CS198326B1 - Process for preparing cinnamylchloride - Google Patents
Process for preparing cinnamylchloride Download PDFInfo
- Publication number
- CS198326B1 CS198326B1 CS781578A CS781578A CS198326B1 CS 198326 B1 CS198326 B1 CS 198326B1 CS 781578 A CS781578 A CS 781578A CS 781578 A CS781578 A CS 781578A CS 198326 B1 CS198326 B1 CS 198326B1
- Authority
- CS
- Czechoslovakia
- Prior art keywords
- chloride
- phenyl
- cinnamyl
- cinnamylchloride
- preparing
- Prior art date
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- IWTYTFSSTWXZFU-QPJJXVBHSA-N [(e)-3-chloroprop-1-enyl]benzene Chemical compound ClC\C=C\C1=CC=CC=C1 IWTYTFSSTWXZFU-QPJJXVBHSA-N 0.000 title description 11
- 238000004519 manufacturing process Methods 0.000 title 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 235000019270 ammonium chloride Nutrition 0.000 description 5
- RCJRILMVFLGCJY-UHFFFAOYSA-N 4-phenyl-1,3-dioxane Chemical compound O1COCCC1C1=CC=CC=C1 RCJRILMVFLGCJY-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- UOUVTDNOZJGQGE-UHFFFAOYSA-N 3-chloro-3-phenylpropan-1-ol Chemical compound OCCC(Cl)C1=CC=CC=C1 UOUVTDNOZJGQGE-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000007265 chloromethylation reaction Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
Cinnamylchlorid se dosud připravoval především chlormethylací styrenu, jak je popsáno v práci O. Wichteríeho a J. Černého v Chem. listech 49, 1038 (1955) a v Collect. Czech. Chem. Comraun. 20, 1288 (1955). Postup je též popsán v čs. pat. č. 83721. jeho nevýhodou jsou nízké výtěžky cinnamylchloridu, neboť styren při reakci značně polymeruje.Cinnamyl chloride has so far been prepared primarily by chloromethylation of styrene, as described in O. Wichteríe and J. Černý in Chem. sheets 49, 1038 (1955) and in Collect. Czech. Chem. Comraun. 20, 1288 (1955). The procedure is also described in MS. U.S. Pat. No. 83721. its disadvantage is the low yields of cinnamyl chloride, since styrene is highly polymerized in the reaction.
Štěpením 4-fenyl-l,3-dioxanu kyselinou chlorovodíkovou vzniká podle práce N. V. Soryginy v Ž. Obšč. Chim. 26, 1460 (1955) 3-fenyl-3-chlor-l-propanol, jehož výtěžek je rovněž nízký.Cleavage of 4-phenyl-1,3-dioxane with hydrochloric acid results from the work of N.V. Sorygina in Ž. Obšč. Chim. 26, 1460 (1955), 3-phenyl-3-chloro-1-propanol, whose yield is also low.
Uvedené nevýhody jsou odstraněny postupem podle vynálezu, jehož podstata spočívá v tom, že se 4-fenyl-l,3-dioxan podrobí působení kyseliny chlorovodíkové za přítomnosti ve vodě rozpustných chloridů, jako chloridu amonného, chloridu vápenatého nebo chloridu zinečnatého, při teplotách 20 až 100 °C.These disadvantages are overcome by the process according to the invention, which comprises treating 4-phenyl-1,3-dioxane with hydrochloric acid in the presence of water-soluble chlorides, such as ammonium chloride, calcium chloride or zinc chloride, at temperatures of 20 to 20 ° C. Mp 100 ° C.
Účinek postupu podle vynálezu spočívá ve snadné dehydrataci primárně vzniklého 3-fenyl-3-chlor-l-propanolu na 3-fenyl-3-chlor-1-propen, který v daném prostředí rychle přesmykuje na l-fenyl-3-chlor-l-propen (cinnamylchlorid). Výtěžky tohoto postupu převyšují výtěžky cinnamylchloridu, jichž bylo dosaženo dosud známými postupy.The effect of the process according to the invention lies in the easy dehydration of the primarily formed 3-phenyl-3-chloro-1-propanol to 3-phenyl-3-chloro-1-propene, which rapidly switches to 1-phenyl-3-chloro-1 in the environment. -propene (cinnamyl chloride). The yields of this process exceed those of cinnamyl chloride obtained by known methods.
Způsob přípravy cinnamylchloridu podle vynálezu je zřejmý z následujících příkladů konkrétního provedení.The process for the preparation of cinnamyl chloride according to the invention is apparent from the following examples of a specific embodiment.
Příklad 1Example 1
Do 2 1 trojhrdlé baňky, opatřené míchadlem, teploměrem a zpětným chladičem bylo předloženo 160 ml vody, 107 g (2 mol) chloridu amonného, 300 ml (2 mol) 4-fenyl-l,3-dioxanu a 320 ml (3,84 mol) 37procentní kyseliny chlorovodíkové. Směs byla za míchání udržována po dobu 1 h. při teplotě 100 °C pomocí olejové lázně s regulovanou teplotou. Poté bylo vypnuto míchání a vrstvy byly za horka odsazeny. K organické vrstvě bylo znovu přidáno stejné množství kyseliny chlorovodíkové, chloridu amonného a vody a směs byla za míchání udržována při teplotě 100 °C další dvě hodiny. Po skončení reakce byla organická vrstva oddělena a zpracována destilací. Bylo získáno 206 g cinnamylchloridu (t.v. 114 až 120°C/l,8 kPa), což představuje 67,5procentní výtěžek na 4-fenyl-l,3-dioxan.A 2 L three-necked flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 160 mL of water, 107 g (2 mol) of ammonium chloride, 300 mL (2 mol) of 4-phenyl-1,3-dioxane and 320 mL (3.84) mol) of 37 percent hydrochloric acid. The mixture was kept under stirring for 1 h at 100 ° C using a temperature controlled oil bath. Stirring was then turned off and the layers were hot offset. An equal amount of hydrochloric acid, ammonium chloride and water were added to the organic layer again and the mixture was kept under stirring at 100 ° C for two hours. After completion of the reaction, the organic layer was separated and worked up by distillation. 206 g of cinnamyl chloride (bp 114-120 ° C / 1.8 kPa) were obtained, which represents a 67.5% yield on 4-phenyl-1,3-dioxane.
Příklad 2Example 2
Příprava cinnamylchloridu byla provedena stejným způsobem jako v příkladu 1, s tím rozdílem, že místo chloridu amonného byl použit chlorid vápenatý. Výtěžek cinnamylchloridu byl 55,4 °/o.The preparation of cinnamyl chloride was carried out in the same manner as in Example 1, except that calcium chloride was used instead of ammonium chloride. The yield of cinnamyl chloride was 55.4%.
Příklad 3Example 3
Příprava cinnamylchloridu byla provedena stejným způsobem jako v příkladu 1, s tím rozdílem, že místo chloridu amonného byl použit chlorid zinečnatý. Výtěžek cinnamylchloridu byl 35 O/o.The preparation of cinnamyl chloride was carried out in the same manner as in Example 1, except that zinc chloride was used instead of ammonium chloride. The yield of cinnamyl chloride was 35 O / o.
PŘEDMETSUBJECT
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS781578A CS198326B1 (en) | 1978-11-28 | 1978-11-28 | Process for preparing cinnamylchloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS781578A CS198326B1 (en) | 1978-11-28 | 1978-11-28 | Process for preparing cinnamylchloride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CS198326B1 true CS198326B1 (en) | 1980-06-30 |
Family
ID=5427973
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS781578A CS198326B1 (en) | 1978-11-28 | 1978-11-28 | Process for preparing cinnamylchloride |
Country Status (1)
| Country | Link |
|---|---|
| CS (1) | CS198326B1 (en) |
-
1978
- 1978-11-28 CS CS781578A patent/CS198326B1/en unknown
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