JP2008037807A - 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and method for producing the same - Google Patents
1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and method for producing the same Download PDFInfo
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Abstract
Description
本発明は、溶剤、洗浄剤、乾燥剤、反応溶媒、伝熱媒体、動力循環作動流体、発泡剤として有用な新規な含フッ素環状化合物及びその製造方法に関する。
The present invention relates to a novel fluorine-containing cyclic compound useful as a solvent, a cleaning agent, a drying agent, a reaction solvent, a heat transfer medium, a power circulation working fluid, and a foaming agent, and a method for producing the same.
従来、伝熱媒体、消火剤、動力循環作動流体、発泡剤、反応溶媒、乾燥剤、洗浄剤などとして、クロロフルオロカーボン（CFC）類が広く利用されてきた。このCFC類は、毒性が少なく、不燃性で、化学的及び熱的に安定であることから各種の産業分野に広く使用されていた。
だが、CFC類は、大気中に放出されると成層圏のオゾン層を破壊する効果が大きいため、人類を含む地球上の生態系に重大な悪影響を及ぼすことが指摘され、その製造が１９９５年末に国際的条約により禁止された。
Conventionally, chlorofluorocarbons (CFCs) have been widely used as heat transfer media, fire extinguishing agents, power circulation working fluids, blowing agents, reaction solvents, desiccants, cleaning agents, and the like. These CFCs have been widely used in various industrial fields because of their low toxicity, nonflammability, and chemical and thermal stability.
However, it has been pointed out that CFCs, when released into the atmosphere, have a significant effect on destroying the ozone layer in the stratosphere, so they have a serious adverse effect on the earth's ecosystems including humans. Banned by international treaties.
このようなCFCの及ぼすオゾン層破壊問題に対処するために、環境負荷が小さく、伝熱媒体、消火剤、動力循環作動流体、発泡剤、反応溶媒、乾燥剤、洗浄剤などとして使用可能な化合物が求められ（非特許文献１）、たとえば、ヒドロクロロフルオロカーボン（HCFC類）に関する検討も行われているが（非特許文献２）、未だ十分なものが得られていないのが現状である。
本発明は、環境負荷の影響が小さく、溶剤、洗浄剤、反応溶媒、消化剤等として有用な新規な含フッ素環状化合物及びこの化合物を収率良く製造する方法を提供することを課題とする。 An object of the present invention is to provide a novel fluorine-containing cyclic compound which is less affected by environmental load and is useful as a solvent, a cleaning agent, a reaction solvent, a digestive agent, and the like, and a method for producing this compound with high yield.
本発明者は、HCFC類の中でも特有な構造を有する含フッ素化合物が上記目的に合致することを見出し、本発明を完成するに至った。
すなわち、この出願によれば、以下の発明が提供される。
〈１〉下記化学式（１）
〈２〉上記化学式（１）のトランス異性体である下記化学式（２）
〈３〉上記化学式（１）のシス異性体である下記化学式（３）
〈４〉3,3,4,4-テトラフルオロシクロブテンに塩素を付加させることを特徴とする1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンの製造方法。
〈５〉塩素の付加反応が光照射下で行われることを特徴とする上記〈４〉に記載の1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンの製造方法。
〈６〉塩素の付加反応が１００℃〜６００℃の加熱下で行われることを特徴とする上記〈４〉に記載の1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンの製造方法。
The present inventor has found that a fluorine-containing compound having a unique structure among HCFCs meets the above purpose, and has completed the present invention.
That is, according to this application, the following invention is provided.
<1> The following chemical formula (1)
<2> The following chemical formula (2) which is a trans isomer of the above chemical formula (1)
<3> The following chemical formula (3) which is a cis isomer of the above chemical formula (1)
<4> A process for producing 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane, wherein chlorine is added to 3,3,4,4-tetrafluorocyclobutene.
<5> The method for producing 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane as described in <4> above, wherein the addition reaction of chlorine is performed under light irradiation.
<6> Production of 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane as described in <4> above, wherein the addition reaction of chlorine is carried out under heating at 100 to 600 ° C Method.
本発明に係る新規な1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンは、環境影響の指標となる大気寿命が短く、環境への影響が小さいという特長を有する。
また、切削油やプレス油などに含まれるたとえばn-エイコサンのトランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンに対する溶解度が大きく、十分な溶解力を持つことから、当該化合物は従来のCFCと同様、溶剤、洗浄剤、反応溶媒などの用途を主に、水切り乾燥剤、伝熱媒体、動力循環作動流体、発泡剤などとして有用である。
The novel 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane according to the present invention has a feature that it has a short atmospheric life as an index of environmental impact and a small impact on the environment.
