CS240706B1 - Method of cinnamaldehyde production - Google Patents
Method of cinnamaldehyde production Download PDFInfo
- Publication number
- CS240706B1 CS240706B1 CS845411A CS541184A CS240706B1 CS 240706 B1 CS240706 B1 CS 240706B1 CS 845411 A CS845411 A CS 845411A CS 541184 A CS541184 A CS 541184A CS 240706 B1 CS240706 B1 CS 240706B1
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- Czechoslovakia
- Prior art keywords
- mol
- parts
- cinnamic aldehyde
- alkali metal
- mixture
- Prior art date
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- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 title claims description 12
- 229940117916 cinnamic aldehyde Drugs 0.000 title claims description 12
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 title claims description 12
- 238000000034 method Methods 0.000 title claims description 6
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 5
- 241000723347 Cinnamomum Species 0.000 description 4
- 235000017803 cinnamon Nutrition 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 150000001299 aldehydes Chemical class 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 238000005882 aldol condensation reaction Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000007342 radical addition reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Description
Vynález se týká způsobu výroby skořicového aldehydu. ...The invention relates to a process for the production of cinnamon aldehyde. ...
Skořicový 'aldehyd: (3-fenyb2-ppoppn'al) je jednou z významných Surovin kosmetického průmyslu. Nejpoužívanéjší· metodou· výroby skořicového aldehydu je alďolóvá kondenzace benzaldehydu s acetaldehydem- (Kirk----Othmer: Encyclopedia of Chemical Technology, sv. 5, str. 520). Skořicový aldehyd lze rovněž získat s nízkým výtěžkem (45 %) z l,l,3-tnchlor-3-fenyLaropa'nu účinkem ethoxidu sodného - (J. Chem. Soc. 1963, 3 921).Cinnamon aldehyde : (3-phenylbiphenyl) is one of the major raw materials of the cosmetic industry. The most commonly used method of making cinnamon aldehyde is the aldol condensation of benzaldehyde with acetaldehyde (Kirk ---- Othmer: Encyclopedia of Chemical Technology, vol. 5, p. 520). Cinnamic aldehyde can also be obtained with a low yield (45%) of 1,3,3-chloro-3-phenylcaropaine by the action of sodium ethoxide (J. Chem. Soc. 1963, 3 921).
Účinnějším způsobem výroby skořicového aadehydu poskytujícím výtěžky přes 90 % je přeměna l,l,3-trichlor'-3-fenз-yooyanu bud současnou katalytickou ee3yeroch-ooací a hydrolýzou (čs. autorské osvědčení č. 226 991) .nebo následnou alkalickou dehзdonc3lnoací a hydrolýzou (čs. autorské osvědčení č. 226 995); l,l,3-trichlor-3-lenз-propan je snadno dostupný katalytickou radikálovou adicí chloroformu na styren (čs. autorské osvědčení č. 236 974].A more efficient way to produce cinnamon aadehyde yielding over 90% yields is to convert 1,1,3-trichloro-3-phenol-yoyan by either catalytic catalytic hydrolysis and hydrolysis (U.S. Pat. No. 226,991) or subsequent alkaline dehydrogenation. hydrolysis (cf. No. 226 995); 1,1,3-trichloro-3-lenzepropane is readily available by catalytic radical addition of chloroform to styrene (US Patent No. 236,974).
Podstatou vynálezu je způsob výroby skořicového aldehydu z lJ.S-trichlór-S-fenýlpropanu spočívající v tom, že se nechá' όβgovat : díl mol. l,l,3-trichlor-3-l:enз-yoopanu, 2 až 10 dílů mol. methanolu nebo ethanolu, 2 až 4 díly mol. hydroxidu alkalického kovu a : až 20 dílů mol. vody nebo 4 až 20 dílů 20 až 50% vodného roztoku hydroxidu alkalického kovu bud najednou nebo jedna až dvě komponenty se přidávají postuphě, přičemž vzniklá směs se zahřívá při teplotě 65 až 120 °C a 'potom se přímo, nebo po oddělení vodné vrstvy anorganickou kyselinou upraví pH na hodnotu 1 až 7, směs se zahřívá k varu dokud se uvolňuje chlorovodík a vzniklý skořicový aldehyd se izoluje.SUMMARY OF THE INVENTION The present invention provides a process for the production of cinnamic aldehyde from 1S, 5-trichloro-S-phenylpropane, which comprises allowing a portion of mol. 1,1,3-trichloro-3-eno-yoopane, 2 to 10 parts by mol. methanol or ethanol, 2-4 parts by mol. alkali metal hydroxide and: up to 20 parts mol. water or 4 to 20 parts of a 20 to 50% aqueous alkali metal hydroxide solution at once or one or two components are added sequentially, the resulting mixture is heated at 65 to 120 ° C and then directly or after separation of the aqueous layer by inorganic the mixture is heated to boiling until the hydrogen chloride is released and the resulting cinnamic aldehyde is isolated.
Výhodou způsobu výroby skořicového - aldehydu podle vynálezu je jednodušší a ekonomicky výhodnější provedení, přičemž rektifikací se získá -skořicový aldehyd o čistotě až 100 %.An advantage of the process of making the cinnamic aldehyde according to the invention is a simpler and more economical embodiment, whereby rectification yields a cinnamic aldehyde having a purity of up to 100%.
Dále uvedené příklady demonstrují způsob výroby skořicového aldehydu podle vynálezu, -aniž by omezovaly nebo vymezovaly rozsah jeho platnosti.The examples below illustrate the process for making cinnamic aldehyde of the invention without limiting or limiting its scope.
•Příklad 1• Example 1
Do skleněné baňky opatřené -zpětným chladičem a míchadlem- se vsadí 67,0 g- - (0-,3 mol) l,l,3-triChlnr-3-feny·lpoóyáηu a 76 ml (1,85 mol) methanolu, po vyhřátí’ _ rea'kční směsi k varu se postupně během, í hodiny přidáš'- g- (0;75 mol) 50% vodnélio' roztoku hydroxidu draselného a v zahřívání k varu se -pokračuje 8 hodin. Potom se k reakční směsí přidá 160 ml zředěné 5% kyseliny chlorovodíkové a nedestiluje se' methanoí. Směs se -ochladí, organická vrstva' se Oddělí a promyje vodou. Destilací· zá snížéného tlaku se získá 36,9 g (93 % teorie) skořicového aldehydu o· t. v. 116 °C/1,47 kPa o čistotě 98,1 %. ·In a glass flask equipped with a reflux condenser and stirrer was charged 67.0 g of - (0-, 3 mol) 1,1,3-tri-chloro-3-phenylpolyol and 76 ml (1.85 mol) of methanol. heating the reaction mixture to boiling is gradually added over a period of 1 h. g (0.75 mol) of a 50% aqueous potassium hydroxide solution is continued for 8 hours while heating to boiling. Thereafter, 160 ml of dilute 5% hydrochloric acid was added to the reaction mixture, and the methanol was not distilled. The mixture was cooled, the organic layer was separated and washed with water. Distillation under reduced pressure yielded 36.9 g (93% of theory) of cinnamic aldehyde, m.p. 116 DEG C./15 mbar, 98.1% purity. ·
Příklad 2Example 2
Do skleněné baňky opatřené chladičem a míchadlem se vloží 67,0 [0,3 mol)’ 1,:^,í^bťr1c3lor-3-fenylyroyanu a 75 ml (1,281 m’ol) ethanolu, po vyhřátí reakční směsi k varu- se postupně během 1 hodiny přidá 90 g (0,9 mol) 40% vodného roztoku hydroxidu sodného a v zahřívání k varu se pokračuj# 3 hodiny. Po' ochlazení' se reakční - směs zňeutóalizuje zředěnou kyselinou chlorovodíkovou na pH 7, oddestiluje ethanol, organická vrstva se oddělí a smísí se 100 -ml 0,4% kyseliny chlorovodíkové a zahřívá se k varu 2,5 h.A glass flask equipped with a condenser and a stirrer was charged with 67.0 [0.3 mol) '1 ^, I ^ b ťr1c3lor 3-fenylyroyanu and 75 ml (1.281 m'ol) ethanol after heating the reaction mixture to varu- 90 g (0.9 mol) of a 40% aqueous solution of sodium hydroxide are gradually added over 1 hour and heating is continued for 3 hours. After 'cooling', the reaction mixture is neutralized with dilute hydrochloric acid to pH 7, ethanol is distilled off, the organic layer is separated and mixed with 100 ml of 0.4% hydrochloric acid and heated to boiling for 2.5 h.
