JPH0137388B2 - - Google Patents
Info
- Publication number
- JPH0137388B2 JPH0137388B2 JP59096618A JP9661884A JPH0137388B2 JP H0137388 B2 JPH0137388 B2 JP H0137388B2 JP 59096618 A JP59096618 A JP 59096618A JP 9661884 A JP9661884 A JP 9661884A JP H0137388 B2 JPH0137388 B2 JP H0137388B2
- Authority
- JP
- Japan
- Prior art keywords
- methacrylic acid
- phosphorus trichloride
- reaction
- acid chloride
- mol
- 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 53
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims description 50
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 8
- -1 phosphorus compound Chemical class 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 238000004821 distillation Methods 0.000 description 15
- 238000003756 stirring Methods 0.000 description 14
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229950000688 phenothiazine Drugs 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 150000003018 phosphorus compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000066 reactive distillation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000473391 Archosargus rhomboidalis Species 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 229940045803 cuprous chloride Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 238000001577 simple distillation Methods 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
【発明の詳細な説明】
本発明はメタクリル酸と三塩化燐とを反応させ
てメタクリル酸クロライドを製造する方法に関す
る。さらに詳しくは、メタクリル酸と三塩化燐と
を反応させるに際し、
(1) メタクリル酸に三塩化燐を添加しながら40〜
90℃の範囲の温度で反応させ
(2) 反応混合物から生成したメタクリル酸クロラ
イドを留去させ
(3) えられた缶液の下層の燐化合物層を分離除去
し、
(4) えられる上層の未反応メタクリル酸層を工程
(1)に再使用し、かつ、反応に使用する全メタク
リル酸に対し三塩化燐を1/3〜1/4倍モルの範囲
で使用することによつてメタクリル酸クロライ
ドを製造するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing methacrylic acid chloride by reacting methacrylic acid and phosphorus trichloride. More specifically, when reacting methacrylic acid and phosphorus trichloride, (1) while adding phosphorus trichloride to methacrylic acid,
(2) distill off the methacrylic acid chloride produced from the reaction mixture; (3) separate and remove the lower phosphorus compound layer of the resulting bottom liquid; (4) remove the resulting upper layer. Process the unreacted methacrylic acid layer
Methacrylic acid chloride is produced by reusing in (1) and using phosphorus trichloride in a molar range of 1/3 to 1/4 times the total methacrylic acid used in the reaction. .
メタクリル酸クロライドはアシル化剤として有
用であり、水酸基、アミノ基、芳香核などの水素
をアシル基で置換すると同時に反応性に富んだ二
重結合を導入する反応に用いることができる。ア
シル化反応による生成物は、主として各種の機能
性高分子の原料や医薬・農薬・殺菌剤等の原料も
しくは中間体として重要である。 Methacrylic acid chloride is useful as an acylating agent, and can be used in reactions that replace hydrogen in hydroxyl groups, amino groups, aromatic nuclei, etc. with acyl groups, and at the same time introduce highly reactive double bonds. Products resulting from acylation reactions are important mainly as raw materials for various functional polymers and raw materials or intermediates for pharmaceuticals, agricultural chemicals, fungicides, and the like.
