JPH04282346A - Production of 1,1,1-trifluro-3-nitro-2-propene - Google Patents
Production of 1,1,1-trifluro-3-nitro-2-propeneInfo
- Publication number
- JPH04282346A JPH04282346A JP4511691A JP4511691A JPH04282346A JP H04282346 A JPH04282346 A JP H04282346A JP 4511691 A JP4511691 A JP 4511691A JP 4511691 A JP4511691 A JP 4511691A JP H04282346 A JPH04282346 A JP H04282346A
- Authority
- JP
- Japan
- Prior art keywords
- nitro
- trifluoro
- propene
- reaction
- acetic acid
- 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
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 4
- -1 acetate ester Chemical class 0.000 claims description 7
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 21
- FCKHHHXXJZMXBH-UHFFFAOYSA-N 3,3,3-trifluoro-1-nitroprop-1-ene Chemical compound [O-][N+](=O)C=CC(F)(F)F FCKHHHXXJZMXBH-UHFFFAOYSA-N 0.000 abstract description 16
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 10
- OKGNJIYNSOKKFT-UHFFFAOYSA-N 1,1,1-trifluoro-3-nitropropan-2-ol Chemical compound FC(F)(F)C(O)C[N+]([O-])=O OKGNJIYNSOKKFT-UHFFFAOYSA-N 0.000 abstract description 7
- 150000002168 ethanoic acid esters Chemical class 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011574 phosphorus Substances 0.000 abstract description 2
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 230000000850 deacetylating effect Effects 0.000 abstract 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 32
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N 2-propanol Substances CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- VLISOFDTMSFZPP-UHFFFAOYSA-N 3-nitroprop-1-ene Chemical compound [O-][N+](=O)CC=C VLISOFDTMSFZPP-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KLXJPQNHFFMLIG-UHFFFAOYSA-N 1-ethoxy-2,2,2-trifluoroethanol Chemical compound CCOC(O)C(F)(F)F KLXJPQNHFFMLIG-UHFFFAOYSA-N 0.000 description 2
- PFNCKQIYLAVYJF-UHFFFAOYSA-N 1-nitropropan-2-ol Chemical compound CC(O)C[N+]([O-])=O PFNCKQIYLAVYJF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005292 vacuum distillation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VGJWVEYTYIBXIA-UHFFFAOYSA-N 2,2,2-trifluoroethane-1,1-diol Chemical compound OC(O)C(F)(F)F VGJWVEYTYIBXIA-UHFFFAOYSA-N 0.000 description 1
- IVDHYYCFEMRCDZ-UHFFFAOYSA-N 2-(trifluoromethyl)-1h-pyrrole Chemical class FC(F)(F)C1=CC=CN1 IVDHYYCFEMRCDZ-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012038 nucleophile Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は、次式（ＩＩＩ）[Industrial Application Field] The present invention is based on the following formula (III)
【００
０２】00
02]
【化４】[C4]
【０００３】で示される１，１，１−トリフルオロ−３
−ニトロ−２−プロペンの製造方法に関するものである
。上式（ＩＩＩ）の１，１，１−トリフルオロ−３−ニ
トロ−２−プロペンは、各種求核試薬と反応させること
によりトリフルオロメチルピロール、トリフルオロメチ
ル−β−ラクタムなどの各種のトリフルオロメチル基を
有する化合物に誘導することができ、医薬、農薬、機能
性材料などの製造中間体として有用な化合物である。1,1,1-trifluoro-3 represented by
-This invention relates to a method for producing nitro-2-propene. 1,1,1-trifluoro-3-nitro-2-propene of the above formula (III) can be reacted with various nucleophiles to form various trifluoromethylpyrroles, trifluoromethyl-β-lactams, etc. It can be derived into a compound having a fluoromethyl group, and is a useful compound as an intermediate in the production of medicines, agricultural chemicals, functional materials, etc.
