CA1041120A - Process for the preparation of 2-amino-n-cyclohexyl-3,5-dibromo-n-methyl-benzylamine - Google Patents
Process for the preparation of 2-amino-n-cyclohexyl-3,5-dibromo-n-methyl-benzylamineInfo
- Publication number
- CA1041120A CA1041120A CA205,645A CA205645A CA1041120A CA 1041120 A CA1041120 A CA 1041120A CA 205645 A CA205645 A CA 205645A CA 1041120 A CA1041120 A CA 1041120A
- Authority
- CA
- Canada
- Prior art keywords
- dibromo
- amino
- methyl
- preparation
- trimethyl
- 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
- 238000000034 method Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims description 3
- OJGDCBLYJGHCIH-UHFFFAOYSA-N bromhexine Chemical compound C1CCCCC1N(C)CC1=CC(Br)=CC(Br)=C1N OJGDCBLYJGHCIH-UHFFFAOYSA-N 0.000 abstract description 5
- GHUMSGGCKVMYGH-UHFFFAOYSA-N (2-amino-3,5-dibromophenyl)methanol Chemical compound NC1=C(Br)C=C(Br)C=C1CO GHUMSGGCKVMYGH-UHFFFAOYSA-N 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000000144 pharmacologic effect Effects 0.000 abstract description 2
- -1 phosphoryl halide Chemical class 0.000 abstract description 2
- PAYDUUFACYKFRI-UHFFFAOYSA-N n-bis[cyclohexyl(methyl)amino]phosphoryl-n-methylcyclohexanamine Chemical compound C1CCCCC1N(C)P(=O)(N(C)C1CCCCC1)N(C)C1CCCCC1 PAYDUUFACYKFRI-UHFFFAOYSA-N 0.000 abstract 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- XTUVJUMINZSXGF-UHFFFAOYSA-N N-methylcyclohexylamine Chemical compound CNC1CCCCC1 XTUVJUMINZSXGF-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 2
- ZLDMZIXUGCGKMB-UHFFFAOYSA-N 3,5-dibromobenzaldehyde Chemical compound BrC1=CC(Br)=CC(C=O)=C1 ZLDMZIXUGCGKMB-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- PAMIQIKDUOTOBW-UHFFFAOYSA-N N-methylcyclohexylamine Natural products CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- SKCNIGRBPJIUBQ-UHFFFAOYSA-N chloroform;ethyl acetate Chemical compound ClC(Cl)Cl.CCOC(C)=O SKCNIGRBPJIUBQ-UHFFFAOYSA-N 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012442 inert solvent Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000007530 organic bases Chemical group 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/224—Phosphorus triamides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
This invention relates to N,N',N"-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide which is a valuable intermediate for a new process for the preparation of 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl benzylamine and its acid addition salts. These latter compounds possess valuable pharmacological activity, in particular a good secretolytic activity. The new process comprises the reaction of 2-amino-3,5-dibromo-benzyl alcohol with N,N',N"-triccyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide at elevated tempera-tures. A process for the preparation og the intermediate N,N',N"-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide which comprises reacting N-methyl-N-cyclohecylamine with a phosphoryl halide is also described.
This invention relates to N,N',N"-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide which is a valuable intermediate for a new process for the preparation of 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl benzylamine and its acid addition salts. These latter compounds possess valuable pharmacological activity, in particular a good secretolytic activity. The new process comprises the reaction of 2-amino-3,5-dibromo-benzyl alcohol with N,N',N"-triccyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide at elevated tempera-tures. A process for the preparation og the intermediate N,N',N"-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide which comprises reacting N-methyl-N-cyclohecylamine with a phosphoryl halide is also described.
Description
This invention relates to a new process for the preparation of 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl benzylamine and acid addition salts thereof possessing interesting pharmacological properties, in particular a good secretolytic activity, and also to a novel intermediate for use in the said process.
According to one feature of the present invention, :
there is provided a process for the preparation of the compound of formula CH3 : :
: .
O ~ ;
Br .
.- :
and acid addition salts thereof which comprises reacting N~N9.,N~'-tricycloh0xyl-N~N~,N"-trimethylphosphoric acid triamide with the compound of formula : ' ' , Br ~ / CH2- OH ~;
: L
~,/ \ '.~ , .
I NH2.
Br and if desired subsequently converting the compound of formula I thereby produced into an acid addition salt thereof.
