DK158837B - Fremgangsmaade til fremstilling af p-hydroxyphenylglycin. - Google Patents
Fremgangsmaade til fremstilling af p-hydroxyphenylglycin. Download PDFInfo
- Publication number
- DK158837B DK158837B DK311878A DK311878A DK158837B DK 158837 B DK158837 B DK 158837B DK 311878 A DK311878 A DK 311878A DK 311878 A DK311878 A DK 311878A DK 158837 B DK158837 B DK 158837B
- Authority
- DK
- Denmark
- Prior art keywords
- salt
- process according
- ammonia
- hydroxyphenylglycine
- acid
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 11
- LJCWONGJFPCTTL-UHFFFAOYSA-N 4-hydroxyphenylglycine Chemical compound OC(=O)C(N)C1=CC=C(O)C=C1 LJCWONGJFPCTTL-UHFFFAOYSA-N 0.000 claims description 8
- YHXHKYRQLYQUIH-UHFFFAOYSA-N 4-hydroxymandelic acid Chemical compound OC(=O)C(O)C1=CC=C(O)C=C1 YHXHKYRQLYQUIH-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 159000000021 acetate salts Chemical class 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- -1 alkali metal salt Chemical class 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims description 2
- 150000003863 ammonium salts Chemical class 0.000 claims 1
- HPQVZCCKGRTPLU-UHFFFAOYSA-M sodium;2-hydroxy-2-(4-hydroxyphenyl)acetate Chemical compound [Na+].[O-]C(=O)C(O)C1=CC=C(O)C=C1 HPQVZCCKGRTPLU-UHFFFAOYSA-M 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- OIKHYMJKSSAAPR-UHFFFAOYSA-M sodium;2-hydroxy-2-(4-hydroxyphenyl)acetate;hydrate Chemical compound O.[Na+].[O-]C(=O)C(O)C1=CC=C(O)C=C1 OIKHYMJKSSAAPR-UHFFFAOYSA-M 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- AYKYOOPFBCOXSL-UHFFFAOYSA-N (4-hydroxyphenyl)acetonitrile Chemical compound OC1=CC=C(CC#N)C=C1 AYKYOOPFBCOXSL-UHFFFAOYSA-N 0.000 description 1
- VGXPXHIRRYBSHZ-UHFFFAOYSA-N 2-amino-2-(4-hydroxyphenyl)acetic acid Chemical compound OC(=O)C(N)C1=CC=C(O)C=C1.OC(=O)C(N)C1=CC=C(O)C=C1 VGXPXHIRRYBSHZ-UHFFFAOYSA-N 0.000 description 1
- NGHVIOIJCVXTGV-ALEPSDHESA-N 6-aminopenicillanic acid Chemical compound [O-]C(=O)[C@H]1C(C)(C)S[C@@H]2[C@H]([NH3+])C(=O)N21 NGHVIOIJCVXTGV-ALEPSDHESA-N 0.000 description 1
- NGHVIOIJCVXTGV-UHFFFAOYSA-N 6beta-amino-penicillanic acid Natural products OC(=O)C1C(C)(C)SC2C(N)C(=O)N21 NGHVIOIJCVXTGV-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- LSQZJLSUYDQPKJ-NJBDSQKTSA-N amoxicillin Chemical compound C1([C@@H](N)C(=O)N[C@H]2[C@H]3SC([C@@H](N3C2=O)C(O)=O)(C)C)=CC=C(O)C=C1 LSQZJLSUYDQPKJ-NJBDSQKTSA-N 0.000 description 1
- 229960003022 amoxicillin Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- LSQZJLSUYDQPKJ-UHFFFAOYSA-N p-Hydroxyampicillin Natural products O=C1N2C(C(O)=O)C(C)(C)SC2C1NC(=O)C(N)C1=CC=C(O)C=C1 LSQZJLSUYDQPKJ-UHFFFAOYSA-N 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
- C07C227/06—Formation of amino groups in compounds containing carboxyl groups by addition or substitution reactions, without increasing the number of carbon atoms in the carbon skeleton of the acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/04—Formation of amino groups in compounds containing carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/34—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
- C07C229/36—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton containing six-membered aromatic rings with at least one amino group and one carboxyl group bound to the same carbon atom of the carbon skeleton
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
i
DK 158837 B
Den foreliggende opfindelse angår en særlig fremgangsmåde til fremstilling af p-hydroxyphenylglycin (2-amino-2-p-hydroxy-phenyleddikesyre).
