DE2545659A1 - Alkyl chloride prodn. from alkyl chloroformates - by thermal decarboxylation in aprotic solvent - Google Patents
Alkyl chloride prodn. from alkyl chloroformates - by thermal decarboxylation in aprotic solventInfo
- Publication number
- DE2545659A1 DE2545659A1 DE19752545659 DE2545659A DE2545659A1 DE 2545659 A1 DE2545659 A1 DE 2545659A1 DE 19752545659 DE19752545659 DE 19752545659 DE 2545659 A DE2545659 A DE 2545659A DE 2545659 A1 DE2545659 A1 DE 2545659A1
- Authority
- DE
- Germany
- Prior art keywords
- alkyl
- aprotic solvent
- degrees
- solvent
- chloroformates
- 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.)
- Withdrawn
Links
- 150000001348 alkyl chlorides Chemical class 0.000 title claims abstract description 12
- 239000000010 aprotic solvent Substances 0.000 title claims abstract description 6
- -1 alkyl chloroformates Chemical class 0.000 title abstract description 7
- 238000006114 decarboxylation reaction Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 150000001408 amides Chemical class 0.000 claims abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 150000003857 carboxamides Chemical class 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 238000003776 cleavage reaction Methods 0.000 claims description 2
- 230000007017 scission Effects 0.000 claims description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- 150000005846 sugar alcohols Polymers 0.000 abstract description 2
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 abstract 1
- 150000003950 cyclic amides Chemical class 0.000 abstract 1
- 230000000911 decarboxylating effect Effects 0.000 abstract 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- 239000007858 starting material Substances 0.000 abstract 1
- 229940050176 methyl chloride Drugs 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KJDRSWPQXHESDQ-UHFFFAOYSA-N 1,4-dichlorobutane Chemical compound ClCCCCCl KJDRSWPQXHESDQ-UHFFFAOYSA-N 0.000 description 1
- VGZOTUWVGXUNRC-UHFFFAOYSA-N 1-butylazepan-2-one Chemical compound CCCCN1CCCCCC1=O VGZOTUWVGXUNRC-UHFFFAOYSA-N 0.000 description 1
- YVAKVTNKLMUNBR-UHFFFAOYSA-N 2-ethyl-n,n-dimethylhexanamide Chemical compound CCCCC(CC)C(=O)N(C)C YVAKVTNKLMUNBR-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- AOGYCOYQMAVAFD-UHFFFAOYSA-N chlorocarbonic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000003840 hydrochlorides Chemical class 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/361—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms
- C07C17/363—Preparation of halogenated hydrocarbons by reactions involving a decrease in the number of carbon atoms by elimination of carboxyl groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
Description
Verfahren zur Herstellung von Alkylchloriden Process for the preparation of alkyl chlorides
Die Erfindung betrifft ein Verfahren z1Jr Herstellung von Alkylchloriden, insbesondere Methylchlorid, durch Abspaltung von Kohlendioxid aus dem Alkylchlorkohlensäureester.The invention relates to a process for the production of alkyl chlorides, in particular methyl chloride, by splitting off carbon dioxide from the alkyl chlorocarbonic acid ester.
Alkylchloride können nach verschiedenen Methoden hergestellt werden,
die z. B. durch die folgenden Gleichungen (1) bis (4) wiedergegeben werden:
Das Verfahren hat den Nachteil, daß sich wälirend der Umsetzung die Hydrochloride der Amine bilden, die Im Reaktlonsgemisch als feste kristalline Phase ausfallen und zu Verstopfungen von Leitungen und Ventilen führen. Außerdem entstehen manchmal Nebenprodukte, so daß die rohen Alkylchloride z. Bo durch Destillation gereinigt werden müssen. Als Nebenprodukte werden z, B. Dialkylcarbonate und wertlose Polykondensate gebildet.The process has the disadvantage that the implementation of the Hydrochlorides of the amines form, which in the reaction mixture as a solid crystalline phase fail and lead to clogging of lines and valves. Also arise sometimes by-products so that the crude alkyl chlorides e.g. Bo by distillation need to be cleaned. By-products are, for example, dialkyl carbonates and worthless Polycondensates formed.
