US3723426A - Benzoxazinediones - Google Patents
Benzoxazinediones Download PDFInfo
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- US3723426A US3723426A US00118544A US3723426DA US3723426A US 3723426 A US3723426 A US 3723426A US 00118544 A US00118544 A US 00118544A US 3723426D A US3723426D A US 3723426DA US 3723426 A US3723426 A US 3723426A
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- United States
- Prior art keywords
- chloro
- benzoxazine
- dione
- nitrophenyl
- tert
- Prior art date
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- UXTZUUVTGMDXNG-UHFFFAOYSA-N 1,2-benzoxazine-3,4-dione Chemical class C1=CC=C2C(=O)C(=O)NOC2=C1 UXTZUUVTGMDXNG-UHFFFAOYSA-N 0.000 title abstract description 4
- 238000000034 method Methods 0.000 abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 abstract description 6
- 239000001257 hydrogen Substances 0.000 abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 abstract description 5
- 241000251745 Petromyzon marinus Species 0.000 abstract description 4
- 125000003710 aryl alkyl group Chemical group 0.000 abstract description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 16
- 241000235789 Hyperoartia Species 0.000 description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 241001465754 Metazoa Species 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 241000251468 Actinopterygii Species 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 241000277275 Oncorhynchus mykiss Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- -1 alpha-methylbenzyl Chemical group 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- RIFGWPKJUGCATF-UHFFFAOYSA-N ethyl chloroformate Chemical compound CCOC(Cl)=O RIFGWPKJUGCATF-UHFFFAOYSA-N 0.000 description 4
- 230000001418 larval effect Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- 231100000167 toxic agent Toxicity 0.000 description 4
- 239000003440 toxic substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- UXOUKMQIEVGVLY-UHFFFAOYSA-N morin Natural products OC1=CC(O)=CC(C2=C(C(=O)C3=C(O)C=C(O)C=C3O2)O)=C1 UXOUKMQIEVGVLY-UHFFFAOYSA-N 0.000 description 3
- 235000007708 morin Nutrition 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- FTCUFQRGPJZIID-UHFFFAOYSA-N [2-(phenylcarbamoyl)phenyl] nitrate Chemical compound [O-][N+](=O)OC1=CC=CC=C1C(=O)NC1=CC=CC=C1 FTCUFQRGPJZIID-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000006916 nutrient agar Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- HTXGLMUZXAFRII-UHFFFAOYSA-N 5-chloro-2-hydroxy-n-(4-nitrophenyl)benzamide Chemical compound OC1=CC=C(Cl)C=C1C(=O)NC1=CC=C([N+]([O-])=O)C=C1 HTXGLMUZXAFRII-UHFFFAOYSA-N 0.000 description 1
- 241000132092 Aster Species 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 241001327647 Oncorhynchus mykiss gairdneri Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- FZFAMSAMCHXGEF-UHFFFAOYSA-N chloro formate Chemical compound ClOC=O FZFAMSAMCHXGEF-UHFFFAOYSA-N 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KWHDXJHBFYQOTK-UHFFFAOYSA-N heptane;toluene Chemical compound CCCCCCC.CC1=CC=CC=C1 KWHDXJHBFYQOTK-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 231100000518 lethal Toxicity 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XMJHPCRAQCTCFT-UHFFFAOYSA-N methyl chloroformate Chemical compound COC(Cl)=O XMJHPCRAQCTCFT-UHFFFAOYSA-N 0.000 description 1
- VBEGHXKAFSLLGE-UHFFFAOYSA-N n-phenylnitramide Chemical compound [O-][N+](=O)NC1=CC=CC=C1 VBEGHXKAFSLLGE-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- AHWALFGBDFAJAI-UHFFFAOYSA-N phenyl carbonochloridate Chemical compound ClC(=O)OC1=CC=CC=C1 AHWALFGBDFAJAI-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- XIPFMBOWZXULIA-UHFFFAOYSA-N pivalamide Chemical compound CC(C)(C)C(N)=O XIPFMBOWZXULIA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- IVRIRQXJSNCSPQ-UHFFFAOYSA-N propan-2-yl carbonochloridate Chemical compound CC(C)OC(Cl)=O IVRIRQXJSNCSPQ-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
- C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
- C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
- C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
- C07D265/24—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with hetero atoms directly attached in positions 2 and 4
- C07D265/26—Two oxygen atoms, e.g. isatoic anhydride
Definitions
- R is hydrogen or methyl and R is hydrogen alkyl of from one to four carbon atoms, or aralkyl of from seven to II carbon atoms; and to a method of controlling sea lamprey.