5 Fra de britiske patentskrifter nr. 1.353.612 og nr. 1.371.896 er det kendt, at p-hydroxyphenylglycin kan opnås ved kondensation af phenol, glyoxylsyre og ammoniak. Mange eksempler på denne fremgangsmåde er beskrevet, men i ingen beskrivelse er der anført et højere udbytte end 50%. Dette arbejde er nu ble-10 vet gentaget, og det blev bekræftet, at det opnåede udbytte af p-hydroxyphenylglycin generelt er ca. 35%, og at dette udbytte ikke kan forøges væsentligt. For at opnå dette udbytte er et væsentligt overskud af phenol endvidere påkrævet. Det er anført i britisk patentskrift nr. 1.371.896, at glyoxylsyren til 15 at begynde med reagerer med ammoniakken, og at dette reaktionsprodukt derpå reagerer med phenolen.
I beskrivelsen til dansk patentansøgning nr. 2121/78 beskrives en hensigtsmæssig fremgangsmåde til opnåelse af p-hydroxyman-20 delsyre (2-hydroxy-2-p-hydroxyphenyleddikesyre) i form af dens faste natriumsalt. Dette salt kan let separeres fra organiske urenheder og kan opnås i højt udbytte.
Det har nu ifølge den foreliggende opfindelse vist sig, at na-2 5 triumsaltet kan omdannes ti 1 p-hydroxyphenyIglycin i højt udbytte og under foretrukne betingelser i et udbytte, som er større end 90%.
p-hydroxyglycin er et værdifuldt mellemprodukt til anvendelse 30 inden for den farmaceutiske industri. Det er anvendeligt til fremstilling af amoxycillin, som er dets amid med 6-amino-pe-nici1lansyre, og som beskrevet i britisk patentskrift nr. 1.576.332 er det også anvendeligt til fremstilling af p-hy-droxybenzylcyanid, hvis værdi eller betydning er omtalt i 35 nævnte britiske patentskrift.
Fremgangsmåden ifølge opfindelsen til fremstilling af p-hydroxyphenylglycin er ejendommelig ved, at p-hydroxymandelsyre
DK 158837 B
2 eller et salt deraf omsættes med ammoniak og/eller et salt deraf i et vandigt medium ved en temperatur fra 100°C til 135eC.
5 p-hydroxymandelsyren anvendes fortrinsvis som et alkalimetalsalt deraf, især natriumsaltet, og ammoniakken anvendes fortrinsvis som et syreadditions salt deraf, f.eks. et chlorid-, sulfat- eller acetatsalt. Det foretrækkes imidlertid, at nogen fri ammoniak er til stede, enten som sådan eller som følge af 10 hydrolyse af et salt med svag syre, såsom eddikesyre.
Omsætningen udføres hensigtsmæssigt i vandig opløsning ved en forøget temperatur, fortrinsvis i kogende vand ved 100°C eller endog ved en højere temperatur, f.eks. indtil 135eC, ved et 15 højere tryk end atmosfærisk tryk i en lukket beholder, f.eks. ved et tryk på indtil 1,76 kp/cm2.
Det hævdes, at det høje udbytte opnås som følge af, at under foretrukne betingelser, hvor såvel p-hydroxymandelsyre som 20 ammoniakken benyttes som salte deraf, men hvor nogen fri ammoniak er til stede, er den opløste koncentration i og pH-vær-dien af reaktionsmediet således, at det ønskede produkt er sparsomt opløseligt og derfor kontinuerligt udfældes fra medi et. Ligevægten for udvekslingsreaktionen mellem aminogrupper 25 og hydroxygrupper bliver derfor kontinuerligt forskudt i den ønskede retning.
Opfindelsen illustreres af de følgende eksempler.
30 Eksempel 1
En blanding af natrium-p-hydroxymandelatmonohydrat (10,6 g), ammoniumchlorid (5,35 g), koncentreret vandig ammoniumhy- droxidopiøsning (0,5 ml) og vand (10 ml) omrøres og opvarmes 35 under tilbagesvaling (indre temperatur 114eC) i 21 timer. Det faste produkt fælder kontinuerligt ud fra opløsningen i løbet af dette tidsrum. Vand (15 ml) tilsættes, og blandingen omrø- 3
DK 158837 B
res, køles og filtreres derpå. Den faste rest vaskes tre gange med vand (2 ml hver gang) og derpå rigeligt med acetone. Der opnås således p-hydroxyphenylglycin (6,91 g, 83% udbytte) med smeltepunkt 225-227°C under dekomponering. Ved hjælp af et 5 forsøg med vandig sølvnitratopløsning viser det sig, at produktet er fri for forurening med ammoniumchlorid.
