DE247145C - - Google Patents
Info
- Publication number
- DE247145C DE247145C DENDAT247145D DE247145DA DE247145C DE 247145 C DE247145 C DE 247145C DE NDAT247145 D DENDAT247145 D DE NDAT247145D DE 247145D A DE247145D A DE 247145DA DE 247145 C DE247145 C DE 247145C
- Authority
- DE
- Germany
- Prior art keywords
- isoprene
- water
- bromide
- chloride
- erythrene
- 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.)
- Active
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- RRHGJUQNOFWUDK-UHFFFAOYSA-N isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 14
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- -1 quaternary ammonium halides Chemical class 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 229910000039 hydrogen halide Inorganic materials 0.000 description 2
- 239000012433 hydrogen halide Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- QDHHCQZDFGDHMP-UHFFFAOYSA-N monochloramine Chemical compound ClN QDHHCQZDFGDHMP-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- RWRDLPDLKQPQOW-UHFFFAOYSA-N pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- YDRWXKNFHCZTJF-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-N-methylethanamine;hydroiodide Chemical compound [I-].C[NH2+]CCC1=CC=C(OC)C(OC)=C1 YDRWXKNFHCZTJF-UHFFFAOYSA-N 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L Barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L Calcium hydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- CAFRSFVVKDCTHL-UHFFFAOYSA-N Cl[NH3+].[Br-] Chemical compound Cl[NH3+].[Br-] CAFRSFVVKDCTHL-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VZEXJUAYWWLSEP-UHFFFAOYSA-N N.[Cl].Cl Chemical compound N.[Cl].Cl VZEXJUAYWWLSEP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 235000015450 Tilia cordata Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GETQZCLCWQTVFV-UHFFFAOYSA-N Trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 1
- UZIQYAYUUNMDMU-UHFFFAOYSA-O [NH4+].[Br+] Chemical compound [NH4+].[Br+] UZIQYAYUUNMDMU-UHFFFAOYSA-O 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229940077484 ammonium bromide Drugs 0.000 description 1
- 229940107816 ammonium iodide Drugs 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 239000010428 baryte Substances 0.000 description 1
- 229910052601 baryte Inorganic materials 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Inorganic materials [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/32—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen
- C07C1/321—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom
- C07C1/323—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from compounds containing hetero-atoms other than or in addition to oxygen or halogen the hetero-atom being a non-metal atom the hetero-atom being a nitrogen atom
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Detergent Compositions (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12 o. GRUPPECLASS 12 or GROUP
FARBENFABRIKEN vorm. FRIEDR. BAYER & CO. in ELBERFELD.FARBENFABRIKEN vorm. FRIEDR. BAYER & CO. in ELBERFELD.
Verfahren zur Darstellung von Erythren und Isopren.Process for the preparation of erythrene and isoprene.
Patentiert im Deutschen Reiche vom 2. Februar 1911 ab.Patented in the German Empire on February 2, 1911.
Es wurde gefunden, daß die quaternären Ammoniumhalogenide der Oxybasen 35 It has been found that the quaternary ammonium halides of the oxybases 35
CH3 CH 3
C H3 — C H — C H2 — C H2 CH 3 - CH - CH 2 - CH 2
OHOH
-NH9 -NH 9
(vgl. Patent 233519) beim Erhitzen mit Halogenwasserstoffsäuren durch Austausch des Hydroxyls gegen Halogen in halogenisierte Ammoniumhalogenide übergehen. Letztere(cf. Patent 233519) when heated with hydrohalic acids convert to halogenated ammonium halides by replacing the hydroxyl with halogen. Latter
CH1,CH 1 , C H3-CH-CH-C H2-NH2 OHCH 3 -CH-CH-C H 2 -NH 2 OH
liefern beim Erhitzen mit Ätzalkalien, Barytoder Kalkhydrat direkt Erythren bzw. Isopren, z. B.when heated with caustic alkalis, barite or hydrated lime, they deliver directly erythrene or isoprene, z. B.
4040
4545
/CH3 / CH 3
Nf-CH3 -f 2K0H
I
Cl Nf-CH 3 -f 2K0H
I.
Cl
-C-H.-C-H.
CH3-CH-CH-CH2
I
Br CH 3 -CH-CH-CH 2 I.
Br
CH3 .
I
CH2 = CH — C = CH2 + N (CH3J3 + KCl + KBr + 2H2O. CH 3 .
I.
