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DE1270040B - Process for the production of ninhydrin - Google Patents

Process for the production of ninhydrin

Info

Publication number
DE1270040B
DE1270040B DEP1270A DER0038160A DE1270040B DE 1270040 B DE1270040 B DE 1270040B DE P1270 A DEP1270 A DE P1270A DE R0038160 A DER0038160 A DE R0038160A DE 1270040 B DE1270040 B DE 1270040B
Authority
DE
Germany
Prior art keywords
ninhydrin
production
water
bromine
methylmercaptoindanedione
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.)
Pending
Application number
DEP1270A
Other languages
German (de)
Inventor
Dr-Ing Horst Liebig
Dr Rer Nat Heinrich Pfetzing
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell Riedel de Haen AG
Original Assignee
Riedel de Haen AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority to DER38122A priority Critical patent/DE1229080B/en
Priority to DER38123A priority patent/DE1207381B/en
Application filed by Riedel de Haen AG filed Critical Riedel de Haen AG
Priority to DEP1270A priority patent/DE1270040B/en
Priority to CH681365A priority patent/CH461472A/en
Priority to GB24588/65A priority patent/GB1035180A/en
Priority to FR20546A priority patent/FR1437103A/en
Publication of DE1270040B publication Critical patent/DE1270040B/en
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/14Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides
    • C07C319/20Preparation of thiols, sulfides, hydropolysulfides or polysulfides of sulfides by reactions not involving the formation of sulfide groups
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C315/00Preparation of sulfones; Preparation of sulfoxides
    • C07C315/02Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61Preparation 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
    • C07C45/67Preparation 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
    • C07C45/673Preparation 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 change of size of the carbon skeleton
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00Systems containing two condensed rings
    • C07C2602/02Systems containing two condensed rings the rings having only two atoms in common
    • C07C2602/04One of the condensed rings being a six-membered aromatic ring
    • C07C2602/08One of the condensed rings being a six-membered aromatic ring the other ring being five-membered, e.g. indane

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Description

BUNDESREPUBLIK DEUTSCHLANDFEDERAL REPUBLIC OF GERMANY

DEUTSCHESGERMAN

PATENTAMTPATENT OFFICE

AUSLEGESCHRIFTEDITORIAL

Int. Cl.: Int. Cl .:

C 07cC 07c

Deutsche Kl.: 12 ο-25German class: 12 ο-25

Nummer: 1270 040Number: 1270 040

Aktenzeichen: P 12 70 040.2-42File number: P 12 70 040.2-42

Anmeldetag: 19. Juni 1964 Filing date: June 19, 1964

Auslegetag: 12. Juni 1968Opening day: June 12, 1968

Es ist bekannt, daß man Ninhydrin herstellen kann, indem man z. B. Indandion-(1,3) mit Selendioxyd oxydiert, 2-Brom-2-nitroindandion-(l,3) thermisch zersetzt oder p-Naphthochinon mit Sauerstoff oxydiert oder 2-Chlor-2-methylmercaptoindandion-(l,3) mit siedendem Wasser hydrolysiert.It is known that ninhydrin can be prepared by e.g. B. Indanedione (1,3) oxidized with selenium dioxide, 2-Bromo-2-nitroindandione- (l, 3) decomposed thermally or oxidized p-naphthoquinone with oxygen or 2-chloro-2-methylmercaptoindandione- (1,3) hydrolyzed with boiling water.

Alle bekannten Verfahren besitzen entscheidende Nachteile, da sie entweder von schwer zugänglichen Produkten ausgehen, auf Grund von Nebenreaktionen mit niedrigen Ausbeuten verlaufen, die Aufreinigung des entstandenen Ninhydrins schwierig ist, arbeitsintensive mehrstufige Reaktionsfolgen notwendig sind oder wie im Fall des 2-Chlor-2-methylmercaptoindandion-(l,3) ein vielstündiges Erhitzen in für eine technische Herstellung unrentabel großer Verdünnung erforderlich ist, erhebliche Geruchsbelästigung durch Bildung des giftigen Methylmercaptans auftritt und ferner schwer verhindert werden kann, daß sich beträchtliche Mengen Phthalsäure bilden.All known methods have significant disadvantages, since they are either difficult to access Run out of products due to side reactions with low yields, the purification of the ninhydrin formed is difficult, labor-intensive multi-stage reaction sequences are necessary or, as in the case of 2-chloro-2-methylmercaptoindanedione- (1.3), heating for many hours for a technical Production unprofitable large dilution is required, considerable odor nuisance through Formation of the poisonous methyl mercaptan occurs and, moreover, it is difficult to prevent considerable Forms quantities of phthalic acid.

Insbesondere konnte ein Nacharbeiten der Versuche zur Hydrolyse des 2-Chlor-2-methylmercaptoindandions (J. Org. Chem. 28 [1963], S. 1896) die günstigen Ausbeuteangaben (100 °/0) nicht bestätigen, vielmehr wurde nur eine Ausbeute von 50,8 °/0 erhalten.In particular, a reworking of the attempts to hydrolyze the 2-chloro-2-methylmercaptoindandions (J. Org Chem 28 [1963] S. 1896th.,) Could not confirm the favorable yield information (100 ° / 0), but only a yield of 50.8 ° / 0 obtained.

