JP5209201B2 - Method for producing high-purity organic acid chloride having an unsaturated group in the molecule - Google Patents
Method for producing high-purity organic acid chloride having an unsaturated group in the molecule Download PDFInfo
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- 150000007524 organic acids Chemical class 0.000 title claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 38
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims description 25
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 19
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 19
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical group ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 17
- 238000004821 distillation Methods 0.000 claims description 10
- 150000003512 tertiary amines Chemical class 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- PSHKMPUSSFXUIA-UHFFFAOYSA-N n,n-dimethylpyridin-2-amine Chemical compound CN(C)C1=CC=CC=N1 PSHKMPUSSFXUIA-UHFFFAOYSA-N 0.000 claims description 3
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000004817 gas chromatography Methods 0.000 description 26
- 239000000047 product Substances 0.000 description 25
- 239000003153 chemical reaction reagent Substances 0.000 description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000005886 esterification reaction Methods 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- -1 Organic acid chlorides Chemical class 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 229940125904 compound 1 Drugs 0.000 description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- 239000012043 crude product Substances 0.000 description 4
- 230000032050 esterification Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- FDYDISGSYGFRJM-UHFFFAOYSA-N (2-methyl-2-adamantyl) 2-methylprop-2-enoate Chemical compound C1C(C2)CC3CC1C(OC(=O)C(=C)C)(C)C2C3 FDYDISGSYGFRJM-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000012776 electronic material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000001577 simple distillation Methods 0.000 description 3
- YRPLSAWATHBYFB-UHFFFAOYSA-N (2-methyl-2-adamantyl) prop-2-enoate Chemical compound C1C(C2)CC3CC1C(C)(OC(=O)C=C)C2C3 YRPLSAWATHBYFB-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- IYKFYARMMIESOX-UHFFFAOYSA-N adamantanone Chemical compound C1C(C2)CC3CC1C(=O)C2C3 IYKFYARMMIESOX-UHFFFAOYSA-N 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 208000012839 conversion disease Diseases 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000002140 halogenating effect Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Description
本発明は、多くの化成品、医薬品、農薬、電子材料の製造原料として重要な、分子内に不飽和基を有する高純度有機酸クロライドの製造方法に関するものである。 The present invention relates to a method for producing a high-purity organic acid chloride having an unsaturated group in the molecule, which is important as a raw material for producing many chemical products, pharmaceuticals, agricultural chemicals and electronic materials.
アルキル、アリル、アラリキル、アルケノイル、アルキニル-クロライドに代表される、有機酸クロライドは、化成品材料、医薬品、農薬、電子材料の製造に欠かせない重要な原料の1つである。中でも分子内に不飽和基を有する有機酸クロライドは、特に需要が多い。 Organic acid chlorides, represented by alkyl, allyl, aralkyl, alkenoyl, and alkynyl-chloride, are one of the important raw materials essential for the production of chemical materials, pharmaceuticals, agricultural chemicals, and electronic materials. Among them, organic acid chloride having an unsaturated group in the molecule is particularly in demand.
分子内に不飽和基を有する有機酸クロライドとして代表的なメタクリル酸クロライドは、メタクリル酸と三塩化リンとの反応により製造できる（特許文献１）。また、アクリル酸又はメタクリル酸を重合禁止剤の存在下、ジメチルフォルムアミドを触媒としホスゲンと反応させて、アクリル酸クロライドまたはメタクリル酸クロライドを製造できる（特許文献２）。さらに、不飽和カルボン酸塩とハロゲン化剤とを反応させて不飽和カルボン酸ハライドを製造できる（特許文献３）。 A typical methacrylic acid chloride as an organic acid chloride having an unsaturated group in the molecule can be produced by a reaction between methacrylic acid and phosphorus trichloride (Patent Document 1). Acrylic acid chloride or methacrylic acid chloride can be produced by reacting acrylic acid or methacrylic acid with phosgene using dimethylformamide as a catalyst in the presence of a polymerization inhibitor (Patent Document 2). Furthermore, an unsaturated carboxylic acid halide can be produced by reacting an unsaturated carboxylate with a halogenating agent (Patent Document 3).
