http://rdf.ncbi.nlm.nih.gov/pubchem/patent/GB-600245-A
Outgoing Links
| Predicate | Object |
|---|---|
| assignee | http://rdf.ncbi.nlm.nih.gov/pubchem/patentassignee/MD5_b4982f67e44e5b9dbfc41ee6302d9468 http://rdf.ncbi.nlm.nih.gov/pubchem/patentassignee/MD5_ecd0e644f48b7424cdf63d1dc4fa7fbf http://rdf.ncbi.nlm.nih.gov/pubchem/patentassignee/MD5_e15c6ee41bcdd88dba0bc5d35b5df1b8 http://rdf.ncbi.nlm.nih.gov/pubchem/patentassignee/MD5_6e889bdccedc80fad953379c4eeba099 |
| classificationCPCInventive | http://rdf.ncbi.nlm.nih.gov/pubchem/patentcpc/C07D513-04 |
| classificationIPCInventive | http://rdf.ncbi.nlm.nih.gov/pubchem/patentipc/C07D513-04 |
| filingDate | 1944-05-12-04:00^^<http://www.w3.org/2001/XMLSchema#date> |
| publicationDate | 1948-04-05-04:00^^<http://www.w3.org/2001/XMLSchema#date> |
| publicationNumber | GB-600245-A |
| titleOfInvention | Improvements in and relating to the synthesis of heterocyclic organic compounds containing sulphur |
| abstract | Thiazolidines of the general formula:-<FORM:0600245/IV(b)/1> are treated with phosphorus oxychloride or less preferably another dehydrating agent such as acetic anhydride to produce compounds of the general formula <FORM:0600245/IV(b)/2> R2 being an alkyl-, aralkyl- or arylacyl radical, R3 being hydrogen or an alkyl, aralkyl or aryl ester radical, R4 and R5 being hydrogen or an alkyl, aralkyl or aryl radical, and R5 and R7 being an alkyl, aralkyl or aryl radical, and the latter compounds are then treated with mercuric chloride, zinc chloride or cadmium chloride to yield by ring-opening 2-substituted a -(1-imidazolyl)-b -thiol carboxylic acids or esters thereof. Advantageously R2 may be a para-hydroxy or para-alkoxy phenyl acetyl group, e.g. a p-acetoxyphenyl acetyl group, R7 therefore becoming a p-hydroxy or p-acyloxy phenyl acetyl group. Such products have a structure analogous to that of a portion of the penicillin-III molecule. In examples: (1) caproylamino thiazolidine hydrochloride, suspended in phosphorus oxychloride, is treated with syrupy phosphoric acid, and the residue after concentrating in vacuo, is diluted with dioxan and added to aqueous sodium bicarbonate, the diketopiperazine derivative:- <FORM:0600245/IV(b)/3> being isolated as by a by-product. The filtrate is extracted with butanol and concentrated in vacuo and the residue, in chloroform, is precipitated with ether to isolate "decarboxy-dihydropenillic-I acid":- <FORM:0600245/IV(b)/4> which is treated in aqueous methanol with aqueous 5 per cent mercuric chloride, and the resulting ppt. is decomposed with hydrogen sulphide to isolate crude r-dihydropenillamine-I hydrochloride:- <FORM:0600245/IV(b)/5> (2) p-Hydroxyphenylacetic acid is acetylated to p-acetoxyphenylacetic acid, which is converted into the corresponding acid chloride, and added to aminoacetal containing saturated aqueous sodium bicarbonate and p-acetoxy phenylacetylamino diethylacetal is isolated, heated with dl-penicillamine (b b -dimethylcysteine) hydrochloride to isolate the corresponding thiazolidine hydrochloride, treated with phosphorus oxychloride, to form crude dl-penillamine-III hydrochloride; (3) l-penicillamine hydrochloride is warmed with caproylaminoacetal to 60 DEG C. to yield the corresponding thiazolidine hydrochloride, and the a -thiazolidine hydrochloride is prepared similarly. The optically pure thiazolidine hydrochlorides are converted by phosphorus oxychloride into d-(-)-, and l-(+)-dihydro-penillamine-I hydrochlorides are each obtained crystalline; (4) l-penicillamine hydrochloride and phenylacetylamino-diethylacetal are melted together to yield l-penilloic-II acid hydrochloride treated with phosphorus oxychloride and l-penillamine-II hydrochloride isolated in the usual way. Similarly, d-penicillamine hydrochloride and phenylacetylamino diethyl acetal yield d-penilloic-II acid hydrochloride, which cyclises in phosphorus oxychloride to give eventually d-penillamine-II hydrochloride. Specification 584,918 is referred to. |
| type | http://data.epo.org/linked-data/def/patent/Publication |
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Total number of triples: 66.