- novel compounds of the invention can be represented by the formula:
- R is hydrogen or methyl and R is hydrogen, alkyl of from one to four carbon atoms, or aralkyl of from seven to 11 carbon atoms.
- suitable alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiarybutyl.
- suitable aralkyl are benzyl, alpha-methylbenzyl, para-methylbenzyl, and paratert.-butylbenzyl.
- the nitro group can be in any substituent position on the phenyl ring, but preferably in positions meta or para to the point of attachment to the nitrogen atom.
- Test animals were larvae of the sea lamprey (Petromyzon marinus) and fingerling rainbow trout (Salmo gairdneri), both ranging from about 3.0 to about 5.0 inches in length. After the animals were tempered and acclimated to the test temperature, appropriate amounts of halo-nitrosalicylanilide, in acetone as intermediate solvent, were added to produce the desired concentrations. Other conditions and results are given in the following tables.
- Test Period 24 Hours.
- Test Period 24 Hours.
- the compound 6-chloro-3-(4-nitrophenyl)-2H-1,3- benzoxazine-2,4-(3H)-dione is also an effective bacteriostat and it inhibits the growth of Staphylococcus aureus at 2ppm in nutrient agar. To test for effect on bacteria the compounds are incorporated in nutrient agar to various dilutions. The plates are inoculated with bacteria and are incubated at 37 C. for 48 hours then observed for evidence of bacterial growth.
- novel compounds of the invention can be prepared by reacting the appropriate nitrosalicylanilide or its alkali metal salt with an alkyl chloroformate ester preferably in the presence of a solvent, which lacks free hydroxyl groups.
- the reaction can be conducted at a temperature between about C. and about 120 C. in between about 1% and about 4 hours.
- chloroformate asters are ethyl chloroformate, methyl chloroformate, isopropyl chloroformate and phenyl chloroformate.
- Suitable solvents are the aliphatic compounds such as heptane, heterocyclic compounds such as pyridine, amides such as N,N-dimethylformamide and aromatic compounds such as benzene and toluene.
- the amides may also serve to catalyze the reaction.
- the substituted nitrosalicylanilides can be prepared by treating the appropriate salicylic acid with a nitroaniline preferably in the presence of a solvent and a dehydrating agent and catalyst.
- suitable solvents are alkanes such as heptane, aromatic compounds such as benzene, toluene and chlorobenzene.
- suitable dehydrating agents are thionyl chloride and phosphorous trichloride.
- suitable catalysts are the N,N-dimethy1amides such as dimethylformamide, dimethylacetamide and dimethylpropionamide.
- the reaction can be conducted at a temperature between about 80 and about 150 C. in a period between about 1 and about 12 hours at atmospheric pressure.
- EXAMPLE 3 8-benzyl-6-chloro-3-(4-nitrophenyl)-l ,3-(2H)- benzoxazine-2 ,4-( 3H )-dione
- EXAMPLE 4 In accordance with the procedure of Example 3, 8- tert.-butyl-6-chloro-5-methyl-3-(4-nitrophenyl)-2H- l,3-benzoxazine-2,4-(3H)-dione was prepared from 3- tert.-butyl-5-chloro-6-methyl-4-nitrosalicylanilide and ethyl chloroformate in 25.7 percent yield; m.p. l43-6 C.