In addition, for example, n-eicosane contained in cutting oil and press oil has high solubility in trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane, and has sufficient dissolving power. Similar to conventional CFC, the compound is useful mainly as a draining desiccant, heat transfer medium, power circulation working fluid, foaming agent, etc., mainly for use as a solvent, cleaning agent, reaction solvent, and the like.
本発明に係る新規な含フッ素化合物は、下記化学式（１）で示される構造を有する。
これらのフッ素化合物は、3,3,4,4-テトラフルオロシクロブテンに塩素を付加させることによって合成することができる。
原料である3,3,4,4-テトラフルオロシクロブテンは、1-クロロ-2,2,3,3-テトラフルオロシクロブタンの脱塩酸反応により容易に合成することができる。
また、塩素は3,3,4,4-テトラフルオロシクロブテンに対して理論的には等モルあればよいが、反応を完結させるために小過剰量用いることが好ましい。したがって、塩素は、3,3,4,4-テトラフルオロシクロブテンの０．１〜１０倍モル、好ましくは０．５〜２倍モル、より好ましくは０．９〜１．１倍モル用いる。
These fluorine compounds can be synthesized by adding chlorine to 3,3,4,4-tetrafluorocyclobutene.
The raw material 3,3,4,4-tetrafluorocyclobutene can be easily synthesized by dehydrochlorination of 1-chloro-2,2,3,3-tetrafluorocyclobutane.
Chlorine may theoretically be equimolar with respect to 3,3,4,4-tetrafluorocyclobutene, but a small excess is preferably used to complete the reaction. Accordingly, chlorine is used in an amount of 0.1 to 10 times mol, preferably 0.5 to 2 times mol, more preferably 0.9 to 1.1 times mol of 3,3,4,4-tetrafluorocyclobutene.
この塩素付加反応は、光照射下または加熱下で行うことが好ましい。光照射下で反応を実施する場合、その光源や照射強度は特に限定されないが、光源としては、水銀ランプ、特に低圧水銀ランプを使用するのが好ましい。反応温度は、光照射反応では−１００℃から１００℃、好ましくは−５０℃から５０℃、加熱反応では０℃から５００℃、好ましくは１００℃から３００℃が適当である。反応時間は、反応条件などにより一概に決定できないが、バッチ式では数時間から数十時間、フロー式では接触時間が数秒から５分程度が適当である。 This chlorine addition reaction is preferably performed under light irradiation or heating. When the reaction is performed under light irradiation, the light source and irradiation intensity are not particularly limited, but it is preferable to use a mercury lamp, particularly a low-pressure mercury lamp as the light source. The reaction temperature is suitably −100 ° C. to 100 ° C., preferably −50 ° C. to 50 ° C. for light irradiation reaction, and 0 ° C. to 500 ° C., preferably 100 ° C. to 300 ° C. for heating reaction. The reaction time cannot be generally determined depending on the reaction conditions and the like, but for the batch method, several hours to several tens of hours, and for the flow method, a contact time of about several seconds to 5 minutes is appropriate.
本発明における反応では、特に溶媒を用いる必要はないが、溶媒を用いても良い。反応は、耐圧容器等を用いたバッチ式、または加圧、大気圧、減圧下、いずれの圧力条件下のフロー式で行うことができる。 In the reaction in the present invention, it is not necessary to use a solvent, but a solvent may be used. The reaction can be performed by a batch method using a pressure vessel or the like, or by a flow method under any pressure condition under pressure, atmospheric pressure, or reduced pressure.
上記のようにして得られる本発明に係る新規な1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンは、環境影響の指標となる大気寿命が短く、したがって、環境への影響が小さいという,従来のCFCやHCFCに見られない環境に配慮された特性を有する。
また、切削油やプレス油などに含まれるたとえばn-エイコサンのトランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンに対する溶解度が大きく、十分な溶解力を持つことから、当該化合物は従来のCFCと同様、溶剤、洗浄剤、反応溶媒などの用途を主に、水切り乾燥剤、伝熱媒体、動力循環作動流体、発泡剤などとして有用である。
The novel 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane according to the present invention obtained as described above has a short atmospheric life as an indicator of environmental impact, and therefore has no impact on the environment. It has an environmentally friendly characteristic that is not seen in conventional CFCs and HCFCs.
In addition, for example, n-eicosane contained in cutting oil and press oil has high solubility in trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane, and has sufficient dissolving power. Similar to conventional CFC, the compound is useful mainly as a draining desiccant, heat transfer medium, power circulation working fluid, foaming agent, etc., mainly for use as a solvent, cleaning agent, reaction solvent, and the like.
以下、本発明について具体例を挙げてさらに詳しく説明するが、本発明はこれら実施例に限定されるものではない。 Hereinafter, the present invention will be described in more detail with specific examples, but the present invention is not limited to these examples.
