CA1138468A - Tricyclic compounds - Google Patents
Tricyclic compoundsInfo
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- CA1138468A CA1138468A CA000393611A CA393611A CA1138468A CA 1138468 A CA1138468 A CA 1138468A CA 000393611 A CA000393611 A CA 000393611A CA 393611 A CA393611 A CA 393611A CA 1138468 A CA1138468 A CA 1138468A
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Abstract
Abstract Novel tricyclic compounds of the formula
Description
1~38~6~
I
Case 3-11580/ZFO/+/B
CANADA
NOVEL TRICYCLIC COMPOUNDS
The present invention relates to novel tricyclic compounds and a process for their preparation. The tricyclic compounds according to the invention can be used for the preparation of novel tricyclic imidyl derivatives which are suitable for the preparation of photo-crosslinkable polymers.
It is known from the literature that diversely substituted imides, in particular maleimides, are suitable for the preparation of crosslinkable (curable) polymers. Japanese Published Specifications 50-5376, 50-5377, 50-5378, 50-5379 and 50-5380 describe generic-ally different ~-arylmaleimides and N-substituted derivatives thereof which are suitable for the preparation of photo-crosslinkable polymers; the said derivatives can be further substituted in the ~-position by a halogen atom, a cyano group or a lower alkyl group and the said alkyl group can also form a ring together with the C atom in the ortho-position of the a-aryl group. The specific disclosure is restricted, however, to a-phenylmaleimides and a-phenyl-~-cyano-maleimides and N-substituted derivatives there-of. In Japanese Published Specifications 49-128,991, 49-128,992, 49-128,993, 50-9682, 50-10884 and 50-77363, the preparation of photocrosslinkable polymers, for example by reacting N-substituted a-arylmaleimides of the abovementioned type, which have hydroxyl, amino, carboxylic a'cid or carboxylic acid chloride groups on the N-substituent, with polymers containing corresponding functional groups, is described. Further imidyl derivatives and photo-cross-linkable polymers containing imidyl groups in end or side positions, especially maleimide, dimethylmaleimide, nadicimide and tetrahydro-113846~
phthalimide groups, are known from German Offenlegungsschriften2,031,573, 2,032,037 and 2,626,795.
These previously known imides and the crosslinkable polymers which can be prepared therefrom have the disadvantage of a relatively low photochemical sensitivity and for this reason they are not 8Ui-table, or not very suitable, for numerous applications for which highly photosensitive substances are required, or they require the additional use of known photosensitisers, such as benzophenone, thioxanthone and the like. Furthermore, some of these previously known imides are also not very suitable for building up polymers by polymerisation or polycondensation of corresponding monomers.
The object of the invention was, therefore, to provide novel tricyclic compounds which are suitable for the preparation of novel tricyclic imidyl derivatives. The latter provide novel highly photosensitive substances which have a high UV absorption and, because of this, also ensure a high rate of crosslinking even without the addition of photosensitisers and are very suitable for building up polymers by polymerisation or polycondensation, if desired together with suitable comonomers.
The novel compounds have the formula I
i/C\
1'`co/ (1) in which A is -CH2CH2- or -OCH2- with the oxygen atom bonded to the aromatic ring and Rl and R2 independently of one another are hydrogen, halogen, alkyl having 1-4 C atoms or methoxy.
113846~3 The compounds of the formula I can be prepared by reacting a compound of the formula IIa or IIb ::~- /(CH2)4CR3 /O(CH2)3COOR3 Rl ~ Rl (IIa) (llb) with an oxalic acid diester of the formula III
COOR
1 4 (III) : COOR4 to give a compound of the formula IVa or IVb O
.~ \ /(cH2)3cH-c-cooR4 Rl--+- i! COOR4 (IVa) .~ R2 or O
.~ ~ /o(cH2)2cH-c-cooR4 Rl---+ i! COOR4 (IVb)
I
Case 3-11580/ZFO/+/B
CANADA
NOVEL TRICYCLIC COMPOUNDS
The present invention relates to novel tricyclic compounds and a process for their preparation. The tricyclic compounds according to the invention can be used for the preparation of novel tricyclic imidyl derivatives which are suitable for the preparation of photo-crosslinkable polymers.