分子内に不飽和結合を有する有機酸クロライドの需要は近年高まっているが、従来工業的に製造されているものは品質が安定せず、純度が低い。市販品に含まれる代表的な不純物は、有機ハロゲン化物、重合物、あるいは遊離HClであるが、製造方法によってはS及びP化合物も含まれる。 In recent years, the demand for organic acid chlorides having an unsaturated bond in the molecule has increased, but those that have been produced industrially are not stable in quality and have low purity. Typical impurities contained in commercially available products are organic halides, polymers, or free HCl, but S and P compounds are also included depending on the production method.
分子内に不飽和結合を有する有機酸クロライドの従来の市販品を、そのまま、あるいは単蒸留したものを出発物質として次の反応を行なわせると、しばしば脱離などの副反応を起こして副生成物を伴う。副生成物は反応率を低下させるばかりでなく、得られた製品の純度を損ない、その精製に多大な時間と経費を要することが問題である。特に高い精度を要する電子材料においては、純度は製品の性能に関係し、SやPの不純物は腐食を誘発して問題を生じている。
かかる背景から、我々は有機酸クロライドの純度を上げるべく鋭意検討し、新しい精製方法を確立した。
When a conventional commercial product of an organic acid chloride having an unsaturated bond in the molecule is used as it is or after simple distillation, the following reaction is carried out, often causing a side reaction such as elimination to produce a by-product. Accompanied by. By-products not only reduce the reaction rate, but also impair the purity of the resulting product, and the purification requires a lot of time and money. Especially in electronic materials that require high accuracy, purity is related to product performance, and impurities such as S and P cause problems by inducing corrosion.
Against this background, we intensively studied to increase the purity of organic acid chloride and established a new purification method.
式１で示される分子内に不飽和基を有する有機酸クロライドは、第3級アミンを加えて蒸留することにより高純度なものとすることができる。
前記第3級アミンとしては、トリエチルアミン、1,8-ジアザビシクロ[5.4.0]-7-ウンデセン、1,4-ジアザビシクロ[2.2.2]オクタン、N,N-ジメチルアミノピリジン、ヘキサメチレンテトラミン及びN,N-テトラメチル-1,2-エチレンジアミンの内のいずれか又はそれらの組み合わせを好適に用いることができる。中でも、環状第3級アミンであるヘキサメチレンテトラミンは、特に好適に用いることができる。ヘキサメチレンテトラミンの分子構造を式２に示す。
この方法は、前記有機酸クロライドがアクリル酸クロライド又はメタクリル酸クロライドである場合、特に好適に用いることができる。 This method can be particularly preferably used when the organic acid chloride is acrylic acid chloride or methacrylic acid chloride.
分子内に不飽和基を有する有機酸クロライドと第3級アミンを十分混合させてから、有機酸クロライドの沸点付近の温度で常圧又は減圧で蒸留することにより、特に好適な結果を得ることができる。 The organic acid chloride and a tertiary amine having an unsaturated group in the molecule from by mixing ten minutes, atmospheric pressure or at a temperature near the boiling point of the organic acid chloride by distillation under reduced pressure, to obtain a particularly favorable results Can do.
本方法により、分子内に不飽和基を有する有機酸クロライドの純度を顕著に向上させることができる。純度95%のメタクリル酸クロライドは、本方法により純度99%以上となった。純度94%のアクリル酸クロライドも、本方法により純度99%以上となった。 By this method, the purity of the organic acid chloride having an unsaturated group in the molecule can be remarkably improved. The purity of methacrylic acid chloride with a purity of 95% became 99% or more by this method. Acrylic acid chloride with a purity of 94% was also more than 99% pure by this method.
他の化合物を製造する原料として本発明に係る高純度な分子内に不飽和基を有する有機酸クロライドを用いると、実施例に示したように、市販品を用いるより純度の高い生成物を高い収率で得ることができる。 When the organic acid chloride having an unsaturated group in the high-purity molecule according to the present invention is used as a raw material for producing another compound, as shown in the examples, a higher-purity product than a commercial product is used. The yield can be obtained.
