1-33. (canceled)
34. A process for the sulfinylation of a pyrazole derivative comprising, reacting 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile (II) with a sulfinylating agent S in the presence of at least one amine acid complex wherein the amine(s) are selected from secondary andor tertiary amines and the acid(s) are selected from the group consisting of hydrochloric acid, hydrofluoric acid, p-toluenesulfonic acid, benzenesulfonic acid, 4-ethyl benzenesulfonic acid, 4-chlorobenzenesulfonic acid, xylene sulfonic acid, 2,3-dimethylbenzene sulfonic acid, 2,4-dimethylbenzene sulfonic acid, 2,5-dimethylbenzene sulfonic acid, 2,6-dimethylbenzene sulfonic acid, 1-napthalenesulfonic acid, 2-napthalenesulfonic acid, mixtures of two or more of the isomers of dimethylbenzene sulfonic acid, mesitylene sulfonic acid, methanesulfonic acid, camphor sulfonic acid, and trifluoromethylsulfonic acid, and of a halogenating agent, wherein
S is CF3S(O)2O; or CF3S(O)X wherein
X is fluoro, chloro, bromo, iodo, a hydroxy group, or an alkaline or alkaline earth metal salt of the hydroxy group; or
mixtures thereof,
wherein the temperature of the reaction mixture at no time exceeds 39\xb0 C.
35. The process of claim 34, wherein said halogenating agent is selected from the group consisting of thionylchloride, thionylbromide, phosphoroxychloride, oxalylchloride, phosgen, triphosgen ((CCl3)2C(\u2550O)), chloroformiates, phosphorpentachloride, phosphortrichloride, trichloromethylchloromethanoat, and xylenesulfonic acid chloride.
36. The process of claim 34, wherein said halogenating agent is a chlorinating agent selected from the group consisting of thionylchloride and phosphoroxychloride.
37. The process of claim 34, wherein the amine of said amine acid complex is selected from the group consisting of
the tertiary alkyl amines trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, dimethyl ethyl amine, diethyl methylamine, dimethyl n-propyl amine, diisopropylethylamine, DBU (1,8-diazabicyclo5.4.0undec-7-ene), DBN (1,5-diazabicyclo4.3.0non-5-ene), methyl morpholine, ethyl morpholine, N,N-dimethylaniline, methyl piperidine, methylpyrrolidine, and methyldibenzylamine;
the tertiary aromatic amines pyridine, DMAP (dimethylaminopyridine), collidine, lutidine, pyrimidine, pyrazine, and piperazine;
the secondary alkyl amines dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, isopropylmethylamine, and isopropylethylamine,
the cyclic secondary amines piperidine, piperidine which is substituted by C1-C8-alkyl or C1-C8-haloalkyl, pyrrolidine, imidazolidine, pyrrole, piperazine, and morpholine.
38. The process of claim 37, wherein said piperidine is 2-methylpiperidine or 4-methylpiperidine.
39. The process of claim 34, wherein said amine of the amine acid complex is selected from the group consisting of trimethylamine, triethylamine, tripropylamine, triisopropylamine, dimethyl ethyl amine, diethyl methylamine, dimethyl n-propyl amine, diisopropylethylamine, DBU (1,8-diazabicyclo5.4.0undec-7-ene), DBN (1,5-diazabicyclo4.3.0non-5-ene), methyl morpholine, ethyl morpholine, N,N-dimethylaniline, methyl piperidine, methylpyrrolidine, methyldibenzylamine, pyridine, DMAP (dimethylaminopyridine), collidine, lutidine, pyrimidine, pyrazine, and piperazine.
40. The process of claim 34, wherein the amine of said amine acid complex is selected from the group consisting of trimethylamine, triethylamine, dimethyl ethyl amine, diethyl methylamine, dimethyl n-propyl amine, methyl morpholine, N,N-dimethylaniline, methyl piperidine, methylpyrrolidine, methyldibenzylamine, and pyridine.
