JPS6252728B2 - - Google Patents
Info
- Publication number
- JPS6252728B2 JPS6252728B2 JP54116651A JP11665179A JPS6252728B2 JP S6252728 B2 JPS6252728 B2 JP S6252728B2 JP 54116651 A JP54116651 A JP 54116651A JP 11665179 A JP11665179 A JP 11665179A JP S6252728 B2 JPS6252728 B2 JP S6252728B2
- Authority
- JP
- Japan
- Prior art keywords
- trichloroethane
- vinylidene
- trihaloethane
- diazabicycloalkene
- chloride
- 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.)
- Expired
Links
- -1 vinylidene halide Chemical class 0.000 claims description 13
- 229910000039 hydrogen halide Inorganic materials 0.000 claims description 10
- 239000012433 hydrogen halide Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 3
- UBOXGVDOUJQMTN-UHFFFAOYSA-N 1,1,2-trichloroethane Chemical compound ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 24
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 6
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- 238000006704 dehydrohalogenation reaction Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910001514 alkali metal chloride Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZDUOUNIIAGIPSD-UHFFFAOYSA-N 1,1,1-tribromoethane Chemical compound CC(Br)(Br)Br ZDUOUNIIAGIPSD-UHFFFAOYSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- QUMDOMSJJIFTCA-UHFFFAOYSA-N 1,1,2-tribromoethane Chemical compound BrCC(Br)Br QUMDOMSJJIFTCA-UHFFFAOYSA-N 0.000 description 1
- SXZSFWHOSHAKMN-UHFFFAOYSA-N 2,3,4,4',5-Pentachlorobiphenyl Chemical compound C1=CC(Cl)=CC=C1C1=CC(Cl)=C(Cl)C(Cl)=C1Cl SXZSFWHOSHAKMN-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000007033 dehydrochlorination reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000011345 viscous material Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明はジアザビシクロアルケンハロゲン化水
素塩の存在下でトリハロエタンを加熱してハロゲ
ン化ビニリデンを製造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing vinylidene halides by heating trihaloethane in the presence of a diazabicycloalkene hydrogen halide salt.
ハロゲン化ビニリデンは高分子合成用の単量体
あるいは合成中間体として有用である。 Vinylidene halides are useful as monomers or synthetic intermediates for polymer synthesis.
ハロゲン化ビニリデンは１，１，１−トリハロ
エタンあるいは、１，１，２−トリハロエタンの
脱ハロゲン化水素反応により合成される。なかん
づく、安価に製造できる１，１，２−トリハロエ
タンの脱ハロゲン化水素反応による方法が多用さ
れている。 Vinylidene halide is synthesized by dehydrohalogenation reaction of 1,1,1-trihaloethane or 1,1,2-trihaloethane. Among these, a method based on a dehydrohalogenation reaction of 1,1,2-trihaloethane, which can be produced at low cost, is often used.
たとえば、１，１，２−トリクロロエタンの熱
的脱塩化水素反応により、塩化ビニリデンが生成
するが、同時に相当量の１，２−ジクロロエチレ
ンが副生し経済的でない。このさい、塩化セシウ
ムなどのアルカリ金属塩化物を共存させることに
より塩化ビニリデンへの選択的合成をする方法が
特許出願されているが（日特開48−62706号）、事
実上、高い選択性を与えるのはアルカリ金属塩化
物中塩化セシウム含有触媒に限られる上、塩化セ
シウムが資源的に希少かつ高価であるため工業的
に利用されていない。 For example, a thermal dehydrochlorination reaction of 1,1,2-trichloroethane produces vinylidene chloride, but at the same time a considerable amount of 1,2-dichloroethylene is produced as a by-product, which is not economical. At this time, a patent application has been filed for a method of selectively synthesizing vinylidene chloride by coexisting an alkali metal chloride such as cesium chloride (Japanese Unexamined Patent Publication No. 48-62706), but in fact, it is difficult to synthesize vinylidene chloride with high selectivity. What is provided is limited to a catalyst containing cesium chloride in an alkali metal chloride, and cesium chloride is not used industrially because it is a rare and expensive resource.
