CH470338A - Process for the production of adamantyl chloroformates - Google Patents
Process for the production of adamantyl chloroformatesInfo
- Publication number
- CH470338A CH470338A CH1420068A CH1420068A CH470338A CH 470338 A CH470338 A CH 470338A CH 1420068 A CH1420068 A CH 1420068A CH 1420068 A CH1420068 A CH 1420068A CH 470338 A CH470338 A CH 470338A
- Authority
- CH
- Switzerland
- Prior art keywords
- adamantyl
- chloroformate
- phosgene
- formula
- reacted
- Prior art date
Links
- -1 adamantyl chloroformates Chemical class 0.000 title claims description 16
- 238000000034 method Methods 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 3
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 claims description 11
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 claims description 11
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 claims description 8
- MYTHPILJALAOHO-UHFFFAOYSA-N 1-adamantyl carbonochloridate Chemical compound C1C(C2)CC3CC2CC1(OC(=O)Cl)C3 MYTHPILJALAOHO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 4
- LBWCITVBZLTEKW-UHFFFAOYSA-N 3,5-dimethyladamantan-1-ol Chemical compound C1C(C2)CC3(C)CC1(C)CC2(O)C3 LBWCITVBZLTEKW-UHFFFAOYSA-N 0.000 claims description 3
- UYAPHBILAQZRSM-UHFFFAOYSA-N 3-homoadamantanol Chemical compound C1C(C2)CC3CC2CC1(O)CC3 UYAPHBILAQZRSM-UHFFFAOYSA-N 0.000 claims description 3
- VLLNJDMHDJRNFK-UHFFFAOYSA-N adamantan-1-ol Chemical compound C1C(C2)CC3CC2CC1(O)C3 VLLNJDMHDJRNFK-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- PJBDPRVLKHVTCY-UHFFFAOYSA-N 3-methyladamantan-1-ol Chemical compound C1C(C2)CC3CC1(C)CC2(O)C3 PJBDPRVLKHVTCY-UHFFFAOYSA-N 0.000 claims 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical class [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical class C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 1
- 230000003113 alkalizing effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004414 alkyl thio group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000006301 indolyl methyl group Chemical group 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/06—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length using protecting groups or activating agents
- C07K1/061—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length using protecting groups or activating agents using protecting groups
- C07K1/064—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length using protecting groups or activating agents using protecting groups for omega-amino or -guanidino functions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/32—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings
- C07C271/34—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of rings other than six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
- C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07K—PEPTIDES
- C07K1/00—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length
- C07K1/06—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length using protecting groups or activating agents
- C07K1/061—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length using protecting groups or activating agents using protecting groups
- C07K1/063—General methods for the preparation of peptides, i.e. processes for the organic chemical preparation of peptides or proteins of any length using protecting groups or activating agents using protecting groups for alpha-amino functions
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/56—Ring systems containing bridged rings
- C07C2603/58—Ring systems containing bridged rings containing three rings
- C07C2603/70—Ring systems containing bridged rings containing three rings containing only six-membered rings
- C07C2603/74—Adamantanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- Biophysics (AREA)
- Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Proteomics, Peptides & Aminoacids (AREA)
- Analytical Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
Verfahren zur Herstellung von Adamantyl-chlorformiaten Gegenstand der vorliegenden Erfindung ist ein Ver fahren zur Herstellung von Adamantyl-chlorformiaten, die die folgende Formel I
EMI0001.0001
aufweisen. In dieser Formel steht der Rest AD für einen Adamantyl-, Methyladamantyl-, Dimethyladamantyl- oder Homoadamantylrest. Das erfindungsgemässe Ver fahren zur Herstellung der Verbindungen der Formel I zeichnet sich dadurch aus, dass man eine Verbindung der Formel II AD-OH II, in der AD die oben angegebene Bedeutung besitzt, mit Phosgen in Anwesenheit eines tertiären Amins in einem inerten Lösungsmittel umsetzt, wobei sich das Adaman- tylchlorformiat der Formel I bildet.
