GB1594450A - 1,3-oxathiolane sulphoxides and their use in the preparation of 5,6-dihydro-2-methyl-1,4-oxathiin derivatives - Google Patents
1,3-oxathiolane sulphoxides and their use in the preparation of 5,6-dihydro-2-methyl-1,4-oxathiin derivatives Download PDFInfo
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- GB1594450A GB1594450A GB17940/78A GB1794078A GB1594450A GB 1594450 A GB1594450 A GB 1594450A GB 17940/78 A GB17940/78 A GB 17940/78A GB 1794078 A GB1794078 A GB 1794078A GB 1594450 A GB1594450 A GB 1594450A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
- C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
- C07D327/06—Six-membered rings
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Description
(54) NOVEL I,3-OXOTHIOLANE SULPHOXIDES AND
THEIR USE IN THE PREPARATION OF
5,6-DIHYDRO-2-METHYL- I ,4-OXATHIIN
DERIVATIVES
(71) I, WHA SUK LEE, a citizen of the Republic of Korea, of 678
Portage Street, Ottawa, Ontario, Canada, do hereby declare the invention, for which I pray that a Patent may be granted to me, and the method by which it is to be performed to be particularly described in and by the following statement:- This invention relates to a new and improved method of preparing 5,6 dihydro - 2 - methyl - 1,4 - oxathiin derivatives represented by the formula:
wherein X is an amino or alkoxy group. The amino group may be primary, secondary or tertiary, and the alkyl moiety of the alkoxy group may be primary, secondary or tertiary. It is apparent that the derivatives I may represent 5,6 dihydro - 2 - methyl - 1,4 - oxathiin - 3 - carboxamides (Ia) when X is the amino group, and 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin - 3 - carboalkoxides (Ib) when X is the alkoxy group.
The compounds Ia and Ib are known chemicals having been described in U.S.
Patents 3,249,499 and 3,393,202, and in Canadian Patents 787,893 and 791,151.
5,6 - Dihydro - 2 - methyl - 1,4 - oxathiin - 3 - carboxamides (Ia) have been described as having fungicidal and bactericidal properties. The compounds Ib are also useful chemicals as these can be converted to compounds Ia.
The prior art preparation of 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin - 3 carboxamides (Ia) has been effected by two methods. The first method has included (1) converting acetoacetamide to alpha-chloroacetoacetamide, (2) reacting this with 2 - mercaptoethanol in a mutual solvent in the presence of a base, (3) subjecting the resulting product to acidic conditions whereby it cyclizes with loss of water to form 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin - 3 carboxamide (Ia) and (4) isolating said product from the reaction mixture. The second method of preparing same has used alkyl acetoacetate in place of acetoacetamide as a starting material. Thus, from the procedure analogous to the first method described above, the resulting 5,6 - dihydro - 2 - methyl - 1,4 oxathiin - 3 - carboalkoxide (Ib) was converted to 5,6 - dihydro - 2 - methyl 1,4 - oxathiin - 3 - carboxamide (Ia).
The prior art process as generally outlined above is subject to certain disadvantages. One disadvantage of the prior art process is that the first method described above is sensitive to side reaction and the yields of 5,6 - dihydro - 2 methyl - 1,4 - oxathiin - 3 - carboxamides (Ia) obtained by such method are lower than desired. Another disadvantage is that, in the first and second methods described above, the preparation of alphahaloacetoacetamide or alkyl alpha haloacetoacetate is a somewhat inconvenient step, and overall the yield of 5,6 dihydro - 2 - methyl - 1,4 - oxathiin - 3 - carboxamide (Ia) via the second method is relatively low.
It is'an object of the present invention to provide a new and improved method for preparing 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin derivatives (I).
It is another object of the present invention to provide methods of preparing the sulfoxides of 1,3 - oxathiolane derivatives, which can be simply and efficiently converted to 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin derivatives (I).
