DE114194C - - Google Patents
Info
- Publication number
- DE114194C DE114194C DENDAT114194D DE114194DA DE114194C DE 114194 C DE114194 C DE 114194C DE NDAT114194 D DENDAT114194 D DE NDAT114194D DE 114194D A DE114194D A DE 114194DA DE 114194 C DE114194 C DE 114194C
- Authority
- DE
- Germany
- Prior art keywords
- formaldehyde
- halogen
- products
- acids
- oxyaldehydes
- 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
- WSFSSNUMVMOOMR-UHFFFAOYSA-N formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 19
- 239000002253 acid Substances 0.000 claims description 11
- 150000007513 acids Chemical class 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000000034 method Methods 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N Salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 8
- -1 chloromethyl alcohol Chemical compound 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Natural products OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N Vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- KPJPHPFMCOKUMW-UHFFFAOYSA-N iodomethane Chemical class I[CH2] KPJPHPFMCOKUMW-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 229960000583 Acetic Acid Drugs 0.000 description 1
- NKDDWNXOKDWJAK-UHFFFAOYSA-N Dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000005997 bromomethyl group Chemical group 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229940117960 vanillin Drugs 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/575—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing ether groups, groups, groups, or groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/70—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form
- C07C45/71—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction with functional groups containing oxygen only in singly bound form being hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
- C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms
- C07C45/72—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms by reaction of compounds containing >C = O groups with the same or other compounds containing >C = O groups
- C07C45/75—Reactions with formaldehyde
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C47/00—Compounds having —CHO groups
- C07C47/52—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings
- C07C47/56—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups
- C07C47/565—Compounds having —CHO groups bound to carbon atoms of six—membered aromatic rings containing hydroxy groups all hydroxy groups bound to the ring
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
KAISERLICHESIMPERIAL
PATENTAMT.PATENT OFFICE.
Entgegen den Angaben der Patentschrift 57621 haben die Einwirkungsproducte von Halogenwasserstoffsäuren auf Formaldehyd, insbesondere der Chlormethylalkohol, technische Verwerthung bis jetzt nicht gefunden, da ihre Wirkung auf aromatische Verbindungen, insbesondere Phenole, in den meisten Fällen eine zu heftige ist und zu hochmolecularen, oft harzartigen Körpern führt, welche mit den von Kleeberg (Annalen 263, S. 284) und in der Patentschrift 101191 beschriebenen complicirten Methylenverbindungen identisch oder verwandt zu sein scheinen.Contrary to the information in patent specification 57621, the products of the action of hydrohalic acids on formaldehyde, especially chloromethyl alcohol, technical recovery not yet found, as their effect on aromatic compounds, in particular Phenols, in most cases one which is too violent and often too high molecular weight resin-like bodies, which with the von Kleeberg (Annalen 263, p. 284) and in the Patent 101191 described complicated Methylene compounds appear to be identical or related.
Es wurde nun gefunden, dafs unter bestimmten, in dem Patent 57621 nicht angegebenen Bedingungen, nämlich wenn man die oben erwähnten Reactionsproducte zwischen Formaldehyd und Halogenwasserstoffsäuren in Gegenwart von wasserentziehenden starken Säuren, insbesondere von concentrirten Halogenwasserstoffsäuren , concentrirter Schwefelsäure, Phosphorsäure oder dergl. auf die in jenem Patent nicht erwähnten aromatischen Oxyaldehyde einwirken läfst, man bisher noch nicht bekannte, halogenhaltige Verbindungen erhalten kann, welche durch die Gruppe C H2 X substituirt sind, wobei X ein Halogen bezeichnet. It has now been found that under certain conditions not specified in patent 57621, namely, when the above-mentioned reaction products between formaldehyde and hydrohalic acids in the presence of dehydrating strong acids, in particular concentrated hydrohalic acids, concentrated sulfuric acid, phosphoric acid or the like, are reduced to the in that aromatic oxyaldehydes not mentioned in that patent can act, one can obtain hitherto unknown halogen-containing compounds which are substituted by the group CH 2 X , where X denotes a halogen.