Nach dem erfindungsgemässen Verfahren können beispielsweise die folgenden Adamantylchlorformiate hergestellt werden: Adamantyl-(1)-chlorformiat, 3,5-Di- methyl-adamantyl-(1)-chlorformiat; Homoadamantyl- (3)-hlorformiat und 3-Methyl-adamantyl-(1)-chlorfor- miat.
Die nach dem erfindungsgemässen Verfahren herge stellten Adamantylchlorformiate können als Zwischen produkte bei der Herstellung von N-Adamantyloxycar- bonyl-derivaten von Aminosäuren verwendet werden. Die nach diesem Verfahren erhaltenen N-Adamantyl- oxycarbonyl-derivate der Aminosäuren weisen die fol gende Formel
EMI0001.0016
auf, wobei in dieser Formel X eine Gruppe der For mel
EMI0001.0017
ist und AD für einen Adamantyl-, Methyladamantyl-, Dimethyladamantyl- oder Homoadamantylrest steht, R' ein Wasserstoffatom oder eine Alkylgruppe mit 1-4.
Kohlenstoffatomen ist, R" ein Wasserstoffatom oder eine Hydroxylgruppe bedeutet und R für ein Wasserstoff atom, eine gegebenenfalls mit Hydroxylgruppen, Carbal- koxygruppen mit 1-4 Kohlenstoffatomen, Mercapto- gruppen, Alkylmercaptogruppen mit 1-4 Kohlenstoff atomen oder Guanidogruppen substituierten Alkylrest mit 1 bis 4 Kohlenstoffatomen, einen gegebenenfalls substituierten Phenylrest, einen gegebenenfalls substi tuierten Benzyl-, Thienyl-, Furyl, Imidazolylmethyl-, Indolylmethyl- oder Hydroxyindolymethylrest steht oder eine Gruppe der Formel
EMI0002.0000
bedeutet, in der R' und AD die oben angegebene Bedeutung besitzen.
Adamantane und Homoadamantane, von denen sich die oben erwähnten Adamantyl-, Methyladamantyl-, Dimethyladamantyl-und Homoadamantylreste ableiten, sind tricyclische, mehrfache Brückenbindungen aufwei sende Kohlenwasserstoffe. Ihre Formeln lassen sich in wie folgt wiedergeben:
EMI0002.0001
Die Herstellung des Adamantylchlorformiate nach dem erfindungsgemässen Verfahren und deren Verwen dung zur Herstellung von weiteren Derivaten sei anhand des folgenden Reaktionsschemas erläutert:
EMI0002.0004
In diesem Formelschema haben die Reste AD, R, R' Sand R" die - oben angegebene Bedeutung.
Bei der Durchführung der obigen Reaktionsfolge wird 1-Hydro- xyadamantan oder 3-Methtyl-l-hydroxadamantan oder 3,5-Dimethyl-l-hydroxyadamantan oder 3-Hydroxyho- moadamantan mit Phosgen in Gegenwart eines tertiären Amins, z. B. Pyridin; Trimethylpyridin, Chinolin oder Triäthylamin, in einem inerten Lösungsmittel, wie was serfreiem Benzol oder Äther oder kohlenwasserstoffarti gen oder ätherischen Lösungsmitteln, umgesetzt unter Bildung des entsprechenden Adamantylchlorformiats, welches in einem geeigneten Lösungsmittel aufbewarht oder als weisser kristalliner Festkörper isoliert werden kann.
Die Herstellung des N-Adamantyloxycarbonylderi- vates der Aminosäure, in der die Aminogruppe geschützt oder blockiert werden soll, geht vonstatten durch einfa ches Vermischen des Adamantylchlorformiats mit der Aminosäureverbindung in einem inerten Lösungsmittel unter leicht alkalischen Bedingungen, die durch Anwen dung eines Lösungsmittels wie Alkohol oder Dioxan, und verdünntem wässrigem Natriumhydroxyd oder einem anderen gleichwertigen Stoff als Alkalisierungs- mittel gesichert sind.
Durch die folgenden speziellen Beispiele soll die Erfindung näher erläutert werden.