41. The process of claim 34, wherein the amine of said amine acid complex is selected from the group consisting of dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, ethylmethylamine, isopropylmethylamine, isopropylethylamine, piperidine, piperidine which is substituted by C1-C8-alkyl or C1-C8-haloalkyl, pyrrolidine, pyrrolidine which is substituted by C1-C8-alkyl or C1-C8-haloalkyl, imidazolidine, pyrrole, piperazine, and morpholine.
42. The process of claim 41, wherein said piperidine is 3-methylpiperidine and 4-methylpiperidine and said pyrrolidine is 2-methylpyrrolidine and 3-methylpyrrolidine.
43. The process of claim 34, wherein the acid of said amine acid complex is selected from the group consisting of hydrochloric acid, p-toluenesulfonic acid, benzene sulfonic acid and xylene sulfonic acid.
44. The process of claim 34, wherein the acid of said amine acid complex is selected from the group consisting of p-toluenesulfonic acid, benzenesulfonic acid, 4-ethyl benzenesulfonic acid, 4-chlorobenzenesulfonic acid, xylene sulfonic acid, 2,3-dimethylbenzene sulfonic acid, 2,4-dimethylbenzene sulfonic acid, 2,5-dimethylbenzene sulfonic acid, 2,6-dimethylbenzene sulfonic acid, 1-napthalenesulfonic acid, 2-napthalenesulfonic acid, mixtures of two or more of the isomers of dimethylbenzene sulfonic acid, mesitylene sulfonic acid, methanesulfonic acid, camphor sulfonic acid, and trifluoromethylsulfonic acid.
45. The process of claim 44, wherein said acid is p-toluenesulfonic acid, benzene sulfonic acid and xylene sulfonic acid.
46. The process of claim 34, wherein said sulfinylating agent S is selected from the group consisting of CF3S(O)C1, CF3S(O)OH, CF3S(O)2O, CF3S(O)ONa, CF3S(O)OK, and mixtures thereof.
47. The process of claim 34, wherein said reaction is conducted in an organic solvent selected from the group consisting of toluene, benzene, xylene, trifluoromethylbenzene, monochlorobenzene, ethylbenzene and dichlorobenzene.
48. The process of claim 34, wherein said sulfinylating agent is added to a reaction solution mixture of said amine acid complex and said halogenting agent before 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile is added.
49. The process of claim 34, wherein 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile is added to a reaction mixture of said sulfinylating agent, said amine acid complex and said halogenating agent.
50. The process of claim 34, wherein 1.4 to 2.2 molar equivalents of said amine acid complex relative to 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile are present.
51. The process of claim 34, wherein 1.15 to 1.35 molar equivalents of said halogenating agent relative to 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile are present.
52. The process of claim 34, wherein 1.0 to 1.35 molar equivalents of said sulfinylating agent relative to 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile are present.
53. The process of claim 34, wherein said reacting comprises after combining of 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-1H-pyrazole-3-carbonitrile, said sulfinylating agent, said amine acid complex, and said halogenating agent, the temperature is raised to 30\xb0 C. to 39\xb0 C. within 5 to 60 minutes.
54. The process of claim 34, further comprising crystallizing 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile from a solution of monochlorobenzene, dichlorobenzene, ethylbenzene or toluene.
55. The process of claim 34, further comprising formulating 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile into a pesticidal composition.
56. The process of claim 34, further comprising formulating 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile into a veterinarily acceptable parasiticidal composition.
57. 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile when prepared by the process of claim 34.
58. 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile prepared by the process of claim 34, which contains less than 20 ppm of bromine.
59. 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile prepared by the process of claim 34 which contains less than 10 ppm of compound D
60. 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile prepared by the process of claim 34 and in an inert atmosphere, which contains less than 200 ppm of compounds containing sulfur in its oxidation state (IV).
61. A pesticidal or parasiticidal composition comprising 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethysulfinyl)-pyrazole-3-carbonitrile of claim 57.
62. A method for the control of insects, acarids or nematodes by contacting the insect, acarid or nematode or their food supply, habitat, breeding ground or their locus with a pesticidally effective amount of 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile of claim 57.
63. A method of protecting growing plants from attack or infestation by insects, acarids or nematodes by applying to the foliage or the seeds of the plants, or to the soil or water in which they are growing, a pesticidally effective amount of 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile of claim 57.
