WO1996002526A1 - Procede de production d'oxyde de cyclohexene - Google Patents

Procede de production d'oxyde de cyclohexene Download PDF

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Publication number
WO1996002526A1
WO1996002526A1 PCT/JP1994/001912 JP9401912W WO9602526A1 WO 1996002526 A1 WO1996002526 A1 WO 1996002526A1 JP 9401912 W JP9401912 W JP 9401912W WO 9602526 A1 WO9602526 A1 WO 9602526A1
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Prior art keywords
cyclohexene
chlorine
organic
water
organic component
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PCT/JP1994/001912
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English (en)
Japanese (ja)
Inventor
Masahisa Yokota
Yuichi Sakai
Ryoji Deguchi
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Asahi Kasei Kogyo Kabushiki Kaisha
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Publication of WO1996002526A1 publication Critical patent/WO1996002526A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms

Definitions

  • the present invention relates to a method for producing cyclohexenoxide useful as an intermediate of a broad medicine. More specifically, it produces hexenechlorohydrin with high selectivity from cyclohexene to the mouth, and furthermore, produces cyclohexene from the produced cyclohexene in a high yield.
  • the present invention relates to a method for producing cyclohexenoxide, which comprises obtaining and obtaining the cyclohexene oxide efficiently without danger of its decomposition.
  • a hypochlorous acid aqueous solution can be used in the form of 130 to 10%.
  • a method for producing chlorohydrin by reacting a ketone solution of HOC 1 extracted with a ketone such as methylethyl ketone at a low temperature of C, water and cyclohexene is disclosed.
  • this method requires a huge amount of energy to create a low-temperature state. It requires lugi and is not only extremely disadvantageous for the riars, but it is not always satisfactory in the yield of cyclohexenechlorohydrin. Thus, no satisfactory method has been found for the production of cyclohexenoxide from cyclohexene via cyclohexenechlorohydrin.
  • the present inventors have overcome the above-mentioned drawbacks of the prior art, and have produced hexene c-hydrin from cyclohexene to mouth with high selectivity, After that, we conducted intensive research on a method for producing xenoxide at high yields.
  • the present inventors first set forth a process for producing chlorohydrin of propylene or phenyl chloride, which is currently industrially carried out, with respect to the synthesis of cyclohexene chlorohydrin.
  • cyclohexene and chlorine were added to the stirred water in approximately equivalent amounts, but by-products such as dichlorocyclohexane, 2,2, dichlorocyclohexyl ether and the like were tried. Generated in large quantities.
  • cyclohexene has a boiling point of 83.2 ° (: its solubility in water is about 0.02% at room temperature.
  • chlorohydrin of propylene / aryl chloride has high solubility in water.
  • the chlorohydrin of propylene dissolves arbitrarily, and the chlorohydrin of aryl chloride is 10 wt%), whereas cyclohexane is Since chlorohydrin is as low as about 3 wt%, cyclohexyl hydrin itself tends to form an oil phase.
  • the present inventors have found that an aqueous solution or a suspension containing 0.1 to 1.0 N of alkaline water is reacted with chlorine to contain available chlorine and have a PH value of 7 or less.
  • the following chlorine water is prepared, and the chlorine water is reacted with an amount of cyclohexene equal to or more than 1.05 times the number of moles of available chlorine contained in the chlorine water.
  • hexenechlorohydrin can be obtained with extremely high selectivity.
  • the present inventors have fundamentally analyzed the reaction between cyclohexenechlorohydrin and alkali and made intensive studies to complete the present invention.
  • one object of the present invention is to provide a process for producing cyclohexene oxoxide from cyclohexene via cyclohexylhydrin to cyclohexene, which is useful for producing cyclohexene from cyclohexene.
  • Xenon cyclohydrin is produced with high selectivity, and cyclohexene oxide is obtained in high yield from the produced cyclohexene hydrohydrin, and the cyclohexene obtained is obtained in high yield.
  • An object of the present invention is to provide a method for efficiently isolating and recovering cyclohexenoxide without the risk of decomposition to produce cyclohexenoxide advantageously. It is another object of the present invention to provide a method for producing cyclohexene from cyclohexene with high selectivity.
  • Figure 1 shows the cyclohexene to cyclohexene of the present invention.
  • FIG. 2 is a flow sheet schematically showing one embodiment of a method for producing cyclohexenoxide via C-hydrin.
  • FIG. 2 shows a cyclohexene in the method of the present invention.
  • FIG. 3 shows a schematic but specific embodiment of one embodiment of the method of the present invention for producing cyclohexenoxide from cyclohexene via cyclohexene cyclohydrin. It is a flow sheet. Detailed description of the invention