脂肪族カルボン酸と各種の燐化合物、チオニル
クロライドまたはホスゲンとを反応させてカルボ
ン酸クロライドを合成する方法は従来から知られ
ている。（Synthetic Organic Chemistry，
Wagner＆Zook編，John Wiley＆Sons Inc.546
頁〜557頁）
しかしながら、チオニルクロライド法では副生
する塩化水素および亜硫酸ガスの処理にコストが
かかるうえに生成物への硫黄化合物の混入が避け
られない。また、ホスゲン法では反応性が低いた
めにジメチルホルムアミド等の高価な触媒を用い
なければならず更にはホスゲンそのものの毒性の
問題もあり、いずれの方法も工業的には優れた方
法とはいいがたい。一方、三塩化燐法は原料価格
的にも安価であり、副生する燐化合物は比較的容
易に有用な無機燐化合物に変換再利用でき、資源
の有効利用の面からも好ましい方法である。ま
た、三塩化燐法については先行文献もあり、例え
ば、Journal of American Chemical Society，
Vol.67，p.208〜210（1945）にC.E.Rehbergらが
報告しており75〜80％の収率でメタクリル酸クロ
ライドがえられるとしているが彼等の実験条件で
反応を行つても上記の収率は得られず、周辺の反
応条件を種々検討してもせいぜい60％程度の収率
に止まることが判明し、工業的に製造するには、
まだまだ解決すべき点が多々あることがわかつ
た。 Methods for synthesizing carboxylic acid chlorides by reacting aliphatic carboxylic acids with various phosphorus compounds, thionyl chloride, or phosgene have been known. (Synthetic Organic Chemistry,
Edited by Wagner & Zook, John Wiley & Sons Inc.546
(pages 557 to 557) However, in the thionyl chloride method, processing of by-product hydrogen chloride and sulfur dioxide gas is costly, and contamination of sulfur compounds into the product is unavoidable. In addition, the phosgene method requires the use of expensive catalysts such as dimethylformamide due to its low reactivity, and there is also the problem of the toxicity of phosgene itself, so although both methods are industrially superior, sea bream. On the other hand, the phosphorus trichloride method is inexpensive in terms of raw material costs, and by-product phosphorus compounds can be converted and reused into useful inorganic phosphorus compounds relatively easily, making it a preferable method from the standpoint of effective resource utilization. There are also prior documents regarding the phosphorus trichloride method, such as the Journal of American Chemical Society,
Vol. 67, p. 208-210 (1945), CERehberg et al. reported that methacrylic acid chloride could be obtained with a yield of 75-80%, but even if the reaction was carried out under their experimental conditions, the above No yield was obtained, and even after various examinations of surrounding reaction conditions, it was found that the yield was only about 60% at most, and in order to produce it industrially,
It turns out that there are still many issues that need to be resolved.
かかる実情によつて本発明者らは、燐化合物、
特に三塩化燐とメタクリル酸とから高収率かつ効
率よくメタクリル酸クロライドを製造することを
目的として鋭意研究した結果本発明を完成するに
いたつた。 Under these circumstances, the present inventors developed a phosphorus compound,
In particular, the present invention has been completed as a result of intensive research aimed at producing methacrylic acid chloride from phosphorus trichloride and methacrylic acid with high yield and efficiency.
すなわち、本発明はメタクリル酸と三塩化燐と
を反応させてメタクリル酸クロライドを製造する
に際し、
(1) メタクリル酸に三塩化燐を添加しながら40〜
90℃の範囲の温度で反応させ
(2) 反応混合物から生成したメタクリル酸クロラ
イドを留去させ
(3) えられた缶液の下層の燐化合物層を分離除去
し、
(4) えられる上層の未反応メタクリル酸層を工程
(1)に再使用し、かつ、反応に使用する全メタク
リル酸に対し三塩化燐を1/3〜1/4倍モルの範囲
で使用することを特徴とするメタクリル酸クロ
ライドの製造方法である。 That is, in the present invention, when producing methacrylic acid chloride by reacting methacrylic acid and phosphorus trichloride, (1) while adding phosphorus trichloride to methacrylic acid,
The reaction is carried out at a temperature in the range of 90°C (2) the methacrylic acid chloride produced from the reaction mixture is distilled off (3) the lower phosphorus compound layer of the resulting bottom liquid is separated and removed, (4) the upper layer Process the unreacted methacrylic acid layer
A method for producing methacrylic acid chloride, which is reused in (1) and is characterized in that phosphorus trichloride is used in a mole range of 1/3 to 1/4 times the total amount of methacrylic acid used in the reaction. .
本発明におけるメタクリル酸と三塩化燐とを反
応させる方法としては、メタクリル酸に三塩化燐
を滴下していくことにより反応させる方法が好適
である。三塩化燐にメタクリル酸を滴下する方法
あるいは三塩化燐とメタクリル酸を一括して仕込
んで反応させる方法のいずれの方法をとつても上
記の方法をとつた場合よりも収率は低い。反応温
度については、40〜90℃の間の任意の温度で行い
うるが50〜60℃がより好ましい。40℃未満では反
応は非常に遅く、また90℃を超える温度では重合
物が増加する。 In the present invention, a suitable method for reacting methacrylic acid with phosphorus trichloride is a method in which phosphorus trichloride is added dropwise to methacrylic acid. The yield is lower than when using the above method, either by dropping methacrylic acid into phosphorus trichloride or by charging phosphorus trichloride and methacrylic acid all at once. The reaction temperature may be any temperature between 40 and 90°C, but 50 to 60°C is more preferable. At temperatures below 40°C, the reaction is very slow, and at temperatures above 90°C, polymerization increases.
