JPH0283358A - Production of unsaturated carboxylic acid amide - Google Patents
Production of unsaturated carboxylic acid amideInfo
- Publication number
- JPH0283358A JPH0283358A JP63233633A JP23363388A JPH0283358A JP H0283358 A JPH0283358 A JP H0283358A JP 63233633 A JP63233633 A JP 63233633A JP 23363388 A JP23363388 A JP 23363388A JP H0283358 A JPH0283358 A JP H0283358A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- carboxylic acid
- reaction
- lower alcohol
- general formula
- 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
- 150000001732 carboxylic acid derivatives Chemical class 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims 1
- 125000005395 methacrylic acid group Chemical group 0.000 claims 1
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 6
- 239000003112 inhibitor Substances 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000003230 hygroscopic agent Substances 0.000 abstract description 2
- 239000012528 membrane Substances 0.000 abstract description 2
- 239000003607 modifier Substances 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 abstract 2
- 125000005396 acrylic acid ester group Chemical group 0.000 abstract 1
- 238000007098 aminolysis reaction Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 53
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- -1 N-substituted amides Chemical class 0.000 description 17
- 239000000047 product Substances 0.000 description 13
- 239000006227 byproduct Substances 0.000 description 8
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 150000003335 secondary amines Chemical class 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NJBCRXCAPCODGX-UHFFFAOYSA-N 2-methyl-n-(2-methylpropyl)propan-1-amine Chemical compound CC(C)CNCC(C)C NJBCRXCAPCODGX-UHFFFAOYSA-N 0.000 description 1
- KEOZIBBDNODPRS-UHFFFAOYSA-N 3-methoxy-2-methyl-n,n-dipropylpropanamide Chemical compound CCCN(CCC)C(=O)C(C)COC KEOZIBBDNODPRS-UHFFFAOYSA-N 0.000 description 1
- OKIVEANXGDAWTC-UHFFFAOYSA-N 3-methoxy-n,n-dipropylpropanamide Chemical compound CCCN(CCC)C(=O)CCOC OKIVEANXGDAWTC-UHFFFAOYSA-N 0.000 description 1
- 238000005698 Diels-Alder reaction Methods 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- QHCCDDQKNUYGNC-UHFFFAOYSA-N n-ethylbutan-1-amine Chemical compound CCCCNCC QHCCDDQKNUYGNC-UHFFFAOYSA-N 0.000 description 1
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- WDFKEEALECCKTJ-UHFFFAOYSA-N n-propylprop-2-enamide Chemical compound CCCNC(=O)C=C WDFKEEALECCKTJ-UHFFFAOYSA-N 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 229950000688 phenothiazine Drugs 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、−船式（Ｖ）
Ｃ）１２＝ＣＣＯＮＲ４
（Ｖ）
（式中、Ｒ＋は一般式（１）におけるＲ５に同じ。Ｒ４
゜Ｒ６は一般式（ＩＶ）におけるＲ、、Ｒ，に同じ。）
で表されるＮ−置換不飽和カルボン酸アミド（以下、Ｎ
−置換アミドと略する。）の製造方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to -ship type (V) C)12=CCONR4 (V) (wherein, R+ is the same as R5 in general formula (1). R4
゜R6 is the same as R in general formula (IV). )
N-substituted unsaturated carboxylic acid amide represented by (hereinafter referred to as N
-Abbreviated as substituted amide. ).
本発明によって提供されるＮ−置換アミドは、吸湿剤、
防曇剤、分離膜、樹脂改質剤等の広い用途を有する有用
な化合物である。The N-substituted amides provided by the present invention are hygroscopic agents,
It is a useful compound with a wide range of uses such as antifogging agents, separation membranes, and resin modifiers.
〔従来の技術及び発明が解決しようとする課題］本発明
のＮ−置換アミドは、一般に不飽和カルボン酸エステル
とアミン化合物とのアミツリシスにより製造することが
できる。[Prior Art and Problems to be Solved by the Invention] The N-substituted amide of the present invention can generally be produced by amicilysis of an unsaturated carboxylic acid ester and an amine compound.