  • reaction solution (1) of the first step An alkali is added to the reaction solution (1) of the first step, and the cyclohexenechlorohydrin is reacted with the added alkali to form an organic solution containing cyclohexene oxide.
  • a method for producing cyclohexenoxide characterized by comprising:
  • chlorine water is prepared by contacting chlorine gas with water containing a predetermined amount of aluminum.
  • chlorine water used in the present invention is a free chlorine molecule effective for chlorhydrination reaction, hypochlorous acid. It means an aqueous solution containing hypochlorite.
  • the alkali metal used here is preferably hydroxide, carbonate, oxide, etc. of aluminum metal and earth metal, such as sodium hydroxide, calcium hydroxide, and oxide. Examples include calcium, sodium carbonate, calcium carbonate and the like. These can be used alone or in combination of two or more.
  • the amount of dissolving or suspending the alcohol in water is preferably an amount corresponding to 0.1 to 1.0 N. It is not preferable to use an amount of alcohol exceeding the above range because it causes inconvenience such as remarkable by-production of dichloride and the like, and intense decomposition of available chlorine in chlorinated water. Below this range, water use S will increase and should be avoided if possible.
  • a stirrer tank ⁇ As an apparatus for preparing chlorinated water, a stirrer tank ⁇ , an absorption apparatus as shown in the Chemical Engineering Association, Japan, edited by the Chemical Engineering Association, revised 5th edition, pp. 495-53, is commonly used.
  • Can be The operation may be continuous or batch type.
  • the operating temperature is not particularly limited, but is usually in the range of 0 to 100 ⁇ .
  • the produced chlorinated water is usually continuously reacted with cyclohexene, but may be temporarily stored in an intermediate storage tank. Hypochlorous acid is relatively unstable and hard, especially at high temperatures, so it is preferable to adopt a method such as cooling the produced chlorinated water. Absent.
  • the method can be carried out in a batch system, for example, a method in which a fixed amount of cyclohexene is added to a fixed amount of chlorine water and reacted, or a continuous system.
  • the reaction temperature is not particularly limited as long as it is 0 ° C or higher, but the reaction is usually carried out at 0 to 100 ° C.
  • the reaction time varies depending on the temperature, concentration, stirring state, etc., but is usually carried out for several seconds to several hours.
  • the reaction pressure is not critical, and the reaction can be carried out under any of atmospheric pressure, pressurized pressure and decompressed pressure conditions.
  • chlorine is reacted with an aqueous solution or suspension containing 0.1 to 1.0 N of an alkali, and the pH is reduced to 7 or less, more preferably 6.
  • chlorine water obtained by adjusting the water content to 5 or less as a chlorine source, the concentration of available chlorine in water that contributes to the production of chlorohydrin can be increased. It has been found that by controlling the PH value, it is possible to generate black mouth hydrin with a high selectivity, in addition to the advantage that the pH can be reduced. .
  • control the PH value by reacting the chlorine contained in the suspension with the amount of chlorine contained in the suspension, and adjusting the amount of chlorine.
  • a method is also possible in which a smaller amount, for example, 0.8 or 0.9 equivalent of chlorine is reacted, and then the pH is adjusted by adding an acid.
  • a smaller amount for example, 0.8 or 0.9 equivalent of chlorine
  • the pH is adjusted by adding an acid.
  • pH there is no particular lower limit for pH, but at an extremely low pH, the content of available chlorine decreases, so that the pH is usually set to 1.0 or more.
  • the available chlorine referred to here is the one required by the iodine titration method in which excess potassium iodide is added to chlorine water and the liberated chlorine is titrated with sodium thiosulfate. To tell. (Japan, published by Maruzen Co., Ltd., “Analytical Chemistry, Revised Third Edition” (1989, 1991), pp. 194-1).
  • the amount of cyclohexene that reacts with the available chlorine in the water has a significant effect on the selectivity of chlorohydrin, and is 1.05 times the available chlorine in the chlorinated water used.
  • By-product hexene in an amount greater than 1 mole, and more preferably greater than 1.10 moles, minimizes by-products.
  • dichlorocyclohexane, 2, 2, dichlorocyclo c Many by-products such as hexyl ether are generated.
  • the use of an excess of c-hexene is an option, given that it has been mentioned in the conventional propylene and phenyl chloride technologies, because it forms an oil phase apparently from the viewpoint of its solubility.
  • the unreacted cyclohexene remains in the reaction solution (1) containing the cyclohexene ⁇ -cohydrin obtained in the first step, but in the second step, Alkaline is added to the reaction solution (1) containing cyclohexene and the night phase is present, and the reaction between the cyclohexene cyclohydrin and the added alcohol is carried out. I prefer to do that.