- EXAMPLE 6 Preparation of 3-tert.-butyl5-chloro- 6-methyl-4'- nitrosalicylanilide
- a 500 ml. reaction flask equipped with a stirrer, thermometer and condenser topped with a drying tube was charged 48.5 grams of 3-tert.-butyl-5-chloro-6-
- EXAMPLE 7 Preparation of 3-benzyl-5-chloro-4-nitrosalicylanilide
- the subject compound was prepared having a m.p. l868
- the concentration of toxicant will vary considerably upon conditions such as temperature, pH of the water, types of food and game fish, and the like and is best determined experimentally by laboratory tests stimulating conditions of actual proposed use.
- the lamprecidal composition can be added directly to the water in the form of a fine powder, with or without wetting or conditioning agents or the compound can be added in liquid form as solutions, suspensions or emulsions.
- the process of the invention is broadly a process for controlling lamprey comprising treating said lamprey with a waterdispersible composition said composition comprising a minor but effective amount of toxicant compound of the invention.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
Novel benzoxazinediones of the formula:
WHEREIN R1 is hydrogen or methyl and R2 is hydrogen, alkyl of from one to four carbon atoms, or aralkyl of from seven to 11 carbon atoms; and to a method of controlling sea lamprey.
WHEREIN R1 is hydrogen or methyl and R2 is hydrogen, alkyl of from one to four carbon atoms, or aralkyl of from seven to 11 carbon atoms; and to a method of controlling sea lamprey.
Description
United States Patent 1 Fuchsman I54] BENZOXAZINEDIONES [75] Inventor: Charles H. Fuchsman, Cleveland Heights, Ohio [73] Assignee: Ferro Corporation, Cleveland, Ohio [22] Filed: Feb. 24, 1971 [21] '-Appl. No.: 118,544
UNITED STATES PATENTS 3,355,453 [1/1967 Hasspacher 260/244 OTHER PUBLICATIONS Veibel et al., Chem. Zentralblatt, (1944) p. I73.
{451 Mar. 27, 1973 Primary ExaminerHarry I Mozitz Att0rneyMilton L. Simmons ABSTRACT Novel benzoxazinediones of the formula:
wherein R is hydrogen or methyl and R is hydrogen alkyl of from one to four carbon atoms, or aralkyl of from seven to II carbon atoms; and to a method of controlling sea lamprey.
4 Claims, No Drawings BENZOXAZINEDIONES BACKGROUND OF THE INVENTION In recent years the lamprey has become a serious threat to the extermination of game fish particularly in the Great Lakes of North America. Several compounds have been suggested for use in controlling lamprey but most of these compounds destroy the game fish at a concentration very close to that which becomes lethal to lamprey larvae. Thus with these compounds it is necessary to destroy the game fish with the lamprey and then restock the stream with more game fish.
DESCRIPTION OF THE INVENTION It is now been discovered that a new class of benzoxazinediones can be employed to control lamprey some of which compounds are selective to lamprey without harming desirable game fish such as rainbow trout.
The novel compounds of the invention can be represented by the formula:
wherein R is hydrogen or methyl and R is hydrogen, alkyl of from one to four carbon atoms, or aralkyl of from seven to 11 carbon atoms. Exemplary of suitable alkyl are methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tertiarybutyl. Exemplary of suitable aralkyl are benzyl, alpha-methylbenzyl, para-methylbenzyl, and paratert.-butylbenzyl. The nitro group can be in any substituent position on the phenyl ring, but preferably in positions meta or para to the point of attachment to the nitrogen atom.