ところが、不飽和カルボン酸エステルとアミノ化合物と
のアミツリシスに際しては、アミノ化合物の二重結合へ
のマイケル付加がおこり反応における目的物の選択率が
低い。また、マイケル付加物から二重結合を再生するに
は、１８０〜３００°Ｃという高温で熱分解をおこない
付加したアミノ化合物を脱離させる工程が必要となるが
、この際、重合物の生成等の副反応が起こり、目的物の
収率が著しく低下する（特開昭５０−１１１０１６号）
。However, in the amitrisis of an unsaturated carboxylic acid ester and an amino compound, Michael addition to the double bond of the amino compound occurs, resulting in a low selectivity of the target product in the reaction. In addition, in order to regenerate double bonds from Michael adducts, it is necessary to perform thermal decomposition at a high temperature of 180 to 300°C to remove the added amino compound, but in this case, the formation of polymers, etc. side reactions occur, and the yield of the target product decreases significantly (Japanese Patent Application Laid-open No. 111016/1983)
.
この副反応を抑制するために、低級アルコールをまず二
重結合に付加させた後、アミツリシスをおこない、次い
で、高温で脱アルコールをおこない二重結合を再生して
目的物を得る方法（特開昭４９−６６６２３号、ＵＳＰ
−２５３４５８５，ＵＳＰ−２７０２８２２）が開示さ
れている。In order to suppress this side reaction, a lower alcohol is first added to the double bond, then amithrisis is performed, and then dealcoholization is performed at high temperature to regenerate the double bond and obtain the desired product. No. 49-66623, USP
-2534585, USP-2702822) is disclosed.
この方法は、低級アルコールより高価なアミン化合物が
二重結合へ付加して消費されるのを防ぐのには有効な手
段であるが、脱アルコール反応を高温でおこなうため重
合等の副反応をおこし、著しく目的物の収率が低下する
。このため、このＮ置換アミド合成法を工業化するには
多大な困難を有する。また、二重結合の保護法としてシ
クロペンタジェンを二重結合へのディールス・アルダ−
反応で付加させ、アミツリシス終了後、熱分解によりシ
クロペンタジェンを脱離させる方法（特開昭４９−６６
６２５号他）も開示されている。This method is effective in preventing amine compounds, which are more expensive than lower alcohols, from being added to double bonds and consumed, but because the dealcoholization reaction is carried out at high temperatures, side reactions such as polymerization occur. , the yield of the target product decreases significantly. Therefore, it is very difficult to commercialize this N-substituted amide synthesis method. In addition, as a protection method for double bonds, cyclopentadiene is added to the Diels-Alder
A method in which cyclopentadiene is added by reaction and removed by thermal decomposition after completion of amitrilysis (Japanese Unexamined Patent Publication No. 49-66
No. 625 et al.) are also disclosed.
しかし、この方法においても、副生成物の生成は免れず
、また、脱離したシクロペンタジェンの目的物からの分
離・回収工程を要し、製品中へのシクロペンタジェンの
微量の混入が避けられず、製品品質を低下させる等の欠
点を有する。However, even in this method, the formation of by-products is inevitable, and a step is required to separate and recover the desorbed cyclopentadiene from the target product, which prevents the contamination of trace amounts of cyclopentadiene into the product. However, it has drawbacks such as deterioration of product quality.
〔課題を解決するための手段及び作用］本発明者らは、
副生成物を伴わずにＮ−置換アミドを収率よく製造する
方法について鋭意検討した結果、−船式（１）
％式％（１）
（式中、Ｒ１は水素またはメチル基を示し、Ｒ２は炭素
数１〜３のアルキル基を示す。）で表されるアクリル酸
エステル類またはメタクリル酸エステル類（以下、（メ
タ）アクリル酸エステル類とする。[Means and effects for solving the problem] The present inventors
As a result of intensive studies on a method for producing N-substituted amides in good yield without producing by-products, we found that -Full formula (1) % Formula % (1) (wherein R1 represents hydrogen or a methyl group, R2 represents an alkyl group having 1 to 3 carbon atoms.) (hereinafter referred to as (meth)acrylic esters).
）に−船式（ｆｆ） Ｒ３−ＯＲ（■） （式中、Ｒｉは炭素数１〜３のアルキル基を示す。) to - ship style (ff) R3-OR(■) (In the formula, Ri represents an alkyl group having 1 to 3 carbon atoms.
