JPS6284037A - Method for producing promoacetals - Google Patents
Method for producing promoacetalsInfo
- Publication number
- JPS6284037A JPS6284037A JP22365585A JP22365585A JPS6284037A JP S6284037 A JPS6284037 A JP S6284037A JP 22365585 A JP22365585 A JP 22365585A JP 22365585 A JP22365585 A JP 22365585A JP S6284037 A JPS6284037 A JP S6284037A
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- vinyl acetate
- alkoxysilane
- producing
- promoacetals
- 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.)
- Pending
Links
- 238000004519 manufacturing process Methods 0.000 title description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 11
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 238000000034 method Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 9
- LILXDMFJXYAKMK-UHFFFAOYSA-N 2-bromo-1,1-diethoxyethane Chemical compound CCOC(CBr)OCC LILXDMFJXYAKMK-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 2
- 238000006359 acetalization reaction Methods 0.000 description 2
- 150000001241 acetals Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 description 2
- YGZQJYIITOMTMD-UHFFFAOYSA-N 1-propoxybutane Chemical compound CCCCOCCC YGZQJYIITOMTMD-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 240000008881 Oenanthe javanica Species 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- CVQVSVBUMVSJES-UHFFFAOYSA-N dimethoxy-methyl-phenylsilane Chemical compound CO[Si](C)(OC)C1=CC=CC=C1 CVQVSVBUMVSJES-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- -1 ethyl ether Chemical class 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- NKLYMYLJOXIVFB-UHFFFAOYSA-N triethoxymethylsilane Chemical compound CCOC([SiH3])(OCC)OCC NKLYMYLJOXIVFB-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- 125000001680 trimethoxyphenyl group Chemical group 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、医薬、農薬等有機ファインケミカル製品の中
間原料として有用な化合物であるブロモアセタール類の
製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing bromoacetals, which are compounds useful as intermediate raw materials for organic fine chemical products such as pharmaceuticals and agricultural chemicals.
ブロモアセタール類の合成方法としてよく知られている
方法は、次の反応式に従う方法である。A well-known method for synthesizing bromoacetals is a method according to the following reaction formula.
０Ｔ１２ ＝ ＣＨＯＡＯ＋Ｂｒｌ ＋ＲＯＨ→Ｂｒ
（３ＨｔＣ１１（ＯＲ）！＋ＡＯＯＲ＋ＨＩＯ＋ｌｌＢ
ｒ
この方法による合成報告例として、Ｏｒｇ。0T12 = CHOAO+Brl +ROH→Br
(3HtC11(OR)!+AOOR+HIO+llB
r As an example of a synthesis report using this method, Org.
８ｙｎｔｈ、、 ｍ 、 １２３．１９５５年およびｔ
−／７特許第２８２！５０１３号（１９７０年）がある
。8ynth,, m, 123.1955 and t
-/7 Patent No. 282!5013 (1970).
Ｏｒｇ、 ８ｙｎｔｈ、、 ＩＩ、 １２５，１９５５
年によると、酢酸ビニルとアルコールとの溶液中にＢｒ
、１を滴下した後アセタール化を行い、反応液を水中に
注いだ後アルカリ洗浄、抽出および蒸留分離を行って６
２〜６３％の収率でブロモアセタールを得ている。Org, 8ynth, II, 125, 1955
According to the year, Br in a solution of vinyl acetate and alcohol
, 1 was added dropwise, acetalization was performed, and the reaction solution was poured into water, followed by alkali washing, extraction, and distillation separation to obtain 6.
Bromoacetals are obtained in yields of 2-63%.
一方、ロシア特許第２８２３５０８号によれば、ジクロ
ロメタン溶媒中で酢酸ビニルにＢｒ、を付加した後、得
られた付加反応液をアルコール溶液中に添加してアセタ
ール化を行い、ついで反応液にｍａＨＯＯａ水溶液を滴
下して中和した後抽出−蒸留分離を行って９０％の収率
でブロモアセタールを得ている。On the other hand, according to Russian Patent No. 2823508, after adding Br to vinyl acetate in a dichloromethane solvent, the resulting addition reaction solution is added to an alcohol solution to perform acetalization, and then a maHOOa aqueous solution is added to the reaction solution. After neutralization by adding dropwise, extraction-distillation separation was performed to obtain bromoacetal with a yield of 90%.
しかしながら、本発明者らがこのロシア特許の方法の追
試を行ったところ、４７％の収率でしか目的生成物は得
られなかった。However, when the present inventors carried out a follow-up test of the method of this Russian patent, the desired product could only be obtained with a yield of 47%.
