CA1040199A - 1,5-diazocine derivatives and process for the preparation thereof - Google Patents
1,5-diazocine derivatives and process for the preparation thereofInfo
- Publication number
- CA1040199A CA1040199A CA196,127A CA196127A CA1040199A CA 1040199 A CA1040199 A CA 1040199A CA 196127 A CA196127 A CA 196127A CA 1040199 A CA1040199 A CA 1040199A
- Authority
- CA
- Canada
- Prior art keywords
- process according
- formula
- formaldehyde
- compounds
- general formula
- 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.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
- C07D471/14—Ortho-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains three hetero rings
- C07D487/14—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Other In-Based Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to compounds of the general formula I and salts thereof:
I
and acid addition salts thereof wherein R1, R2, R3 and R4 are the same or different and each stands for a hydrogen atom or alkoxy group of 1 to 4 carbon atoms. These compounds are prepared by reacting a compound of the formula II:
II
or a tautomer thereof wherein the various symbols are as previously defined with formaldehyde or a compound capable of releasing formaldehyde e.g.
paraformaldehyde. The compounds of formula I are useful intermediates in the preparation of therapeutically valuable compounds.
This invention relates to compounds of the general formula I and salts thereof:
I
and acid addition salts thereof wherein R1, R2, R3 and R4 are the same or different and each stands for a hydrogen atom or alkoxy group of 1 to 4 carbon atoms. These compounds are prepared by reacting a compound of the formula II:
II
or a tautomer thereof wherein the various symbols are as previously defined with formaldehyde or a compound capable of releasing formaldehyde e.g.
paraformaldehyde. The compounds of formula I are useful intermediates in the preparation of therapeutically valuable compounds.
Description
35~
It is known for a long time that on reacting l-ben7yl-1,2,3,4-tetrahydro-isoquinoline derivatives with formaldehyde a Mannich-condensation takes place between the secondary amino group of the isoquinoline and the position 2 of the benzyl group and compounds of berbine-structure are formed (e.g. Berichte 71, 2135-40/1938/; ChemO Phanm.Bull. 18, 763-5 and 896-900/
1970/; Hungarian Patent No. 151 750, etc).
It has been found in surprising manner that when reacting l-ben~yl-3,4~dihydroisoquinoline derivatives of the general formula II
Rl ~ ~ Rl ~ RR
4 R3 ~ R3 R4 (II) 4 (IIa) `:
or an acid addition salt thereof wherein Rl, R2, R3 and R4 are the same or different and each stands ~or a hydrogen atom or an aIkoxy group of 1 to 4 carbon atoms :`
. .......... - .
,,.; .~, ~` q' _2-with farmaldehyde or a compound delivering formaldehyde the 1,5-diazocine derivatives of the general formula I R R
are ~rmed~ ~in ~hich formula Rl, R2, R3 and R4 have ~he same meaning as stated above). ~hen a corresponding and addition salt is required the base of formula (I) obtained is reacted with an acid.
According to the present invention there are pTovided new compounds o the formula I and a process for their preparation as disclosed above.
The starting materials of the general formula II can be prepared in an analogous manner to the preparation of known compounds or by methods known from prior art.
As starting materials compounds of the general formula II may be used advantageously in which Rl and R2 and/or R3 and R4 respectively are hyd~ogen atoms, or alkoxy groups of l - 4 carbon atoms, e.gO a methoxy group or ethoxy group.
The compounds of the general formula II react with formaldehyde in the tautomeric form of the general formula IIa. A specific Mannich-condensation takes place intramolecularly between two compounds of the general formula IIa and two formaldehyde molecules.
2a The compounds of the general formula II can be applied advantageously in the form of bases or acid addition salts ~e~gO hydrochlorides, hydrobromides etc. or other mineral or organic acid salts).
The ormaldehyde can be used advantageously in the form of an aqueous solution (e.g. aqueous formaline of 40 %) or in a solid fo~m (e.g.
LT~.
~; -3-para~ormaldehyde).
The compounds of the general formula II are reacted advantageously in an aqueous m~dium at a temperature between oC and 100C wi~h formaldehyde (e.g. paraformaldehyde).