  • the product cyclohexenoxide is secondarily reacted with water as a side reaction when producing cyclohexene oxide from cyclohexene chlorohydrin. Then, there is a reaction that produces one or two cycles of hexanediol.
  • an oil phase containing cyclohexene is present. If the reaction of the second step is carried out as it is, surprisingly, the reaction yield in this step is improved, and it is possible to obtain cyclohexenoxide with high selectivity and high yield. It was found. This is because the presence of cyclohexene in the oil phase lowers the polarity of the oil phase and suppresses side reactions in the oil phase, and the effect of cyclohexene in the oil phase.
  • the alkali used in the second step of the method of the present invention is preferably a hydroxide, carbonate, oxide or the like of each of an alkali metal and an alkaline earth metal, such as sodium hydroxide, Examples include calcium hydroxide, calcium oxide, sodium carbonate, calcium carbonate, and the like. These may be used alone or in combination of two or more.
  • the alkali may be subjected to the reaction in any form of an aqueous solution, a suspension, or a solid. There is no particular limitation on the amount used. Available chlorine used in the first step! If too small an amount is used, unreacted cyclohexenechlorohydrin will remain in a large amount, so the amount is usually 0.9 times the available chlorine used in the first step.
  • the t- reaction carried out in an amount of 2 to 2 equivalents, preferably 1 to 1.5 equivalents is usually performed in the range of 0 to 100 ° C. Since the reaction in the second step is carried out in the presence of an aqueous phase, an oil phase and, in some cases, an alkali solid, it is desirable to carry out the reaction under a good mixing state. As a method for this, see “Chemical Engineering Handbook Revised 5th Edition”, edited by The Chemical Engineering Association of Japan, pages 538-589, 888-919, 988-118, page 183.
  • the reaction time which can be exemplified by the liquid-liquid mixing apparatus as shown, varies depending on the reaction conditions and the stirring state, but is carried out between several minutes and several hours.
  • reaction pressure is not critical, and the reaction can be carried out under any of atmospheric pressure, pressurized pressure and reduced pressure conditions.
  • the reaction solution of the first step is directly introduced into the reactor, and alkali is added to react.
  • the reaction solution of the first step (1) Can be introduced into the second step after adding cyclohexene, removing some of the hexene by distillation or other methods, and adding or removing water.
  • the amount of cyclohexene present in the reaction of the second step is preferably 3 to 300% of the amount of available chlorine in the chlorine water used in the first step. In some cases, it is also possible to carry out the reaction of the second step in the absence of hexene.
  • the oxen oxoxide generated in the second step is distributed to both the oil phase and the aqueous phase in the reaction solution, and the above-mentioned 0 rg.
  • Co 1. vol.1, pp. 185-186, John Wiley & Sons Inc. (1951) it was found that simply separating and recovering the oil phase resulted in large losses.
  • a method of distilling and recovering the oxide at the same time as the reaction is adopted. If this method is applied to cyclohexene oxide, the boiling point of cyclohexenoxide is higher than that of water, so it is essential to remove all the water in the system by distillation. The fools who need gibbons. According to the study of the present inventors, it has been found that the hydration of the oxide proceeds during the operation.
  • an organic component is recovered from the reaction solution (2) in the second step to obtain an organic mixed solution containing the organic component. Separate and recover from the organic mixture obtained in the three steps into ordinary distillation residue, cyclohexene, cyclohexene oxide, solvent, etc.
  • reaction solution (2) containing an organic component containing cyclohexenoxide is obtained.
  • organic component refers to unreacted cyclohexene in the first step, cyclohexene oxide which is the target compound in the second step, unreacted cyclohexene hydroxide, And by-products of the first and second steps.
  • an organic component is recovered from the reaction solution (2) in the second step, and an organic mixed solution containing the organic component is recovered. obtain.
  • the reaction solution (2) obtained in the second step is composed of an organic phase composed of one part of the organic component, and an aqueous phase containing the remainder of the organic component.
  • the reaction solution (2) is phase-separated into an organic phase and an aqueous phase, and an organic component is extracted from the separated aqueous phase using a solvent to obtain an extract.
