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GB2067551A - Phthalidyl eaters of the acetone adduct of epicillin - Google Patents

Phthalidyl eaters of the acetone adduct of epicillin Download PDF

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Publication number
GB2067551A
GB2067551A GB8000970A GB8000970A GB2067551A GB 2067551 A GB2067551 A GB 2067551A GB 8000970 A GB8000970 A GB 8000970A GB 8000970 A GB8000970 A GB 8000970A GB 2067551 A GB2067551 A GB 2067551A
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United Kingdom
Prior art keywords
methoxy
hydrogen
formula
oxo
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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GB8000970A
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ER Squibb and Sons LLC
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ER Squibb and Sons LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by ER Squibb and Sons LLC filed Critical ER Squibb and Sons LLC
Priority to GB8000970A priority Critical patent/GB2067551A/en
Priority to DE19803001590 priority patent/DE3001590A1/en
Priority claimed from DE19803001590 external-priority patent/DE3001590A1/en
Priority to IE10580A priority patent/IE800105L/en
Priority claimed from IE10580A external-priority patent/IE800105L/en
Priority to FR8001202A priority patent/FR2474033A1/en
Priority to BE0/199077A priority patent/BE881304A/en
Priority to NL8000512A priority patent/NL8000512A/en
Publication of GB2067551A publication Critical patent/GB2067551A/en
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D499/00Heterocyclic compounds containing 4-thia-1-azabicyclo [3.2.0] heptane ring systems, i.e. compounds containing a ring system of the formula:, e.g. penicillins, penems; Such ring systems being further condensed, e.g. 2,3-condensed with an oxygen-, nitrogen- or sulfur-containing hetero ring

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Penicillin esters and their acid addition salts of the formula <IMAGE> wherein X is hydrogen, methyl, methoxy, chloro, or bromo and n is an integer from 1 to 3 provided that n is 2 or 3 only when X is hydrogen or methoxy; are disclosed. Upon oral administration, these esters provide improved absorption and result in high concentrations of the antibacterially active parent penicillin in the blood, tissues and urine.

