US3687975A - SUBSTITUTED DIBENZ{8 a,h{9 AZULENONES AND 8-(OXA OR THIA) SUBSTITUTED DIBENZ{8 a,h{9 AZULENONES - Google Patents

SUBSTITUTED DIBENZ{8 a,h{9 AZULENONES AND 8-(OXA OR THIA) SUBSTITUTED DIBENZ{8 a,h{9 AZULENONES Download PDF

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US3687975A
US3687975A US37342A US3687975DA US3687975A US 3687975 A US3687975 A US 3687975A US 37342 A US37342 A US 37342A US 3687975D A US3687975D A US 3687975DA US 3687975 A US3687975 A US 3687975A
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azulenones
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dihydro
indeno
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Jeffrey Nadelson
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
    • C07D313/02—Seven-membered rings
    • C07D313/06—Seven-membered rings condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D337/00—Heterocyclic compounds containing rings of more than six members having one sulfur atom as the only ring hetero atom
    • C07D337/02—Seven-membered rings
    • C07D337/06—Seven-membered rings condensed with carbocyclic rings or ring systems

Definitions

  • R and R are independently, hydrogen, halo having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, or isobutyl or lower alkoxy having one tofour carbon atoms, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy;
  • R andR or R, and R or R and R together are .methylenedioxy
  • R, and R or R and R or R and R together are The compounds of this invention may be represented 1'0' methylenedioxy; by the followingstruct'ural formula: x is p S or 0;
  • the process for preparing the compounds of formula (I) may be represented by the following reaction scheme A.
  • R8 R7 /X R7- /X wherein R is hydrogen, halo having an atomic weight of 19 to 36, or lower alkoxy having one to four carbon atoms, ll R e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy or l 3 isobutoxy;
  • R and R are independently, hydrogen", lower alkyl (H) (I) having one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl or isobutyl, lower alkoxy having one to four carbon atoms, e.g., methoxy, ethoxy, wherein R R R R R R R R and X have the propoxy, isopropoxy, butoxy or isobutoxy, or trifluoromethyl',
  • R is hydrogen, halo having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl or isobutyl, lower alkoxy having one to four carbonatoms, e,g., methoxy, ethoxy, propoxy, i sopropoxy, butoxy or isobutoxy, or trifluoromethyl;
  • R and R are independently hydrogen, halo having 45 R8 H Li 1 X NCH3 R i Ral.
  • the compounds offormula (I) are prepared by treatingv a compound of formula (II) with a concentrated mineral acid such as sulfuric acid or phosphoric acid, (sulfuric acid is preferred) at a temperature of from about "20 to 10 C. preferably from l0 to 0C. for
  • the compounds of formula (I) may be recovered using conventional recovery techniques such as crystallization.
  • the compounds of formula (II) may be prepared by the following reaction scheme B:
  • the compounds of formula (II) and formula (III) are prepared by treating a compound of formula(V) with a compound of formula (IV) in the presence of an inert gas, in an inert solvent such as diethyl ether, tetrahydrofuran, hexane, heptane, benzene and the like and subjecting the reaction mixture to hydrolysis, preferably with aqueous ammonium chloride.
  • an inert gas such as diethyl ether, tetrahydrofuran, hexane, heptane, benzene and the like
  • hydrolysis preferably with aqueous ammonium chloride.
  • reaction scheme b The reaction may be carried out at atemperature of from about 80 to 20 C., preferably 60 to -40 C. for about 1 to 3 hours.
  • Compound (IV) is preferably added in inert solvent (as described above) to a cold (60 to 40 C.) inert solvent solution of compound (V).
  • the solvents and the temperature used are not critical.
  • Compounds (II) may be separated from compounds (III) by conventional means such as filtration and/or crystallization.
  • Compounds (III) may be converted into compounds (II) by subjecting the reaction mixture of compounds (II) and (III) from scheme b in a solvent as described in process b to a temperature of from 60 to the reflux temperature of the solvent, preferably from 100 to 120 C. for to 48 hours, preferably 24 hours. This is represented by reaction scheme b Alternatively compounds (III) may be separated (as described above) from compounds (II) and treated as described in scheme b Neither the solvents nor the temperatures used are critical. The compounds of formulas (II) and (111) may be recovered using conventional recovery techniques such as crystallization.
