JPH0242819B2 - - Google Patents
Info
- Publication number
- JPH0242819B2 JPH0242819B2 JP57087607A JP8760782A JPH0242819B2 JP H0242819 B2 JPH0242819 B2 JP H0242819B2 JP 57087607 A JP57087607 A JP 57087607A JP 8760782 A JP8760782 A JP 8760782A JP H0242819 B2 JPH0242819 B2 JP H0242819B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- water
- sulfur
- iron
- oxygen
- 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 - Lifetime
Links
- 239000002253 acid Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 150000002506 iron compounds Chemical class 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 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 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002898 organic sulfur compounds Chemical class 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 16
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- -1 polyaldehyde acid Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- UMHJEEQLYBKSAN-UHFFFAOYSA-N Adipaldehyde Chemical compound O=CCCCCC=O UMHJEEQLYBKSAN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- GUUVPOWQJOLRAS-UHFFFAOYSA-N Diphenyl disulfide Chemical compound C=1C=CC=CC=1SSC1=CC=CC=C1 GUUVPOWQJOLRAS-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- LJSQFQKUNVCTIA-UHFFFAOYSA-N diethyl sulfide Chemical compound CCSCC LJSQFQKUNVCTIA-UHFFFAOYSA-N 0.000 description 2
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- WHMDPDGBKYUEMW-UHFFFAOYSA-N pyridine-2-thiol Chemical compound SC1=CC=CC=N1 WHMDPDGBKYUEMW-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 2
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 description 2
- OGYGFUAIIOPWQD-UHFFFAOYSA-N 1,3-thiazolidine Chemical compound C1CSCN1 OGYGFUAIIOPWQD-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- RNHDAKUGFHSZEV-UHFFFAOYSA-N 1,4-dioxane;hydrate Chemical compound O.C1COCCO1 RNHDAKUGFHSZEV-UHFFFAOYSA-N 0.000 description 1
- FHTDDANQIMVWKZ-UHFFFAOYSA-N 1h-pyridine-4-thione Chemical compound SC1=CC=NC=C1 FHTDDANQIMVWKZ-UHFFFAOYSA-N 0.000 description 1
- LXUNZSDDXMPKLP-UHFFFAOYSA-N 2-Methylbenzenethiol Chemical compound CC1=CC=CC=C1S LXUNZSDDXMPKLP-UHFFFAOYSA-N 0.000 description 1
- LFSAPCRASZRSKS-UHFFFAOYSA-N 2-methylcyclohexan-1-one Chemical compound CC1CCCCC1=O LFSAPCRASZRSKS-UHFFFAOYSA-N 0.000 description 1
- AXBVSRMHOPMXBA-UHFFFAOYSA-N 4-nitrothiophenol Chemical compound [O-][N+](=O)C1=CC=C(S)C=C1 AXBVSRMHOPMXBA-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005749 Copper compound Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 description 1
- 229920001744 Polyaldehyde Polymers 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 description 1
- 150000002019 disulfides Chemical class 0.000 description 1
- WFCLYEAZTHWNEH-UHFFFAOYSA-N ethylthiocyanate Chemical compound CCSC#N WFCLYEAZTHWNEH-UHFFFAOYSA-N 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 150000002504 iridium compounds Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- 229930182817 methionine Natural products 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 150000003556 thioamides Chemical class 0.000 description 1
- 150000003566 thiocarboxylic acids Chemical class 0.000 description 1
- 150000003567 thiocyanates Chemical class 0.000 description 1
- 150000003568 thioethers Chemical class 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
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
本発明は、オキソカルボン酸類の製造方法に関
するものである。オキソカルボン酸の代表的な化
合物として、合成的に有用な中間体であるアジポ
アルデヒド酸が知られているが、従来、このもの
の製造方法としては、例えば、シクロヘキサノン
を水および銅化合物の存在下、分子状酸素により