三塩化燐をメタクリル酸に添加する方法は連続
的または継続的方法で行うことができる。通常、
滴下時間は0.5〜２時間が好ましい。滴下時間が
0.5時間より短すぎる場合は収率の向上が小さく、
２時間以上長くしてもさらなる収率の向上は得ら
れず、滴下時間をこれ以上長くする必要がない。 The method of adding phosphorus trichloride to methacrylic acid can be carried out in a continuous or continuous manner. usually,
The dropping time is preferably 0.5 to 2 hours. Dripping time
If it is shorter than 0.5 hours, the improvement in yield will be small;
Even if the time is increased by 2 hours or more, no further improvement in yield is obtained, and there is no need to further increase the dropping time.
三塩化燐の滴下終了後、直ちにメタクリル酸ク
ロライドを留出させても差支えないが、未反応三
塩化燐が製品に多量に混入する場合があるので1/
４〜２時間の熟成時間をとることが好ましい。 There is no problem in distilling methacrylic acid chloride immediately after dropping phosphorus trichloride, but since a large amount of unreacted phosphorus trichloride may be mixed into the product,
It is preferable to allow a maturing time of 4 to 2 hours.
反応終了後、反応液を静置すると、メタクリル
酸クロライドを含有する上層部分と亜燐酸を含む
下層部分の二層に分離するが、この下層部分を分
離除去することなく、メタクリル酸クロライドを
留去させることが好ましい。下層の亜燐酸を含む
層を分離してから上層部分のみを蒸留すると収率
は低くなる。メタクリル酸クロライドを留去させ
る方法としては特別な蒸留塔は必要としないが、
ミストセパレーターまたは簡単な蒸留塔を使用し
ても差し支えない。メタクリル酸クロライドを留
去させる際、常圧でも差支えないが重合等による
収率の損失を確実に少なくするために400mmHg以
下の減圧下で行うとが好ましい。好ましい実施態
様として200mmHg位からひきはじめ最終的に30mm
Hg位で留去させる方法を例示することができる。 After the reaction is complete, when the reaction solution is allowed to stand still, it separates into two layers: an upper layer containing methacrylic acid chloride and a lower layer containing phosphorous acid. However, the methacrylic acid chloride is distilled off without separating and removing this lower layer. It is preferable to let If the lower layer containing phosphorous acid is separated and only the upper layer is distilled, the yield will be low. Although the method of distilling off methacrylic acid chloride does not require a special distillation column,
A mist separator or simple distillation column may be used. When methacrylic acid chloride is distilled off, normal pressure may be used, but it is preferably carried out under reduced pressure of 400 mmHg or less in order to reliably reduce yield loss due to polymerization, etc. In a preferred embodiment, start at around 200mmHg and eventually reach 30mmHg.
An example is a method of distilling off at the Hg position.
このようにしてメタクリル酸クロライドを留去
した後の缶液は、静置すると未反応メタクリル酸
を含有する上層部分と、亜燐酸を含有する下層部
分の二層に分離する。本発明者等は、理由は明ら
かではないが、この上層部分の液を三塩化燐との
反応に再使用することにより、メタクリル酸クロ
ライドの収率がさらに向上することを見い出し
た。この再使用に用いる未反応メタクリル酸を含
有する液を得るためには、仕込みの三塩化燐の量
はメタクリル酸に対して1/3倍モル以下でなけれ
ばならない。1/3倍モルを超ええる量の三塩化燐
を用いた場合は、残液は二層に分離しにくくなり
従つて未反応のメタクリル酸を循環再使用するこ
とはできないばかりか、メタクリル酸クロライド
と三塩化燐の沸点が近くきれいな分離が難しいの
で製品中に三塩化燐が多量に混入し製品の純度を
著しく低下させることになる。 After the methacrylic acid chloride has been distilled off, the liquid can be left to stand and separate into two layers: an upper layer containing unreacted methacrylic acid and a lower layer containing phosphorous acid. Although the reason is not clear, the present inventors have found that the yield of methacrylic acid chloride can be further improved by reusing this upper layer liquid for the reaction with phosphorus trichloride. In order to obtain a liquid containing unreacted methacrylic acid for reuse, the amount of phosphorus trichloride charged must be 1/3 times the mole or less relative to methacrylic acid. If phosphorus trichloride is used in an amount exceeding 1/3 mole, the residual liquid will be difficult to separate into two layers, and therefore unreacted methacrylic acid cannot be recycled and reused, and methacrylic acid chloride Since the boiling points of phosphorus trichloride and phosphorus trichloride are close to each other and it is difficult to separate them cleanly, a large amount of phosphorus trichloride will be mixed into the product, significantly reducing the purity of the product.