分子内に不飽和基を有する有機酸クロライドの試薬及び工業品は多くの不純物を含む。どのような不純物がどの程度混在するかはその製造方法に依存するが、よく見られるのは式３に示されるような有機ハロゲン化合物、遊離酸、遊離塩酸、重合物、P又はS化合物等である。
有機酸クロライドに含まれる有機酸、及び遊離HClは、第3級アミン塩と加熱蒸留することにより、式４に示すようにアミン塩となり釜残渣として残る。
有機酸クロライドのHCl付加体は系内でHClが脱離し、式５に示すように目的物に戻る。よって、蒸留物中に遊離HCl及び、HCl付加体が含まれることはない。
ヘキサメチレンテトラミンを有機アミンとして用いると次のような特徴が生じる。
(1) 分子内に４つの塩基末端を有するので、不純物の１つであるHCl及び遊離有機酸を強く捕捉する。
(2) 不飽和基を有する有機酸クロライドは重合しやすいが、ヘキサメチレンテトラミンはその重合を促進しない。
(3) 合成法によっては、PやS化合物を含むものがある。このものを強く捕捉する。
(4) 蒸留後の残渣が液状であって、蒸留釜からの取り出しが容易である。
(5) 蒸留後の残渣を取り出した後、直ちに仕込みができる。
(6) 価格が安価である。
When hexamethylenetetramine is used as an organic amine, the following characteristics occur.
(1) Since it has four base ends in the molecule, it strongly captures one of impurities, HCl and free organic acid.
(2) An organic acid chloride having an unsaturated group is easily polymerized, but hexamethylenetetramine does not accelerate the polymerization.
(3) Some synthetic methods contain P and S compounds. Capture this thing strongly.
(4) The residue after distillation is liquid and can be easily taken out from the still.
(5) After taking out the residue after distillation, it can be charged immediately.
(6) The price is low.
ヘキサメチレンテトラミンを用いた場合、1%以下でホルムアルデヒドが生成されるが、次の反応には影響しない。オリゴマーやポリマーを含む副生成物は、有機酸クロライドとの沸点差が大きいため、蒸留により容易に分離除去することができる。 When hexamethylenetetramine is used, formaldehyde is produced at 1% or less, but this does not affect the next reaction. By-products containing oligomers and polymers have a large boiling point difference from organic acid chlorides, and can be easily separated and removed by distillation.
本発明の具体的な実施形態は、実施例として以下に述べる。しかし、もとより本発明は実施例に示された実施形態に限定されるものではない。 Specific embodiments of the present invention are described below as examples. However, the present invention is not limited to the embodiments shown in the examples.
工業用メタクリル酸クロライドから、ヘキサメチレンテトラミンを用いて高純度なメタクリル酸クロライドを製造する例を以下に示す。
工業用メタクリル酸クロライド（ガスクロマトグラフ（GC）分析純度95%）1kgに100ppmのMEHQ（ハイドロキノンモノメチルエーテル）とヘキサメチレンテトラミンを濃度2.5%になるように添加し、70-75℃（バス温度）で加熱下、一夜攪拌した。続いて、約65℃/200mmHgで蒸留した。収量は0.9kg（回収率90%）で、GC分析純度は99%以上であった。
釜残渣は液状で、容易に除去できた。釜残渣を除去した後、精製工程を再開した。精製工程を10回繰り返し行っても、収率は最初と同様の80-90%であり、GC分析の結果によれば、FID検出器（水素炎イオン化検出器）で100%、TCD検出器（熱伝導度検出器：ハロゲンに活性なもの）で99％以上の純度であった。
An example of producing high-purity methacrylic acid chloride from industrial methacrylic acid chloride using hexamethylenetetramine is shown below.
Add 100ppm MEHQ (hydroquinone monomethyl ether) and hexamethylenetetramine to 2.5kg in industrial methacrylic acid chloride (Gas chromatograph (GC)
The kettle residue was liquid and could be easily removed. After removing the kettle residue, the purification process was resumed. Even if the purification process is repeated 10 times, the yield is 80-90%, which is the same as the first. According to the results of GC analysis, 100% with the FID detector (flame ionization detector) and TCD detector ( The thermal conductivity detector (active to halogen) had a purity of 99% or more.
