NO117856B - PROCEDURE FOR PREPARING 1,2-DIFENYL-3,5-DIOXO-4- (3'-OXOBUTYL) -PYRAZOLIDINE - Google Patents
PROCEDURE FOR PREPARING 1,2-DIFENYL-3,5-DIOXO-4- (3'-OXOBUTYL) -PYRAZOLIDINE Download PDFInfo
- Publication number
- NO117856B NO117856B NO16549666A NO16549666A NO117856B NO 117856 B NO117856 B NO 117856B NO 16549666 A NO16549666 A NO 16549666A NO 16549666 A NO16549666 A NO 16549666A NO 117856 B NO117856 B NO 117856B
- Authority
- NO
- Norway
- Prior art keywords
- diphenyl
- pyrazolidine
- dioxo
- oxobutyl
- salt
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 9
- XDPKQGKEOCYMQC-UHFFFAOYSA-N 1,2-diphenylpyrazolidine-3,5-dione Chemical compound O=C1CC(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 XDPKQGKEOCYMQC-UHFFFAOYSA-N 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 8
- LGYTZKPVOAIUKX-UHFFFAOYSA-N kebuzone Chemical compound O=C1C(CCC(=O)C)C(=O)N(C=2C=CC=CC=2)N1C1=CC=CC=C1 LGYTZKPVOAIUKX-UHFFFAOYSA-N 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000001340 alkali metals Chemical class 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 239000000460 chlorine Substances 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229960000194 kebuzone Drugs 0.000 description 5
- -1 1,2-diphenyl-3,5-dioxo-4 -(ethylenedi-oxybutyl )-pyrazolidine Chemical compound 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GVNNGJMKAFLSHZ-NSCUHMNNSA-N (e)-1,3-dichlorobut-1-ene Chemical compound CC(Cl)\C=C\Cl GVNNGJMKAFLSHZ-NSCUHMNNSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- IYXGSMUGOJNHAZ-UHFFFAOYSA-N Ethyl malonate Chemical compound CCOC(=O)CC(=O)OCC IYXGSMUGOJNHAZ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
- C07D231/28—Two oxygen or sulfur atoms
- C07D231/30—Two oxygen or sulfur atoms attached in positions 3 and 5
- C07D231/32—Oxygen atoms
- C07D231/36—Oxygen atoms with hydrocarbon radicals, substituted by hetero atoms, attached in position 4
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
Description
Fremgangsmåte ved fremstilling av 1,2-difenyl-3,5-dioxo-4-(3'-oxobutyl)-pyrazolidin. Process for the production of 1,2-diphenyl-3,5-dioxo-4-(3'-oxobutyl)-pyrazolidine.
Foreliggende oppfinnelse angår en fremgangsmåte ved fremstilling av 1,2-difeny1-3,5-dioxo-4-(3 *-oxobutyl)-pyrazolidin, som også kalles ketofenylbutazon og som anvendes som legemiddel med betydelig antiinflammatorisk virkning. The present invention relates to a method for the production of 1,2-diphenyl-3,5-dioxo-4-(3*-oxobutyl)-pyrazolidine, which is also called ketophenylbutazone and which is used as a drug with significant anti-inflammatory action.
De kjente fremgangsmåter for fremstilling av denne forbindelse starter tildels med 1,2-difenyl-3»5-dioxo-4-(3'-klorcroty1)-pyrazolidin, og tildels med 1,2-difenyl-3,5-dioxo-4-(ethylendi-oxybutyl )-pyrazolidin (Dense og medarb. Heiv. China. Acta kO, k02, En ytterligere metode går ut på å addere 1,2-difényl-3,5-dioxopyrazo'lidin eller et salt av dette til methylvinylketon eller å alkylere med den tilsvarende kvartære Mannich-base. The known methods for the preparation of this compound start partly with 1,2-diphenyl-3,5-dioxo-4-(3'-chlorochloroyl)-pyrazolidine, and partly with 1,2-diphenyl-3,5-dioxo-4 -(ethylenedi-oxybutyl )-pyrazolidine (Dense et al. Heiv. China. Acta kO, k02, A further method consists in adding 1,2-diphenyl-3,5-dioxopyrazolidine or a salt thereof to methyl vinyl ketone or to alkylate with the corresponding quaternary Mannich base.