一方、アルコキシシランを用いてアセタールを製造する
方法としては、トリメチルシリルトリフレートを用いて
カルボニル化合物をアルコキシシランでアセタール化す
る方法（特開昭５６−１３１５５６号公報）や、ヨード
トリメチルシランを用いてアルデヒド化合物をアルコキ
シシランでアセタール化する方法（特開昭５７−４８９
３０号公報）などが知られているが、アルコキシシラン
を用いてブロモアセタールを合成した例はない。On the other hand, methods for producing acetal using alkoxysilane include a method of acetalizing a carbonyl compound with alkoxysilane using trimethylsilyl triflate (Japanese Patent Application Laid-open No. 131556/1983), and a method of producing an acetal using iodotrimethylsilane. Method of acetalizing a compound with alkoxysilane (Japanese Patent Application Laid-Open No. 57-489
30), but there is no example of synthesizing bromoacetal using an alkoxysilane.
前述の酢酸ビニル、臭素及びアルコールよジブロモアセ
タールを合成する方法は、収率が低く、かつ反応の安定
性に問題がある。The aforementioned method of synthesizing dibromoacetal from vinyl acetate, bromine, and alcohol has low yields and problems with reaction stability.
その主たる原因は前に反応式で示したようにＢＢｒと馬
０が副生し、これらにより生成したブロモアセタールが
加水分解されるためであると考えられる。The main reason for this is thought to be that BBr and 0 are by-produced as shown in the reaction equation above, and the bromoacetal produced by these is hydrolyzed.
本発明者らは、ＨＢｒとＨ，Ｏとを副生じないブロモア
セタールの合成法について鋭意検討を行った結果本発明
に到達した。The present inventors have conducted extensive studies on a method for synthesizing bromoacetal that does not produce HBr, H, and O as by-products, and have arrived at the present invention.
本発明は、酢酸ビニルと、臭素および一般式（Ｒ’０）
ＳｉＲ鵞、−ｎ 〔式中、Ｒ′は低級アルキル基、芹は
メチル基またはフェニル基を示し、ｎは１から４までの
整数を示す〕で示されるアルコキシシランとを反応させ
ることを特徴とするブロモアセタール類の製造方法であ
る。The present invention relates to vinyl acetate, bromine and general formula (R'0)
SiR is characterized by reacting with an alkoxysilane represented by -n [wherein R' represents a lower alkyl group, Seri represents a methyl group or phenyl group, and n represents an integer from 1 to 4]. This is a method for producing bromoacetals.
次に、本発明の方法分詳しく説明する。Next, the method of the present invention will be explained in detail.
本発明において、酢酸ビニル、臭素およびアルコキシシ
ランを反応させる方法としては次の２つの方法がある。In the present invention, there are the following two methods for reacting vinyl acetate, bromine, and alkoxysilane.
１）酢酸ビニルとアルコキシシランの溶液中にＢｒｌ
を滴下して反応を行わせる方法。1) Brl in a solution of vinyl acetate and alkoxysilane
A method of causing a reaction to occur by dropping .
２）予め酢酸ビニルとＢｒｌとの付加物を生成させ、つ
いでこの付加物とアルコキシシランとを反応させる方法
。2) A method in which an adduct of vinyl acetate and Brl is generated in advance, and then this adduct is reacted with an alkoxysilane.
本発明方法において使用しつるアルコキシシランとして
は、テトラメトキシシラン、テトラエトキシシラン、ト
リメトキシメチルシラン、トリエトキシメチルシラン、
トリメトキシフェニル７ラン、トリエトキシフェニルシ
ラン、ジェトキシジメチルシラン、ジェトキシジメチル
シラン、ジメトキシメチルフェニルシラン、ジェトキシ
メチルフェニルシラン、メトキシトリメチルシラン、ニ
ドキシトリメチルシラン等があげられる。Examples of the alkoxysilane used in the method of the present invention include tetramethoxysilane, tetraethoxysilane, trimethoxymethylsilane, triethoxymethylsilane,
Examples include trimethoxyphenyl 7rane, triethoxyphenylsilane, jetoxydimethylsilane, jetoxydimethylsilane, dimethoxymethylphenylsilane, jetoxymethylphenylsilane, methoxytrimethylsilane, and nidoxytrimethylsilane.
前記１）、２）の方法とも反応条件は次のとおりである
。The reaction conditions for both methods 1) and 2) above are as follows.
使用するＢｒ２の量は、酢酸ビニル１モルに対しＩＩＬ
５〜５モルの割合で使用するのが好ましく、α８〜１．
５モルの割合で使用するのが更に好ましい。またアルコ
キシシランは、酢酸ビニル１モルに対し０．５〜２０モ
ルの割合で使用するのが好ましく、α８〜１０モルの割
合で使用するのが更に好ましい。The amount of Br2 used is IIL per mole of vinyl acetate.
It is preferably used in a ratio of 5 to 5 moles, and α8 to 1.
More preferably, it is used in a proportion of 5 moles. The alkoxysilane is preferably used in a proportion of 0.5 to 20 moles, more preferably α8 to 10 moles, per mole of vinyl acetate.