  • an organic component is directly extracted from the reaction solution (2) containing the organic phase and the aqueous phase using a solvent, and the extract as an organic mixed solution containing the organic component is extracted. How to get.
  • Examples of the solvent used herein include aliphatic hydrocarbons such as heptane and nonane and their halides, alicyclic hydrocarbons such as cyclohexene and cyclohexene, and their halogens. , Aromatic hydrocarbons such as benzene and toluene, their halides, ethers such as anisol and their ⁇ -genides, ketones such as methylisobutyl ketone, esters such as ethyl benzoate, etc. These can be used alone or in combination of two or more. It is particularly preferable to use hexene hexene, so that the burden on the separation of the extraction solvent in the fourth step can be reduced.
  • the apparatus used for the extraction may be a commonly known apparatus. Engineering Association, “Chemical Engineering Handye Revised 5th Edition”, pp. 537-583.
  • each organic component is separated by ordinary distillation.
  • a distillation column or the like is appropriately designed depending on the properties of the solvent used.
  • the cyclohexane and solvent recovered in this process are usually reused.
  • Each of the first to fourth steps of the present invention may be a batch type or a continuous type, and the steps may be connected to perform continuous production.
  • FIG. 1 is a flow sheet schematically showing one embodiment of the method of the present invention for producing cyclohexene from cyclohexene via cyclohexene chlorohydrin.
  • A is a process for preparing chlorinated water in the first step, in which water containing chlorine 2 and water 1 containing alcohol are mixed while adjusting the pH to prepare chlorinated water, and the chlorinated water and cyclohexene are prepared.
  • 3 is introduced into B, which performs chlorohydrin synthesis.
  • a chlorohydrination reaction is performed by mixing an oil phase (cyclohexene) and an aqueous phase (chlorine water), and this reaction solution is introduced into the second step C.
  • alkali 4 is introduced, and an oxide is synthesized under stirring and mixing.
  • the aqueous phase 6 and the oil phase 5 of the reaction solution are separated, the aqueous phase 6 is introduced into the third step D, and the organic component is extracted with the solvent 7, and the extract 8 containing the organic component is extracted into the oil phase. 5 together with the fourth process E
  • the unreacted cyclohexene 10, cyclohexene oxide 12, solvent 11, by-product 13 are separated.
  • Figure 9 shows the aqueous phase of the extraction residue.
  • the reaction liquid in step C was used for organic component extraction in D without separating the aqueous phase 6 and oil phase 5 of the reaction liquid. It can be directly applied and the resulting extract 8 can be sent directly to the fourth step.
  • FIG. 3 is a schematic but specific illustration of one embodiment of the method of the present invention for producing cyclohexene from cyclohexene via cyclohexene cyclohydrin. This is the flow sheet shown.
  • a is a chlorine water preparation reactor
  • b is an absorption tower
  • c is a chlorohydrination reactor
  • d is an oxidization reactor
  • e is a countercurrent extractor
  • f and g Distilled water is indicated, respectively.
  • M indicates a motor.
  • the present inventors have conducted intensive studies and found that an aqueous solution or a suspension containing 0.1 to 1.0 N of aluminum chloride and chlorine were used. And chlorine to prepare a chlorine water containing available chlorine and having a pH value of 7 or less, and an amount of water equivalent to 1.05 times or more of the number of moles of available chlorine contained therein. Surprisingly, it was found that cyclohexene reacts with cyclohexene to obtain cyclohexene mouth-to-mouth hydrin with extremely high selectivity.
  • 0.1 to 1.0 N By reacting an aqueous solution or a suspension of water containing water with chlorine and chlorine to prepare chlorine water containing available chlorine and having a pH value of 7 or less, the chlorine water is added to the chlorine water.
  • a process for producing cyclohexene hydrohydrin which comprises reacting xen to at least 1.05 times the molar amount of the cyclohexene.
  • the oil phase is separated from the reaction liquid containing cyclohexenechlorohydrin and then distilled. Separation, if necessary, extraction of organic components such as cyclohexene chlorohydrin, cyclohexene, and by-products remaining in the aqueous phase with a solvent, and extraction with the oil phase separated earlier Usually, a method of separating by distillation is usually performed. However, a method of directly separating and distilling the reaction solution can also be performed.
  • Examples of the solvent used for the extraction include aliphatic hydrocarbons such as heptane and nonane and their halides, alicyclic hydrocarbons such as cyclohexane and cyclohexene and their halides and benzene.
  • Aromatic hydrocarbons such as benzene and toluene, their halogenated compounds, ethers such as anisol and their halides, ketones such as methylisobutyl ketone, and esters such as ethyl benzoate. These may be used alone or in combination of two or more.
