FI92054B - Process for the preparation of 3- (o-methoxyphenoxy) -1,2-propanediol-1-carbamate - Google Patents
Process for the preparation of 3- (o-methoxyphenoxy) -1,2-propanediol-1-carbamate Download PDFInfo
- Publication number
- FI92054B FI92054B FI891068A FI891068A FI92054B FI 92054 B FI92054 B FI 92054B FI 891068 A FI891068 A FI 891068A FI 891068 A FI891068 A FI 891068A FI 92054 B FI92054 B FI 92054B
- Authority
- FI
- Finland
- Prior art keywords
- methoxyphenoxy
- methyl
- methoxyphenyl
- propanediol
- dioxolane
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Epoxy Compounds (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
9205492054
Menetelmä 3-(o-metoksifenoksi)-1,2-propaanidioli-l-kar- bamaatin valmistamiseksi - Förfarande för framställning av 3- (o-metoxifenoxi)-1,2-propandiol-l-karbamat r 5 Keksinnön kohteena on entistä parempi menetelmä 3-(o-metoksifenoksi) -1,2-propaanidioli-l-karbamaatin valmistamiseksi muodostamalla propyyliryhmän 2,3-asemassa substituoidusta propyyli (o-metoksifenyyli)eetteristä inertissä liuottimessa 4-t (o-metoksifenoksi)-metyyli]-2-okso-dioksolaania, joka 10 lohkaistaan ammoniakilla.The invention relates to a process for the preparation of 3- (o-methoxyphenoxy) -1,2-propanediol-1-carbamate - for the preparation of 3- (o-methoxyphenoxy) -1,2-propanediol-1-carbamate Process for the preparation of 3- (o-methoxyphenoxy) -1,2-propanediol-1-carbamate by formation of a propyl group from a 2,3-substituted propyl (o-methoxyphenyl) ether in an inert solvent 4-t (o-methoxyphenoxy) methyl] -2- oxo-dioxolane, which is cleaved with ammonia.
Metokarbamolia tiedetään voitavan valmistaa siten, että guajakoli saatetaan reagoimaan 3-kloori-l,2-propaanidiolin kanssa, reaktiotuotteessa vaihdetaan pääteaseman OH-ryhmät 15 klooriin fosgeenin vaikutuksen avulla ja kloorijohdos saatetaan reagoimaan ammoniakin kanssa (A. Kleemann, Pharmz. Wirkstoffe, 2. painos 81982), s. 578; US-PS 2 770 649).Methocarbamol is known to be prepared by reacting guaiacol with 3-chloro-1,2-propanediol, converting the OH groups of the terminal product to chlorine by the action of phosgene, and reacting the chlorine derivative with ammonia (A. Kleemann, Pharmz. Wirkstoffe, 2nd ed. 81982), pp. 578; US-PS 2,770,649).
Saanto ei ole täysin tyydyttävä. f 20The yield is not entirely satisfactory. f 20
Nyttemmin on havaittu, että metokarbamolin synteesi voidaan edullisesti suorittaa seuraavan reaktiokaavion mukaisesti 1 ochj 25 °ch3 Ϊ : 0-°» * —V»· — Οτ°Ηιν" (I) (ID (III) 30 OCH, 2. ϊIt has now been found that the synthesis of methocarbamol can advantageously be carried out according to the following reaction scheme: 1-h 25 ° ch3 Ϊ: 0- ° »* —V» · - Οτ ° Ηιν "(I) (ID (III) 30 OCH, 2. ϊ
co. /Vc/o. / V
('s' OCHj-HC — CH,('s' OCHj-HC - CH,
' 111 -► I A A'111 -► I A A
Dabco \ /Dabco \ /
s Cs C
‘ II‘II
o 35 (IV) 92054 2 OCH, “» X.o 35 (IV) 92054 2 OCH, “» X.
>-OCH, — CH- CH, - O · CONH, 3- IV -* 'm (metokarbamoli)> -OCH, - CH- CH, - O · CONH, 3- IV - * 'm (methocarbamol)
Vaiheen 1 reaktio onnistuu hyvällä saannolla, kun yhdisteen I ja II annetaan reagoida vesipitoisessa alkalihydroksidi-10 liuoksessa (alkalihydroksidin ja guajakolin moolisuhde noin 1:1, epikloorihydriiniä ylimäärä) lisäämällä pieni määrä bentsyylitrietyyliammoniumkloridia. Tuloksena oleva 2,3-epoksipropyyli-2-metoksifenyylieetteri, sp. 31 - 33°C, voidaan saada hyvällä saannolla fraktiotislaamalla alipai-15 neessa.The reaction of Step 1 is accomplished in good yield when the compounds I and II are reacted in aqueous alkali hydroxide-10 solution (molar ratio of alkali hydroxide to guaiacol about 1: 1, excess epichlorohydrin) by adding a small amount of benzyltriethylammonium chloride. The resulting 2,3-epoxypropyl-2-methoxyphenyl ether, m.p. 31-33 ° C, can be obtained in good yield by fractional distillation under reduced pressure.
