JPH04182452A - Production of aliphatic dicarboxylic acid monoester - Google Patents
Production of aliphatic dicarboxylic acid monoesterInfo
- Publication number
- JPH04182452A JPH04182452A JP2314780A JP31478090A JPH04182452A JP H04182452 A JPH04182452 A JP H04182452A JP 2314780 A JP2314780 A JP 2314780A JP 31478090 A JP31478090 A JP 31478090A JP H04182452 A JPH04182452 A JP H04182452A
- Authority
- JP
- Japan
- Prior art keywords
- formula
- dicarboxylic acid
- acid
- aliphatic dicarboxylic
- compound expressed
- 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
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 125000001931 aliphatic group Chemical group 0.000 title claims abstract description 26
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- -1 aliphatic dicarboxylic acid diester Chemical class 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- LBLYYCQCTBFVLH-UHFFFAOYSA-N 2-Methylbenzenesulfonic acid Chemical compound CC1=CC=CC=C1S(O)(=O)=O LBLYYCQCTBFVLH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 11
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 4
- 239000003905 agrochemical Substances 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000003814 drug Substances 0.000 abstract description 2
- 229940079593 drug Drugs 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract 8
- 239000003054 catalyst Substances 0.000 abstract 2
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 150000005690 diesters Chemical class 0.000 description 4
- WLJVNTCWHIRURA-UHFFFAOYSA-N pimelic acid Chemical compound OC(=O)CCCCCC(O)=O WLJVNTCWHIRURA-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 150000008282 halocarbons Chemical class 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 229940098779 methanesulfonic acid Drugs 0.000 description 2
- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 2
- LQVYKEXVMZXOAH-UHFFFAOYSA-N oct-4-enedioic acid Chemical compound OC(=O)CCC=CCCC(O)=O LQVYKEXVMZXOAH-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- BTVZFIIHBJWMOG-UHFFFAOYSA-N 2,2-dimethylhexanedioic acid Chemical compound OC(=O)C(C)(C)CCCC(O)=O BTVZFIIHBJWMOG-UHFFFAOYSA-N 0.000 description 1
- NQYXFXWKKYGBNL-UHFFFAOYSA-N 7-ethoxy-7-oxoheptanoic acid Chemical compound CCOC(=O)CCCCCC(O)=O NQYXFXWKKYGBNL-UHFFFAOYSA-N 0.000 description 1
- PYPIVBPZJONSOB-UHFFFAOYSA-N 8-methoxy-8-oxooct-4-enoic acid Chemical compound COC(=O)CCC=CCCC(O)=O PYPIVBPZJONSOB-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- WAGQZQAZCIOEDU-UHFFFAOYSA-N dec-5-enedioic acid Chemical compound OC(=O)CCCC=CCCCC(O)=O WAGQZQAZCIOEDU-UHFFFAOYSA-N 0.000 description 1
- MYYSSKJPRXUJHE-UHFFFAOYSA-N dec-5-ynedioic acid Chemical compound OC(=O)CCCC#CCCCC(O)=O MYYSSKJPRXUJHE-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- LKKOGZVQGQUVHF-UHFFFAOYSA-N diethyl heptanedioate Chemical compound CCOC(=O)CCCCCC(=O)OCC LKKOGZVQGQUVHF-UHFFFAOYSA-N 0.000 description 1
- OBUKBMOOXPTJOJ-UHFFFAOYSA-N dimethyl oct-4-enedioate Chemical compound COC(=O)CCC=CCCC(=O)OC OBUKBMOOXPTJOJ-UHFFFAOYSA-N 0.000 description 1
- ALOUNLDAKADEEB-UHFFFAOYSA-N dimethyl sebacate Chemical compound COC(=O)CCCCCCCCC(=O)OC ALOUNLDAKADEEB-UHFFFAOYSA-N 0.000 description 1
- OUYFGQOLBODYOK-UHFFFAOYSA-N dipropyl oct-4-ynedioate Chemical compound CCCOC(=O)CCC#CCCC(=O)OCCC OUYFGQOLBODYOK-UHFFFAOYSA-N 0.000 description 1
- YSZHWEFMJGSGMS-UHFFFAOYSA-N dodec-6-enedioic acid Chemical compound OC(=O)CCCCC=CCCCCC(O)=O YSZHWEFMJGSGMS-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- AMSLCAXTKHXISX-UHFFFAOYSA-N hex-3-ynedioic acid Chemical compound OC(=O)CC#CCC(O)=O AMSLCAXTKHXISX-UHFFFAOYSA-N 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- YHGNXQAFNHCBTK-OWOJBTEDSA-N trans-3-hexenedioic acid Chemical compound OC(=O)C\C=C\CC(O)=O YHGNXQAFNHCBTK-OWOJBTEDSA-N 0.000 description 1
- 239000002023 wood 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〉
本発明は医農薬中間体あるいは化成品中間体と巳で利用
される脂肪族ジカルボン酸モノエステルの製造方法に関
する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing an aliphatic dicarboxylic acid monoester that is used as a pharmaceutical or agrochemical intermediate or a chemical product intermediate.