It is known from the literature that diversely substituted imides, in particular maleimides, are suitable for the preparation of crosslinkable (curable) polymers. Japanese Published Specifications 50-5376, 50-5377, 50-5378, 50-5379 and 50-5380 describe generic-ally different ~-arylmaleimides and N-substituted derivatives thereof which are suitable for the preparation of photo-crosslinkable polymers; the said derivatives can be further substituted in the ~-position by a halogen atom, a cyano group or a lower alkyl group and the said alkyl group can also form a ring together with the C atom in the ortho-position of the a-aryl group. The specific disclosure is restricted, however, to a-phenylmaleimides and a-phenyl-~-cyano-maleimides and N-substituted derivatives there-of. In Japanese Published Specifications 49-128,991, 49-128,992, 49-128,993, 50-9682, 50-10884 and 50-77363, the preparation of photocrosslinkable polymers, for example by reacting N-substituted a-arylmaleimides of the abovementioned type, which have hydroxyl, amino, carboxylic a'cid or carboxylic acid chloride groups on the N-substituent, with polymers containing corresponding functional groups, is described. Further imidyl derivatives and photo-cross-linkable polymers containing imidyl groups in end or side positions, especially maleimide, dimethylmaleimide, nadicimide and tetrahydro-113846~
phthalimide groups, are known from German Offenlegungsschriften2,031,573, 2,032,037 and 2,626,795.
These previously known imides and the crosslinkable polymers which can be prepared therefrom have the disadvantage of a relatively low photochemical sensitivity and for this reason they are not 8Ui-table, or not very suitable, for numerous applications for which highly photosensitive substances are required, or they require the additional use of known photosensitisers, such as benzophenone, thioxanthone and the like. Furthermore, some of these previously known imides are also not very suitable for building up polymers by polymerisation or polycondensation of corresponding monomers.
The object of the invention was, therefore, to provide novel tricyclic compounds which are suitable for the preparation of novel tricyclic imidyl derivatives. The latter provide novel highly photosensitive substances which have a high UV absorption and, because of this, also ensure a high rate of crosslinking even without the addition of photosensitisers and are very suitable for building up polymers by polymerisation or polycondensation, if desired together with suitable comonomers.
The novel compounds have the formula I
i/C\
1'`co/ (1) in which A is -CH2CH2- or -OCH2- with the oxygen atom bonded to the aromatic ring and Rl and R2 independently of one another are hydrogen, halogen, alkyl having 1-4 C atoms or methoxy.
113846~3 The compounds of the formula I can be prepared by reacting a compound of the formula IIa or IIb ::~- /(CH2)4CR3 /O(CH2)3COOR3 Rl ~ Rl (IIa) (llb) with an oxalic acid diester of the formula III
COOR
1 4 (III) : COOR4 to give a compound of the formula IVa or IVb O
.~ \ /(cH2)3cH-c-cooR4 Rl--+- i! COOR4 (IVa) .~ R2 or O
.~ ~ /o(cH2)2cH-c-cooR4 Rl---+ i! COOR4 (IVb)
2 - .
in which formulae Rl and R2 are as defined under formula I and R3 and R4 independently of one another are alkyl having 1-6 C atoms or phenyl, and then treating the compound of the formulae IVa or IVb with a strong acid.
11384~i~
~ 4 --Alkyl groups Rl or R2 according to the definition, can be straight-chain or branched. Examples of alkyl groups according to the definition are: the methyl, ethyl, propyl, isopropyl, n-butyl and tert.-butyl, group.
A halogen atom R or R2 is in particular a chlorine, bromine or fluorine atom. Alkyl groups Rl and R2 are advantageously straight-chain and ha~e 1 or 2 C atoms. Preferably, however, Rl and R2 are each hydrogen.
The compounds of the formula I are valuable intermediates for the preparation of novel tricyclic imidyl derivatives which are 5Ui-table for the preparation of photo-crosslinkable polymers, such as polyesters, polyamides, polyimides, polyester-polyamides, polyethers, polyamines, gelatine, polysaccharides, polycondensates, for example based on phenol-formaldehyde, and homo- and co-polymers which are derived from monomers containing reactive C=C double bonds.