Nyt on havaittu, että saattamalla saatu yhdiste reagoimaan hiilidioksidin kanssa korotetussa paineessa ja korotetussa lämpötilassa katalyyttisen määrän 1,4-diatsabisyklo[2.2.2]-20 oktaania (Dabco) läsnäollessa pienessä määrässä inerttiä liuotinta, esimerkiksi tolueenia, saadaan 4-[(o-metoksi-fenoksi)-metyyli]-2-oksodioksolonia hyvällä saannolla, kun käytetään 400 - 1000 kPa C02-painetta ja lämpötilaa 110 - 160°C. mieluummin 120 - 140°C. Reaktio sujuu suhteel-25 lisen hitaasti. Sen jälkeen, kun hiilidioksidia on reagoi-• nut lähes teoreettinen määrä, lopetetaan reaktio.It has now been found that reacting the resulting compound with carbon dioxide under elevated pressure and elevated temperature in the presence of a catalytic amount of 1,4-diazabicyclo [2.2.2] -20 octane (Dabco) in a small amount of an inert solvent, e.g. toluene, gives 4 - [(o- methoxy-phenoxy) -methyl] -2-oxodioxolone in good yield when a CO2 pressure of 400 to 1000 kPa and a temperature of 110 to 160 ° C are used. preferably 120-140 ° C. The reaction proceeds relatively slowly. After almost a theoretical amount of carbon dioxide has reacted, the reaction is stopped.
4-[o-metoksifenoksi]-metyyli]-2-oksodioksolaanin lohkaisu suoritetaan ilman välierotusta 26°C:ssa, edullisesti käyt-30 tämällä kaasumaista tai nestemäistä ammoniakkia.The cleavage of 4- [o-methoxyphenoxy] methyl] -2-oxodioxolane is carried out without intermediate separation at 26 ° C, preferably using gaseous or liquid ammonia.
Esimerkki .Example.
a) 2,3-epoksipropyyli-2-metoksifenyylieetteri : 35(a) 2,3-epoxypropyl-2-methoxyphenyl ether: 35
Liuos, joka sisältää 200 g (5 moolia) natriumhydroksidia 200 ml:ssa vettä, jäähdytetään 10°C:een. 10 minuutin ku- 3 92054 luessa lisätään seos, jossa on 1300 g (14 moolia) epikloo-rihydriiniä, 620,7 g (5 moolia) guajakolia ja 6,3 g (0,028 moolia) bentsyylitrietyyliammoniumkloridia. Lämpötila nousee 80°C:een ja pidetään tämän jälkeen tunnin ajan 5 65°C:ssa. Huoneen lämpötilaan jäähdyttämisen jälkeen lisä tään 100 ml dikloorimetaania ja saostunut natriumkloridi erotetaan imun avulla. Pestään kaksi kertaa 100 ml:11a dikloorimetaania ja orgaaninen faasi haihdutetaan alipaineessa (2,5 kPa) ja 70°C haudelämpötilassa. Jäljelle jäänyt 10 oranssin värinen öljy fraktioidaan 3 kPa paineessa ja 110°C:ssa, jolloin saadaan 633,6 g (70,3 %) otsikkoyhdis-tettä, sp. 31 - 33°C.A solution of 200 g (5 moles) of sodium hydroxide in 200 ml of water is cooled to 10 ° C. After 10 minutes, a mixture of 1300 g (14 moles) of epichlorohydrin, 620.7 g (5 moles) of guaiacol and 6.3 g (0.028 moles) of benzyltriethylammonium chloride is added. The temperature rises to 80 ° C and is then maintained at 65 ° C for one hour. After cooling to room temperature, 100 ml of dichloromethane are added and the precipitated sodium chloride is filtered off with suction. Wash twice with 100 ml of dichloromethane and evaporate the organic phase under reduced pressure (2.5 kPa) and at a bath temperature of 70 ° C. The residual orange oil is fractionated at 3 kPa and 110 ° C to give 633.6 g (70.3%) of the title compound, m.p. 31-33 ° C.