~ ~ ' $p~ , :
.-~
10411~0 According to a further feature of the present invention, there is provided the novel compound N,NI,Nn-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide of formula 0==P (N )3 ' :' .' : -\/ .' .'''' "' ' the said compound being of use in the abovementioned processaccording to the invention.
Using the process according to the invention we have prepared 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl-benzylamine and acid addition salts thereof in good yield.
. .
The reaction may if desired be carried out in thepresence of an inert solvent, for example tetraline, or in the presence of an excess of the amide of formula III as solvent.
It may, however, also be carried out in the absence of a solvent.
The reaction is preferably effected at temperatures from 200 to 280C.
The compound of formula I obtained by means of the process according to the invention may after having been isolated if desired, be converted into its acid addition salts~ preferably its physiologically compatible acid addition salts with inorganic and organic acids. Suitable acids for this purpose include for example hydrochloric acid, '.''~ ', :' : . .
~ 4 ~ ~ ~
~0411~V
hydrobromic acid, sulfuric acid, phosphoric acid, latic acid, citric acid and maleic acid. -It is considered surprising that the new process according to the invention produces 2-amino-N~cyclohexyl-3,5-dibromo-N-methyl-benzylamine of formula I in such good yield ~-since in general the benzyl alcohol of formula II decomposes at elevated temperatures. Thus it would not have been predicted that the benzyl alcohol of formula II would react cleanly with the triamide of formula III to produce the desired product.
The benzyl alcohol of formula II used as starting material may for example be obtained by reduction of 2-amino- ~
3,5-dibromo-benzaldehyde. ~ -N,N',N"-Tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide (the compound of formula III) also used as starting material is a new compound and constitutes a further feature of the present invention. It may be prepared in accordance with a still further feature of the present invention by reaction of a phosphoryl halide with N-methyl-N-cyclo-hexylamine, preferably in the presence of a tertiary organic base. This reaction constitutes a relatively easy process for the preparation of the new compound of formula III and thus makes a valuable contribution to the good workability of the proceæs accordir~ to the irvertior:
_ 5 1al41~ZV
The following Examples serve to illustrate the preparation of N,N',N"-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid and -its conversion to 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl-benzylamine in accordance with the present invention:
Example A
N~NI N~-Tricyclohexyl-N,N~.N''~trimethyl-phosphoric acid triamide 306 g of N-methyl-cyclohexylamine were mixed with 46 g of phos-phorus oxychloride with stirrir,g for 20 minutes and then refluxed for 3 hours (oil bath, 170C). Subsequently 1.2 1 of chloroform and 0.8 1 of water were added to the cooled reaction solution and the organic layer was separated and extracted twice with water, twice with 2N acetic acid and once with 2N ammonia, dried with sodium sulfate and evaporated. The residue was purified by column chromatography on silica gel with chloroform-ethyl acetate (1:1) as eluent. The fractions containing the required product were combined, evaporated and the residue was dissolved in petroleum ether whereupon a small quantity of a by-product crystallized out. The crystals were suction filtered after standirg for some time.
The filtrate was evaporated to dryness, finally at 100C under 1$ torr. N~NI~N~-Tricyclohexyl-N,N',N''-trimethyl-phosphoric acid triamide was obtained as an oil which crystallized slowly.
.p.: 60 to 64e.
;':
~ :. . , -~,..
~411ZO
Example 1
According to one feature of the present invention, :
there is provided a process for the preparation of the compound of formula CH3 : :
: .
O ~ ;
Br .
.- :
and acid addition salts thereof which comprises reacting N~N9.,N~'-tricycloh0xyl-N~N~,N"-trimethylphosphoric acid triamide with the compound of formula : ' ' , Br ~ / CH2- OH ~;
: L
~,/ \ '.~ , .
I NH2.
Br and if desired subsequently converting the compound of formula I thereby produced into an acid addition salt thereof.
~ ~ ' $p~ , :
.-~
10411~0 According to a further feature of the present invention, there is provided the novel compound N,NI,Nn-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide of formula 0==P (N )3 ' :' .' : -\/ .' .'''' "' ' the said compound being of use in the abovementioned processaccording to the invention.
Using the process according to the invention we have prepared 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl-benzylamine and acid addition salts thereof in good yield.
. .
The reaction may if desired be carried out in thepresence of an inert solvent, for example tetraline, or in the presence of an excess of the amide of formula III as solvent.
It may, however, also be carried out in the absence of a solvent.
The reaction is preferably effected at temperatures from 200 to 280C.