These and other objects of the present invention are achieved in accordance with the present invention which provides a process of preparing a 5,6 - dihydro 2 - methyl - 1,4 - oxathiin derivative of the formula (I), wherein X is an amino group having the formula,
wherein R and R' are the same or different and each represents hydrogen, phenyl, alkyl having up to 15 carbon atoms, cyclohexyl, nitrophenyl, alkoxyphenyl in which the alkoxy group has up to 4 carbon atoms, benzyl, carboxyphenyl, furfuryl, halophenyl, tolyl, naphthyl, biphenyl or hydroxyphenyl; or X is an alkoxy group
OR", in which R" is a primary, secondary or tertiary alkyl group having up to 6 carbon atoms; comprising subjecting a 1,3 - oxathiolane sulfoxide of the formula
wherein X is as defined above, in a solvent to slightly acidic conditions whereby ring expansion takes place via a sulfenic acid intermediate to form compound I with loss of water, and subsequently isolating this from the resulting mixture.
The 1,3 - oxathiolane sulfoxide of formula (V) may readily be prepared by reacting a 1,3 - oxathiolane of the formula
wherein X is as defined hereinbefore, with an organic peracid, hydrogen peroxide or other oxidizing agent in a solvent to form sulfoxide V, and subsequently isolating said sulfoxide V from the resulting mixture. Ideally the isolated 1,3 - oxathiolane sulfoxide of formula V is separated into the cis and trans isomers Va and Vb, respectively, of the formula
by thin layer or column chromatography using silica gel and chloroform-methanol -as a developing solvent.
The process of the invention, represented by the follo.wing.equations, involves preparing the appropriate 1,3 - oxathiolane sulfoxide V, and then subjecting this sulfoxide to a ring expansion reaction.
In the above equations X is an amino group having the formula,
wherein R and R' are the same or different and each represents hydrogen, phenyl, alkyl having up to 15 carbon atoms, cyclohexyl, nitrophenyl, alkoxyphenyl in which the alkoxy group has up to 4 carbon atoms, benzyl, carboxyphenyl, furfurvl.
halophenyl, tolyl, naphthyl, biphenyl or hydroxyphenyl; or X is an alkoxy group -OR", in which R" is a primary, secondary or tertiary alkyl group having up to 6 carbon atoms.
A 1,3 - oxathiolane derivative IV, which is an ethylene hemithioketal of the carbonyl compound III, can be prepared by reacting a compound of formula III with 2 - mercaptoethanol (II) in the presence of an acid catalyst in a refluxing solvent such as benzene or ether. The compounds of formula IV are described and claimed in my copending application No. 17939/78, (Serial No. 1594449). The sulfoxidation of 1,3 - oxatholane IV may be carried out with an organic peracid or hydrogen peroxide in methylene chloride, chloroform or acetic acid at a temperature of from 0 to 200 C. It has been found in the present invention that the sulfoxide V thus formed is a mixture of cis and trans isomeric sulfoxides Va and Vb as shown in the formula below.
In sulfoxide Va, the SeO bond and
group are cis to each other and in sulfoxide Vb these two groups are trans to each other. These isomeric sulfoxides can be identified from the nuclear magnetic resonance spectroscopic data and other physical and chemical properties of the compounds. If desired, these isomers can be separated by column or preparative thin layer chromatography.
1,3 - Oxathiolane sulfoxides V are new compounds, and since they are valuable intermediates in the process of this invention, they also form part of the invention.
It has been also found in the present invention that both the sulfoxides Va and
Vb undergo facile rearrangement under very mild conditions to give a 5,6 dihydro - 2 - methyl - 1,4 - oxathiin derivative I. The ring expansion reaction can be conducted preferably in solution in the presence of an acid catalyst at a temperature of from 25 to 1000C. The acid catalysts employed are organic acids such as p - toluenesulfonic acid, methanesulfonic acid, and the suitable solvents are dimethylformide, dimethylacetamide, benzene, chloroform and methylene chloride. The reaction may proceed through intermediates VI and VII, neither of which need be isolated. The internal alkene-sulfenic acid intermediate VI readily cyclizes to VII. The intermediate VII is dehydrated readily to yield the desired product I under slightly acidic conditions. The dehydration is facilitated by heating, and particularly by heating under reflux conditions to drive off the water formed, conveniently as an azeotrope with benzene.