CH 2 = CH - C = CH 2 + N (CH 3 J 3 + KCl + KBr + 2H 2 O.
5555
Dieser Reaktionsverlauf ist insofern überraschend, als die Abspaltung von Halogenwasserstoff (im Beispiel Bromwasserstoff) nicht, wie man hätte erwarten sollen, nach dem tertiär gebundenen Wasserstoff atom, sondern ausschließlich nach der endständigen Methylgruppe hin erfolgt, ein Vorgang, der wohl ohne Beispiel dastehen dürfte und sich infolgedessen in keiner Weise voraussehen ließ. Daß die Neigung des Halogens, mit einem Wasserzutreten, hier auffallenderweise eine sehr große ist, folgt auch daraus, daß ζ. B. auch aus den halogenisierten Basen von der FormelThis course of the reaction is surprising insofar as the elimination of hydrogen halide (in the example hydrogen bromide) not, as one should have expected, after the tertiary hydrogen atom, but takes place exclusively after the terminal methyl group, a process that probably could stand there without example and, as a result, could not be foreseen in any way. That the tendency of halogen to step into water with a water, strikingly a very great one here is, it also follows that ζ. B. also from the halogenated bases of the formula
CF, — CH- CH- CH. CF, - CH-CH-CH.
CH,CH,
(vgl. Patent 247144, Kl. 120) beim Kochen(see patent 247144, cl. 120) during cooking
stoffatom der endständigen Methylgruppe aus- j mit Alkalilauge oder mit Sodalösung neben a- atom of the terminal methyl group from- j with alkali lye or with soda solution next to a-
ß-Dimethyltrimethylendimethylammoniumhalogenid ausschließlich die ungesättigte Baseβ-dimethyltrimethylene dimethylammonium halide only the unsaturated base
'CH3 'CH 3
CH,CH,
CH, = CH -CH — CH9 — N(' CH, = CH -CH - CH 9 - N ('
(in Wasser schwer lösliches, piperidin artig riechendes öl vom Siedepunkt 1130) entsteht, die, nebenbei bemerkt, identisch ist mit Eule rs sogenanntem » ß-Methyldimethyl pyrrolidin« (Journ. für prakt. Chemie [2] 57, 151).(Piperidine-like smelling oil with a boiling point of 113 0 , which is sparingly soluble in water) is formed, which, incidentally, is identical to Euler's so-called "ß-methyldimethyl pyrrolidine" (Journ. für Prakt. Chemie [2] 57, 151).
Darstellung von Isopren aus dem quaternären AmmoniumchloridRepresentation of isoprene from the quaternary ammonium chloride
/CH3 / CH 3
CH3 -CH-CH(CH3) -~CH.2—N(- C H3 CH 3 -CH-CH (CH 3 ) - ~ CH. 2 -N (- CH 3
Die Lösung von einem Teil des durch direkte Vereinigung der OxybaseThe solution of part of the by direct union of the Oxybase
CH3-CH-CH(CH3)-CH0-CH 3 -CH-CH (CH 3 ) -CH 0 -
II.
OHOH
OHOH
ClCl
mit Chlormethyl oder durch Umsetzung ihres Ammoniumjodids (Schmelzpunkt 145 bis 1460) mit Chlorsilber erhältlichen Ammoniumchlorids, einer farblosen, zerfließlichen Kristallmasse, in etwa 5 Teilen Wasser wird mit Bromwasserstoffgas oder Chlorwasserstoffgas unter Kühlen mit Eis gesättigt und etwa 24 Stunden lang im geschlossenen Gefäß im siedenden Wasserbad erhitzt. Nach dem Abdunsten der klaren Lösung im Wasserbad oder nach Entfernung von Wasser und überschüssigem Halogenwasserstoff auf andere geeignete Weise bleibt das Brom- bzw. Chlorammoniumchloridwith chloromethyl or by reacting your ammonium iodide (melting point 145 to 146 0 ) with chlorine silver available ammonium chloride, a colorless, deliquescent crystal mass, in about 5 parts of water is saturated with hydrogen bromide gas or hydrogen chloride gas while cooling with ice and in a closed vessel in the boiling for about 24 hours Heated water bath. After the clear solution has evaporated in a water bath or after removal of water and excess hydrogen halide in another suitable manner, the bromine or chlorine ammonium chloride remains
CH3 CH 3
CH3- CH -CH (CH3)- CH2- n(-C H3 (X = Cl oder Br) I . | CH 3 - CH - CH (CH 3 ) - CH 2 - n (-CH 3 (X = Cl or Br) I. |
X ClX Cl
BrBr
und deren Spaltung durch Alkali usw. erfolgt genau in der gleichen Weise, wie im Beispiel 1 für das Oxyammoniumchlorid angegeben. Auch hier sind die Ausbeuten an Isopren so gut wie quantitativ.and their cleavage by alkali, etc. is carried out in exactly the same manner as in Example 1 given for the oxyammonium chloride. Again, the isoprene yields are so good how quantitative.