Det er kjent at man lett kan alkylere 1,2-difeny1-3,5-dioxo- pyazolidin med reaktive halogenforbindelser. Mens alltylerings-forsok med n-butylbromid ikke har fort frem (Chaleckij og medarb. Z.obsc.chim. 28, 2355»1958), gir det reaktive 1,3-diklorbuten~2 godt utbytte av det tilsvarende 4-(3 '-klorcroty1)-derivat. Reak-sjonen forloper best i nærvær av en ekvivalent av et alkali. Eventuelt anvendes difenyldioxopyrazolidin i form av et salt, dvs» i en form hvor et aktivt hydrogenatom er erstattet med et kation. Overskudd av alkali forer til disubstituering og til andre uon~skede reaksjoner. It is known that 1,2-diphenyl-3,5-dioxopyazolidine can be easily alkylated with reactive halogen compounds. While alltylation attempts with n-butyl bromide have not been successful (Chaleckij et al. Z.obsc.chim. 28, 2355»1958), the reactive 1,3-dichlorobutene~2 gives a good yield of the corresponding 4-(3' -chlorocroty1) derivative. The reaction proceeds best in the presence of an equivalent of an alkali. Optionally, diphenyldioxopyrazolidine is used in the form of a salt, i.e. in a form where an active hydrogen atom has been replaced by a cation. An excess of alkali leads to disubstitution and to other undesired reactions.
Efter inngående studier av reaksjonsbetingelsene har det nu lykkes å finne frem til en fremgangsraåte for fremstilling av 1,2-dif eny1-3,5-dioxo-4-(31-oxobutyl)-pyrazolidin. Den nye fremgangsmåte utmerker seg ved at en forbindelse av den generelle formel: After in-depth studies of the reaction conditions, it has now succeeded in finding a process for the production of 1,2-diphenyl-3,5-dioxo-4-(31-oxobutyl)-pyrazolidine. The new method is distinguished by the fact that a compound of the general formula:
CH3COCH2CH2X CH3COCH2CH2X
hvor X betegner et halogenatom. fortrinsvis klor, kondenseres med 1,2-difeny1-3»5-dioxopyrazolidin eller et salt derav, i nærvær av et alkalisk kondenseringsmiddel, fortrinsvis et alkalime-tallalkoholat i en mengde storre enn 1 ekvivalent og ikke over 4 ekvivalenter, fortrinsvis i en mengde av 2 ekvivalenter, beregnet på den anvendte mengde av 1,2-difenyl-3,5-dioxopyrazolidinet eller av anionet av dets salt. where X denotes a halogen atom. preferably chlorine, is condensed with 1,2-diphenyl-3'5-dioxopyrazolidine or a salt thereof, in the presence of an alkaline condensing agent, preferably an alkali metal alcoholate in an amount greater than 1 equivalent and not more than 4 equivalents, preferably in an amount of 2 equivalents, calculated on the amount used of the 1,2-diphenyl-3,5-dioxopyrazolidine or of the anion of its salt.
Denne kondensering forloper uten vanskeligheter i alkanoler med 1-4 carbonatomer, fortrinsvis methanol. Som 1,2-difenyl-3,5-dioxopyrazolidinsalt kan der anvendes et alkalimetallsalt, fortrinsvis natriumsaltet. Kondenseringen kan utfores ved tempe-raturer fra 30°C til reaksjonsblandingens koketemperatur. This condensation proceeds without difficulty in alkanols with 1-4 carbon atoms, preferably methanol. An alkali metal salt, preferably the sodium salt, can be used as 1,2-diphenyl-3,5-dioxopyrazolidine salt. The condensation can be carried out at temperatures from 30°C to the boiling temperature of the reaction mixture.