Example 1: 6,7-Dihydro-5H-benzocycloheptene-8,9-dicarboxylic acid anhydride 1~3 cooc235 ~ ~co/
(A) ~ (B) 240 ml of 90 ~ sulphuric acid are cooled to 0 - 5C. 30 g of ester A are added dropwise at this temperature in the course of about 15 - 20 minutes. A dark yellow to reddish solution forms. The reaction mixture is then allowed to warm to room temperature and :, :
11384~
the course of the reaction is followed by means of thin layer chromatography. After about 3 to 4 hours no further starting material is visible.
Thin layer chromatogram (CHC13) starting material: Rf about 0.7;
reaction product: Rf about 0.8.
The reaction mixture is poured onto 1.5 litres of ice and sufficient NaCl to saturate the resulting aqueous phase (about 500 g). With vigorous stirring, a white, crystalline precipitate separates out.
This is filtered off with suction, the material on the filter is subjected to strong suction and taken up in diethyl ether and insoluble constituents are separated off. The ether solution is dried over MgS04, concentrated on a rotary evaporator and dried under a high vacuum.
(3 1st portion of product B).
The aqueous phase is extracted with diethyl ether and the diethyl ether phase is washed with NaCl solution and dried and the ether is removed on a rotary evaporator, (= 2nd portion of product B). On the basis of the thin layer chromatogram, this portion is virtually identical to the first portion.
The two portions are combined and recrystallised from isopropanol.
This yields 10 g (47 % of theory) of compound B in the form of pale yellowish crystals; melting point 112-113C.
The preparation of product A is described in paragraphs a) and b) below:
a) Ethyl 5~phenylvalerate ~-\ /COOH ~-\ /COO-ethyl ! i! '. EtOH ! i! '.
- H2S04 ~- --250 8 (1.4 mols) of 5-phenylvaleric acid are dissolved in 450 ml of absolute ethanol. 114 ml of concentrated sulphuric acid are added to the clear colourless solution and the reaction mixture is refluxed for 48 hours. The reaction mix,ture,which initially i5 two-phase, becomes almost homogeneous and separates into two phases again on cooling. The cold two-phase reaction mixture is poured on~o di-ethyl ether and about 1 kg of ice. The aqueous phase is extracted with ether twice more; the ether phases are washed twice with 2 N
sodium carbonate solution and twice with NaCl solution. The com-bined ether phases are dried over MgS04 and the solvent is removed on a rotary evaporator. After drying under a high vacuum at room temperature, 281.7 g of a colourless oil (97.5 % of theory) are obtained.
The rude product is used further in paragraph b).
A sample distilled in a bulb tube at 120-140C/O.l mm Hg is used for characterisation.
NMR ~pectrum (CDC13): = 7.4-7.0 ppm (5H, m);
4.08 ppm (q, 2H, J = 8 Hz); ~.6 ppm (m, 2H); 2.28 ppm (m, 2H);
1.65 ppm (2H, m); 1.02 ppm (3H, t, J = 8 Hz).
IR spectrum (CH2C12~): inter alia 1,740 cm b) Diethyl 3-phenylpropyl-oxaloacetate ~ \./(CH2)4cOOc2H5 C100-ethyl .~ \ /(cH2)3cHcocooc2H5 1~ ll COO-ethyl ~ / COOC2H5 NaH, diethyl ether -:
- ., ~- ' '' , 1~384t~8 A suspension of oil-free sodium hydride in diethyl ether, prepared by decanting and twice washing with diethyl ether 71.8 g of a sodium hydride dispersion (55 % in oil) in n-pentane under nitrogen and adding 3 litres of absolute diethyl ether, are refluxed. A mixture of 281.7 g (1.36 mols) of ethyl 5-phenylvalerate and 297 g (1.36 mols + 50 %) of diethyl oxalate is added dropwise to the boiling suspension in the course of about 6 hours. The reaction mixture is then kept under reflux for a total of 66 hours. The thin layer chromatogram(CHC13) shows, in addition to a very small amount of starting material (Rf about 0.6), a main spot with a Rf of about 0.5. After cooling, the reaction mixture is poured onto 500 g of ice and 1.05 equivalents of HCl (= 530 ml of 2 N HCl). The aqueous phase is extracted with diethyl ether, the diethyl ether phase is dried over MgS04 and the ether is removed in vacuo. After drying in vacuo, 520 g of a reddish oil, which still contains oxalate, are obtained. The crude product is used further direct, since it decomposes with decarbonylation when subjected to purification by distillation.
In addition to the signals of the desired product, the signals of the excess diethyl oxalate are still visible in the NMR æpectrum of the crude product.