試薬用メタクリル酸クロライドから、ヘキサメチレンテトラミンを用いて高純度なメタクリル酸クロライドを製造する例を以下に示す。
市販品試薬メタクリル酸クロライド（GC分析純度98%）500gに100ppmのMEHQとヘキサメチレンテトラミンを濃度2.5%になるように添加し、70-75℃（バス温）で加熱下、1時間攪拌した。続いて、75℃（バス温）/200mmHgで蒸留した。収量は470g（回収率94%）で、GC分析純度は99%以上であった。
釜残渣は液状で、容易に除去することができた。実施例１と同様に、釜残渣除去後、同様の方法で酸クロライドの精製工程を数10回繰り返しても、同様に高純度品を得ることができた。
An example of producing high purity methacrylic acid chloride from methacrylic acid chloride for reagents using hexamethylenetetramine is shown below.
100 ppm of MEHQ and hexamethylenetetramine were added to 500 g of commercially available reagent methacrylic acid chloride (GC analysis purity 98%) to a concentration of 2.5%, and the mixture was stirred at 70-75 ° C. (bath temperature) for 1 hour. Subsequently, it was distilled at 75 ° C. (bath temperature) / 200 mmHg. The yield was 470 g (recovery rate 94%), and the GC analysis purity was 99% or more.
The kettle residue was liquid and could be easily removed. In the same manner as in Example 1, after removing the kettle residue and repeating the acid chloride purification step several tens of times in the same manner, a high-purity product was obtained in the same manner.
工業用アクリル酸クロライドから、ヘキサメチレンテトラミンを用いて高純度なアクリル酸クロライドを製造する例を以下に示す。
工業品アクリル酸クロライド（GC分析純度94%）1kgに100ppmのMEHQとヘキサメチレンテトラミンを濃度2.5%になるように添加し、45-50℃（バス温）で加熱下、1時間攪拌した。続いて、48〜55℃（バス温）/200mmHgで蒸留した。収量は0.87kg（回収率87%）で、GC分析純度は99%以上であった。
釜残渣は液状で、容易に除去できた。釜残渣除去後、酸クロライドを新たに投入し、精製工程を10回繰り返し行っても、収率は80-95%であった。GC分析の結果、FID検出器で100%、TCD検出器（ハロゲンに活性）で99%以上の純度であった。
An example of producing high-purity acrylic acid chloride from industrial acrylic acid chloride using hexamethylenetetramine is shown below.
100 ppm of MEHQ and hexamethylenetetramine were added to 1 kg of industrial product acrylic acid chloride (GC analysis purity 94%) to a concentration of 2.5%, and the mixture was stirred at 45-50 ° C. (bath temperature) for 1 hour. Subsequently, it was distilled at 48 to 55 ° C. (bath temperature) / 200 mmHg. The yield was 0.87 kg (recovery rate 87%), and the GC analysis purity was 99% or more.
The kettle residue was liquid and could be easily removed. After removing the kettle residue, acid chloride was newly added and the purification process was repeated 10 times. The yield was 80-95%. As a result of GC analysis, the purity was 100% with an FID detector and 99% or more with a TCD detector (active to halogen).
試薬用アクリル酸クロライドから、ヘキサメチレンテトラミンを用いて高純度なアクリル酸クロライドを製造する例を以下に示す。
試薬用アクリル酸クロライド（GC分析純度98%）500gに100ppmのMEHQとヘキサメチレンテトラミンを濃度2.5%になるように添加し、45-50℃（バス温）で加熱下、一夜攪拌した。続いて、48〜55℃（バス温）/200mmHgで蒸留した。収量は480g（回収率96%）で、GC分析純度は99%以上であった。
釜残渣は液状で容易に除去できた。実施例３と同様に、釜残渣を除去し、同様の精製工程を数10回繰り返しても、同様に高純度品を得ることができた。
An example of producing high-purity acrylic acid chloride from reagent-use acrylic acid chloride using hexamethylenetetramine is shown below.
100 ppm of MEHQ and hexamethylenetetramine were added to 500 g of reagent acrylic acid chloride (GC analysis purity 98%) to a concentration of 2.5%, and the mixture was stirred overnight at 45-50 ° C. (bath temperature). Subsequently, it was distilled at 48 to 55 ° C. (bath temperature) / 200 mmHg. The yield was 480 g (recovery 96%), and the GC analysis purity was 99% or more.
