CA1060901A - Continuous process for the production of cyclohexyl magnesium halides - Google Patents
Continuous process for the production of cyclohexyl magnesium halidesInfo
- Publication number
- CA1060901A CA1060901A CA254,270A CA254270A CA1060901A CA 1060901 A CA1060901 A CA 1060901A CA 254270 A CA254270 A CA 254270A CA 1060901 A CA1060901 A CA 1060901A
- Authority
- CA
- Canada
- Prior art keywords
- column
- cyclohexyl
- halide
- magnesium
- production
- 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
- -1 cyclohexyl magnesium halides Chemical class 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 238000010924 continuous production Methods 0.000 title claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 150000004820 halides Chemical class 0.000 abstract description 3
- 239000004009 herbicide Substances 0.000 abstract description 2
- 239000011261 inert gas Substances 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- RNVJQUPAEIQUTC-UHFFFAOYSA-N tricyclohexyltin Chemical class C1CCCCC1[Sn](C1CCCCC1)C1CCCCC1 RNVJQUPAEIQUTC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007818 Grignard reagent Substances 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- UNFUYWDGSFDHCW-UHFFFAOYSA-N monochlorocyclohexane Chemical compound ClC1CCCCC1 UNFUYWDGSFDHCW-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- WCMMILVIRZAPLE-UHFFFAOYSA-M cyhexatin Chemical class C1CCCCC1[Sn](C1CCCCC1)(O)C1CCCCC1 WCMMILVIRZAPLE-UHFFFAOYSA-M 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/02—Magnesium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
A process and apparatus for the continuous production of cyclohexyl magnesium halide. Cyclohexyl halide is fed at a constant rate into a thermostatized column from the bottom thereof, the column containing magnesium shavings fed from the top thereof, and the desired cyclohexyl magnesium halide is recovered from the top of the column. According to the invention, there is no need to carry out the reaction in an inert gas atmosphere, such as always required in known discontinuous processes. The invention has the further advantage of enabling one to obtain a complete reaction with a single passage of the halide into the column, without having to resort to recycles, since the path followed by the magnesium allows the same to reach the reaction area in conditions of maximum reactivity. Cyclohexyl magnesium halides are products particularly useful in the production of tricyclo-hexyl tin derivatives which are valuable herbicides.
A process and apparatus for the continuous production of cyclohexyl magnesium halide. Cyclohexyl halide is fed at a constant rate into a thermostatized column from the bottom thereof, the column containing magnesium shavings fed from the top thereof, and the desired cyclohexyl magnesium halide is recovered from the top of the column. According to the invention, there is no need to carry out the reaction in an inert gas atmosphere, such as always required in known discontinuous processes. The invention has the further advantage of enabling one to obtain a complete reaction with a single passage of the halide into the column, without having to resort to recycles, since the path followed by the magnesium allows the same to reach the reaction area in conditions of maximum reactivity. Cyclohexyl magnesium halides are products particularly useful in the production of tricyclo-hexyl tin derivatives which are valuable herbicides.
Description
The present invention relatcs to a process for the production, in a continuous cycle, of cyclohexyl magnesium halides.
As known, the cyclohexyl magnesium halides are products which have recently acquired a lot of importance, for example for the production of tricyclohexyl tin derlvatives, as the tricyclohexyl tin halides and the tricyclohexyl tin hydroxides, which are very useful as herbicides.
The cyclohexyl magnesium halides are at present produced with a discontinuous process. Such a process has its drawbacks, as there is always - while carrying out the reaction at the basis thereof:
C6HllX~ Mg----~ C6HllMgX
wherein X is a halogen (especially C1) - the possibility of explosions, in the event that an excessive amount of halide should be fed when the reaction has not yet started. Moreover, the reaction does not always develop in a complete way, and it is anyhow necessary for it to be carried out in an inert atmosphere.
All such drawbacks are eliminated by the continuous proeess aceording to the present invention, which further includes, compared to the known process, all the advantages of eontinuous productions.
In aeeordanee with the invention, there is therefore provided a continuous process for the production of cyclohexyl magnesium halide, whieh comprises feeding cyclohexyl halide at a constant rate into a thermostatized column from the bottom thereof, the eolumn containing magnesium shavings fed from the top thereof, and recovering the desired cyclohexyl magnesium halide from the top of the column.
The present invention also provides an apparatus for carrying out the above process, which comprises a thermostatized ~.
. . .
~. 10~0901 column having a bottom part and a top part, the bottom part containing a filling of Rasching rings and being connected to means for feeding cyclohexyl halide, the top part being provided with means for feeding magnesium shavings and with means for discharging the desired cyclohexyl magnesium halide.