Kombinationen af filtrat og vandige vaskevæsker inddampes til 17 ml, koncentreret vandig ammoniumhydroxidopløsning (0,25 ml) 10 tilsættes, og blandingen omrøres og opvarmes under tilbagesvaling i 20 timer. Blandingen fortyndes med vand (13 ml), køles, indstilles til pH 5 med eddikesyre og filtreres derpå. Den faste rest vaskes to gange med vand (2 ml hver gang) og derpå rigeligt med acetone, og der opnås således yderligere 0,66 g 15 p-hydroxyphenylglycin, hvilket bringer det totale udbytte op på 91%.
Eksempel 2 20 En blanding af natrium-p-hydroxymandelatmonohydrat (1,04 g), ammoniumacetat (2,0 g) og vand (0,5 ml) omrøres og opvarmes under tilbagesvaling (indre temperatur 125“C) i 1\ time. Vand (3 ml) sættes til den således opnåede tyktflydende opslæmning, blandingen køles og filtreres, og den faste rest vaskes to 25 gange med vand og derpå med acetone. Der opnås således p-hydroxyphenylglycin (0,56 g, 66% udbytte).
Eksempel 3 30 En blanding af natrium-p-hydroxymandelatmonohydrat (2,08 g), ammoniumsulfat (13,2 g), koncentreret vandig ammoniumhydroxidopløsning (1 ml) og vand (15 ml) omrøres og opvarmes under tilbagesvaling (indre temperatur 1030 C) i 30 timer. Vand (10 ml) sættes til den således opnåede tyktflydende, varme opslæm-35 ning, og blandingen køles derefter og filtreres. Den faste rest vaskes med vand og acetone, og der opnås således p-hydroxyphenylglycin (1,08 g, 65% udbytte).
Claims (9)
15 Patentkrav.
1. Fremgangsmåde til fremstilling af p-hydroxyphenylglycin, kendetegnet ved, at p-hydroxymandelsyre eller et 20 salt deraf omsættes med ammoniak og/eller et salt deraf i et vandigt medium ved en temperatur fra 100°C til 135°C.
2. Fremgangsmåde ifølge krav 1, kendetegnet ved, at p-hydroxymandelsyren anvendes som et alkalimetalsalt deraf. 25
3. Fremgangsmåde ifølge krav 2, kendetegnet ved, at saltet er natriumsaltet.
4. Fremgangsmåde ifølge ethvert af kravene 1-3, kende-30 tegnet ved, at ammoniakken hovedsagelig anvendes som et syreadditionssalt deraf.
5. Fremgangsmåde ifølge krav 4, kendetegnet ved, at saltet er chlorid-, sulfat- eller acetatsaltet. 35
5. Fremgangsmåde ifølge ethvert af kravene 1-5, kendetegnet ved, at fri ammoniak er til stede. DK 158837 B
7. Fremgangsmåde ifølge ethvert af kravene 1-6, kendetegnet ved, at reaktionen udføres i vandig opløsning ved en temperatur mellem 100eC og 135°C.
