CA1072561A - Preparation of n,n-dimethylpiperidinium chloride and n,n-dimethylmorpholinium chloride - Google Patents
Preparation of n,n-dimethylpiperidinium chloride and n,n-dimethylmorpholinium chlorideInfo
- Publication number
- CA1072561A CA1072561A CA288,706A CA288706A CA1072561A CA 1072561 A CA1072561 A CA 1072561A CA 288706 A CA288706 A CA 288706A CA 1072561 A CA1072561 A CA 1072561A
- Authority
- CA
- Canada
- Prior art keywords
- chloride
- reaction
- dimethylpiperidinium
- dimethylmorpholinium
- methyl
- 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
- VHOVSQVSAAQANU-UHFFFAOYSA-M mepiquat chloride Chemical compound [Cl-].C[N+]1(C)CCCCC1 VHOVSQVSAAQANU-UHFFFAOYSA-M 0.000 title claims abstract description 9
- RBIPMCDRANHGQI-UHFFFAOYSA-M 4,4-dimethylmorpholin-4-ium;chloride Chemical compound [Cl-].C[N+]1(C)CCOCC1 RBIPMCDRANHGQI-UHFFFAOYSA-M 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title abstract description 4
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229940050176 methyl chloride Drugs 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 13
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 claims description 12
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012022 methylating agents Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000000243 solution Substances 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001510 metal chloride Inorganic materials 0.000 description 2
- -1 sodiu~ hydroxide Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- HSQOPVUSHBNOOL-UHFFFAOYSA-M 1,1-dimethylpiperidin-1-ium;iodide Chemical compound [I-].C[N+]1(C)CCCCC1 HSQOPVUSHBNOOL-UHFFFAOYSA-M 0.000 description 1
- YGNXNQMVWHPUET-UHFFFAOYSA-M 4,4-dimethylmorpholin-4-ium;iodide Chemical compound [I-].C[N+]1(C)CCOCC1 YGNXNQMVWHPUET-UHFFFAOYSA-M 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 101100087530 Caenorhabditis elegans rom-1 gene Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 101100305983 Mus musculus Rom1 gene Proteins 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- QDUXDCXILAPLAG-UHFFFAOYSA-N hydron;1-methylpiperidine;chloride Chemical compound Cl.CN1CCCCC1 QDUXDCXILAPLAG-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000010808 liquid waste Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000011987 methylation Effects 0.000 description 1
- 238000007069 methylation reaction Methods 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Hydrogenated Pyridines (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pyridine Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
O.Z. 32,292 ABSTRACT OF THE DISCLOSURE: The preparation of N,N-dimethylpiperi-dinium chloride and N,N-dimethylmorpholinium chloride from the corresponding monomethyl compounds with methyl chloride in the presence of water.
Description
:~O~Z~l o, zo 32, 292 PREPARATION OF N,N-DIMETHYLPIPERIDINIUM CHLORIDE
AND N,N DIMETH~LMORPHOLINIUM CHLORIDE
The present invention relates to a process for the preparation o~ N,N-dimethylpiperidinium chloride and N,N-dimethylmorpholinium chloride from the corresponding monomethyl compounds with methyl chloride in the presence of waterO
It is known (German 1,642,215 and German Laid-Open ~pplication DOS 2,207,57~) to use N,N-dimethylpiperidinium chloride and N3N-dimethylmorpholinium chloride as agents for influencing plant growth. They are applied as an aqueous solution. They are prepared - -in conventional manner by conversion o~ N,N-dimethylpiperidinium iodide and N,N-dimethylmorpholinium iodide into the corresponding chlorides (Helv. Chim. Acta, 39, 399, 1956; Chem. Ber., 22, 2091, 1889).