工業的には、たとえば、１，１，２−トリクロ
ロエタンより水酸化ナトリウムあるいは水酸化カ
ルシウムを脱ハロゲン化水素試薬として用いて塩
化ビニリデンを製造する方法が利用されている。
この方法の欠点は１，１，２−トリクロロエタン
から脱取した塩化水素は塩化ナトリウムあるいは
塩化カルシウムになり経済的に再利用出来ない事
と水酸化ナトリウムなどが化学量論的に消費され
る事にある。 Industrially, for example, a method for producing vinylidene chloride from 1,1,2-trichloroethane using sodium hydroxide or calcium hydroxide as a dehydrohalogenation reagent is used.
The disadvantages of this method are that the hydrogen chloride removed from 1,1,2-trichloroethane becomes sodium chloride or calcium chloride and cannot be reused economically, and that sodium hydroxide etc. are consumed stoichiometrically. be.
本発明者らはハロゲン化ビニリデンの製法につ
いて鋭意検討を行つた結果、ジアザビシクロアル
ケンハロゲン化水素塩の存在下でトリハロエタン
を加熱して脱ハロゲン化水素反応を行わせること
によりハロゲン化ビニリデンを製造する方法を見
出した。 The inventors of the present invention conducted intensive studies on the method for producing vinylidene halides, and found that vinylidene halides can be produced by heating trihaloethane in the presence of a diazabicycloalkene hydrogen halide to perform a dehydrohalogenation reaction. I found a way to do it.
本発明におけるジアザビシクロアルケンハロゲ
ン化水素塩とは式〔〕で表わされるジアザビシ
クロアルケンの塩化水素塩あるいは臭化水素塩で
ある。 The diazabicycloalkene hydrohalide in the present invention is a diazabicycloalkene hydrochloride or hydrobromide represented by the formula [].
ただし、ｎは３または５
ジアザビシクロアルケンをハロゲン化アルカン
の脱ハロゲン化水素試薬として用いる事はすでに
知られているが、その際、ジアザビシクロアルケ
ンは化学量論的に消費される。かつハロゲン化ア
ルカンのハロゲン原子が２ケ以上の場合、ハロゲ
ン化アルカン１分子当り１分子のハロゲン化水素
が脱取されるにとゞまらず２分子以上のハロゲン
化水素が脱取されるばかりでなく、黒色粘稠状の
いわゆるハルツの生成に及んでしまう。 However, n is 3 or 5. It is already known that diazabicycloalkene is used as a dehydrohalogenation reagent for halogenated alkanes, but in this case, diazabicycloalkene is consumed stoichiometrically. When the halogenated alkane has two or more halogen atoms, not only one molecule of hydrogen halide is removed per molecule of the halogenated alkane, but two or more molecules of hydrogen halide are removed per molecule of the halogenated alkane. Instead, it leads to the formation of so-called Harz, which is a black viscous substance.
これに反し、本発明においては、ジアザビシク
ロアルケンハロゲン化水素塩は化学量論的に消費
されることなく触媒的に作用するものである。か
つ、トリハロエタンに対して適用した場合、トリ
ハロエタン１分子につき１分子のハロゲン化水素
を脱取し選択的にハロゲン化ビニリデンを生成さ
せるのである。驚くべき事には、１，１，２−ト
リハロエタンに適用した場合においても選択的に
ハロゲン化ビニリデンが生成するのである。 In contrast, in the present invention, the diazabicycloalkene hydrogen halide acts catalytically without being consumed stoichiometrically. Furthermore, when applied to trihaloethane, one molecule of hydrogen halide is removed per molecule of trihaloethane to selectively produce vinylidene halide. Surprisingly, even when applied to 1,1,2-trihaloethane, vinylidene halide is selectively produced.