The in~ention will now be described in further detail with reference to the accompanying drawing, which schematically il]us-trates an apparatus in accordance with this invention.
With reference to the drawing, use is made of a column 10 1, having a diameter of 5 cm. and a volume of 2000 ml., containing at the bottom 2 a filling of about 3 cm. of Rasching rings !
and being thermostated at 58-60C through circulation from the hottom upwards of H2O into a jacket 3. Said column comprises at the top a feeding mouth 4 and in its top part a spillway 5, connected through a discharge 5' to a tank 6, while in the lower part of the column, which also CompriSes a drain cock 7, there is a feed pipe 8, into which the product contained in a tank 9 is caused to flow through a constant delivery pump 10.
The column 1 is filled from the feeding mouth 4, with shavings (about 420 gr.), Up to the height of the discharge 5'. About 200 ml. of 34-35% Grignard reagent solution in tetrahydrofuran are then charged into the column; one waits for ~ -the inner temperature to reach 58-60C and then one starts to feed through the pipe 8 an anhydrous solution of cyclohexyl chloride in tetrahydrofuran - in the proportions of 650 gr. of tetrahydro-furan and 290 gr. of cyclohexyl chloride - in a quantity o 1 kg.
per hour. As one continues to feed said solùtion from the pipe 8, the reaction product consisting of a 34-35% Grignard reagent solution in tetrahydrofuran, starts to come out from the spillway 5. Said solution is collected into the appropriate tank 6.
The reaction yield, calculated on the cyclohexyl chloride, is of 96-98~. The magnesium wastesaway mainly onto 10G09~
the bottom of the column 1, whercby the shavings of this metal slowly drop down along the column itself; this latter is kept constantly filled by frequently adding shavings through the feeding mouth.
With this technique, there appears to be no formation of residues, whereby there is no need for a periodic cleaning of the column.
To interrupt the production, it is anyhow sufficient to stop the feeding from the pipe 8, to cool down the apparatus and to keep the column 1 filled in anhydrous conditions. To start again the production, the inner temperature is brought back to 58-60C and the cyclohexyl chloride solution is fed again from the pipe 8.
Compared to the known discontinuous techniques, the continuous process according to the invention, for the preparing of cyclohexyl magnesium halides, has first of all the advantage of being less dangerous, both because of the reduced quantities of products in the cycle, and because of the elimination of the risks connected with the starting of the reaction. In fact, the reaction column can be kept full of Grignard reagent and of Mg, in rest conditions at ambient temperature, even for prolonged periods of time, and then it can be started again, in conditions of normal efficiency, after having been brought back to the reaction temperature. (On the other hànd, this make it indispensable to use a solvent, which will keep the Grignard reagent in solution, at ambient temperature, so as not to have precipitations in the column).
~ further advantage of the process according to the invention is that the path followed by the magnesium, according to the type of feeding adopted, allows the same to reach the reaction area in conditions of maximum reactivity. It is hence possible to obtain a complete react1on with a single passage of the halide into the column, without having to resort to recycles.
The fact should not be neglected, moreover, that the tests carried out so far have not revealed the need to carry out the reaction in an inert gas atmosphere, as was always required in the known discontinuous processes; this is probably due to the fact that, in the process using the apparatus according to the invention, the reaction takes place in an area which is definitely out of contact with air.
i - 4 -,
As known, the cyclohexyl magnesium halides are products which have recently acquired a lot of importance, for example for the production of tricyclohexyl tin derlvatives, as the tricyclohexyl tin halides and the tricyclohexyl tin hydroxides, which are very useful as herbicides.
The cyclohexyl magnesium halides are at present produced with a discontinuous process. Such a process has its drawbacks, as there is always - while carrying out the reaction at the basis thereof:
C6HllX~ Mg----~ C6HllMgX
wherein X is a halogen (especially C1) - the possibility of explosions, in the event that an excessive amount of halide should be fed when the reaction has not yet started. Moreover, the reaction does not always develop in a complete way, and it is anyhow necessary for it to be carried out in an inert atmosphere.
All such drawbacks are eliminated by the continuous proeess aceording to the present invention, which further includes, compared to the known process, all the advantages of eontinuous productions.
In aeeordanee with the invention, there is therefore provided a continuous process for the production of cyclohexyl magnesium halide, whieh comprises feeding cyclohexyl halide at a constant rate into a thermostatized column from the bottom thereof, the eolumn containing magnesium shavings fed from the top thereof, and recovering the desired cyclohexyl magnesium halide from the top of the column.
The present invention also provides an apparatus for carrying out the above process, which comprises a thermostatized ~.
. . .
~. 10~0901 column having a bottom part and a top part, the bottom part containing a filling of Rasching rings and being connected to means for feeding cyclohexyl halide, the top part being provided with means for feeding magnesium shavings and with means for discharging the desired cyclohexyl magnesium halide.