Example 2: 2,4-dihydro-1-benzoxepine-4,5-dicarboxylic acid anhydride ~ ~0/
113B46~
30.8 g (0.10 mol) of crude diethyl 2-phenoxyethyl-oxaloacetate are allowed to run dropwise in the course of 15 minutes, at a temperature of 5 - 10C, into an ice-cooled mixture of 225 ml of concentrated sulphuric acid and 25 ml of water, with stirring.
The reaction temperature is then allowed to rise to 15C and the reaction mixture is stirred for one hour at this temperature. The reaction mixture is then poured into a mixture of 1,000 g of ice and 1,500 ml of water, with stirring, whereupon 2,3-dihydro-1-benzoxe-pine-4,5-dicarboxylic acid anhydride precipitates out. This is filtered off with suction and recrystallised from isopropanol.
This yields 14.0 g of 2,3-dihydro-1-benzoxepine-4,5-dicarboxylic acid anhydride (64.7 % of theory) with a melting point of 142 -143C.
The starting material (diethyl 2-phenoxyethyl-oxaloacetate) for the preparation of the abovementioned anhydride can be prepared as follows:
~;~ \ /oc~2cH2-cH-cocooc2H5 !~ ,'! CC2H5 A solution of 22 g (0.15 mol) of diethyl oxalate in 100 ml of diethyl ether is added dropwise, at a temperature of 15C, to a suspension of 5 g (0.104 mol) of a 50 ~ dispersion of sodium hydride in mineral oil in 50 ml of diethyl ether, with stirring.
The reaction mixtu~e is then stirred for 2 hours at room temperature.
A solution of 21 g (0.10 mol) of ethyl phenoxy-butyrate [prepared according to Powell and Adams, J.Amer.Chem.Soc., 42, 652 (1920)]
in 100 ml of diethyl ether is allowed to run in and the resulting mixture is then refluxed for 10 hours. After cooling, 1 ml of ethanol is added and the mixture is then poured onto a mixture of 1138~68 100 g of ice and 150 ml of water. The pH of the aqueous phase is adjusted to 3 with 2 N hydrochloric acid. The layers are separated in a separating funnel and the aqueous phase is again extracted with 250 ml of diethyl ether. The combined ether extracts are washed with 100 ml of water, then dried over magnesium sulphate and then evaporated under a waterpump vacuum. 30.8 g (100 ~ of theory) of crude diethyl 2-phenoxyethyl-oxaloacetate in the form of a pale reddish oil remain as the residue.
in which formulae Rl and R2 are as defined under formula I and R3 and R4 independently of one another are alkyl having 1-6 C atoms or phenyl, and then treating the compound of the formulae IVa or IVb with a strong acid.
11384~i~
~ 4 --Alkyl groups Rl or R2 according to the definition, can be straight-chain or branched. Examples of alkyl groups according to the definition are: the methyl, ethyl, propyl, isopropyl, n-butyl and tert.-butyl, group.
A halogen atom R or R2 is in particular a chlorine, bromine or fluorine atom. Alkyl groups Rl and R2 are advantageously straight-chain and ha~e 1 or 2 C atoms. Preferably, however, Rl and R2 are each hydrogen.
The compounds of the formula I are valuable intermediates for the preparation of novel tricyclic imidyl derivatives which are 5Ui-table for the preparation of photo-crosslinkable polymers, such as polyesters, polyamides, polyimides, polyester-polyamides, polyethers, polyamines, gelatine, polysaccharides, polycondensates, for example based on phenol-formaldehyde, and homo- and co-polymers which are derived from monomers containing reactive C=C double bonds.
Example 1: 6,7-Dihydro-5H-benzocycloheptene-8,9-dicarboxylic acid anhydride 1~3 cooc235 ~ ~co/
(A) ~ (B) 240 ml of 90 ~ sulphuric acid are cooled to 0 - 5C. 30 g of ester A are added dropwise at this temperature in the course of about 15 - 20 minutes. A dark yellow to reddish solution forms. The reaction mixture is then allowed to warm to room temperature and :, :
11384~
the course of the reaction is followed by means of thin layer chromatography. After about 3 to 4 hours no further starting material is visible.
Thin layer chromatogram (CHC13) starting material: Rf about 0.7;
reaction product: Rf about 0.8.