また、工業的生産性を考慮するならば、三塩化
燐の使用量はメタクリル酸に対してて1/4倍モル
以上が好ましい。メタクリル酸に対して1/4倍モ
ル未満の三塩化燐を用いた場合、製品に混入する
三塩化燐は少なくなるが、未反応のメタクリル酸
が多くなり経済的に不利である。すなわち本発明
の実施において、三塩化燐の使用量は再使用され
る蒸留残渣の上層部分に含有される未反応メタク
リル酸と新たに仕込まれるメタクリル酸の合計量
に対して1/3〜1/4倍モルの範囲であることが好ま
しい。 Furthermore, in consideration of industrial productivity, the amount of phosphorus trichloride used is preferably 1/4 or more times the mole of methacrylic acid. When phosphorus trichloride is used in an amount less than 1/4 times the mole of methacrylic acid, less phosphorus trichloride is mixed into the product, but unreacted methacrylic acid increases, which is economically disadvantageous. That is, in carrying out the present invention, the amount of phosphorus trichloride used is 1/3 to 1/3 of the total amount of unreacted methacrylic acid contained in the upper layer of the distillation residue to be reused and methacrylic acid newly charged. A range of 4 times the mole is preferred.
上述のようにして得られる未反応メタクリル酸
を含有する上層液を再使用する場合有利な工業的
製造方法としては二回目以降の反応において未反
応のメタクリル酸量が毎回ほぼ一定になるように
することが望ましい。従つて三塩化燐の使用量
は、新たに仕込むメタクリル酸も含めた反応に使
用する全メタクリル酸に対して1/3倍モルの85〜
95％の範囲であることが特に好ましい。この範囲
の量において未反応メタクリル酸をほぼ一定量に
することができる三塩化燐とメタクリル酸のモル
比が適宜決定される。 When reusing the upper layer liquid containing unreacted methacrylic acid obtained as described above, an advantageous industrial production method is to keep the amount of unreacted methacrylic acid approximately constant in each subsequent reaction. This is desirable. Therefore, the amount of phosphorus trichloride used is 85 to 1/3 times the mole of all methacrylic acid used in the reaction, including the newly charged methacrylic acid.
A range of 95% is particularly preferred. The molar ratio of phosphorus trichloride and methacrylic acid that can maintain a substantially constant amount of unreacted methacrylic acid within this range is appropriately determined.
また、反応蒸留後の亜燐酸を含む層は有用な無
機燐化合物に変換し再利用することが可能であ
る。 Furthermore, the layer containing phosphorous acid after reactive distillation can be converted into a useful inorganic phosphorus compound and reused.
本発明に従い上記のような方法でメタクリル酸
クロライドを製造すれば工業的に効率よくかつ高
収率で連続的に純度の高い製品を得ることができ
る。 If methacrylic acid chloride is produced by the method described above according to the present invention, a product of high purity can be obtained industrially efficiently and continuously with high yield.
以下、実施例にて本発明を更に具体的に説明す
る。 Hereinafter, the present invention will be explained in more detail with reference to Examples.
参考例 １
撹拌後、温度計、還流冷却器および滴下ロート
を取りつけた300mlフラスコに100ｇ（1.162mol）
のメタクリル酸と0.1ｇのフエノチアジンを仕込
み500rpmで回転撹拌しながら53℃まで加熱した。
同温度に保ちながら53.2ｇ（0.387mol）の三塩化
燐を80分で滴下した。同撹拌転数、同温度で100
分間撹拌を続け、撹拌終了後静置すると反応液は
二層に分離した。反応終了後のフラスコから還流
冷却器、滴下ロートをはずし、フエノチアジン
0.02ｇを追加した。留出温度計、リービツヒ冷却
器、吸引口および蒸留受器付簡易冷却装置をとり
つけ、冷却器と受器を−10℃の冷媒で冷却し、70
〜100rpmで撹拌しながらゆつくり吸引した。
徐々に減圧度、撹拌速度及び温度を上げていき最
終的には減圧度35mmHg、撹拌速度700rpm、溶液
温度70℃の条件で、留出しなくなるまで反応蒸留
を行なつた。0.5重量％以下の三塩化燐を含む
87.4ｇ（0.836mol、仕込んだメタクリル酸に対す
る収率71.9％）のメタクリル酸クロライドを得
た。Reference Example 1 After stirring, add 100 g (1.162 mol) to a 300 ml flask equipped with a thermometer, reflux condenser, and dropping funnel.