The kettle residue was liquid and could be easily removed. Similarly to Example 3, even when the kettle residue was removed and the same purification process was repeated several tens of times, a high-purity product could be obtained similarly.
工業用メタクリル酸クロライドから、4-ジメチルアミノピリジンを用いて高純度なメタクリル酸クロライドを製造する例を以下に示す。
工業品メタクリル酸クロライド（GC分析純度95%）1kgに100ppmのMEHQと4-N,N'ジメチルアミノピリジンを濃度2.5%になるように添加し、70-75℃（バス温）に保持しつつ、一夜攪拌した。続いて、75℃（バス温）/200mmHgで蒸留した。収量は0.8kg（回収率80%）で、GC分析純度は99%以上であった。
釜残渣は固体であった。その除去のために、まずIPA（イソプロピルアルコール）を入れて釜を洗浄した。続いてメタノールを発熱を抑えながら徐々に加え、さらにIPA/水（1:1）の10%NaOH溶液にて、完全に酸クロライドを中和した。そのIPA溶液を除去後、水洗し、THF（テトラヒドロフラン）及びメタノールにて洗浄した。また、蒸留塔を洗浄するために、まずTHF、続いてメタノールにて常圧蒸留し、洗浄後、真空下において乾燥した。
An example of producing high-purity methacrylic acid chloride from industrial methacrylic acid chloride using 4-dimethylaminopyridine is shown below.
While adding 100ppm MEHQ and 4-N, N'dimethylaminopyridine to 2.5kg in 1kg of industrial product methacrylic acid chloride (
The kettle residue was a solid. For the removal, IPA (isopropyl alcohol) was first added to wash the kettle. Subsequently, methanol was gradually added while suppressing heat generation, and the acid chloride was completely neutralized with a 10% NaOH solution of IPA / water (1: 1). The IPA solution was removed, washed with water, and washed with THF (tetrahydrofuran) and methanol. Further, in order to wash the distillation tower, first, atmospheric distillation was carried out with THF and then with methanol, and after washing, it was dried under vacuum.
本実施例に示したように、ヘキサメチレンテトラミン以外の有機アミンを用いた場合は、高純度品を得るという本来の目的は達成できるが、固体残渣が釜に残るため、その除去が煩雑になる。工業的には、釜を容易に繰り返し使用できることが重要であるため、ヘキサメチレンテトラミンを用いることが望ましい。 As shown in this example, when an organic amine other than hexamethylenetetramine is used, the original purpose of obtaining a high-purity product can be achieved, but the solid residue remains in the kettle, so that the removal becomes complicated. . Industrially, it is important to use the kettle easily and repeatedly, so it is desirable to use hexamethylenetetramine.
実施例１で得られた高純度メタクリル酸クロライドと市販試薬用メタクリル酸クロライドとの活性を、式６に示すエステル化法により比較した。
2-アダマンタノン20gにTHF180mLを添加して、-20℃付近で冷却下、メチルクロライドを10.1gバブリングした。続いてLiを添加し、完全に溶解させてLi体（式６、化合物１）をほぼ99%の収量で得た。
上記Li体に、1.2当量のいろいろな純度のメタクリル酸クロライドを滴下し、生成物（式６、化合物３）をGC（ガスクロマトグラフィー）法により分析した。使用した量を1として、目的物（式６、化合物３）の転化率を求めた。
180 mL of THF was added to 20 g of 2-adamantanone, and 10.1 g of methyl chloride was bubbled under cooling at around -20 ° C. Subsequently, Li was added and completely dissolved to obtain a Li form (formula 6, compound 1) with a yield of approximately 99%.
1.2 equivalents of methacrylic acid chloride of various purity was dropped into the Li body, and the product (formula 6, compound 3) was analyzed by GC (gas chromatography) method. Taking the amount used as 1, the conversion of the target product (formula 6, compound 3) was determined.