The pH value of the solution is adjusted to the desired value by adding a buffer solution, an inorganic or organic acid (e.g. hydrochloric acid) etc.), or an inorganic or organic base (e.g. triethylamine, alkali hydroxides, etc.).
The isolation of the 1,5-diazocine formed from the aqueous reaction mixture is carried out by dissolving the same in a water-inmiscible solvent.
The compounds of the general formula I can be obtained from the organic solvent by known methods (e.g. vacuum distillation and recrystallisation of the resi-due) .
The obtained compounds of the general formula I are useful inter-mediates in the preparation of therapeutically valuable compounds.
; Further details of the present invention are described in the Exam-; ples without limiting the invention to the specific Examples.
Example 1 8.0 g ~0.02 moles) of 1-~3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline and 1,2 ml of glacial acetic acid are stirred for 3 hours at 90C in 200 ml of water with 1,8 g ~0,06 moles) of paraformaldehyde, where-upon the solution obtained is cooled to room temperature and extracted with 50 ml of benzene. The extract is dried over sodium sulphate, filtered and distilled in vacuo. A pale-yellow oil (6.0 g) is obtained, which is dissolved in 20 ml of warm ethanol. By cooling and scrapping yellowish crystals are precipita~ed from the solution. The obtained crystals are filtered and washed with cold ethanol. 3.5 g (42 %) of yellow-coloured 9,18-di-(3,4-diethoxy-phenyl)-2,3,11,12-tetraethoxy-5,6,14,15-tetrahydro-8H,17H-(1,5)-diazocino(2,1a, 6,5a')-diisoquinoline are obtained, mp.: 152 - 153C. On recrystallizing the product from ethanol the melting point rises to 164 - 165C.
3~
Analysis:
Calculated:C 73.32 % H 7.63 % N 3.42 %
Found: C 73. 65 % H 7 . 33 % N 3.15 Exam~le 2 ; 172.6 g ~0.4 moles) of 1-~3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline in 1400 ml of a buffer solution (containing in 1400 ml of water 9,6 ml of acetic acid, 10.5 ml of 85 % phosphoric acid, 11.3 g of boric acid and 19.3 g of sodium hydroxide) are stirred for l hour at 80 - 85C
with 18 g (0.6 moles) of para~ormaldehyde, then the mixture is cooled to room temperature and vigorously shaken with 600 ml of benzene. The organic and aqueous phases are separated. The extr2ct is dried over sodium sulphate, fil~ered and distilled off in vacuo. 162.4 g of an oil are obtained, ~hich is dissolved in 350 ml of ethanol while heating. On cooling and scrapping the product crystallizes. 112.5 g (68 %) of the yellow-coloured 9,18-di-(3,4-diethoxy-phenyl)-2,3,11,12-tetraethoxy-5,6,14,15-tetrahydro-8H,17H-~1,5)-diazocino-~2,1a; 6,5a') diisoquinoline are obtained, melting at 153 - 155C.
On further recrystallisation from ethanol the melting point rises to 164 -165C. The products prepared by the methods of Example 1 and Example 2 show no melting point depression.
On using as starting material instead of the 1-(3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline-hydrochloride the 1-benzyl-3,4-dihydro-isoquinoline-hydrochloride, the 9,18-diphenyl-5,6,14,15-tetrahydro-8H,17H-~1,5)-diazocino~2,1a; 6,5a') diisoquinoline is obtained with a yield of 60 %
in the form of a not crystallizab}e oil. (The structure of the compound is provëd by a mass-spectrographic test. Molecular peak 466).
On using as starting material instead of the 1-(3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline-hydrochloride the 1-(3,4~dimethoxy-benzyl)-6,7-dimethoxy-3,4-dihydro-isoquinoline-hydrochloride, the 9,18-di-~3, 4-dimethoxyphenyl)-2,3,11,12-tetramethoxy-5,6,14,15-tetrahydro-8H,17H-(1,5) diazocionot2,1a; 6,5a')-diisoquinoline is obtained with a yield of 50 % in the form of a not crystallizable oil.
.
:. . . .
.