酸化する方法（特公昭47−26768号公報）が報告
されている。しかしながら本法は原料の転化率、
目的物の収率がいずれも高くない欠点を有する。
一方、本発明者らは、先にシクロヘキサノン
を、水および鉄もしくはイリジウムの化合物の存
在下、酸化反応を行なうと、速やかにアジポアル
デヒド酸が生成することを見出した。本発明者ら
はその後、目的物の収率をさらに高めるべく、引
き続き検討を続けた結果、シクロヘキサノンを水
および鉄化合物、さらにイオウまたはイオウ化合
物を存在させて酸素により酸化反応を行なうこと
により、アジポアルデヒド酸をはじめとする、オ
キソカルボン酸類の収率が改善されることを見い
出し本発明に到達した。
以下本発明を詳細に説明する。
本発明においては下記一般式（）
で表わされるシクロヘキサノン類を、水、鉄
化合物ならびにイオウおよび／または有機イオ
ウ化合物の存在下、酸素により酸化することによ
り下記一般式（）
RCO（CH2）4COOH ……（）
で表わされるオキソカルボン酸類を製造する。
一般式（）および（）におけるＲは同義で
あり、水素またはアルキル基を示す。アルキル基
としては特に限定されないが炭素数６以下のもの
が実用上好ましい。
鉄化合物としては水に可溶なものが好ましく、
具体的に例示すると、例えば塩化第一鉄、塩化第
二鉄、臭化第二鉄、硫酸第一鉄、硫酸第二鉄、硝
酸第二鉄等の無機酸塩あるいは酢酸塩のような有
機酸塩等があげられる。またアセチルアセトン鉄
のような原料に溶解するものでもよい。鉄化合物
の使用量は広汎に変化させ得るが、例えばシクロ
ヘキサノン類に対し、鉄として0.1〜100モル％、
より好ましくは１〜30モル％程度が良い。
本発明においては鉄化合物に加えて、イオウま
たは有機イオウ化合物を使用することが必須であ
る。具体的に例示すると、単体イオウ、二硫化炭
素、メルカプタン類例えばエチルメルカプタン、
２−メルカプトエタノール、２−メルカプトエチ
ルアミン、２−メルカプトピリジン、４−メルカ
プトピリジン、チオグリコール酸、システイン
等、チオフエノール類例えばチオフエノール、チ
オクレゾール、ｐ−ニトロチオフエノール等、ス
ルフイド類例えばジエチルスルフイド、ジフエニ
ルスルフイド、チアゾリジン、メチオニン等、ジ
スルフイド類例えばジフエニルジスルフイド等、
チオアミド類例えばチオ尿素、チオアセトアミド
等、スルホキシド類例えばジメチルスルホキシ
ド、スルホン類例えばジフエニルスルホン、チオ
シアン酸エステル類例えばチオシアン酸エチル
等、その他スルホニウム化合物、チウロニウム化
合物、チオカルボン酸類、ジチオカルバミン酸
類、キサントゲン酸類等の広範囲の化合物があげ
られる。これらの使用量は、鉄に対し、イオウと
して0.1〜100モル％、より好ましくは５〜100モ
ル％程度が良い。特に鉄に対し当量以上を使用し
ないことが好ましい。
本発明方法を実施するには水の存在が必要であ
り、その使用量はシクロヘキサノン類に対し、重
量比で0.05倍ないし1000倍、より好ましくは0.1
倍ないし100倍程度とするのが良い。水の使用量
により、反応系は均一相あるいは懸濁相となる
が、本発明方法を実施するにはそのいずれでも可
である。また、反応系の均一化を促進するため
に、溶媒を使用することもできる。溶媒としては
ジオキサン、テトラヒドロフランのような非プロ
トン性極性溶媒が好ましい。
本反応を実施する際の反応温度はかなり広い範
囲にわたり変化させ得るが、例示すれば０℃〜
200℃、より好ましくは30℃〜90℃程度が好適で
ある。圧力は常圧で十分反応を進行させ得るが、
加圧としても良い。
酸素源としては純酸素を用い得るが、また空気
等の希釈された形態で用いても差し支えない。シ
クロヘキサノン類の転化率は任意に選び得るが、
高転化率では過度酸化生成物が増加する傾向にあ
り、例えば50％以下に留めると、目的とするオキ
ソカルボン酸類の選択率がより良好となる。
次に実施例によつて本発明を更に具体的に説明
するが、本発明はその要旨を越えない限り以下の
実施例に制約されるものではない。
比較例
シクロヘキサノン１ｇ（10.2ミリモル）、水
10.6ｇ、無水塩化第二鉄0.165ｇ（1.02ミリモル）
の混合物を60℃に加熱し、激しく撹拌しながら、
常圧で酸素を吸収させた。酸素の吸収量が約２ミ
リモルに到達したとき反応を停止し、生成物をガ
スクロマトグラフイーにより分析した。結果は次
の通りであつた。
The present invention relates to a method for producing oxocarboxylic acids. Adipaldehyde acid, which is a synthetically useful intermediate, is known as a representative compound of oxocarboxylic acids. Conventionally, this product has been produced by mixing cyclohexanone in the presence of water and a copper compound. , a method of oxidizing with molecular oxygen (Japanese Patent Publication No. 47-26768) has been reported. However, this method
Both methods have the disadvantage that the yield of the target product is not high. On the other hand, the present inventors have discovered that adipaldehyde acid is rapidly produced when cyclohexanone is first subjected to an oxidation reaction in the presence of water and an iron or iridium compound. Subsequently, the present inventors continued to study in order to further increase the yield of the target product. As a result, the present inventors conducted an oxidation reaction with oxygen in the presence of water, an iron compound, and sulfur or a sulfur compound to cyclohexanone. The inventors have discovered that the yield of oxocarboxylic acids, including polyaldehyde acid, can be improved and have arrived at the present invention. The present invention will be explained in detail below. In the present invention, the following general formula () By oxidizing cyclohexanones represented by with oxygen in the presence of water, an iron compound, and sulfur and/or organic sulfur compounds, an oxocarboxylic acid represented by the following general formula () RCO (CH 2 ) 4 COOH ... () is obtained. Manufacture acids. R in the general formulas () and () have the same meaning and represent hydrogen or an alkyl group. The alkyl group is not particularly limited, but those having 6 or less carbon atoms are practically preferred. Preferably, the iron compound is one that is soluble in water.
