CA1050995A - Process for the production of heterocyclic compounds and products obtained thereby - Google Patents
Process for the production of heterocyclic compounds and products obtained therebyInfo
- Publication number
- CA1050995A CA1050995A CA205,349A CA205349A CA1050995A CA 1050995 A CA1050995 A CA 1050995A CA 205349 A CA205349 A CA 205349A CA 1050995 A CA1050995 A CA 1050995A
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- Canada
- Prior art keywords
- reaction
- carried out
- process according
- formula
- oxygen
- 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
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- 238000000034 method Methods 0.000 title claims abstract description 15
- 150000002391 heterocyclic compounds Chemical class 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 5
- 239000011669 selenium Substances 0.000 claims abstract description 18
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 15
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052717 sulfur Chemical group 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000004699 copper complex Chemical class 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 3
- 239000011593 sulfur Substances 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052799 carbon Inorganic materials 0.000 claims abstract 2
- 239000002904 solvent Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- IZXIZTKNFFYFOF-UHFFFAOYSA-N 2-Oxazolidone Chemical compound O=C1NCCO1 IZXIZTKNFFYFOF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- -1 alkyl radical Chemical class 0.000 description 2
- 230000000063 preceeding effect Effects 0.000 description 2
- DHBXNPKRAUYBTH-UHFFFAOYSA-N 1,1-ethanedithiol Chemical compound CC(S)S DHBXNPKRAUYBTH-UHFFFAOYSA-N 0.000 description 1
- SLYRGJDSFOCAAI-UHFFFAOYSA-N 1,3-thiazolidin-2-one Chemical compound O=C1NCCS1 SLYRGJDSFOCAAI-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- FZLSDZZNPXXBBB-KDURUIRLSA-N 5-chloro-N-[3-cyclopropyl-5-[[(3R,5S)-3,5-dimethylpiperazin-1-yl]methyl]phenyl]-4-(6-methyl-1H-indol-3-yl)pyrimidin-2-amine Chemical compound C[C@H]1CN(Cc2cc(Nc3ncc(Cl)c(n3)-c3c[nH]c4cc(C)ccc34)cc(c2)C2CC2)C[C@@H](C)N1 FZLSDZZNPXXBBB-KDURUIRLSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- UFULAYFCSOUIOV-UHFFFAOYSA-N cysteamine Chemical compound NCCS UFULAYFCSOUIOV-UHFFFAOYSA-N 0.000 description 1
- 230000009089 cytolysis Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- WQABCVAJNWAXTE-UHFFFAOYSA-N dimercaprol Chemical compound OCC(S)CS WQABCVAJNWAXTE-UHFFFAOYSA-N 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical group CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229960003151 mercaptamine Drugs 0.000 description 1
- FYFFGSSZFBZTAH-UHFFFAOYSA-N methylaminomethanetriol Chemical compound CNC(O)(O)O FYFFGSSZFBZTAH-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- XOVSRHHCHKUFKM-UHFFFAOYSA-N s-methylthiohydroxylamine Chemical compound CSN XOVSRHHCHKUFKM-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/22—Oxygen atoms attached in position 2 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, directly attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D263/00—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings
- C07D263/02—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings
- C07D263/08—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D263/16—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D263/18—Oxygen atoms
- C07D263/20—Oxygen atoms attached in position 2
- C07D263/24—Oxygen atoms attached in position 2 with hydrocarbon radicals, substituted by oxygen atoms, attached to other ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/08—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
- C07D277/14—Oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/02—Five-membered rings
- C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
- C07D339/08—Six-membered rings
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE:
The present invention relates to a process for the production of five membered ketonic heterocyclic compounds of the general formula:
(l) wherein:
- R1, R2, R3, R4 and R6 are identical or different and each represent n hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, which may be substituted by an hydroxy group or a radical of the formula -COOR5 in which R5 represents an alkyl radical having from 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and - m is the valence of Y.
This process comprises reacting a difunctional compound of the formula:
(2) wherein R1, R2, R3, R4, R6, X, Y and m have the above meanings;
with carbon monoxyde and oxygen in the presence of a ctalyst selected among the soluble catalyst consisting of selenium or its derivatives, and the unsoluble catalyst consisting of a copper complex.