Diese neue Körperklasse besitzt die charakteristische Eigenschaft, dafs das Halogen überaus leicht beweglich ist, so dafs es schon durch Wasser in der Kälte in Form von Halogenwasserstoff abgespalten wird, wobei aromatische Alkohole gebildet werden. Durch Behandlung der Halogenverbindungen mit Alkoholen der Fettreihe werden die entsprechenden Aether dieser aromatischen Alkohole gebildet, während durch Einwirkung von Phenolen bezw. Aminen werthvolle Condensationsproducte erhalten werden. Läfst man Metallsalze auf die neuen Körper einwirken, so wird ein Austausch des Halogens gegen den betreffenden Säurerest erzielt. This new class of bodies has the characteristic property that halogen is extremely is easily mobile, so that it is already in cold water in the form of hydrogen halide is split off, whereby aromatic alcohols are formed. By treating the halogen compounds with alcohols of the The corresponding ethers of these aromatic alcohols are formed during fat series by the action of phenols respectively. Amines valuable condensation products can be obtained. If you let metal salts act on the new body, an exchange of the Halogen against the acid residue in question achieved.
Es ist zur Aasführung der Reaction nicht nöthig, die Einwirkungsproducte von Formaldehyd auf Halogen wasserstoffsäuren, wie z. B. ■Chlormethylalkohol, Bro.mmethylalkohol, Jodmethylalkohol etc;, zu reinigen oder zu isoliren, es lassen sich auch die bei der Einwirkung von Formaldehyd oder Formaldehyd abspaltenden Körpern, wie Methylal, Paraform, Oxychlormethyläther, Oxymethylsulfosäure etc., auf concentrirten Halogenwasserstoffsäuren erhaltenen Rohproducte und Laugen verwenden, und andererseits kann die Bildung dieser Einwirkungsproducte bei Anwesenheit der Oxyaldehyde stattfinden, so dafs sie also nur intermediär entstehen und zugleich mit letzteren unter Bildung der neuen Körper in Reaction treten.In order to carry out the reaction, it is not necessary for the action products of formaldehyde on halogen hydrogen acids, such as. B. ■ chloromethyl alcohol, bromethyl alcohol, iodomethyl alcohol etc .; to be purified or isolated; those which are split off under the action of formaldehyde or formaldehyde can also be used Solids, such as methylal, paraform, oxychloromethyl ether, oxymethylsulfonic acid, etc., on use crude products and lyes obtained from concentrated hydrohalic acids, and on the other hand, the formation of these action products can occur in the presence of oxyaldehydes take place, so that they arise only intermediately and at the same time as the latter enter into reaction with the formation of the new bodies.
Das Verfahren zur Darstellung dieser Körper wird durch folgende Beispiele erläutert.The method for representing these bodies is illustrated by the following examples.
i. 1220 g Salicylaldehyd werden in 10 kg concentrate Salzsäure suspendirt, mit 665 g Chlormethylalkohol gemischt und die Mischung unter Schütteln auf 25 bis 300 angewärmt. Nach einiger Zeit beginnen sich aus der Reactionsflüssigkeit lange Krystallnadeln auszuscheiden, welche bald das ganze Gefäfs erfüllen. Sie werden abfütrirt, getrocknet, ausi. 1220 g of salicylaldehyde are suspended in 10 kg of concentrate hydrochloric acid, mixed with 665 g of chlorine, methyl alcohol, and the mixture with shaking at 25 to 30 0 warmed. After a while, long crystal needles begin to separate out of the reaction liquid, which soon fill the entire vessel. They are carried away, dried, out
Benzol umkrystallisirt und hieraus in farblosen, dicken Nadeln vom Smp. 88 ° erhalten, welche unter Wasser zu einem OeI schmelzen ynd iri den meisten organischen Lösungsmittelf^ijSifelii löslich sind. i .^S' Benzene recrystallizes and is obtained therefrom in colorless, thick needles with a melting point of 88 °, which melt under water to an oil and are soluble in most organic solvents. i. ^ S '
Analyse:Analysis:
...' Gefunden:...' Found:
C = 56,32 pCt.