It is known for a long time that on reacting l-ben7yl-1,2,3,4-tetrahydro-isoquinoline derivatives with formaldehyde a Mannich-condensation takes place between the secondary amino group of the isoquinoline and the position 2 of the benzyl group and compounds of berbine-structure are formed (e.g. Berichte 71, 2135-40/1938/; ChemO Phanm.Bull. 18, 763-5 and 896-900/
1970/; Hungarian Patent No. 151 750, etc).
It has been found in surprising manner that when reacting l-ben~yl-3,4~dihydroisoquinoline derivatives of the general formula II
Rl ~ ~ Rl ~ RR
4 R3 ~ R3 R4 (II) 4 (IIa) `:
or an acid addition salt thereof wherein Rl, R2, R3 and R4 are the same or different and each stands ~or a hydrogen atom or an aIkoxy group of 1 to 4 carbon atoms :`
. .......... - .
,,.; .~, ~` q' _2-with farmaldehyde or a compound delivering formaldehyde the 1,5-diazocine derivatives of the general formula I R R
are ~rmed~ ~in ~hich formula Rl, R2, R3 and R4 have ~he same meaning as stated above). ~hen a corresponding and addition salt is required the base of formula (I) obtained is reacted with an acid.
According to the present invention there are pTovided new compounds o the formula I and a process for their preparation as disclosed above.
The starting materials of the general formula II can be prepared in an analogous manner to the preparation of known compounds or by methods known from prior art.
As starting materials compounds of the general formula II may be used advantageously in which Rl and R2 and/or R3 and R4 respectively are hyd~ogen atoms, or alkoxy groups of l - 4 carbon atoms, e.gO a methoxy group or ethoxy group.
The compounds of the general formula II react with formaldehyde in the tautomeric form of the general formula IIa. A specific Mannich-condensation takes place intramolecularly between two compounds of the general formula IIa and two formaldehyde molecules.
2a The compounds of the general formula II can be applied advantageously in the form of bases or acid addition salts ~e~gO hydrochlorides, hydrobromides etc. or other mineral or organic acid salts).
The ormaldehyde can be used advantageously in the form of an aqueous solution (e.g. aqueous formaline of 40 %) or in a solid fo~m (e.g.
LT~.
~; -3-para~ormaldehyde).
The compounds of the general formula II are reacted advantageously in an aqueous m~dium at a temperature between oC and 100C wi~h formaldehyde (e.g. paraformaldehyde).
The pH value of the solution is adjusted to the desired value by adding a buffer solution, an inorganic or organic acid (e.g. hydrochloric acid) etc.), or an inorganic or organic base (e.g. triethylamine, alkali hydroxides, etc.).
The isolation of the 1,5-diazocine formed from the aqueous reaction mixture is carried out by dissolving the same in a water-inmiscible solvent.
The compounds of the general formula I can be obtained from the organic solvent by known methods (e.g. vacuum distillation and recrystallisation of the resi-due) .
The obtained compounds of the general formula I are useful inter-mediates in the preparation of therapeutically valuable compounds.
; Further details of the present invention are described in the Exam-; ples without limiting the invention to the specific Examples.
Example 1 8.0 g ~0.02 moles) of 1-~3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline and 1,2 ml of glacial acetic acid are stirred for 3 hours at 90C in 200 ml of water with 1,8 g ~0,06 moles) of paraformaldehyde, where-upon the solution obtained is cooled to room temperature and extracted with 50 ml of benzene. The extract is dried over sodium sulphate, filtered and distilled in vacuo. A pale-yellow oil (6.0 g) is obtained, which is dissolved in 20 ml of warm ethanol. By cooling and scrapping yellowish crystals are precipita~ed from the solution. The obtained crystals are filtered and washed with cold ethanol. 3.5 g (42 %) of yellow-coloured 9,18-di-(3,4-diethoxy-phenyl)-2,3,11,12-tetraethoxy-5,6,14,15-tetrahydro-8H,17H-(1,5)-diazocino(2,1a, 6,5a')-diisoquinoline are obtained, mp.: 152 - 153C. On recrystallizing the product from ethanol the melting point rises to 164 - 165C.
