DE99057C - - Google Patents
Info
- Publication number
- DE99057C DE99057C DENDAT99057D DE99057DA DE99057C DE 99057 C DE99057 C DE 99057C DE NDAT99057 D DENDAT99057 D DE NDAT99057D DE 99057D A DE99057D A DE 99057DA DE 99057 C DE99057 C DE 99057C
- Authority
- DE
- Germany
- Prior art keywords
- phenol
- carbonate
- guaiacol
- phenols
- carbonates
- 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
Links
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- YGYAWVDWMABLBF-UHFFFAOYSA-N phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 150000002989 phenols Chemical class 0.000 claims description 5
- AOGYCOYQMAVAFD-UHFFFAOYSA-N Chloroformic acid Chemical class OC(Cl)=O AOGYCOYQMAVAFD-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N Carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims 1
- LHGVFZTZFXWLCP-UHFFFAOYSA-N Guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 14
- 229960001867 Guaiacol Drugs 0.000 description 7
- NOOLISFMXDJSKH-UTLUCORTSA-N (+)-Neomenthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@@H]1O NOOLISFMXDJSKH-UTLUCORTSA-N 0.000 description 6
- BJIOGJUNALELMI-ONEGZZNKSA-N Isoeugenol Natural products COC1=CC(\C=C\C)=CC=C1O BJIOGJUNALELMI-ONEGZZNKSA-N 0.000 description 6
- 229960004873 LEVOMENTHOL Drugs 0.000 description 6
- 229940041616 Menthol Drugs 0.000 description 6
- CQDGTJPVBWZJAZ-UHFFFAOYSA-M ethyl carbonate Chemical compound CCOC([O-])=O CQDGTJPVBWZJAZ-UHFFFAOYSA-M 0.000 description 5
- -1 phenols chlorocarbonic acid esters Chemical class 0.000 description 5
- ROORDVPLFPIABK-UHFFFAOYSA-N Diphenyl carbonate Chemical compound C=1C=CC=CC=1OC(=O)OC1=CC=CC=C1 ROORDVPLFPIABK-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate dianion Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000004651 carbonic acid esters Chemical class 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- UCRUTNJGISGZMY-UHFFFAOYSA-N 2-(hydroxymethyl)-3-methyl-6-propan-2-ylcyclohexan-1-ol Chemical compound CC(C)C1CCC(C)C(CO)C1O UCRUTNJGISGZMY-UHFFFAOYSA-N 0.000 description 1
- 210000002588 AT2 Anatomy 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- RIFGWPKJUGCATF-UHFFFAOYSA-N Ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 1
- 241000207923 Lamiaceae Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ORUJFMPWKPVXLZ-UHFFFAOYSA-N bis(2-methoxyphenyl) carbonate Chemical compound COC1=CC=CC=C1OC(=O)OC1=CC=CC=C1OC ORUJFMPWKPVXLZ-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- OFDKFNZHXJWFNS-UHFFFAOYSA-N ethyl (2-methoxyphenyl) carbonate Chemical compound CCOC(=O)OC1=CC=CC=C1OC OFDKFNZHXJWFNS-UHFFFAOYSA-N 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229950010370 guaiacol carbonate Drugs 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QIIPQYDSKRYMFG-UHFFFAOYSA-M phenyl carbonate Chemical class [O-]C(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-M 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000035943 smell Effects 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/96—Esters of carbonic or haloformic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/02—Preparation of esters of carbonic or haloformic acids from phosgene or haloformates
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
PATENTSCHRIFTPATENT LETTERING
KLASSE 12: Chemische Verfahren und Apparate.CLASS 12: Chemical processes and apparatus.
CHEMISCHE FABRIK von HEYDEN,CHEMICAL FACTORY by HEYDEN,
in RADEBEUL b. DRESDEN.in RADEBEUL b. DRESDEN.
Patentirt im Deutschen Reiche vom 24. Oktober 1897 ab.Patented in the German Empire on October 24, 1897.