The compound of formula I obtained by means of the process according to the invention may after having been isolated if desired, be converted into its acid addition salts~ preferably its physiologically compatible acid addition salts with inorganic and organic acids. Suitable acids for this purpose include for example hydrochloric acid, '.''~ ', :' : . .
~ 4 ~ ~ ~
~0411~V
hydrobromic acid, sulfuric acid, phosphoric acid, latic acid, citric acid and maleic acid. -It is considered surprising that the new process according to the invention produces 2-amino-N~cyclohexyl-3,5-dibromo-N-methyl-benzylamine of formula I in such good yield ~-since in general the benzyl alcohol of formula II decomposes at elevated temperatures. Thus it would not have been predicted that the benzyl alcohol of formula II would react cleanly with the triamide of formula III to produce the desired product.
The benzyl alcohol of formula II used as starting material may for example be obtained by reduction of 2-amino- ~
3,5-dibromo-benzaldehyde. ~ -N,N',N"-Tricyclohexyl-N,N',N"-trimethyl-phosphoric acid triamide (the compound of formula III) also used as starting material is a new compound and constitutes a further feature of the present invention. It may be prepared in accordance with a still further feature of the present invention by reaction of a phosphoryl halide with N-methyl-N-cyclo-hexylamine, preferably in the presence of a tertiary organic base. This reaction constitutes a relatively easy process for the preparation of the new compound of formula III and thus makes a valuable contribution to the good workability of the proceæs accordir~ to the irvertior:
_ 5 1al41~ZV
The following Examples serve to illustrate the preparation of N,N',N"-tricyclohexyl-N,N',N"-trimethyl-phosphoric acid and -its conversion to 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl-benzylamine in accordance with the present invention:
Example A
N~NI N~-Tricyclohexyl-N,N~.N''~trimethyl-phosphoric acid triamide 306 g of N-methyl-cyclohexylamine were mixed with 46 g of phos-phorus oxychloride with stirrir,g for 20 minutes and then refluxed for 3 hours (oil bath, 170C). Subsequently 1.2 1 of chloroform and 0.8 1 of water were added to the cooled reaction solution and the organic layer was separated and extracted twice with water, twice with 2N acetic acid and once with 2N ammonia, dried with sodium sulfate and evaporated. The residue was purified by column chromatography on silica gel with chloroform-ethyl acetate (1:1) as eluent. The fractions containing the required product were combined, evaporated and the residue was dissolved in petroleum ether whereupon a small quantity of a by-product crystallized out. The crystals were suction filtered after standirg for some time.
The filtrate was evaporated to dryness, finally at 100C under 1$ torr. N~NI~N~-Tricyclohexyl-N,N',N''-trimethyl-phosphoric acid triamide was obtained as an oil which crystallized slowly.
.p.: 60 to 64e.
;':
~ :. . , -~,..
~411ZO
Example 1
2-Amino-N-cyclohexyl-3~5-dibromo-N-methyl-benzylamine 0.56 g (0.002 mol) of 2-amino-3,5-dibromo-benzyl alcohol and -~
3.1 g (0.008 mol) of N~N~N"-tricyclohexyl-N,N~,N"-trimethyl-phosphoric acid triamide were heated for 1 hour at 230C.
After cooling~ ether and 2N ammonia were added to the mixture. ;~
The organic layer was separated and washed with water, dried with ~odium sulfate and a small quantity of absolute ethanol was added. After addition of ethanolic hydrochloric acid, 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl-benzylamine crystallized out as the hydrochloride.
Yield: 0.46 g (55.8% of theory);
m.p. of the hydrochloride: 232 to 235 C (decomp.).
, :: . , ':', :
'
After cooling~ ether and 2N ammonia were added to the mixture. ;~
The organic layer was separated and washed with water, dried with ~odium sulfate and a small quantity of absolute ethanol was added. After addition of ethanolic hydrochloric acid, 2-amino-N-cyclohexyl-3,5-dibromo-N-methyl-benzylamine crystallized out as the hydrochloride.
Yield: 0.46 g (55.8% of theory);
m.p. of the hydrochloride: 232 to 235 C (decomp.).
, :: . , ':', :
'
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A process for the preparation of the compound of formula (I) and acid addition salts thereof which comprises reacting N,N',N''-tricyclo-hexyl-N,N,N"-trimethyl-phosphoric acid triamide with the compound of formula (II) and if desired subsequently converting the compound of formula I thereby produced into an acid addition salt thereof.
