US2937169A - Toiutf alrtqn of h - Google Patents
Toiutf alrtqn of h Download PDFInfo
- Publication number
- US2937169A US2937169A US2937169DA US2937169A US 2937169 A US2937169 A US 2937169A US 2937169D A US2937169D A US 2937169DA US 2937169 A US2937169 A US 2937169A
- Authority
- US
- United States
- Prior art keywords
- formic acid
- moles
- sulfamylaniline
- compound
- formamide
- 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.)
- Expired - Lifetime
Links
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 42
- 235000019253 formic acid Nutrition 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- QRKDOAWSBBGNLE-UHFFFAOYSA-N 2h-1,2,4-benzothiadiazine Chemical compound C1=CC=C2N=CNSC2=C1 QRKDOAWSBBGNLE-UHFFFAOYSA-N 0.000 claims 1
- ZHNUHDYFZUAESO-NJFSPNSNSA-N aminoformaldehyde Chemical compound N[14CH]=O ZHNUHDYFZUAESO-NJFSPNSNSA-N 0.000 claims 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 18
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 16
- 238000006798 ring closing metathesis reaction Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- -1 sulfoxide compound Chemical class 0.000 description 5
- 150000001408 amides Chemical class 0.000 description 4
- 229940113088 dimethylacetamide Drugs 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IHJCXVZDYSXXFT-UHFFFAOYSA-N chloraminophenamide Chemical compound NC1=CC(Cl)=C(S(N)(=O)=O)C=C1S(N)(=O)=O IHJCXVZDYSXXFT-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- CGVXNZNOSZFBCD-UHFFFAOYSA-N 1,1-dioxo-4h-1$l^{6},2,4-benzothiadiazine-7-sulfonamide Chemical compound N1=CNS(=O)(=O)C2=CC(S(=O)(=O)N)=CC=C21 CGVXNZNOSZFBCD-UHFFFAOYSA-N 0.000 description 1
- BOZSDDFQWJUBNG-UHFFFAOYSA-N 4-aminobenzene-1,3-disulfonamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1S(N)(=O)=O BOZSDDFQWJUBNG-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MYWUZJCMWCOHBA-VIFPVBQESA-N methamphetamine Chemical compound CN[C@@H](C)CC1=CC=CC=C1 MYWUZJCMWCOHBA-VIFPVBQESA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/15—Six-membered rings
- C07D285/16—Thiadiazines; Hydrogenated thiadiazines
- C07D285/18—1,2,4-Thiadiazines; Hydrogenated 1,2,4-thiadiazines
- C07D285/20—1,2,4-Thiadiazines; Hydrogenated 1,2,4-thiadiazines condensed with carbocyclic rings or ring systems
- C07D285/22—1,2,4-Thiadiazines; Hydrogenated 1,2,4-thiadiazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D285/24—1,2,4-Thiadiazines; Hydrogenated 1,2,4-thiadiazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with oxygen atoms directly attached to the ring sulfur atom
Definitions
- My invention relatesto the production of- 1,2,4-benzothiadiazine-1,1-dioxides, and particularly to a process fl;
- the benzenoid nucleus may carry oneor more substituents in addition to the amino and sulfamyl radicals.
- Such other radicals may be another amino or sulfamyl group, halogen, lower alkyl which may or may not be substituted with halogens, hydroxy or alkoxy or nitro radicals.
- Representative of such substituted benzenoid starting materials are the ones described and claimed in Novello Patent 2,809,194.
- the aforementioned patent proposes etfectingthe de sired ring closure by the use of large amounts of formic acid. ' While this mode of preparation is in many respects highly satisfactory, it has the disadvantage that a very large molar excess of formic acidmust be used.
- Another method proposes to use formamide to effect the ring closure in place of formic acid. This proposed method has the advantage of requiring a relatively small molar excess of formamide but has the disadvantage that con siderably reduced yields and lower quality are incidental high quality based on both the aniline derivative and onthe material employed to effect the ring closure. This is accomplished by using a mixture of formic acid and another compound which may be formamide, dimethylformamide, dimethylacet-amide, or dimethylsulfoxide. Formamide is the preferred material.
- the reduction in the amount of formic acid required to efiect the ring closure is very considerable.
- the molar ratio of formic acid to the sulfamylaniline is in excess of about 30 to 1 to obtain yields in therange of 80 to 90%.
- the method of this invention produces up to 97 yields with the use of -a much smaller amount of formic acid, for example, a molar proportion of 4 moles of formic acid to 1 mole of the sulfamylaniline.
- the ring closure is effected by admixing the sulfamylaniline, formic acid,"and an amide or sulfoxide of the aforementioned group;
- the temperature is in the range of 100-150 C., and the preferred range is125- 140 C.