3~
Analysis:
Calculated:C 73.32 % H 7.63 % N 3.42 %
Found: C 73. 65 % H 7 . 33 % N 3.15 Exam~le 2 ; 172.6 g ~0.4 moles) of 1-~3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline in 1400 ml of a buffer solution (containing in 1400 ml of water 9,6 ml of acetic acid, 10.5 ml of 85 % phosphoric acid, 11.3 g of boric acid and 19.3 g of sodium hydroxide) are stirred for l hour at 80 - 85C
with 18 g (0.6 moles) of para~ormaldehyde, then the mixture is cooled to room temperature and vigorously shaken with 600 ml of benzene. The organic and aqueous phases are separated. The extr2ct is dried over sodium sulphate, fil~ered and distilled off in vacuo. 162.4 g of an oil are obtained, ~hich is dissolved in 350 ml of ethanol while heating. On cooling and scrapping the product crystallizes. 112.5 g (68 %) of the yellow-coloured 9,18-di-(3,4-diethoxy-phenyl)-2,3,11,12-tetraethoxy-5,6,14,15-tetrahydro-8H,17H-~1,5)-diazocino-~2,1a; 6,5a') diisoquinoline are obtained, melting at 153 - 155C.
On further recrystallisation from ethanol the melting point rises to 164 -165C. The products prepared by the methods of Example 1 and Example 2 show no melting point depression.
On using as starting material instead of the 1-(3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline-hydrochloride the 1-benzyl-3,4-dihydro-isoquinoline-hydrochloride, the 9,18-diphenyl-5,6,14,15-tetrahydro-8H,17H-~1,5)-diazocino~2,1a; 6,5a') diisoquinoline is obtained with a yield of 60 %
in the form of a not crystallizab}e oil. (The structure of the compound is provëd by a mass-spectrographic test. Molecular peak 466).
On using as starting material instead of the 1-(3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline-hydrochloride the 1-(3,4~dimethoxy-benzyl)-6,7-dimethoxy-3,4-dihydro-isoquinoline-hydrochloride, the 9,18-di-~3, 4-dimethoxyphenyl)-2,3,11,12-tetramethoxy-5,6,14,15-tetrahydro-8H,17H-(1,5) diazocionot2,1a; 6,5a')-diisoquinoline is obtained with a yield of 50 % in the form of a not crystallizable oil.
.
:. . . .
.
Claims (15)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of compounds of the general formula I and salts thereof I
or an acid addition salt thereof, wherein R1, R2, R3 and R4 are the same or different and each stands for a hydrogen atom or an alkoxy group of 1 to 4 carbon atoms which comprises reacting a compound of the general formula II or its tautomer of the formula IIa II IIa (in which formula R1, R2, R3 and R4 have the same meanings as indicated above) or its acid addition salt with formaldehyde or a compound capable of delivering formaldehyde and when an addition salt is required reacting a base of formula I with an acid.
or an acid addition salt thereof, wherein R1, R2, R3 and R4 are the same or different and each stands for a hydrogen atom or an alkoxy group of 1 to 4 carbon atoms which comprises reacting a compound of the general formula II or its tautomer of the formula IIa II IIa (in which formula R1, R2, R3 and R4 have the same meanings as indicated above) or its acid addition salt with formaldehyde or a compound capable of delivering formaldehyde and when an addition salt is required reacting a base of formula I with an acid.
2. A process according to claim 13 which comprises using as starting material a compound of the general formula II or its acid addition salt in which R1, R2, R3 and R4 are as defined in claim 1.
3. A process according to claim 1, which comprises, carrying out the reaction in an aqueous medium.
4. A process according to claims 1 to 3, which comprises carrying out the reaction at a pH value of 1 to 12.
5. A process according to claim 1, 2 or 3 which comprises carrying out the reaction at a pH value of 5 to 8.
6. A process according to any of the claims 1 to 3 which comprises carrying out the reaction at a temperature between 0°C and 100°C, advantage-ously at 60°C to 100°C.
7. A process according to any of the claims 1 to 3 which comprises using the formaldehyde in an aqueous solution or in a solid form.
8. A process according to any of claims 1 to 3 which comprises using the formaldehyde in a 40% aqueous solution or in the form of paraformaldehyde.