  • R R R and R have the above-stated signifrcance and R is lower alkyl having 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
  • the compounds of formula (V) are prepared by treating a compound of formula (VI) with an organo lithium compound of formula (VII) in an inert solvent (as described in reaction scheme b,) in the presence of an inert gas at a temperature of from about 10 to 10 C., preferably 5 to 5 C. for about 1 to 3 hours.
  • an inert gas at a temperature of from about 10 to 10 C., preferably 5 to 5 C. for about 1 to 3 hours.
  • the solvents and the temperatures used are not critical.
  • the compounds of formula (I) are useful because they possess pharmacological activity in animals.
  • the compounds possess central nervous system activity and can be used as anti-depressants as indicated by their activity in the mouse in reversing reserpine hypothermia (spencer, P.S.J., antagonism of Hypothermia in the Mouse by. Anti-depressants, in Anti-depressant Drugs, p. 194 204, Eds, S. Garattini and N.N.G. Dukes, Excerpta Medica Foundation, 1967).
  • the compounds may be administered orally or parenterally.
  • the dosage administered will vary depending on the particular compound employed, the therapy desired and the severity of the condition being treated. In general, satisfactory results are obtained when the compounds are administered at a daily dosage of from about 1 30 mg/kg of animal body weight, preferably given in divided dosages, 2 to 4 times a day or in sustained release form. For most larger mammals (e.g., primates) the total daily dosage is from about 20 milligrams to about 100 milligrams. Dosage forms suitable for internal use comprise from about 5 milligrams to about 50 milligrams of the active compound in intimate admixture with a solid or liquid pharmaceutically acceptable carrier or diluent.
  • a representative formulation suitable for oral administration is a capsule prepared by standard techniques which contain the following:
  • the reaction flask was immersed in an ice bath and cooled to an internal temperature of 5. Stirring was initiated and 38 ml of 15% n-butyl lithium (0.06 mole) in hexane was added dropwise in about 40 minutes maintaining the temperature below 8. The resulting N-methylbenzamide lithium adduct was stirred at 5 for 1 hour longer and then the reaction flask was immersed in a dry-ice acetone bath and cooled to an internal temperature of -60.
  • Step 1 By using the conditions of Example I, step 1 and in place of N-methyl-benzamide and 3,4-dihydro-lbenzothiepin-5-(2H)-one starting with l 3 ,4-methylenedioxy-N-methylbenzamide 2. 3 ,4-dihydrol -benzoxaepin-5-( 2H )-one,
  • step 1 2,3-dihydro-5 ,6-methylenedioxy-spiro[ 1- benzoxepin- 5(4H)-l -phthalan]-3 -one 2.
  • step 2 The reaction mixture of step 1 of this example is refluxed in anhydrous tetrahydrofuran, and the resulting 2,3-dihyrdo-5,6'-methylene-dioxy-spiro-[ l-benzox- 5 epin-5(4H)-l'-phthalan]-3'-one is treated following the procedure of Example I, step 2, to obtain the product, 6,7-dihydrol 0,1 l-methylenedioxy benz[b]indenod[ l ,2-d]thiepin-8-(8H )-one.
  • R is hydrogen, halo having an atomic weight 19 to 36, or lower alkoxy having one to four carbon atoms;
  • R and R are independently hydrogen, lower alkyl having one to four carbon atoms, lower alkoxy having one to four carbon atoms or trifluoromethyl;
  • R is hydrogen, halo, having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, lower alkoxy having one to four carbon atoms, or trifluoromethyl;
  • R and R are independently hydrogen, halo having an atomic weight of 19 to 36, or lower alkyl having one to four carbon atoms;
  • R, and R are independently hydrogen, halo having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, or lower alkoxy having one to four carbon atoms;
  • R and R or R and R or R and R together are methylenedioxy
  • R and R or R, and R or R and R together are methylenedioxy; and X is CI-l S or 0;

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

Abstract

Substituted dibenz(a,h)azulenones and 8-(oxa or thia) substituted dibenz(a,h)azulenones, e.g., 6,7-dihydrobenz(b)indeno(1,2-d)thiepin-8(8H)-one, prepared by treating a substituted spiro(1-benzoxa or thia-5(4H)-1''-isobenzofuran)-3''one with concentrated mineral acid. The compounds are useful as anti-depressants.