The reaction mixture is poured onto 1.5 litres of ice and sufficient NaCl to saturate the resulting aqueous phase (about 500 g). With vigorous stirring, a white, crystalline precipitate separates out.
This is filtered off with suction, the material on the filter is subjected to strong suction and taken up in diethyl ether and insoluble constituents are separated off. The ether solution is dried over MgS04, concentrated on a rotary evaporator and dried under a high vacuum.
(3 1st portion of product B).
The aqueous phase is extracted with diethyl ether and the diethyl ether phase is washed with NaCl solution and dried and the ether is removed on a rotary evaporator, (= 2nd portion of product B). On the basis of the thin layer chromatogram, this portion is virtually identical to the first portion.
The two portions are combined and recrystallised from isopropanol.
This yields 10 g (47 % of theory) of compound B in the form of pale yellowish crystals; melting point 112-113C.
The preparation of product A is described in paragraphs a) and b) below:
a) Ethyl 5~phenylvalerate ~-\ /COOH ~-\ /COO-ethyl ! i! '. EtOH ! i! '.
- H2S04 ~- --250 8 (1.4 mols) of 5-phenylvaleric acid are dissolved in 450 ml of absolute ethanol. 114 ml of concentrated sulphuric acid are added to the clear colourless solution and the reaction mixture is refluxed for 48 hours. The reaction mix,ture,which initially i5 two-phase, becomes almost homogeneous and separates into two phases again on cooling. The cold two-phase reaction mixture is poured on~o di-ethyl ether and about 1 kg of ice. The aqueous phase is extracted with ether twice more; the ether phases are washed twice with 2 N
sodium carbonate solution and twice with NaCl solution. The com-bined ether phases are dried over MgS04 and the solvent is removed on a rotary evaporator. After drying under a high vacuum at room temperature, 281.7 g of a colourless oil (97.5 % of theory) are obtained.
The rude product is used further in paragraph b).
A sample distilled in a bulb tube at 120-140C/O.l mm Hg is used for characterisation.
NMR ~pectrum (CDC13): = 7.4-7.0 ppm (5H, m);
4.08 ppm (q, 2H, J = 8 Hz); ~.6 ppm (m, 2H); 2.28 ppm (m, 2H);
1.65 ppm (2H, m); 1.02 ppm (3H, t, J = 8 Hz).
IR spectrum (CH2C12~): inter alia 1,740 cm b) Diethyl 3-phenylpropyl-oxaloacetate ~ \./(CH2)4cOOc2H5 C100-ethyl .~ \ /(cH2)3cHcocooc2H5 1~ ll COO-ethyl ~ / COOC2H5 NaH, diethyl ether -:
- ., ~- ' '' , 1~384t~8 A suspension of oil-free sodium hydride in diethyl ether, prepared by decanting and twice washing with diethyl ether 71.8 g of a sodium hydride dispersion (55 % in oil) in n-pentane under nitrogen and adding 3 litres of absolute diethyl ether, are refluxed. A mixture of 281.7 g (1.36 mols) of ethyl 5-phenylvalerate and 297 g (1.36 mols + 50 %) of diethyl oxalate is added dropwise to the boiling suspension in the course of about 6 hours. The reaction mixture is then kept under reflux for a total of 66 hours. The thin layer chromatogram(CHC13) shows, in addition to a very small amount of starting material (Rf about 0.6), a main spot with a Rf of about 0.5. After cooling, the reaction mixture is poured onto 500 g of ice and 1.05 equivalents of HCl (= 530 ml of 2 N HCl). The aqueous phase is extracted with diethyl ether, the diethyl ether phase is dried over MgS04 and the ether is removed in vacuo. After drying in vacuo, 520 g of a reddish oil, which still contains oxalate, are obtained. The crude product is used further direct, since it decomposes with decarbonylation when subjected to purification by distillation.
In addition to the signals of the desired product, the signals of the excess diethyl oxalate are still visible in the NMR æpectrum of the crude product.
Example 2: 2,4-dihydro-1-benzoxepine-4,5-dicarboxylic acid anhydride ~ ~0/
113B46~
30.8 g (0.10 mol) of crude diethyl 2-phenoxyethyl-oxaloacetate are allowed to run dropwise in the course of 15 minutes, at a temperature of 5 - 10C, into an ice-cooled mixture of 225 ml of concentrated sulphuric acid and 25 ml of water, with stirring.