Es wurde nun überraschenderweise gefunden, daß man eine sonst bei Oxydationen von 2-substituierten Indandion-(1,3)-Derivaten leicht eintretende Molekülverdoppelung vermeiden kann und in hoher Ausbeute Ninhydrin erhält, wenn man 2-Hydroxy-2-methylmercaptoindandion-(l,3) in wäßriger Suspension etwa bei Raumtemperatur mit Chlor oder Brom oxydiert. Vorteilhafterweise geht man so vor, daß man 2-Hydroxy-2-methylmercaptoindandion-(l,3) in Wasser suspendiert, mit Chlor oder Brom oxydiert und das sich kristallin abscheidende Ninhydrin nach bekannten Verfahren abtrennt. Nebenprodukte können durch Extraktion mit einem geeigneten organischen Lösungsmittel entfernt werden. Als organisches Lösungsmittel ist vor allem Chloroform geeignet.It has now been found, surprisingly, that one would otherwise oxidize 2-substituted Indanedione (1,3) derivatives can easily avoid molecular doubling and in high yield Ninhydrin is obtained when 2-hydroxy-2-methylmercaptoindanedione- (l, 3) oxidized in aqueous suspension at about room temperature with chlorine or bromine. It is advantageous to proceed in such a way that 2-hydroxy-2-methylmercaptoindanedione (l, 3) suspended in water, oxidized with chlorine or bromine and the ninhydrin which separates out in crystalline form according to known methods Process separates. By-products can be removed by extraction with a suitable organic solvent removed. A particularly suitable organic solvent is chloroform.

Ein Überschuß von Chlor oder Brom als Oxydationsmittel führt nicht zur Bildung von Nebenprodukten. Überschüssiges Halogen kann nach Beendigung der Reaktion durch einen Gasstrom, ζ. Β. durch Stickstoff oder Luft, verdrängt werden. Das auskristallisierte Ninhydrin wird abgesaugt und getrocknet.An excess of chlorine or bromine as an oxidizing agent does not lead to the formation of by-products. After the reaction has ended, excess halogen can be removed by a stream of gas, ζ. Β. by nitrogen or air, to be displaced. The ninhydrin which has crystallized out is filtered off with suction and dried.

Das als Ausgangsstoff verwendete 2-Hydroxy-2-methylmercaptoindandion-(l,3) kann nach den deutschen Patenten 1 207 381 und 1 229 080 hergestellt werden, indem man Phthalsäureester mit Dimethylsulfoxyd in Gegenwart von Alkalialkoholaten umsetzt und das entstehende Zwischenprodukt mit wäßriger Schwefelsäure umlagert oder auf 2-Chlor- oder 2-Brom-Verfahren zur Herstellung von NinhydrinThe 2-hydroxy-2-methylmercaptoindanedione (l, 3) used as starting material can be prepared according to German patents 1 207 381 and 1 229 080 by mixing phthalic acid esters with dimethyl sulfoxide in Reacts the presence of alkali alcoholates and the intermediate product formed with aqueous sulfuric acid rearranged or on 2-chloro or 2-bromine processes for the production of ninhydrin

Anmelder:Applicant:

Riedel-de Haen Aktiengesellschaft, 3016 SeelzeRiedel-de Haen Aktiengesellschaft, 3016 Seelze

Als Erfinder benannt:
Dr.-Ing. Horst Liebig,
Dr. rer. nat. Heinrich Pfetzing,
3052 Bad Nenndorf
Named as inventor:
Dr.-Ing. Horst Liebig,
Dr. rer. nat. Heinrich Pfetzing,
3052 Bad Nenndorf

methylmercaptoindandion-(l,3) Wasser einwirken läßt.methylmercaptoindandione- (l, 3) water can act.

Beispiel 1example 1

10 g 2-Hydroxy-2-methylmercaptoindandion-(l,3) werden in etwa 100 ml Wasser suspendiert. Anschließend wird so lange Chlor eingeleitet, bis ein Überschuß in der Lösung verbleibt. Dabei entsteht zunächst eine klare Lösung, aus der Ninhydrin auskristallisiert.10 g of 2-hydroxy-2-methylmercaptoindandione- (l, 3) are suspended in about 100 ml of water. Afterward chlorine is passed in until an excess remains in the solution. First of all, a clear solution from which ninhydrin crystallizes out.

Die abgeschiedenen Kristalle werden abgesaugt, mit wenig Wasser gewaschen, die Mutterlauge mit Chloroform extrahiert und im Vakuum eingeengt, wobei sich weiteres Ninhydrin abscheidet, das wie oben isoliert wird.The deposited crystals are filtered off with suction, washed with a little water, the mother liquor with chloroform extracted and concentrated in vacuo, further ninhydrin separating out, which is isolated as above will.