of methacrylic acid and 0.1 g of phenothiazine were heated to 53° C. with rotational stirring at 500 rpm.
While maintaining the same temperature, 53.2 g (0.387 mol) of phosphorus trichloride was added dropwise over 80 minutes. 100 at the same stirring rotation speed and temperature
Stirring was continued for a minute, and when the mixture was left to stand after stirring, the reaction solution was separated into two layers. After the reaction is complete, remove the reflux condenser and dropping funnel from the flask, and add the phenothiazine.
Added 0.02g. A distillation thermometer, a Liebig condenser, a suction port, and a simple cooling device with a distillation receiver were installed, and the condenser and receiver were cooled with a -10℃ refrigerant.
Slow suction was applied while stirring at ~100 rpm.
The degree of vacuum, stirring speed, and temperature were gradually increased, and finally, reactive distillation was carried out under conditions of a degree of vacuum of 35 mmHg, a stirring speed of 700 rpm, and a solution temperature of 70° C. until no more distillation occurred. Contains less than 0.5% by weight of phosphorus trichloride
87.4 g (0.836 mol, yield 71.9% based on the charged methacrylic acid) of methacrylic acid chloride was obtained.
比較例 １
参考例において、53.2ｇ（0.387mol）の三塩化
燐をフラスコに仕込み、100ｇ（1.162mol）のメ
タクリル酸と0.1ｇのフエノチアジンの混合物を
滴下した以外は参考例に記載の方法に従つた。留
去して得たメタクリル酸クロライドは78.7ｇ
（0.753mol、仕込んだメタクリル酸に対する収率
64.8％）で、0.5重量％以下の三塩化燐を含んで
いた。Comparative Example 1 The method described in Reference Example was followed except that 53.2 g (0.387 mol) of phosphorus trichloride was charged into a flask, and a mixture of 100 g (1.162 mol) methacrylic acid and 0.1 g of phenothiazine was added dropwise. Ivy. 78.7g of methacrylic acid chloride obtained by distillation
(0.753mol, yield based on charged methacrylic acid
64.8%) and contained less than 0.5% by weight of phosphorus trichloride.
比較例 ２
参考例において、滴下ロートを必要としない以
外は同様の器具を取りつけた300mlフラスコに100
ｇ（1.162mol）のメタクリル酸、53.2ｇ
（0.387mol）の三塩化燐及び0.1ｇのフエノチアジ
ンを仕込む以外は、参考例に記載の方法に従つ
た。留共して得たメタクリル酸クロライドは76.7
ｇ（0.734mol、仕込んだメタクリル酸に対する
収率63.1％）で、0.5重量％以下のの三塩化燐を
含んでいた。Comparative Example 2 In the Reference Example, 100 g
g (1.162 mol) of methacrylic acid, 53.2 g
The method described in Reference Example was followed except that (0.387 mol) of phosphorus trichloride and 0.1 g of phenothiazine were charged. The methacrylic acid chloride obtained by distillation is 76.7
g (0.734 mol, yield 63.1% based on the charged methacrylic acid), and contained less than 0.5% by weight of phosphorus trichloride.