Die Patentschriften Nr. 58129, 60716, 61848 und 72806 enthalten ein Verfahren, gewisse heilkräftige, phenolartige Stoffe für Heilzwecke dadurch verwendbar zu machen, dafs dieselben in ihre Carbonate umgewandelt werden, welche im Gegensatze zu ihren Ausgangsproducten von Geruch, Geschmack und Aetzwirkung frei sind. Das Verfahren besteht in der Einwirkung von Kohlensäurechlorid, CO Cl2, auf die betreffenden Phenole bezw. ihre Salze. Man kann aber auch so verfahren, dafs man das Kohlensäurechlorid nicht unmittelbar auf die betreffenden phenolartigen Stoffe einwirken läfst, sondern es vorher mit Alkoholen oder anderen Phenolen behandelt und dann erst die entstandenen Chlorkohlensäureester bezw. Kohlensäureester zusammen mit denjenigen phenolartigen Stoffen erhitzt, deren Carbonate man darstellen will. Man vermeidet auf diese Weise die Möglichkeit einer schädlichen Einwirkung des Phosgens auf leicht veränderliche Stoffe, wie Isoeugenol, welches durch Phosgen verharzt wird, Menthol, welches durch Phosgen unter Wasserabspaltung in Kohlenwasserstoff verwandelt wird u. s. f. Nach dem neuen Arbeitsverfahren bildet man zunächst durch Einwirkung von Phosgen auf Alkohole oder Phenole Chlorkohlensäureester, z. B.Patents Nos. 58129, 60716, 61848 and 72806 contain a process for making certain medicinal, phenol-like substances usable for medicinal purposes by converting them into their carbonates, which, in contrast to their starting products, are free of smell, taste and caustic effect. The process consists in the action of carbonic acid chloride, CO Cl 2 , respectively on the phenols in question. their salts. But one can also proceed in such a way that the carbonic acid chloride is not allowed to act directly on the phenol-like substances in question, but is treated beforehand with alcohols or other phenols and only then is the chlorocarbonic acid esters or chlorocarbonic acid esters formed. Carbonic acid esters are heated together with those phenol-like substances whose carbonates are to be represented. In this way one avoids the possibility of a harmful effect of phosgene on easily changeable substances such as isoeugenol, which is resinified by phosgene, menthol, which is converted into hydrocarbons by phosgene with elimination of water, etc. Alcohols or phenols chlorocarbonic acid esters, e.g. B.
,OH,OH
ClCl
oderor
oder Kohlensäureester, z. B. Diäthylcarbonator carbonic acid esters, e.g. B. diethyl carbonate
oder Diphenylcarbonator diphenyl carbonate
und erhitzt erst mit diesen Zwischenproducten diejenigen Phenole, deren Carbonate hergestellt werden sollen. Während die Anwendung des Phosgens zur Herstellung des Diphenylcarbonats bereits bekannt war, ist die Anwendung der oben genannten Zwischenproducte zur Herstellung der Carbonate sowohl im Allgemeinen, wie in den vorliegenden besonderen Fällen etwas Neues.and only with these intermediate products heats those phenols whose carbonates are produced should be. During the use of phosgene to produce diphenyl carbonate was already known, the use of the above-mentioned intermediate products for the production of carbonates is both in general, as in the present special cases, something new.
Man erhitzt zwei Aequivalente Isoeugenol oder einen Ueberschufs davon mit einem Aequivalent Diphenylcarbonat so lange, wie noch Phenol abdestillirt. Die Reaction vollzieht sich nach der Gleichung:Two equivalents of isoeugenol or an excess thereof are heated with one Equivalent of diphenyl carbonate as long as phenol is still distilled off. The reaction takes place according to the equation:
= co/ = co /
OCOC Ή -"β Ή - "β
2C6H5OH.2C 6 H 5 OH.
Der Rückstand giebt beim Umkrystallisiren aus Alkohol Isoeugenolcarbonat. 'The residue gives isoeugenol carbonate on recrystallization from alcohol. '
+ 2 C6H3^OH+ 2 C 6 H 3 ^ OH
OCH,OCH,
Während das alte Verfahren durch die Gleichung:While the old procedure is through the equation:
gekennzeichnet ist, wird das abgeänderte Verfahren durch die folgende Gleichung versinnlicht:is indicated, the modified procedure is illustrated by the following equation:
;(C3 , 0
; (C 3
-OCh
"OH , C 3 Ti 5
-OCh
"OH
deren Summe: 00 ^ OC 6 If
their sum:
H5 H 5
"OCH"OCH
+ 2NaCl + 2H2O + 2NaCl + 2H 2 O
C H3 CH 3
\oc h/c,h\ + 2 \ oc h / c, h \ + 2
O C H/C*Hi OC H / C * Hi
CO( CO ( CC. 3^r0J*3 +2NaCl + XOCK "/{^a- 3 ^ r 0 J * 3 + 2NaCl + X OC K " / { ^ a -
mit der obigen Gleichung übereinstimmt, welche das ältere Verfahren kennzeichnet.agrees with the above equation which characterizes the older method.
Statt des Diphenylcarbonats kann man auch Kresylcarbonate und andere Phenylcarbonate anwenden, deren Phenol niedriger siedet als das Isoeugenol oder dasjenige Phenol, dessen Carbonat hergestellt werden soll.Instead of diphenyl carbonate, cresyl carbonates and other phenyl carbonates can also be used use whose phenol has a lower boiling point than isoeugenol or the phenol whose Carbonate is to be produced.