We have now found that N,N-dimethylpiperidinium chloride and NgN-dimethylmorpholinium chloride are easily obtained from N-methyl piperidine and N-methylmorpholine respectively, in excellent yields, when the monomethyl compounds are reacted with methyl chloride in the presence of water as diluent at a temperature of ~rom 0 to 100C and a pressure of ~rom 1 to 7 bars This is surprisin~ and could not have been foreseen, because methylation with methyl chloride hitherto has been carried out in non-aqueous solvents, or, when water has been used as diluent, temperatures far in excess (120C) o~ room temperature and high pressures (20 to 60 bars) have been employedO
The process according to the invention has two essential advan-tages: a) the process is very simple and thus extremely econo~ical as a result of the use of water as diluent, because the aqueous .~
~ S~ OOZo 32,~92 solution of the end products can be employed direct for biolo~ical purposes; b) as the reaction takes place at atmospheric or sli~htly superatmospheric pressure, inexpensive standard stirred vessels may be used, as they are usually~ even when intended for pressureless reactions, designed for safety reasons to withstand a pressure of from 4 to 7 barsO
When N-methylpiperidine is used, the reaction may be represented as follows:
C 3 3 ~ CH3 Compared with prior art processes, the process of the invention provides, in a simpler and more economic manner, the desired quaternary ammonium chlorides in good yield and high purityO Whereas prior art processes were cumbersome because they had to be carried out in two stages, the reaction in the process according to the invention is carried out in one step.
Starting materials for the process are N-methylpiperidine3 N-methylrnorpholine and methyl chloride. They are used for instance in approximately equivalent amounts, optionally with a slight excess of methyl chloride.
The reaction may be carried out for instance as follows~ Water and the monomethylarnine are placed in the reaction vessel, and the mixture is heated to the desired reaction temperature and ~hen treated with methyl chloride. Advantageously, the reaction components are mixed with each other, for example by stirringO A~ter the reaction is over, the reaction solution is cooled to room tempera-ture and then diluted with water to the desired active ingredient concentration.
The monomethylamine concentration in the water upon cornmencement of the reaction may be varied within wide limits. It is preferred to use concentrations whlch, upon completion Or the reaction~ give end product concentrations slightly above the concentration of the 7Z~6~
0 ZO 32,292 aqueous solutlons when marketedD However~ it is also possible to start with more dilute aqueous solution and to distil off some~of the water used after che reaction is over without the quality of the end products sufferingO The concentration of the monomethyl~
amines in the water may also be so high that they are not fully -dissolved, either initially or during the reactionc As methyl chloride is a gas, it is advantageous to employ a closed apparatusO The process according to the invention may be operated at atmospheric or superatmospheric pressureO In the latter case the reaction proceeds somewhat more quicklyO I~ the process is operated at atmospheric pressure, it is expedient to free the reaction vessel substantially from air by partial evacuation; the desired pressure can now be set up by introduction of the methyl chlorideO
If the pressure is constant during the reaction, the progress of the reaction can be followed by the amount of methyl chloride suppliedO
The reaction is carried out at from 0 to 100C, preferably ~-at at least 20C, advantageously from 30 to 80C, and especially at from 40 to 60C, and continuously or batchwiseO
The duration of the reaction is without relevance for the quality of the end products~ The reaction period can therefore be chosen in accordance with economic considerations. It may for instance be more favorable to operate at atmospheric pressure because only a vessel designed for atmospheric operation is available, and to accept a longer reaction periodD
Upon conclusion of the reaction no more methyl chloride is taken up; the pH of the reaction solution is 6 to 70 The solution is a clear almost colorless liquidO
In the reaction according to the invention, the desired end products are formed practically exclusively, iOeO, no byproducts are obtained, and consequently the yield is practically quantitative.
The only byproducts which may occur are those from impurities ~3--O~Z 32,292 in the starting materialsO If~ for example~ the N-methylpiperidine still contains small amounts of unsubstituted piperldine, N-methyl-piperidine hydrochloride, which is not further methylated because of the hydrochloride formation3 is formed in the reaction with methyl chlorideO If basic compounds which liberate the amines from amins hydrochlorides, eOg., sodiu~ hydroxide, are added to the starting solution, the formation of the hydrochloride of the tertiary amine described above can be preventedO I~ the metal chloride formed from the amine hydrochloride and the basic additive is no handicap, it is possible to make the process even more econo-mical by starting from impure amihesO If a fairly large amount of metal chloride is no drawback, it is even possible to start from the secondary amines, iOe., from piperidine and morpholine, and ~o react them under the abovementioned reaction conditions with methyl chloride in the presence of an equivalent of a basic additiveO The end product obtained is an aqueous solution of a mixture of 1 mole of quaternary ammonium chloride and an equivalent of metal chlorideO
The process of the invention also represents an advance because it does not harm the environment. There is absolutely no solid or liquid waste, as the reaction solution is the desired end product.
Gaseous emissions can be substantially avoided if the reaction vessel is emptied and charged with the starting materials without being previously vented; this can be done without dif~iculty with the aid of pumps.
As the aqueous solution contains some methyl chloride upon completion of the reaction, this solution might be considered to be a source of impurities. In this case, the solution may~ a~ter completion of the reaction, be passed through an evaporator or a distillation column to free it from methyl chlorideO The aqueous distillate thus obtained can then be added to the next production batch as a diluent.
Both N,N-dimethylpiperidinium chloride and N,N-dimethylmorpho-linium chloride can be produced with the same equipment 9 which can 5~ OOZo 32g292 conceivably be of economic importanceO If desiredg both products may be produced together in admixture; this measure can definit~ely be meaning~ul3 because both products can also be particularly success-fully applied together in some cropsO
If it is desired to isolate both products in the form of solid crystalline substances, this can readily be achieved by evaporating the aqueous solutionsO They are obtained as coarse colorless crystals of hi~h purity which have melting points of more than 300Co EXAMPLE
30 parts by volurne of water and 15 o 6 parts by weight o~
N-methylpiperidine (parts by volume bear the same relationship to parts by weight as liters to kilo~rams) were introduced into a -jacketed s~irred vessel having a volume of 100 parts by volume.
The apparatus was evacuated and heated to 50Co At this temperature, ~.
a maximum of 1,000 parts by volume of methyl chloride was intro-duced per hour through a flowmeter, and the mixture was stirred.
After about 2 hours a pressure of 2 bars had been reached, which was maintained by continuously controlled addition of methyl chlorideO
During the reaction, water at 55C was passed through the jacketing, thus maintaining the internal temperature at 49~50C.
After 7025 hours, the pressure remained constant without methyl chloride being passed inO The mixture was stirred for a further 0075 hour, and the apparatus was then emptied in such a manner that the bottom valve just stayed covered, thus preventing the pressure on the vessel from being releasedO
The solution thus obtained was a yellowish clear li~uid having a pH of 6.9 and containing, in accordance with a test in which the N,N-dimethylpiperidinium chloride was precipitated and determined gravimetricallyg 0 46 part by weight per part by volume.
The yield was thus quantitativeO
Methyl chloride consumption corresponded to a molar ratio of N-methylpiperidine to methyl chloride of 1 : 1~02 o~
o~Zo 3~,292 Completely analogously, N,N dimethylmorpholiniuM chloride is obtained ~rom N~methylmorpholine and methyl chloride~ In this ~case the reaction period is 14 hoursO
AND N,N DIMETH~LMORPHOLINIUM CHLORIDE
The present invention relates to a process for the preparation o~ N,N-dimethylpiperidinium chloride and N,N-dimethylmorpholinium chloride from the corresponding monomethyl compounds with methyl chloride in the presence of waterO
It is known (German 1,642,215 and German Laid-Open ~pplication DOS 2,207,57~) to use N,N-dimethylpiperidinium chloride and N3N-dimethylmorpholinium chloride as agents for influencing plant growth. They are applied as an aqueous solution. They are prepared - -in conventional manner by conversion o~ N,N-dimethylpiperidinium iodide and N,N-dimethylmorpholinium iodide into the corresponding chlorides (Helv. Chim. Acta, 39, 399, 1956; Chem. Ber., 22, 2091, 1889).
We have now found that N,N-dimethylpiperidinium chloride and NgN-dimethylmorpholinium chloride are easily obtained from N-methyl piperidine and N-methylmorpholine respectively, in excellent yields, when the monomethyl compounds are reacted with methyl chloride in the presence of water as diluent at a temperature of ~rom 0 to 100C and a pressure of ~rom 1 to 7 bars This is surprisin~ and could not have been foreseen, because methylation with methyl chloride hitherto has been carried out in non-aqueous solvents, or, when water has been used as diluent, temperatures far in excess (120C) o~ room temperature and high pressures (20 to 60 bars) have been employedO
The process according to the invention has two essential advan-tages: a) the process is very simple and thus extremely econo~ical as a result of the use of water as diluent, because the aqueous .~
~ S~ OOZo 32,~92 solution of the end products can be employed direct for biolo~ical purposes; b) as the reaction takes place at atmospheric or sli~htly superatmospheric pressure, inexpensive standard stirred vessels may be used, as they are usually~ even when intended for pressureless reactions, designed for safety reasons to withstand a pressure of from 4 to 7 barsO
When N-methylpiperidine is used, the reaction may be represented as follows:
C 3 3 ~ CH3 Compared with prior art processes, the process of the invention provides, in a simpler and more economic manner, the desired quaternary ammonium chlorides in good yield and high purityO Whereas prior art processes were cumbersome because they had to be carried out in two stages, the reaction in the process according to the invention is carried out in one step.
Starting materials for the process are N-methylpiperidine3 N-methylrnorpholine and methyl chloride. They are used for instance in approximately equivalent amounts, optionally with a slight excess of methyl chloride.
The reaction may be carried out for instance as follows~ Water and the monomethylarnine are placed in the reaction vessel, and the mixture is heated to the desired reaction temperature and ~hen treated with methyl chloride. Advantageously, the reaction components are mixed with each other, for example by stirringO A~ter the reaction is over, the reaction solution is cooled to room tempera-ture and then diluted with water to the desired active ingredient concentration.
The monomethylamine concentration in the water upon cornmencement of the reaction may be varied within wide limits. It is preferred to use concentrations whlch, upon completion Or the reaction~ give end product concentrations slightly above the concentration of the 7Z~6~
0 ZO 32,292 aqueous solutlons when marketedD However~ it is also possible to start with more dilute aqueous solution and to distil off some~of the water used after che reaction is over without the quality of the end products sufferingO The concentration of the monomethyl~
amines in the water may also be so high that they are not fully -dissolved, either initially or during the reactionc As methyl chloride is a gas, it is advantageous to employ a closed apparatusO The process according to the invention may be operated at atmospheric or superatmospheric pressureO In the latter case the reaction proceeds somewhat more quicklyO I~ the process is operated at atmospheric pressure, it is expedient to free the reaction vessel substantially from air by partial evacuation; the desired pressure can now be set up by introduction of the methyl chlorideO
If the pressure is constant during the reaction, the progress of the reaction can be followed by the amount of methyl chloride suppliedO
The reaction is carried out at from 0 to 100C, preferably ~-at at least 20C, advantageously from 30 to 80C, and especially at from 40 to 60C, and continuously or batchwiseO
The duration of the reaction is without relevance for the quality of the end products~ The reaction period can therefore be chosen in accordance with economic considerations. It may for instance be more favorable to operate at atmospheric pressure because only a vessel designed for atmospheric operation is available, and to accept a longer reaction periodD
Upon conclusion of the reaction no more methyl chloride is taken up; the pH of the reaction solution is 6 to 70 The solution is a clear almost colorless liquidO
In the reaction according to the invention, the desired end products are formed practically exclusively, iOeO, no byproducts are obtained, and consequently the yield is practically quantitative.
The only byproducts which may occur are those from impurities ~3--O~Z 32,292 in the starting materialsO If~ for example~ the N-methylpiperidine still contains small amounts of unsubstituted piperldine, N-methyl-piperidine hydrochloride, which is not further methylated because of the hydrochloride formation3 is formed in the reaction with methyl chlorideO If basic compounds which liberate the amines from amins hydrochlorides, eOg., sodiu~ hydroxide, are added to the starting solution, the formation of the hydrochloride of the tertiary amine described above can be preventedO I~ the metal chloride formed from the amine hydrochloride and the basic additive is no handicap, it is possible to make the process even more econo-mical by starting from impure amihesO If a fairly large amount of metal chloride is no drawback, it is even possible to start from the secondary amines, iOe., from piperidine and morpholine, and ~o react them under the abovementioned reaction conditions with methyl chloride in the presence of an equivalent of a basic additiveO The end product obtained is an aqueous solution of a mixture of 1 mole of quaternary ammonium chloride and an equivalent of metal chlorideO
The process of the invention also represents an advance because it does not harm the environment. There is absolutely no solid or liquid waste, as the reaction solution is the desired end product.