The reaction temperature is then allowed to rise to 15C and the reaction mixture is stirred for one hour at this temperature. The reaction mixture is then poured into a mixture of 1,000 g of ice and 1,500 ml of water, with stirring, whereupon 2,3-dihydro-1-benzoxe-pine-4,5-dicarboxylic acid anhydride precipitates out. This is filtered off with suction and recrystallised from isopropanol.
This yields 14.0 g of 2,3-dihydro-1-benzoxepine-4,5-dicarboxylic acid anhydride (64.7 % of theory) with a melting point of 142 -143C.
The starting material (diethyl 2-phenoxyethyl-oxaloacetate) for the preparation of the abovementioned anhydride can be prepared as follows:
~;~ \ /oc~2cH2-cH-cocooc2H5 !~ ,'! CC2H5 A solution of 22 g (0.15 mol) of diethyl oxalate in 100 ml of diethyl ether is added dropwise, at a temperature of 15C, to a suspension of 5 g (0.104 mol) of a 50 ~ dispersion of sodium hydride in mineral oil in 50 ml of diethyl ether, with stirring.
The reaction mixtu~e is then stirred for 2 hours at room temperature.
A solution of 21 g (0.10 mol) of ethyl phenoxy-butyrate [prepared according to Powell and Adams, J.Amer.Chem.Soc., 42, 652 (1920)]
in 100 ml of diethyl ether is allowed to run in and the resulting mixture is then refluxed for 10 hours. After cooling, 1 ml of ethanol is added and the mixture is then poured onto a mixture of 1138~68 100 g of ice and 150 ml of water. The pH of the aqueous phase is adjusted to 3 with 2 N hydrochloric acid. The layers are separated in a separating funnel and the aqueous phase is again extracted with 250 ml of diethyl ether. The combined ether extracts are washed with 100 ml of water, then dried over magnesium sulphate and then evaporated under a waterpump vacuum. 30.8 g (100 ~ of theory) of crude diethyl 2-phenoxyethyl-oxaloacetate in the form of a pale reddish oil remain as the residue.
Claims (2)
1. A compound of the formula I
(I) in which A is -CH2CH2- or -OCH2- with the oxygen atom bonded to the aromatic ring and R1 and R2 independently of one another are hydrogen, halogen, alkyl having 1-4 C atoms or methoxy.
(I) in which A is -CH2CH2- or -OCH2- with the oxygen atom bonded to the aromatic ring and R1 and R2 independently of one another are hydrogen, halogen, alkyl having 1-4 C atoms or methoxy.
2. A process for the preparation of a compound of the formula I
according to claim 1, which comprises reacting a compound of the formula IIa or IIb or (IIa) (IIb) with an oxalic acid diester of the formula III
(III) to give a compound of the formula IVa or IVb (IVa) or (IVb) .
in which formulae R1 and R2 are as defined under formula I in Claim 1 and R3 and R4 independently of one another are alkyl having 1 - 6 C atoms or phenyl, and then treating the compound of the formula IVa or IVb with a strong acid.
according to claim 1, which comprises reacting a compound of the formula IIa or IIb or (IIa) (IIb) with an oxalic acid diester of the formula III
(III) to give a compound of the formula IVa or IVb (IVa) or (IVb) .
in which formulae R1 and R2 are as defined under formula I in Claim 1 and R3 and R4 independently of one another are alkyl having 1 - 6 C atoms or phenyl, and then treating the compound of the formula IVa or IVb with a strong acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA000393611A CA1138468A (en) | 1978-02-08 | 1982-01-05 | Tricyclic compounds |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH140078 | 1978-02-08 | ||
| CH1400/78-3 | 1978-02-08 | ||
| CA320,890A CA1128950A (en) | 1978-02-08 | 1979-02-06 | Tricyclic imidyl derivatives |
| CA000393611A CA1138468A (en) | 1978-02-08 | 1982-01-05 | Tricyclic compounds |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1138468A true CA1138468A (en) | 1982-12-28 |
Family
ID=27166066
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000393611A Expired CA1138468A (en) | 1978-02-08 | 1982-01-05 | Tricyclic compounds |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1138468A (en) |
-
1982
- 1982-01-05 CA CA000393611A patent/CA1138468A/en not_active Expired
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