本発明におけるトリハロエタンとは１，１，１
−トリクロロエタン、１，１，２−トリクロロエ
タン、１，１，１−トリブロモエタン、１，１，
２−トリブロモエタンなどであり、１，１，２−
トリクロロエタンが特に適している。 Trihaloethane in the present invention is 1,1,1
-trichloroethane, 1,1,2-trichloroethane, 1,1,1-tribromoethane, 1,1,
2-tribromoethane, etc., and 1,1,2-
Trichloroethane is particularly suitable.
本発明においてハロゲン化ビニリデンは塩化ビ
ニリデンあるいは臭化ビニリデンである。 In the present invention, vinylidene halide is vinylidene chloride or vinylidene bromide.
本発明において、加熱温度は150℃ないし400℃
が好ましく、180℃ないし350℃がさらに好まし
く、230℃ないし320℃がもつとも好ましい。本発
明は加圧下、大気圧下、減圧下のいずれで実施し
ても良い。 In the present invention, the heating temperature is 150℃ to 400℃
is preferable, 180°C to 350°C is more preferable, and 230°C to 320°C is also preferable. The present invention may be carried out under increased pressure, atmospheric pressure, or reduced pressure.
本発明は気相、液相いずれで実施しても良い。
気相で実施する場合、ジアザビシクロアルケンハ
ロゲン化水素塩は担体に担持して用いる方が望ま
しい。担体としてはシリカゲルが望ましい。本発
明を気相で実施する場合、不活性ガスが共存して
も良い。本発明の方法を液相で実施する場合、溶
剤を用いても良い。また、液相で実施の場合、酸
化防止剤を微量添加しても良い。 The present invention may be carried out in either a gas phase or a liquid phase.
When carrying out the reaction in a gas phase, it is preferable that the diazabicycloalkene hydrogen halide salt be supported on a carrier. Silica gel is preferred as the carrier. When carrying out the present invention in a gas phase, an inert gas may coexist. When carrying out the method of the invention in liquid phase, a solvent may be used. Moreover, when carrying out in a liquid phase, a trace amount of antioxidant may be added.
本発明の実施の方法を例示すると、シリカゲル
などの担体に担持したジアザビシクロアルケンハ
ロゲン化水素塩とトリハロエタンの蒸気を150℃
ないし400℃で接触させハロゲン化ビニリデンを
製造する方法とかジアザビシクロアルケンハロゲ
ン化水素塩の溶液にトリハロエタンと必要により
微量の酸化防止剤を添加し150℃ないし400℃に加
熱しハロゲン化ビニリデンを製造する方法であ
る。 To illustrate the method of carrying out the present invention, vapors of diazabicycloalkene hydrogen halide and trihaloethane supported on a carrier such as silica gel are heated at 150°C.
A method of producing vinylidene halide by contacting the solution at 150 to 400°C, or adding trihaloethane and a trace amount of antioxidant if necessary to a solution of diazabicycloalkene hydrogen halide and heating it to 150 to 400°C to produce vinylidene halide. This is the way to do it.
実施例 １
１，５−ジアザビシクロ〔５・４・０〕ウンデ
セン−７・塩酸塩〔（）式、以下DBU・HClと
略称する〕の水溶液にシリカゲルを浸し、111℃
で乾燥した。DBU・HClの担持量は5.6重量％で
あつた。Example 1 Silica gel was soaked in an aqueous solution of 1,5-diazabicyclo[5.4.0]undecene-7.hydrochloride [formula (), hereinafter abbreviated as DBU.HCl] and heated at 111°C.
It was dried. The amount of DBU/HCl supported was 5.6% by weight.
このDBU・HCl−シリカゲルをガラス管に充填
し、250℃で１，１，２−トリクロロエタンをヘ
リウムで希釈した気体（１，１，２−トリクロロ
エタン濃度２体積％）を空間速度250Hr-1で送入
した。送入した１，１，２−トリクロロエタン当
り90モル％の収率で塩化ビニリデンが、10モル％
の収率で１，２−ジクロロエチレンが得られた。 This DBU・HCl-silica gel was filled in a glass tube, and a gas prepared by diluting 1,1,2-trichloroethane with helium (1,1,2-trichloroethane concentration 2% by volume) was delivered at a space velocity of 250 Hr -1 at 250°C. I entered. Vinylidene chloride with a yield of 90 mol% based on 1,1,2-trichloroethane fed, 10 mol%
1,2-dichloroethylene was obtained in a yield of .