）で表される低級アルコール（以下、低級アルコールと
する。）を触媒を用いて付加させて一般式（［）
％式％（）
（式中、ｌ！１．Ｒｚは一般式＜１）におけるＩ？、、
Ｒ，に同じ。Ｒ１は一般式（ＩＩ）におけるＲ１に同じ
。）で表されるβ−アルコキシ置換カルボン酸エステル
（以下、β−アルコキシ置換カルボン酸エステルとする
。）を合成し、次に、これと−船式（ＩＶ）ＨＮ−Ｒ４
（ＩＶ ）
（式中、Ｒａ、Ｒｓは炭素数１〜５のアルキル基を示す
。）で表される第二級アミン（以下、二級アミンとする
。）とをアミツリシス反応させてβ−アルコキシ置換カ
ルボン酸アミドを合成し、次いで、触媒を用いて温和な
条件でアルコールを脱離させて二重結合を再生すること
により、高収率で目的物を製造する方法、すなわち、β
−アルコキシ置換カルボン酸アミドからのアルコールＦ
ＩＩＩＭ反応において触媒を用いて温和な条件で実行す
ることにより、特開昭４９−６６６２３号記載の方法の
欠点を解消し、工業的に有利にβ−アルコキシ置ｔＡカ
ルボン酸エステルを原料にしてＮ−置換アミドを製造す
る方法を確立したものである。) (hereinafter referred to as "lower alcohol") is added using a catalyst to form a compound of the general formula ([) % formula % () (in the formula, l!1.Rz is the general formula <1). I? ,,
Same as R. R1 is the same as R1 in general formula (II). ) is synthesized (hereinafter referred to as β-alkoxy substituted carboxylic acid ester), and then, this and -ship formula (IV) HN-R4 are synthesized.
(IV) (In the formula, Ra and Rs represent an alkyl group having 1 to 5 carbon atoms) is subjected to an amithrisis reaction with a secondary amine (hereinafter referred to as secondary amine) to produce β-alkoxy A method for producing the target product in high yield by synthesizing a substituted carboxylic acid amide and then eliminating the alcohol under mild conditions using a catalyst to regenerate the double bond.
-Alcohol F from alkoxy-substituted carboxylic acid amide
By carrying out the IIIM reaction under mild conditions using a catalyst, the drawbacks of the method described in JP-A-49-66623 can be overcome, and N - A method for producing substituted amides has been established.
すなわち、本発明シよ、（メタ）アクリル酸エステル類
と低級アルコールとを塩基性触媒存在下に反応させてβ
−アルコキン置換カルボン酸エステルを合成し、次いで
、これに二級アミンを反応させてβ−アルコキシ置換カ
ルボン酸アミドを生成させ、次いで、塩基性触媒存在下
に低級アルコールを脱離させることにより不飽和基を形
成せしめることをｗｅとするＮ−置換アミドの製造方法
である。That is, according to the present invention, (meth)acrylic esters and lower alcohols are reacted in the presence of a basic catalyst to form β
-Synthesize an alkoxy-substituted carboxylic acid ester, then react it with a secondary amine to produce a β-alkoxy-substituted carboxylic acid amide, and then remove the lower alcohol in the presence of a basic catalyst to create an unsaturated This is a method for producing an N-substituted amide in which we form a group.
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用する（メタ）アクリル酸エステル類として
は、アクリル酸メチル、アクリル酸エチル、アクリル酸
ｎ−プロピル、アクリル酸イソプロピル、メタクリル酸
メチル、メタクリル酸エチル、メタフリルミｎ−プロピ
ル、メタクリル酸イソプロピル等が挙げられる。Examples of (meth)acrylic esters used in the present invention include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, methyl methacrylate, ethyl methacrylate, methafurylumi n-propyl, isopropyl methacrylate, etc. can be mentioned.
（メタ）アクリル酸エステル類と反応させる低級アルコ
ールとしては、メタノール、エタノール、ロープロバノ
ール、イソプロパツール等が挙げられる。Examples of lower alcohols to be reacted with (meth)acrylic esters include methanol, ethanol, lowobanol, isopropanol, and the like.