Description

SPECIFICATION Phthalidyl esters of the acetone adduct of epicillin This invention is directed to phthalidyl penicillin esters of the formula
and acid addition salts thereof wherein X is hydrogen, methyl, methoxy, chloro, or bromo and n is an integer from 1 to 3 provided that n is 2 or 3 only when X is hydrogen or methoxy.
The ester products of formula I can be prepared by several methods. For example, epicillin can be reacted with acetone in the presence of triethylamine to yield the intermediate of the formula
The intermediate of formula II can then be reacted with an isobenzofuran of the formula
wherein L is hydroxy or bromo to yield the ester product of formula I.
The ester products of formula- I can also be prepared by reacting epicillin with the isobenzofuran of formula Ill to yield the intermediate of the formula
The intermediate of formula IV is then treated with acetone to yield the ester product of formula 1.
The intermediate of formula IV can also be obtained by reacting the phthalidyl ester of 6aminopenicillanic acid (6-APA) with an a-(protected amino)-1 4-cyclohexadienyl acylating agent followed by removal of the a-amino protecting group.
The ester products of formula I are conveniently isolated in the form of their acid addition salt.
Acids useful for this purpose include inorganic acids such as hydrochloric, hydrobromic, sulfuric, nitric, and phosphoric acid, and organic acids such as maleic, furmaric, tartaric, citric, acetic, benzoic, 2-acetoxybenzoic, salicylic, succinic, nicotinic, methansulfonic, and cyclohexanesulfamic acid. These acid addition salts can be converted into the free form by reacting with a basic agent and, if desired, then converted to a different acid addition salt.
Preferred compounds of this invention are those of the formula
wherein X6 is hydrogen, methoxy, bromo, or chloro; X5 is hydrogen or methoxy provided that X5 is methoxy only when X6 is methoxy, and X4 is hydrogen or methoxy provided X4 is methoxy only when X6 and X5 are both methoxy.
Most preferred is the unsubstituted phthalidyl ester of formula V wherein X4, X5, and X6 are all hydrogen.
The esters of formula I upon administration act as prod rug of epicillin having the identical spectra of antibacterial activity. Thus, these esters are particularly useful in treating respiratory tract, gastrointestinal tract and genitourinary tract infections and skin and soft tissue infections due to susceptible strains of various gram-positive and gram-negative bacteria. Among the grampositive bacteria that can be treated are beta-hemolytic streptococci, Streptococcus viridans, Streptococcus faecalis, Diplococcus pneumonia, Staphylococcus albus, and non-penicillanase producing strains of Straphylococcus aureus and among the gram-negative bacteria are Escherichia coli, Proteus mirabilis, Hemophilus influenzae, Salmonella typhi, Salmonella paratyphi, Shigella and Neisseria gonorrhoeae.
The esters of formula I are particularly useful when administered orally due to their improved rate of absorption. These esters provide higher concentrations of epicillin in the blood, tissues and urine that can be achieved by the oral administration of epicillin itself and they also decrease the incidence of gastrointestinal distress such as diarrhea and loose stools. The esters of formula I can be administered to the infected mammal in amounts ranging from about 1 5 to about 50 mg./kg./day in one or more doses. The amount of compound administered will vary, of course, depending upon the severity and nature of the infection; i.e. a urinary tract infection will in general require a higher dose of antibacterial agent than a respiratory tract infection.
The esters of formula I and their acid addition salts are formulated for oral administration according to conventional pharmaceutical procedures. For example, the compounds can be encapsulated along with conventional excipients and preservatives, as may be necessary, so as to provide in a unitary dose the equivalent of 250 mg. or 500 mg. of epicillin. The compounds can also be formulated as a concentrate containing conventional excipients and flavoring agents which when reconstituted will provide a flavored suspension containing the equivalent of 1 25 mg. and 250 mg. of epicillin per 5 ml. teaspoonful. The compound can also be formulated as pediatric drops which provide after reconstitution a flavored suspension containing the equivalent of 100 mg. of epicillin per one ml.
Illustrative process details are provided in the examples for the various reactions. All temperatures are on the centigrade scale.
Example 1 6-[-4-(1, 4-Cyclohexadien- -yl)-2, 2-dimethyl-5-oxo- I 4midazolidinylj-3, 3-dimethyl- 7-oxo-4-thia 1 -azabicyclof3. 2. Ojheptane-2-carboxylic acid, 1, 3-dih ydro-3-oxo- 1 -isobenzofuranyl ester, hydrochloride (1:1) a) 6-[4-(1, 4-Cyclohexadien- 1 -yl)-2, 2-dim ethyl-5-oxo- 1 -imidazolidinyl]-3, 3-dimethyl- 7-oxo-4-thia 1 -azabicyclo[3. 2. Ojheptane-2-carboxylic acid A suspension of 10 g of epicillin in 50 ml. of acetone (previously dried over Linde 4A molecular sieves) is stirred with 7 ml. of triethylamine for 24 hours at 25 and an additional 24 hours at 30'.The resulting solution is filtered and added dropwise to 50 ml. of water maintained at 0-10 and pH 2.5-3.0 by the simultaneous addition of cold 30% sulfuric acid solution. The resulting slurry is stirred for 2 hours at 0" and pH 2.55 and is then filtered. The crystalline product is washed with 20 ml. of cold water and dried at 40-50" over P205 in vacuo to yield 6.1 9 g. of 6-[4-( 1 ,4-cyclohexadien-1 -yl)-2,2-dimethyl-5-oxo- 1 -imidazolidinyl3, 3-dime- thyl-7-oxo-5-thia-1-azabicyclo[3.2.OJ heptane-2-carboxylic acid; m.p. 186 (dec., browns at 1 74').
Analysis Calculated for C19H2sSN304: C, 58.29; H, 6.44; N, 10.73; S, 8.19.
Found: C, 58.06; H, 6.52; N, 10.62; S 7.99.
b) 6-f4-( 1, 4-Cyclohexadien- 1 -yl)-2, 2-dimethyl-5-oxo- 1-imidazolidinyl]-3, 3dimethyl- 7-oxo-4-thia- 1-azabicyclof3. 2. O]heptane-2-carboxylic acid, 1, 3-dihydro-3-oxo- 1-isobenzofuranyl ester, hydrochloride (1:1) A mixture of 14.81 g. (0.0378) mole) of the acid product from part (a) and 5.3 ml. (0.0378 mole) of triethylamine in 265 ml. of acetone (previously dried over Linde 4A molecular sieves) is stirred at room temperature for 30 minutes. 3.78 g. of potassium bicarbonate and 8 g. of 3bromophthalide are added.After four hours, the resulting mixture is filtered and the filtrate is concentrated in vacuoto about 9.5 ml. 375 ml. of ethyl acetate is added and the resulting solution is washed with 2% sodium bicarbonate solution (2 x 40 ml.), water (2 X 40 ml.), dried, and concentrated to yield 19.89 9. of crude product. This crude material is passed through a column containing 800 g. of silica gel (sili CAR CC-7) and eluted with (1:1) EtOAc: benzene to give one fraction containing 3.55 g. of product and a second fraction containing 8.34 g. of purer product. The 8.34 9. purer fraction is dissolved in 140 ml. of (1:1) EtOAc: ethyl ether and 1.66 mmoles/ ml. of HCI solution in ethyl ether (as determined by trituration) is added. The HCI salt product is filtered immediately, washed with ether and dried overnight without heating to yield 8.33 g. of 6-E4-(1 ,4-cyclohexadien-l -yl)-2,2-dimethyl-5-oxo-l -imidazolidinyl]-3, 3-dimethyl- 7-oxo-4-thia- 1 -azabicyclo[3.2.0] heptane-2-carboxylic acid, 1 , 3-dihydro-3-oxo- 1 -isobenzofuranyl ester, hydrochloride (1:1); m.p. 160-162".
Analysis Calculated for C27H29N306S.HCI: C, 57.90; H, 5.40; S, 5.72; Cl, 6.33; N, 7.50 Found: C, 57.01; H, 5.78; S, 5.61; Cl, 5.93; N, 7.25.
Examples 2-10 Following the procedure of Example 1 but employing the substituted isobenzofuran shown in Col. I one obtains the phthalidyl ester product shown in Col. II.
Col. I
Col. ll
Ex. X4 X5 X6 X7 2 H H CH3 H 3 H H OCH3 H 4 H H Br H 5 H H Cl H 6 H SOCH, OCH3 H 7 0CH3 OCH3 OCH3 H 8 Cl H H H 9 OCH3 H H H 10 CH3 H H H