〈従来の技術〉
脂肪族ジカルボン酸とアルコールとを脱水縮合し、モノ
エステル体を得る場合、目的のモノエステル体以外にジ
エステル体を副生ずることが知られている。<Prior Art> It is known that when an aliphatic dicarboxylic acid and an alcohol are dehydrated and condensed to obtain a monoester, a diester is produced as a by-product in addition to the desired monoester.
そこでジエステル体の副生をを抑える目的で、アルコー
ルの使用量を少なくすることが考えられるが、その場合
には未反応の脂肪族ジカルボン酸の回収が多くなり、転
化率の大幅な低下が避けられない。かかる方法の改良的
手段として特開昭５４−２２３１６においては、ジエス
テルの生成を抑制する目的で、アジピン酸ジメチルエス
テルを共存させるとともに、当モル以上の水を使用し、
酸性イオン交換樹脂に接触させて、アノピン酸モノメチ
ルエステルを得ている。しかしながら木方法においても
水を共存させる為、転化率が低く、満足できる方法では
なかった。Therefore, it may be possible to reduce the amount of alcohol used in order to suppress the by-product of diesters, but in that case, a large amount of unreacted aliphatic dicarboxylic acid would be recovered, and a significant drop in the conversion rate would be avoided. I can't. As an improvement to this method, in JP-A-54-22316, in order to suppress the production of diester, dimethyl adipic acid is allowed to coexist and water is used in an amount equal to or more than the same molar amount.
Anopic acid monomethyl ester is obtained by contacting with an acidic ion exchange resin. However, even in the wood method, the conversion rate was low due to the coexistence of water, and it was not a satisfactory method.
〈発明が解決しようとする課題〉
本発明者らは、より効率的な脂肪族ジカルボン酸モノエ
ステルの製造方法を検討し、原料である脂肪族ジカルボ
ン酸の転化率を高め、副生ずる脂肪族ジカルボン酸ジエ
ステル体の生成を抑え、しかも後の精製も有利に反応を
行う方法を見出し本発明を完成した。<Problems to be Solved by the Invention> The present inventors investigated a more efficient method for producing aliphatic dicarboxylic acid monoester, increased the conversion rate of the raw material aliphatic dicarboxylic acid, and reduced the by-produced aliphatic dicarboxylic acid monoester. The present invention has been completed by discovering a method for suppressing the formation of acid diesters and for conducting the reaction in an advantageous manner for subsequent purification.
〈解決するための手段〉
即ち、本発明は一般式ＣＩ［）
ＨｏｏＣ（ＣＨ１２）、Ｃ−Ｃ（ＣＨ２）、Ｃ０ＯＨ（
ＩＩ ］（式中、ｎおよびｍは１〜４の整数を表わし、
−は単結合、二重結合または三重結合を表わす。但し、
−が二重結合または三重結合である時はｎ＝用である。<Means for Solving> That is, the present invention provides the general formula CI[) HooC(CH12), C-C(CH2), C0OH(
II] (where n and m represent integers of 1 to 4,
- represents a single bond, double bond or triple bond. however,
When - is a double bond or triple bond, n=.
）
で示される脂肪族ジカルボン酸と、−数式ＣＩ［１３Ｒ
−ＯＨ（Ｉ［ｌ）
（式中、Ｒは炭素数１〜６のアルキル基を表わす。）
で示されるアルコールとを、酸触媒存在下、−数式Ｃ■
ｒ ’。) an aliphatic dicarboxylic acid represented by -formula CI[13R
-OH(I[l) (wherein, R represents an alkyl group having 1 to 6 carbon atoms) in the presence of an acid catalyst, -formula C■
r'.