比較例 ３
撹拌機、温度計、還流冷却器、滴下ロートを取
りつけた300mlフラスコに100ｇ（1.162mol）の
メタクリル酸と0.1ｇのフエノチアジンを仕込ん
だ。500rpmで回転撹拌しながら53℃まで加熱し
た。同温度に保ちながら53.2ｇ（0.387mol）の三
塩化燐を80分で滴下した。同撹拌回転数、同温度
で100分間撹拌を続け、撹拌終了後静置すると反
応液は二層に分離した。反応終了後、溶液の上層
のみを200mlのフラスコに移し減圧蒸留した。蒸
留器具、減圧度及び蒸留温度は参考例に記載した
ものと同じだが、撹拌棒は使わずキヤピラリーを
用いた。留去して得たメタクリル酸クロライドは
67.7ｇ（0.648mol、仕込んだメタクリル酸に対す
る収率55.7％）で、0.5重量％以下の三塩化燐を
含んでいた。Comparative Example 3 A 300 ml flask equipped with a stirrer, thermometer, reflux condenser, and dropping funnel was charged with 100 g (1.162 mol) of methacrylic acid and 0.1 g of phenothiazine. The mixture was heated to 53° C. with rotational stirring at 500 rpm. While maintaining the same temperature, 53.2 g (0.387 mol) of phosphorus trichloride was added dropwise over 80 minutes. Stirring was continued for 100 minutes at the same stirring speed and temperature, and when the stirring was completed and left to stand, the reaction solution was separated into two layers. After the reaction was completed, only the upper layer of the solution was transferred to a 200 ml flask and distilled under reduced pressure. The distillation equipment, degree of vacuum, and distillation temperature were the same as those described in the reference example, but a capillary was used instead of a stirring bar. The methacrylic acid chloride obtained by distillation is
It was 67.7 g (0.648 mol, yield 55.7% based on the charged methacrylic acid) and contained 0.5% by weight or less of phosphorus trichloride.
実施例 １
参考例に記載の方法に従つて反応・蒸留の後、
フラスコに残つた蒸留残渣は二層に分離した。こ
のうち上層（18ｇ）のみを別のフラスコに移し
た。参考例に示したものと同じ装置をこのフラス
コに取りつけ、新たに100ｇ（1.162mol）のメタ
クリル酸と0.1ｇのフエノチアジンを加えた。
58.0ｇ（0.422mol）の三塩化燐を参考例に記載の
方法に従つて滴下・反応させた。その結果得られ
たメタクリル酸クロライドは97.2ｇ（0.930mol、
新たに仕込んだメタクリル酸に対する収率80.0
％）で、0.5重量％以下の三塩化燐を含んでいた。
この時の残渣も二層に分離しており、上層は18ｇ
と一回目の残渣上層と同じ量であつた。この上層
を用いて再度同じ反応を繰り返した。その結果得
られたメタクリル酸クロライドは98.0ｇ
（0.937mol、新たに仕込んだメタクリル酸に対す
る収率80.7％）で、0.5重量％以下の三塩化燐を
含んでいた。残渣上層も18ｇと前回と同量となつ
た。以後、定常的に約80％の収率でメタクリル酸
クロライドがえられた。Example 1 After reaction and distillation according to the method described in Reference Example,
The distillation residue remaining in the flask was separated into two layers. Of these, only the upper layer (18 g) was transferred to another flask. The same apparatus as shown in the reference example was attached to this flask, and 100 g (1.162 mol) of methacrylic acid and 0.1 g of phenothiazine were added.
58.0 g (0.422 mol) of phosphorus trichloride was added dropwise and reacted according to the method described in Reference Example. The resulting methacrylic acid chloride was 97.2g (0.930mol,
Yield 80.0 based on freshly charged methacrylic acid
%) and contained less than 0.5% by weight of phosphorus trichloride.
The residue at this time was also separated into two layers, and the upper layer weighed 18g.
The amount was the same as the upper layer of the residue from the first time. The same reaction was repeated again using this upper layer. The resulting methacrylic acid chloride was 98.0g.
(0.937 mol, yield 80.7% based on freshly charged methacrylic acid), and contained less than 0.5% by weight of phosphorus trichloride. The upper layer of residue was also 18g, the same amount as last time. Thereafter, methacrylic acid chloride was consistently obtained at a yield of about 80%.