O HO H
Benutzt man die Chlorkohlensäureester derIf you use the chlorocarbonic acid esters of the
Cl
Alkohole, z.B. C 0<^^ ^ ττ , so bildet sich
zunächst nach der Gleichung: Cl
Alcohols, e.g. C 0 <^^ ^ ττ , are initially formed according to the equation:
2 δ2 δ
-OCH3 -OCH 3
ff Clff Cl
das Aethylcarbonat z. B. des Guajacols, wie bereits in der Patentschrift Nr. 60716 gezeigt ist. Man führt die Reaction am besten bei Gegenwart von Salzsäure bindenden Mitteln, z. B. den Alkalisalzen des Guajacols aus. Beithe ethyl carbonate z. B. of guaiacol, as already shown in Patent No. 60716 is. The reaction is best carried out in the presence of hydrochloric acid binding agents, z. B. the alkali salts of guaiacol. at
weiterem Erhitzen für sich oder mit überschüssigem Guajacol entsteht aus dem Aethylcarbonat des Guajacols das Guajacolcarbonat nach der Gleichung:Further heating by itself or with excess guaiacol results from the ethyl carbonate of guaiacol, the guaiacol carbonate according to the equation:
OCHOCH
+ CO(OC0H41-OCHJ3 + CO (OC 0 H 41 -OCHJ 3
oder bei Gegenwart überschüssigen Guajacols:or in the presence of excess guaiacol:
5- O C H3 + C*H*<°0CH3= CO(OC6^-OCH3J2 +C2H5OH. 5- OCH 3 + C * H * <° OCH 3 = CO (OC 6 ^ -OCH 3 J 2 + C 2 H 5 OH.
Es ist nicht nöthig, das Guajacol-Aethylcarbonat zu isoliren; man erhitzt vielmehr das Gemisch yon 1 Aequivalent Chlorkohlensäurealkylester mit 1 Aequivalent oder besser mit 2 Äquivalenten bezw. mit einem Ueberschusse von Guajacol u. U. bei Gegenwart von 1 Mol. Guajacolalkali. Es ist vortheilhaft, den Chlorkohlensäureäthylester nicht mit dem freien Phenol, sondern mit einem seiner Metallsalze zu erhitzen.It is not necessary to isolate the guaiacol ethyl carbonate; rather, the mixture of 1 equivalent of alkyl chlorocarbonate is heated with 1 equivalent or, better, with 2 equivalents, respectively. with an excess of guaiacol, possibly in the presence of 1 mol of guaiacol alkali. It is advantageous not to heat the ethyl chlorocarbonate with the free phenol but with one of its metal salts.
C0<Cl C0 <Cl
Beispiel TII.Example TII.
Menthol wird in Toluol gelöst, mit NatriumMenthol is dissolved in toluene with sodium
O C TfO C Tf
erhitzt und mit 1 Aequivalent C heated and with 1 equivalent of C
O C TfO C Tf
versetzt. Man destillirt, bis der Dampf die Temperatur von etwa 1400 besitzt. Der Rückstand besteht aus Mentholcarbonat, welches nach dem Umkrystallisiren aus Alkohol bei 105 ° schmilzt. Die Reaction -verläuft nach folgenden Gleichungen:offset. One distilled until the vapor temperature of about 140 has 0th The residue consists of menthol carbonate, which melts at 105 ° after recrystallizing from alcohol. The reaction proceeds according to the following equations:
C2H5OHC 2 H 5 OH
H5 H 5
+ HCl.+ HCl.
Menthol — Na + ClCOO C2 2f5 = Mentholäthylcarbonat + Na Cl, 2 Mentholäthylcarbonat = ι Mentholcarbonat -f- ι Aethylcarbonat. Menthol - Na + ClCOO C 2 2f 5 = menthol ethyl carbonate + Na Cl, 2 menthol ethyl carbonate = ι menthol carbonate -f- ι ethyl carbonate.
Die Menthen- Bildung wird auf diese Weise vermieden.The menth formation is avoided in this way.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE99057C true DE99057C (en) |
Family
ID=369966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT99057D Active DE99057C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE99057C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009123355A2 (en) * | 2008-04-01 | 2009-10-08 | Takasago International Corporation | Cooling sensation agent composition and sensory stimulation agent composition |
-
0
- DE DENDAT99057D patent/DE99057C/de active Active
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009123355A2 (en) * | 2008-04-01 | 2009-10-08 | Takasago International Corporation | Cooling sensation agent composition and sensory stimulation agent composition |
| WO2009123355A3 (en) * | 2008-04-01 | 2009-12-10 | Takasago International Corporation | Cooling sensation agent composition and sensory stimulation agent composition |
| US8632792B2 (en) | 2008-04-01 | 2014-01-21 | Takasago International Corporation | Cooling sensation agent composition and sensory stimulation agent composition |
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