ＲＯＯＣ（ＣＨｚ）−Ｃ−Ｃ（ＣＨｚ）。Ｃ０ＯＲ〔ｒ
ｖ：（式中、ｎ、ｍ、−及びＲは前記と同し意味を表わ
す。）
で示される脂肪族ジカルボン酸ノエステルを共存させ、
実質的に水を添加せずに反応させることを特徴とする一
般式〔１〕
ＲＯＯＣ（ＣＨ２）、（−Ｃ（ＣＨＩ）、Ｃ００）ｌ
Ｃｌ ）（式中、ｎ、ｍ、−及びＲは前記と同し意味
を表わす。）
で示される脂肪族ジカルボン酸モノエステルの製造方法
に関するものである。ROOC(CHz)-C-C(CHz). C0OR [r
v: (in the formula, n, m, - and R have the same meanings as above) coexisting with an aliphatic dicarboxylic acid noester,
General formula [1] ROOC(CH2), (-C(CHI), C00)l characterized in that the reaction is carried out without substantially adding water
The present invention relates to a method for producing an aliphatic dicarboxylic acid monoester represented by the following formula: Cl 2 ) (wherein n, m, - and R have the same meanings as above).
以下、本発明の詳細な説明する。The present invention will be explained in detail below.
本発明で使用される一般式［１１）で示される脂肪族ジ
カルボン酸としては、例えば、アジピン酸、ピメリン酸
、スペリン酸、アゼライン酸、セバシン酸、２−ブテン
−１，４−ジカルボン酸、３−ヘキセン−１，６−ジカ
ルボン酸、４−オクテン−１，８−ジカルボン酸、５−
デセン−１，１０−ジカルボン酸、２−ブチン−１，４
−ジカルボン酸、３−ヘキシン−１，６−ンカルボン酸
、４−オクチン−１，８−ジカルボン酸、５−デシン−
ＬＩＯ−ジカルボン酸等を例示することができる。Examples of the aliphatic dicarboxylic acids represented by the general formula [11] used in the present invention include adipic acid, pimelic acid, superric acid, azelaic acid, sebacic acid, 2-butene-1,4-dicarboxylic acid, -hexene-1,6-dicarboxylic acid, 4-octene-1,8-dicarboxylic acid, 5-
Decene-1,10-dicarboxylic acid, 2-butyne-1,4
-dicarboxylic acid, 3-hexyne-1,6-onecarboxylic acid, 4-octyne-1,8-dicarboxylic acid, 5-decyne-
Examples include LIO-dicarboxylic acid.
もう一方の原料である一般式（ｍ ３で示されるアルコ
ールとしては、例えば、メタノール、エタノール、ｎ−
プロパツール、イソプロパツール、ｎ−ブタノール、イ
ソブタノール、し−ブタノール、ｎ−オクタツール、イ
ソオクタツール、ｎ −ヘキサノール等を例示すること
ができる。The alcohol represented by the general formula (m3), which is the other raw material, includes, for example, methanol, ethanol, n-
Examples include propatool, isoproptool, n-butanol, isobutanol, thi-butanol, n-octatool, isooctatool, n-hexanol, and the like.
該アルコール［ｌｌ１）の使用量は脂肪族ジカルボン酸
〔ＩＩ〕１モルに対し、０７モル以上、１４モル以下が
好ましい。The amount of alcohol [ll1) to be used is preferably 0.7 mol or more and 14 mol or less per 1 mol of aliphatic dicarboxylic acid [II].
共存させる一般式（ＩＶＩで示される脂肪族ジカルボン
酸ジエステルの量は、脂肪族ジカルボン酸Ｃｌｌ１１モ
ルに対し、０．３モル以上、１．３モル以下が好ましい
。The amount of the aliphatic dicarboxylic acid diester represented by the general formula (IVI) to be coexisting is preferably 0.3 mol or more and 1.3 mol or less per 11 mol of aliphatic dicarboxylic acid Cl.
本反応においては有機溶媒の使用が有効である。In this reaction, it is effective to use an organic solvent.