The present invention relates to a process for the production of five membered ketonic heterocyclic compounds of the general formula:
(l) wherein:
- R1, R2, R3, R4 and R6 are identical or different and each represent n hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, which may be substituted by an hydroxy group or a radical of the formula -COOR5 in which R5 represents an alkyl radical having from 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and - m is the valence of Y.
This process comprises reacting a difunctional compound of the formula:
(2) wherein R1, R2, R3, R4, R6, X, Y and m have the above meanings;
with carbon monoxyde and oxygen in the presence of a ctalyst selected among the soluble catalyst consisting of selenium or its derivatives, and the unsoluble catalyst consisting of a copper complex.
Description
9~5 The present invention relates to a process or the production of five membered ke-tonic heterocyclic compounds having two heteroatoms in the ring.
More especially the present invention relates to a process for the production of heterocyclic compounds of the general formula:
R - C C - R (1) X ~ 6)m-2 , ~ '.
wherein:
- Rl, R2j R3, R4 and R6 are identical or different and each represent a hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, wh.ich may be substituted by an hydroxy group or a radical of the formula - COOR5 in which R5 represents an alkyl radical having Erom 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and ~ m is the valence of Y, Up to now, the above products have been prepared through a reaction between a difunctional compound and phosgene or through a more complex syntheses. The use o phosgene involves several drawbacks because its toxicity and its reactivity with other functional groups present in the molecule.
It has now been found a simple and cheap process for :
obtaining these heterocyclic compounds at very high yields.
The process according to the invention comprises reacting a difunctional compound of the general ormula ~ 12 13 Rl - C . Y(R6)m_l (2) in which Rl, R2, R3, R4, R6, X, Y and m have the above meanings, with carbon monoxide and oxygen in presence ~
9~5 o~ a soluble or unsoluble catalyst, the former being selected between selenium and derivatives thereof, the la-tt.er being a copper complex.
The reaction may be carried out either in homogeneous phase by dissolving the reagents and the catalyst into a sui-table solvent or in heterogeneous phase by using an unsoluble catalyst. Unrestrictive examples of compounds according to the formula (2) may be ethanolamine, 2-aminopropano~ 3-aminopro-pano], diethanblamine, 1,2-ethandithiole, 1,3-propandithiole, 1,2-propandithiole, 2-aminoethanthiole, 2-aminopropanthiole, 3-aminopropanthiole. The reaction may be carried out under a pressure ranging from 1 to 100 atmospheres. For practical reasons, it is preferable to operate ~nder a pressu~e rang~g between l to 10 atmospheres.
As 2~resaid, the catalyst may be soluble into the reagents or in suitable solvents, or it may be unsoluble.
Among the soluble catalysts, it is possible to mention metallic selenium and the derivatives thereof whereas, as to the unso-luble catalysts, an advantageous use can be made of complexes containing Cu. The reaction may be carried out at temperatures ranging from 0 to 100C, preferably from the room temperature to 80C.
The Eollowing examples illustrate the invention, but are not limitative thereof.
Example 1:
23.8 mmoles of 1-2 dimercaptoethane,~l mmole of triethylamine and 0.5 mmole o Se were reacted ln 10 ml of T~F at 25C with a CO:O2 mixture in the molar ratio 10:1 at 3.5 atmos~heres.
After 40 hours, selenium was recovered and the solvent was 1~50~9'~
evaporated from the resulting suspension. The residual was distilled under vacuum. The IR analysis showed that the dis-tilled product was ethylenedithiocarbonate. Yield=90%.
Example 2 :
lO moles of 2,3-dimercaptopropanol-l, l mole of triethylamine and l mmole of Se were reacted in 10 ml of THF at 25C with a CO:O2 mixture in the molar ratio lO: l at 3.5 atmospheres.
After 16 hours, selenium was recovered from the resulting suspen5ion and the solvent was evaporated. The residual was distilled under vacuum. The distilled product, at IR and mass analysis, was 1-3 dithiolan-2-one-4-hydroxymethyl.
Yield = 90%.