8. Fremgangsmåde ifølge krav 1, kendetegnet ved, at natrium-p-hydroxymandelat omsættes med ammoniak og et ammoniumsalt i vandig opløsning ved en temperatur mellem 100°C og 135°C. 10 15 20 25 30 35
Priority Applications (17)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8069/76A GB1576334A (en) | 1977-05-26 | 1977-05-26 | N-alkyl and n,n-dialkyl derivatives thereof process for the manufacture of p-hydroxyphenylglycine and |
| ZA00782655A ZA782655B (en) | 1977-05-26 | 1978-05-09 | Salt |
| AU37924/78A AU520192B2 (en) | 1977-05-26 | 1978-07-11 | A process forthe manufacture ofp-hydroxyphenylglycine |
| ZA00783965A ZA783965B (en) | 1977-05-26 | 1978-07-11 | A process for the manufacture of p-hydroxy-phenylglycine |
| DK311878A DK158837C (da) | 1977-05-26 | 1978-07-11 | Fremgangsmaade til fremstilling af p-hydroxyphenylglycin. |
| SE7807719A SE439482B (sv) | 1977-05-26 | 1978-07-11 | Sett att framstella p-hydroxifenylglycin |
| FI782241A FI68809C (fi) | 1977-05-26 | 1978-07-13 | Foerfarande foer framstaellning av p-hydroxifenylglycin |
| BE189307A BE869021A (fr) | 1977-05-26 | 1978-07-14 | Procede pour produire la p-hydroxyphenylglycine |
| DE19782831118 DE2831118C2 (de) | 1977-05-26 | 1978-07-14 | Verfahren zur herstellung von p-hydroxyphenylglycin und seiner n-alkyl- und n,n-dialkylderivate |
| LU79985A LU79985A1 (fr) | 1977-05-26 | 1978-07-17 | Procede pour produire la p-hydroxyphenylglycine |
| FR7821174A FR2431485A1 (fr) | 1977-05-26 | 1978-07-17 | Procede pour produire la p-hydroxyphenylglycine |
| NLAANVRAGE7807630,A NL187745C (nl) | 1977-05-26 | 1978-07-17 | Werkwijze voor de bereiding van p-hydroxyfenylglycine of een n-alkyl- of n.n-dialkylderivaat daarvan. |
| IT2580078A IT1158888B (it) | 1977-05-26 | 1978-07-17 | Procedimento per la fabbricazione di p-idrossifenilglicina e suoi derivati |
| JP8684178A JPS5515414A (en) | 1977-05-26 | 1978-07-18 | Manufacture of pphydroxyphenylglycine or its nnalkyl or n*nndialkyl derivative |
| CH773278A CH634825A5 (de) | 1977-05-26 | 1978-07-18 | Verfahren zur herstellung von p-hydroxyphenylglycin oder dessen n-alkyl- bzw. n,n-dialkylderivaten. |
| PT68324A PT68324A (en) | 1977-05-26 | 1978-07-19 | Process for preparing p-hydroxyphenylglycine or an n-alkyl or n,n-dialkyl derivative thereof |
| US06/215,872 US4350826A (en) | 1977-05-26 | 1980-12-12 | Process for preparing p-hydroxy phenylglycine |
Applications Claiming Priority (34)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8069/76A GB1576334A (en) | 1977-05-26 | 1977-05-26 | N-alkyl and n,n-dialkyl derivatives thereof process for the manufacture of p-hydroxyphenylglycine and |
| GB806976 | 1977-05-26 | ||
| ZA00782655A ZA782655B (en) | 1977-05-26 | 1978-05-09 | Salt |
| ZA7802655 | 1978-05-09 | ||
| DK311878A DK158837C (da) | 1977-05-26 | 1978-07-11 | Fremgangsmaade til fremstilling af p-hydroxyphenylglycin. |
| AU3792478 | 1978-07-11 | ||
| ZA00783965A ZA783965B (en) | 1977-05-26 | 1978-07-11 | A process for the manufacture of p-hydroxy-phenylglycine |
| SE7807719A SE439482B (sv) | 1977-05-26 | 1978-07-11 | Sett att framstella p-hydroxifenylglycin |
| AU37924/78A AU520192B2 (en) | 1977-05-26 | 1978-07-11 | A process forthe manufacture ofp-hydroxyphenylglycine |
| SE7807719 | 1978-07-11 | ||
| DK311878 | 1978-07-11 | ||
| ZA7803965 | 1978-07-11 | ||
| FI782241 | 1978-07-13 | ||
| FI782241A FI68809C (fi) | 1977-05-26 | 1978-07-13 | Foerfarande foer framstaellning av p-hydroxifenylglycin |