  • Example 1 Example 1
  • chlorine water was prepared by blowing chlorine gas into a 0.25 mol / ⁇ aqueous sodium hydroxide solution until the water content reached 5.0.
  • the available chlorine amount was 0.24 mol / ⁇ .
  • 15 g / hr of hexene and 600 ml / hr of chlorinated water were introduced into a complete mixed flow reactor with a content of 10 Om1 as shown in Fig. 2.
  • the reaction was carried out at 40 ° C. with stirring (cyclohexene / effective chlorine molar ratio: 1.27). After the reaction reached a steady state, analysis of the extracted reaction solution revealed that the conversion rate of cyclohexene was 78.3% and the selectivity of cyclohexene hydrohydrin was 94.4. It was 5%.
  • the reaction was carried out in the same manner as in Example 7, except that the pH was changed to 7.5 in the preparation of the chlorine water. After the reaction reached a steady state, the reaction mixture withdrawn was analyzed to find that the conversion of cyclohexene was 30.0% and the selectivity of cyclohexene chlorohydrin was 43.0%. Was.
  • This reaction solution was continuously withdrawn, and a reactor equipped with a stirrer connected in series to two tanks (1.8 pounds in each tank) was connected to a reactor d containing 12 wt% calcium hydroxide suspended water (1.2 wt%). It was supplied with 6 kg / hr and reacted at 60 kg / hr. Analysis of the reaction mixture revealed that the yield of cyclohexene oxenoxide relative to consumed cyclohexene was 91.1%.
  • the reaction liquid continuously withdrawn from reactor d was separated from oil and water, and the aqueous phase was extracted with a 0.2 kg / hr cyclohexene extractor using a countercurrent continuous extractor e. went.
  • the extracted oil phase was continuously supplied to the first distillation column f together with the oil separated in d, and lithohexene was recovered from the top of the column (0.83 kg Z hr). . Further, the bottom liquid was continuously supplied to the second distillation column g, and xylene oxide was recovered from the top of the column (0.441 kg / hr). From the bottom of the tower, by-products such as xanthic mouth rides to the mouth and a mixture of xenoxoxide and the like were continuously discharged to a small amount of mouths. In the aqueous phase discharged from the extraction unit e, about 0.02 wt% of cyclohexene and about 0.01 wt% of cyclohexene were added. Was detected.
  • Example 8 The same operation as in Example 8 was performed except that the amount of cyclohexene supplied to the reactor c was 0.53 kg / hr (molar ratio of chlorine to 1.26).
  • the cyclohexenoxide recovered at the top of the second distillation column g was 0.444 kg / hr. From the bottom of the column, by-products such as cyclohexanedichloride and a mixture of xenoxoxide and the like were continuously discharged into a small amount of the mouth of the cylinder. Approximately 0.02 wt% of cyclohexene and approximately 0.01 wt% of cyclohexene were detected in the aqueous phase discharged from the extraction unit.
  • Example 8 The operation was performed in the same manner as in Example 8 except that the amount of cyclohexene supplied to the reactor c was 0.42 kg / hr (the molar ratio to chlorine was 1.02).
  • the yield of the consumed cyclohexene oxide relative to the consumed cyclohexene was 82%. It can be seen that the decrease in yield is large.
  • Example 6 The operation was performed in the same manner as in Example 8 except that the pH of the reactor a was set to 8.0.
  • the reaction solution discharged from the reactor d was analyzed, The yield of ox-hexoxenide to ox-hexene consumed was 40%. It can be seen that the decrease in yield is large Comparative Example 6
  • Example 10 After oil-water separation in the reactor d, the same operation as in Example 8 was performed, except that the extraction with the continuous extractor e was not performed, and only the oil phase separated in the reactor d was distilled.
  • the cyclohexenoxide recovered from the upper part of the second distillation column g was 0.344 kg / hr, and the yield was greatly reduced as compared with Example 8.
  • the aqueous phase separated in the reactor d was distilled and, following the removal of water, recovery of cyclohexenoxide was attempted, but most of it was hydrated to form diol, and cyclohexenoxide was removed. Can not be recovered.
  • Example 10 Example 10
  • the reaction liquid continuously withdrawn from the reactor d was directly introduced into the countercurrent type continuous extractor e without oil / water separation, using 0.42 kg / hr cyclohexene. Extraction was carried out except that the extracted oil phase was continuously supplied to the first distillation column. The operation was performed as in Example 9.
  • the cyclohexenoxide recovered from the upper part of the second distillation column g was 0.444 kg / hr, which was the same as in Example 9.
  • cyclohexene oxide useful as an intermediate for pesticides and the like can be industrially advantageously produced from cyclohexene, chlorine and alkali at a high selectivity.