比較例 ４
参考例に記載の方法に従つて反応・蒸留の後、
フラスコに残つた蒸留残渣は二層に分離した。こ
のうち上層（18ｇ）のみを別のフラスコに移し
た。参考例に示したものと同じ装置をこのフラス
コに取りつけ、新たに100ｇ（1.162mol）のメタ
クリル酸と0.1ｇのフエノチアジンを加えた。
46.7ｇ（0.340mol、仕込みの全メタクリル酸に対
し1/4モル以下）の三塩化燐を参考例に記載の方
法に従つて滴下・反応させた。その結果得られた
メタクリル酸クロライドは79.8ｇ（0.763mol、新
たに仕込んだメタクリル酸に対する収率65.7％）
で、0.4重量％以下の三塩化燐を含んでいた。こ
の時の残渣も二層に分離しており、上層は37ｇで
あつた。この上層を用いて先と同じ操作を行なつ
た。得られたメタクリル酸クロライドは78.8ｇ
（0.754mol、新たに仕込んだメタクリル酸に対す
る収率64.9％）で、0.4重量％の三塩化燐を含ん
でいた。残渣は上層が58ｇと増加した。Comparative Example 4 After reaction and distillation according to the method described in Reference Example,
The distillation residue remaining in the flask was separated into two layers. Of these, only the upper layer (18 g) was transferred to another flask. The same apparatus as shown in the reference example was attached to this flask, and 100 g (1.162 mol) of methacrylic acid and 0.1 g of phenothiazine were added.
46.7 g (0.340 mol, 1/4 mol or less based on the total amount of methacrylic acid charged) of phosphorus trichloride was added dropwise and reacted according to the method described in Reference Example. The resulting methacrylic acid chloride was 79.8g (0.763mol, yield 65.7% based on newly charged methacrylic acid)
and contained less than 0.4% by weight of phosphorus trichloride. The residue at this time was also separated into two layers, and the upper layer weighed 37 g. The same operation as before was carried out using this upper layer. The obtained methacrylic acid chloride was 78.8g.
(0.754 mol, yield 64.9% based on freshly charged methacrylic acid) and contained 0.4% by weight of phosphorus trichloride. The amount of residue in the upper layer increased to 58g.
比較例 ５
参考例において100ｇ（1.162mol）のメタクリ
ル酸と0.1ｇのフエノチアジンを仕込み、79.8ｇ
（0.581mol、仕込みのメタクリル酸に対し1/2倍
モル）の三塩化燐を滴下する以外は参考例に記載
の方法に従つた。留去して得たメタクリル酸クロ
ライドは、109.0ｇ（1.043mol、仕込んだメタク
リル酸に対する収率89.7％）で、10.2重量％の三
塩化燐を含んでいた。Comparative Example 5 In the reference example, 100g (1.162mol) of methacrylic acid and 0.1g of phenothiazine were charged, and 79.8g
The method described in Reference Example was followed except that phosphorus trichloride (0.581 mol, 1/2 mole relative to the methacrylic acid used) was added dropwise. The amount of methacrylic acid chloride obtained by distillation was 109.0 g (1.043 mol, yield 89.7% based on the charged methacrylic acid), and contained 10.2% by weight of phosphorus trichloride.
比較例 ６
本比較例は、Journol of American Chemical
Society 67巻 208頁（1945年）に記載の方法を
追試したものである。Comparative Example 6 This comparative example is based on the Journal of American Chemical
This is a re-examination of the method described in Society Vol. 67, p. 208 (1945).
参考例において滴下ロートをとりつけない以外
は同様の装置を取りつけた300mlフラスコに、100
ｇ（1.162mol）のメタクリル酸および53.2ｇ
（0.387mol）の三塩化燐を一括して仕込んだ。ゆ
つくり70℃まで加熱し、15分間70℃を保つた後、
室温下120分撹拌を続けた。上層と下層を分離し、
上層のみに１ｇの塩化第一銅を加え、比較例３と
同じ方法で減圧蒸留した。得られたメタクリル酸
クロライドは71.9ｇ（0.688mol、仕込んだメタク
リル酸に対する収率59.2％）で、0.5重量％以下
の三塩化燐を含んでいた。 A 300 ml flask equipped with the same equipment as in the reference example except that the dropping funnel was not attached was filled with 100
g (1.162 mol) of methacrylic acid and 53.2 g
(0.387 mol) of phosphorus trichloride was charged all at once. After slowly heating to 70℃ and keeping it at 70℃ for 15 minutes,
Stirring was continued for 120 minutes at room temperature. Separate the upper and lower layers,
1 g of cuprous chloride was added only to the upper layer, and vacuum distillation was performed in the same manner as in Comparative Example 3. The obtained methacrylic acid chloride weighed 71.9 g (0.688 mol, yield 59.2% based on the charged methacrylic acid) and contained 0.5% by weight or less of phosphorus trichloride.