【０００４】0004
【従来技術およびその問題点】前記の式（ＩＩＩ）で示
される１，１，１−トリフルオロ−３−ニトロ−２−プ
ロペンの従来の合成方法としては、■１，１，１−トリ
フルオロ−３−ニトロ−２−プロパノールを無水フタル
酸と反応させてエステルとした後、脱酸することにより
合成する方法、■１，１，１−トリフルオロ−３−ニト
ロ−２−プロパノールを直接Ｐ２Ｏ５中に滴下して脱水
することにより合成する方法［Ｈ．Ｓｈｅｈｔｅｒ，Ｄ
．Ｅ．Ｌｅｙ，Ｅ．Ｂ．Ｒｏｂｅｒｓｏｎ，Ｊｒ．，Ｊ
．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，７８，４９８４，１９５
６］などが知られている。[Prior art and its problems] Conventional methods for synthesizing 1,1,1-trifluoro-3-nitro-2-propene represented by the above formula (III) include: - A method in which 3-nitro-2-propanol is reacted with phthalic anhydride to form an ester, and then deacidified. ■ 1,1,1-trifluoro-3-nitro-2-propanol is directly converted to P2O5 A method of synthesis by dropping water into a liquid and dehydrating it [H. Shehter, D.
．． E. Ley, E. B. Roberson, Jr. ,J
．． Am. Chem. Soc. ,78,4984,195
6] etc. are known.
【０００５】しかし、■の方法においてはエステル化反
応および脱酸による１，１，１−トリフルオロ−３−ニ
トロ−２−プロペンの合成に１４０〜１８０℃という高
温を必要とするという問題があり、また■の方法におい
ては反応後のリンを含む廃液の処理の問題があるため、
いずれも工業化するには問題が多い方法である。However, the method (2) has the problem that a high temperature of 140 to 180°C is required for the synthesis of 1,1,1-trifluoro-3-nitro-2-propene by esterification reaction and deacidification. , In addition, in method
Both methods are fraught with problems for industrialization.
【０００６】[0006]
【問題点を解決するための手段】本発明者らは、次式（
Ｉ）[Means for solving the problem] The present inventors have developed the following formula (
I)
【０００７】[0007]
【化５】[C5]
【０００８】で示される１，１，１−トリフルオロ−３
−ニトロ−２−プロパノールからの次式（ＩＩＩ）1,1,1-trifluoro-3 represented by
-Nitro-2-propanol from formula (III)
【０
００９】0
009]
【化６】[C6]
【００１０】で示される１，１，１−トリフルオロ−３
−ニトロ−２−プロペンの製造において温和な条件で進
行すると予想される脱酢酸に着目して鋭意検討を行なっ
た結果、上式（Ｉ）の１，１，１−トリフルオロ−３−
ニトロ−２−プロパノールを無水酢酸と反応させること
により次式（ＩＩ）1,1,1-trifluoro-3 represented by
- As a result of intensive studies focusing on deacetic acid removal which is expected to proceed under mild conditions in the production of nitro-2-propene, we found that the 1,1,1-trifluoro-3-
By reacting nitro-2-propanol with acetic anhydride, the following formula (II)
【００１１】[0011]
【化７】[C7]
【００１２】で示される酢酸エステルとした後、この酢
酸エステルを減圧下で加熱した無水炭酸ナトリウムまた
は無水炭酸カリウムに滴下して脱酢酸することにより上
式（ＩＩＩ）の１，１，１−トリフルオロ−３−ニトロ
−２−プロペンが高収率で得られることを見出し、本発
明に到達した。After obtaining the acetic ester represented by the formula (III), this acetic ester is dropped into anhydrous sodium carbonate or anhydrous potassium carbonate heated under reduced pressure to remove acetic acid, thereby producing the 1,1,1-tri-trifluoride of the above formula (III). It was discovered that fluoro-3-nitro-2-propene can be obtained in high yield, and the present invention was achieved.
【００１３】すなわち本発明は、次式（Ｉ）That is, the present invention provides the following formula (I)
【００１４
】0014
]
【化８】[Chemical formula 8]
【００１５】で示される１，１，１−トリフルオロ−３
−ニトロ−２−プロパノールを次式（ＩＩ）1,1,1-trifluoro-3 represented by
-Nitro-2-propanol according to the following formula (II)
【００１６
】0016
]
【化９】[Chemical formula 9]
【００１７】で示される酢酸エステルとした後、減圧下
で加熱した無水炭酸ナトリウムまたは無水炭酸カリウム
に滴下することを特徴とする次式（ＩＩＩ）The following formula (III) is obtained by forming an acetate ester represented by:
【００１８
】0018
]
【化１０】[Chemical formula 10]
【００１９】で示される１，１，１−トリフルオロ−３
−ニトロ−２−プロペンの製造方法である。本発明にお
いて原料である上式（Ｉ）の１，１，１−トリフルオロ
−３−ニトロ−２−プロパノールは、トリフルオロアセ
トアルデヒドエチルヘミアセタールまたはトリフルオロ
メチルメタンジオールとニトロメタンを反応させること
により容易に製造することができる。1,1,1-trifluoro-3 represented by
- A method for producing nitro-2-propene. In the present invention, 1,1,1-trifluoro-3-nitro-2-propanol of the above formula (I), which is a raw material, can be easily obtained by reacting trifluoroacetaldehyde ethyl hemiacetal or trifluoromethylmethanediol with nitromethane. can be manufactured.