Description

United States Patent Houlihan et al. 1 Aug. 29, 1972 [54] SUBSTITUTED DIBENZla, h] [56] References Cited AZULENONES AND S-(OXA OR THIA) SUBSTITUTED DlBENZ 21, h] OTHER PUBLICATIONS AZULENONES Layton, Chem Abs. 55: 20615 10-1961).
[72] Inventors: William J. Houlihan, 15 Raynold Road, Mountain Lakes, NJ. 07046;
Jeffrey Nadelson, Troy Hills Village, 1480 Route 46, Parsippany, NJ. 07054 Filed: May 14, 1970 Appl. No.: 37,342
US. Cl. ..260/327 B, 260/333, 260/340.5, 260/343.3, 260/559 R, 260/559 S, 260/590,
Int. Cl ..A61k 27/00, C07d 67/00, C07d 9/00 Field of Search ..260/327 B, 333, 340.5, 590
Primary Examiner-Henry R. Jiles Assistant Examiner-Cecilia M. Shurko Attorney-Gerald D. Sharkin, Frederick H. -Weinfeldt, Robert S. Honor, Walter F. Jewell and Richard E. Vila ABSTRACT Substituted dibenz[a,h]azulenones and v8-(oxa or thia) substituted dibenz[a,h]azulenones, e.g., 6,7-dihydrobenz[b]indenod[1,2-d]thiepin-8(8l-l)-one, prepared by treating a substituted spiro[l-benzoxa or thia-5(4l-l)- 1'-isobenzofuran]-3-one with concentrated mineral acid. The compounds are useful as anti-depressants.
4 Claims, No Drawings I SUBSTITUTED DIBENZMMMZULENONES 8-(0XA OR THIA) SUBSTITUTED DIBENZ[ AH] AZULENONES This invention relates to dibenz['a,h]azulen'ones and 8-(oxaor thia')dibenz[a,h]azulenones-. More particularly, it relates to substituted dibenz[a,h]azulenones and 8'-(oxa or thia-)substituted dibenzEaJflazulbnones, intermediates thereof and processes for their preparation.
R and R are independently, hydrogen, halo having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl, or isobutyl or lower alkoxy having one tofour carbon atoms, e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy;
R andR or R, and R or R and R together are .methylenedioxy;
R, and R or R and R or R and R together are The compounds of this invention may be represented 1'0' methylenedioxy; by the followingstruct'ural formula: x is p S or 0;
provided that 1. maximum number of substituents on ring Aand/or D is two, and 2. there are no adjacent trifluoromethyl groups.
The process for preparing the compounds of formula (I) may be represented by the following reaction scheme A. g (I) R8 R7 /X R7- /X wherein R is hydrogen, halo having an atomic weight of 19 to 36, or lower alkoxy having one to four carbon atoms, ll R e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy or l 3 isobutoxy;
R and R are independently, hydrogen", lower alkyl (H) (I) having one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl or isobutyl, lower alkoxy having one to four carbon atoms, e.g., methoxy, ethoxy, wherein R R R R R R R R and X have the propoxy, isopropoxy, butoxy or isobutoxy, or trifluoromethyl',
R is hydrogen, halo having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl or isobutyl, lower alkoxy having one to four carbonatoms, e,g., methoxy, ethoxy, propoxy, i sopropoxy, butoxy or isobutoxy, or trifluoromethyl;
R and R are independently hydrogen, halo having 45 R8 H Li 1 X NCH3 R i Ral.
above-stated significance. I
, The compounds offormula (I) are prepared by treatingv a compound of formula (II) with a concentrated mineral acid such as sulfuric acid or phosphoric acid, (sulfuric acid is preferred) at a temperature of from about "20 to 10 C. preferably from l0 to 0C. for
about 10 to 15 hours, preferably about 12 hours. The temperature used are not critical. The compounds of formula (I) may be recovered using conventional recovery techniques such as crystallization.
The compounds of formula (II) may be prepared by the following reaction scheme B:
adduet hydrolysis W) R. e I
I x R /X R,- 7
R5 R4 Ru- R4 l R5 H0 R3 R Rs O R R2 2 HN-C (H) 1 2 (III) 1H R1 1 a wherein R R R R R R R R and X have the above-stated significance.
The compounds of formula (II) and formula (III) are prepared by treating a compound of formula(V) with a compound of formula (IV) in the presence of an inert gas, in an inert solvent such as diethyl ether, tetrahydrofuran, hexane, heptane, benzene and the like and subjecting the reaction mixture to hydrolysis, preferably with aqueous ammonium chloride. This is represented by reaction scheme b The reaction may be carried out at atemperature of from about 80 to 20 C., preferably 60 to -40 C. for about 1 to 3 hours. Compound (IV) is preferably added in inert solvent (as described above) to a cold (60 to 40 C.) inert solvent solution of compound (V). The solvents and the temperature used are not critical. Compounds (II) may be separated from compounds (III) by conventional means such as filtration and/or crystallization.