9. Compounds of the general formula I and salts thereof I
or an acid addition salt thereof, wherein R1, R2, R3 and R4 are the same or different and each stands for a hydrogen atom or an alkoxy group of 1 to 4 carbon atoms whenever prepared by the process of claim 1, 2 or 3 or by an obvious chemical equivalent thereof.
or an acid addition salt thereof, wherein R1, R2, R3 and R4 are the same or different and each stands for a hydrogen atom or an alkoxy group of 1 to 4 carbon atoms whenever prepared by the process of claim 1, 2 or 3 or by an obvious chemical equivalent thereof.
10. A process according to claim 1 in which in the reactions of formula II or IIa, R1, R2, R3 and R4 are ethoxy groups.
11. A process according to claim 1 in which 9,18-di-(3,4-diethoxy-phenyl)-2,3,11,12-tetraethoxy-5,6,14,15-tetrahydro-8H,17H-(1,5)-diazocino-(2,1a; 6,5a')-diisoquinoline is prepared by reacting 1-(3,4-diethoxy-benzyl)-6,7-diethoxy-3,4-dihydro-isoquinoline with paraformaldehyde.
12. 9,18-di-(3,4-diethoxy-phenyl)-2,3,11,12-tetraethoxy-5,6,14,15-tetrahydro-8H,17H-(1,5)-diazocino(2,1a; 6,5a')-diisoquinoline whenever prepared by the process of claim 10 or 11 or by an obvious chemical equivalent thereof.
13. A process according to claim 1 in which in the reactants of formula II or IIa, R1, R2, R3 and R4 are hydrogen atoms.
14. A process according to claim 1 in which 9,18-diphenyl-5,6,14,15-tetrahydro-8H,17H-(1,5)-diazocino(2,1a; 6,5a') diisoquinoline is prepared by reacting 1-benzyl-3,4-dihydro-isoquinoline with paraformaldehyde.
15. 9,18-diphenyl-5,6,14,15-tetrahydro-8H,17H-(1,5)-diazocino(2, 1a;
6,5a') diisoquinoline whenever prepared by the process of claim 13 or 14 or by an obvious chemical equivalent thereof.
6,5a') diisoquinoline whenever prepared by the process of claim 13 or 14 or by an obvious chemical equivalent thereof.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| HUCI001362 HU166689B (en) | 1973-03-30 | 1973-03-30 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1040199A true CA1040199A (en) | 1978-10-10 |
Family
ID=10994474
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA196,127A Expired CA1040199A (en) | 1973-03-30 | 1974-03-27 | 1,5-diazocine derivatives and process for the preparation thereof |
Country Status (9)
| Country | Link |
|---|---|
| JP (1) | JPS5035184A (en) |
| AT (1) | AT337187B (en) |
| CA (1) | CA1040199A (en) |
| CH (1) | CH590281A5 (en) |
| ES (1) | ES424658A1 (en) |
| FR (1) | FR2223368B1 (en) |
| GB (1) | GB1468392A (en) |
| HU (1) | HU166689B (en) |
| SU (1) | SU511857A3 (en) |
-
1973
- 1973-03-30 HU HUCI001362 patent/HU166689B/hu unknown
-
1974
- 1974-03-19 GB GB1214974A patent/GB1468392A/en not_active Expired
- 1974-03-26 ES ES424658A patent/ES424658A1/en not_active Expired
- 1974-03-26 FR FR7410248A patent/FR2223368B1/fr not_active Expired
- 1974-03-27 AT AT252574A patent/AT337187B/en not_active IP Right Cessation
- 1974-03-27 CA CA196,127A patent/CA1040199A/en not_active Expired
- 1974-03-29 SU SU2011086A patent/SU511857A3/en active
- 1974-03-29 CH CH447074A patent/CH590281A5/xx not_active IP Right Cessation
- 1974-03-30 JP JP3658374A patent/JPS5035184A/ja active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FR2223368B1 (en) | 1976-06-25 |
| ATA252574A (en) | 1976-10-15 |
| GB1468392A (en) | 1977-03-23 |
| HU166689B (en) | 1975-05-28 |
| AT337187B (en) | 1977-06-10 |
| FR2223368A1 (en) | 1974-10-25 |
| JPS5035184A (en) | 1975-04-03 |
| CH590281A5 (en) | 1977-07-29 |
| ES424658A1 (en) | 1976-06-01 |
| SU511857A3 (en) | 1976-04-25 |
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