| BE189307 | 1978-07-14 | ||
| BE189307A BE869021A (fr) | 1977-05-26 | 1978-07-14 | Procede pour produire la p-hydroxyphenylglycine |
| DE19782831118 DE2831118C2 (de) | 1977-05-26 | 1978-07-14 | Verfahren zur herstellung von p-hydroxyphenylglycin und seiner n-alkyl- und n,n-dialkylderivate |
| DE2831118 | 1978-07-14 | ||
| IT2580078 | 1978-07-17 | ||
| LU79985A LU79985A1 (fr) | 1977-05-26 | 1978-07-17 | Procede pour produire la p-hydroxyphenylglycine |
| FR7821174 | 1978-07-17 | ||
| NL7807630 | 1978-07-17 | ||
| FR7821174A FR2431485A1 (fr) | 1977-05-26 | 1978-07-17 | Procede pour produire la p-hydroxyphenylglycine |
| IT2580078A IT1158888B (it) | 1977-05-26 | 1978-07-17 | Procedimento per la fabbricazione di p-idrossifenilglicina e suoi derivati |
| NLAANVRAGE7807630,A NL187745C (nl) | 1977-05-26 | 1978-07-17 | Werkwijze voor de bereiding van p-hydroxyfenylglycine of een n-alkyl- of n.n-dialkylderivaat daarvan. |
| LU79985 | 1978-07-17 | ||
| CH773278A CH634825A5 (de) | 1977-05-26 | 1978-07-18 | Verfahren zur herstellung von p-hydroxyphenylglycin oder dessen n-alkyl- bzw. n,n-dialkylderivaten. |
| JP8684178A JPS5515414A (en) | 1977-05-26 | 1978-07-18 | Manufacture of pphydroxyphenylglycine or its nnalkyl or n*nndialkyl derivative |
| CH773278 | 1978-07-18 | ||
| JP8684178 | 1978-07-18 | ||
| PT6832478 | 1978-07-19 | ||
| PT68324A PT68324A (en) | 1977-05-26 | 1978-07-19 | Process for preparing p-hydroxyphenylglycine or an n-alkyl or n,n-dialkyl derivative thereof |
| US06/215,872 US4350826A (en) | 1977-05-26 | 1980-12-12 | Process for preparing p-hydroxy phenylglycine |
| US21587280 | 1980-12-12 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| DK311878A DK311878A (da) | 1980-01-12 |
| DK158837B true DK158837B (da) | 1990-07-23 |
| DK158837C DK158837C (da) | 1990-12-24 |
Family
ID=38922765
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DK311878A DK158837C (da) | 1977-05-26 | 1978-07-11 | Fremgangsmaade til fremstilling af p-hydroxyphenylglycin. |
Country Status (16)
| Country | Link |
|---|---|
| US (1) | US4350826A (da) |
| JP (1) | JPS5515414A (da) |
| AU (1) | AU520192B2 (da) |
| BE (1) | BE869021A (da) |
| CH (1) | CH634825A5 (da) |
| DE (1) | DE2831118C2 (da) |
| DK (1) | DK158837C (da) |
| FI (1) | FI68809C (da) |
| FR (1) | FR2431485A1 (da) |
| GB (1) | GB1576334A (da) |
| IT (1) | IT1158888B (da) |
| LU (1) | LU79985A1 (da) |
| NL (1) | NL187745C (da) |
| PT (1) | PT68324A (da) |
| SE (1) | SE439482B (da) |
| ZA (2) | ZA782655B (da) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2427322A1 (fr) * | 1979-06-15 | 1979-12-28 | Hoechst France | Parahydroxymandelate de sodium racemique cristallise, son procede de preparation et son application a la preparation du paraformylphenolate de sodium cristallise |
| FR2518540A1 (fr) * | 1981-12-23 | 1983-06-24 | Hoechst France | Dimethylamino-2 parahydroxyphenyl-2 acetate de sodium, son procede de preparation et son application a la fabrication du cyanure de parahydroxybenzyle |
| DE3531067A1 (de) * | 1985-08-30 | 1987-03-05 | Dynamit Nobel Ag | Verfahren zur herstellung von 3-aminoacrylsaeureestern |
| JP3762980B2 (ja) * | 2000-11-17 | 2006-04-05 | 独立行政法人産業技術総合研究所 | アミノ基導入法及びアミノ酸の合成方法 |
| JP3605635B2 (ja) * | 2000-12-11 | 2004-12-22 | 独立行政法人産業技術総合研究所 | アミノ基導入方法及びアミノ酸化合物合成方法 |
| JP2015504872A (ja) * | 2011-12-19 | 2015-02-16 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | 製造ラセミα−アミノ酸又はグリシンの製造方法、混合物、組成物及び錯体形成剤の製造方法 |
| US9512061B2 (en) | 2011-12-19 | 2016-12-06 | Basf Se | Process for the preparation of racemic alpha-amino acids |
| CN104370765A (zh) * | 2013-08-13 | 2015-02-25 | 成都化工股份有限公司 | D-苯甘氨酸和dl-苯甘氨酸的合成方法 |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH369468A (de) * | 1957-10-17 | 1963-05-31 | Hoffmann La Roche | Verfahren zur Herstellung von a-tert.-Aminoessigsäuren |
| GB1353612A (en) * | 1970-07-11 | 1974-05-22 | Sterling Winthrop Group Ltd | Process for the preparation of a glycine derivative |
| GB1371896A (en) * | 1970-10-15 | 1974-10-30 | Beecham Group Ltd | Hydroxyaryl amino acids |
| DE2115551C3 (de) * | 1971-03-31 | 1980-01-10 | Haarmann & Reimer Gmbh, 3450 Holzminden | Verfahren zur Herstellung von aromatischen Hydroxyaldehyden |
| FR2205895A5 (en) * | 1972-11-08 | 1974-05-31 | Aries Robert | Alpha-amino-hydroxyphenylacetic acids prepn. - by cheap, three-stage process from hydroxyphenylglyoxylic acids via mandelic acids |
| US3860631A (en) * | 1973-12-06 | 1975-01-14 | Smithkline Corp | Process for the preparation of n-acyl-2- and 4-hydroxyphenylglycines |
| CH614928A5 (da) * | 1975-09-12 | 1979-12-28 | Nobel Hoechst Chimie | |
| SE441524B (sv) * | 1978-05-19 | 1985-10-14 | Ici Ltd | Fast natrium- eller kalium-p-hydroximandelat-monohydrat och sett for dess framstellning |
-
1977
- 1977-05-26 GB GB8069/76A patent/GB1576334A/en not_active Expired
-
1978
- 1978-05-09 ZA ZA00782655A patent/ZA782655B/xx unknown
- 1978-07-11 DK DK311878A patent/DK158837C/da not_active IP Right Cessation
- 1978-07-11 AU AU37924/78A patent/AU520192B2/en not_active Expired
- 1978-07-11 ZA ZA00783965A patent/ZA783965B/xx unknown
- 1978-07-11 SE SE7807719A patent/SE439482B/sv not_active IP Right Cessation
- 1978-07-13 FI FI782241A patent/FI68809C/fi not_active IP Right Cessation
- 1978-07-14 BE BE189307A patent/BE869021A/xx not_active IP Right Cessation
- 1978-07-14 DE DE19782831118 patent/DE2831118C2/de not_active Expired
- 1978-07-17 NL NLAANVRAGE7807630,A patent/NL187745C/xx not_active IP Right Cessation
- 1978-07-17 LU LU79985A patent/LU79985A1/fr unknown
- 1978-07-17 FR FR7821174A patent/FR2431485A1/fr active Granted
- 1978-07-17 IT IT2580078A patent/IT1158888B/it active
- 1978-07-18 JP JP8684178A patent/JPS5515414A/ja active Granted
- 1978-07-18 CH CH773278A patent/CH634825A5/de not_active IP Right Cessation
- 1978-07-19 PT PT68324A patent/PT68324A/pt unknown
-
1980
- 1980-12-12 US US06/215,872 patent/US4350826A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| IT1158888B (it) | 1987-02-25 |
| PT68324A (en) | 1978-08-01 |
| DE2831118A1 (de) | 1980-01-24 |
| DK158837C (da) | 1990-12-24 |
| FI68809B (fi) | 1985-07-31 |
| ZA782655B (en) | 1979-05-30 |
| ZA783965B (en) | 1979-12-27 |
| LU79985A1 (fr) | 1980-02-14 |
| GB1576334A (en) | 1980-10-08 |
| FI782241A7 (fi) | 1980-01-14 |
| BE869021A (fr) | 1979-01-15 |
| NL7807630A (nl) | 1980-01-21 |
| JPS6256859B2 (da) | 1987-11-27 |
| JPS5515414A (en) | 1980-02-02 |
| FR2431485B1 (da) | 1983-11-18 |
| NL187745C (nl) | 1992-01-02 |
| DE2831118C2 (de) | 1989-11-02 |
| AU3792478A (en) | 1980-01-17 |
| IT7825800A0 (it) | 1978-07-17 |
| NL187745B (nl) | 1991-08-01 |
| CH634825A5 (de) | 1983-02-28 |
| SE439482B (sv) | 1985-06-17 |
| DK311878A (da) | 1980-01-12 |
| US4350826A (en) | 1982-09-21 |
| SE7807719L (sv) | 1980-01-12 |
| FR2431485A1 (fr) | 1980-02-15 |
| AU520192B2 (en) | 1982-01-21 |
| FI68809C (fi) | 1985-11-11 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PUP | Patent expired |