Compounds (III) may be converted into compounds (II) by subjecting the reaction mixture of compounds (II) and (III) from scheme b in a solvent as described in process b to a temperature of from 60 to the reflux temperature of the solvent, preferably from 100 to 120 C. for to 48 hours, preferably 24 hours. This is represented by reaction scheme b Alternatively compounds (III) may be separated (as described above) from compounds (II) and treated as described in scheme b Neither the solvents nor the temperatures used are critical. The compounds of formulas (II) and (111) may be recovered using conventional recovery techniques such as crystallization.
Certain of the compounds of formula (V) are known and may be prepared by methods disclosed in the literature, e. g., by the following reaction scheme C:
wherein R R R and R have the above-stated signifrcance and R is lower alkyl having 1 to 4 carbon atoms, e.g., methyl, ethyl, propyl, isopropyl, butyl or isobutyl.
The compounds of formula (V) are prepared by treating a compound of formula (VI) with an organo lithium compound of formula (VII) in an inert solvent (as described in reaction scheme b,) in the presence of an inert gas at a temperature of from about 10 to 10 C., preferably 5 to 5 C. for about 1 to 3 hours. The solvents and the temperatures used are not critical.
Certain of the compounds of formulas (IV), (VI) and (VII) are known and may be prepared according to methods disclosed in the literature. Those compounds of formulas (IV), (VI) and (VII) not specifically disclosed are prepared according to analogous methods from known materials.
The compounds of formula (I) are useful because they possess pharmacological activity in animals. In particular, the compounds possess central nervous system activity and can be used as anti-depressants as indicated by their activity in the mouse in reversing reserpine hypothermia (spencer, P.S.J., antagonism of Hypothermia in the Mouse by. Anti-depressants, in Anti-depressant Drugs, p. 194 204, Eds, S. Garattini and N.N.G. Dukes, Excerpta Medica Foundation, 1967). I
The compounds may be administered orally or parenterally.
The dosage administered will vary depending on the particular compound employed, the therapy desired and the severity of the condition being treated. In general, satisfactory results are obtained when the compounds are administered at a daily dosage of from about 1 30 mg/kg of animal body weight, preferably given in divided dosages, 2 to 4 times a day or in sustained release form. For most larger mammals (e.g., primates) the total daily dosage is from about 20 milligrams to about 100 milligrams. Dosage forms suitable for internal use comprise from about 5 milligrams to about 50 milligrams of the active compound in intimate admixture with a solid or liquid pharmaceutically acceptable carrier or diluent.
A representative formulation suitable for oral administration is a capsule prepared by standard techniques which contain the following:
Ingredients Parts by Weight EXAMPLE I 6,7-dihydro-benz[b]indeno[ 1 ,2-d]thiepin-8(8H)- one Step 1 2,3-dihydro-spiro[ l-benzothiepine-5-(4H)-l '-phthalan]-3-one and o-(2,3,4,5-tetrahydro-5- hydroxyl benzothiepin-S -yl) To a flask equipped with a stirrer, dropping funnel, condenser and gas inlet tube and maintained under a nitrogen atmosphere there was added at room temperature 3.8 g (0.027 mole) N-methyl benzamide and ml anhydrous tetrahydrofuran. The reaction flask was immersed in an ice bath and cooled to an internal temperature of 5. Stirring was initiated and 38 ml of 15% n-butyl lithium (0.06 mole) in hexane was added dropwise in about 40 minutes maintaining the temperature below 8. The resulting N-methylbenzamide lithium adduct was stirred at 5 for 1 hour longer and then the reaction flask was immersed in a dry-ice acetone bath and cooled to an internal temperature of -60. To the cold reaction mixture a solution of 5.35 g (0.03 mole) of 3,4-dihydro-l-benzothiepin-5-(2l-I)-one in 30 ml anhydrous tetrahydrofuran was added dropwise in about 30 minutes maintaining the temperature between 60 to 5. The resulting adduct was stirred at 60 for 1 hour and then allowed to warm to 0 in about 1 hour and then treated with 35 ml saturated ammonium chloride. The layers were separated and the organic phase was washed once with 30 ml saturated ammonium chloride, dried over anhydrous Mg SO and evaporated in vacuo. The resulting oil was triturated with ether and the 0-(2,3,4,S-tetrahydro-S-hydroxy-lbenzothiepin-S-yl)-N-methyl benzamide, mp 128 to l6. 2-[ 2,3,4,5-tetrahydro--hydroxy-6-methyll benzothiepin-S -y1 ]-N,3-dimethyl-benzamide Following the procedure of Example I, step 2, and in place of 2,3-dihydro-spiro [l-benzothiepin-S-(4I-I)-l phthalan-3 -one, starting with the appropriate intermediate of formula II of step 1 of this example, the following products are obtained:
1. 6,7-dihydro-8H-benz[b]indeno[ l ,2-d]oxepin-8- one 2. 5,6-dihydro-dibenz[a,h]azulen-8(7H)-one 3. 6, 7-dihydro-l l-methyl-benz[b]indeno[1,2-d ]thiepin-8( 8l-I)-one 4. l l-chloro-6,7-dihydro-benz[b]indeno[ 1,2-d ]thiepin-8( 8H )-one 5. 6,7dihydro-l l-methyl-benz[b]indeno[ l,2-d ]thiepin-8( 8I-l)-one 6. 3-chloro6,7-dihydro-2-methoxy-benz[b]indeno[ l,2-d]thiepin-8-(8H)-one 7. 6,7-dihydro-3-methoxy-2-methyl-benz[b]indeno[ l,2-d]thiepin-8(8H)-one 8 2-chloro-6,7 -dihydro-3-methyl-benz[b]indeno[ l,2-d]thiepin-8(8H)-one 9. 6,7-dihydro-2,3-methylenedioxy-benz[b]indeno[ l,2-d]thiepin-8(8H)-one l0. 6,7-dihydrol O, l 2-bis trifluoromethyl-benz[ b] indeno[ l ,2-d]thiepin-8( 8H)-one l l. 9-chloro-6,7-dihydro-l l-trifluoromethyl-benz [b]indeno[-d]thiepin-8(8H)-one l 2. l-chloro-6,7-dihydrol O-methyl-benz [b]indeno l ,2-d]thiepin-8(8H)-one l 3. 4-chloro6,7-dihydrol 2-methoxy-benz[ b] indeno[ l,2-d]thiepin-8-( 8H)-one 14. 6,7-dihydro-4-methyll O-methoxy-benz[b]indeno[ 1,2-d]thiepin-8( 8H)-one l 5. 6,7-dihydrol -methyl-9-methoxy-benz[b] indeno[ l ,2-d]thiepin-8( 8H)-one l6. 6,7-dihydro-l2-methyl-benz[b]indeno[1,2-d ]thiepin-8( 8I-I)-one EXAMPLE Ill This example describes the procedure for preparing compounds of formula I following the procedure of reaction schemes A, b,, b and C. The conditions of Example I, steps 1 and 2, are followed, with the exception that the compounds of the hydrolysis reaction mixture of step 1 (Ex. I) are not separated but instead are refluxed in anhydrous tetrahydrofuran to convert the intermediate of formula III into the intermediate of formula II.
Step 1 By using the conditions of Example I, step 1 and in place of N-methyl-benzamide and 3,4-dihydro-lbenzothiepin-5-(2H)-one starting with l 3 ,4-methylenedioxy-N-methylbenzamide 2. 3 ,4-dihydrol -benzoxaepin-5-( 2H )-one,
a reaction mixture of the following intermediates of formula II and formula III respectively are prepared:
1 2,3-dihydro-5 ,6-methylenedioxy-spiro[ 1- benzoxepin- 5(4H)-l -phthalan]-3 -one 2. 2-[2,3,4,5-tetrahydro-5-hydroxyl -benzoxepin-5- yl ]-N-methyl-4,5-methylenedioxy-benzamide Step2 The reaction mixture of step 1 of this example is refluxed in anhydrous tetrahydrofuran, and the resulting 2,3-dihyrdo-5,6'-methylene-dioxy-spiro-[ l-benzox- 5 epin-5(4H)-l'-phthalan]-3'-one is treated following the procedure of Example I, step 2, to obtain the product, 6,7-dihydrol 0,1 l-methylenedioxy benz[b]indenod[ l ,2-d]thiepin-8-(8H )-one.
What is claimed is:
wtherein R is hydrogen, halo having an atomic weight 19 to 36, or lower alkoxy having one to four carbon atoms;
R and R are independently hydrogen, lower alkyl having one to four carbon atoms, lower alkoxy having one to four carbon atoms or trifluoromethyl;
R is hydrogen, halo, having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, lower alkoxy having one to four carbon atoms, or trifluoromethyl;
R and R are independently hydrogen, halo having an atomic weight of 19 to 36, or lower alkyl having one to four carbon atoms;
R, and R are independently hydrogen, halo having an atomic weight of 19 to 36, lower alkyl having one to four carbon atoms, or lower alkoxy having one to four carbon atoms;
R and R or R and R or R and R together are methylenedioxy; or
R and R or R, and R or R and R together are methylenedioxy; and X is CI-l S or 0;
provided that 1. maximum number of substituents on each of rings A and D is two, and 2. there are no ad- 5 5 jacent tn'fiuromethyl groups.
2. The compound according to claim 1 which is 6,7-
dihydro-benzo[b]indeno[ l ,2-d]thiepin-8( 8H )-one.
3. The compound according to claim 1 which is 6,7-
dihydro-8H -benz[b]indeno[ l,2-d]oxepin-8-one.
4. The compound according to claim 1 which is 5,6-
dihydro-dibenz[a,h]azulen-8(7H)-one.