The in~ention will now be described in further detail with reference to the accompanying drawing, which schematically il]us-trates an apparatus in accordance with this invention.
With reference to the drawing, use is made of a column 10 1, having a diameter of 5 cm. and a volume of 2000 ml., containing at the bottom 2 a filling of about 3 cm. of Rasching rings !
and being thermostated at 58-60C through circulation from the hottom upwards of H2O into a jacket 3. Said column comprises at the top a feeding mouth 4 and in its top part a spillway 5, connected through a discharge 5' to a tank 6, while in the lower part of the column, which also CompriSes a drain cock 7, there is a feed pipe 8, into which the product contained in a tank 9 is caused to flow through a constant delivery pump 10.
The column 1 is filled from the feeding mouth 4, with shavings (about 420 gr.), Up to the height of the discharge 5'. About 200 ml. of 34-35% Grignard reagent solution in tetrahydrofuran are then charged into the column; one waits for ~ -the inner temperature to reach 58-60C and then one starts to feed through the pipe 8 an anhydrous solution of cyclohexyl chloride in tetrahydrofuran - in the proportions of 650 gr. of tetrahydro-furan and 290 gr. of cyclohexyl chloride - in a quantity o 1 kg.
per hour. As one continues to feed said solùtion from the pipe 8, the reaction product consisting of a 34-35% Grignard reagent solution in tetrahydrofuran, starts to come out from the spillway 5. Said solution is collected into the appropriate tank 6.
The reaction yield, calculated on the cyclohexyl chloride, is of 96-98~. The magnesium wastesaway mainly onto 10G09~
the bottom of the column 1, whercby the shavings of this metal slowly drop down along the column itself; this latter is kept constantly filled by frequently adding shavings through the feeding mouth.
With this technique, there appears to be no formation of residues, whereby there is no need for a periodic cleaning of the column.
To interrupt the production, it is anyhow sufficient to stop the feeding from the pipe 8, to cool down the apparatus and to keep the column 1 filled in anhydrous conditions. To start again the production, the inner temperature is brought back to 58-60C and the cyclohexyl chloride solution is fed again from the pipe 8.
Compared to the known discontinuous techniques, the continuous process according to the invention, for the preparing of cyclohexyl magnesium halides, has first of all the advantage of being less dangerous, both because of the reduced quantities of products in the cycle, and because of the elimination of the risks connected with the starting of the reaction. In fact, the reaction column can be kept full of Grignard reagent and of Mg, in rest conditions at ambient temperature, even for prolonged periods of time, and then it can be started again, in conditions of normal efficiency, after having been brought back to the reaction temperature. (On the other hànd, this make it indispensable to use a solvent, which will keep the Grignard reagent in solution, at ambient temperature, so as not to have precipitations in the column).
~ further advantage of the process according to the invention is that the path followed by the magnesium, according to the type of feeding adopted, allows the same to reach the reaction area in conditions of maximum reactivity. It is hence possible to obtain a complete react1on with a single passage of the halide into the column, without having to resort to recycles.
The fact should not be neglected, moreover, that the tests carried out so far have not revealed the need to carry out the reaction in an inert gas atmosphere, as was always required in the known discontinuous processes; this is probably due to the fact that, in the process using the apparatus according to the invention, the reaction takes place in an area which is definitely out of contact with air.
i - 4 -,
Claims (4)
1. A continuous process for the production of cyclohexyl magnesium halide, which comprises feeding cyclohexyl halide at a constant rate into a thermostatized column from the bottom thereof, said column containing magnesium shavings fed from the top thereof, and recovering the desired cyclohexyl magnesium halide from the top of the column.
2. Process as claimed in claim 1, wherein the temperature of the column is kept at about 58-60°C and the cyclo-hexyl halide is fed in a solution of tetrahydrofuran, the cyclo-hexyl magnesium halide being thereby obtained in a tetra-hydrofuran solution.
3. Process as claimed in claim 1, wherein, upon starting, a solution of cyclohexyl magnesium halide in tetrahydro-furan is introduced into the column, before feeding the cyclohexyl halide.
