JPS5948817B2 - Simultaneous production method of ε-caprolactone and carboxylic acids - Google Patents
Simultaneous production method of ε-caprolactone and carboxylic acidsInfo
- Publication number
- JPS5948817B2 JPS5948817B2 JP51099001A JP9900176A JPS5948817B2 JP S5948817 B2 JPS5948817 B2 JP S5948817B2 JP 51099001 A JP51099001 A JP 51099001A JP 9900176 A JP9900176 A JP 9900176A JP S5948817 B2 JPS5948817 B2 JP S5948817B2
- Authority
- JP
- Japan
- Prior art keywords
- caprolactone
- reaction
- acetaldehyde
- carboxylic acids
- chromium
- 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
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 title claims description 12
- 150000001735 carboxylic acids Chemical class 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims description 22
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 20
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 8
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 claims description 8
- 229910052804 chromium Inorganic materials 0.000 claims description 8
- 239000011651 chromium Substances 0.000 claims description 8
- 150000001845 chromium compounds Chemical class 0.000 claims description 8
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 6
- AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 claims description 6
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical group [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- NIOYUNMRJMEDGI-UHFFFAOYSA-N hexadecanal Chemical compound CCCCCCCCCCCCCCCC=O NIOYUNMRJMEDGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 239000001361 adipic acid Substances 0.000 description 3
- 235000011037 adipic acid Nutrition 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- FJJYHTVHBVXEEQ-UHFFFAOYSA-N 2,2-dimethylpropanal Chemical compound CC(C)(C)C=O FJJYHTVHBVXEEQ-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- JARKCYVAAOWBJS-UHFFFAOYSA-N hexanal Chemical compound CCCCCC=O JARKCYVAAOWBJS-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- ZUYKJZQOPXDNOK-UHFFFAOYSA-N 2-(ethylamino)-2-thiophen-2-ylcyclohexan-1-one;hydrochloride Chemical class Cl.C=1C=CSC=1C1(NCC)CCCCC1=O ZUYKJZQOPXDNOK-UHFFFAOYSA-N 0.000 description 1
- LGYNIFWIKSEESD-UHFFFAOYSA-N 2-ethylhexanal Chemical compound CCCCC(CC)C=O LGYNIFWIKSEESD-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- -1 chromate ester Chemical class 0.000 description 1
- GEKDHJTUYGMYFB-UHFFFAOYSA-N chromium;pentane-2,4-dione Chemical compound [Cr].CC(=O)CC(C)=O GEKDHJTUYGMYFB-UHFFFAOYSA-N 0.000 description 1
- AHXGRMIPHCAXFP-UHFFFAOYSA-L chromyl dichloride Chemical compound Cl[Cr](Cl)(=O)=O AHXGRMIPHCAXFP-UHFFFAOYSA-L 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance 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
Landscapes
- Furan Compounds (AREA)
- Pyrane Compounds (AREA)
- 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ε一カプロラク１・ンとカルボン酸類との同時
製造法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for simultaneously producing ε-caprolactone and carboxylic acids.
詳しくはシクロヘキサノン類とアルデヒド類とを分子状
酸素で共酸化して、１５ε一カプロラクトンと該アルデ
ヒド類に対応するカルボン酸類とを製造する方法の改良
に関する。ε一カプロラクトンはポリウレタンの原料と
なるポリエステルの製造原料として重要な物質である。
２０シクロヘキサノンとアルデヒド類とを分子状酸素で
共酸化して、ε一カプロラクトン類とカルボン酸類とを
製造することは公知である（米国特許第３、０２５、３
０６号及び’＄、４８３、２２２号参照）。Specifically, the present invention relates to an improvement in a method for co-oxidizing cyclohexanones and aldehydes with molecular oxygen to produce 15ε-caprolactone and carboxylic acids corresponding to the aldehydes. ε-caprolactone is an important substance as a raw material for producing polyester, which is a raw material for polyurethane.
It is known to co-oxidize cyclohexanone and aldehydes with molecular oxygen to produce ε-caprolactones and carboxylic acids (U.S. Pat. No. 3,025,3).
06 and '$, 483, 222).
