CS196686B1 - Process for preparing indanoles and homolges thereof - Google Patents
Process for preparing indanoles and homolges thereof Download PDFInfo
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- CS196686B1 CS196686B1 CS128877A CS128877A CS196686B1 CS 196686 B1 CS196686 B1 CS 196686B1 CS 128877 A CS128877 A CS 128877A CS 128877 A CS128877 A CS 128877A CS 196686 B1 CS196686 B1 CS 196686B1
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- Czechoslovakia
- Prior art keywords
- methyl
- indanol
- catalyst
- gas
- weight
- Prior art date
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- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 238000000034 method Methods 0.000 claims description 11
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- XEZMWIFCFZCFPJ-UHFFFAOYSA-N 2-hydroxy-2,3-dihydroinden-1-one Chemical class C1=CC=C2C(=O)C(O)CC2=C1 XEZMWIFCFZCFPJ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- YIAPLDFPUUJILH-UHFFFAOYSA-N indan-1-ol Chemical class C1=CC=C2C(O)CCC2=C1 YIAPLDFPUUJILH-UHFFFAOYSA-N 0.000 claims description 3
- 150000002475 indoles Chemical class 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims 3
- 230000008018 melting Effects 0.000 claims 3
- UGAKSUDKRHFNQW-UHFFFAOYSA-N 5-methyl-2,3-dihydro-1h-inden-4-ol Chemical compound CC1=CC=C2CCCC2=C1O UGAKSUDKRHFNQW-UHFFFAOYSA-N 0.000 claims 2
- ZYSDYEFSMQZMQA-UHFFFAOYSA-N 6-methyl-2,3-dihydro-1h-inden-4-ol Chemical compound OC1=CC(C)=CC2=C1CCC2 ZYSDYEFSMQZMQA-UHFFFAOYSA-N 0.000 claims 2
- XHMLXYGITDAGDN-UHFFFAOYSA-N 7-methyl-2,3-dihydro-1h-inden-4-ol Chemical compound CC1=CC=C(O)C2=C1CCC2 XHMLXYGITDAGDN-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000000203 mixture Substances 0.000 claims 2
- 229920013636 polyphenyl ether polymer Polymers 0.000 claims 2
- 239000011541 reaction mixture Substances 0.000 claims 2
- ARYNNMVDWALCPX-UHFFFAOYSA-N 1-methyl-2,3-dihydroinden-1-ol Chemical class C1=CC=C2C(C)(O)CCC2=C1 ARYNNMVDWALCPX-UHFFFAOYSA-N 0.000 claims 1
- AJZJWTXGQXUPNB-UHFFFAOYSA-N 2-methyl-2,3-dihydro-1h-inden-4-ol Chemical compound C1=CC(O)=C2CC(C)CC2=C1 AJZJWTXGQXUPNB-UHFFFAOYSA-N 0.000 claims 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 claims 1
- 238000009835 boiling Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 238000004821 distillation Methods 0.000 claims 1
- 238000004817 gas chromatography Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 239000003921 oil Substances 0.000 claims 1
- 239000012188 paraffin wax Substances 0.000 claims 1
- 239000003208 petroleum Substances 0.000 claims 1
- 238000003822 preparative gas chromatography Methods 0.000 claims 1
- 238000010183 spectrum analysis Methods 0.000 claims 1
- 101150035983 str1 gene Proteins 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic hydroxyketones Chemical class 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- GQUURXIPNRUAQK-UHFFFAOYSA-N 2-hydroxy-2-methyl-3h-inden-1-one Chemical class C1=CC=C2C(=O)C(C)(O)CC2=C1 GQUURXIPNRUAQK-UHFFFAOYSA-N 0.000 description 1
- 238000006214 Clemmensen reduction reaction Methods 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical class 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N indan-1-one Chemical class C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
československá socialistická REPUBLIKA (19) POPIS VYNÁLEZU 196686 (11) (Bl) K AUTORSKÉMU OSVĚDČENÍ (51) Int. Cl.3 C 07 C 39/225 Uf (22) Přihlášeno 28 02 77(21) (PV 1288-77) (40) Zveřejněno 31 07 79 · ÚŘAD RROVYNALEZY A OBJEVY (45) Vydáno 15 07 81 (75) · z.-Czechoslovak Socialist Republic (19) DESCRIPTION OF THE INVENTION 196686 (11) (Bl) TO COPYRIGHT CERTIFICATE (51) Int. Cl.3 C 07 C 39/225 Uf (22) Registered 28 02 77 (21) (PV 1288-77) (40) Published 31 07 79 · RROVYNALEZ AND OFFICE OFFICE (45) Issued 15 07 81 (75) · of .-
Autor vynálezu BURYAN PETR ing. CSc., a MACÁK JIŘÍ prof. ing. DrSc., PRAHA (54) Způsob výroby butanolů a jejich liomolopůAuthor of the invention BURYAN PETR ing. CSc., And MACÁK JIŘÍ prof. DrSc., PRAGUE (54) Method of production of butanols and their liomolopes
Vynález se týká způsobu výroby indanolů a jejichliomologů. Syntéza hydroxysubstituováných aro-matických systémů mono- nebo polytopicky sub-stituovaných alkyly je prováděna často přes mezi-produkty, zahrnující ve své molekule «-karbony -lovou skupinu. Jedná se především o aromatickéhydroxyketony, ale také o hydroxyaldehydy a aro-matické hydroxykarboxylové kyseliny.BACKGROUND OF THE INVENTION The present invention relates to a process for the production of indoles and their malliomologists. The synthesis of hydroxy-substituted aromatic systems of mono- or polytopically substituted alkyls is often carried out via inter-products, including in the molecule a -carbonyl group. These are mainly aromatic hydroxyketones, but also hydroxyaldehydes and aromatic hydroxycarboxylic acids.