Represent examples of compounds of the invention are:
8-tert.-butyl-6-chloro-3-(4-nitrophenyl)-2H-l ,3-
benzoxazine-2,4-(3H)-dione 8-benzyl-6-chloro-3-( 4-nitrophenyl )-2H-l ,3-benzoxazine-2,4-(3H)-dione 6-chloro-3-(4-nitrophenyl)-2H- l ,3-benzoxazine-2,4-
(3H)-dione 8-tert.-butyl-6-chloro-5-methyl-3-(4-nitrophenyl)- 2H-l,3-benzoxazine-2,4-(3H)-dione 6-chloro-5-methyl-3-(4-nitrophenyl)-2H-1,3-
benzoxazine-2,4-(3H)-dione 8-tert.-butyl-6-chloro-3-( 3-nitrophenyl)-2H-l ,3-
benzoxazine-2,4-(3H)dione 6-chloro-3-(2-nitrophenyl)-2H- l ,3-benzoxazine-2,4-
(3H)-dione 8-alpha-methylbenzyl-o-chloro-3-(4-nitrophenyl)- 2H-l ,3-benzoxazine-2,4-( 3H )-dione 8-p-tert.-butylbenzyl-6-chloro-3-(4-nitrophenyl)- 2H-1,3-benzoxazine-2,4-(3H)-dione The utility of the compounds of the invention as lamprecides and the selectivity of certain compounds with respect to larval lampreys over rainbow trout, are illustrated by the following examples. The tests were carried out in lO-liter glass battery jars (IO-inch diameter), each containing 6 liters of solution. The jars were aerated by means of standard stone airbreakers to maintain oxygen levels at near-saturation. Temperatures (55 F.) were held constant by immersion of the testjars in a water bath.
Test animals were larvae of the sea lamprey (Petromyzon marinus) and fingerling rainbow trout (Salmo gairdneri), both ranging from about 3.0 to about 5.0 inches in length. After the animals were tempered and acclimated to the test temperature, appropriate amounts of halo-nitrosalicylanilide, in acetone as intermediate solvent, were added to produce the desired concentrations. Other conditions and results are given in the following tables.
TABLE I 8-tert.-butyl-6-chloro-3-(4-nitrophenyl)-2H-l ,3- benzoxazine-2,4-(3H)-dione.
[Water Source: Lake Huron.
Test Period: 24 hours' Water Temperature: 55 F. ]v
Larval lampreys Rainbow trout Concentration Num-Num- Morin parts/' her her tality Number Mortality million of of of of test (percentage tests test total animals of total anitest test animals) mals animals) 0.01 l 2 0.0 2 0.0 0.05 l 2 100.0 2 0.0 0.07 l 2 100.0 2 0.0 0.09 l 2 100.0 2 0.0 0.1 l 2 100.0 2 0.0 0.3 l 2 100.0 2 l00.0
TABLE II 6-chloro-3-(4-nitrophenyl)-2H-l ,3-benzoxazine-2,4-
(3H )-dione [Water Source: Lake Huron.
Test Period: 24 Hours.
Water Temperature: 5 5 F.]
Larval lampreys Rainbow trout Concen- Numtration ber Num- Morin parts] of her tality Number Mortality million tests of of of test (percentage tests test total animals of total ani test anitest animals) mals) mals) 0.07 l 2 0.0 2 0.0 0.09 l 2 100.0 2 0.0 0.1 I 2 100.0 2 0.0 0.3 l 2 l00.0 2 50.0 0.5 l 2 I00.0 2 [00.0
TABLE III 8-benzyl-6-chIoro-3-(4-nitrophenyl)-2H-l ,3- benzoxazine-2,4-(3H )-dione [Water Source: Lake Huron.
Test Period: 24 Hours.
Water Temperature: 5 5 F.]
Larval lampreys Rainbow trout Concen- Numtration ber Num- Morin parts/ of her tality Number Mortality million tests of of of test (percentage test total animals of total anitest anitest animals) mals mals 0.1 l 2 0.0 2 0.0 0.3 l 2 100.0 2 50.0 0.5 1 2 100.0 2 100.0
It is apparent from the above data that the compounds of Tables 1, 11 and Ill and particularly 1 and 11, are selective toxicants to lamprey larva and for this reason are the preferred compounds of the invention.