米国特許第３、０２５、３０６号には、この反応をコ２
５バルト、マンガン等の存在下に行なうことが開示され
ている。しかし、この方法はアジピン酸等の酸化分解生
成物が多く、またアルデヒドの利用効率が低い欠点があ
る。本発明者らは、カプロラクトンを高収率かつ高３０
選択率で製造することを目的として検討した結果、反応
系に可溶性クロム化合物を溶存させると、十分な酸素吸
収速度を保持しながらカプロラクトンの選択率を向上さ
せることを見出し、本発明を完成した。U.S. Pat. No. 3,025,306 describes this reaction as
It is disclosed that the process is carried out in the presence of 5 balt, manganese, etc. However, this method has the disadvantage that it produces many oxidative decomposition products such as adipic acid and has low aldehyde utilization efficiency. The present inventors have developed caprolactone with high yield and high 30%
As a result of studies aimed at manufacturing with high selectivity, it was discovered that dissolving a soluble chromium compound in the reaction system improves the selectivity of caprolactone while maintaining a sufficient oxygen absorption rate, and completed the present invention.
３５本発明を以下に詳細に説明するに、本発明は下記の
反応式で表わされる。35 To explain the present invention in detail below, the present invention is represented by the following reaction formula.
ただし、上記反応式中でＲ，は炭素数１〜２０のアルキ
ル基を表わす。However, in the above reaction formula, R represents an alkyl group having 1 to 20 carbon atoms.
本発明方法の原料として適当なアルデヒド類（１）の具
体例としては、アセトアルデヒド、プロピオンアルデヒ
ド、ブチルアルデヒド、イソブチルアルデヒド、ヘキサ
ナール、２−エチルヘキサナール、トリメチルアセトア
ルデヒド、ヘキサデカナール等を挙げることができる。Specific examples of aldehydes (1) suitable as raw materials for the method of the present invention include acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, hexanal, 2-ethylhexanal, trimethylacetaldehyde, hexadecanal, and the like.
このうち好ましいものは、アセトアルデヒド、プロピオ
ンアルデヒド、ブチルアルデヒド、イソブチルアルデヒ
ドである。Among these, preferred are acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde.
アルデヒド類とシクロヘキサノンとの反応系への供給比
率は任意であるが、通常はシクロヘキサノン類を過剰に
供給するのが好ましい。Although the ratio of feeding aldehydes and cyclohexanone to the reaction system is arbitrary, it is usually preferable to feed cyclohexanone in excess.
本発明方法は通常反応溶媒の不存在下に実施される。The process of the invention is usually carried out in the absence of a reaction solvent.
しかし、所望ならば反応溶媒を使用してもよい。反応溶
媒としては、反応により生成したカルボン酸を使用する
ことができる。また、酸化反応に不活性な有機溶媒を使
用することもできる。このような有機溶媒としてはヘキ
サン、シクロヘキサン、ベンゼン等の炭化水素類；アセ
トン、メチルエチルケトン等のケトン類；酢酸エチル、
安息香酸メチル等のエステル類；アセトニトリル、ベン
ゾニトリル等のニトリル類等が挙げられる。本発明の酸
化反応は分子状酸素を酸化剤として行なわれる。分子状
酸素は、純酸素、空気、酸素濃度を高めた空気、酸素と
不活性ガス（二酸化炭素、窒素等）からなる混合ガス等
の形態で供給される。反応温度は−２０〜１５０℃の範
囲から選ばれる。However, a reaction solvent may be used if desired. As the reaction solvent, a carboxylic acid produced by the reaction can be used. Moreover, an organic solvent inert to the oxidation reaction can also be used. Examples of such organic solvents include hydrocarbons such as hexane, cyclohexane, and benzene; ketones such as acetone and methyl ethyl ketone; ethyl acetate,
Examples include esters such as methyl benzoate; nitrites such as acetonitrile and benzonitrile. The oxidation reaction of the present invention is carried out using molecular oxygen as an oxidizing agent. Molecular oxygen is supplied in the form of pure oxygen, air, air with increased oxygen concentration, or a mixed gas of oxygen and an inert gas (carbon dioxide, nitrogen, etc.). The reaction temperature is selected from the range of -20 to 150°C.
反応温度が高いほどシクロヘキサノンの転化率は増加す
るが、同時にアジピン酸等の好ましくない副生物の収量
も増加するため、ε一カプロラクトンの選択率が減少す
る。従つて好ましい反応温度は１０〜１２０℃、特に３
０〜８０℃である。As the reaction temperature increases, the conversion rate of cyclohexanone increases, but at the same time, the yield of undesirable by-products such as adipic acid increases, so the selectivity for ε-caprolactone decreases. Therefore, the preferred reaction temperature is 10 to 120°C, especially 3
The temperature is 0 to 80°C.