20 mmoles of 2,3-dimercaptopropanol, l mmole of thiethylamine and O.S mmole o~ Se were reacted with C0 and 2 in condi-tions simllar to the precedi,ng ones. After 16 'hours the oolution was yellowish and homogeneous. The solverit was evaporated and the residual was distilled.
18 mmoles of 1-3 dithiolan-2-one-4-hydroxymethyl were obtained.
Yield = 90%~
Example 3:
14.8 mmoles of 2-mercaptoe-thylamine and 0.5 mmole of amorphous Se, in lO mI of THF, were reacted at 60C with a C0:02 mixture in the molar ratio lO:l at 3.5 atmospheres.
After 4 hours, the solution was filtered from selenium and the solvent was evaporated. The residual was again crystallized in CS2 (m.p.=50C). 1.4 g of 2-thiazolidinone were obtained, ' identified by IR and mass spectoscopy. Yield = 93%. ' ~ ' : .
.. . . . . . . . . . . . . . .. . .
105099~ -Example 4:
82 mmoles of ethanolamine and 1 mmole of amorphous selenium were reacted in 25 ml of THF with a CO:O2 mixture in the molar ratio 4:1 at 4 atmospheres. After 3 hours at 70 C selenium was filtered and the solvent was evaporated. The rèsidual was crystalIized from chloroform (m.p. 87 C).
6.8 g of product was o~tained. The IR ana:Lysis showed that it was 2-oxazolidone. Yield= 95%.
Example 5:
12.7 mmoles of 1-amino-2-propanol and 0.3 mmole of selenium were reacted at 60 C under conditions similar to the preceeding ones. After 3 hours selenium was filtered, the solvent was evaporated and the residual product was distilled under vacuum.
1.2 g of an oily product were obtained. The IR and mass analysis showed that it was 2-oxazolidone-5-methyl. Yield~ 95~.
Example 6:
10 mmoles of diethanolamine and 0.3 mmole of selenium were reacted at 60 C under conditions similar to the preceeding ones.
After 10 hours selenium was filtered, the solvent was evapora-ted and the residual was distilled under vacuum. 1.2 g of liquid product were obtained. The IR and mass analysis showed that it was 2-oxazolidone-3-hydroxyethyl~ Yield =91~.
Example 7:
: .
10.3 mmoles of trihydroxymethylaminomethane and 0.5 mmole of selentum were reacted in 20 ml of ethyl alcohol at 70C with a CO:O2 mixture in the molar ratio 4:1 at 4 atmospheres.
After 5 hours selenium was filtered and the solvent was eva-porated. The residual was crystallized from chloroform (m.p.=
104C). 1.5 g of product were obtained. The IR analysis showed that it was 2-oxazolidone-4, 4-bishydroxymethyl. Yield~ 99%.
, 4 _ L.~ , , , .. . . .: . . :. .. . ". .,. . .. ; , . . . . . . .. ..
Example_8:
16.~ mmoles of ethanolamine and 10 mmoles of CuCl in 10 ml of pyridine were treated, in autoclave at 70C, with a CO:O2 mixture in the molar ratio 4:1. After 16 hours the solution was filtered and the solvent evaporated under vacuum. The residual was crystallized from chloroform. 0.78 g of 2-oxazolidone was obtained. Yield = 55%.
.
' ~
.... . . . . . - . . . . . . .
. : . . .. . . . ... . . ..
More especially the present invention relates to a process for the production of heterocyclic compounds of the general formula:
R - C C - R (1) X ~ 6)m-2 , ~ '.
wherein:
- Rl, R2j R3, R4 and R6 are identical or different and each represent a hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, wh.ich may be substituted by an hydroxy group or a radical of the formula - COOR5 in which R5 represents an alkyl radical having Erom 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and ~ m is the valence of Y, Up to now, the above products have been prepared through a reaction between a difunctional compound and phosgene or through a more complex syntheses. The use o phosgene involves several drawbacks because its toxicity and its reactivity with other functional groups present in the molecule.
It has now been found a simple and cheap process for :
obtaining these heterocyclic compounds at very high yields.
