JPS6313418B2 - - Google Patents
Info
- Publication number
- JPS6313418B2 JPS6313418B2 JP57140657A JP14065782A JPS6313418B2 JP S6313418 B2 JPS6313418 B2 JP S6313418B2 JP 57140657 A JP57140657 A JP 57140657A JP 14065782 A JP14065782 A JP 14065782A JP S6313418 B2 JPS6313418 B2 JP S6313418B2
- Authority
- JP
- Japan
- Prior art keywords
- butene
- acid diester
- adipic acid
- producing
- butadiene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- WNLRTRBMVRJNCN-UHFFFAOYSA-N hexanedioic acid Natural products OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 32
- -1 3-pentenoic acid ester Chemical class 0.000 claims description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 26
- IAQRGUVFOMOMEM-UHFFFAOYSA-N but-2-ene Chemical compound CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 claims description 24
- 239000001361 adipic acid Substances 0.000 claims description 22
- 235000011037 adipic acid Nutrition 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 14
- XNMQEEKYCVKGBD-UHFFFAOYSA-N dimethylacetylene Natural products CC#CC XNMQEEKYCVKGBD-UHFFFAOYSA-N 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 238000005649 metathesis reaction Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 4
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- 150000001869 cobalt compounds Chemical class 0.000 claims 2
- 150000003512 tertiary amines Chemical class 0.000 claims 2
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 claims 1
- 150000005690 diesters Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- KJALUUCEMMPKAC-ONEGZZNKSA-N methyl (e)-pent-3-enoate Chemical compound COC(=O)C\C=C\C KJALUUCEMMPKAC-ONEGZZNKSA-N 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- UDSFAEKRVUSQDD-UHFFFAOYSA-N Dimethyl adipate Chemical compound COC(=O)CCCCC(=O)OC UDSFAEKRVUSQDD-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- CPSQPCGPYWRIPB-UHFFFAOYSA-N dimethyl hex-3-enedioate Chemical compound COC(=O)CC=CCC(=O)OC CPSQPCGPYWRIPB-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N DMSO Substances CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MQIKJSYMMJWAMP-UHFFFAOYSA-N dicobalt octacarbonyl Chemical group [Co+2].[Co+2].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] MQIKJSYMMJWAMP-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 229910052718 tin Inorganic materials 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【発明の詳細な説明】
本発明は１，３−ブタジエンのヒドロエステル
化反応により３−ペンテン酸エステルを製造し、
続いて３−ペンテン酸エステルのメタセシス反応
により２−ブテン−１，４−ジカルボン酸ジエス
テルと２−ブテンを製造し、２−ブテンは脱水素
し１，３−ブタジエンとして第１工程に循環さ
せ、続いて２−ブテン−１，４−ジカルボン酸ジ
エステルを水添してアジピン酸ジエステルを工業
的に有利に製造する方法、およびさらに、アジピ
ン酸ジエステルを加水分解してアジピン酸を工業
的に有利に製造する方法に関する。Detailed Description of the Invention The present invention produces 3-pentenoic acid ester by hydroesterification reaction of 1,3-butadiene,
Subsequently, 2-butene-1,4-dicarboxylic acid diester and 2-butene are produced by a metathesis reaction of 3-pentenoic acid ester, and 2-butene is dehydrogenated and recycled to the first step as 1,3-butadiene. Subsequently, a method for producing adipic acid diester industrially advantageously by hydrogenating 2-butene-1,4-dicarboxylic acid diester, and further a method for producing adipic acid diester industrially advantageously by hydrolyzing the adipic acid diester. Relating to a method of manufacturing.
さらに詳しくは、１，３−ブタジエンのヒドロ
エステル化反応により製造される３−ペンテン酸
エステルのメタセシス反応をMo塩化物と低級ア
ルキルSn化合物からなる触媒に接触させて２−
ブテン−１，４−ジカルボン酸ジエステルと２−
ブテンを製造し、２−ブテンは脱水素し１，３−
ブタジエンとして第１工程に循環させ、続いて２
−ブテン−１，４−ジカルボン酸ジエステルを水
添してアジピン酸ジエステルを高収率、高選択率
で工業的に製造する方法、およびさらにアジピン
酸ジエステルを加水分解してアジピン酸を高収
率、高選択率で工業的に製造する方法に関するも
のである。 More specifically, 2-
Butene-1,4-dicarboxylic acid diester and 2-
Butene is produced, 2-butene is dehydrogenated and 1,3-
recycled to the first step as butadiene, followed by 2
- A method for industrially producing adipic acid diester in high yield and high selectivity by hydrogenating butene-1,4-dicarboxylic acid diester, and further hydrolyzing adipic acid diester to produce adipic acid in high yield. , relates to a method for industrial production with high selectivity.
アジピン酸はナイロン６，６の原料、あるいは
エステル化して可塑剤および潤滑油添加剤またポ
リアルコールとエステル化しポリエステルとして
用いられる工業上有用な化合物であり、その製造
方法は種々知られているが、メタセシス反応を用
いた製造方法は知られていない。 Adipic acid is an industrially useful compound that is used as a raw material for nylon 6,6, or as a polyester by esterifying it with plasticizers and lubricating oil additives or polyalcohols, and various methods for its production are known. A production method using a metathesis reaction is not known.
本願発明者らは、１，３−ブタジエンを出発原
料とするアジピン酸製造の新プロセスを開発すべ
く鋭意研究を行なつた結果、第１工程で１，３−
ブタジエンをヒドロエステル化して３−ペンテン
酸エステルを製造し、第２工程で３−ペンテン酸
メチルを、Mo塩化物と低級アルキルSn化合物と
からなる触媒を用いてメタセシス反応を行ない、
２−ブテン−１，４−ジカルボン酸ジエステルと
２−ブテンを製造し、さらに２−ブテンを酸化的
脱水素して１，３−ブタジエンを製造し第１工程
に循環させ、第３工程で２−ブテン−１，４−ジ
カルボン酸ジエステルを水添してアジピン酸ジエ
ステルを製造する全く新規なプロセスを、および
さらに第４工程でアジピン酸ジエステルを加水分
解してアジピン酸を製造する全く新規なプロセス
を見い出し、本発明に到達したものである。 The inventors of the present application have conducted intensive research to develop a new process for producing adipic acid using 1,3-butadiene as a starting material.
butadiene is hydroesterified to produce 3-pentenoic acid ester, and in the second step, methyl 3-pentenoate is subjected to a metathesis reaction using a catalyst consisting of Mo chloride and a lower alkyl Sn compound,
2-butene-1,4-dicarboxylic acid diester and 2-butene are produced, and 2-butene is further oxidatively dehydrogenated to produce 1,3-butadiene, which is recycled to the first step, and in the third step, 2-butene is produced. - A completely new process for producing adipic acid diester by hydrogenating butene-1,4-dicarboxylic acid diester, and a completely new process for producing adipic acid by further hydrolyzing the adipic acid diester in the fourth step. This is what led to the present invention.
本発明の各工程の先行技術として次の様なこと
が知られている。すなわち第１工程の１，３−ブ
タジエンのヒドロエステル化による３−ペンテン
酸メチルの製造には、例えば特公昭49−20177号
公報、特開昭53−119816号公報、特開昭57−
48941号公報が知られており、これらいずれの方
法も採用し得る。第２工程のメタセシスの先行技
術としては、触媒がWCl6とMe4Snからなる方法
（E.Verkuijlen.R.J.Dirks and C.Boelhouwer、
Red Trav Chim.〔Pays Bas〕、96（1977）M86）
および触媒がWCl6とEt3Bからなる方法（中村
ら、Chem.Lete.、（1976）253、特開昭50−
100011号公報）が知られている。 The following is known as prior art for each step of the present invention. That is, for the production of methyl 3-pentenoate by hydroesterification of 1,3-butadiene in the first step, for example, Japanese Patent Publication No. 49-20177, JP-A-53-119816, JP-A-57-
No. 48941 is known, and any of these methods can be adopted. The prior art for metathesis in the second step is a method in which the catalyst consists of WCl 6 and Me 4 Sn (E. Verkuijlen, RJ Dirks and C. Boelhouwer,
Red Trav Chim. [Pays Bas], 96 (1977) M86)
and a method in which the catalyst consists of WCl 6 and Et 3 B (Nakamura et al., Chem. Lete., (1976) 253, JP-A-1972-
100011) is known.
しかし第２工程においてWCl6とMe4Snからな
る触媒系では２−ブテン−１，４−ジカルボン酸
ジエステルの収率は24％と低く、WCl6とEt3Bか
らなる触媒系では90℃で14時間反応させて収率60
％を得ているに過ぎない。 However, in the second step, the yield of 2-butene-1,4-dicarboxylic acid diester was as low as 24% with the catalyst system consisting of WCl 6 and Me 4 Sn, and the yield of 2-butene-1,4-dicarboxylic acid diester was as low as 24% with the catalyst system consisting of WCl 6 and Et 3 B. Yield 60 after 14 hours reaction
It's just a percentage.
本願発明者らは第２工程の改良を鋭意検討した
結果驚くべきことにはMo塩化物と低級アルキル
Sn化合物からなる触媒系、特にMoCl5とMe4Sn
からなる触媒系が前記触媒系よりも高活性である
ことを見い出し、すでに特許出願中である。 The inventors of the present application conducted intensive studies to improve the second step, and surprisingly found that Mo chloride and lower alkyl
Catalytic systems consisting of Sn compounds, especially MoCl 5 and Me 4 Sn
It has been discovered that a catalyst system consisting of the above-mentioned catalyst system has higher activity than the above-mentioned catalyst system, and a patent application is already pending.
２−ブテンの酸化的脱水素による１，３−ブタ
ジエンの製造には、例えばUSP3801670明細書、
USP3824195明細書およびUSP3828101明細書が
知られており、これらいずれの方法も採用し得
る。第３工程の２−ブテン−１，４−ジカルボン
酸ジエステルの水添は通常行われている方法でよ
く、例えばパラジウム／活性炭、ラネーニツケル
等が触媒として用いられる。第４工程のアジピン
酸ジエステルの加水分解は通常行われている方法
でよく、例えば塩酸、水酸化ナトリウム等が触媒
として用いられる。 For the production of 1,3-butadiene by oxidative dehydrogenation of 2-butene, for example, USP 3801670,
USP3824195 specification and USP3828101 specification are known, and any of these methods can be adopted. The hydrogenation of 2-butene-1,4-dicarboxylic acid diester in the third step may be carried out by a conventional method, for example, palladium/activated carbon, Raney nickel, etc. are used as a catalyst. Hydrolysis of the adipic acid diester in the fourth step may be carried out by a commonly used method, and for example, hydrochloric acid, sodium hydroxide, etc. are used as a catalyst.
本発明の第１、３、４工程は公知の技術である
が、第２工程の３−ペンテン酸エステルのメタセ
シス反応は全く新期なプロセスであり、第２工程
を経由する点で本発明は新規なプロセスである。 The first, third, and fourth steps of the present invention are known techniques, but the second step, the metathesis reaction of 3-pentenoic acid ester, is a completely new process, and the present invention is unique in that it goes through the second step. This is a new process.
本発明は、各工程ともに選択率が高いことを特
徴とする。特に新規なプロセスである第２工程に
おいて選択率が高いことを特徴とする。 The present invention is characterized by high selectivity in each step. It is characterized by a particularly high selectivity in the second step, which is a new process.
以下実施例により本発明をさらに詳細に説明を
するが本発明はこれに限定されるものではない。 The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited thereto.
実施例 １
ステンレス製、内容積50mlの電磁撹拌式オート
クレーブにブタジエン15.1ｇ（0.280モル）、メタ
ノール10.9ｇ（0.340モル）、ジコバルトオクタカ
ルボニル0.512ｇ（0.0015モル）、およびイソキノ
リン19.4ｇ（0.150モル）を加えた。一酸化炭素
を室温下300Kg／cm2充填して120℃で２時間反応さ
せた。続いて冷却後、反応混合物より一酸化炭素
を放圧し、常法により蒸留すると、３−ペンテン
酸メチルが27.6ｇ（0.240モル）、収率86％、選択
率96％で得られた。Example 1 15.1 g (0.280 mol) of butadiene, 10.9 g (0.340 mol) of methanol, 0.512 g (0.0015 mol) of dicobalt octacarbonyl, and 19.4 g (0.150 mol) of isoquinoline were placed in a stainless steel, electromagnetic stirring autoclave with an internal volume of 50 ml. added. Carbon monoxide was charged at 300 kg/cm 2 at room temperature, and the reaction was carried out at 120° C. for 2 hours. Subsequently, after cooling, carbon monoxide was released from the reaction mixture and distillation was performed by a conventional method to obtain 27.6 g (0.240 mol) of methyl 3-pentenoate in a yield of 86% and a selectivity of 96%.
３−ペンテン酸メチルNMR（CCl4／TMS）
δ1.60（3H、ｍ、CH3−Ｃ）
2.83（2H、ｍ、−CH2−）
3.47（3H、ｓ、CH3−Ｏ）
5.30（2H、ｍ、−CH＝CH−）
実施例 ２
あらかじめよく乾燥し窒素置換された500mlフ
ラスコに五塩化モリブデン2.2ｇ（0.008モル）、
３−ペンテン酸メチル27.6ｇ（0.240モル）、およ
び１，２−ジクロルエタン160mlを加えて浴温80
℃で0.5時間加熱、撹拌した後、テトラメルスズ
1.4ｇ（0.008モル）を加えて浴温100℃で２時間
還流反応させた。続いて常法により後処理して蒸
留すると２−ブテン−１，４−ジカルボン酸ジメ
チルが13.8ｇ（0.0804モル）、メタセシス収率67
％、選択率96％で得られた。Methyl 3-pentenoate NMR (CCl 4 /TMS) δ1.60 (3H, m, CH 3 -C) 2.83 (2H, m, -CH 2 -) 3.47 (3H, s, CH 3 -O) 5.30 (2H , m, -CH=CH-) Example 2 2.2 g (0.008 mol) of molybdenum pentachloride was placed in a 500 ml flask that had been thoroughly dried and purged with nitrogen.
Add 27.6 g (0.240 mol) of methyl 3-pentenoate and 160 ml of 1,2-dichloroethane and bring the bath temperature to 80 ml.
After heating and stirring for 0.5 h at °C, tetrameltin
1.4 g (0.008 mol) was added and the mixture was refluxed for 2 hours at a bath temperature of 100°C. Subsequently, by post-treatment and distillation using a conventional method, 13.8 g (0.0804 mol) of dimethyl 2-butene-1,4-dicarboxylate was obtained, with a metathesis yield of 67.
%, with a selectivity of 96%.
２−ブテン−１，４−ジカルボン酸ジメチル
NMR（CCl4／TMS）
δ2.96（4H、ｄ、−CH2−）
3.57（3H、ｓ、CH3−）
5.56（2H、ｍ、−CH＝CH−）
実施例 ３
あらかじめよく窒素置換した1000mlフラスコに
５％パラジウム／活性炭２ｇ、２−ブテン−１，
４−ジカルボン酸ジメチル13.8ｇ（0.0804モル）、
およびメタノール400mlを加え系内を水素置換し
た後に常温、常圧で70分間反応させた。反応混合
物よりパラジウム／活性炭をろ別した。濃縮後、
蒸留したところアジピン酸ジメチルが13.6ｇ
（0.0780モル）、収率97％、選択率100％で得られ
た。Dimethyl 2-butene-1,4-dicarboxylate
NMR (CCl 4 /TMS) δ2.96 (4H, d, -CH 2 -) 3.57 (3H, s, CH 3 -) 5.56 (2H, m, -CH=CH-) Example 3 Thorough nitrogen substitution in advance 5% palladium/activated carbon 2g in a 1000ml flask, 2-butene-1,
Dimethyl 4-dicarboxylate 13.8g (0.0804mol),
After adding 400 ml of methanol and purging the system with hydrogen, the reaction was carried out at room temperature and pressure for 70 minutes. Palladium/activated carbon was filtered off from the reaction mixture. After concentration,
When distilled, 13.6g of dimethyl adipate was obtained.
(0.0780 mol) with a yield of 97% and a selectivity of 100%.
アジピン酸ジメチルNMR（CCl4／TMS）
δ1.64（4H、txt、Ｃ−CH2−CH2−Ｃ）
2.30（4H、ｔ、−CH2−CO−）
3.59（3H、ｓ、CH2−Ｏ−）
IR（liq.Film） 〓Ｃ＝Ｏ 1730cm-1
GC 保持時間 11.0分（標品と一致）
カラム；10％Therm on3000on
Celite545S
ステンレス2m
条件 100−250℃（８℃／minで昇温）
実施例 ４
200mlフラスコに0.5％塩酸水溶液80ml、アジピ
ン酸ジメチル13.6ｇ（0.0780モル）を加え、浴温
120℃で３時間還流、反応させた。反応終了後常
法によりアジピン酸をアルカリ抽出、酸析した結
果、アジピン酸が11.4ｇ（0.0780モル）、収率100
％で得られた。Dimethyl adipate NMR (CCl 4 /TMS) δ1.64 (4H, txt, C-CH 2 -CH 2 -C) 2.30 (4H, t, -CH 2 -CO-) 3.59 (3H, s, CH 2 - O-) IR (liq.Film) C=O 1730cm -1 GC Retention time 11.0 minutes (same as standard) Column: 10% Therm on3000on
Celite545S Stainless steel 2m Conditions 100-250℃ (Temperature increase at 8℃/min) Example 4 Add 80ml of 0.5% hydrochloric acid aqueous solution and 13.6g (0.0780mol) of dimethyl adipate to a 200ml flask, and bring the temperature to the bath.
The mixture was refluxed and reacted at 120°C for 3 hours. After the reaction was completed, adipic acid was extracted with alkali and acid precipitated using a conventional method. As a result, adipic acid was 11.4g (0.0780 mol), yield 100.
Obtained in %.
アジピン酸NMR（d6−DMSO／TMS） δ1.49（4H、txt、−Ｃ−CH2−CH2−Ｃ−） 2.16（4H、ｍ、−CH2−CO−） 11.2〜12.6（2H、ｂ、−COOH） IR（KBr disk） 〓Ｃ＝Ｏ 1684cm-1 Adipic acid NMR (d 6 -DMSO/TMS) δ1.49 (4H, txt, -C-CH 2 -CH 2 -C-) 2.16 (4H, m, -CH 2 -CO-) 11.2-12.6 (2H, b, -COOH) IR (KBr disk) 〓C=O 1684cm -1
Claims (1)
コールを３級アミンの存在下、コバルト化合物を
触媒としてヒドロエステル化反応を行い、３−ペ
ンテン酸エステルを得る第一工程、３−ペンテン
酸エステルをMo塩化物と低級アルキルSn化合物
とからなる触媒を用いてメタセシス反応を行い、
２−ブテン−１，４−ジカルボン酸ジエステルと
２−ブテンとを製造する第２工程、２−ブテン−
１，４−ジカルボン酸ジエステルを水添して、ア
ジピン酸ジエステルを得る第３工程とからなるア
ジピン酸ジエステルの製造方法。 ２ ２−ブテンを酸化的脱水素して１，３−ブタ
ジエンを製造し第１工程に循環する特許請求の範
囲第１項記載のアジピン酸ジエステルの製造方
法。 ３ １，３−ブタジエン、一酸化炭素およびアル
コールを３級アミンの存在下、コバルト化合物を
触媒としてヒドロエステル化反応を行い、３−ペ
ンテン酸エステルを得る第１工程、３−ペンテン
酸エステルをMo塩化物と低級アルキルSn化合物
とからなる触媒を用いてメタセシス反応を行い、
２−ブテン−１，４−ジカルボン酸ジエステルと
２−ブテンとを製造する第２工程、２−ブテン−
１，４−ジカルボン酸ジエステルを水添して、ア
ジピン酸ジエステルを得る第３工程、アジピン酸
ジエステルを加水分解してアジピン酸を得る第４
工程とからなるアジピン酸の製造方法。 ４ ２−ブテンを酸化的脱水素して１，３−ブタ
ジエンを製造し第１工程に循環する特許請求の範
囲第３項記載のアジピン酸の製造方法。[Claims] 1. A first step in which 1,3-butadiene, carbon monoxide and alcohol are subjected to a hydroesterification reaction in the presence of a tertiary amine using a cobalt compound as a catalyst to obtain a 3-pentenoic acid ester; - Performing a metathesis reaction of pentenoic acid ester using a catalyst consisting of Mo chloride and a lower alkyl Sn compound,
2nd step of producing 2-butene-1,4-dicarboxylic acid diester and 2-butene, 2-butene-
A method for producing an adipic acid diester, which comprises a third step of hydrogenating a 1,4-dicarboxylic acid diester to obtain an adipic acid diester. 2. The method for producing an adipic diester according to claim 1, wherein 1,3-butadiene is produced by oxidative dehydrogenation of 2-butene and recycled to the first step. 3 The first step is to perform a hydroesterification reaction of 1,3-butadiene, carbon monoxide, and alcohol in the presence of a tertiary amine using a cobalt compound as a catalyst to obtain 3-pentenoic acid ester. A metathesis reaction is carried out using a catalyst consisting of chloride and a lower alkyl Sn compound,
2nd step of producing 2-butene-1,4-dicarboxylic acid diester and 2-butene, 2-butene-
The third step is to hydrogenate the 1,4-dicarboxylic acid diester to obtain the adipic acid diester, and the fourth step is to hydrolyze the adipic acid diester to obtain the adipic acid.