かかる溶媒としては、例えば、トルエン、ヘンゼン、キ
シレン、クロルベンゼン、ジクロルベンゼン、メチルエ
チルケトン、メチルイソブチルケトン、ジクロルエタン
、ジオキサン等の芳香族炭化水素、ハロゲン化炭化水素
、ケトン、エーテル類を挙げることができる。Examples of such solvents include aromatic hydrocarbons, halogenated hydrocarbons, ketones, and ethers such as toluene, henzene, xylene, chlorobenzene, dichlorobenzene, methyl ethyl ketone, methyl isobutyl ketone, dichloroethane, and dioxane. .
なかでも後処理の点から、原料の脂肪族ジカルボン酸（
ＩＩ）に対し、冷時溶解度の低いものが好ましく、かか
る意味からトルエン、ベンゼン、キシレン、クロルベン
ゼン等の芳香族炭化水素や、ジクロルエタン等のハロゲ
ン化炭化水素が好ましい。Among these, from the point of view of post-processing, the raw material aliphatic dicarboxylic acid (
In contrast to II), those having low cold solubility are preferable, and from this point of view, aromatic hydrocarbons such as toluene, benzene, xylene, and chlorobenzene, and halogenated hydrocarbons such as dichloroethane are preferable.
かかる溶媒の使用量は特に制限されないが、通常、原料
の、脂肪族ジカルボン酸に対し０．５〜５重量倍程度で
ある。The amount of the solvent to be used is not particularly limited, but is usually about 0.5 to 5 times the weight of the aliphatic dicarboxylic acid as the raw material.
酸触媒としては、例えば、硫酸、トルエンスルホン酸、
メタンスルホン酸、酸性イオン交換樹脂、リン酸、塩化
水素、硝酸等の無機または有機の酸が利用されるが、中
でも、トルエンスルホン酸、ｇｆｍ、メタンスルホン酸
が好ましい。Examples of acid catalysts include sulfuric acid, toluenesulfonic acid,
Inorganic or organic acids such as methanesulfonic acid, acidic ion exchange resins, phosphoric acid, hydrogen chloride, and nitric acid are used, and among them, toluenesulfonic acid, gfm, and methanesulfonic acid are preferred.
該酸触媒の使用量は通常、原料である脂肪族ジカルボン
酸〔ＩＩ］に対して０．５〜５重量％の範囲である。The amount of the acid catalyst used is usually in the range of 0.5 to 5% by weight based on the raw material aliphatic dicarboxylic acid [II].
また本発明において、実質的己こ水を添加セずとは、水
を意図的に加えることを行わないと言う意味であり、全
く水が存在してはならないということではない。従って
、酸触媒中の水分等、例えば硫酸、リン酸、硝酸中に含
まれる水は十分許容されるのである。Furthermore, in the present invention, not adding substantial water means not intentionally adding water, but does not mean that water should not be present at all. Therefore, water in acid catalysts, such as water contained in sulfuric acid, phosphoric acid, and nitric acid, is fully tolerated.
反応温度は通常、６０〜１２０°Ｃの範囲であり、溶媒
の沸点により適宜定めることができる。The reaction temperature is usually in the range of 60 to 120°C and can be appropriately determined depending on the boiling point of the solvent.
反応時間は特に制限されないが、通常１〜８時間の範囲
である。The reaction time is not particularly limited, but is usually in the range of 1 to 8 hours.
反応終了後、反応混合物からの脂肪族ジカルボン酸モノ
エステル〔Ｉ〕の単離は、例えば、反応液を冷却し、未
反応の脂肪族ジカルボン酸を結晶として除いたあと、有
機層を濃縮、蒸留してもよいし、有機層をアルカリを用
いて抽出し、水層を酸析後さらに溶媒にて抽出後、濃縮
、蕉留によっても精製できる。After the reaction is completed, the aliphatic dicarboxylic acid monoester [I] can be isolated from the reaction mixture by, for example, cooling the reaction solution, removing unreacted aliphatic dicarboxylic acid as crystals, and then concentrating and distilling the organic layer. Alternatively, the organic layer can be extracted with an alkali, the aqueous layer can be acid-precipitated, further extracted with a solvent, concentrated, and purified by distillation.
かかる操作により、−数式（１）で示される脂肪族ジカ
ルボン酸モノエステルが効率よく得られる。Through this operation, an aliphatic dicarboxylic acid monoester represented by formula (1) can be efficiently obtained.
〈発明の効果〉
本発明により、原料である脂肪族ジカルボン酸（Ｉｔ）
の転化率を高め、脂肪族ジカルボン酸ジエステルＣｒＶ
）の副生を抑えることにより、−数式〔ＩＩで示される
脂肪族ジカルボン酸モノエステルが高い収率で、しかも
工業的にも有利に得られる。該脂肪族ジカルボン酸モノ
エステルは医薬、農薬、添加剤、化成品等の中間体とし
て有用である。<Effects of the Invention> According to the present invention, the raw material aliphatic dicarboxylic acid (It)
Increases the conversion rate of aliphatic dicarboxylic acid diester CrV
By suppressing the by-product of ), the aliphatic dicarboxylic acid monoester represented by formula [II] can be obtained in high yield and industrially advantageously. The aliphatic dicarboxylic acid monoester is useful as an intermediate for medicines, agricultural chemicals, additives, chemical products, and the like.
〈実施例〉 以下、実施例により本発明を更に詳細に説明する。<Example> Hereinafter, the present invention will be explained in more detail with reference to Examples.
実施例１
ピメリンＭ１６．０２ｇ（０，１ｍｏｌ）、ピメリン酸
ジエチルエステル１２．９７ｇ（０，０６ｍｏｌ） 、
エタノール４．６１ｇ（０，１ｍｏｌ） 、濃硫酸０．
３２ｇ及びベンゼン３２ｇを加え、攪拌下５時間還流し
た。反応終了後、反応液を分析したところ、ピメリン酸
の消費は８６Ｘであり、ピメリン酸モノエチルエステル
の選択率は９０χであった。Example 1 Pimeline M 16.02g (0.1mol), pimelic acid diethyl ester 12.97g (0.06mol),
Ethanol 4.61g (0.1mol), concentrated sulfuric acid 0.
32 g and 32 g of benzene were added, and the mixture was refluxed for 5 hours while stirring. After the reaction was completed, the reaction solution was analyzed, and the consumption of pimelic acid was 86X, and the selectivity of pimelic acid monoethyl ester was 90X.
実施例２
スペリンＭ１７．４２ｇ（０，１ｍｏｌ）、スヘリン酸
ジメチルエステル１６．１８ｇ（０，０８ｍｏｌ） 、
メタノール２．８８ｇ（０，０９ｍｏｌ）、ｐ−トルエ
ンスルホン酸０．２６ｇ及びトルエン４０ｇを加え、８
０〜８５°Ｃにて７時間加熱攪拌した。反応終了後、反
応液を分析したところ、スヘリン酸の消費量は８２χで
あり、スペリン酸モノメチルエステルの選択率は９３′
Ａであった。反応？Ｆｌは０〜５°Ｃに冷却し、未反応
のスヘリン酸をろ別して除き、ろ液を蕉留にて精製し、
後留として、スペリン酸モノメチルエステルを得た。Example 2 Sperine M 17.42 g (0.1 mol), sheric acid dimethyl ester 16.18 g (0.08 mol),
Add 2.88 g (0.09 mol) of methanol, 0.26 g of p-toluenesulfonic acid and 40 g of toluene,
The mixture was heated and stirred at 0 to 85°C for 7 hours. After the reaction was completed, the reaction solution was analyzed, and the consumption amount of sheric acid was 82χ, and the selectivity of speric acid monomethyl ester was 93'
It was A. reaction? Fl was cooled to 0-5°C, unreacted sheric acid was removed by filtration, and the filtrate was purified by distillation.
Monomethyl sperate was obtained as a residue.