【００２０】また、上式（ＩＩ）の１，１，１−トリフ
ルオロ−３−ニトロ−２−プロパノールの酢酸エステル
は常法により製造できる。すなわち、上式（Ｉ）の１，
１，１−トリフルオロ−３−ニトロ−２−プロパノール
と無水酢酸を硫酸の存在下で加熱反応させることにより
製造することができる。得られた上式（ＩＩ）の１，１
，１−トリフルオロ−３−ニトロ−２−プロパノールの
酢酸エステルは精製することなく粗体のまま次の脱酢酸
反応に使用することができる。Further, the acetic acid ester of 1,1,1-trifluoro-3-nitro-2-propanol of the above formula (II) can be produced by a conventional method. That is, 1 of the above formula (I),
It can be produced by heating and reacting 1,1-trifluoro-3-nitro-2-propanol and acetic anhydride in the presence of sulfuric acid. The obtained 1,1 of the above formula (II)
, 1-trifluoro-3-nitro-2-propanol acetate can be used in the next acetic acid removal reaction in its crude form without purification.
【００２１】本発明の生成物である上式（ＩＩＩ）の１
，１，１−トリフルオロ−３−ニトロ−２−プロペンは
常圧において沸点８９℃の淡黄色の刺激臭のある液体で
あるが、本発明は減圧および加熱下で行なっているため
、生成した１，１，１−トリフルオロ−３−ニトロ−２
−プロペンは直ちに気化する。そのため、反応器に側管
を通して受器を直結し、この受器を冷却することによっ
て気化した１，１，１−トリフルオロ−３−ニトロ−２
−プロペンを液化して回収することができる。また、こ
の際に酢酸が副生するがこの酢酸も同時に気化して回収
されるので、副生した酢酸と炭酸塩とが反応して炭酸ガ
スが発生することもない。回収した１，１，１−トリフ
ルオロ−３−ニトロ−２−プロペンと酢酸の混合物を蒸
留することにより１，１，１−トリフルオロ−３−ニト
ロ−２−プロペンを分離精製することができる。1 of the above formula (III) which is a product of the present invention
, 1,1-trifluoro-3-nitro-2-propene is a pale yellow liquid with a boiling point of 89°C and a pungent odor at normal pressure, but since the present invention is carried out under reduced pressure and heating, the produced 1,1,1-trifluoro-3-nitro-2
- Propene vaporizes immediately. Therefore, by directly connecting a receiver to the reactor through a side pipe and cooling the receiver, the vaporized 1,1,1-trifluoro-3-nitro-2
- Propene can be liquefied and recovered. Further, at this time, acetic acid is produced as a by-product, but this acetic acid is also vaporized and recovered at the same time, so that the by-produced acetic acid and carbonate do not react to generate carbon dioxide gas. By distilling the recovered mixture of 1,1,1-trifluoro-3-nitro-2-propene and acetic acid, 1,1,1-trifluoro-3-nitro-2-propene can be separated and purified. .
【００２２】本発明の方法を用いれば、酢酸エステルの
脱酢酸反応を行ないながら生成した１，１，１−トリフ
ルオロ−３−ニトロ−２−プロペンおよび酢酸の混合物
の受器での回収、受器からの抜き出し、蒸留を行なうこ
とができ、酢酸エステルの脱酢酸反応から１，１，１−
トリフルオロ−３−ニトロ−２−プロペンの蒸留による
分離精製までを脱酢酸反応を中断することなく連続的に
行なうことができるため、本発明方法は１，１，１−ト
リフルオロ−３−ニトロ−２−プロペンの工業的な製造
方法である。By using the method of the present invention, the mixture of 1,1,1-trifluoro-3-nitro-2-propene and acetic acid produced during the deacetic acid reaction of acetic acid ester can be recovered in a receiver, It can be extracted from the vessel and distilled, and 1,1,1-
Since the process of separating and purifying trifluoro-3-nitro-2-propene by distillation can be carried out continuously without interrupting the deacetic acid reaction, the method of the present invention This is an industrial method for producing -2-propene.