上記エステル化反応の結果を図１に示す。図１において、横軸は反応時間を、縦軸はエステル化率を示す。反応時間０は、滴下終了直後とした。反応は速いので、この時点でかなり進行している。◆は、実施例１で得られた高純度メタクリル酸クロライドを用いた場合（Lot101）を示す。■は、メタクリル酸クロライド市販試薬を単に減圧蒸留したものを用いた場合を示す（Lot102）。▲は、メタクリル酸クロライド市販試薬をそのまま使用した場合を示す（Lot103）。
The result of the esterification reaction is shown in FIG. In FIG. 1, the horizontal axis represents the reaction time, and the vertical axis represents the esterification rate.
実施例１の方法で得られた16.5gの高純度メタクリル酸クロライドを上記Li体（式６、化合物１）に-20℃位で、滴下して反応させた場合、反応は約30分後には終了し、転化率は99.45%(GC)であった。反応終了後、洗浄、濃縮すると32.1g（粗収率:103%）の2-メチル-2-アダマンチルメタクリレート（式６、化合物３）を得た。そのときのGC純度は99.4%で、ほぼ定量的に目的物が得られる（図１、Lot101）。この得られた粗体を精製すると、約90%の実収率で高純度品を得た。 When 16.5 g of high-purity methacrylic acid chloride obtained by the method of Example 1 was reacted dropwise at about −20 ° C. to the above Li-form (formula 6, compound 1), the reaction was carried out after about 30 minutes. Upon completion, the conversion was 99.45% (GC). After completion of the reaction, washing and concentration yielded 32.1 g (crude yield: 103%) of 2-methyl-2-adamantyl methacrylate (formula 6, compound 3). The GC purity at that time is 99.4%, and the target product can be obtained almost quantitatively (FIG. 1, Lot 101). The crude product thus obtained was purified to obtain a high-purity product with an actual yield of about 90%.
市販試薬品を単蒸留して得たメタクリル酸クロライド16.5gを、上記と同様にLi体（式６、化合物１）に滴下し反応させた。反応終了後、洗浄、濃縮すると31.2g（収率:100%）の粗2-メチル-2-アダマンチルメタクリレートを得た（図１、Lot102）。そのときのGC純度は約87%であった。この粗体を精製すると約59%の実収率で目的物を得た。
市販試薬品を蒸留せずにそのまま用いて、同様の反応を試みた。その結果、29g（平均収率：93%）の粗2-メチル-2-アダマンチルメタクリレート（式６、化合物３）を得た。その時のGC純度は、73%（図１、Lot103）であった。この粗体を精製すると、約45%の実収率で目的物を得た。以上の結果が示すように、本発明の方法により得た酸クロライドを用いると、高収率で目的物を得ることができる。
16.5 g of methacrylic acid chloride obtained by simple distillation of a commercially available reagent product was dropped into a Li form (formula 6, compound 1) and reacted as described above. After completion of the reaction, washing and concentration yielded 31.2 g (yield: 100%) of crude 2-methyl-2-adamantyl methacrylate (FIG. 1, Lot 102). The GC purity at that time was about 87%. The crude product was purified to obtain the target product with an actual yield of about 59%.
A similar reaction was attempted using the commercial reagent as it was without distillation. As a result, 29 g (average yield: 93%) of crude 2-methyl-2-adamantyl methacrylate (formula 6, compound 3) was obtained. The GC purity at that time was 73% (FIG. 1, Lot103). The crude product was purified to obtain the target product with an actual yield of about 45%. As the above results show, when the acid chloride obtained by the method of the present invention is used, the target product can be obtained in high yield.
図１によれば、本発明の方法で精製したメタクリル酸クロライドを用いると99.45%(GC)の転化率が得られ、エステル化はほぼ完全であった。これに対し不純な酸クロライドを用いると、収率が大幅に下った。また、本発明の方法で精製した有機酸クロライドを用いれば、反応性も高く約30分以内に反応が終了する。 According to FIG. 1, when using the methacrylic acid chloride purified by the method of the present invention, a conversion of 99.45% (GC) was obtained and the esterification was almost complete. On the other hand, when an impure acid chloride was used, the yield was greatly reduced. If the organic acid chloride purified by the method of the present invention is used, the reactivity is high and the reaction is completed within about 30 minutes.