ｂ、ｐ、１３３〜１３５°（１０，５ｍｍｌ（ｇ実施例
３
３−ヘキセン−１，６−ジカルボン酸１７．２２ｇ（０
，１ｍｏ！ 、３−ヘキセン−１，６−ジカルボン酸ジ
メチルエステル２４．０３ｇ（０，１２ｍｏｌ） 、メ
タノール２．５６ｇ（０，０８ｍｏｌ）、濃硫酸０．５
１ｇ及びトルエン５１ｇを７０〜７５°Ｃにて８時間加
熱した。反応終了後、反液を分析したところ、３−ヘキ
セン−１，６−ジカルボン酸の消費量は、７３Ｘであり
、３−ヘキセン−１，６−ジカルボン酸モノメチルエス
テルの選択率は９１χであった。b, p, 133-135° (10,5 mml (g) Example 3 3-hexene-1,6-dicarboxylic acid 17.22 g (0
,1mo! , 3-hexene-1,6-dicarboxylic acid dimethyl ester 24.03 g (0.12 mol), methanol 2.56 g (0.08 mol), concentrated sulfuric acid 0.5
1 g and 51 g of toluene were heated at 70-75°C for 8 hours. After the reaction was completed, the reaction solution was analyzed, and the consumption amount of 3-hexene-1,6-dicarboxylic acid was 73X, and the selectivity of 3-hexene-1,6-dicarboxylic acid monomethyl ester was 91χ .
実施例４
３−ハキノン−１，６−ジカルボン酸１７．０２ｇ（０
，１ｍｏｌ） 、３−ヘキシン−１，６−ジカルボン酸
ジｎ−プロピルエステル１２．７１ｇ（０，０５ｍｏｌ
） 、ｎ−プロパツール８．４１ｇ（０，１４ｍｏｌ）
、ｐ−トルエンスルホン酸０．３４ｇ及びメチルイソブ
チルケトン３５ｇを９０°Ｃにて６時間加熱した。反応
終了後、反応液を分析すると、３−ヘキシン−１，６−
ジカルボン酸の消費は９１χであり、３−ヘキシン−１
，６−ジカルボン酸モノｎ−プロピルエステルの選択率
は８０％であった。Example 4 17.02 g of 3-haquinone-1,6-dicarboxylic acid (0
, 1 mol), 12.71 g (0.05 mol) of 3-hexyne-1,6-dicarboxylic acid di-n-propyl ester
), n-propatool 8.41g (0.14mol)
, 0.34 g of p-toluenesulfonic acid and 35 g of methyl isobutyl ketone were heated at 90°C for 6 hours. After the reaction was completed, the reaction solution was analyzed and found that 3-hexyne-1,6-
Consumption of dicarboxylic acid is 91χ, 3-hexyne-1
, 6-dicarboxylic acid mono-n-propyl ester selectivity was 80%.
実施例５
セバシン酸２０．２２ｇ（０，１ｍｏｌ）、セバシン酸
ジメチルエステル２０．７２ｇ（０，０９ｍｏｌ） 、
メタノール２．８８ｇ（０，０９ｍｏｌ）、ｐ−）ルエ
ンスルホンｌｔ０．２０ｇ及びシクロルエタン４０ｇを
還流下に８時間反応した。反応混合物を分析したところ
、セバシン酸の転化率は８０χであり、セハンン酸モノ
メチルエステルの選択率は８３ｚであった。Example 5 20.22 g (0.1 mol) of sebacic acid, 20.72 g (0.09 mol) of sebacic acid dimethyl ester,
2.88 g (0.09 mol) of methanol, 0.20 g of p-)luenesulfone, and 40 g of cycloethane were reacted under reflux for 8 hours. Analysis of the reaction mixture revealed that the conversion rate of sebacic acid was 80x and the selectivity of sehanic acid monomethyl ester was 83z.
比較例〔実施例２に水を１０ｗｔχ （対ジカルボン酸
）加えた例〕
スペリンａ１７．４２ｇ（０，１ｍｏｌ）、スヘリン酸
ジメチルエステル１６．１８ｇ（０，０８ｍｏｌ） 、
メタノール２．８８ｇ（０，０９ｍｏｌ）、ｐ−）ルエ
ンスルホン酸０．２６ｇ及びトルエン４０ｇ 、水１．
７４ｇ（スヘリン酸に対し１（ｈｔえ、０．０９７ｍｏ
ｌ）を加え、８０〜８５°Ｃにて７時間加熱攪拌した。Comparative example [Example in which 10 wtx (to dicarboxylic acid) of water was added to Example 2] 17.42 g (0.1 mol) of sperine a, 16.18 g (0.08 mol) of sheric acid dimethyl ester,
2.88 g (0.09 mol) of methanol, 0.26 g of p-)luenesulfonic acid and 40 g of toluene, 1.