The following examples illustrate in more detail the practice of the invention.
It will be understood that the invention is not confined to the specific limitations set forth in the following examples but rather, to the scope of the appended claims.
Example 1
Preparation of 2-methyl-2-carboxanilidomethyl-1,3-oxathiolane (IV, X=C6H,NH)
A solution of acetoacetanilide (17.72 g., 0.1 mole), 2 - mercaptoethanol (7.81 g., 0.1 mole) and p - toluenesulfonic acid monohydrate (0.16 g.) in anhydrous benzene (40 ml.) was refluxed in a round bottomed flask connected to a Dean-Stark water separator for 5 hours until no more water appeared in the separator. The water collected was 1.8 ml. (theory 1.8 ml.). The benzene solution was cooled, washed with sodium bicarbonate solution and water, dried (MgSO4) and decolorized (charcoal). Solvent was evaporated at 400C under reduced pressure to give gummy residue (24.7 g.). The residue was crystallized from ethyl acetatepetroleum ether to obtain colourless short needles (21.4 g., 90.2%); m.p. 85-870C.
Example 2
Preparation of 2-methyl-2-carboethoxymethyl- 1,3-oxathiolane (IV, X=OEt)
Method A. A solution of ethyl acetoacetate (13.02 g., 0.10 mole) and 2 mercaptoethanol (7.81 g., 0.10 mole) in anhydrous benzene (40 ml.) containing 0.16 g. of p-toluenesulfonic acid monohydrate was refluxed in a round bottomed flask connected to a Dean-Stark water separator for 4 hours until no more water appeared in the separator. The water collected was 1.8 ml. (theory 1.8 ml.). The benzene solution was cooled, washed with sodium bicarbonate solution and with water, and dried (MgSO4). Solvent was evaporated at room temperature under reduced pressure to obtain colorless oily residue (17.38 g., 91.30%).
Method B. To a stirred and refluxing solution of ethyl acetoacetate (32.54 g., 0.25 mole) and 2 - mercaptoethanol (19.53 g., 0.25 mole) in anhydrous ether (200 ml.) was added BF3.Et2O (35.48 g., 0.25 mole) dropwise over 1 hour. The mixture was allowed to reflux for an additional hour. The resulting reaction mixture was cooled, washed with sodium bicarbonate solution and water, and dried (MgSO4). Solvent was evaporated at room temperature under reduced pressure to give colorless oily residue (42.1 g., 88.48%).
Example 3
Preparation of 2-methyl-2-carboxanilidomethyl- 1 ,3-oxathiolane-3-oxide (V, X=C6H5NH)
Method A. A solution of 1,3-oxathiolane (IV, X=C6HsNH) (7.12 g., 0.03 mole) in acetic acid (30 ml.) was cooled to 15-200C in the ice bath and 35% hydrogen peroxide (6 ml., about 0.06 mole) in water was added dropwise over 30 min. while stirring the mixture. Stirring was continued at the same temperature for 1 hour 45 min. To the resulting mixture in the same bath was added in portion 6 N. NaOH solution until the mixture reached pH 7. The product was extracted with methylene chloride, and the extract washed with water and dried (Na2SO4). Solvent was evaporated at room temperature under reduced pressure to obtain white foamy solid residue (7.09 g., 93.33%), as a mixture of cis and trans (ca. 70:30) sulfoxides (Va and Vb, X=C6HsNH) as determined by nmr spectra (benzene-d6). These isomeric sulfoxides were separated by preparative thin layer chromatography. Thus 1.0 g. of the above mixture was chromatographed on silica gel (GF 254) plates using chloroform-methanol as developing solvent (flow rate:VavVb) to obtain 0.4968 g. of cis isomer (Va), and 0.2368 g. of trans isomer (Vb). Recrystallized from ethyl acetate-petroleum ether: Va, prisms, m.p. 97-1030C dec.; Vb, crystalline powder, m.p. 121--125"C dec. Nmr (Va+Vb) (C6D6):81.27 (s, 2.1 H)a, 1.58 (s, 0.9
H)b, 2.32 (m, 3H), 2.90 (s, 0.6H), 3.06 (q, 1.4H), 3.37--4.19 (m, 2H), 6.79-7.88 (m, 5H), 9.22 (s, 0.3H), 9.44 (s, 0.7H), a/b=Va/Vb=2. 1/0.9=70/30; Va (C6D6): 1.27 (s, 3H), 2.32 (m, 2H), 3.06 (q, 2H), 3.37--4.19 (m, 2H), 6.79-7.88 (m, 5H), 9.44 (s, 1H); Vb (CDCl3): sal.54 (s, 3H), 2.74-3.54 (m, 2H), 3.01 (s, 2H), 4.34 (q, 2H), 6.96-7.52 (m, 5H), 8.94 (s, 1H), Found for Va: C, 57.0; H, 5.8; N, 5.3, S, 12.4%; for Vb: C, 57.0,
H, 5.7, N, 5.4, S, 12.5% C12111,NS requires C, 56.89; H, 5.97; N, 5.53; S, 12.66%.