Směs se ochladí, organická vrstva se oddělí, promyje vodou a destiluje za sníženého - tlaku, čímž se izoluje: 36,5 g (92 % teorie) skořicového aldehydu o t. v. 122 °C na 1,7 kPa a čistotě 97,7 %.The mixture is cooled, the organic layer is separated, washed with water and distilled under reduced pressure to isolate: 36.5 g (92% of theory) of cinnamic aldehyde, m.p. 122 DEG C. at 1.7 kPa and a purity of 97.7%.
P ř í k 1 a d 3Example 1 a d 3
Do -skleněné baňky opatřené - . chladičem a míchadlem se vs-adí 720 ml (.40’ mol) vody, 432 g- (10,8 mol) hydroxidu sodného- -á 8ŮÍ5 gramů (3,6 mol) l,l,3-trichϊόг-3-fenylpy'opanu, po vyhřátí ná 78 °G- se postupně _ během 4 hodin -přidává- 1 800 ml (30,8’ moí) - etfiánolu a v zahřívání se pokračuje ještě 0,5 hodiny. Potom se přidá- k reakční směsí 330 mililitrů 30% kyseliny chlorovodíkové a oddestiluje se ethanol. Směs se ochladí, organická vrstva se oddělí a promyje vodou,, načež se destilací za sníženého tlaku izolufe 476 g (91 % teorie)- skořicového aldehydu o t. v. 127 °C/2,1 kPa a čistotě 96,0 %.Into a glass flask fitted with. 720 ml (40 moles) of water, 432 g (10.8 moles) of sodium hydroxide and 8.5 g (3.6 moles) of 1,1,3-trichloro-3-phenylpyride are charged with a condenser and stirrer. After heating to 78 [deg.] C., 1800 ml (30.8 mol) of ethanesium is added gradually over 4 hours and heating is continued for 0.5 hours. Then, 330 ml of 30% hydrochloric acid are added to the reaction mixture, and ethanol is distilled off. The mixture was cooled, the organic layer was separated and washed with water, and then 476 g (91% of theory) of cinnamic aldehyde, m.p.
Claims (1)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS845411A CS240706B1 (en) | 1984-07-12 | 1984-07-12 | Method of cinnamaldehyde production |
| DD27769385A DD255045A3 (en) | 1984-07-12 | 1985-06-25 | PROCESS FOR THE PREPARATION OF CINNAMENTALDEHYDE |
| BG7083985A BG46524A1 (en) | 1984-07-12 | 1985-06-25 | Method for preparing of cinnamon aldehyde |
| SU857773898A SU1451139A1 (en) | 1984-07-12 | 1985-07-03 | Method of producing cinnamaldehyde |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CS845411A CS240706B1 (en) | 1984-07-12 | 1984-07-12 | Method of cinnamaldehyde production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CS541184A1 CS541184A1 (en) | 1985-07-16 |
| CS240706B1 true CS240706B1 (en) | 1986-02-13 |
Family
ID=5398960
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CS845411A CS240706B1 (en) | 1984-07-12 | 1984-07-12 | Method of cinnamaldehyde production |
Country Status (4)
| Country | Link |
|---|---|
| BG (1) | BG46524A1 (en) |
| CS (1) | CS240706B1 (en) |
| DD (1) | DD255045A3 (en) |
| SU (1) | SU1451139A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6566557B2 (en) * | 2001-03-14 | 2003-05-20 | Council Of Scientific And Industrial Research | Process for the preparation of substituted trans-cinnamaldehyde, a natural yellow dye, from phenylpropane derivatives |
| FR2822473B1 (en) * | 2001-03-23 | 2005-02-18 | Council Scient Ind Res | PROCESS FOR PREPARING SUBSTITUTED NATURAL TRANS-CINNAMALDEHYDE YELLOW DYE FROM PHENYLPROPANE DERIVATIVES |
-
1984
- 1984-07-12 CS CS845411A patent/CS240706B1/en unknown
-
1985
- 1985-06-25 DD DD27769385A patent/DD255045A3/en not_active IP Right Cessation
- 1985-06-25 BG BG7083985A patent/BG46524A1/en unknown
- 1985-07-03 SU SU857773898A patent/SU1451139A1/en active
Also Published As
| Publication number | Publication date |
|---|---|
| SU1451139A1 (en) | 1989-01-15 |
| CS541184A1 (en) | 1985-07-16 |
| DD255045A3 (en) | 1988-03-23 |
| BG46524A1 (en) | 1990-01-15 |
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