4. An apparatus for the continuous production of cyclohexyl magnesium halide, which comprises a thermostatized column having a bottom part and a top part, the bottom part containing a filling of Rasching rings and being connected to means for feeding cyclohexyl halide, the top part being provided with means for feeding magnesium shavings and with means for discharging the desired cyclohexyl magnesium halide.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT24100/75A IT1038754B (en) | 1975-06-06 | 1975-06-06 | CONTINUOUS PROCEDURE FOR THE PRODUCTION OF CICLOESILMAGNESIOALOGE NURI |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1060901A true CA1060901A (en) | 1979-08-21 |
Family
ID=11211976
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA254,270A Expired CA1060901A (en) | 1975-06-06 | 1976-06-07 | Continuous process for the production of cyclohexyl magnesium halides |
Country Status (15)
| Country | Link |
|---|---|
| JP (1) | JPS5257148A (en) |
| AR (1) | AR216441A1 (en) |
| AU (1) | AU506343B2 (en) |
| BE (1) | BE842631A (en) |
| BR (1) | BR7603596A (en) |
| CA (1) | CA1060901A (en) |
| DE (1) | DE2625216A1 (en) |
| ES (1) | ES448618A1 (en) |
| FR (1) | FR2313390A1 (en) |
| GB (1) | GB1546143A (en) |
| IL (1) | IL49722A (en) |
| IT (1) | IT1038754B (en) |
| NL (1) | NL7605992A (en) |
| NZ (1) | NZ181096A (en) |
| ZA (1) | ZA763283B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IT1121958B (en) * | 1979-06-27 | 1986-04-23 | Oxon Italia Spa | PROCEDURE FOR OBTAINING HIGH-PURITY TRICYCLEHEXHYLIDE HYDROXIDE WITH HIGH YIELDS |
| DE10304006B3 (en) * | 2003-02-01 | 2004-08-19 | Merck Patent Gmbh | Continuous method for preparing Grignard adducts, on column of magnesium turnings through which a mixture of halide and cyclohexanone reactant is passed, optionally with direct hydrolysis and dehydration to cyclohexene derivative |
| WO2021153422A1 (en) * | 2020-01-27 | 2021-08-05 | 株式会社トクヤマ | Method for producing halogenated hydrocarbon magnesium compound and methods for producing tertiary alcohol compound and organosilicon compound |
| KR20230172459A (en) * | 2021-04-22 | 2023-12-22 | 가부시키가이샤 도쿠야마 | Method for producing organic compounds and apparatus for producing organic compounds |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2464685A (en) * | 1946-12-02 | 1949-03-15 | Diamond Alkali Co | Continuous grignard method |
| FR1295954A (en) * | 1961-04-28 | 1962-06-15 | Cfmc | Apparatus and method for the continuous manufacture of organomagnesium derivatives |
| DE1293767B (en) * | 1967-08-26 | 1969-04-30 | Basf Ag | Process for making Grignard compounds |
| US3911037A (en) * | 1973-11-21 | 1975-10-07 | Nalco Chemical Co | Continuous Grignard reactors |
-
1975
- 1975-06-06 IT IT24100/75A patent/IT1038754B/en active
-
1976
- 1976-06-03 NL NL7605992A patent/NL7605992A/en not_active Application Discontinuation
- 1976-06-03 AU AU14585/76A patent/AU506343B2/en not_active Expired
- 1976-06-03 ZA ZA763283A patent/ZA763283B/en unknown
- 1976-06-04 DE DE19762625216 patent/DE2625216A1/en not_active Withdrawn
- 1976-06-04 FR FR7617018A patent/FR2313390A1/en active Granted
- 1976-06-04 BR BR3596/76A patent/BR7603596A/en unknown
- 1976-06-04 BE BE167658A patent/BE842631A/en not_active IP Right Cessation
- 1976-06-05 ES ES448618A patent/ES448618A1/en not_active Expired
- 1976-06-06 IL IL49722A patent/IL49722A/en unknown
- 1976-06-07 CA CA254,270A patent/CA1060901A/en not_active Expired
- 1976-06-07 AR AR263540A patent/AR216441A1/en active
- 1976-06-07 GB GB23390/76A patent/GB1546143A/en not_active Expired
- 1976-06-07 JP JP51066405A patent/JPS5257148A/en active Pending
- 1976-06-08 NZ NZ181096A patent/NZ181096A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR7603596A (en) | 1977-01-18 |
| NZ181096A (en) | 1978-04-28 |
| AU506343B2 (en) | 1979-12-20 |
| BE842631A (en) | 1976-10-01 |
| IL49722A (en) | 1978-08-31 |
| AU1458576A (en) | 1977-12-08 |
| ZA763283B (en) | 1977-07-27 |
| AR216441A1 (en) | 1979-12-28 |
| FR2313390B1 (en) | 1982-11-05 |
| IT1038754B (en) | 1979-11-30 |
| FR2313390A1 (en) | 1976-12-31 |
| DE2625216A1 (en) | 1976-12-23 |
| GB1546143A (en) | 1979-05-16 |
| IL49722A0 (en) | 1976-08-31 |
| ES448618A1 (en) | 1977-07-01 |
| JPS5257148A (en) | 1977-05-11 |
| NL7605992A (en) | 1976-12-08 |
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