Claims (9)

1. Compounds of the formula:
wherein X is hydrogen, methyl, methoxy, bromo, or chloro; n is an integer from 1 to 3 provided that n is 2 or 3 only when X is hydrogen or methoxy; and acid addition salts thereof.
2. A compound according to Claim 1 having the formula:
wherein X6 is hydrogen, methoxy, bromo, or chloro; X5 is hydrogen or methoxy provided that X5 is methoxy only if X6 is methoxy; X4 is hydrogen or methoxy provided that X4 is methoxy only if both X5 and X6 are methoxy; and acid addition salts thereof.
3. The compound of Claim 2 wherein X4, X5, and X6 are all hydrogen.
4. The hydrochloride salt of the compound of Claim 3.
5. An antibacterial pharmaceutical composition comprising a pharmaceutically acceptable carrier and, as the active antibacterial agent, one or more of the compounds or salts claimed in claim 1 or 2.
6. A composition according to Claim 5, wherein the antibacterial agent is 6-[4-(1,4cyclohexadien- 1 -yl)-2, 2-dimethyl-5-oxo- 1 -imiflazolidinyl]-3,3-dimethyl-7-oxo-4-th ia- 1 -azabicy cloL3.2 .0]heptane-2-carboxylic acid, 1 , 3-dihydro-3-oxo- 1 -isobenzofuranyl ester.
7. A method of treating a bacterial infection in a mammalian specie other than homo sapiens which comprises orally administering an effective amount of a compound or salt as claimed in any one of claims 1-4.
8. A method of treating a bacterial infection in a mammalian specie other than homo sapiens which comprises orally administering an effective amount of a composition according to claim 5 or 6.
9. A compound or salt according to any one of claims 1-4 for use in the treatment of bacterial infections in homo sapiens.
GB8000970A 1980-01-11 1980-01-11 Phthalidyl eaters of the acetone adduct of epicillin Withdrawn GB2067551A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
GB8000970A GB2067551A (en) 1980-01-11 1980-01-11 Phthalidyl eaters of the acetone adduct of epicillin
DE19803001590 DE3001590A1 (en) 1980-01-11 1980-01-17 PHTHALIDYLESTER OF THE ACETONE ADDUCT OF EPICILLIN AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS
IE10580A IE800105L (en) 1980-01-11 1980-01-18 Phthalidyl esters of the acetone adduct of epicillin
FR8001202A FR2474033A1 (en) 1980-01-11 1980-01-21 Phthalide ester(s) of epicillin-acetone addn. cpd. - useful as antibacterials rapidly absorbed after oral admin.
BE0/199077A BE881304A (en) 1980-01-11 1980-01-23 PHTHALIDYL ESTERS OF THE ACETONIC ADDITION PRODUCT OF EPICILLIN, WITH ANTIBACTERIAL ACTION
NL8000512A NL8000512A (en) 1980-01-11 1980-01-28 PHTHALIDYL ESTERS OF AN ACETONE ADDUCT FROM EPICILLIN.

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
GB8000970A GB2067551A (en) 1980-01-11 1980-01-11 Phthalidyl eaters of the acetone adduct of epicillin
DE19803001590 DE3001590A1 (en) 1980-01-11 1980-01-17 PHTHALIDYLESTER OF THE ACETONE ADDUCT OF EPICILLIN AND MEDICINAL PRODUCTS CONTAINING THESE COMPOUNDS
IE10580A IE800105L (en) 1980-01-11 1980-01-18 Phthalidyl esters of the acetone adduct of epicillin
FR8001202A FR2474033A1 (en) 1980-01-11 1980-01-21 Phthalide ester(s) of epicillin-acetone addn. cpd. - useful as antibacterials rapidly absorbed after oral admin.
BE0/199077A BE881304A (en) 1980-01-11 1980-01-23 PHTHALIDYL ESTERS OF THE ACETONIC ADDITION PRODUCT OF EPICILLIN, WITH ANTIBACTERIAL ACTION
BE881304 1980-01-23
NL8000512A NL8000512A (en) 1980-01-11 1980-01-28 PHTHALIDYL ESTERS OF AN ACETONE ADDUCT FROM EPICILLIN.

Publications (1)

Publication Number Publication Date
GB2067551A true GB2067551A (en) 1981-07-30

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GB8000970A Withdrawn GB2067551A (en) 1980-01-11 1980-01-11 Phthalidyl eaters of the acetone adduct of epicillin

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GB (1) GB2067551A (en)

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