The process according to the invention comprises reacting a difunctional compound of the general ormula ~ 12 13 Rl - C . Y(R6)m_l (2) in which Rl, R2, R3, R4, R6, X, Y and m have the above meanings, with carbon monoxide and oxygen in presence ~
9~5 o~ a soluble or unsoluble catalyst, the former being selected between selenium and derivatives thereof, the la-tt.er being a copper complex.
The reaction may be carried out either in homogeneous phase by dissolving the reagents and the catalyst into a sui-table solvent or in heterogeneous phase by using an unsoluble catalyst. Unrestrictive examples of compounds according to the formula (2) may be ethanolamine, 2-aminopropano~ 3-aminopro-pano], diethanblamine, 1,2-ethandithiole, 1,3-propandithiole, 1,2-propandithiole, 2-aminoethanthiole, 2-aminopropanthiole, 3-aminopropanthiole. The reaction may be carried out under a pressure ranging from 1 to 100 atmospheres. For practical reasons, it is preferable to operate ~nder a pressu~e rang~g between l to 10 atmospheres.
As 2~resaid, the catalyst may be soluble into the reagents or in suitable solvents, or it may be unsoluble.
Among the soluble catalysts, it is possible to mention metallic selenium and the derivatives thereof whereas, as to the unso-luble catalysts, an advantageous use can be made of complexes containing Cu. The reaction may be carried out at temperatures ranging from 0 to 100C, preferably from the room temperature to 80C.
The Eollowing examples illustrate the invention, but are not limitative thereof.
Example 1:
23.8 mmoles of 1-2 dimercaptoethane,~l mmole of triethylamine and 0.5 mmole o Se were reacted ln 10 ml of T~F at 25C with a CO:O2 mixture in the molar ratio 10:1 at 3.5 atmos~heres.
After 40 hours, selenium was recovered and the solvent was 1~50~9'~
evaporated from the resulting suspension. The residual was distilled under vacuum. The IR analysis showed that the dis-tilled product was ethylenedithiocarbonate. Yield=90%.
Example 2 :
lO moles of 2,3-dimercaptopropanol-l, l mole of triethylamine and l mmole of Se were reacted in 10 ml of THF at 25C with a CO:O2 mixture in the molar ratio lO: l at 3.5 atmospheres.
After 16 hours, selenium was recovered from the resulting suspen5ion and the solvent was evaporated. The residual was distilled under vacuum. The distilled product, at IR and mass analysis, was 1-3 dithiolan-2-one-4-hydroxymethyl.
Yield = 90%.
20 mmoles of 2,3-dimercaptopropanol, l mmole of thiethylamine and O.S mmole o~ Se were reacted with C0 and 2 in condi-tions simllar to the precedi,ng ones. After 16 'hours the oolution was yellowish and homogeneous. The solverit was evaporated and the residual was distilled.
18 mmoles of 1-3 dithiolan-2-one-4-hydroxymethyl were obtained.
Yield = 90%~
Example 3:
14.8 mmoles of 2-mercaptoe-thylamine and 0.5 mmole of amorphous Se, in lO mI of THF, were reacted at 60C with a C0:02 mixture in the molar ratio lO:l at 3.5 atmospheres.
After 4 hours, the solution was filtered from selenium and the solvent was evaporated. The residual was again crystallized in CS2 (m.p.=50C). 1.4 g of 2-thiazolidinone were obtained, ' identified by IR and mass spectoscopy. Yield = 93%. ' ~ ' : .
.. . . . . . . . . . . . . . .. . .
105099~ -Example 4:
82 mmoles of ethanolamine and 1 mmole of amorphous selenium were reacted in 25 ml of THF with a CO:O2 mixture in the molar ratio 4:1 at 4 atmospheres. After 3 hours at 70 C selenium was filtered and the solvent was evaporated. The rèsidual was crystalIized from chloroform (m.p. 87 C).
6.8 g of product was o~tained. The IR ana:Lysis showed that it was 2-oxazolidone. Yield= 95%.
Example 5:
12.7 mmoles of 1-amino-2-propanol and 0.3 mmole of selenium were reacted at 60 C under conditions similar to the preceeding ones. After 3 hours selenium was filtered, the solvent was evaporated and the residual product was distilled under vacuum.
1.2 g of an oily product were obtained. The IR and mass analysis showed that it was 2-oxazolidone-5-methyl. Yield~ 95~.