二級アミンとしては、ジメチルアミン、ジエチルアミン
、Ｎ、Ｎ−エチルプロピルアミン、Ｎ、Ｎ−メチルブチ
ルアミン、ジ−ｎ−プロピルアミン、ジイソプロピルア
ミン、Ｎ、Ｎ−エチルブチルアミン、ジ−ミーブチルア
ミン、ジイソブチルアミン、ジイソチルアミン等を挙げ
ることができる。Examples of secondary amines include dimethylamine, diethylamine, N,N-ethylpropylamine, N,N-methylbutylamine, di-n-propylamine, diisopropylamine, N,N-ethylbutylamine, di-butylamine, and diisobutylamine. , diisotylamine, and the like.
本発明においては、先ず前記（メタ）アクリル酸エステ
ル類への低級アルコールの付加によりβ−アルコキシ置
換カルボン酸エステルを得る。In the present invention, a β-alkoxy-substituted carboxylic acid ester is first obtained by adding a lower alcohol to the (meth)acrylic acid ester.
（メタ）アクリル酸エステル類に対する低級アルコール
の仕込みモル比は、０．３〜３の範囲が好ましく、反応
温度は６０’Ｃ−１２５°Ｃが好ましい。The molar ratio of the lower alcohol to the (meth)acrylic ester is preferably in the range of 0.3 to 3, and the reaction temperature is preferably 60'C to 125C.
低級アルコールを付加させる触媒としては塩基性触媒が
よく、例えば、ナトリウムメチラート、水酸化カリウム
、水酸化ナトリウム等が挙げられる。The catalyst for adding the lower alcohol is preferably a basic catalyst, such as sodium methylate, potassium hydroxide, sodium hydroxide, and the like.
次に得られたβ−アルコキシ置換カルボン酸エステルと
二級アミンとのアミツリシスによりβアルコキン置換カ
ルボン酸アミドを合成することができる。Next, a β-alcokyne-substituted carboxylic acid amide can be synthesized by amicilysis of the obtained β-alkoxy-substituted carboxylic acid ester and a secondary amine.
β−アルコキシ置換カルボン酸エステルに対する二級ア
ミンの仕込みモル比は、０．３〜３の範囲が好ましい。The molar ratio of the secondary amine to the β-alkoxy substituted carboxylic acid ester is preferably in the range of 0.3 to 3.
反応温度は、４０〜１８０ ’Ｃが望ましい。アミツリ
シスに際しては、副生アルコールの沸点が二級アミンよ
り低い場合は、副生ずるアルコールを反応系から留去し
ながら反応を進めるのが反応速度を高め転化率を上げる
うえで有利である。また、反応は二級アミンの塩基性の
ため、無駐媒でも進行するが公知の塩基性のアミツリシ
ス触媒を添加することも可能である。The reaction temperature is preferably 40 to 180'C. During amitrilysis, if the boiling point of the by-product alcohol is lower than that of the secondary amine, it is advantageous to proceed with the reaction while distilling the by-product alcohol from the reaction system in order to increase the reaction rate and conversion rate. Further, since the reaction is basic to the secondary amine, the reaction proceeds even in the absence of a solvent, but it is also possible to add a known basic amithrisis catalyst.
１尋られたβ−アル２干シ置換カルボン酸アミドは、減
圧蒸留により精製して次の工程に使用してもよいが、反
応終了後、未反応の原料及び低沸副生成物を留去するの
みで次の反応に使用することも可能である。1. The β-Al 2-substituted carboxylic acid amide may be purified by vacuum distillation and used in the next step, but after the reaction is complete, unreacted raw materials and low-boiling byproducts must be distilled off. It is also possible to use it in the next reaction by simply adding it.
次にβ−アルコキシ置換カルボン酸アミドより低級アル
コールを脱離させてＮ−置換アミドを合成するが、この
際、従来おこなわれている高温でのクラッキングにより
目的物を製造した場合には重合物等の好ましくない副生
成物を多量に生じ、目的物の精製を煩雑にし収率を著し
く低下させるから、本発明においては、触媒を使用して
温和な条件でアルコールを脱離させることが肝要である
。Next, the lower alcohol is eliminated from the β-alkoxy-substituted carboxylic acid amide to synthesize the N-substituted amide. In the present invention, it is important to eliminate the alcohol under mild conditions using a catalyst, since a large amount of undesirable by-products are produced, which complicates the purification of the target product and significantly reduces the yield. .
低級アルコールを脱離させる触媒としては、酸塩基触媒
でもよく、特に塩基性触媒が良い。The catalyst for eliminating the lower alcohol may be an acid-base catalyst, and a basic catalyst is particularly preferred.
塩基性触媒としては、例えば、ナトリウムメチラート、
水酸化リチウム、水酸化ナトリウム、水酸化カルシウム
等が挙げられる。As the basic catalyst, for example, sodium methylate,
Examples include lithium hydroxide, sodium hydroxide, calcium hydroxide, and the like.
触媒の添加に際しては、不活性な溶剤に溶かして反応系
へ添加することも固体のまま添加することも可能である
。When adding the catalyst, it can be dissolved in an inert solvent and added to the reaction system, or it can be added in the form of a solid.
反応は副反応を抑えるため低温でおこなうことが好まし
く、反応温度は５０〜１７０ ’Ｃの範囲が好ましい。The reaction is preferably carried out at a low temperature in order to suppress side reactions, and the reaction temperature is preferably in the range of 50 to 170'C.
反応圧力は５０〜７６０ｍｍＨｇで、生成する低級アル
コールを留去しつつ反応を進めることが反応速度を高め
る点から望ましい。The reaction pressure is 50 to 760 mmHg, and it is desirable to proceed with the reaction while distilling off the lower alcohol produced, from the viewpoint of increasing the reaction rate.
副反応を防ぐもう一つの手段として、溶剤を使用するこ
とも可能である。本発明においては溶剤を使用しなくて
もよいが、溶剤を使用した場合でも生成物の収率の低下
をまね（ことはなく、良好な方法である。溶剤としては
、Ｎ、Ｎ−ジメチルホルムアミド、Ｎ、Ｎ−ジメチルア
セトアミド、Ｎ、Ｎ−ジメチルスルホキシド、トルエン
、キシレン等が挙げられる。As another means of preventing side reactions, it is also possible to use a solvent. In the present invention, it is not necessary to use a solvent, but even if a solvent is used, the yield of the product will not be reduced (this is a good method. As a solvent, N,N-dimethylformamide is used. , N,N-dimethylacetamide, N,N-dimethylsulfoxide, toluene, xylene, and the like.
反応終了後、反応液の塩基性触媒を中和するか、抽出操
作により塩基性触媒を除去するか、不溶の塩基性触媒を
濾過または遠心分離により除去した後、目的物を蒸留等
により精製する。After the reaction is completed, the basic catalyst in the reaction solution is neutralized, the basic catalyst is removed by an extraction operation, or the insoluble basic catalyst is removed by filtration or centrifugation, and then the target product is purified by distillation, etc. .
なお、反応中及び目的物の精製中には、公知の重合禁止
剤を添加することが好ましく、重合禁止剤としては、例
えば、ハイドロキノン、ハイドロキノンモノメチルエー
テル、フェノチアジン、クペロン等が適当である。Note that during the reaction and during the purification of the target product, it is preferable to add a known polymerization inhibitor, and suitable examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, phenothiazine, cuperone, and the like.
〔実施例］ 以下、実施例により本発明を具体的に説明する。〔Example] Hereinafter, the present invention will be specifically explained with reference to Examples.
実施例１
〔アルコール付加〕
還流器をつけたナス型フラスコにメタクリル酸メチル２
００．２ｇ（２モル）、メタノール１６０．２ｇ（５モ
ル）、触媒としてナトリウムメチラート６．０ｇを入れ
、温度を８３°Ｃにして５時間反応させた。Example 1 [Alcohol addition] Methyl methacrylate 2 was added to an eggplant-shaped flask equipped with a reflux device.
00.2 g (2 moles) of methanol, 160.2 g (5 moles) of methanol, and 6.0 g of sodium methylate as a catalyst were added, and the temperature was raised to 83° C. and the reaction was carried out for 5 hours.
反応終了後、当量の酢酸を加えて触媒を中和した。低沸
分を除去して、β−メトキシイソ酪酸メチル２１３．６
ｇを得た。純度は９９．０％であった。After the reaction was completed, an equivalent amount of acetic acid was added to neutralize the catalyst. After removing low boiling components, methyl β-methoxyisobutyrate 213.6
I got g. Purity was 99.0%.
