコール性溶媒が環状エーテルである特許請求
の範囲第2項記載の2−#換−1,3−ブタジェンの製
造法。 4、構造式 〔■〕 H2C−C−CH= CH2[111)(但し、A’
l A2# A’のいずれか一つは/% eIj’ン、
他は低級アルキル基又は低級アルコキシ基を示す。) で表わされる化合物を低級アルコールと反応させて、2
位のケイ素に結合しているハロゲン原子を低級アルコキ
シ基で置換することを特徴とする構造式〔■〕 H2C=C−CH=CH2〔■〕 (但し、R” 、 R” 、 R”のいずれが一つが低
級アルコキシ基であり、他は低級アルキル基である)で
表わされる2−置換−1,3−ブタジェンの製造法0 5、構造式[11で表わされる化合物と低級アルコール
とを塩基の存在下に反応させる特許請求の範囲第4項記
載の2−置換−1,3−ブタジェンの製造法。 6、塩基がトリエチルアミンで代表される有機脂肪族ア
ミンである特許請求の範囲第5項記載の2−置換−1,
3−ブタジェンの製造法。[Claims] 1. Structural formula [1) %formula%) (However, R' l R21n'u each represents a halodane, a lower alkyl group, or a lower alkoxy group. However, Rl
r *21 Except when R3 is also a lower alkyl group. ) 2-substituted-1,3-butadiene. 2. Structural formula [11] X-CH2-C= CM-CH2. e
When R21R3 are both lower alkyl groups, □ is excluded. Moreover, X represents halodan. ) 2-substituted-1,4-dihalogeno-2-ptene is dehalogenated in the presence of a non-alcoholic solvent. A method for producing 2-substituted-1,3-butadiene represented by H2CR"? has the same meaning as above. 3. 2- according to claim 2, wherein the non-alcoholic solvent is a cyclic ether. # Production method of 1,3-butadiene. 4. Structural formula [■] H2C-C-CH= CH2[111) (However, A'
l A2# Any one of A' is /% eIj',
Others represent a lower alkyl group or a lower alkoxy group. ) is reacted with a lower alcohol to form 2.
[■] H2C=C-CH=CH2 [■] (However, any of R", R", R" One is a lower alkoxy group and the other is a lower alkyl group) Method for producing 2-substituted-1,3-butadiene 5. A compound represented by the structural formula [11] and a lower alcohol are combined in a base. 6. A method for producing 2-substituted-1,3-butadiene according to claim 4, in which the reaction is carried out in the presence of an organic aliphatic amine represented by triethylamine. 2-substitution-1 of
Method for producing 3-butadiene.
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59033733A JPS60197694A (en) | 1984-02-24 | 1984-02-24 | 2-substituted-1,3-butadiene derivative and its preparation |
DE8585101980T DE3577439D1 (en) | 1984-02-24 | 1985-02-22 | 2-SUBSTITUTED 1,3-BUTADIENE AND METHOD FOR THE PRODUCTION THEREOF. |
EP85101980A EP0154867B1 (en) | 1984-02-24 | 1985-02-22 | 2-substituted-1,3-butadiene derivatives and process for producing same |
US06/704,088 US4677216A (en) | 1984-02-24 | 1985-02-22 | 2-Substituted-1,3-butadiene derivatives and process for producing same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP59033733A JPS60197694A (en) | 1984-02-24 | 1984-02-24 | 2-substituted-1,3-butadiene derivative and its preparation |
Publications (2)
Publication Number | Publication Date |
---|---|
JPS60197694A true JPS60197694A (en) | 1985-10-07 |
JPH0240074B2 JPH0240074B2 (en) | 1990-09-10 |
Family
ID=12394603
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP59033733A Granted JPS60197694A (en) | 1984-02-24 | 1984-02-24 | 2-substituted-1,3-butadiene derivative and its preparation |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPS60197694A (en) |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2974062A (en) * | 1956-02-14 | 1961-03-07 | Owens Corning Fiberglass Corp | Epoxy-glass fiber systems and method for improving the bonding relation therebetween |
-
1984
- 1984-02-24 JP JP59033733A patent/JPS60197694A/en active Granted
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2974062A (en) * | 1956-02-14 | 1961-03-07 | Owens Corning Fiberglass Corp | Epoxy-glass fiber systems and method for improving the bonding relation therebetween |
Also Published As
Publication number | Publication date |
---|---|
JPH0240074B2 (en) | 1990-09-10 |
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