BE536034A - - Google Patents
Info
- Publication number
- BE536034A BE536034A BE536034DA BE536034A BE 536034 A BE536034 A BE 536034A BE 536034D A BE536034D A BE 536034DA BE 536034 A BE536034 A BE 536034A
- Authority
- BE
- Belgium
- Prior art keywords
- thio
- acid
- ester
- ethyl
- ethanol
- Prior art date
Links
- 150000002895 organic esters Chemical class 0.000 claims description 3
- ZSMVYYXSXNGAGQ-UHFFFAOYSA-N 2-[2-(diethylamino)ethylsulfanyl]ethanol Chemical compound CCN(CC)CCSCCO ZSMVYYXSXNGAGQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000002148 esters Chemical class 0.000 description 10
- 239000002253 acid Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 4
- -1 2-diethylaminoethyl-thio Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-K 2qpq Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OROGSEYTTFOCAN-DNJOTXNNSA-N Codeine Chemical compound C([C@H]1[C@H](N(CC[C@@]112)C)C3)=C[C@H](O)[C@@H]1OC1=C2C3=CC=C1OC OROGSEYTTFOCAN-DNJOTXNNSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N HCl Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N o-xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- JHZRNLRTNIDFKG-UHFFFAOYSA-N 1-phenylcyclobutane-1-carboxylic acid Chemical compound C=1C=CC=CC=1C1(C(=O)O)CCC1 JHZRNLRTNIDFKG-UHFFFAOYSA-N 0.000 description 1
- CJRBXJZXMQJTPB-UHFFFAOYSA-N C1(=CC=CC=C1)C1(CCCCC1)C(=O)OCC Chemical compound C1(=CC=CC=C1)C1(CCCCC1)C(=O)OCC CJRBXJZXMQJTPB-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 230000001476 alcoholic Effects 0.000 description 1
- 230000001147 anti-toxic Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atoms Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229960004126 codeine Drugs 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000001184 potassium carbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propanol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C323/24—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/25—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
<Desc/Clms Page number 1>
La présente invention concerne des esters 'organiques de formule générale.
EMI1.1
EMI1.2
dans laquelle R représente un radical -CH 2CH 2-9 -CH2CE2CH2- 9-CH2CH CH2 r-u- 2-9 -CH2CH2CH2CH2CH2 et -CH2CH2OCH2CH2-, ainsi-que leurs sels avec un acide organique ou minéral.
Certains de ces esters possèdent une activité antito considé- rable,supérieure à celle de la codéine.
Selon la présente invention, on prépare ces esters eri faisant
EMI1.3
réagir le 2-("2-diéthylaminJµthyl-tÀio)-éthanol avec un composé de formule
EMI1.4
dans laquelle R a la même signification que plus haut et R' représente un atome de chlore, un groupe hydroxyle ou un groupe -OR", R" étant un radical hydrocarboné contenant de 1 à 3 atomes(de carbone.
Si l'on utilise comme produit de départ un chlorure d'acide,la réaction peut être effectuée en présence d'un accepteur d'acide chlorhydri-
EMI1.5
quen%ns le cas d9 ester, il y a formation de méthanol, d'éthanol ou de propanol qui distille à la température de la réaction.
Les exemples suivants illustrent l'invention sans la limiter ;
EMI1.6
gemple 1 0 1 hén 1-ccloentane-carbo late de 20 2d.it lam5..oêt 1- thio)-éthyle et son citrate.
EMI1.7
EMI1.8
Un mélange de 0,5 mole de chlorure de l'acide 1phényl-oyoIQ- pentane-1-carboxylique et de 0,5 mole de 2-(2-diéthylaminoéthyl-thio)-étha- bol dans 300 cm3 de toluène est chauffé à reflux pendant 20 heures.