Claims (1)
クリル酸クロライドを製造するに際し、 (1) メタクリル酸に三塩化燐を添加しながら40〜
90℃の範囲の温度で反応させ (2) 反応混合物から生成したメタクリル酸クロラ
イドを留去させ (3) えられた缶液の下層の燐化合物層を分離除去
し (4) えられる上層の未反応メタクリル酸層を工程
(1)に再使用し、かつ、反応に使用する全メタク
リル酸に対し三塩化燐を1/3〜1/4倍モルの範囲
で使用することを特徴とするメタクリル酸クロ
ライドの製法。[Claims] 1. When producing methacrylic acid chloride by reacting methacrylic acid and phosphorus trichloride, (1) while adding phosphorus trichloride to methacrylic acid,
The reaction is carried out at a temperature in the range of 90°C. (2) The methacrylic acid chloride produced from the reaction mixture is distilled off. (3) The lower phosphorus compound layer of the resulting bottom liquid is separated and removed. (4) The resulting upper layer is removed. Process the reaction methacrylic acid layer
A method for producing methacrylic acid chloride, which is reused in (1) and is characterized in that phosphorus trichloride is used in a mole range of 1/3 to 1/4 times the total amount of methacrylic acid used in the reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9661884A JPS60243041A (en) | 1984-05-16 | 1984-05-16 | Production of methacryl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9661884A JPS60243041A (en) | 1984-05-16 | 1984-05-16 | Production of methacryl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60243041A JPS60243041A (en) | 1985-12-03 |
| JPH0137388B2 true JPH0137388B2 (en) | 1989-08-07 |
Family
ID=14169835
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9661884A Granted JPS60243041A (en) | 1984-05-16 | 1984-05-16 | Production of methacryl chloride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60243041A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002047280A (en) * | 2000-08-02 | 2002-02-12 | Mitsubishi Rayon Co Ltd | Method for producing lactone (meth)acrylates |
| JP5108249B2 (en) * | 2006-04-20 | 2012-12-26 | 三井化学株式会社 | Method for producing thiol compound |
-
1984
- 1984-05-16 JP JP9661884A patent/JPS60243041A/en active Granted
Non-Patent Citations (1)
| Title |
|---|
| JOURNAL OF AMERICAN CHEMICAL SOCIETY=1945 * |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60243041A (en) | 1985-12-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4914221A (en) | Dimethylsilyl-substituted benzoyl chlorides and a process for preparing the same | |
| JPH0121834B2 (en) | ||
| JP3540822B2 (en) | Method for producing glycerol carbonate | |
| US5003117A (en) | Process for decabromodiphenyl methane | |
| EP0270724B1 (en) | Preparation of alkyl trifluoroacetoacetate | |
| US4595541A (en) | Process for the preparation of trifluoroacetic anhydride | |
| JPH0137388B2 (en) | ||
| US4136113A (en) | Process for preparation of organic acid halide | |
| JPH09227498A (en) | Production of high-purify fluoroalkylsulfonic anhydride | |
| US6476271B2 (en) | Process for the preparation of ether-free salts of tetrakis(pentafluorophenyl) borate | |
| JPS6334856B2 (en) | ||
| JPH11255703A (en) | Production of acid chloride | |
| US6162946A (en) | Processing for producing allyl 2-hydroxyisobutyrate | |
| US6235924B1 (en) | Continuous process for preparing benzoic acid esters | |
| JP6074670B2 (en) | Process for producing arene compounds containing perfluoroalkenyloxy groups | |
| US4322373A (en) | Process for the preparation of aromatic dicarboxylic acid dichlorides | |
| JPS6296493A (en) | Synthesis of tricyclazole | |
| JP2558497B2 (en) | Method for producing alkyldihalogenophosphane | |
| EP0484742B1 (en) | 2-Chloropropionaldehyde trimer and production process thereof | |
| CA2007530C (en) | Preparation of 2-chloroterephthaloyl chloride | |
| JP3892137B2 (en) | Tetrakis (fluoroaryl) borate ether complex and method for producing the same | |
| JPH0324021A (en) | Production of 5-tert-butyl-m-xylene | |
| KR900001075B1 (en) | Preparation of alkyl trifluroaceto acetate | |
| RU2126789C1 (en) | Process for preparing n,n-diphenyl-p-phenylene diamine | |
| JPS6121617B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |