DE1001989B - Process for the preparation of oxazolthione (2) - Google Patents
Process for the preparation of oxazolthione (2)Info
- Publication number
- DE1001989B DE1001989B DEB32922A DEB0032922A DE1001989B DE 1001989 B DE1001989 B DE 1001989B DE B32922 A DEB32922 A DE B32922A DE B0032922 A DEB0032922 A DE B0032922A DE 1001989 B DE1001989 B DE 1001989B
- Authority
- DE
- Germany
- Prior art keywords
- heated
- oxazolthione
- preparation
- boiling
- theory
- 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.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims description 4
- 238000002360 preparation method Methods 0.000 title claims description 3
- CLEJZSNZYFJMKD-UHFFFAOYSA-N 3h-1,3-oxazole-2-thione Chemical compound SC1=NC=CO1 CLEJZSNZYFJMKD-UHFFFAOYSA-N 0.000 title description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 4
- CYQAYERJWZKYML-UHFFFAOYSA-N phosphorus pentasulfide Chemical compound S1P(S2)(=S)SP3(=S)SP1(=S)SP2(=S)S3 CYQAYERJWZKYML-UHFFFAOYSA-N 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BVEYJWQCMOVMAR-UHFFFAOYSA-N 5-Hydroxy-4-octanone Chemical compound CCCC(O)C(=O)CCC BVEYJWQCMOVMAR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 244000028419 Styrax benzoin Species 0.000 description 1
- 235000000126 Styrax benzoin Nutrition 0.000 description 1
- 235000008411 Sumatra benzointree Nutrition 0.000 description 1
- 229960002130 benzoin Drugs 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000001953 recrystallisation Methods 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
- C07D263/30—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D263/34—Heterocyclic compounds containing 1,3-oxazole or hydrogenated 1,3-oxazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
- C07D263/46—Sulfur atoms
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)
Description
Verfahren zur Herstellung von Oxazolthionen-(2) Oxazolthione-(2) wurden bis jetzt noch nicht beschrieben.Process for the preparation of oxazolthiones- (2) oxazolthiones- (2) were not yet described.
Es wurde jedoch gefunden, daß man Oxazolthione-(2) durch Erhitzen von Oxazolonen-(2) mit Phosphorpentasulfid in Gegenwart eines Lösungsmittels erhält. Auf diese Weise sind sowohl die 3, 4, 5-trisubstituierten als auch die N-unsubstituierten Oxazolthione-(2) sehr gut zugänglich. Die Umsetzung verläuft nach folgendem Schema: in dem R, R', R" Alkyl-, Arylgruppen oder Wasserstoffatome bedeuten.However, it has been found that oxazolthione- (2) can be obtained by heating oxazolonene- (2) with phosphorus pentasulfide in the presence of a solvent. In this way, both the 3, 4, 5-trisubstituted and the N-unsubstituted oxazolthiones (2) are very easily accessible. The implementation proceeds according to the following scheme: in which R, R ', R "denote alkyl, aryl groups or hydrogen atoms.
Die Oxazolthione-(2) lassen sich als Zwischenprodukte verwenden.The oxazolthiones (2) can be used as intermediates.
Beispiele 1. 4, 5-Diphenyloxazolthion-(2) : 26,5 g Benzoin und 57 g Urethan (Molverhältnis 1 : 5) wurden am absteigenden Kühler 3 Stunden zum gelinden Sieden erhitzt. Nach Abkühlen auf etwa 100° wurde das Reaktionsgemisch in Wasser gegossen und der Niederschlag aus Methanol umkristallisiert. Ausbeute 27g 4, 5-Diphenyloxazolon-(2) (91% der Theorie) vom Schmp. 202°.Examples 1. 4, 5-Diphenyloxazolthione- (2): 26.5 g of benzoin and 57 g urethane (molar ratio 1: 5) were allowed to soften on the descending cooler for 3 hours Boiling heated. After cooling to about 100 °, the reaction mixture was dissolved in water poured and the precipitate recrystallized from methanol. Yield 27g of 4,5-diphenyloxazolone- (2) (91% of theory) of melting point 202 °.
40g 4, 5-Diphenyloxazolon-(2) und 80g P2 S5 wurden in 700 ml Xylol unter Rühren 12 Stunden zum Sieden erhitzt. Aus der Xylollösung wurden 11 g Substanz erhalten; weitere 22 g wurden durch mehrmaliges Auskochen des Rückstandes mit Xylol isoliert. Ausbeute 33 g (77,5% der Theorie) vom Schmp. 256°. Weiße Kristalle aus Methanol.40g of 4, 5-diphenyloxazolone- (2) and 80g of P2 S5 were in 700 ml of xylene heated to boiling with stirring for 12 hours. 11 g of substance were obtained from the xylene solution obtain; a further 22 g were obtained by boiling the residue several times with xylene isolated. Yield 33 g (77.5% of theory) with a melting point of 256 °. White crystals off Methanol.
2. 4, 5-Di-n-propyloxazolthion-(2) : 29g Butyroin und 60 g Urethan wurden in 100 ml Dimethylformannid zusammen mit 3 ml Pyridin 15 Stunden am Rückfluß zum Sieden erhitzt. Aufarbeitung durch Eingießen des Reaktionsproduktes in Wasser, Ausschütteln mit Äther und Destillation. Kp.0,01 155 bis 165°. Ausbeute 15,5g 4, 5-Di-n-propyloxazolon-(2) (70% der Theorie, bezogen auf umgesetztes Butyroin), gelbliches Öl.2. 4, 5-di-n-propyloxazolthione- (2): 29g butyroin and 60g urethane were refluxed in 100 ml of dimethylformannide together with 3 ml of pyridine for 15 hours heated to boiling. Working up by pouring the reaction product into water, Shake out with ether and distillation. Bp 0.01 155 to 165 degrees. Yield 15.5g 4, 5-Di-n-propyloxazolon- (2) (70% of theory, based on converted butyroin), yellowish Oil.
15 g 4, 5-Di-n-propyloxazolon-(2) und 30 g P2 S5 wurden in 300 ml Xylol 10 Stunden unter Rückfluß erhitzt (Rühren!). Es wurde heiß vom Ungel-östen abfiltriert, das Lösungsmittel im Wasserstrahlvakuum und der Rückstand an der Ölpumpe destilliert. Kp.0,1 185 bis 190°. Ausbeute 10 g (62% der Theorie), gelbliches Öl.15 g of 4,5-di-n-propyloxazolon- (2) and 30 g of P2 S5 were in 300 ml Xylene heated under reflux for 10 hours (stirring!). It got hot from the unsolved problem filtered off, the solvent in a water jet vacuum and the residue on the oil pump distilled. Bp 0.1 185 to 190 °. Yield 10 g (62% of theory), yellowish oil.
3. 3, 4, 5-Triphenyloxazolthion-(2) : 10 g 3, 4, 5-Triphenyloxazolon-(2) (H. M c C o m b i e und J. W. P a r -kes, Journ. Chem. Soc. [Lomdan], 101, S. 1991 [1912]) und 20g pulverisiertes Phosphorpentasulfid wurden in 160m1 absolutem Xylol unter kräftigem Rühren 16 Stunden zum Sieden erhitzt. Es wurde heiß vom P2 S5 abgesaugt. Aus dem Filtrat schieden sich rasch Kristalle ab. Ausbeute 9,5g (90% der Theorie) vom Schmp. 229°. Durch Umkristallisieren aus Butylacetat (unter Zusatz von Aktivkohle) erhält man die Substanz in Form weißer Kristalle.3. 3, 4, 5-triphenyloxazolthione- (2): 10 g of 3, 4, 5-triphenyloxazolone- (2) (H. M c C o m b i e and J. W. Par-kes, Journ. Chem. Soc. [Lomdan], 101, p. 1991 [1912]) and 20g of powdered phosphorus pentasulphide were dissolved in 160m1 of absolute xylene heated to boiling with vigorous stirring for 16 hours. It was sucked hot from the P2 S5. Crystals quickly separated out from the filtrate. Yield 9.5g (90% of theory) of m.p. 229 °. By recrystallization from butyl acetate (with the addition of activated charcoal) the substance is obtained in the form of white crystals.
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB32922A DE1001989B (en) | 1954-10-08 | 1954-10-08 | Process for the preparation of oxazolthione (2) |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEB32922A DE1001989B (en) | 1954-10-08 | 1954-10-08 | Process for the preparation of oxazolthione (2) |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| DE1001989B true DE1001989B (en) | 1957-02-07 |
Family
ID=6963883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DEB32922A Pending DE1001989B (en) | 1954-10-08 | 1954-10-08 | Process for the preparation of oxazolthione (2) |
Country Status (1)
| Country | Link |
|---|---|
| DE (1) | DE1001989B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130563A (en) | 1976-03-13 | 1978-12-19 | Bayer Aktiengesellschaft | Δ4-Oxazolin-2-ones and process therefor |
-
1954
- 1954-10-08 DE DEB32922A patent/DE1001989B/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4130563A (en) | 1976-03-13 | 1978-12-19 | Bayer Aktiengesellschaft | Δ4-Oxazolin-2-ones and process therefor |
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