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  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Epoxy Compounds (AREA)

Abstract

Procédé de préparation d'oxyde de cyclohexène consistant, dans une première étape, à préparer un fluide réactionnel (1) contenant de la chlorohydrine de cyclohexène par réaction du chlore avec une solution ou une suspension aqueuse alcaline de 0,1-1 N, afin d'obtenir de l'eau de chlore contenant du chlore disponible et possédant un pH égal ou inférieur à 7 et par réaction de l'eau de chlore avec du cyclohexène en une quantité d'au moins 1,05 moles par unité molaire de chlore disponible; dans une deuxième étape, à préparer un fluide réactionnel (2) contenant des constituants organiques, y compris de l'oxyde de cyclohexène par addition d'un alcali au fluide réactionnel (1) obtenu à la première étape, afin de faire réagir la chlorohydrine de cyclohexène avec l'alcali; dans une troisième étape, à préparer un mélange organique liquide contenant les constituants organiques par récupération des constituants depuis le fluide réactionnel (2) obtenu à la deuxième étape; enfin, dans une quatrième étape, à isoler et à récupérer l'oxyde de cyclohexène par distillation à partir du mélange organique liquide obtenu à la troisième étape. Ce procédé permet d'obtenir hautement sélectivement de la chlorohydrine de cyclohexène à partir de cyclohexène, puis d'obtenir de l'oxyde de cyclohexène, à haut rendement, à partir de la chlorohydrine de cyclohexène ainsi obtenue. On peut isoler l'oxyde de cyclohexène et le récupérer efficacement sans risques de décomposition, afin de l'utiliser en tant qu'intermédiaire de pesticides, par exemple.
PCT/JP1994/001912 1994-07-19 1994-11-11 Procede de production d'oxyde de cyclohexene WO1996002526A1 (fr)

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JP16650294A JPH0827137A (ja) 1994-07-19 1994-07-19 シクロヘキセンオキサイドの製造方法

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993131A (zh) * 2012-12-27 2013-03-27 南京工业大学 一种邻氯环己醇环化制备环氧环己烷的方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5084506A (fr) * 1973-11-30 1975-07-08
US5146011A (en) * 1990-03-05 1992-09-08 Olin Corporation Preparation of chlorohydrins

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5084506A (fr) * 1973-11-30 1975-07-08
US5146011A (en) * 1990-03-05 1992-09-08 Olin Corporation Preparation of chlorohydrins

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Vol. 97, (1982), Abstract No. 71698. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102993131A (zh) * 2012-12-27 2013-03-27 南京工业大学 一种邻氯环己醇环化制备环氧环己烷的方法
CN102993131B (zh) * 2012-12-27 2014-12-10 南京工业大学 一种邻氯环己醇环化制备环氧环己烷的方法

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