- Lower temperatures than those mentioned can beemployed, such as room temperature but the reaction time increases appreciably at such lowtemperatures and-. accordingly,-it will notfnormally be desirable to operate at such low temperatures.
- the proportions of the formic acid-and the amide or sulfoxide: compound with res'pectto each other and the sulfamylaniline can be varied over a rather wide range.- These proportions shouldbe from one-half to ten moles of formic acid withrespect to" thesulfamylaniline and from one-half to ten moles of amide or sulfoxide compound. Preferably, from one to six moles of the formic acid and forniamide or sulfoxide compound should be used for eachirnole of sulfamylaniline.
- Example 2 A solution of 25 g. of 2,4-di-sulfamylaniline in 25 ml. dimethylsulfoxide at 140 treated under conditions similar to those described in Example 1 in which formic acid is also present, yielded solid 7-sulfamyl-1,2,4-benzothiadiazine-1,1-dioxide, also in nearly quantitative yield.
- Examples 1 and 2 also serve to illustrate other examples involving corresponding reactions in which formamide, and dimeth-ylacetamide are used in combination with formic acid. 7
- Example 3 A slurry 6:375 g. (.131 mole) of purified 5-chloro 2,4-disulfamylaniline in 25 ml. (.586 mole) of formic acid and 25 ml. of formamide (.633 mole) was heated at 125 C. During the heating, which was continued for lffhours, a solution formed and thereafter a precipitate appeared. After the heatingperiod, the mass was cooled to 50 C., ml. of water was then added while stirring the mass, and the diluted mass was then cooled to 5- -.C. and aged for 1 hour at this temperature while"- being -stirred.
- Example 3 The process of Example 3 is carried out but about one 1 mole of the formic acidand about 011525151; of the iorm- 7v amide per mole of the aniline compound is employed.
- Example 5 Theiprocess of Example 3-is carried out but about six moles of the formic acid and about six-moles of the formamide per mole of the aniline compound is employed.
- 4-benzothiadiazinc-l,l-dioxide which comprises mixing together 5-chloro-2,4-disulfamylaniline, from one to six moles of formic acid and from'one to six moles of founam ep o eo thel ne.
- ir p l References (:i ted'iri the file of this patent I UNITED STATE S PATENTS l filovello Oct. 8, 1957 OTHER REFERENCES Freeman et al.: J. Org. Chem vol. 16, p. 816 (1951).
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
- Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
Description
. ..Phtented ma 17,- .1960
aomnimr rz ER I YC iCSRwQ David F. Hinkley, riainfiuii',Mana ua:term-era.
00., Inc, Rahway, NJ., a corporation of New'jersey 1 No Drawing. .A lication wast... is, 1958 Serial N0."76'3,1' 91 I 4 Claims. (Cl. 2150:2213
' My invention relatesto the production of- 1,2,4-benzothiadiazine-1,1-dioxides, and particularly to a process fl;
which produces these compounds by a ring-closure meth od which may be represented asfollows:
The benzenoid nucleus may carry oneor more substituents in addition to the amino and sulfamyl radicals.
which are shown. Such other radicals may be another amino or sulfamyl group, halogen, lower alkyl which may or may not be substituted with halogens, hydroxy or alkoxy or nitro radicals. Representative of such substituted benzenoid starting materials are the ones described and claimed in Novello Patent 2,809,194.
The aforementioned patent proposes etfectingthe de sired ring closure by the use of large amounts of formic acid. 'While this mode of preparation is in many respects highly satisfactory, it has the disadvantage that a very large molar excess of formic acidmust be used. Another method proposes to use formamide to effect the ring closure in place of formic acid. This proposed method has the advantage of requiring a relatively small molar excess of formamide but has the disadvantage that con siderably reduced yields and lower quality are incidental high quality based on both the aniline derivative and onthe material employed to effect the ring closure. This is accomplished by using a mixture of formic acid and another compound which may be formamide, dimethylformamide, dimethylacet-amide, or dimethylsulfoxide. Formamide is the preferred material.
When the method of the invention is employed, the reduction in the amount of formic acid required to efiect the ring closure is very considerable. Thus, by the method of the aforementioned patent, the molar ratio of formic acid to the sulfamylaniline is in excess of about 30 to 1 to obtain yields in therange of 80 to 90%. The method of this invention produces up to 97 yields with the use of -a much smaller amount of formic acid, for example, a molar proportion of 4 moles of formic acid to 1 mole of the sulfamylaniline.