On alcalinise par une solution aqueuse contenant 5% de soude caustique.On décante la solution toluénique, on la lave à l'eau ;on la sèche sur carbonate de potassium puis on la concentre sous vide.Le résidu est fractionné par distillation sous vide.On obtient le 1-phényl-cyclopentane-
EMI1.9
1-carboxylate de #-(2-diéthylaminoéthyl-thio)-éthyle de point d'ébullition 190-193 0/0905 mm Hg avec un rendement de 50%-
On prépare le citrate acide de l'ester par addition.d'une solu- tion alcoolique concentrée d'acide citrique à une solution éthérée'?de l'ester.Point de fusion du citrate: 98 C.
EMI1.10
Exemple 2. 1 -phényl-cyclo'propane-1-carbpxylate de 2-( 2-diéthylaminoéthyl- thio ) -éthyle.
EMI1.11
<Desc/Clms Page number 2>
Selon l'exemple 1, par réaction entre le chlorure de l'acide T-phé-
EMI2.1
nyl-cyclopropane-1-carboxylique et le 2-(2-diéthyl-aminoéthyl-thio)-éh.anol.
Point d'ébullition de l'ester (base) : 150-155 C/0,01 mm Hg.. - Exemple 3. 1-phényl-cyclobutane-1-car'boxylate de 2'- 2-diéthylamino êthyl- thio ) -éthyle.
EMI2.2
Selon l'exemple 1, par réaction entre le chlorure de l'acide
EMI2.3
1-phényl-cyclobutane-1-carboxylique et le 2-(2-àiéthylaminoéthyl-thio)- éthanol.
Point d'ébullition de l'ester (base) ô 150-155 C0005 m;m Hg.
. - hén 1-tétnah dro ane-4-carbo late de 2- 2-diéth lamino- éth.vl io)---6thyle.
EMI2.4
Selon l'exemple 1, par réaction entre le chlorure de l'acide
EMI2.5
4-phényl-tê't;rahydropyrane-4-carboxylique et le 2-(2-diêthylaminoêthyl-thio)- éthanol.
Point d'ébullition de l'ester (base); 185-19000/0,005 mra ]9- Exemple 5. 1- hén l-c clohexane-1-carbox late de 2-(2-di,éthvlaminoéthyl- thio ) -éthyle.
EMI2.6
EMI2.7
On prépare l'ester éthylique de L'acide 1-phénycyclohe:x:ane- 1-carboxylique en faisant barboter de l'acide ohlorhydrique dans une solution éthanolique de l'acide.On ajoute de l'eau, on décante l'ester qui s'est séparé, on sèche puis on distille.Point d'ébullition de l'ester éthylique 100-105 C/0,1 mm Hg.
EMI2.8
On prépare une solution de 17,7 g de 2-C$-diéthylaminoéthyl- thio) -éthanol dans 60 cm3 de xylène; on y ajoute 0,2 g de sodium puis on y introduit 20,1 g de 1-phényl-cyclohexane-1-carboxylate d'éthyle.On chauffe graduellement en distillant lentement l'éthanol formé et le xylène jusqu'au moment où on atteint une température de 14000.Cette opération demande de 2 à 3 heures.
On traite le résidu par le benzène, on lave à l'eau puis on dé- cante.On sèche la solution benzénique, on chasse le solvant puis on distille.
<Desc/Clms Page number 3>
EMI3.1
On recueille ainsi 129 2 g d'ester distillant entre 190-195C/0,1 mm Hg.
R é s u m é.
1 Esters organiques et leurs sels de formule générale
EMI3.2
EMI3.3
dans laquelle R représente un radical-DH2CH2-' -CH2CH2CH2-' -CH2CH2CH2CH2' -CH2CH2CH2CH2CH 2-9 et -CH2CH20CH2CH2-' et EX un acide organique ou mineral.
**ATTENTION** fin du champ DESC peut contenir debut de CLMS **.
<Desc / Clms Page number 1>
The present invention relates to organic esters of general formula.