また、反応温度は一５０℃〜１０１１℃の範囲内の温度
で反応させるのが好ましく、−２０”Ｃ〜６０℃の範囲
内の温度で反応させるのが更に好ましい。Further, the reaction temperature is preferably within the range of -50°C to 1011°C, and more preferably within the range of -20''C to 60°C.
反応溶媒としては、反応に対し不活性な溶媒ならばどの
ような溶媒を用いてもよいが、溶媒の不存在下に反応を
行ってもよい。As the reaction solvent, any solvent may be used as long as it is inert to the reaction, but the reaction may be carried out in the absence of a solvent.
反応溶媒としては、塩化メチレンが好ましい。As the reaction solvent, methylene chloride is preferred.
反応生成物は、Ｃ烏Ｃ／ｌ 、ＣｊＨＣ！ ／３、Ｃｏ
／、の如きハロゲン化炭化水素、エチルエーテル、ｎ−
ブチル−ｎ−プロピルエーテルの如キエーテル又はベン
ゼン、トルエン、キシレンの如＠ ”Ｊ 香族Ｒ化水素
で抽出し、抽出溶媒を留去した後蒸留分離する等、既知
の方法で分離することができる。The reaction products are Crow C/l, CjHC! /3,Co
/, halogenated hydrocarbons such as ethyl ether, n-
Ethers such as butyl-n-propyl ether, or benzene, toluene, xylene, etc. can be separated by known methods such as extraction with aromatic R hydrogen, distillation after distilling off the extraction solvent, etc. .
実施例−に
ロフラスコに酢酸ビニル（１８６４（１０ｍｍｏ１）、
テトラメトキシシラン五〇４１Ｆ（２０ｍｍｏ１）およ
び塩化メチレン１０−を仕込み、臭素ｔ ５２ ｔ （
９，５ｍｍｏｌ）を２０℃で滴下し、室温（２５℃）で
２［１ｈｒ反応を行ない、反応液のＧＯ分析を行ったと
ころ、ブロモアセタールが１、２８ ？ （７，６ｍｍ
ｏｌ、）収率（対Ｂｒ、 ） ’８０％で生成した。Example - Vinyl acetate (1864 (10 mmol),
Tetramethoxysilane 5041F (20 mmol) and methylene chloride 10- were charged, and bromine t 52 t (
9.5 mmol) was added dropwise at 20°C, the reaction was carried out for 2 [1 hr] at room temperature (25°C), and GO analysis of the reaction solution revealed that bromoacetal was 1.28%. (7.6mm
ol, ) was produced in a yield (vs. Br, )' of 80%.
実施例−２
三日フラスコに酢酸ビニル０．８６ ｔ （１０ｍｍｏ
ｌ）および塩化メチレン１０ｍ１を仕込み、臭素１．５
７ ｔ （９，８ｍｍｏｌ）を滴下ロートより０℃で滴
下した。得られたＢｒｌ付加体をテトラメトキシシラン
１５４ Ｆ （２２ｍｍｏｌ）のＯＨ，ＣＩ、 １ ｎ
−溶液に一１０℃で滴下し、室温（２５℃）で２０ｈｒ
反応を行ない、反応液のＧｏ分析を行ったところブロモ
アセタールが１．３２ ｔ （７，８ｍｍｏｌ）収率（
対Ｂｒ、） ８０％で生成した。Example-2 0.86 t of vinyl acetate (10 mmo
1) and 10 ml of methylene chloride, and 1.5 ml of bromine
7 t (9.8 mmol) was added dropwise from the dropping funnel at 0°C. The obtained Brl adduct was mixed with tetramethoxysilane 154 F (22 mmol) OH, CI, 1 n
- Add dropwise to the solution at -10°C and leave at room temperature (25°C) for 20 hours.
The reaction was carried out and Go analysis of the reaction solution revealed that the yield of bromoacetal was 1.32 t (7.8 mmol) (
vs. Br, ) 80%.
Claims (1)
Ｒ＾２＿４＿−＿ｎ〔式中Ｒ′は低級アルキル基、Ｒ＾
２はメチル基またはフェニル基を示し、ｎは１から４ま
での整数を示す〕で示されるアルコキシシランとを反応
させることを特徴とするブロモアセタール類の製造方法
。[Claims] 1. Vinyl acetate, bromine and general formula (R'O)_nSi
R^2_4_-_n [in the formula, R' is a lower alkyl group, R^
2 represents a methyl group or a phenyl group, and n represents an integer from 1 to 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22365585A JPS6284037A (en) | 1985-10-09 | 1985-10-09 | Method for producing promoacetals |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22365585A JPS6284037A (en) | 1985-10-09 | 1985-10-09 | Method for producing promoacetals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS6284037A true JPS6284037A (en) | 1987-04-17 |
Family
ID=16801584
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22365585A Pending JPS6284037A (en) | 1985-10-09 | 1985-10-09 | Method for producing promoacetals |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6284037A (en) |
-
1985
- 1985-10-09 JP JP22365585A patent/JPS6284037A/en active Pending
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