Gaseous emissions can be substantially avoided if the reaction vessel is emptied and charged with the starting materials without being previously vented; this can be done without dif~iculty with the aid of pumps.
As the aqueous solution contains some methyl chloride upon completion of the reaction, this solution might be considered to be a source of impurities. In this case, the solution may~ a~ter completion of the reaction, be passed through an evaporator or a distillation column to free it from methyl chlorideO The aqueous distillate thus obtained can then be added to the next production batch as a diluent.
Both N,N-dimethylpiperidinium chloride and N,N-dimethylmorpho-linium chloride can be produced with the same equipment 9 which can 5~ OOZo 32g292 conceivably be of economic importanceO If desiredg both products may be produced together in admixture; this measure can definit~ely be meaning~ul3 because both products can also be particularly success-fully applied together in some cropsO
If it is desired to isolate both products in the form of solid crystalline substances, this can readily be achieved by evaporating the aqueous solutionsO They are obtained as coarse colorless crystals of hi~h purity which have melting points of more than 300Co EXAMPLE
30 parts by volurne of water and 15 o 6 parts by weight o~
N-methylpiperidine (parts by volume bear the same relationship to parts by weight as liters to kilo~rams) were introduced into a -jacketed s~irred vessel having a volume of 100 parts by volume.
The apparatus was evacuated and heated to 50Co At this temperature, ~.
a maximum of 1,000 parts by volume of methyl chloride was intro-duced per hour through a flowmeter, and the mixture was stirred.
After about 2 hours a pressure of 2 bars had been reached, which was maintained by continuously controlled addition of methyl chlorideO
During the reaction, water at 55C was passed through the jacketing, thus maintaining the internal temperature at 49~50C.
After 7025 hours, the pressure remained constant without methyl chloride being passed inO The mixture was stirred for a further 0075 hour, and the apparatus was then emptied in such a manner that the bottom valve just stayed covered, thus preventing the pressure on the vessel from being releasedO
The solution thus obtained was a yellowish clear li~uid having a pH of 6.9 and containing, in accordance with a test in which the N,N-dimethylpiperidinium chloride was precipitated and determined gravimetricallyg 0 46 part by weight per part by volume.
The yield was thus quantitativeO
Methyl chloride consumption corresponded to a molar ratio of N-methylpiperidine to methyl chloride of 1 : 1~02 o~
o~Zo 3~,292 Completely analogously, N,N dimethylmorpholiniuM chloride is obtained ~rom N~methylmorpholine and methyl chloride~ In this ~case the reaction period is 14 hoursO
Claims
O.Z. 32,292 The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:-A process for the manufacture of N,N-dimethylpiperidinium chloride by reacting N-methylpiperidine, or of N,N-dimethylmorpho-linium chloride by reacting N-methylmorpholine, with a methylating agent, wherein the monomethyl compounds are reacted with methyl chloride in the presence of water as diluent, at a temperature of from 0° to 100°C and a pressure of from 1 to 7 bars.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE2651984A DE2651984C2 (en) | 1976-11-15 | 1976-11-15 | Process for the preparation of N, N-dimethylpiperidinium chloride or N, N-dimethylmorpholinium chloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1072561A true CA1072561A (en) | 1980-02-26 |