EMI1.1
EMI1.2
in which R represents a radical -CH 2CH 2-9 -CH2CE2CH2- 9-CH2CH CH2 r-u- 2-9 -CH2CH2CH2CH2CH2 and -CH2CH2OCH2CH2-, as well as their salts with an organic or inorganic acid.
Some of these esters have a considerable antitoxic activity, superior to that of codeine.
According to the present invention, these esters are prepared by making
EMI1.3
reacting 2 - ("2-diethylaminJµthyl-tÀio) -ethanol with a compound of formula
EMI1.4
in which R has the same meaning as above and R 'represents a chlorine atom, a hydroxyl group or a group -OR ", R" being a hydrocarbon radical containing from 1 to 3 atoms (of carbon.
If an acid chloride is used as the starting material, the reaction can be carried out in the presence of a hydrochloric acid acceptor.
EMI1.5
that in the case of ester, there is formation of methanol, ethanol or propanol which distils at the temperature of the reaction.
The following examples illustrate the invention without limiting it;
EMI1.6
Example 1 0 1 hen 1-cloentane-carbo late of 20 2d.it lam5..oet 1-thio) -ethyl and its citrate.
EMI1.7
EMI1.8
A mixture of 0.5 mole of 1phenyl-oyoIQ-pentane-1-carboxylic acid chloride and 0.5 mole of 2- (2-diethylaminoethyl-thio) -ethalol in 300 cm3 of toluene is heated to reflux for 20 hours.
It is basified with an aqueous solution containing 5% of caustic soda. The toluene solution is decanted, washed with water, dried over potassium carbonate and then concentrated in vacuo. The residue is fractionated by distillation under vacuum. This gives 1-phenyl-cyclopentane-
EMI1.9
# - (2-Diethylaminoethyl-thio) -ethyl 1-carboxylate of boiling point 190-193 0/0905 mm Hg with a yield of 50% -
The acidic citrate of the ester is prepared by adding a concentrated alcoholic solution of citric acid to an ethereal solution of the ester. Melting point of citrate: 98 ° C.
EMI1.10
Example 2. 2- (2-Diethylaminoethyl-thio) -ethyl 1 -phenyl-cyclo'propane-1-carbpxylate.
EMI1.11
<Desc / Clms Page number 2>
According to Example 1, by reaction between the chloride of the acid T-phé
EMI2.1
nyl-cyclopropane-1-carboxylic acid and 2- (2-diethyl-aminoethyl-thio) -éh.anol.
Boiling point of the ester (base): 150-155 C / 0.01 mm Hg .. - Example 3. 2'- 2-diethylamino ethyl-thio 1-phenyl-cyclobutane-1-carboxylate) -ethyl.
EMI2.2
According to Example 1, by reaction between the chloride of the acid
EMI2.3
1-phenyl-cyclobutane-1-carboxylic acid and 2- (2-ethylaminoethyl-thio) - ethanol.
Boiling point of ester (base) ô 150-155 C0005 m; m Hg.
. - hén 1-tetnah dro ane-4-carbo late de 2- 2-diéth lamino- éth.vl io) --- 6thyle.
EMI2.4
According to Example 1, by reaction between the chloride of the acid
EMI2.5
4-phenyl-tet; rahydropyran-4-carboxylic and 2- (2-diethylaminoethyl-thio) - ethanol.
Boiling point of ester (base); 185-19000 / 0.005 mra] 9- Example 5. 2- (2-di, ethvlaminoethyl-thio) -ethyl 1- hen 1-c clohexane-1-carbox late.
EMI2.6
EMI2.7
The ethyl ester of 1-Phenycyclohe: x: ane-1-carboxylic acid is prepared by bubbling ohhydrochloric acid in an ethanolic solution of the acid. Water is added and the ester is decanted. which separated, dried and then distilled. Boiling point of ethyl ester 100-105 C / 0.1 mm Hg.