A method for producing adipic acid, which comprises the steps of: 4. The method for producing adipic acid according to claim 3, wherein 1,3-butadiene is produced by oxidative dehydrogenation of 2-butene and recycled to the first step.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57140657A JPS5929634A (en) | 1982-08-12 | 1982-08-12 | Preparation of adipic acid and diester of adipic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57140657A JPS5929634A (en) | 1982-08-12 | 1982-08-12 | Preparation of adipic acid and diester of adipic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5929634A JPS5929634A (en) | 1984-02-16 |
| JPS6313418B2 true JPS6313418B2 (en) | 1988-03-25 |
Family
ID=15273733
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57140657A Granted JPS5929634A (en) | 1982-08-12 | 1982-08-12 | Preparation of adipic acid and diester of adipic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5929634A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19907519A1 (en) * | 1999-02-22 | 2000-08-31 | Basf Ag | Process for the preparation of substituted olefins |
| JP2005281175A (en) * | 2004-03-29 | 2005-10-13 | Asahi Kasei Chemicals Corp | Method of manufacturing polycarboxylic acid |
-
1982
- 1982-08-12 JP JP57140657A patent/JPS5929634A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5929634A (en) | 1984-02-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mitsudo et al. | Ruthenium complex-catalyzed carbonylation of allylic compounds | |
| JP2523753B2 (en) | Method for producing 2,3-dichloropyridine | |
| JPS6313418B2 (en) | ||
| JPH0213653B2 (en) | ||
| US4485254A (en) | Process for preparing phenoxybenzoic acids | |
| IE851781L (en) | Preparation of fluorinated alcohols. | |
| JP3815795B2 (en) | Method for producing 3-pentenoic acid ester by carbonylation of alkoxybutene | |
| JPS5843936A (en) | Manufacture of glycol aldehyde | |
| JP2548590B2 (en) | Method for selective oxidative carbonylation of conjugated dienes | |
| JP2001158754A (en) | Method for producing tetrafluorobenzenedimethanol | |
| JPH0534346B2 (en) | ||
| JPH0816101B2 (en) | Process for producing 3,5-dichloropyridine | |
| JPS6244539B2 (en) | ||
| JP4586568B2 (en) | Method for producing tetralones | |
| JPS6038343A (en) | Production of phenylacetic acid derivative | |
| JP2618442B2 (en) | Method for producing benzonitrile | |
| JP3396097B2 (en) | Method for producing 4-isopropylcyclohexanecarboxylic acid ester derivative | |
| JPS5865238A (en) | Simultaneous manufacture of carboxylic acid and carboxylic acid ester | |
| JPS5951934B2 (en) | Method for producing 4-aminomethylcyclohexanecarboxylic acid and its mineral acid salt | |
| JP3008296B2 (en) | Method for producing diaryl glycolic acid | |
| JPH07116095B2 (en) | Method for producing cyclohexanone carboxylic acids | |
| JPS5916846A (en) | Manufacture of glycol aldehyde and manufacture of ethylene glycol therefrom | |
| JPS63233948A (en) | Alpha-(3-(1-phenylethenyl)phenyl)propionic acid and alkyl ester thereof | |
| JPH0578541B2 (en) | ||
| JP4709369B2 (en) | Esters and their synthesis |