Specific examples include inorganic acid salts such as ferrous chloride, ferric chloride, ferric bromide, ferrous sulfate, ferric sulfate, and ferric nitrate, or organic acids such as acetate. Examples include salt. It may also be one that dissolves in raw materials such as iron acetylacetonate. The amount of iron compound used can vary widely, but for example, 0.1 to 100 mol% iron relative to cyclohexanones,
More preferably, it is about 1 to 30 mol%. In the present invention, it is essential to use sulfur or organic sulfur compounds in addition to iron compounds. Specific examples include elemental sulfur, carbon disulfide, mercaptans such as ethyl mercaptan,
2-mercaptoethanol, 2-mercaptoethylamine, 2-mercaptopyridine, 4-mercaptopyridine, thioglycolic acid, cysteine, etc., thiophenols such as thiophenol, thiocresol, p-nitrothiophenol, etc., sulfides such as diethyl sulfide. di, diphenyl sulfide, thiazolidine, methionine, etc., disulfides such as diphenyl disulfide, etc.
Thioamides such as thiourea and thioacetamide, sulfoxides such as dimethyl sulfoxide, sulfones such as diphenyl sulfone, thiocyanate esters such as ethyl thiocyanate, and other sulfonium compounds, thiuronium compounds, thiocarboxylic acids, dithiocarbamic acids, xanthogenic acids, etc. A wide range of compounds can be mentioned. The amount of these used is preferably about 0.1 to 100 mol%, more preferably about 5 to 100 mol% of sulfur, based on iron. In particular, it is preferable not to use more than the equivalent amount to iron. The presence of water is necessary to carry out the method of the present invention, and the amount used is 0.05 to 1000 times, more preferably 0.1 times, the weight of cyclohexanone.
It is best to set it to about twice to 100 times. Depending on the amount of water used, the reaction system can be either a homogeneous phase or a suspended phase, either of which is acceptable for carrying out the method of the present invention. Moreover, a solvent can also be used to promote homogenization of the reaction system. As the solvent, aprotic polar solvents such as dioxane and tetrahydrofuran are preferred. The reaction temperature when carrying out this reaction can be varied over a fairly wide range, but for example, from 0°C to
The temperature is preferably about 200°C, more preferably about 30°C to 90°C. Although the reaction can proceed sufficiently at normal pressure,
It may also be pressurized. Pure oxygen may be used as the oxygen source, but it may also be used in a diluted form such as air. The conversion rate of cyclohexanones can be selected arbitrarily, but
At high conversion rates, excessive oxidation products tend to increase; for example, if the conversion rate is kept at 50% or less, the selectivity of the target oxocarboxylic acids becomes better. 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 the gist thereof is exceeded. Comparative example cyclohexanone 1g (10.2 mmol), water
10.6g, anhydrous ferric chloride 0.165g (1.02 mmol)
Heat the mixture to 60°C and, with vigorous stirring,
Oxygen was absorbed at normal pressure. The reaction was stopped when the amount of oxygen absorbed reached approximately 2 mmol, and the product was analyzed by gas chromatography. The results were as follows.