なお、試薬用メタクリル酸クロライドをそのまま、或いは単に蒸留してエステル化反応に用いた場合には、反応は完全には進まず収率が低い。この結果は、GCでは分析しえない不純物が共存していると予測している。特に、そのまま用いた場合において120分後に転化率が低下しているのは、不純物による副反応の進行によると思われる。 When the methacrylic acid chloride for reagent is used as it is or simply distilled and used for the esterification reaction, the reaction does not proceed completely and the yield is low. This result predicts the presence of impurities that cannot be analyzed by GC. In particular, when used as it is, the decrease in the conversion rate after 120 minutes seems to be due to the progress of side reactions due to impurities.
アクリル酸クロライドについても式７で示されるように同様の方法で比較した。
得られたLi体（式７、化合物１）に実施例３の方法で蒸留したアクリル酸クロライドを14.5g滴下して反応させた。反応終了後、洗浄、濃縮すると32.1g（収率:110%）の粗2-メチル-2-アダマンチルアクリレートを得た。そのときのGC純度は98%で、ほぼ定量的に目的物を得ていることを転化率で示していた。この得られた粗体を精製し、約85%の実収率で目的物を得た。
試薬用を単蒸留して得たアクリル酸クロライドを用いて同様にエステル化反応を行った。同様に得られたLi体（式７）に、単蒸留したアクリル酸クロライドを14.5g滴下して反応させた。反応終了後、洗浄、濃縮して27.8g（収率:95%）の粗2-メチル-2-アダマンチルアクリレートを得た。そのときのGC純度は約75%であった。
14.5 g of acrylic acid chloride distilled by the method of Example 3 was dropped and reacted with the obtained Li form (formula 7, compound 1). After completion of the reaction, washing and concentration yielded 32.1 g (yield: 110%) of crude 2-methyl-2-adamantyl acrylate. The GC purity at that time was 98%, and the conversion rate showed that the target product was obtained almost quantitatively. The resulting crude product was purified to obtain the target product with an actual yield of about 85%.
The esterification reaction was similarly carried out using acrylic acid chloride obtained by simple distillation of the reagent. Similarly, 14.5 g of simple distilled acrylic acid chloride was added dropwise to the Li body (formula 7) obtained and reacted. After completion of the reaction, washing and concentration yielded 27.8 g (yield: 95%) of crude 2-methyl-2-adamantyl acrylate. The GC purity at that time was about 75%.
結果を図２に示す。反応時間０は、滴下終了直後としているので、この時点で反応は殆ど完結している。◆は、実施例３の方法で精製した高純度アクリル酸クロライドを用いた場合を示す（Lot105）。■は、試薬用アクリル酸クロライドを単に減圧蒸留したものを用いた場合を示す（Lot106）。
この図によれば、本発明の方法で精製した有機酸クロライドを用いると98%(GC)を超える高い転化率が得られ、ほぼ完全にエステル化されていた。これに対し不純な酸クロライドを用いると、収率が大幅に下がった。また、本発明の方法で精製した有機酸クロライドを用いれば、反応は極めて速く終了する。
The results are shown in FIG. Since the
According to this figure, when the organic acid chloride purified by the method of the present invention was used, a high conversion rate exceeding 98% (GC) was obtained, and the esterification was almost complete. In contrast, the use of impure acid chloride significantly reduced the yield. Moreover, if the organic acid chloride refine | purified by the method of this invention is used, reaction will be complete | finished very rapidly.
なお、有機酸クロライドを蒸留する際に添加する有機アミンの濃度は、蒸留前の有機酸クロライドの純度に応じて適宜増減させると良い。市販されている有機酸クロライドの純度を考慮すると、一般的には、有機アミンを濃度1〜20％となるように添加すれば、高純度有機酸クロライドを製造することができる。
また、試薬用をそのままあるいは単に蒸留してエステル化反応に用いると反応は完全に進まず収率が低い。これはGCでは分析しえない不純物の共存のためと予測している。
In addition, it is good to increase / decrease the density | concentration of the organic amine added when distilling an organic acid chloride suitably according to the purity of the organic acid chloride before distillation. Considering the purity of the commercially available organic acid chloride, generally, a high-purity organic acid chloride can be produced by adding an organic amine to a concentration of 1 to 20%.
If the reagent is used as it is or simply distilled and used in the esterification reaction, the reaction does not proceed completely and the yield is low. This is due to the coexistence of impurities that cannot be analyzed by GC.
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