Es wurde gefunden, daß man in praktisch quantitativer Ausbeute Alkylchloride durch Abspaltung von Kohlendioxid aus Alkylchlorkohlensäure-Estern erhält, wenn die Abspaltung in einem aprotischen Lösungsmittel bei einer Temperatur von 80 bis 2000C, vorzugsweise 110 bis 1400C, vorgenommen wird. Die Anwesenheit eines Katalysators ist in diesem Falle nicht erforderlIch0 Als aprotische Lösungsmittel können z. B. verwendet werden: Dimethylsulfoxid (DMSO), Dimethylsulfon, Sulfolan, Diåthoxyäthan und Verbindungen, wie sie in "Organikum", VEB Deutscher Verlag der Wissenschaften, Berlin 1965, S. 166 bis 167, beschrieben sind. Es ist zweckmäßig, wenn der Siedepunkt des Lösungsmittels bei atmosphärischem Druck über 1800C liegt.It has been found that alkyl chlorides can be obtained in virtually quantitative yield obtained by splitting off carbon dioxide from alkylchlorocarbonic acid esters, if the cleavage in an aprotic solvent at a temperature of 80 to 2000C, preferably 110 to 1400C. The presence of a catalyst is not required in this case As aprotic solvents can e.g. B. can be used: dimethyl sulfoxide (DMSO), dimethyl sulfone, sulfolane, Dietoxyethane and compounds as described in "Organikum", VEB Deutscher Verlag der Sciences, Berlin 1965, pp. 166 to 167, are described. It is appropriate when the boiling point of the solvent is above 1800C at atmospheric pressure.
Vorteilhart verwendet man als aprotisches Lösungsmittel ein cyclisches, N-alkyliertes Amid der allgemeinen Formel (I): R = Alkylrest C1-Cl8 Ein sehr zweckmäßiges Lösungsmittel ist N-Nethylpyrrolidon (NMP); gut geeignet sind aber auch andere, gut zugängliche cyclische, N-alkylierte Carbonsäureamide wie N-Athylpyrrolidon-(2), N-Isopropylpyrrolidon-(2), N-Athylpiperidin-(2)9 N-Bu'yl-£-caprolactam und ganz allgemein alkylierte Carbonsäureamide, z. Bo N,N-DI-methylformamid, Di-(N-2-Äthylhexyl)-formamid, N,N-Dimethyl- (2-Athyl-hexansäure)-amid.A cyclic, N-alkylated amide of the general formula (I) is advantageously used as the aprotic solvent: R = alkyl radical C1-Cl8 A very useful solvent is N-methylpyrrolidone (NMP); However, other readily accessible cyclic, N-alkylated carboxamides such as N-ethylpyrrolidone- (2), N-isopropylpyrrolidone- (2), N-ethylpiperidine- (2) 9, N-butyl- ε-caprolactam and very generally alkylated carboxamides, e.g. Bo N, N-DI-methylformamide, di- (N-2-ethylhexyl) -formamide, N, N-dimethyl- (2-ethylhexanoic acid) -amide.
Das Verfahren kann absatzweise oder in beliebiger Weise fortlaurend gestaltet werden.The process can be intermittent or continuous in any manner be designed.
Eine technisch besonders wirtschaftliche Methode besteht darin, daß man fortlaufend (kontinuierlich) in einem mit dem Lösungsmittel ganz oder teilweise gefüllten Reaktor üblicher Bauart, z. B. in einen Rührbehälter, den Chrorkohlensäure-Ester bei 120 bis 14000 einleitet und das entstandene Alkylchlorid huber eine Kolonne abdestilliert, danach das Alkylchlorid kondensiert und ausgast.A technically particularly economical method is that one continuously (continuously) in one with the solvent in whole or in part filled reactor of conventional design, e.g. B. in a stirred tank, the carbonic acid ester at 120 to 14000 and the resulting alkyl chloride over a column distilled off, then the alkyl chloride is condensed and degassed.