【００２３】本発明における酢酸エステルの脱酢酸反応
の反応温度は８０〜１４０℃の範囲がよいが、温度が高
過ぎると装置の安全性や反応原料、反応生成物の分解な
どの問題が生じ、また温度が低過ぎると反応速度の低下
などの問題が生じることから８０〜１１０℃の範囲とす
るのがより好ましい。[0023] The reaction temperature for the acetic acid deacetation reaction of acetate ester in the present invention is preferably in the range of 80 to 140°C, but if the temperature is too high, problems such as equipment safety, reaction raw materials, and decomposition of reaction products may occur. Further, if the temperature is too low, problems such as a decrease in the reaction rate will occur, so it is more preferably in the range of 80 to 110°C.
【００２４】また、本発明における酢酸エステルの脱酢
酸反応の減圧度は１００ｍｍＨｇ以下とするのがよいが
、減圧度が低過ぎると生成する１，１，１−トリフルオ
ロ−３−ニトロ−２−プロペンと酢酸の気化が不充分と
なって連続的な回収ができなくなり、特に副生した酢酸
は炭酸塩と反応して炭酸ガスを発生して減圧度をさらに
下げる原因となり、また減圧度が高過ぎると原料である
１，１，１−トリフルオロ−３−ニトロ−２−プロパノ
ールが反応前に気化して回収され、生成物の純度や収率
の低下の原因となることから、２０〜４０ｍｍＨｇとす
るのがより好ましい。[0024] Furthermore, the degree of vacuum in the deacetic acid reaction of acetic acid ester in the present invention is preferably 100 mmHg or less; however, if the degree of vacuum is too low, 1,1,1-trifluoro-3-nitro-2- The vaporization of propene and acetic acid becomes insufficient, making continuous recovery impossible. In particular, by-produced acetic acid reacts with carbonates to generate carbon dioxide gas, causing a further decrease in the degree of decompression. If the temperature exceeds 20 to 40 mmHg, the raw material 1,1,1-trifluoro-3-nitro-2-propanol will be vaporized and recovered before the reaction, causing a decrease in product purity and yield. It is more preferable that
【００２５】[0025]
【実施例】以下、実施例により本発明を具体的に説明す
る。
参考例１
トリフルオロアセトアルデヒドエチルヘミアセタール（
６０．０ｇ）およびニトロメタン（２８．４ｇ）を無水
炭酸カリウム（０．９１ｇ）の存在下、５０〜６０℃で
５時間反応させた。反応終了後、反応液を水に展開し、
エーテルで抽出し、常法により処理した。粗生成物を減
圧蒸留に付して精製し、１，１，１−トリフルオロ−３
−ニトロ−２−プロパノール（４２ｇ、６３％）を得た
。[Examples] The present invention will be specifically explained below with reference to Examples. Reference Example 1 Trifluoroacetaldehyde ethyl hemiacetal (
60.0 g) and nitromethane (28.4 g) were reacted at 50 to 60° C. for 5 hours in the presence of anhydrous potassium carbonate (0.91 g). After the reaction is completed, the reaction solution is developed in water,
It was extracted with ether and processed in a conventional manner. The crude product was purified by vacuum distillation to give 1,1,1-trifluoro-3
-Nitro-2-propanol (42 g, 63%) was obtained.
【００２６】実施例１
１，１，１−トリフルオロ−３−ニトロ−２−プロパノ
ール（８５ｇ）と無水酢酸（８７ｇ）を硫酸（３ｍｌ）
の存在下、８０〜９０℃で１時間反応させた。反応終了
後、反応液をエーテルで抽出し、常法により処理して１
，１，１−トリフルオロ−３−ニトロ−２−プロパノー
ルの酢酸エステルを得た。この酢酸エステルは精製する
ことなく次の反応に使用した。Example 1 1,1,1-trifluoro-3-nitro-2-propanol (85 g) and acetic anhydride (87 g) were dissolved in sulfuric acid (3 ml).
The reaction was carried out at 80 to 90°C for 1 hour in the presence of. After the reaction was completed, the reaction solution was extracted with ether and treated in a conventional manner to obtain 1
, 1,1-trifluoro-3-nitro-2-propanol acetate ester was obtained. This acetate ester was used in the next reaction without purification.