Ή— 4,63 - .
, Cl =z 20,29C = 56.32 pct.
Ή— 4.63 -.
, Cl = z 20.29
Berechnet für
QH1O2Cl: Calculated for
QH 1 O 2 Cl:
56,30 pCt.
4,10 -56.30 pCt.
4.10 -
Hieraus ergiebt sich mit grofser Wahrscheinlichkeit die Constitution des Körpers alsFrom this the constitution of the body follows with great probability as
,CHO CeHsi~0H, CHO C e H s i ~ 0H
^CH2 Cl.^ CH 2 Cl.
2. 122 g Salicylaldehyd werden in 67 g Chlormethylalkohol gelöst und die entstandene Lösung mit 200 g Eisessig verdünnt. Man trägt darauf 30 g concentrirte H2 S O4 langsam unter Kühlung in die Lösung ein und läfst dann die so erhaltene Mischung mehrere Tage bei 20 bis 300 stehen, bis sich das im Beispiel ι beschriebene Chlormethylderivat als ein dicker Krystallbrei abgeschieden hat. Derselbe ,wird wie in Beispiel 1 angegeben isolirt.2. 122 g of salicylaldehyde are dissolved in 67 g of chloromethyl alcohol and the resulting solution is diluted with 200 g of glacial acetic acid. 30 g of concentrated H 2 S O 4 are then slowly introduced into the solution with cooling and the mixture thus obtained is then allowed to stand for several days at 20 to 30 ° until the chloromethyl derivative described in Example 1 has separated out as a thick crystal paste. The same is isolated as indicated in Example 1.
3. 122 g Salicylaldehyd werden in ein Gemisch von 75 g 4oproc. Formaldehyd mit ι kg starker Bromwasserstoffsäure in der Kälte eingerührt und durch das Gemenge ein Strom trockner Bromwasserstoffsäure so lange durchgeleitet, bis die sich anfangs erwärmende Flüssigkeit sich wieder völlig abgekühlt und ein weifser krystallinischer Niederschlag sich abgeschieden hat. Nach dem Abfiltriren und Trocknen stellt das so erhaltene Brommethylderivat ein weifses Krystallpulver vom Smp. io6° dar.3. 122 g of salicylaldehyde are put into a Mixture of 75 g of 4oproc. Formaldehyde with ι kg of strong hydrobromic acid in stirred in the cold and a stream of dry hydrobromic acid through the mixture passed through for a long time until the liquid, which initially warms up, cools down again completely and a white crystalline precipitate has deposited. After filtering off and drying, the bromomethyl derivative thus obtained turns into a white crystal powder of m.p. 10.6 °.
In analoger Weise verfährt man bei Verwendung anderer Aldehyde oder zur Darstellung der sich ganz analog verhaltenden Jodmethylderivate. So erhält man z. B. aus Salicylaldehyd ein Jodmethylderivat vom Smp. 870, aus Vanillin ein Chlormethylderivat vom Smp. 1270 (farblose Blättchen).An analogous procedure is followed when using other aldehydes or for the preparation of the iodomethyl derivatives, which behave quite analogously. So you get z. B. from salicylaldehyde an iodomethyl derivative of m.p. 87 0 , from vanillin a chloromethyl derivative of m.p. 127 0 (colorless leaves).
Die neuen Körper sollen als pharmaceutische Producte und als Zwischenproducte für die Darstellung von Theerfarbstoffen Verwendung finden.The new bodies should be used as pharmaceutical products and as intermediate products for the Find representation of tar dyes use.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE114194C true DE114194C (en) |
Family
ID=383714
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DENDAT114194D Active DE114194C (en) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE114194C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE951927C (en) * | 1943-08-21 | 1956-11-08 | Basf Ag | Process for the preparation of meta- (chloromethyl) benzoic acid |
-
0
- DE DENDAT114194D patent/DE114194C/de active Active
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE951927C (en) * | 1943-08-21 | 1956-11-08 | Basf Ag | Process for the preparation of meta- (chloromethyl) benzoic acid |
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