74g (1 (ht), 0.097mo for sheric acid)
1) was added, and the mixture was heated and stirred at 80 to 85°C for 7 hours.
反応終了後、反応液を分析したところ、スヘリン酸の消
費量は６８χであり、スヘリン酸モノメチルエステルの
選択率は９１χであった。反応液は０〜５°Ｃに冷却し
、未反応のスヘリン酸をろ別して除き、ろ液を遺留にて
晴製し、復習として、スヘリン酸モノメチルエステルを
得た。After the reaction was completed, the reaction solution was analyzed, and the consumption amount of schelic acid was 68χ, and the selectivity of schelic acid monomethyl ester was 91χ. The reaction solution was cooled to 0 to 5°C, unreacted schelic acid was removed by filtration, and the filtrate was distilled to obtain schelic acid monomethyl ester as a review.
Claims (5)
合、二重結合または三重結合を表わす。但し、■が二重
結合または三重結合である時はｎ＝ｍである。） で示される脂肪族ジカルボン酸と、一般式〔III〕Ｒ−
ＯＨ〔III〕 （式中、Ｒは炭素数１〜６のアルキル基を表わす。） で示されるアルコールとを、酸触媒存在下、一般式〔I
V〕 ▲数式、化学式、表等があります▼〔IV〕 （式中、ｎ、ｍ、■及びＲは前記と同じ意味を表わす。 ） で示される脂肪族ジカルボン酸ジエステルを共存させ、
実質的に水を添加せずに反応させることを特徴とする一
般式〔 I 〕 ▲数式、化学式、表等があります▼〔 I 〕 （式中、ｎ、ｍ、■及びＲは前記と同じ意味を表わす。 ） で示される脂肪族ジカルボン酸モノエステルの製造方法
。(1) General formula [II] ▲Mathematical formulas, chemical formulas, tables, etc.▼[II] (In the formula, n and m represent integers from 1 to 4, and ■ represents a single bond, double bond, or triple bond. (However, when ■ is a double bond or triple bond, n=m.) An aliphatic dicarboxylic acid represented by the formula [III] R-
An alcohol represented by OH [III] (in the formula, R represents an alkyl group having 1 to 6 carbon atoms) is reacted with the alcohol represented by the general formula [I] in the presence of an acid catalyst.
V] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[IV] (In the formula, n, m, ■ and R represent the same meanings as above.) Coexisting with an aliphatic dicarboxylic acid diester,
General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼[I] (In the formula, n, m, ■, and R have the same meanings as above. ) A method for producing an aliphatic dicarboxylic acid monoester.
カルボン酸〔II〕に対し０．７モル以上１．４モル以下
であることを特徴とする請求項１記載の方法。(2) The method according to claim 1, wherein the molar ratio of the alcohol [III] to the aliphatic dicarboxylic acid [II] is 0.7 mol or more and 1.4 mol or less.
モル比が脂肪族ジカルボン酸〔II〕に対し０．３モル以
上１．３モル以下であることを特徴とする請求項１また
は２記載の方法。(3) The molar ratio of the coexisting aliphatic dicarboxylic acid diester [IV] to the aliphatic dicarboxylic acid [II] is 0.3 mol or more and 1.3 mol or less Method.
求項１、２または３記載の方法。(4) The method according to claim 1, 2 or 3, characterized in that the reaction is carried out in an organic solvent.