<I>Beispiel 1</I> Eine Lösung enthaltend 20 g Phosgen in 100 ml wasserfreiem Benzol wurde mit Hilfe eines Eiswasser- Bades bei etwa 20 C gehalten. Ein Gemisch enthaltend 8 g 1-Hydroxyadamantan, 6 g Pyridin und 200 ml Äther wurde tropfenweise unter Rühren während eines Zeit raumes von etwa 1 Stunde zu der Phosgenlösung hinzugefügt. Dann wurden 100 ml wasserfreies Benzol zugesetzt, und das Umsetzungsgemisch wurde während etwa 1 Stunde bei Umgebungstemperatur gehalten und sodann filtriert.
Das Filtrat wurde über ein Eis-Wasser- Gemisch gegossen und die organische Schicht, die das Adamantyl-(1)-chlorformiat enthielt, abgetrennt und ge trocknet. Eindampfen der Lösung im Vakuum bei Zimmertemperatur ergab Adamantyl-(1)-chlorformiat als weissen kristallinen Festkörper, der bei 40-4.2 C schmolz. Das Material wurde weiterhin gereinigt durch Umkristallisieren aus wasserfreiem niedrig siedendem Petroläther bei -20 C, wobei sich bei etwa 46-47 C schmelzende Kristalle ergaben.
Adamantylchlorformiat kann im wesentlichen ohne Zersetzung bei 4 C in Benzol-Äther-Lösung gelagert werden, die eine geringe Menge Calciumcarbonat als Stabilisator enthält.
<I>Beispiel 2</I> Gemäss der Arbeitsweise von Beispiel 1 wurde 3,5- Dimethyl-l-hydroxyadamantan mit Phosgen in Benzol lösung in Gegenwart von Pyridin unter Bildung des Chlorformiats umgesetzt. Die Verbindung schmolz bei etwa 5-10 C.
<I>Beispiel 3</I> Homoadamantyl-(3)-chlorformiat wurde gemäss der Arbeitsweise von Beispiel 1 aus Phosgen und 3-Hydro- xyhomoadamantan hergestellt. Die Verbindung, die in kristalliner Form aus Petroläther bei -50 C isoliert wurde, schmolz unter etwa 0 C.
Process for the preparation of adamantyl chloroformates The present invention provides a process for the preparation of adamantyl chloroformates which have the following formula I
EMI0001.0001
exhibit. In this formula, the radical AD stands for an adamantyl, methyladamantyl, dimethyladamantyl or homoadamantyl radical. The inventive method for the preparation of the compounds of the formula I is characterized in that a compound of the formula II AD-OH II, in which AD has the meaning given above, is reacted with phosgene in the presence of a tertiary amine in an inert solvent, whereby the adamantyl chloroformate of the formula I is formed.
The following adamantyl chloroformates, for example, can be prepared by the process according to the invention: adamantyl (1) chloroformate, 3,5-dimethyl adamantyl (1) chloroformate; Homoadamantyl (3) chloroformate and 3-methyl adamantyl (1) chloroformate.
The adamantyl chloroformates produced by the process according to the invention can be used as intermediate products in the production of N-adamantyloxycarbonyl derivatives of amino acids. The N-adamantyl oxycarbonyl derivatives of the amino acids obtained by this process have the following formula
EMI0001.0016
on, where in this formula X is a group of the formula
EMI0001.0017
and AD stands for an adamantyl, methyladamantyl, dimethyladamantyl or homoadamantyl radical, R 'is a hydrogen atom or an alkyl group with 1-4.
Is carbon atoms, R "denotes a hydrogen atom or a hydroxyl group and R denotes a hydrogen atom, an alkyl radical with 1 to 4 which is optionally substituted with hydroxyl groups, carbalkoxy groups with 1-4 carbon atoms, mercapto groups, alkyl mercapto groups with 1-4 carbon atoms or guanido groups 4 carbon atoms, an optionally substituted phenyl radical, an optionally substituted benzyl, thienyl, furyl, imidazolylmethyl, indolylmethyl or hydroxyindolymethyl radical or a group of the formula
EMI0002.0000
means in which R 'and AD have the meaning given above.