実施例 ２
実施例１と同じ触媒を用い、300℃，0.04気圧
で１，１，２−トリクロロエタンを空間速度
20Hr-1で送入した。送入した１，１，２−トリ
クロロエタン当り85モル％の収率で塩化ビニリデ
ンが得られた。 Example 2 Using the same catalyst as in Example 1, 1,1,2-trichloroethane was heated at 300°C and 0.04 atm at a space velocity of
It was delivered at 20Hr -1 . Vinylidene chloride was obtained in a yield of 85 mol % based on the 1,1,2-trichloroethane fed.
実施例 ３
１，１，２−トリクロロエタン40ｇ，DBU・
HCl4.8ｇ、エチルアルコール４ｇ、酸化防止剤
BHT0.4ｇをステンレスオートクレーブに仕込
み、150℃で５時間加熱した。塩化ビニリデンの
生成が認められたが、１，２−ジクロロエチレン
の生成は認められなかつた。Example 3 1,1,2-trichloroethane 40g, DBU・
HCl 4.8g, ethyl alcohol 4g, antioxidant
0.4 g of BHT was placed in a stainless steel autoclave and heated at 150°C for 5 hours. Production of vinylidene chloride was observed, but production of 1,2-dichloroethylene was not observed.
実施例 ４
１，５−ジアザビシクロ〔４・３・０〕ノネン
−５・塩酸塩〔（）式、以下DBN・HClと略称
する〕の水溶液にシリカゲルを浸し、115℃で乾
燥した。DBN・HClの担持量は5.2重量％であつ
た。Example 4 Silica gel was immersed in an aqueous solution of 1,5-diazabicyclo[4.3.0]nonene-5.hydrochloride [formula (), hereinafter abbreviated as DBN.HCl] and dried at 115°C. The amount of DBN/HCl supported was 5.2% by weight.
このDBN・HCl−シリカゲル20ｇをガラス管に
充填し、245℃で１，１，２−トリクロロエタン
−ヘリウム混合ガス（１，１，２−トリクロロエ
タン２体積％）を空間速度200Hr-1で送入した。
90モル％の収率で塩化ビニリデンが得られた。 A glass tube was filled with 20 g of this DBN/HCl-silica gel, and a 1,1,2-trichloroethane-helium mixed gas (2% by volume of 1,1,2-trichloroethane) was introduced at a space velocity of 200 Hr -1 at 245°C. .
Vinylidene chloride was obtained with a yield of 90 mol%.
Claims (1)
ハロゲン化水素塩の存在下でトリハロエタンを加
熱してハロゲン化ビニリデンを製造する方法。 ただし、ｎは３または５[Scope of Claims] 1. A method for producing vinylidene halide by heating trihaloethane in the presence of a hydrogen halide salt of diazabicycloalkene represented by the following formula. However, n is 3 or 5
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11665179A JPS5640621A (en) | 1979-09-13 | 1979-09-13 | Production of vinylidene halide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11665179A JPS5640621A (en) | 1979-09-13 | 1979-09-13 | Production of vinylidene halide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5640621A JPS5640621A (en) | 1981-04-16 |
| JPS6252728B2 true JPS6252728B2 (en) | 1987-11-06 |
Family
ID=14692499
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11665179A Granted JPS5640621A (en) | 1979-09-13 | 1979-09-13 | Production of vinylidene halide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5640621A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016528224A (en) * | 2013-08-01 | 2016-09-15 | ソルヴェイ（ソシエテ アノニム） | Process for dehydrohalogenation of halogenated organic non-polymeric compounds |
-
1979
- 1979-09-13 JP JP11665179A patent/JPS5640621A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5640621A (en) | 1981-04-16 |
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