【００２７】減圧蒸留装置を備えた三口フラスコに無水
炭酸ナトリウム（５７ｇ）を入れ、油浴で１００〜１２
０℃に加熱した。アスピレーターで系内を２０〜３０ｍ
ｍＨｇに減圧し、酢酸エステルを少量ずつ滴下すると淡
黄色の液体および酢酸が４１〜４５℃で留出した。留出
物を再蒸留し７７〜８３℃の留分を集め、淡黄色の刺激
臭のある液体である１，１，１−トリフルオロ−３−ニ
トロ−２−プロペン（４６ｇ、６１％）を得た。[0027] Anhydrous sodium carbonate (57 g) was placed in a three-necked flask equipped with a vacuum distillation apparatus, and heated to 100 to 12 g in an oil bath.
Heated to 0°C. 20-30m inside the system with an aspirator
When the pressure was reduced to mHg and acetic acid ester was added dropwise little by little, a pale yellow liquid and acetic acid were distilled out at 41-45°C. The distillate was redistilled and the fractions at 77-83°C were collected to obtain 1,1,1-trifluoro-3-nitro-2-propene (46 g, 61%), a pale yellow liquid with a pungent odor. Obtained.
【００２８】[0028]
【発明の効果】本発明方法によれば、高温を必要とする
ことなく１，１，１−トリフルオロ−３−ニトロ−２−
プロペンを製造することができ、また反応後にリンなど
の処理の困難な物質を含む廃液が生成することもない。
また、酢酸エステルの脱酢酸反応から１，１，１−トリ
フルオロ−３−ニトロ−２−プロペンの蒸留による分離
精製までを脱酢酸反応を中断することなく連続的に行な
うことができ、１，１，１−トリフルオロ−３−ニトロ
−２−プロペンの工業的な製造方法である。Effect of the invention: According to the method of the present invention, 1,1,1-trifluoro-3-nitro-2-
Propene can be produced, and no waste liquid containing difficult-to-treat substances such as phosphorus is produced after the reaction. In addition, the steps from the deacetic acid reaction of acetate ester to the separation and purification of 1,1,1-trifluoro-3-nitro-2-propene by distillation can be carried out continuously without interrupting the deacetic acid reaction. This is an industrial method for producing 1,1-trifluoro-3-nitro-2-propene.
Claims (1)
−プロパノールを次式（ＩＩ） 【化２】 で示される酢酸エステルとした後、減圧下で加熱した無
水炭酸ナトリウムまたは無水炭酸カリウムに滴下するこ
とを特徴とする次式（ＩＩＩ） 【化３】 で示される１，１，１−トリフルオロ−３−ニトロ−２
−プロペンの製造方法。Claim 1: 1,1,1-trifluoro-3-nitro-2 represented by the following formula (I):
-Propanol is converted into an acetate ester represented by the following formula (II) [Chemical formula 2], and then added dropwise to anhydrous sodium carbonate or anhydrous potassium carbonate heated under reduced pressure.The following formula (III) [Chemical formula 3] 1,1,1-trifluoro-3-nitro-2 represented by
-Production method of propene.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4511691A JP2756373B2 (en) | 1991-03-11 | 1991-03-11 | Method for producing 1,1,1-trifluoro-3-nitro-2-propene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4511691A JP2756373B2 (en) | 1991-03-11 | 1991-03-11 | Method for producing 1,1,1-trifluoro-3-nitro-2-propene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04282346A true JPH04282346A (en) | 1992-10-07 |
| JP2756373B2 JP2756373B2 (en) | 1998-05-25 |
Family
ID=12710297
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4511691A Expired - Fee Related JP2756373B2 (en) | 1991-03-11 | 1991-03-11 | Method for producing 1,1,1-trifluoro-3-nitro-2-propene |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2756373B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679832A (en) * | 1995-10-10 | 1997-10-21 | Rohm And Haas Company | Method for making α,β-unsaturated-β-trifluoromethyl-carboxylates and related compounds |
-
1991
- 1991-03-11 JP JP4511691A patent/JP2756373B2/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679832A (en) * | 1995-10-10 | 1997-10-21 | Rohm And Haas Company | Method for making α,β-unsaturated-β-trifluoromethyl-carboxylates and related compounds |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2756373B2 (en) | 1998-05-25 |
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