According to the invention, the ring closure is effected by admixing the sulfamylaniline, formic acid,"and an amide or sulfoxide of the aforementioned group; and
heating the resulting mixture at a temperature between 75 C. and 175 C. for a time sufficient to permit ring closure to occur. Advantageously, the temperature is in the range of 100-150 C., and the preferred range is125- 140 C. Lower temperatures than those mentioned can beemployed, such as room temperature but the reaction time increases appreciably at such lowtemperatures and-. accordingly,-it will notfnormally be desirable to operate at such low temperatures. Th'e pressure for the reactionis not critical. Conveniently, atmospheric;pressureviszzeinployed: but reduced or increased, pressurecan-fbezused. *Appreciable amounts of the desired=endlp'roductvwilltbe.obtainedin one-half hour ids best to. let the' reaction-continue foriat least an hour and in four hours time-ithe maximum-yield ordinarily a The proportions of the formic acid-and the amide or sulfoxide: compound with res'pectto each other and the sulfamylaniline can be varied over a rather wide range.- These proportions shouldbe from one-half to ten moles of formic acid withrespect to" thesulfamylaniline and from one-half to ten moles of amide or sulfoxide compound. Preferably, from one to six moles of the formic acid and forniamide or sulfoxide compound should be used for eachirnole of sulfamylaniline.
The invention will further be clarified by the following examples:
' Example 1 v To a solution of 25 g. O-sulfamylaniline (0.145 mole) in 25ml. (0.323 mole) dimethylformamide at- 125 C. was added 25ml. (0.586 mole) 90% formic acid. The
solution was heated 2 hours at 125, cooled to and'v the solid product precipitated from solution by slow addition of 200 ml. of water. The resulting slurry was cooled to 10?, and aged 1 hour under stirring at this temperature. The slurry was filtered, the cake washed with 50% methanol (v./v.), and the solid 1,2,4-benzo thiadiazine-l,l-dioxide dried to constant weight. The yield was essentially quantitative.
Example 2 A solution of 25 g. of 2,4-di-sulfamylaniline in 25 ml. dimethylsulfoxide at 140 treated under conditions similar to those described in Example 1 in which formic acid is also present, yielded solid 7-sulfamyl-1,2,4-benzothiadiazine-1,1-dioxide, also in nearly quantitative yield.
Examples 1 and 2 also serve to illustrate other examples involving corresponding reactions in which formamide, and dimeth-ylacetamide are used in combination with formic acid. 7
Example 3 A slurry 6:375 g. (.131 mole) of purified 5-chloro 2,4-disulfamylaniline in 25 ml. (.586 mole) of formic acid and 25 ml. of formamide (.633 mole) was heated at 125 C. During the heating, which was continued for lffhours, a solution formed and thereafter a precipitate appeared. After the heatingperiod, the mass was cooled to 50 C., ml. of water was then added while stirring the mass, and the diluted mass was then cooled to 5- -.C. and aged for 1 hour at this temperature while"- being -stirred. Following the aging, the diluted mass was filtered to separate the product benzothiadiazine compound as filter cake. The cake was washed with water and methanol and then dried to constant weight. This procedure yielded a crude desired product in the form of .,$vhite crystals having M.P. 358.2 C. The crude product was purified and an overall yield of puripurified product was in the form of white crystals, M.P.
The process of Example 3 is carried out but about one 1 mole of the formic acidand about 011525151; of the iorm- 7v amide per mole of the aniline compound is employed.
Example 5 Theiprocess of Example 3-is carried out but about six moles of the formic acid and about six-moles of the formamide per mole of the aniline compound is employed.
What is claimed is: v I
1. The process of producinga 1,2,4-benzothiadiazine-1, l-dioxide compound which comprises mixing together at a temperature .of from 75 C. to 175 C. for a periodof from' to:4 hours; ortho'sul'famylaniline, formieacid and a compound selected from the group's consisting of formamide, dimethylformamide, dimethylacetamide and dimethylsulfoxide, said selected compound being present in the' ratioof from one-half to'ten molesof the sulfamylaniline, and the formic acid being present in the ratio from one-half to ten moles of the sulfamylaniline.
2. The process according to claim 1 in ivhichthe temperature is between 100 and 150 C.
3. The process according to claim 1 in which said selected compound is present in the ratio of from one to six moles of the sulfamylanilinc, and the formic acid is present in the ratio of from one to six moles of the sulfamylaniline.
4. The process for producing 6-chloro-7-sulfamyl-L2,
4-benzothiadiazinc-l,l-dioxide,which comprises mixing together 5-chloro-2,4-disulfamylaniline, from one to six moles of formic acid and from'one to six moles of founam ep o eo thel ne. ir p l References (:i ted'iri the file of this patent I UNITED STATE S PATENTS l filovello Oct. 8, 1957 OTHER REFERENCES Freeman et al.: J. Org. Chem vol. 16, p. 816 (1951).