反応圧力は通常、大気圧〜３０ｋｇ／ｃ：ｉｌの範囲か
ら選択されるが、この範囲外でも勿論反応を実施するこ
とはできる。反応は町溶性クロム化合物の溶存下に行な
われる。町溶性クロム化合物としては通常、ナフテン酸
クロム、アセチルアセトンクロム、クロム酸エステル、
塩化クロミル等が用いられるが、反応系に町溶な他のク
ロム化合物も用いることができる。反応系中の町溶性ク
ロム化合物の濃度はクロムとして通常０．００１〜５０
０（重量）酵、好ましくは０．２〜２０卿の範囲である
。反応は回分法、連続法のいずれでも実施することがで
きる。The reaction pressure is usually selected from the range of atmospheric pressure to 30 kg/c:il, but it is of course possible to carry out the reaction outside this range. The reaction is carried out in the presence of dissolved chromium compounds. Soluble chromium compounds usually include chromium naphthenate, chromium acetylacetone, chromate ester,
Although chromyl chloride or the like is used, other chromium compounds that are soluble in the reaction system can also be used. The concentration of soluble chromium compounds in the reaction system is usually 0.001 to 50% as chromium.
0 (weight) fermentation, preferably in the range of 0.2 to 20 kg. The reaction can be carried out either batchwise or continuously.
反応混合物からは、常法に従つて蒸留することにより、
未反応原料、ε一カプロラクトン及びカルボン酸が分離
回収される。本発明方法によれば高収率でε一カプロラ
クトンを製造することができ、且つアジピン酸等の副生
物の生成が少ない。From the reaction mixture, by distillation according to a conventional method,
Unreacted raw materials, ε-caprolactone and carboxylic acid are separated and recovered. According to the method of the present invention, ε-caprolactone can be produced in high yield, and less by-products such as adipic acid are produced.
また、生成するε一カプロラクトンの熱安定性が良好で
あり、従つて反応生成物の蒸留分離が容易である。次に
実施例により本発明を更に詳細に説明するが、本発明は
その要旨を超えない限り以下の実施例に限定されるもの
ではない。Furthermore, the thermal stability of the produced ε-caprolactone is good, and therefore the reaction product can be easily separated by distillation. Next, the present invention will be explained in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof.
，なお、以下の実施例及び比較例において、特記しない
限り、「％」はモル％を、「μ」は重量―を表わす。In the following Examples and Comparative Examples, unless otherwise specified, "%" represents mol% and "μ" represents weight.
実施例 １
攪拌機、ガス吹込管、ドライアイスで冷却した還流冷却
器及び定量ポンプに接続した液体導入管を備えた５００
ａ容のガラス製フラスコに、シクロヘキサノン１５６９
（１．５９モル）を仕込み、且つこれにトリス（アセチ
ルアセトナート）クロム（ＮＩ）をクロムとして１Ｉ）
Ｐｌになるように添加した。Example 1 500 equipped with a stirrer, a gas blowing tube, a reflux condenser cooled with dry ice and a liquid inlet tube connected to a metering pump.
In a glass flask, add cyclohexanone 1569.
(1.59 mol) and add tris(acetylacetonato)chromium (NI) to it as chromium (1I)
It was added so that it became Pl.
攪拌下に５０℃に保持して空気を３０１／Ｈｒで吹込み
、同時にアセトアルデヒド１９．０９（０．４３２モル
）とシクロヘキサノン８０ｆ！（０．８２モノりとの混
合液を定量ポンプにより２時間を要して添加した。酸素
の吸収は順調であつた。アセトアルデヒドの添加が終了
したのち、更に１時間空気の吹込みを継続した。While stirring, the temperature was maintained at 50°C and air was blown in at a rate of 301/hr, and at the same time 19.09 (0.432 mol) of acetaldehyde and 80f of cyclohexanone! (The mixed solution with 0.82 monomer was added using a metering pump over a period of 2 hours. Oxygen absorption was smooth. After the addition of acetaldehyde was completed, air was continued to be blown for another hour. .
反応液を蒸留して酢酸を分離したのら、ガスクロマトグ
ラフイ一で分析した結果、シクロヘキサノンの転化率は
３．０８％、ε一カプロラクトンの選択率は８６．９％
、不揮発囲酸の選択率は３．２％（転化したシクロヘキ
サノン基準）であつた。After distilling the reaction solution to separate acetic acid, analysis using gas chromatography revealed that the conversion rate of cyclohexanone was 3.08% and the selectivity of ε-caprolactone was 86.9%.