Method B. To a solution of 1,3 - oxathiolane (IV, X=CsHsNH) (8.000 g., 0.0337 mole) in chloroform (200 ml.) cooled in the ice-salt bath at 0--50C was added dropwise while stirring the mixture a cool solution of 85% m - chloroperbenzoic acid (6.84 g., 0.0337 mole) in chloroform (200 ml.) over 60 min. Stirring was continued at the same temperature for 3 hours. The resulting reaction mixture was washed with cold saturated sodium bicarbonate solution and water, and dried (Na2SO4). Solvent was evaporated at room temperature under reduced pressure to give oily residue. This was dissolved in methylene chloride and the solvent evaporated as above to obtain white foamy solid residue (8.5 g., 99.5%), as a mixture of cis and trans (ca. 85:15) isomeric sulfoxides (Va and Vb, X=C6HsNH) as determined by nmr spectrum (benzene-d6). (See Method A).
Example 4
Preparation of 2-methyl-2-carboethoxymethyl- 1 ,3-oxathiolane-3-oxide (V, X=OEt)
Method A. To a stirred solution of 1,3 - oxathiolane (IV, X=OEt) (3.806 g., 0.02 mole) in acetic acid (20 ml.) at 15--200C was added 35% hydrogen peroxide (4 mi.
about 0.04 mole) in water dropwise over 30 min. Stirring was continued at the same temperature for 2 hours. The resulting reaction mixture was placed in the ice-salt bath at -3 to 30C and diluted with ice-cold chloroform (200 ml.). Keeping the stirred mixture at 3-80C 6.25 N. NaOH (about 60 ml.) was added dropwise until it showed pH 7.0. The mixture was shaken and the organic phase separated. The aqueous phase was extracted again with ice-cold chloroform (200 ml.). The combined extract was washed with ice-water and dried (Na2SO4). Solvent was evaporated at ice-bath temperature under reduced pressure to obtain colorless oily residue (4.076 g. 98.8%), as a mixture of cis and trans (ca. 60:40) isomeric sulfoxides (Va and. Vb, X=OEt) as determined by nmr spectrum (benzene-d6): a0.99 (2t, 3H), 1.32 (s, 1.8H)a, 1.48 (s, 1.2H)b, 2.18-3.03 (m, 4H) 3.404.28 (m, 4H), a/b=Va/Vb=1.8/1.2=60/40 Found: C, 46.0; H, 6.7; S, 14.5% C8H,4SO4 requires C, 46.58; H, 6.84, S, 15.55%. These sulfoxides, particularly cis isomer, are unstable, and decompose to compound VII (X=OEt) even at room temperature. It is hard to obtain analytically pure sample due to the instability under the condition of purification. However, these sulfoxides were confirmed by converting to the known compound (see Example 6).