Novello: I. Am. Chem. Soc., vol. 79, pp. 2028-2029 (1957 I; I
Claims (1)
1. THE PROCESS OF PRODUCING A 1,2,4-BENZOTHIADIAZINE,-1, 1-DIOXIDE COMPOUND WHICH COMPRISES MIXING TOGETHER AT A TEMPERATURE OF FROM 75*C. TO 175*C. FOR A PERIOD OF FROM 1/2 TO 4 HOURS, ORTHO SULFAMYL ANILINE, FORMIC ACID AND A COMPOUND SELECTED FROM THE GROUPS CONSISTING OF FORMAMIDE, DIMETHYLFORMAMIDE, DIMETHYLACETAMIDE AND DIMETHYLSULFOXIDE, SAID SELECTED COMPOUND BEING PRESENT IN THE RATIO OF FROM ONE-HALF TO TEN MOLES OF THE SULFAMYLANILINE, AND THE FORMIC ACID BEING PRESENT IN THE RATIO FROM ONE-HALF TO TEN MOLES OF THE SULFAMYLANILINE.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2937169A true US2937169A (en) | 1960-05-17 |
Family
ID=3449336
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US2937169D Expired - Lifetime US2937169A (en) | Toiutf alrtqn of h |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US2937169A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004017964A1 (en) | 2002-08-19 | 2004-03-04 | Pfizer Products Inc. | Combination therapy for hyperproliferative diseases |
| US20050037063A1 (en) * | 2003-07-21 | 2005-02-17 | Bolton Anthony E. | Combined therapies |
| US20050101661A1 (en) * | 1996-09-04 | 2005-05-12 | Soldato Piero D. | Use of nitroderivatives in urinary incontinence |
| US20060247272A1 (en) * | 2004-09-23 | 2006-11-02 | Pfizer Inc | 4-Amino Substituted-2-Substituted-1,2,3,4-tetrahydroquinoline Compounds |
| WO2007062314A2 (en) | 2005-11-23 | 2007-05-31 | Bristol-Myers Squibb Company | Heterocyclic cetp inhibitors |
| WO2008070496A2 (en) | 2006-12-01 | 2008-06-12 | Bristol-Myers Squibb Company | N- ( (3-benzyl) -2, 2- (bis-phenyl) -propan-1-amine derivatives as cetp inhibitors for the treatment of atherosclerosis and cardiovascular diseases |
| EP2392567A1 (en) | 2005-10-21 | 2011-12-07 | Bristol-Myers Squibb Company | Benzothiazine derivatives and their use as lxr modulators |
| WO2014170786A1 (en) | 2013-04-17 | 2014-10-23 | Pfizer Inc. | N-piperidin-3-ylbenzamide derivatives for treating cardiovascular diseases |
| WO2016055901A1 (en) | 2014-10-08 | 2016-04-14 | Pfizer Inc. | Substituted amide compounds |
| WO2020150473A2 (en) | 2019-01-18 | 2020-07-23 | Dogma Therapeutics, Inc. | Pcsk9 inhibitors and methods of use thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809194A (en) * | 1957-10-08 | Thiadiazine type natriuretic agents |
-
0
- US US2937169D patent/US2937169A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2809194A (en) * | 1957-10-08 | Thiadiazine type natriuretic agents |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050101661A1 (en) * | 1996-09-04 | 2005-05-12 | Soldato Piero D. | Use of nitroderivatives in urinary incontinence |
| US7544711B2 (en) | 1996-09-04 | 2009-06-09 | Nicox S.A. | Use of nitroderivatives in urinary incontinence |
| WO2004017964A1 (en) | 2002-08-19 | 2004-03-04 | Pfizer Products Inc. | Combination therapy for hyperproliferative diseases |
| US20050037063A1 (en) * | 2003-07-21 | 2005-02-17 | Bolton Anthony E. | Combined therapies |
| US20060247272A1 (en) * | 2004-09-23 | 2006-11-02 | Pfizer Inc | 4-Amino Substituted-2-Substituted-1,2,3,4-tetrahydroquinoline Compounds |
| EP2392567A1 (en) | 2005-10-21 | 2011-12-07 | Bristol-Myers Squibb Company | Benzothiazine derivatives and their use as lxr modulators |
| WO2007062314A2 (en) | 2005-11-23 | 2007-05-31 | Bristol-Myers Squibb Company | Heterocyclic cetp inhibitors |
| WO2008070496A2 (en) | 2006-12-01 | 2008-06-12 | Bristol-Myers Squibb Company | N- ( (3-benzyl) -2, 2- (bis-phenyl) -propan-1-amine derivatives as cetp inhibitors for the treatment of atherosclerosis and cardiovascular diseases |
| WO2014170786A1 (en) | 2013-04-17 | 2014-10-23 | Pfizer Inc. | N-piperidin-3-ylbenzamide derivatives for treating cardiovascular diseases |
| WO2016055901A1 (en) | 2014-10-08 | 2016-04-14 | Pfizer Inc. | Substituted amide compounds |
| WO2020150473A2 (en) | 2019-01-18 | 2020-07-23 | Dogma Therapeutics, Inc. | Pcsk9 inhibitors and methods of use thereof |
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