2. A process as claimed in claim 1 wherein the reaction is effected at an elevated temperature.
3. A process as claimed in claim 1 wherein the reaction is effected at a temperature from 200 to 280°C
4. A process as claimed in claim 1, 2 or 3 wherein the reaction is effected in the absence of a solvent.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19732337931 DE2337931A1 (en) | 1973-07-26 | 1973-07-26 | 2-Amino-N-cyclohexyl-3,5-dibromo-N-methylbenzyl-amine prepn - by reacting benzylalcohol with N,N',N''-tricyclohexyl-N,N',N''-trimethyl-phosphoric acid triamide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1041120A true CA1041120A (en) | 1978-10-24 |
Family
ID=5888014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA205,645A Expired CA1041120A (en) | 1973-07-26 | 1974-07-25 | Process for the preparation of 2-amino-n-cyclohexyl-3,5-dibromo-n-methyl-benzylamine |
Country Status (14)
| Country | Link |
|---|---|
| JP (2) | JPS5515465B2 (en) |
| AT (1) | AT330739B (en) |
| BG (1) | BG24231A3 (en) |
| CA (1) | CA1041120A (en) |
| CH (1) | CH597147A5 (en) |
| CS (2) | CS184839B2 (en) |
| DE (1) | DE2337931A1 (en) |
| DK (1) | DK135837C (en) |
| ES (1) | ES427954A1 (en) |
| FI (1) | FI177674A (en) |
| HU (2) | HU167868B (en) |
| NL (1) | NL7409046A (en) |
| PL (1) | PL94273B1 (en) |
| SE (2) | SE7409685L (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3107760C2 (en) * | 1981-02-28 | 1987-01-08 | Gebr. Happich Gmbh, 5600 Wuppertal | Upholstery for the interior of vehicles, especially armrests |
| JPH061882Y2 (en) * | 1988-11-16 | 1994-01-19 | 株式会社東海理化電機製作所 | Mirror body holding structure for vehicle outside mirror |
-
1973
- 1973-07-26 DE DE19732337931 patent/DE2337931A1/en active Pending
-
1974
- 1974-06-11 FI FI1776/74A patent/FI177674A/fi unknown
- 1974-06-20 AT AT510674A patent/AT330739B/en not_active IP Right Cessation
- 1974-06-25 CS CS7500001285A patent/CS184839B2/en unknown
- 1974-06-25 CS CS4467A patent/CS170115B2/cs unknown
- 1974-06-28 BG BG031992A patent/BG24231A3/en unknown
- 1974-07-04 ES ES427954A patent/ES427954A1/en not_active Expired
- 1974-07-04 NL NL7409046A patent/NL7409046A/en not_active Application Discontinuation
- 1974-07-23 DK DK397274A patent/DK135837C/en active
- 1974-07-24 HU HUTO972A patent/HU167868B/hu unknown
- 1974-07-24 HU HUTO1000A patent/HU168460B/hu unknown
- 1974-07-24 CH CH1023574A patent/CH597147A5/xx not_active IP Right Cessation
- 1974-07-25 JP JP8559074A patent/JPS5515465B2/ja not_active Expired
- 1974-07-25 SE SE7409685A patent/SE7409685L/xx unknown
- 1974-07-25 PL PL1974173005A patent/PL94273B1/pl unknown
- 1974-07-25 CA CA205,645A patent/CA1041120A/en not_active Expired
-
1977
- 1977-09-01 SE SE7709869A patent/SE7709869L/en unknown
-
1978
- 1978-01-24 JP JP664878A patent/JPS53101344A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| FI177674A (en) | 1975-01-27 |
| CS170115B2 (en) | 1976-08-27 |
| DK135837C (en) | 1977-12-05 |
| SE7409685L (en) | 1975-01-27 |
| ATA510674A (en) | 1975-10-15 |
| DK397274A (en) | 1975-04-01 |
| HU168460B (en) | 1976-04-28 |
| SE7709869L (en) | 1977-09-01 |
| DE2337931A1 (en) | 1975-02-13 |
| ES427954A1 (en) | 1976-09-01 |
| BG24231A3 (en) | 1978-01-10 |
| JPS5047945A (en) | 1975-04-28 |
| HU167868B (en) | 1975-12-25 |
| CS184839B2 (en) | 1978-09-15 |
| CH597147A5 (en) | 1978-03-31 |
| PL94273B1 (en) | 1977-07-30 |
| NL7409046A (en) | 1975-01-28 |
| DK135837B (en) | 1977-07-04 |
| JPS53101344A (en) | 1978-09-04 |
| JPS5515465B2 (en) | 1980-04-23 |
| AT330739B (en) | 1976-07-12 |
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