Method B. To a stirred solution of 1,3 - oxathiolane (IV, X=OEt) (2.000 g., 0.0105 mole) in chloroform (50 ml.) cooled in the ice-bath at 0-50C was added dropwise a solution of m - chloroperbenzoic acid in chloroform (50 ml.) over 60 min. Stirring was continued at the same temperature for 4 hours. The resulting reaction mixture was washed with ice-cold saturated sodium bicarbonate solution and ice-water, and dried (Na2SO4). Solvent was evaporated at the ice-bath temperature under reduced pressure to obtain odorless liquid residue (2.07 g., 95.0%), as a mixture of cis and trans (ca. 70:30) isomeric sulfoxides (Va and Vb, X=OEt) as determined by nmr spectrum. (See Method A).
Example 5
Preparation of 5,6-dihydro-2-methyl-1,4-oxathiin-3-carboxanilide (Ia=C6HsNH) (A) From a mixture of cis and trans isomeric sulfoxides. A solution of a mixture of cis and trans (ca. 85:15) isomeric sulfoxide (Va and Vb, X=C6HsNH) (0.5000 g., 0.00197 mole) in 1:1 mixture (20 ml.) of benzene-dimethylformamide containing a catalytic amount of p - toluenesulfonic acid monohydrate was placed in the water-bath at 500C and allowed to stir for 26 hours. Solvent was evaporated at 25-500C to give oily residue (0.5538). This residue was redissolved in benzene (20 ml.) and the solution refluxed with Dean-Stark water trap for 7 hours. The resulting reaction mixture was washed with sodium bicarbonate solution and with water, and dried (Na2SO4). Benzene was evaporated at 400C under reduced pressure to obtain crystalline solid residue (0.4455 g., 96.05%), Ia (X=C6H5NH) as shown by nmr spectrum. Recrystallization from ethyl acetate-petroleum ether gave colorless needles (0.3942 g., 85.0%), m.p. 9091 C. Nmr (CDCl3): a2.24 (s, 3H), 2.92 (t, 2H), 4.34 (t, 2H), 6.96-7.54 (m, 5H), 7.94 (s, 1H). This product is identical in every respect to that prepared. by the previously known method [U.S. Patent 3,393,202] [Note]: In the above patent, compound Ia (X=C6HsNH) was alternatively named 2,3 - dihydro - 5 - carboxanilido - 6 - methyl - 1,4 - oxathiin.
(B) From cis sulfoxide
A solution of cis sulfoxide (Va, X=C6HsNH) (0.250 g., 0.000987 mole) in 1:1 mixture (10 ml.) of benzene - dimethylformamide containing catalytic amount of
p - toluenesulfonic acid monohydrate was placed in the water-bath at 500C and
allowed to stir for 21 hours. Solvent was evaporated at 25-500C to give oily
residue (0.5538 g.). This residue was redissolved in benzene (20 ml.) and the
solution was refluxed with Dean-Stark water traD for 4 hours. The resulting
reaction mixture was washed with water and dried (Na2SO4). Benzene was
evaporated at 400C under reduced pressure to obtain crystalline solid residue
(0.2144 g., 92.45%), Ia (X=C6H5NH). This product is identical to that obtained
from the preceding reaction (A).
(C) From trans sulfoxide
A solution of trans sulfoxide (Vb, X=C6HsNH) (0.1124 g., 0.0004436 mole) in
1:1 mixture (5 ml.) of benzene - dimethylformamide containing catalytic amount of
p-toluenesulfonic acid monohydrate was placed in the water-bath at 500C and allowed to stir for 48 hours. Solvent was evaporated at 25-500C to give oily
residue (0.118 g.). This residue was redissolved in benzene (20 ml.) and the solution
refluxed with Dean-Stark water trap for 5 hours. Solvent was evaporated at 400C
under reduced pressure to obtain solid residue (0.0974 g., 93.42%), Ia (X=C6HsNH). This product is identical to that obtained from the preceding
reaction (B).
Example 6
Preparation of 5 ,6-dihydro-2-methyl- 1 ,4-oxathiin-3-carboethoxide
(Ib, X=OEt)
A solution of a mixture of cis and trans (ca. 70:30) isomeric sulfoxides (Va and
Vb, X=OEt) (0.500 g., 0.00242 mole) in 1:1 mixture (20 ml.) of benzene
dimethylformamide containing catalytic amount of p - toluenesulfonic acid
monohydrate was placed in the water-bath at 500C and allowed to stir for 6 hours.