/CH3 CH -CH2- CH2- n(- C H3 / CH 3 CH -CH 2 - CH 2 - n (- CH 3
OH ClOH Cl
als dicket bräunlicher Sirup zurück, der mit ; einer mit Eis gekühlten Vorlage aufgefangen,
der etwa dreifachen Menge gepulverten Ätz- I von Trimethylamin durch Waschen mit ver- 90
kalis oder -natrons oder auch mit Kalk- oder ■ dünnter Schwefelsäure befreit, getrocknet und
Barythydrat mit oder ohne Zusatz von etwas j destilliert. Es siedet vollkommen konstant
Wasser oder Alkohol der Destillation unter- , bei 34 °. Die Ausbeute ist nahezu quantiworfen
wird. Schon bei gelindem Erhitzern j tativ.
destilliert Isopren lebhaft über; es wird in I 95back as a thick brownish syrup with; collected in an ice-cooled template, the approximately three times the amount of powdered caustic is freed from trimethylamine by washing with potassium or soda or with lime or ■ dilute sulfuric acid, dried and barythydrate is distilled with or without the addition of something. It boils completely constant water or alcohol of the distillation, at 34 °. The yield is almost quantitative. Even with mild heating j tative.
isoprene vigorously distilled over; it will be in I 95
Beispiel 2.
Darstellung von Isopren aus dem quaternären Ammoniumbromid 100 Example 2.
Representation of isoprene from the quaternary ammonium bromide 100
/CH3 / CH 3
CH3- CH -CH (CH3)- CH2- N(-CH3 (eine farblose, zerfl. Kristallmasse). I IX CH 3 - CH - CH (CH 3 ) - CH 2 - N (-CH 3 (a colorless, disintegrated crystal mass). II X
OH BrOH Br
Die Umwandlung dieses Oxyammoniumbromids in das Bromammoniumbromid oder Chlorammoniumbromid The conversion of this oxyammonium bromide into the bromammonium bromide or chlorammonium bromide
/CH3 CH3-CH-CH (CH3)-CH2-n(~C H3 (X = Br oder Cl) / CH 3 CH 3 -CH-CH (CH 3 ) -CH 2 -n (~ CH 3 (X = Br or Cl)
Die Überführung des Oxyammoniumchlorids in das entsprechende Chlor- oder Bromammo- 120 Darstellung von Erythren aus dem quater- ! niumchlorid und die Verarbeitung des letznären Ammoniumchlorid j teren auf Erythren erfolgt genau so, wie imThe conversion of the oxyammonium chloride into the corresponding chlorine or bromine ammonium 120 Representation of Erythren from the quater-! nium chloride and the processing of the final Ammonium chloride j teren on Erythren takes place exactly as in
Beispiel ι für die homologen Verbindungen angegeben.Example given for the homologous compounds.
Das Erythren wird in einer durch Kältemischung gekühlten Vorlage verdichtet und in bekannter Weise gereinigt.The erythrene is compressed and cooled in a template that is cooled by a cold mixture cleaned in a known manner.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE247145C true DE247145C (en) |
Family
ID=505960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT247145D Active DE247145C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE247145C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2931833A (en) * | 1954-12-29 | 1960-04-05 | Armour & Co | Benzyldialkyl-2-(1-hydroxy-alkyl) alkyl ammonium chloride compounds |
| US4871874A (en) * | 1987-06-15 | 1989-10-03 | Ethyl Corporation | Process for producing dienes |
-
0
- DE DENDAT247145D patent/DE247145C/de active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2931833A (en) * | 1954-12-29 | 1960-04-05 | Armour & Co | Benzyldialkyl-2-(1-hydroxy-alkyl) alkyl ammonium chloride compounds |
| US4871874A (en) * | 1987-06-15 | 1989-10-03 | Ethyl Corporation | Process for producing dienes |
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