Claims (3)

  1. 2. The compound according to claim 1 which is 6,7-dihydro-benzo(b)indeno(1,2-d)thiepin-8(8H)-one.
  2. 3. The compound according to claim 1 which is 6,7-dihydro-8H -benz(b)indeno(1,2-d)oxepin-8-one.
  3. 4. The compound according to claim 1 which is 5,6-dihydro-dibenz(a,h)azulen-8(7H)-one.
US37342A 1970-05-14 1970-05-14 SUBSTITUTED DIBENZ{8 a,h{9 AZULENONES AND 8-(OXA OR THIA) SUBSTITUTED DIBENZ{8 a,h{9 AZULENONES Expired - Lifetime US3687975A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3879469A (en) * 1972-02-23 1975-04-22 Zyma Sa Process for preparing 6,9-dioxo-3,8-dihydroxy-2-substituted-bicyclo-3,3,1-nonenes-7
US4078074A (en) * 1974-12-03 1978-03-07 Rikagaku Kenkyusho And Mitsubishi Petrochemical Company Limited 2H-Chromene-2-spiro-3'-phthalides useful as horticultural and agricultural fungicides

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Layton, Chem Abs. 55: 20615 (10-1961). *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3879469A (en) * 1972-02-23 1975-04-22 Zyma Sa Process for preparing 6,9-dioxo-3,8-dihydroxy-2-substituted-bicyclo-3,3,1-nonenes-7
US4078074A (en) * 1974-12-03 1978-03-07 Rikagaku Kenkyusho And Mitsubishi Petrochemical Company Limited 2H-Chromene-2-spiro-3'-phthalides useful as horticultural and agricultural fungicides

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