Je nach dem Siedepunkt des Alkylchlorids kann bei gewöhnlichem oder vermindertem Druck gearbeitet werden0 Das Verfahren eignet sich für die Decarboxylierung von Alkylchlorkohlensäureestern mit z. B. 1 bis 30 C-Atomen Je Alkylgruppe.Depending on the boiling point of the alkyl chloride, ordinary or reduced pressure0 The process is suitable for decarboxylation of alkyl chlorocarbonic acid esters with z. B. 1 to 30 carbon atoms per alkyl group.
Ebenso sind aber auch mehrwertige Chlorkohlensäureester, z. 3.However, polyvalent chlorocarbonic acid esters, e.g. 3.
von 2- oder mehrwertigen AlkohiSn mit 2 bis 30 5-Atomen in entsprechende Chlorverbindungen uberführbar.of 2 or polyhydric alcohols with 2 to 30 5 atoms in corresponding Chlorine compounds can be converted.
siel1 Als Reaktor dient ein Rührbehälter aus V2A-Stahl mit einem Inhalt von 100 1, der mit Blattrührer und einer kurzen Kolonne zur Ableitung des Methylchlorids sowie einem Kühler und einer Vorlage für Methylchlorid ausgerüstet ist. siel1 A stirred tank made of V2A steel with a Content of 100 1, which is equipped with a paddle stirrer and a short column for the discharge of the Methyl chloride as well as a cooler and a receiver for methyl chloride is.
In den Rührbehälter werden 50 kg N-Methylpyrrolidon (NMP) eingefüllt. Im Reaktor wird eine Temperatur von 120 bis 130°C und ein Druck von 25 bar aufrechterhalten. Die Temperatur in der Vorlage beträgt OOC. Man pumpt aus einem Vorratsbehälter stündlich 30 kg Methylchlorkohlensäure-Ester kontinuierlich in den Reaktor und leitet das Methylchlorid im Maße des Ester-Zulaufs in die Vorlage ab.50 kg of N-methylpyrrolidone (NMP) are poured into the stirred tank. A temperature of 120 to 130 ° C. and a pressure of 25 bar are maintained in the reactor. The temperature in the template is OOC. One pumps from a storage container every hour 30 kg of methylchlorocarbonic acid ester continuously into the reactor and directs it Methyl chloride in the amount of the ester feed into the template.
Man erhält pro Stunde 16,0 kg Methylchlorid, das genügend rein ist, um unmittelbar weiter verwendet zu werden.16.0 kg of methyl chloride are obtained per hour, which is sufficiently pure to be used immediately.
Die Ausbeute ist besser als 98 %.The yield is better than 98%.
Vergleichsversuch Der Reaktor wird mit 50 kg Ghlorbenzol gefüllt, das ein normales, polarisierbares Lösungsmittel darstellt. Im übrigen wird nach Beispiel 1 gearbeitet. Comparative experiment The reactor is filled with 50 kg of chlorobenzene, which is a normal, polarizable solvent. Otherwise, after Example 1 worked.
Der Chlorkohlensäure-Ester wird praktisch quantitativ zurUckgewonnen; eine Zersetzung in Kohlendioxid und Methylchlorid findet nicht statt, wenn kein Katalysator zugesetzt wird.The chlorocarbonic acid ester is recovered practically quantitatively; decomposition into carbon dioxide and methyl chloride does not take place if none Catalyst is added.
Beispiel 2 Herstellung von 114-Dichlorbutan Aus einem Vorratsbehälter werden stündlich wie vorstehend beschrieben in den Reaktor 45 kg 1,4-3utandiol-di-chlorkohlensäure-Ester bei 130 bis 13500 Innentemperatur und einem Druck von 130 mbar gepumpt. Es werden stündlich 26,0 kg 1,4-Dichlorbutan (Reinheit = 99 %) erhalten. Die Ausbeute beträgt 98 %. Example 2 Preparation of 114-dichlorobutane From a storage container 45 kg of 1,4-3utanediol-dichlorocarbonic acid ester are put into the reactor every hour as described above pumped at an internal temperature of 130 to 13500 and a pressure of 130 mbar. It will 26.0 kg of 1,4-dichlorobutane (purity = 99%) are obtained per hour. The yield is 98%.