Forsokene på å alkylere 1,2-difeny1-3,5-dioxopyrazolidinet med methyl-fi-halogenketoner, forst og fremst med methyl-(i-klor- , ethylketon, under de hittil benyttede betingelser, forte ikke frem, dvs. forte ikke til ketofenylbutazonet. Som reaksjonspro-dukt fikk, man en i alkalier bare delvis ppploselig blanding av forskjellige forbindelser. Forst efter den uventede erkjennelse at omsetningen, stikk i strid ved h<y>a man tidligere har ment, for-drer et overskudd av det alkaliske kondenseringsmidde!, fortrinsvis 2 ekvivalenter, har det lyktes å fremstille ketofenylbutazon uten vanskelighet og i hoyt utbytte. Som alkalisk kondenseringsmiddel kan man foruten alkaliraetallalkoholatene også anvende andre egnede, basisk reagerende uorganiske og organiske forbindelser. The attempts to alkylate the 1,2-diphenyl-3,5-dioxopyrazolidine with methyl-fi-halo ketones, primarily with methyl-(i-chloro-, ethyl ketone), under the conditions used up to now, did not progress, i.e. did not to the ketophenylbutazone. As a reaction product, a mixture of different compounds only partially soluble in alkalis was obtained. After the unexpected realization that the reaction, contrary to what was previously thought, requires an excess of alkaline condensing agent!, preferably 2 equivalents, it has been possible to prepare ketophenylbutazone without difficulty and in high yield. As an alkaline condensing agent, in addition to the alkali metal alcoholates, other suitable, alkaline-reacting inorganic and organic compounds can also be used.
Som ovenfor nevnt kan man ved fremgangsmåten ifolge oppfinnel-sen starte med 1,2-difeny1-3,5-dioxopyrazolidin eller med et salt av denne forbindelse. Forbindelsen kan lett fremstilles i hoyt utbytte ved kondensering av malonsyrediethylester med hydrazobenzen (Ruhkoph, Ber. 73, 820,1940). As mentioned above, the method according to the invention can start with 1,2-diphenyl-3,5-dioxopyrazolidine or with a salt of this compound. The compound can easily be prepared in high yield by condensation of malonic acid diethyl ester with hydrazobenzene (Ruhkoph, Ber. 73, 820, 1940).
Blant methyl-£-halogenethylketonene er raethyl-|i-klor-ethy 1-keton best egnet. Dette kan lett fremstilles ved omsetning av hydrogenklorid med paraformaldehyd og aceton. (Dermer, J. Am. Chem.Soc. 74,3417,1952). Among the methyl-£-haloethyl ketones, raethyl-|i-chloro-ethyl 1-ketone is most suitable. This can be easily produced by reacting hydrogen chloride with paraformaldehyde and acetone. (Dermer, J. Am. Chem. Soc. 74, 3417, 1952).
Det erholdte urene ketofenylbutazon kan renses enten ved kry-stallisasjon eller ved overforing i natriumsaltet og påfblgende surgjoring av dette salt. The impure ketophenylbutazone obtained can be purified either by crystallization or by conversion into the sodium salt and subsequent acidification of this salt.