撹拌器及び塔頂に分留装置をつけてガラス製うッシヒリ
ングを充填した塔を有する四ツロフラスコに前記アルコ
ール付加で得られた反応液を入れ、ジ−ｎ−プロピルア
ミン２８３．３ｇ （２，８モル）を入れ、１２８°Ｃ
で生成するメタノールを留去しな−がら反応を進めた０
反応は２４時間で終了し、反応終了後、未反応のジ−ｎ
−プロピルアミンを減圧下で留去した。さらに低沸分留
去後３２１．６ｇの反応液を得た。The reaction solution obtained by the alcohol addition was placed in a four-bottle flask equipped with a stirrer and a column equipped with a fractionator at the top and filled with a glass Uschig ring, and 283.3 g (2,8 128°C
The reaction proceeded while distilling off the methanol produced.
The reaction was completed in 24 hours, and after the reaction, unreacted di-n
-Propylamine was distilled off under reduced pressure. Further, after distilling off the low-boiling fraction, 321.6 g of the reaction solution was obtained.
反応液のＮ、Ｎ−ジ−ｎ−プロピル−β−メトキシイソ
ブチルアミドの含有率は９０％であった。The content of N,N-di-n-propyl-β-methoxyisobutyramide in the reaction solution was 90%.
前記アミツリシスで得られた反応液を前記アミツリシス
と同様に反応器に入れ、触媒として水酸化リチウム５．
６ｇ、重合禁止剤としてクペロン０．８ｇを添加して１
３５°Ｃ１２０Ｃ１２０Ｏで反応をおこなった。The reaction solution obtained in the above amithrisis was put into a reactor in the same manner as in the above amithrisis, and 5. lithium hydroxide was added as a catalyst.
6g, adding 0.8g of cuperone as a polymerization inhibitor to 1
The reaction was carried out at 35°C, 120C, and 120O.
反応の際に副生ずる低級アルコールを反応系から留去し
ながら反応を進めた０反応は８時間で終了し、得られた
反応液を減圧蒸留で精製してＮ、Ｎ−ジ−ｎ−プロピル
メタクリルアミド２１４．６ｇを得た。純度は９９．８
％で、収率は６３％（仕込メタクリル酸メチル基準）で
あった。The reaction proceeded while distilling off the lower alcohol by-product from the reaction system. The reaction was completed in 8 hours, and the resulting reaction solution was purified by vacuum distillation to produce N,N-di-n-propyl. 214.6 g of methacrylamide was obtained. Purity is 99.8
%, and the yield was 63% (based on the charged methyl methacrylate).
実施例２ 〔アルコール付加〕 還流器をつけたナス型フラスコにアクリル酸メ。Example 2 [Alcohol addition] Add acrylic acid to an eggplant-shaped flask equipped with a reflux device.
チル１７２．２ｇ（２モル）、メタノール１６０．２ｇ
（５モル）、触媒として水酸化カリウム５．０ｇを入れ
、温度を６９°Ｃにして４時間反応させた。反応終了後
、当量の酢酸を加えて触媒を中和した。低沸分を除去し
て、β−メトキシプロピオン酸メチル２０３．５ｇを得
た。純度は９８．７％であった。Chill 172.2g (2 moles), methanol 160.2g
(5 mol) and 5.0 g of potassium hydroxide as a catalyst were added, the temperature was raised to 69°C, and the reaction was carried out for 4 hours. After the reaction was completed, an equivalent amount of acetic acid was added to neutralize the catalyst. Low boiling components were removed to obtain 203.5 g of methyl β-methoxypropionate. Purity was 98.7%.
〔アミツリシス］
攪拌器及び塔頂に分留装置をつけ、ガラス製うフシヒリ
ングを充填した塔を有する四ツロフラスコに前記アルコ
ール付加で得られた反応液を入れ、ジ−ｎ−プロピルア
ミン３６４．２ｇ （３，６モル）を入れ、１４３°Ｃ
で生成するメタノールを留去しながら反応を進めた０反
応は１８時間で終了し、反応終了後、未反応のジ−ｎ−
プロピルアミンを減圧下で留去した。さらに低沸分留去
後、３１０．９ｇの反応液を得た。[Amiturisis] The reaction solution obtained by the alcohol addition was put into a four-bottle flask equipped with a stirrer and a column equipped with a fractionator at the top and filled with a glass Ufushig ring, and 364.2 g of di-n-propylamine ( 3.6 mol) and heated to 143°C.