実施例１
内容量約200ｍｌの石英製フラスコに、3,3,4,4-テトラフルオロシクロブテン40.0mmolを仕込み、液体窒素で冷却しながら脱気を行った。反応器を室温に戻し、低圧水銀ランプによる光照射を行いながら、塩素41.2mmolをゆっくり加えた。さらに２時間光照射を行うことにより得られた組成生物を1H-NMR、19F-NMRおよびGC-MSにより測定した結果、2.0mmolの3,3,4,4-テトラフルオロシクロブテンを回収し、30.4mmol（収率：７６％）のトランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンと5.2mmol（収率：１３％）のシス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンを得た。生成物の１Ｈ−ＮＭＲ、１９Ｆ−ＮＭＲおよびＭＳデータを以下に示す。なお、１Ｈ−ＮＭＲおよび１９Ｆ−ＮＭＲスペクトルの測定には、溶媒に重クロロホルムを用い、内部標準物質としてそれぞれテトラメチルシランとクロロトリフルオロメタンを用いた。
［トランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタン］
沸点：78.7℃
1H−NMR(CDCl3)、δ 4.30 (m)
19F-NMR(CFCl3)、δ -112.8（2F, d of m）、-128.7（2F, d of m）
［シス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタン］
沸点：109.7℃
1H−NMR(CDCl3)、δ 4.69 (m)
19F-NMR(CFCl3)、δ -113.7（2F, d of m）、-121.1 (2F, d of m）
MS（トランス、シス混合物）, m/z 163, 161 (M+-Cl), 142, 129, 127, 113, 111, 100 (CF2CF2 +), 98 (CF2CHCl+), 96 (CHClCHCl+), 85, 75, 69, 67, 63, 61, 57, 51,31
Example 1
A quartz flask having an internal volume of about 200 ml was charged with 40.0 mmol of 3,3,4,4-tetrafluorocyclobutene, and deaerated while being cooled with liquid nitrogen. The reactor was returned to room temperature, and 41.2 mmol of chlorine was slowly added while irradiating with a low-pressure mercury lamp. Furthermore, as a result of measuring the composition organism obtained by light irradiation for 2 hours by 1 H-NMR, 19 F-NMR and GC-MS, 2.0 mmol of 3,3,4,4-tetrafluorocyclobutene was recovered. 30.4 mmol (yield: 76%) of trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and 5.2 mmol (yield: 13%) of cis-1,2-dichloro- 3,3,4,4-Tetrafluorocyclobutane was obtained. The 1 H-NMR, 19 F-NMR and MS data of the product are shown below. For the measurement of 1 H-NMR and 19 F-NMR spectra, deuterated chloroform was used as a solvent, and tetramethylsilane and chlorotrifluoromethane were used as internal standard substances, respectively.
[Trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane]
Boiling point: 78.7 ° C
1 H-NMR (CDCl 3 ), δ 4.30 (m)
19 F-NMR (CFCl 3 ), δ-112.8 (2F, d of m), -128.7 (2F, d of m)
[Cis-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane]
Boiling point: 109.7 ° C
1 H-NMR (CDCl 3 ), δ 4.69 (m)
19 F-NMR (CFCl 3 ), δ-113.7 (2F, d of m), -121.1 (2F, d of m)
MS (trans, cis mixture), m / z 163, 161 (M + -Cl), 142, 129, 127, 113, 111, 100 (CF 2 CF 2 + ), 98 (CF 2 CHCl + ), 96 ( CHClCHCl + ), 85, 75, 69, 67, 63, 61, 57, 51, 31
実施例２
実施例１の同様の反応を０℃条件下で行った。反応により、3,3,4,4-テトラフルオロシクロブテンは消失し、33.2mmol（収率：８３％）のトランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンと5.2mmol（収率：１３％）のシス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンを得た。
Example 2
The same reaction as in Example 1 was performed at 0 ° C. By the reaction, 3,3,4,4-tetrafluorocyclobutene disappeared and 33.2 mmol (yield: 83%) of trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and 5.2 mmol (yield: 13%) of cis-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane was obtained.
実施例３
実施例１の同様の反応を−２０℃条件下で行った。反応により、3,3,4,4-テトラフルオロシクロブテンは消失し、33.6mmol（収率：８４％）のトランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンと6.0mmol（収率：１５％）のシス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンを得た。
Example 3
The same reaction as in Example 1 was performed under the condition of -20 ° C. By the reaction, 3,3,4,4-tetrafluorocyclobutene disappeared and 33.6 mmol (yield: 84%) of trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and 6.0 mmol (yield: 15%) of cis-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane was obtained.