EksempelExample
Til en ved opplosning av 4,6 g natrium i 120 ml methanol frem-stilt natriummethylatopplosning tilsettes 25,3 g 1,2-difenyl-3,5-dioxopyrazolidin. Efter oppvarmning til 6o°C tildryppes der ved denne temperatur i ldpet av 30 minutter under omroring 12 g methyl-(3-klorethylketon.Reaksjonsblandingen holdes under stadig omroring i 3 timer ved 6o°C, hvor den kokes i 3 timer med tilbake-lbpskjdling. Opplosningsmidlet avdestiUeres i vakuua, residuet opploses i 250 ml vann, og opplosningen filtreres efter tilset-ning av avfarvningskull. Efter avkjoling av filtratet til 0°C ut-felles produktet ved surgjoring med saltsyre. Utfelningen fra-filtreres, vaskes med 50 ml vann og tdrkes. Utbyttet av råpro-dukt er 27,5 g«Efter omkrystallisering, henholdsvis efter rens-ning over natriumsaltet, smelter det erholdte ketofenylbutazon ved 125 - 127°C. To a sodium methylate solution prepared by dissolving 4.6 g of sodium in 120 ml of methanol, 25.3 g of 1,2-diphenyl-3,5-dioxopyrazolidine is added. After heating to 6o°C, 12 g of methyl-(3-chloroethylketone) are added dropwise at this temperature over 30 minutes with stirring. The reaction mixture is kept under constant stirring for 3 hours at 6o°C, where it is boiled for 3 hours with reflux . The solvent is distilled off in vacuo, the residue is dissolved in 250 ml of water, and the solution is filtered after adding decolorizing charcoal. After cooling the filtrate to 0°C, the product is precipitated by acidification with hydrochloric acid. The precipitate is filtered off, washed with 50 ml of water The yield of crude product is 27.5 g After recrystallization, respectively after purification over the sodium salt, the ketophenylbutazone obtained melts at 125 - 127°C.
Claims (1)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS676865 | 1965-11-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NO117856B true NO117856B (en) | 1969-10-06 |
Family
ID=5415440
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NO16549666A NO117856B (en) | 1965-11-12 | 1966-11-08 | PROCEDURE FOR PREPARING 1,2-DIFENYL-3,5-DIOXO-4- (3'-OXOBUTYL) -PYRAZOLIDINE |
Country Status (11)
| Country | Link |
|---|---|
| AT (1) | AT260231B (en) |
| BE (1) | BE689531A (en) |
| CH (1) | CH511234A (en) |
| DE (1) | DE1620423A1 (en) |
| DK (1) | DK114484B (en) |
| FI (1) | FI46509C (en) |
| FR (1) | FR1500627A (en) |
| GB (1) | GB1161688A (en) |
| NL (1) | NL6615918A (en) |
| NO (1) | NO117856B (en) |
| SE (1) | SE314378B (en) |
-
1966
- 1966-11-03 CH CH1594866A patent/CH511234A/en not_active IP Right Cessation
- 1966-11-08 GB GB4987866A patent/GB1161688A/en not_active Expired
- 1966-11-08 NO NO16549666A patent/NO117856B/en unknown
- 1966-11-09 FI FI295366A patent/FI46509C/en active
- 1966-11-09 DE DE19661620423 patent/DE1620423A1/en active Pending
- 1966-11-09 AT AT1035966A patent/AT260231B/en active
- 1966-11-09 BE BE689531D patent/BE689531A/xx unknown
- 1966-11-10 FR FR83369A patent/FR1500627A/en not_active Expired
- 1966-11-10 NL NL6615918A patent/NL6615918A/xx unknown
- 1966-11-11 DK DK588066A patent/DK114484B/en unknown
- 1966-11-11 SE SE1547866A patent/SE314378B/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| SE314378B (en) | 1969-09-08 |
| FR1500627A (en) | 1967-11-03 |
| CH511234A (en) | 1971-08-15 |
| DK114484B (en) | 1969-07-07 |
| GB1161688A (en) | 1969-08-20 |
| AT260231B (en) | 1968-02-12 |
| DE1620423A1 (en) | 1970-04-09 |
| FI46509B (en) | 1973-01-02 |
| NL6615918A (en) | 1967-05-16 |
| BE689531A (en) | 1967-04-14 |
| FI46509C (en) | 1973-04-10 |
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