Solvent was evaporated at 25-500C under reduced pressure to give oily liquid
residue (0.4342 g.). The residue was dissolved in benzene (20 ml.) and the solution
refluxed with Dean-Stark water trap for 4 hours. The resulting reaction mixture
was washed with sodium bicarbonate solution and with water, dried (Na2SO4) and
decolorized (charcoal). Benzene was evaporated at 400C under reduced pressure
to obtain brown oily liquid residue (0.4106 g., 90.0%), Ib (X=OEt). Nmr (CDCl3): a 1.29 (t, 3H), 2.30 (s, 3H), 2.94 (t, 2H), 4.20 (q, 2H), 4.32 (t, 2H); The product is
identical in every respect to that prepared by the previously known method [U.S.
Patent 3,393,202] [Note]: In the above patent the compound Ib (X=OEt) was
alternatively named ethyl 2,3 - dihydro - 6 - methyl - 1,4 - oxathiin - 5
carboxylate.
WHAT I CLAIM IS: 1. The process of preparing a 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin
derivative of the formula
wherein X is an amino group having the formula,
wherein R and R' are the same or different and each represents hydrogen, phenyl, alkyl having up to 15 carbon atoms, cyclohexyl, nitrophenyl, alkoxyphenyl in which the alkoxy group has up to 4 carbon atoms, benzyl, carboxyphenyl, furfuryl, halophenyl, tolyl, naphthyl, biphenyl or hydroxyphenyl; or X is an alkoxy group
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (8)
1. The process of preparing a 5,6 - dihydro - 2 - methyl - 1,4 - oxathiin
derivative of the formula
wherein X is an amino group having the formula,
wherein R and R' are the same or different and each represents hydrogen, phenyl, alkyl having up to 15 carbon atoms, cyclohexyl, nitrophenyl, alkoxyphenyl in which the alkoxy group has up to 4 carbon atoms, benzyl, carboxyphenyl, furfuryl, halophenyl, tolyl, naphthyl, biphenyl or hydroxyphenyl; or X is an alkoxy group
-OR", in which R" is a primary, secondary or tertiary alkyl group having up to 6 carbon atoms; comprising subjecting a 1,3 - oxathiolane sulfoxide of the formula
wherein X is as defined above, in a solvent to slightly acidic conditions whereby ring expansion takes place via a sulfenic acid intermediate to form compound I with loss of water, and subsequently isolating this from the resulting mixture.
2. The process of claim 1 wherein the 1,3 - oxathiolane sulfoxide of formula V is prepared by reacting a 1,3 - oxathiolane of the formula
wherein X is as defined in claim 1, with an organic peracid, hydrogen peroxide or other oxidizing agent in a solvent to form sulfoxide V, and subsequently isolating said sulfoxide V from the resulting mixture.
3. The process of claim 2 wherein the isolated 1,3 - oxathiolane sulfoxide of formula V is separated into the cis and trans isomers Va and Vb, respectively, of the formula
by thin layer or column chromatography using silica gel and chloroform methanol as a developing solvent.
4. A 1,3 - oxathiolane sulfoxide of the formula
wherein X is an amino group having the formula,
wherein R and R' are the same or different and each represents hydrogen, phenyl alkyl having up to 15 carbon atoms, cyclohexyl, nitrophenyl, alkoxyphenyl in which the alkoxy group has up to 4 carbon atoms, benzyl, carboxyphenyl, furfuryl, halophenyl, tolyl, naphthyl, biphenyl or hydroxyphenyl; or X is an alkoxy group
OR", in which R" is a primary, secondary or tertiary alkyl group having up to 6 carbon atoms.
5. 2 - methyl - 2 - carboxanilidomethyl - 1,3 - oxathiolane - 3 - oxide, the cis and trans isomers thereof and mixtures thereof.
6. 2 - methyl - 2 - carboethoxymethyl - 1,3 - oxathiolane - 3 - oxide.
7. A process as claimed in claim 1 and substantially as hereinbefore described with reference to the disclosure and examples.