Family
ID=5993174
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA288,706A Expired CA1072561A (en) | 1976-11-15 | 1977-10-13 | Preparation of n,n-dimethylpiperidinium chloride and n,n-dimethylmorpholinium chloride |
Country Status (14)
| Country | Link |
|---|---|
| JP (1) | JPS5363384A (en) |
| BE (1) | BE860788A (en) |
| CA (1) | CA1072561A (en) |
| CH (1) | CH630913A5 (en) |
| DD (1) | DD132342A5 (en) |
| DE (1) | DE2651984C2 (en) |
| DK (1) | DK159682C (en) |
| FR (1) | FR2370740A1 (en) |
| GB (1) | GB1587925A (en) |
| IL (1) | IL53112A (en) |
| IT (1) | IT1091782B (en) |
| NL (1) | NL189131C (en) |
| SE (1) | SE7712787L (en) |
| SU (1) | SU671730A3 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU670783B2 (en) * | 1992-06-04 | 1996-08-01 | Micro Flo Company | Mepiquat chloride |
| US9321723B2 (en) * | 2013-08-28 | 2016-04-26 | Johnson Matthey Plc | Method of making a templating agent |
| CN113024413B (en) * | 2019-12-25 | 2022-12-06 | 北京颖泰嘉和生物科技股份有限公司 | Synthesis method of salicylonitrile co-produced plant growth regulator |
| CN117756748A (en) * | 2023-12-26 | 2024-03-26 | 中棉小康生物科技有限公司 | Synthesis method of mepiquat chloride |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE756185C (en) * | 1939-08-27 | 1952-05-19 | Onderzoekings Inst Res | Process for the preparation of quaternary aliphatic ammonium chlorides |
| US3928423A (en) * | 1972-07-17 | 1975-12-23 | Kendall & Co | Monomeric emulsion stabilizers |
| DE2247501A1 (en) * | 1971-10-02 | 1973-04-05 | Inst Przemyslu Organiczego | Quaternary ammonium halides prepn - from sec amines |
| BE795534A (en) * | 1972-02-18 | 1973-08-16 | Basf Ag | AGENTS FOR REGULATING PLANT GROWTH, CONTAINING NITROGEN SALT AS ACTIVE INGREDIENT |
-
1976
- 1976-11-15 DE DE2651984A patent/DE2651984C2/en not_active Expired
-
1977
- 1977-10-12 IL IL53112A patent/IL53112A/en unknown
- 1977-10-13 CA CA288,706A patent/CA1072561A/en not_active Expired
- 1977-11-07 JP JP13260077A patent/JPS5363384A/en active Granted
- 1977-11-10 FR FR7733898A patent/FR2370740A1/en active Granted
- 1977-11-10 NL NLAANVRAGE7712395,A patent/NL189131C/en not_active IP Right Cessation
- 1977-11-11 SE SE7712787A patent/SE7712787L/en not_active Application Discontinuation
- 1977-11-11 DD DD7700202046A patent/DD132342A5/en unknown
- 1977-11-11 IT IT51785/77A patent/IT1091782B/en active
- 1977-11-14 GB GB47238/77A patent/GB1587925A/en not_active Expired
- 1977-11-14 BE BE182589A patent/BE860788A/en not_active IP Right Cessation
- 1977-11-14 CH CH1387677A patent/CH630913A5/en not_active IP Right Cessation
- 1977-11-14 DK DK503177A patent/DK159682C/en active
- 1977-11-14 SU SU772541700A patent/SU671730A3/en active
Also Published As
| Publication number | Publication date |
|---|---|
| FR2370740B1 (en) | 1981-06-19 |
| SE7712787L (en) | 1978-05-16 |
| NL7712395A (en) | 1978-05-17 |
| DK159682C (en) | 1991-04-15 |
| IT1091782B (en) | 1985-07-06 |
| DD132342A5 (en) | 1978-09-20 |
| DK159682B (en) | 1990-11-19 |
| JPS6225144B2 (en) | 1987-06-01 |
| IL53112A0 (en) | 1977-12-30 |
| DE2651984A1 (en) | 1978-05-18 |
| FR2370740A1 (en) | 1978-06-09 |
| GB1587925A (en) | 1981-04-15 |
| SU671730A3 (en) | 1979-06-30 |
| DE2651984C2 (en) | 1983-01-27 |
| BE860788A (en) | 1978-05-16 |
| DK503177A (en) | 1978-05-16 |
| NL189131C (en) | 1993-01-18 |
| JPS5363384A (en) | 1978-06-06 |
| CH630913A5 (en) | 1982-07-15 |
| IL53112A (en) | 1981-03-31 |
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