Example 6:
10 mmoles of diethanolamine and 0.3 mmole of selenium were reacted at 60 C under conditions similar to the preceeding ones.
After 10 hours selenium was filtered, the solvent was evapora-ted and the residual was distilled under vacuum. 1.2 g of liquid product were obtained. The IR and mass analysis showed that it was 2-oxazolidone-3-hydroxyethyl~ Yield =91~.
Example 7:
: .
10.3 mmoles of trihydroxymethylaminomethane and 0.5 mmole of selentum were reacted in 20 ml of ethyl alcohol at 70C with a CO:O2 mixture in the molar ratio 4:1 at 4 atmospheres.
After 5 hours selenium was filtered and the solvent was eva-porated. The residual was crystallized from chloroform (m.p.=
104C). 1.5 g of product were obtained. The IR analysis showed that it was 2-oxazolidone-4, 4-bishydroxymethyl. Yield~ 99%.
, 4 _ L.~ , , , .. . . .: . . :. .. . ". .,. . .. ; , . . . . . . .. ..
Example_8:
16.~ mmoles of ethanolamine and 10 mmoles of CuCl in 10 ml of pyridine were treated, in autoclave at 70C, with a CO:O2 mixture in the molar ratio 4:1. After 16 hours the solution was filtered and the solvent evaporated under vacuum. The residual was crystallized from chloroform. 0.78 g of 2-oxazolidone was obtained. Yield = 55%.
.
' ~
.... . . . . . - . . . . . . .
. : . . .. . . . ... . . ..
Claims (7)
1. Process for the production of five membered ketonic heterocyclic compounds of the general formula:
(1) wherein:
- R1, R2, R3, R4 and R6 are identical or different and each represent a hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, which may be substituted by an hydroxy group or a radical of the formula - COOR5 in which R5 represents an alkyl radical having from 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and - m is the valence of Y, said process comprising reacting a difunctional compound of the formula:
(2) wherein R1, R2, R3, R4 R6, X, Y and m have the above meanings with carbon monoxyde and oxygen in the presence of a catalyst selected among the soluble catalyst consisting of selenium or its derivatives, and the unsoluble catalyst consisting of a copper complex.
(1) wherein:
- R1, R2, R3, R4 and R6 are identical or different and each represent a hydrogen atom or an alkyl radical having from 1 to 3 carbon atoms, which may be substituted by an hydroxy group or a radical of the formula - COOR5 in which R5 represents an alkyl radical having from 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and - m is the valence of Y, said process comprising reacting a difunctional compound of the formula:
(2) wherein R1, R2, R3, R4 R6, X, Y and m have the above meanings with carbon monoxyde and oxygen in the presence of a catalyst selected among the soluble catalyst consisting of selenium or its derivatives, and the unsoluble catalyst consisting of a copper complex.
2. Process according to claim 1, characterized in that the reaction is carried out in homogeneous phase, the catalyst and the reagents being dissolved in a solvent.
3. Process according to claim 1, characterized in that the reaction is carried out in heterogeneous phase.
4. Process according to claim 1, characterized in that the reaction is carried out under a pressure ranging from 1 to 100 atmospheres.
5. Process according to claim 4, characterized in that the reaction is carried out under a pressure ranging from 1 to 10 atmospheres.
6. Process according to claim 1, characterized in that the reaction is carried out at a temperature ranging from 0 to 100°C.