b) 3-(o-metoksifenoksi)-1,2-propaanidioli-l-karbamaatti 15 540,7 g (3 moolia) kohdan a) mukaisesti saatua yhdistettä ja 3,4 g (0,03 moolia) Dabco'a liuotetaan 125 ml:aan ksy-leeniä. Liuosta sekoitetaan 4 tuntia 130°C:ssa 650 kPa C02-paineessa ja sen jälkeen jäähdytetään 24°C:een. Lisä-20 tään 2012 ml tolueenia, minkä jälkeen seokseen lisätään nestemäistä ammoniakkia, jolloin otsikkoyhdiste alkaa kiteytyä. Tunnin kuluttua lisätään 200 ml isopropyylialkoholia, kidepuuro liuotetaan 70°C:ssa ja sen jälkeen jäähdytetään. Otsikkoyhdiste erotetaan imulla, pestään 300 ml :11a 25 tolueenia ja kuivataan.b) 3- (o-Methoxyphenoxy) -1,2-propanediol-1-carbamate 54040 g (3 moles) of the compound obtained in a) and 3.4 g (0.03 moles) of Dabco are dissolved in 125 ml of xylene. The solution is stirred for 4 hours at 130 ° C under a pressure of 650 kPa CO 2 and then cooled to 24 ° C. 2012 ml of toluene are added, followed by the addition of liquid ammonia, whereupon the title compound begins to crystallize. After 1 hour, 200 ml of isopropyl alcohol are added, the crystalline porridge is dissolved at 70 ° C and then cooled. The title compound is filtered off with suction, washed with 300 ml of toluene and dried.
• Saanto 674,8 (93 % teoreettisesta).• Yield 674.8 (93% of theory).
ff
Claims (1)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3807522 | 1988-03-08 | ||
DE19883807522 DE3807522C1 (en) | 1988-03-08 | 1988-03-08 |
Publications (4)
Publication Number | Publication Date |
---|---|
FI891068A0 FI891068A0 (en) | 1989-03-07 |
FI891068A FI891068A (en) | 1989-09-09 |
FI92054B true FI92054B (en) | 1994-06-15 |
FI92054C FI92054C (en) | 1994-09-26 |
Family
ID=6349127
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
FI891068A FI92054C (en) | 1988-03-08 | 1989-03-07 | Process for the preparation of 3- (o-methoxyphenoxy) -1,2-propanediol-1-carbamate |
Country Status (4)
Country | Link |
---|---|
DE (1) | DE3807522C1 (en) |
FI (1) | FI92054C (en) |
FR (1) | FR2628420B1 (en) |
GB (1) | GB2216520B (en) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5093456A (en) * | 1989-06-14 | 1992-03-03 | Minnesota Mining And Manufacturing Company | Monocarbamate diols, polymers derived from them and nlo-active materials therefrom |
WO1998051680A1 (en) * | 1997-05-12 | 1998-11-19 | Daiso Co., Ltd. | Process for producing 1,4-benzodioxane derivatives |
CN101838249B (en) * | 2010-03-19 | 2015-08-19 | 浙江华海药业股份有限公司 | A kind of method preparing high-purity guaiacol glycidyl ether |
CN106349112A (en) * | 2016-08-24 | 2017-01-25 | 浙江海洲制药有限公司 | Preparation method of methocarbamol beta isomer |
CN115043811A (en) * | 2022-06-10 | 2022-09-13 | 苏州敬业医药化工有限公司 | Preparation method of 4- [ (2-methoxyphenoxy) methyl ] -1, 3-dioxolane-2-one |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB861960A (en) * | 1957-01-22 | 1961-03-01 | A H Robins Company Ltd | Preparation of monocarbamates |
DE1249852B (en) * | 1964-10-07 | 1967-09-14 | Dr Christian Brunnengraber Che mische Fabrik &. Co mbH Lübeck | Process for the production of carbam acid esters from a glycermathers |
-
1988
- 1988-03-08 DE DE19883807522 patent/DE3807522C1/de not_active Expired
-
1989
- 1989-03-07 GB GB8905218A patent/GB2216520B/en not_active Expired - Fee Related
- 1989-03-07 FI FI891068A patent/FI92054C/en not_active IP Right Cessation
- 1989-03-07 FR FR8902977A patent/FR2628420B1/en not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
---|---|
GB2216520B (en) | 1991-06-26 |
GB2216520A (en) | 1989-10-11 |
FI891068A (en) | 1989-09-09 |
GB8905218D0 (en) | 1989-04-19 |
DE3807522C1 (en) | 1989-03-30 |
FI92054C (en) | 1994-09-26 |
FR2628420A1 (en) | 1989-09-15 |
FI891068A0 (en) | 1989-03-07 |
FR2628420B1 (en) | 1993-08-20 |
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Owner name: BOEHRINGER INGELHEIM KG |