The selectivity of non-volatile surrounding acid was 3.2% (based on converted cyclohexanone).
また、酢酸の収率はアセトアルデヒドの仕込量を基準に
して６６．５％であつた。実施例 ２〜４
町溶性クロム化合物の種類、クロム濃度及び反応温度を
変化させた以外は実施例１と同様にして反応を行なつた
。Further, the yield of acetic acid was 66.5% based on the amount of acetaldehyde charged. Examples 2 to 4 Reactions were carried out in the same manner as in Example 1, except that the type of town-soluble chromium compound, chromium concentration, and reaction temperature were changed.
結果を表１に示す。実施例 ５
攪拌機、ガス吹込管、ドライアイスで冷却した還流冷却
器及び定量ポンプに接続した液体導入管を備えた１００
１ｎ１容のガラスフラスコに、シクロヘキサノン３０９
（０．３０６モノりを仕込み、且つこれにトリス（アセ
チルアセトナート）クロム（１！０をクロムとして１Ｐ
Ｉ］ｌになるように添加した。The results are shown in Table 1. Example 5 100 with a stirrer, a gas blowing tube, a reflux condenser cooled with dry ice and a liquid inlet tube connected to a metering pump
In a 1n1 volume glass flask, add cyclohexanone 309
(Prepare 0.306 monomer, and add tris(acetylacetonato)chromium (1P with 1!0 as chromium)
I]l.
Claims (1)
。 ）で表わされるアルデヒド類との混合物を分子状酸素に
より共酸化して、ε−カプロラクトンと一般式（II）Ｒ
＿１−ＣＯＯＨ（II） （式中、Ｒ＿１は前記の定義に同じ） で表わされるカルボン酸類とを製造するに際し、反応系
に可溶性クロム化合物を溶存させることを特徴とする方
法。 ２ 特許請求の範囲第１項において、アルデヒド類がア
セトアルデヒド、プロピオンアルデヒド、アセトアルデ
ヒド、ヘキサデカナールである方法。 ３ 特許請求の範囲第１項において、アルデヒド類がア
セトアルデヒド、プロピオンアルデヒド、ブチルアルデ
ヒド、イソブチルアルデヒドである方法。 ４ 特許請求の範囲第１項において、反応系中の可溶性
クロム化合物の濃度がクロムとして０．００１〜５００
ｐｐｍ（重量）である方法。[Claims] 1. A mixture of cyclohexanone and an aldehyde represented by the general formula (I) R_1-CHO(I) (wherein R_1 represents an alkyl group having 1 to 20 carbon atoms) is treated with molecular oxygen. Co-oxidation with ε-caprolactone and general formula (II) R
_1-COOH(II) (wherein R_1 is the same as defined above) A method characterized by dissolving a soluble chromium compound in the reaction system. 2. The method according to claim 1, wherein the aldehyde is acetaldehyde, propionaldehyde, acetaldehyde, or hexadecanal. 3. The method according to claim 1, wherein the aldehyde is acetaldehyde, propionaldehyde, butyraldehyde, or isobutyraldehyde. 4 In claim 1, the concentration of the soluble chromium compound in the reaction system is 0.001 to 500 as chromium.
Method in ppm (by weight).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51099001A JPS5948817B2 (en) | 1976-08-19 | 1976-08-19 | Simultaneous production method of ε-caprolactone and carboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP51099001A JPS5948817B2 (en) | 1976-08-19 | 1976-08-19 | Simultaneous production method of ε-caprolactone and carboxylic acids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5325516A JPS5325516A (en) | 1978-03-09 |
| JPS5948817B2 true JPS5948817B2 (en) | 1984-11-29 |
Family
ID=14234735
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP51099001A Expired JPS5948817B2 (en) | 1976-08-19 | 1976-08-19 | Simultaneous production method of ε-caprolactone and carboxylic acids |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5948817B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61235108A (en) * | 1985-04-12 | 1986-10-20 | Daiichi Kasei Kk | Structure of ejector mechanism for metal mold |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102108048A (en) * | 2009-12-24 | 2011-06-29 | 四川省申联生物科技有限责任公司 | Method for preparing acetic acid and carboxylic ester |
-
1976
- 1976-08-19 JP JP51099001A patent/JPS5948817B2/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61235108A (en) * | 1985-04-12 | 1986-10-20 | Daiichi Kasei Kk | Structure of ejector mechanism for metal mold |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5325516A (en) | 1978-03-09 |
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