7. Process according to claim 6, characterized in that the reaction is carried out at a temperature ranging from the room temperature to 80°C.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT27389/73A IT995110B (en) | 1973-08-01 | 1973-08-01 | PROCEDURE FOR THE PRODUCTION OF HETEROCYCLIC COMPOUNDS AND OBTAINED PRODUCTS |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1050995A true CA1050995A (en) | 1979-03-20 |
Family
ID=11221549
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA205,349A Expired CA1050995A (en) | 1973-08-01 | 1974-07-22 | Process for the production of heterocyclic compounds and products obtained thereby |
Country Status (16)
| Country | Link |
|---|---|
| JP (1) | JPS5616790B2 (en) |
| BE (1) | BE818139A (en) |
| CA (1) | CA1050995A (en) |
| CH (1) | CH606025A5 (en) |
| DE (1) | DE2437132C3 (en) |
| DK (1) | DK409174A (en) |
| ES (1) | ES429501A1 (en) |
| FR (1) | FR2239469B1 (en) |
| GB (1) | GB1471007A (en) |
| IE (1) | IE40506B1 (en) |
| IT (1) | IT995110B (en) |
| LU (1) | LU70600A1 (en) |
| NL (1) | NL160560C (en) |
| NO (1) | NO144018C (en) |
| SU (1) | SU654169A3 (en) |
| ZA (1) | ZA744929B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2655369A1 (en) * | 1976-12-03 | 1978-06-08 | Schering Ag | 5- (SUBST. PHENYL) -OXAZOLIDINONE AND THEIR SULFUR ANALOGS AND PROCESS FOR THEIR PRODUCTION |
| SE8605573D0 (en) * | 1986-12-29 | 1986-12-29 | Haessle Ab | NOVEL COMPOUNDS |
| ATE156823T1 (en) * | 1990-06-07 | 1997-08-15 | Zeneca Ltd | THERAPEUTIC HETEROCYCLIC COMPOUNDS |
| EP2736890A4 (en) * | 2011-07-28 | 2015-07-15 | Promentis Pharm Inc | Cysteine prodrugs |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2868801A (en) * | 1959-01-13 | Preparation of substituted |
-
1973
- 1973-08-01 IT IT27389/73A patent/IT995110B/en active
-
1974
- 1974-07-08 IE IE1442/74A patent/IE40506B1/en unknown
- 1974-07-09 CH CH942674A patent/CH606025A5/xx not_active IP Right Cessation
- 1974-07-12 GB GB3108474A patent/GB1471007A/en not_active Expired
- 1974-07-18 FR FR7425071A patent/FR2239469B1/fr not_active Expired
- 1974-07-22 CA CA205,349A patent/CA1050995A/en not_active Expired
- 1974-07-24 LU LU70600A patent/LU70600A1/xx unknown
- 1974-07-26 BE BE146988A patent/BE818139A/en not_active IP Right Cessation
- 1974-07-31 JP JP8709774A patent/JPS5616790B2/ja not_active Expired
- 1974-07-31 DK DK409174*A patent/DK409174A/da not_active Application Discontinuation
- 1974-07-31 ES ES429501A patent/ES429501A1/en not_active Expired
- 1974-07-31 NO NO742773A patent/NO144018C/en unknown
- 1974-08-01 NL NL7410385.A patent/NL160560C/en not_active IP Right Cessation
- 1974-08-01 SU SU742048531A patent/SU654169A3/en active
- 1974-08-01 DE DE2437132A patent/DE2437132C3/en not_active Expired
- 1974-08-01 ZA ZA00744929A patent/ZA744929B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NL160560B (en) | 1979-06-15 |
| FR2239469B1 (en) | 1978-01-20 |
| IT995110B (en) | 1975-11-10 |
| ES429501A1 (en) | 1976-09-01 |
| JPS5047984A (en) | 1975-04-28 |
| DK409174A (en) | 1975-03-24 |
| NO144018C (en) | 1981-06-10 |
| SU654169A3 (en) | 1979-03-25 |
| BE818139A (en) | 1974-11-18 |
| DE2437132C3 (en) | 1981-09-10 |
| LU70600A1 (en) | 1974-11-28 |
| GB1471007A (en) | 1977-04-21 |
| NL160560C (en) | 1979-11-15 |
| CH606025A5 (en) | 1978-10-13 |
| ZA744929B (en) | 1975-08-27 |
| NO742773L (en) | 1975-03-03 |
| NO144018B (en) | 1981-02-23 |
| IE40506B1 (en) | 1979-06-20 |
| IE40506L (en) | 1975-02-01 |
| DE2437132B2 (en) | 1980-10-16 |
| DE2437132A1 (en) | 1975-02-27 |
| FR2239469A1 (en) | 1975-02-28 |
| JPS5616790B2 (en) | 1981-04-18 |
| NL7410385A (en) | 1975-02-04 |
| AU7162474A (en) | 1976-01-29 |
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