【表】
実施例 １〜15
比較例と同一の反応条件で、反応系に各種のイ
オウ化合物を表−１に示す量添加して反応を行な
わせた。結果を表−１に示す。[Table] Examples 1 to 15 Under the same reaction conditions as in the comparative example, various sulfur compounds were added to the reaction system in the amounts shown in Table 1 to carry out the reaction. The results are shown in Table-1.
【表】
実施例 16〜21
実施例１〜15と同一の条件で、溶媒として水に
替えてジオキサン−水混合物（８：５（重量比））
13mlを使用して反応を行なつた。結果を表−２に
示す。[Table] Examples 16-21 Under the same conditions as Examples 1-15, dioxane-water mixture (8:5 (weight ratio)) was used instead of water as the solvent.
The reaction was carried out using 13 ml. The results are shown in Table-2.
【表】
実施例 22
実施例１と同一の反応を、２−メルカプトピリ
ジンの添加量を0.01ミリモルに減じて同様に行な
わせた。結果を次に示す。[Table] Example 22 The same reaction as in Example 1 was carried out except that the amount of 2-mercaptopyridine added was reduced to 0.01 mmol. The results are shown below.
【表】
実施例 23
塩化第二鉄に替えて無水臭化第二鉄0.30ｇ
（1.02ミリモル）を用いた他は実施例１と同一の
反応を行なつた。結果を次に示す。[Table] Example 23 Anhydrous ferric bromide 0.30g instead of ferric chloride
The same reaction as in Example 1 was carried out except that (1.02 mmol) was used. The results are shown below.
【表】
実施例 24
２−メチルシクロヘキサノン１ｇ（8.91ミリモ
ル）、水10.3ｇ、無水塩化第二鉄0.144ｇ（0.89ミ
リモル）、チオ尿素0.034ｇ（0.45ミリモル）の混
合物について実施例１と同一の条件で反応を行つ
た。結果を次に示す。[Table] Example 24 Same conditions as Example 1 for a mixture of 1 g (8.91 mmol) of 2-methylcyclohexanone, 10.3 g of water, 0.144 g (0.89 mmol) of anhydrous ferric chloride, and 0.034 g (0.45 mmol) of thiourea. I did the reaction. The results are shown below.
Claims (1)
化合物ならびにイオウおよび／または有機イオ
ウ化合物の存在下、酸素により酸化することを特
徴とする一般式（） RCO（CH2）4COOH ……（） （式中Ｒは一般式（）のＲと同義である。） で表わされるオキソカルボン酸類の製造方法。[Claims] 1 General formula () (In the formula, R represents hydrogen or an alkyl group.) A general formula () characterized in that cyclohexanones represented by RCO are oxidized with oxygen in the presence of water, an iron compound, and sulfur and/or an organic sulfur compound. (CH 2 ) 4 COOH ... () (In the formula, R has the same meaning as R in the general formula ().) A method for producing oxocarboxylic acids represented by the following.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57087607A JPS58203936A (en) | 1982-05-24 | 1982-05-24 | Preparation of oxocarboxylic acid |
| US06/475,646 US4649217A (en) | 1982-04-02 | 1983-03-15 | Process for producing oxocarboxylic acids |
| DE8383103186T DE3360258D1 (en) | 1982-04-02 | 1983-03-30 | A process for producing oxocarboxylic acids |
| EP83103186A EP0091091B1 (en) | 1982-04-02 | 1983-03-30 | A process for producing oxocarboxylic acids |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57087607A JPS58203936A (en) | 1982-05-24 | 1982-05-24 | Preparation of oxocarboxylic acid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58203936A JPS58203936A (en) | 1983-11-28 |
| JPH0242819B2 true JPH0242819B2 (en) | 1990-09-26 |
Family
ID=13919648
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57087607A Granted JPS58203936A (en) | 1982-04-02 | 1982-05-24 | Preparation of oxocarboxylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS58203936A (en) |
-
1982
- 1982-05-24 JP JP57087607A patent/JPS58203936A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58203936A (en) | 1983-11-28 |
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