The reaction proceeded while distilling off the methanol produced. The reaction was completed in 18 hours, and after the completion of the reaction, the unreacted di-n-
Propylamine was distilled off under reduced pressure. After further distilling off the low-boiling fraction, 310.9 g of the reaction solution was obtained.
反応液のＮ、Ｎ−ジ−ｎ−プロピル−β−メトキシプロ
ピオアミドの含有率は９２％であった。The content of N,N-di-n-propyl-β-methoxypropioamide in the reaction solution was 92%.
前記アミツリシスで得られた反応液を前記アミツリシス
と同様に反応器にいれ、触媒として水酸化カルシウム９
．２ｇ、重合禁止剤としてクペロン０゜９ｇを添加して
１３２°Ｃ１２００＋ａｍＨｇで反応をおこなった０反
応の隙に副生ずる低級アルコールを反応系から留去しな
がら反応を進めた０反応は６時間で終了し、得られた反
応液を減圧蒸留で精製してＮ。The reaction solution obtained in the above amithrisis was put into a reactor in the same manner as in the above amithrisis, and calcium hydroxide 9 was added as a catalyst.
．． The reaction was carried out at 132°C and 1200+amHg with the addition of 0.9 g of Cuperone as a polymerization inhibitor.The reaction proceeded while distilling off the lower alcohol by-product from the reaction system during the 0 reaction.The 0 reaction was completed in 6 hours. The resulting reaction solution was purified by vacuum distillation to obtain N.
Ｎ−ジーｎ−プロピルアクリルアミド２５８．５ｇを得
た。258.5 g of N-gie n-propylacrylamide was obtained.
純度は９９．６％で、収率は６８．９％（仕込アクリル
酸メチル基準）であった。The purity was 99.6%, and the yield was 68.9% (based on the charged methyl acrylate).
これまで知られていた高温によるβ−アルコキン置換カ
ルボン酸アミドの脱メタノール化の方法は、重合物等の
生成等により著しく収率が低下するという欠点を存し、
このため工業化が困難であったが、本発明のβ−アルコ
キシ置換カルボン酸アミドからのアルコール脱離を触媒
を用いて温和な条件で実行する方法は、不飽和カルボン
酸エステルを原料として工業的に有利にＮ−置換アミド
を製品品質に問題を生ずることなく製造することを可能
にした。The previously known methods of demethanolizing β-alcoquine-substituted carboxylic acid amides at high temperatures have the drawback that the yield is significantly reduced due to the formation of polymers, etc.
For this reason, industrialization has been difficult, but the method of the present invention, in which alcohol is eliminated from β-alkoxy-substituted carboxylic acid amide using a catalyst under mild conditions, can be applied industrially using an unsaturated carboxylic ester as a raw material. Advantageously, it has become possible to produce N-substituted amides without causing problems in product quality.
特許出願人 三井東圧化学株式会社Patent applicant: Mitsui Toatsu Chemical Co., Ltd.