The compound 6-chloro-3-(4-nitrophenyl)-2H-1,3- benzoxazine-2,4-(3H)-dione is also an effective bacteriostat and it inhibits the growth of Staphylococcus aureus at 2ppm in nutrient agar. To test for effect on bacteria the compounds are incorporated in nutrient agar to various dilutions. The plates are inoculated with bacteria and are incubated at 37 C. for 48 hours then observed for evidence of bacterial growth.
The novel compounds of the invention can be prepared by reacting the appropriate nitrosalicylanilide or its alkali metal salt with an alkyl chloroformate ester preferably in the presence of a solvent, which lacks free hydroxyl groups. The reaction can be conducted at a temperature between about C. and about 120 C. in between about 1% and about 4 hours.
Exemplary of suitable chloroformate asters are ethyl chloroformate, methyl chloroformate, isopropyl chloroformate and phenyl chloroformate.
Exemplary of suitable solvents are the aliphatic compounds such as heptane, heterocyclic compounds such as pyridine, amides such as N,N-dimethylformamide and aromatic compounds such as benzene and toluene. The amides may also serve to catalyze the reaction.
The substituted nitrosalicylanilides can be prepared by treating the appropriate salicylic acid with a nitroaniline preferably in the presence of a solvent and a dehydrating agent and catalyst. Exemplary of suitable solvents are alkanes such as heptane, aromatic compounds such as benzene, toluene and chlorobenzene. Exemplary of suitable dehydrating agents are thionyl chloride and phosphorous trichloride. Exemplary of suitable catalysts are the N,N-dimethy1amides such as dimethylformamide, dimethylacetamide and dimethylpropionamide. The reaction can be conducted at a temperature between about 80 and about 150 C. in a period between about 1 and about 12 hours at atmospheric pressure.
The following examples will serve to illustrate the invention. All percentages are by weight.
EXAMPLE 1 8-t-butyl-6-chloro-3 4-nitrophenyl)-2l-l-l ,3- benzoxazine-2,4-(3H)-dione To a 200 ml. reaction flask equipped with a stirrer, thermometer, dropping funnel and reflux condenser with drying tube were charged 30 ml. of pyridine and 10.0 grams of 3-tert.-butyl-5-chloro-4'-nitrosalicylanilide (0.029 mole). Ethyl chloroformate (3.1 grams, 0.029 mole) was added dropwise to the solution in onehalf hour at 25-30 C. The reaction mixture was stirred at 25 C. for 1 hour and then at 110 C. for 2 hours. After cooling to 25 C. the mixture was poured into 300 ml. of ice water. The precipitate was filtered,
washed with water and recrystallized from methanol to produce 2.6 grams (24.2 percent) of the subject product; m.p. l834 C.
EXAMPLE 2 In accordance with the procedure of Example l, 6- ch1oro-3-(4-nitropheny1)-2H-l ,3-benzoxazine-2,4- (3H)-dione was produced in 12.5 percent yield from an equivalent quantity of 5-chloro-4'-nitrosalicylanilide; (m.p. 299 300c.
EXAMPLE 3 8-benzyl-6-chloro-3-(4-nitrophenyl)-l ,3-(2H)- benzoxazine-2 ,4-( 3H )-dione A mixture of 38.2 grams of 3-benzyl-5-chloro-4- nitrosalicylanilide (0.1 mole), 5.4 grams of NaOCH (0.1 mole) and 100 ml. of dimethylformamide was heated to boiling and 10 ml. of distillate was collected. After cooling to 25 C., 10.8 grams of ethyl chloroformate (0.1 mole) was added dropwise during a h-hour period. The solution was then stirred at reflux for 3 hours, cooled to 25 C. and poured into 600 ml. of water. The solids were collected on a Buchner funnel, washed with water and dried. After recrystallization from a heptane-toluene mixture, the subject product, 19.8 grams (48.5 percent) of crystals was recovered; m.p. l4l-4C.