とを特徴とする請求項１、２、３または４に記載の方法
。(5) The method according to claim 1, 2, 3 or 4, wherein the acid catalyst is toluenesulfonic acid or sulfuric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2314780A JP2943318B2 (en) | 1990-11-19 | 1990-11-19 | Method for producing aliphatic dicarboxylic acid monoester |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2314780A JP2943318B2 (en) | 1990-11-19 | 1990-11-19 | Method for producing aliphatic dicarboxylic acid monoester |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04182452A true JPH04182452A (en) | 1992-06-30 |
| JP2943318B2 JP2943318B2 (en) | 1999-08-30 |
Family
ID=18057506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2314780A Expired - Fee Related JP2943318B2 (en) | 1990-11-19 | 1990-11-19 | Method for producing aliphatic dicarboxylic acid monoester |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2943318B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016495A1 (en) * | 1996-10-15 | 1998-04-23 | Mitsubishi Rayon Co., Ltd. | Processes for the preparation of dicarboxylic acid monoesters |
| CN102826998A (en) * | 2012-05-23 | 2012-12-19 | 四川西普化工股份有限公司 | Method for catalyzing synthesizing diisooctyl azelate through load type heteropolyacid |
| CN113880715A (en) * | 2021-10-08 | 2022-01-04 | 万华化学集团股份有限公司 | Purification method for electrochemically synthesizing dimethyl sebacate |
-
1990
- 1990-11-19 JP JP2314780A patent/JP2943318B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998016495A1 (en) * | 1996-10-15 | 1998-04-23 | Mitsubishi Rayon Co., Ltd. | Processes for the preparation of dicarboxylic acid monoesters |
| US6355830B1 (en) | 1996-10-15 | 2002-03-12 | Mitsubishi Rayon Co., Ltd. | Process for preparation of dicarboxylic acid monoesters |
| CN1125808C (en) * | 1996-10-15 | 2003-10-29 | 三菱丽阳株式会社 | Process for preparation of dicarboxylic acid monoesters |
| CN102826998A (en) * | 2012-05-23 | 2012-12-19 | 四川西普化工股份有限公司 | Method for catalyzing synthesizing diisooctyl azelate through load type heteropolyacid |
| CN113880715A (en) * | 2021-10-08 | 2022-01-04 | 万华化学集团股份有限公司 | Purification method for electrochemically synthesizing dimethyl sebacate |
| CN113880715B (en) * | 2021-10-08 | 2024-02-02 | 万华化学集团股份有限公司 | Purification method for electrochemical synthesis of dimethyl sebacate |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2943318B2 (en) | 1999-08-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6143133A (en) | Manufacture of anhydrous or almost anhydrous formic acid | |
| JPH04182452A (en) | Production of aliphatic dicarboxylic acid monoester | |
| KR970009318B1 (en) | Process for the preparation of stilbenedicarboxylic derivatives | |
| US6491795B2 (en) | Process for recovering benzyl benzoate | |
| US6235924B1 (en) | Continuous process for preparing benzoic acid esters | |
| JPH0840983A (en) | Production of lactic acid ester | |
| JP3682805B2 (en) | Method for producing saturated aliphatic carboxylic acid amide | |
| JPH061752A (en) | Production of arylacrylic acids and their esters | |
| JP3640319B2 (en) | Method for producing benzamide derivative | |
| CN113801125B (en) | Preparation method of cyclic anhydride | |
| JPH0643367B2 (en) | Benzoic acid purification method | |
| JPH01233255A (en) | Cyclopentenone derivative and production thereof | |
| JPS59137431A (en) | Production of trimethylolheptane | |
| JPS63250353A (en) | Production of terephthalic acid dianilides | |
| CN115232058A (en) | Synthesis method of gliclazide intermediate 1,2-cyclopentanedicarboxamide | |
| JP3287682B2 (en) | Method for producing N-cyanoethane imidate | |
| US2338569A (en) | Preparation of coumarin-3-carboxylic acid | |
| JPS617262A (en) | Preparation of 2-oxazolidinone compound | |
| JPS63130564A (en) | Production of benzoylacrylic acid esters | |
| JP3164666B2 (en) | Process for producing N-substituted carbamate aryl esters | |
| SU798095A1 (en) | Method of preparing 4(2)-dimethylaminonaphthalene-1,8-dicarboxylic acid anhydride | |
| RU2106349C1 (en) | Method of preparing phenicaberane | |
| JPH07233130A (en) | Production of aminobenzoic alkyl ester | |
| JPH1180088A (en) | Production of ethyl pyruvate | |
| JPH03148239A (en) | Preparation of carboxylic polycyclic alkyl ester |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| S533 | Written request for registration of change of name |
Free format text: JAPANESE INTERMEDIATE CODE: R313533 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080625 Year of fee payment: 9 |
|
| RD05 | Notification of revocation of power of attorney |
Free format text: JAPANESE INTERMEDIATE CODE: R3D05 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090625 Year of fee payment: 10 |
|
| LAPS | Cancellation because of no payment of annual fees |