EMI2.8
A solution of 17.7 g of 2-C $ -diethylaminoethylthio) -ethanol in 60 cm3 of xylene is prepared; 0.2 g of sodium is added thereto, then 20.1 g of ethyl 1-phenyl-cyclohexane-1-carboxylate are added to it. The ethanol formed and the xylene are gradually heated by slowly distilling off until the moment when reaches a temperature of 14000, which takes 2 to 3 hours.
The residue is treated with benzene, washed with water and then decanted. The benzene solution is dried, the solvent is removed and then distilled.
<Desc / Clms Page number 3>
EMI3.1
129 2 g of ester distilling between 190-195C / 0.1 mm Hg are thus collected.
Summary.
1 Organic esters and their salts of general formula
EMI3.2
EMI3.3
in which R represents a radical-DH2CH2- '-CH2CH2CH2-' -CH2CH2CH2CH2 '-CH2CH2CH2CH2CH 2-9 and -CH2CH20CH2CH2-' and EX an organic or mineral acid.
** ATTENTION ** end of DESC field can contain start of CLMS **.
Claims (1)
Publications (1)
| Publication Number | Publication Date |
|---|---|
| BE536034A true BE536034A (en) |
Family
ID=166860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| BE536034D BE536034A (en) |
Country Status (1)
| Country | Link |
|---|---|
| BE (1) | BE536034A (en) |
-
0
- BE BE536034D patent/BE536034A/fr unknown
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CH651561A5 (en) | DERIVATIVES OF NOR-TROPANE AND GRANATANE AND THEIR PREPARATION PROCESS. | |
| CH646969A5 (en) | NOR-TROPANE BETA-AMINO-3 DERIVATIVES. | |
| FR2472564A1 (en) | 1-Aryl-4-aryl:sulphonyl-3-amino-propoxy-1H-pyrazole derivs. - hypolipaemics and hypocholesterolaemics of low toxicity and non-ulcerogenic | |
| EP0102283B1 (en) | Process for the preparation of quinuclidine derivatives substituted in position 3 | |
| BE536034A (en) | ||
| FR2560194A1 (en) | 3-AMINOAZETIDINE, ITS SALTS, PROCESS FOR THEIR PREPARATION AND SYNTHESIS INTERMEDIATES | |
| EP0005654B1 (en) | Process for the isomerization of 3-vinyl-piperidine derivatives | |
| FR2602228A1 (en) | New phenoxyisobutyric acids, their derivatives and processes for producing them | |
| EP0103503A2 (en) | N-substituted amides, their salts, process for their preparation and pharmaceutical compositions containing them | |
| JPH05508633A (en) | Intermediates used in the preparation of deferoxamine | |
| BE642084A (en) | ||
| BE569836A (en) | ||
| BE475031A (en) | ||
| EP0100257A2 (en) | Aminoalkyl naphthalene derivatives, their salts, process for their preparation and the therapeutical use of these derivatives and salts | |
| CA1099718A (en) | Process for the preparation of novel napthalene derivatives | |
| BE556239A (en) | ||
| FR2494696A1 (en) | NOVEL PROCESS FOR THE PREPARATION OF 3-AMINO STEROIDS AND THEIR SALTS | |
| CH385209A (en) | Process for the preparation of new phenothiazines | |
| CH617696A5 (en) | Process for the preparation of new derivatives of isoindoline | |
| CH350296A (en) | Process for the preparation of N- (o-halo-phenyl) -piperazines N'-alkylated | |
| BE530796A (en) | ||
| BE480546A (en) | ||
| FR2584403A1 (en) | HALOGENO BIPHENYL PRIMARY ALCOHOL DERIVATIVES USEFUL IN THERAPEUTICS FOR THE TREATMENT OF ATHEROSCLEROSIS | |
| CH342950A (en) | Process for the preparation of cyclohexylamine derivatives | |
| CH509978A (en) | Preparation of aromatic amides |