Tyto meziprodukty je nutné redukovat selektiv-ně, přičemž je nahrazována karbonylová skupinaskupinou methylenovou. Tento stupeň syntézylze provádět různě výhodnými cestami. Při přípravě indanolů z odpovídajících indanonů ,bylo až dosud nutné používat časově náročnýcha pracných metod klasické preparace napříkladClemmensenovy redukce, nebo redukční metodyWolf-Kižněrovy.These intermediates need to be selectively reduced while being replaced by a carbonyl group with methylene. It is possible to carry out this synthesis step in different ways. In the preparation of indanol from the corresponding indanones, it has so far been necessary to use time-consuming and laborious methods of classical preparation, for example, Clemmensen reduction, or reduction methods of Wolf-Kizhnev.
Proto byla pro tento účel vyzkoušena již dřívepopsaná metoda katalytické hydrogenace a re-dukce α-karbonylové skupiny plynným vodíkemv rotačním autoklávu za tlaku. Katalyzátorembyl sirník molybdeničitý.Therefore, a previously described method of catalytic hydrogenation and reduction of the α-carbonyl group with hydrogen gas in a rotary autoclave under pressure was tested. The catalyst was molybdenum disulfide.
Podstata způsobu výroby indanolů a jejichhomologů spočívá v tom, že se na hydroxyindanonypůsobí plynným vodíkem za teploty 100 až 300 °Ca tlaku 5 až 25 MPa a za katalytického působenísirníku molybdeničitého, načež se po provedenéhydrogenaci indanoly od katalyzátoru odfiltrují.The principle of the process for the production of indoles and their homologues is that the hydroxyindanone is treated with hydrogen gas at a temperature of 100 to 300 ° C and a pressure of 5 to 25 MPa and a catalytic action of molybdenum disulphide, whereupon the indanols are filtered off from the catalyst after the hydrogenation.
Je výhodné, provádí-li se hydrogenace v pro-středí organického rozpouštědla, které usnadňujezpracování produktu i průběh hydrogenace, zejmé-na při přípravě menšího množství látky.It is advantageous to carry out the hydrogenation in the medium of an organic solvent, which facilitates the treatment of the product and the course of the hydrogenation, in particular in the preparation of a smaller amount of the substance.
Použití katalytické hydrogenace na sirníku mo-lybdeničitém v porovnání s klasickými způsobyredukce umožňuje podstatné zkrácení reakční doby(z několika hodin na několik minut) při zachovánínebo zlepšení reakčních výtěžků a při vyšší indi-vidualitě produktu.The use of catalytic hydrogenation on polybdenum sulfide compared to conventional reduction methods allows a substantial reduction in reaction time (from several hours to several minutes) while maintaining or improving reaction yields and at higher product individuality.
Postup přípravy podle vynálezu je v dalšímblíže popsán na příkladu provedení. Příklad V první fázi se připraví «-brompropionylbromidpodle rovnic: 4 CH3CH2COOH + 5/2 Br2 + P = 4 CH8CH2COBr ++ P0(0H)3 + HBr (1), CH3CH2COBr + Br2 = CH3CHBrCOBr + HBr (2) Dále následuje esterifikace o-, m-, a p-kresolu«-brompropionylbromidem. Z připravených esterůse katalytickým účinkem A1C13 připraví methyl-hydr oxyindanony.The preparation process according to the invention is described in the following with reference to an exemplary embodiment. Example In the first phase, «-bromopropionyl bromide is prepared according to equations: 4 CH 3 CH 2 COOH + 5/2 Br 2 + P = 4 CH 8 CH 2 COBr ++ P 0 (OH) 3 + HBr (1), CH 3 CH 2 COBr + Br 2 = CH 3 CHBrCOBr + HBr (2) Next followed by esterification of -, m-, and p-cresol with -bromopropionyl bromide. From the prepared esters, the methylhydroxyindanones are prepared by the catalytic action of AlCl 3.
Redukce karbonylové skupiny hydroxyindanonů se provedou v rotačním autoklávu plynným vo- díkem v prostředí cyklohexanu za katalytického působení sirníku molybdeničitého. Počáteční tlak 1 H « # 6The reduction of the carbonyl group of the hydroxyindanones is carried out in a rotary autoclave with gaseous water in a cyclohexane environment under the catalytic action of molybdenum disulfide. Initial Pressure 1 H «# 6
Claims (2)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS128877A CS196686B1 (en) | 1977-02-28 | 1977-02-28 | Process for preparing indanoles and homolges thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS128877A CS196686B1 (en) | 1977-02-28 | 1977-02-28 | Process for preparing indanoles and homolges thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS196686B1 true CS196686B1 (en) | 1980-03-31 |
Family
ID=5346893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS128877A CS196686B1 (en) | 1977-02-28 | 1977-02-28 | Process for preparing indanoles and homolges thereof |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS196686B1 (en) |
-
1977
- 1977-02-28 CS CS128877A patent/CS196686B1/en unknown
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