Nach dem Trocknen erhält man insgesamt 7,2 g = 84,2 % der Theorie Ninhydrin vom Schmelzpunkt 239 bis 2400C.After drying, a total of 7.2 g = 84.2% of theory of ninhydrin with a melting point of 239 to 240 ° C. is obtained.

Beispiel 2Example 2

10 g 2-Hydroxy-2-methylmercaptoindandion-(l,3) werden in etwa 75 ml Wasser suspendiert und unter mechanischem Rühren so lange tropfweise mit elementarem Brom versetzt, bis ein Überschuß erkennbar bleibt.10 g of 2-hydroxy-2-methylmercaptoindandione- (l, 3) are suspended in about 75 ml of water and under Elemental bromine is added dropwise to mechanical stirring until an excess can be seen remain.

Aus der zunächst entstehenden klaren Lösung scheidet sich Ninhydrin kristallin aus, das durch Absaugen, Waschen mit Wasser und Trocknen isoliert wird. Die entstehende, mit dem Waschwasser vereinigte Mutterlauge wird mit Chloroform extrahiert, im Vakuum eingeengt und das sich abscheidende kristalline Ninhydrin wie oben isoliert.Ninhydrin precipitates in crystalline form from the initially resulting clear solution, which by suction, Wash with water and dry is isolated. The resulting mother liquor combined with the wash water is extracted with chloroform, concentrated in vacuo and the crystalline ninhydrin which separates out isolated as above.

Insgesamt erhält man 6,3 g = 73,5 °/0 der Theorie Ninhydrin vom Schmelzpunkt 239 bis 2400C.Overall, one obtains 6.3 g = 73.5 ° / 0 of theory ninhydrin of melting point 239-240 0 C.

809 559/496809 559/496

Claims (1)

3 43 4 Patentanspruch· tiger Suspension etwa bei Raumtemperatur mitClaim · tiger suspension with about room temperature Chlor oder Brom oxydiert. Verfahren zur Herstellung von Ninhydnn, d a-Chlorine or bromine oxidizes. Process for the production of ninhydnn, d a- durch gekennzeichnet, daß man 2-Hy- In Betracht gezogene Druckschriften:characterized in that 2-Hy- Considered publications: droxy-2-methylmercaptoindandion-(l,3) in wäß- 5 Journal of Organic Chemistry, Bd. 28 (1963), S. 1896.Droxy-2-methylmercaptoindanedione- (1,3) in aqueous 5 Journal of Organic Chemistry, Vol. 28 (1963), p. 1896. 809 559/496 5.58 © Bundesdruckerei Berlin809 559/496 5.58 © Bundesdruckerei Berlin
DEP1270A 1964-06-12 1964-06-19 Process for the production of ninhydrin Pending DE1270040B (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
DER38122A DE1229080B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-methylmercapto-indandione (1, 3) derivatives
DER38123A DE1207381B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-hydroxy-2-methylmercapto-indandione- (1, 3)
DEP1270A DE1270040B (en) 1964-06-12 1964-06-19 Process for the production of ninhydrin
CH681365A CH461472A (en) 1964-06-12 1965-05-14 Process for the production of ninhydrin
GB24588/65A GB1035180A (en) 1964-06-12 1965-06-10 Process for the preparation of ninhydrin
FR20546A FR1437103A (en) 1964-06-12 1965-06-11 Process for the preparation of ninhydrin

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DER38122A DE1229080B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-methylmercapto-indandione (1, 3) derivatives
DER38123A DE1207381B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-hydroxy-2-methylmercapto-indandione- (1, 3)
DEP1270A DE1270040B (en) 1964-06-12 1964-06-19 Process for the production of ninhydrin

Publications (1)

Publication Number Publication Date
DE1270040B true DE1270040B (en) 1968-06-12

Family

ID=27212157

Family Applications (3)

Application Number Title Priority Date Filing Date
DER38122A Pending DE1229080B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-methylmercapto-indandione (1, 3) derivatives
DER38123A Pending DE1207381B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-hydroxy-2-methylmercapto-indandione- (1, 3)
DEP1270A Pending DE1270040B (en) 1964-06-12 1964-06-19 Process for the production of ninhydrin

Family Applications Before (2)

Application Number Title Priority Date Filing Date
DER38122A Pending DE1229080B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-methylmercapto-indandione (1, 3) derivatives
DER38123A Pending DE1207381B (en) 1964-06-12 1964-06-12 Process for the preparation of 2-hydroxy-2-methylmercapto-indandione- (1, 3)

Country Status (4)

Country Link
CH (1) CH461472A (en)
DE (3) DE1229080B (en)
FR (1) FR1437103A (en)
GB (1) GB1035180A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385894A (en) * 1965-06-30 1968-05-28 Shulton Inc Oxidation of activated methylene group containing compounds to the corresponding carbonyl compounds
CN108047018B (en) * 2017-12-12 2022-07-22 上海三爱思试剂有限公司 Synthetic method of ninhydrin

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
DE1207381B (en) 1965-12-23
DE1229080B (en) 1966-11-24
FR1437103A (en) 1966-04-29
CH461472A (en) 1968-08-31
GB1035180A (en) 1966-07-06

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