Claims (1)
炭素数１〜３のアルキル基を示す。）で表されるアクリ
ル酸エステル類またはメタクリル酸エステル類と一般式
（II） Ｒ＿３−ＯＨ（II） （式中、Ｒ＿３は炭素数１〜３のアルキル基を示す。 ）で表される低級アルコールとを塩基性触媒存在下に反
応させて一般式（III） ▲数式、化学式、表等があります▼（III） （式中、Ｒ＿１、Ｒ＿２は一般式（ I ）におけるＲ＿
１、Ｒ＿２に同じ。Ｒ＿３は一般式（II）におけるＲ＿
３に同じ。）で表されるβ−アルコキシ置換カルボン酸
エステルを合成し、次いで、これに一般式（IV） ▲数式、化学式、表等があります▼（IV） （式中、Ｒ＿４、Ｒ＿５は炭素数１〜５のアルキル基を
示す。）で表される第二級アミンを反応させてβ−アル
コキシ置換カルボン酸アミドを生成させ、次いで、塩基
性触媒存在下に低級アルコールを脱離させることにより
不飽和基を形成せしめることを特徴とする一般式（Ｖ） ▲数式、化学式、表等があります▼（Ｖ） （式中、Ｒ＿１は一般式（ I ）におけるＲ＿１に同じ
。Ｒ＿４、Ｒ＿５は一般式（VI）におけるＲ＿４、Ｒ＿
５に同じ。）で表されるＮ−置換不飽和カルボン酸アミ
ドの製造方法。[Claims] 1. General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. ▼ (I) (In the formula, R_1 represents hydrogen or a methyl group, and R_2 represents an alkyl group having 1 to 3 carbon atoms. ) and acrylic esters or methacrylic esters represented by the general formula (II) R_3-OH(II) (wherein R_3 represents an alkyl group having 1 to 3 carbon atoms) A lower alcohol is reacted in the presence of a basic catalyst to form the general formula (III) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(III) (In the formula, R_1 and R_2 are R_ in the general formula (I)
1. Same as R_2. R_3 is R_ in general formula (II)
Same as 3. ), and then synthesize the β-alkoxy-substituted carboxylic acid ester represented by the general formula (IV) ▲ Numerical formula, chemical formula, table, etc. ▼ (IV) (In the formula, R_4 and R_5 have 1 to 1 carbon atoms 5) to form a β-alkoxy-substituted carboxylic acid amide, and then remove the lower alcohol in the presence of a basic catalyst to form an unsaturated group. General formula (V) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(V) (In the formula, R_1 is the same as R_1 in general formula (I). R_4 and R_5 are the general formula (VI ) in R_4, R_
Same as 5. ) A method for producing an N-substituted unsaturated carboxylic acid amide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233633A JPH082850B2 (en) | 1988-09-20 | 1988-09-20 | Method for producing unsaturated carboxylic acid amide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63233633A JPH082850B2 (en) | 1988-09-20 | 1988-09-20 | Method for producing unsaturated carboxylic acid amide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0283358A true JPH0283358A (en) | 1990-03-23 |
| JPH082850B2 JPH082850B2 (en) | 1996-01-17 |
Family
ID=16958101
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63233633A Expired - Lifetime JPH082850B2 (en) | 1988-09-20 | 1988-09-20 | Method for producing unsaturated carboxylic acid amide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH082850B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008102615A1 (en) * | 2007-02-20 | 2008-08-28 | Idemitsu Kosan Co., Ltd. | PROCESS FOR PRODUCING β-ALKOXYPROPIONAMIDE |
| WO2010067589A1 (en) * | 2008-12-10 | 2010-06-17 | 出光興産株式会社 | Method for producing β-alkoxypropionamide |
| US20110263898A1 (en) * | 2008-04-30 | 2011-10-27 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
-
1988
- 1988-09-20 JP JP63233633A patent/JPH082850B2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008102615A1 (en) * | 2007-02-20 | 2008-08-28 | Idemitsu Kosan Co., Ltd. | PROCESS FOR PRODUCING β-ALKOXYPROPIONAMIDE |
| US8338645B2 (en) | 2007-02-20 | 2012-12-25 | Idemitsu Kosan Co., Ltd. | Method for producing a β-alkoxypropionamide |
| JP5188492B2 (en) * | 2007-02-20 | 2013-04-24 | 出光興産株式会社 | Process for producing β-alkoxypropionamides |
| KR101410256B1 (en) * | 2007-02-20 | 2014-06-20 | 이데미쓰 고산 가부시키가이샤 | PROCESS FOR PRODUCING β-ALKOXYPROPIONAMIDE |
| US20110263898A1 (en) * | 2008-04-30 | 2011-10-27 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
| US8969621B2 (en) * | 2008-04-30 | 2015-03-03 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
| US9371273B2 (en) | 2008-04-30 | 2016-06-21 | Rhodia Operations | Ether-amide compounds and preparation and uses thereof |
| WO2010067589A1 (en) * | 2008-12-10 | 2010-06-17 | 出光興産株式会社 | Method for producing β-alkoxypropionamide |
| JP2010138094A (en) * | 2008-12-10 | 2010-06-24 | Idemitsu Kosan Co Ltd | METHOD FOR PRODUCING beta-ALKOXYPROPIONAMIDE |
| US8604240B2 (en) | 2008-12-10 | 2013-12-10 | Idemitsu Kosan Co., Ltd. | Method for producing β-alkoxypropionamide |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH082850B2 (en) | 1996-01-17 |
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