Adamantanes and homoadamantanes, from which the above-mentioned adamantyl, methyladamantyl, dimethyladamantyl and homoadamantyl radicals are derived, are tricyclic hydrocarbons with multiple bridge bonds. Their formulas can be expressed as follows:
EMI0002.0001
The preparation of the adamantyl chloroformate by the process according to the invention and its use for the preparation of further derivatives will be explained using the following reaction scheme:
EMI0002.0004
In this equation, the radicals AD, R, R 'Sand R "have the meaning given above.
When carrying out the above reaction sequence, 1-hydroxyadamantane or 3-methyl-1-hydroxadamantane or 3,5-dimethyl-1-hydroxyadamantane or 3-hydroxyho- moadamantane with phosgene in the presence of a tertiary amine, eg. B. pyridine; Trimethylpyridine, quinoline or triethylamine, in an inert solvent, such as serfreiem benzene or ether or kohlenwasserstoffarti conditions or ethereal solvents, converted to form the corresponding Adamantylchlorformat, which can be stored in a suitable solvent or isolated as a white crystalline solid.
The preparation of the N-adamantyloxycarbonyl derivative of the amino acid in which the amino group is to be protected or blocked is done by simply mixing the adamantyl chloroformate with the amino acid compound in an inert solvent under slightly alkaline conditions, which can be achieved by using a solvent such as alcohol or Dioxane, and dilute aqueous sodium hydroxide or another equivalent substance are secured as alkalizing agents.
The invention is illustrated by the following specific examples.
<I> Example 1 </I> A solution containing 20 g of phosgene in 100 ml of anhydrous benzene was kept at about 20 ° C. using an ice-water bath. A mixture containing 8 g of 1-hydroxyadamantane, 6 g of pyridine and 200 ml of ether was added dropwise to the phosgene solution with stirring over a period of about 1 hour. 100 ml of anhydrous benzene was then added and the reaction mixture was held at ambient temperature for about 1 hour and then filtered.
The filtrate was poured over an ice-water mixture and the organic layer, which contained the adamantyl (1) chloroformate, was separated off and dried. Evaporation of the solution in vacuo at room temperature gave adamantyl (1) chloroformate as a white crystalline solid which melted at 40-4.2 ° C. The material was further purified by recrystallization from anhydrous low-boiling petroleum ether at -20.degree. C., which resulted in crystals melting at about 46-47.degree.
Adamantyl chloroformate can be stored essentially without decomposition at 4 C in a benzene-ether solution that contains a small amount of calcium carbonate as a stabilizer.
<I> Example 2 </I> According to the procedure of Example 1, 3,5-dimethyl-l-hydroxyadamantane was reacted with phosgene in benzene solution in the presence of pyridine to form the chloroformate. The compound melted at around 5-10 C.
<I> Example 3 </I> Homoadamantyl (3) chloroformate was prepared according to the procedure of Example 1 from phosgene and 3-hydroxyhomoadamantane. The compound, which was isolated in crystalline form from petroleum ether at -50 C, melted below about 0 C.
Claims (1)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US427124A US3345399A (en) | 1965-01-21 | 1965-01-21 | Carbamate esters of adamantane, mono-and di-methyladamantane and homoadamantane |
| CH71066A CH475209A (en) | 1965-01-21 | 1966-01-19 | Process for the preparation of N-adamantyloxycarbonyl derivatives of x-amino acids and L-amino acid esters |
| US615356A US3369041A (en) | 1965-01-21 | 1967-02-13 | Adamantyl carbazates |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CH470338A true CH470338A (en) | 1969-03-31 |
Family
ID=27172338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CH1420068A CH470338A (en) | 1965-01-21 | 1966-01-19 | Process for the production of adamantyl chloroformates |
Country Status (1)
| Country | Link |
|---|---|
| CH (1) | CH470338A (en) |
-
1966
- 1966-01-19 CH CH1420068A patent/CH470338A/en not_active IP Right Cessation
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