8. A compound as claimed in any one of claims 4 to 6 and substantially as hereinbefore described with reference to the disclosure and examples.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA277,860A CA1036167A (en) | 1977-05-06 | 1977-05-06 | Process for preparing 5,6-dihydro-2-methyl-1,4-oxathiin derivatives |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| GB1594450A true GB1594450A (en) | 1981-07-30 |
Family
ID=4108593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB17940/78A Expired GB1594450A (en) | 1977-05-06 | 1978-05-05 | 1,3-oxathiolane sulphoxides and their use in the preparation of 5,6-dihydro-2-methyl-1,4-oxathiin derivatives |
Country Status (6)
| Country | Link |
|---|---|
| JP (2) | JPS6016954B2 (en) |
| AU (1) | AU516809B2 (en) |
| CA (1) | CA1036167A (en) |
| FR (2) | FR2401150B1 (en) |
| GB (1) | GB1594450A (en) |
| IN (1) | IN148905B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4189435A (en) * | 1977-05-06 | 1980-02-19 | Lee Wha S | Process for preparing 5,6-dihydro-2-methyl-1,4-oxathiin derivatives |
| CA1124248A (en) * | 1978-08-27 | 1982-05-25 | Andrew A. Znotins | Method of making 5,6-dihydro-2-methyl-n-phenyl-1,4- oxathiin-3-carboxamide |
| IL58177A (en) * | 1978-08-27 | 1984-08-31 | Uniroyal Ltd | Method of making 5,6-dihydro-2-methyl-n-phenyl-1,4-oxathiin-3-carboxamide |
| CA1109073A (en) * | 1978-09-05 | 1981-09-15 | Uniroyal Chemical Co./Uniroyal Chemical Cie. | Method of making 5,6-dihydro-2-methyl-n-phenyl-1,4- oxathiin-3-carboxamide |
| US4182716A (en) * | 1978-09-05 | 1980-01-08 | Uniroyal, Ltd. | Method of making 5,6-dihydro-2-methyl-N-phenyl-1,4-oxathiin-3-carboxamide |
| CA1166262A (en) * | 1981-08-11 | 1984-04-24 | Frederick M.M. Hager | Synthesis of intermediate for the manufacture of 5,6- dihydro-2-methyl-n-phenyl-1,4-oxathiin-3-carboxamide |
| JPS5922547A (en) * | 1982-07-28 | 1984-02-04 | 富士電機株式会社 | Apparatus for controlling medical bed |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5010597A (en) * | 1973-05-25 | 1975-02-03 |
-
1977
- 1977-05-06 CA CA277,860A patent/CA1036167A/en not_active Expired
-
1978
- 1978-05-03 IN IN323/DEL/78A patent/IN148905B/en unknown
- 1978-05-05 AU AU35837/78A patent/AU516809B2/en not_active Expired
- 1978-05-05 FR FR7814495A patent/FR2401150B1/en not_active Expired
- 1978-05-05 GB GB17940/78A patent/GB1594450A/en not_active Expired
- 1978-05-06 JP JP53054007A patent/JPS6016954B2/en not_active Expired
- 1978-09-15 FR FR7827026A patent/FR2396010A1/en active Granted
-
1982
- 1982-01-04 JP JP57000157A patent/JPS57131786A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS53149976A (en) | 1978-12-27 |
| FR2401150A1 (en) | 1979-03-23 |
| JPS6135194B2 (en) | 1986-08-12 |
| JPS6016954B2 (en) | 1985-04-30 |
| IN148905B (en) | 1981-07-18 |
| FR2396010A1 (en) | 1979-01-26 |
| AU516809B2 (en) | 1981-06-25 |
| FR2401150B1 (en) | 1985-08-30 |
| JPS57131786A (en) | 1982-08-14 |
| AU3583778A (en) | 1979-11-08 |
| CA1036167A (en) | 1978-08-08 |
| FR2396010B1 (en) | 1985-02-22 |
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| Date | Code | Title | Description |
|---|---|---|---|
| PS | Patent sealed [section 19, patents act 1949] | ||
| PCNP | Patent ceased through non-payment of renewal fee |