EXAMPLE 4 In accordance with the procedure of Example 3, 8- tert.-butyl-6-chloro-5-methyl-3-(4-nitrophenyl)-2H- l,3-benzoxazine-2,4-(3H)-dione was prepared from 3- tert.-butyl-5-chloro-6-methyl-4-nitrosalicylanilide and ethyl chloroformate in 25.7 percent yield; m.p. l43-6 C.
EXAMPLE 5 Preparation of 3-tert.-butyl-5-chloro-4- nitrosalicylanilide To a 500 ml. reaction flask fitted with a stirrer, thermometer and condenser topped with a drying tube was charged 45.6 grams (0.2 mole) of 3-tert.-butyl-5- chlorosalicylic acid, 200 ml. of heptane and 26.3 grams of thionyl chloride (0.223 mole), and 5 ml. of dimethylformamide. The mixture was slowly warmed to C.
EXAMPLE 6 Preparation of 3-tert.-butyl5-chloro- 6-methyl-4'- nitrosalicylanilide In a 500 ml. reaction flask equipped with a stirrer, thermometer and condenser topped with a drying tube was charged 48.5 grams of 3-tert.-butyl-5-chloro-6- EXAMPLE 7 Preparation of 3-benzyl-5-chloro-4-nitrosalicylanilide In accordance with the procedure of Example 6 the subject compound was prepared having a m.p. l868 The concentration of toxicant will vary considerably upon conditions such as temperature, pH of the water, types of food and game fish, and the like and is best determined experimentally by laboratory tests stimulating conditions of actual proposed use. To employ the toxicant, the lamprecidal composition can be added directly to the water in the form of a fine powder, with or without wetting or conditioning agents or the compound can be added in liquid form as solutions, suspensions or emulsions. These procedures are more fully discussed in US. Pat. No. 2,821,499 which is herein incorporated by reference. Accordingly the process of the invention is broadly a process for controlling lamprey comprising treating said lamprey with a waterdispersible composition said composition comprising a minor but effective amount of toxicant compound of the invention.
I claim:
1. 8-tert.-butyl-6-chloro-3-(4-nitrophenyl )-2H-1 ,3- benzoxazine-2,4-( 3H)-dione.
2. 6-chloro-3-(4-nitrophenyl)-2H-l ,3-benzoxazine- 2,4-(3H)-dione.
3. 8-benzyl-6-chloro-3-(4-nitrophenyl)-2H-l ,3- benzoxazine-2,4-( 3H)-dione.
4. 8-tert.-butyl-6-chloro-5-methyl-3-(4-nitrophenyl)- 2H 1 ,3-benzoxazine-2,4-( 3H)-dione.
Claims (3)
- 2. 6-chloro-3-(4-nitrophenyl)-2H-1,3-benzoxazine-2,4-(3H)-dione.
- 3. 8-benzyl-6-chloro-3-(4-nitrophenyl)-2H-1,3-benzoxazine-2,4-(3H)-dione.
- 4. 8-tert.-butyl-6-chloro-5-methyl-3-(4-nitrophenyl)-2H-1,3-benzoxazine-2,4 -(3H)-dione.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11854471A | 1971-02-24 | 1971-02-24 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3723426A true US3723426A (en) | 1973-03-27 |
Family
ID=22379258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US00118544A Expired - Lifetime US3723426A (en) | 1971-02-24 | 1971-02-24 | Benzoxazinediones |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3723426A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3355453A (en) * | 1960-05-25 | 1967-11-28 | Boehringer Sohn Ingelheim | Nu-substituted benzo-1, 3-oxazine-dione |
-
1971
- 1971-02-24 US US00118544A patent/US3723426A/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3355453A (en) * | 1960-05-25 | 1967-11-28 | Boehringer Sohn Ingelheim | Nu-substituted benzo-1, 3-oxazine-dione |
Non-Patent Citations (1)
| Title |
|---|
| Veibel et al., Chem. Zentralblatt, (1944) p. 173. * |
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