実施例４
内容量約10ｍｌのSUS製耐圧容器に、真空ラインを用いて3,3,4,4-テトラフルオロシクロブテン2.0mmolおよび塩素2.0mmolを仕込み、２００℃で２時間反応を行った。反応により得られた組成生物を真空ラインで生成し、1H-NMR、19F-NMRおよびGC-MSにより測定した結果、0.44mmolの3,3,4,4-テトラフルオロシクロブテンを回収し、1.24mmol（収率：６２％）のトランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンと0.20mmol（収率：１０％）のシス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンを得た。
Example 4
Using a vacuum line, 2.0 mmol of 3,3,4,4-tetrafluorocyclobutene and 2.0 mmol of chlorine were charged into a SUS pressure-resistant container having an internal volume of about 10 ml, and reacted at 200 ° C. for 2 hours. The composition product obtained by the reaction was generated on a vacuum line and measured by 1 H-NMR, 19 F-NMR and GC-MS. As a result, 0.44 mmol of 3,3,4,4-tetrafluorocyclobutene was recovered. 1.24 mmol (yield: 62%) of trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane and 0.20 mmol (yield: 10%) of cis-1,2-dichloro-3 3,3,4,4-Tetrafluorocyclobutane was obtained.
実施例５
トランス-1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンの溶解特性として、切削油やプレス油などに含まれるn-エイコサンの24℃における溶解度測定を行った結果、１５．９ｇ／１００ｇであった。
Example 5
As a dissolution property of trans-1,2-dichloro-3,3,4,4-tetrafluorocyclobutane, the solubility of n-eicosane contained in cutting oil or press oil at 24 ° C. was measured. As a result, 15.9 g / 100g.
実施例６
1,2-ジクロロ-3,3,4,4-テトラフルオロシクロブタンの環境影響を評価するために、トランス体およびシス体のOHラジカルとの反応速度測定（298K）を行うことにより大気寿命（τOH）を算出した結果、トランス体が０．９８年、シス体が０．３２年であった。
なお、従来公知のHCFC-225ca（CF3CF2CHCl2）の大気寿命は２．１年、HCFC-225cb（CClF2CF2CHClF）の大気寿命は６．２年である（IPCC第3次レポート、2001年）。
Example 6
In order to evaluate the environmental impact of 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane, the atmospheric lifetime (τ) was measured by measuring the reaction rate (298K) with trans and cis OH radicals. As a result of calculating OH ), the trans isomer was 0.98 years and the cis isomer was 0.32 years.
In addition, the atmospheric lifetime of the conventionally known HCFC-225ca (CF 3 CF 2 CHCl 2 ) is 2.1 years, and the atmospheric lifetime of HCFC-225cb (CClF 2 CF 2 CHClF) is 6.2 years (IPCC Third Stage Report, 2001).
本発明の新規な含フッ素環状化合物は、溶剤、洗浄剤、乾燥剤、反応溶媒、伝熱媒体、消火剤、動力循環作動流体、発泡剤などとして有用なCFC類に代替し得る化合物として極めて有用なものである。
The novel fluorine-containing cyclic compound of the present invention is extremely useful as a compound that can be substituted for CFCs useful as a solvent, a cleaning agent, a drying agent, a reaction solvent, a heat transfer medium, a fire extinguishing agent, a power circulation working fluid, a foaming agent, and the like. It is a thing.
Claims (6)
The method for producing 1,2-dichloro-3,3,4,4-tetrafluorocyclobutane according to claim 4, wherein the addition reaction of chlorine is performed under heating at 100 ° C to 600 ° C.
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| JP2020164505A (en) * | 2019-03-27 | 2020-10-08 | ダイキン工業株式会社 | Method for Producing Halogenated Cycloalkane Compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4828453A (en) * | 1971-08-09 | 1973-04-14 | ||
| JPS4828452A (en) * | 1971-08-09 | 1973-04-14 | ||
| JP2006225298A (en) * | 2005-02-16 | 2006-08-31 | National Institute Of Advanced Industrial & Technology | Method for producing 3,3,4,4-tetrafluorocyclobutene |
| JP2006225296A (en) * | 2005-02-16 | 2006-08-31 | National Institute Of Advanced Industrial & Technology | Method for producing trans-1,1,2,2,3,4-hexafluorocyclobutane |
Non-Patent Citations (1)
| Title |
|---|
| CHMEICAL PHYSICS LETTERS, vol. 439, JPN6012002809, 24 March 2007 (2007-03-24), pages 40 - 45, ISSN: 0002126790 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020164505A (en) * | 2019-03-27 | 2020-10-08 | ダイキン工業株式会社 | Method for Producing Halogenated Cycloalkane Compound |
| JP7206501B2 (en) | 2019-03-27 | 2023-01-18 | ダイキン工業株式会社 | Method for producing halogenated cycloalkane compound |
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| JP4919270B2 (en) | 2012-04-18 |
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