Vergleichsversuch Die Umsetzung wird in Dichlorbenzol versucht. Comparative experiment The reaction is attempted in dichlorobenzene.
Ergebnis: Es findet keine Decarboxylierung des Esters statt Beispiel 3 Herstellung von n-Butylchlorid Wie vorstehend beschrieben werden bei einer Reaktionstemperatur von 120 bis 13500 und gewöhnlichem Druck stündlich 60 kg n-Butylchlorkohlensäure-Ester zugepumpt. Es werden jeweils 39,5 kg n-Butylchlorid (Reinheit = 99 %) kondensiert, die Ausbeute beträgt 97 %.Result: There is no decarboxylation of the ester. Example 3 Preparation of n-butyl chloride As described above, at a reaction temperature from 120 to 13500 and normal pressure 60 kg per hour of n-butylchlorocarbonic acid ester pumped in. 39.5 kg of n-butyl chloride (purity = 99%) are condensed in each case, the yield is 97%.
Claims (4)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752545659 DE2545659A1 (en) | 1975-10-11 | 1975-10-11 | Alkyl chloride prodn. from alkyl chloroformates - by thermal decarboxylation in aprotic solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19752545659 DE2545659A1 (en) | 1975-10-11 | 1975-10-11 | Alkyl chloride prodn. from alkyl chloroformates - by thermal decarboxylation in aprotic solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE2545659A1 true DE2545659A1 (en) | 1977-04-21 |
Family
ID=5958937
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE19752545659 Withdrawn DE2545659A1 (en) | 1975-10-11 | 1975-10-11 | Alkyl chloride prodn. from alkyl chloroformates - by thermal decarboxylation in aprotic solvent |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE2545659A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0025829A1 (en) * | 1979-08-04 | 1981-04-01 | BASF Aktiengesellschaft | Process for the preparation of alkyl chlorides |
| EP0240871A1 (en) * | 1986-04-05 | 1987-10-14 | BASF Aktiengesellschaft | Process for the production of aliphatic chlorine compounds |
| EP0375920A1 (en) * | 1988-11-30 | 1990-07-04 | BASF Aktiengesellschaft | Method for the production of (substituted) alkyl or alkenyl chlorides |
| JP2812418B2 (en) | 1993-05-21 | 1998-10-22 | 宇部興産株式会社 | Method for producing ester compound |
| JP2812419B2 (en) | 1993-05-21 | 1998-10-22 | 宇部興産株式会社 | Decomposition method of chloroformate |
| US5869729A (en) * | 1993-05-21 | 1999-02-09 | Ube Industries, Ltd. | Method of producing an ester compound |
-
1975
- 1975-10-11 DE DE19752545659 patent/DE2545659A1/en not_active Withdrawn
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0025829A1 (en) * | 1979-08-04 | 1981-04-01 | BASF Aktiengesellschaft | Process for the preparation of alkyl chlorides |
| EP0240871A1 (en) * | 1986-04-05 | 1987-10-14 | BASF Aktiengesellschaft | Process for the production of aliphatic chlorine compounds |
| US4734535A (en) * | 1986-04-05 | 1988-03-29 | Basf Aktiengesellschaft | Preparation of aliphatic chlorine compounds |
| EP0375920A1 (en) * | 1988-11-30 | 1990-07-04 | BASF Aktiengesellschaft | Method for the production of (substituted) alkyl or alkenyl chlorides |
| JP2812418B2 (en) | 1993-05-21 | 1998-10-22 | 宇部興産株式会社 | Method for producing ester compound |
| JP2812419B2 (en) | 1993-05-21 | 1998-10-22 | 宇部興産株式会社 | Decomposition method of chloroformate |
| US5869729A (en) * | 1993-05-21 | 1999-02-09 | Ube Industries, Ltd. | Method of producing an ester compound |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8141 | Disposal/no request for examination |