64. The method of claim 62, wherein 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile is applied in an amount of from 5 gha to 2000 gha.
65. The method of claim 63, wherein 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile is applied in an amount of from 5 gha to 2000 gha.
66. A method for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises orally, topically or parenterally administering or applying to the animals or their habitat a parasiticidally effective amount of 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile of claim 57 or its veterinarily acceptable enantiomers or salts.
67. A process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises admixing 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile of claim 57 or its veterinarily acceptable enantiomers or salts with a veterinarily acceptable carrier.
68. The process of claim 67, wherein 5-amino-1-2,6-dichloro-4-(trifluoromethyl)phenyl-4-(trifluoromethylsulfinyl)-pyrazole-3-carbonitrile or its veterinarily acceptable enantiomer or salt is present in a parasiticidally effective amount.
The claims below are in addition to those above.
All refrences to claim(s) which appear below refer to the numbering after this setence.
1. A bubble generating assembly comprising:
a housing shaped as an animal and defining a mouth having a head section that pivots along a first axis with respect to the housing to open and close, with a stationary member secured to a permanent location extending across a portion of the mouth;
a reservoir provided inside the housing and retaining bubble solution, the reservoir having an interior;
a trigger mechanism;
a bubble generating ring positioned inside the mouth for pivoting movement inside the mouth, the ring pivoting along a second axis that is perpendicular to the first axis and not being carried by the head section;
a tubing that couples the interior of the reservoir with the ring; and
a link assembly that couples the trigger mechanism and the ring in a manner in which actuation of the trigger mechanism simultaneously causes the head section to be raised, and the ring to be pivoted from a first position to a second position across the stationary member.
2. The assembly of claim 1, further including:
a motor operatively coupled to the trigger mechanism;
an air generator coupled to the motor and directing air towards the ring; and
a gear system coupled to the motor and applying pressure to the tubing to cause bubble solution to be delivered from the reservoir to the ring.
3. The assembly of claim 2, wherein actuation of the trigger mechanism simultaneously causes (i) the air generator to direct air towards the ring, (ii) the gear system to deliver bubble solution from the reservoir to the ring, and (iii) the ring to move from the first position to the second position.
4. The assembly of claim 1, wherein release of the trigger will cause the ring to pivot downwardly from the second position to the first position across the stationary member.
5. The assembly of claim 1, further including means for drawing bubble solution from the reservoir, and to deliver the bubble solution to the ring.
6. The assembly of claim 5, wherein actuation of the trigger mechanism simultaneously causes (i) the drawing means to deliver bubble solution from the reservoir to the ring, and (ii) the ring to move from the first position to the second position.
7. The assembly of claim 5, wherein the drawing means includes the trigger mechanism, at least one rotating pressure roller and a guide wall, the pressure roller having a base section and an end that has a smaller diameter than the base section, with the tubing positioned between the end of the pressure roller and the guide wall when the trigger mechanism is not actuated, and with the tubing positioned between the base section of the pressure roller and the guide wall when the trigger mechanism is actuated.
8. The assembly of claim 7, wherein actuation of the trigger mechanism pushes the pressure roller against the tubing.
9. The assembly of claim 1, wherein the mouth is defined by two portions of the housing that pivot with respect to each other such that the ring is housed completely inside the housing when the two portions of the housing are pivoted to a closed position.
10. The assembly of claim 3, wherein the mouth is defined by two portions of the housing that pivot with respect to each other, and wherein actuation of the trigger mechanism also simultaneously causes the two portions of the housing to pivot away from each other.
11. The assembly of claim 1, wherein the ring experiences a curved movement as the ring moves from the first position to the second position across the stationary member.
12. The assembly of claim 1, wherein the housing is shaped like one of the following animals: a pony, a dog, a horse, a lion, a tiger, a bear, a giraffe, an elephant, a hippopotamus, a crocodile, an alligator, a rabbit and a cat.
13. The assembly of claim 1, wherein the housing has an opening, and a portion of the reservoir is positioned adjacent the opening, with the reservoir being made of a transparent material.
14. The assembly of claim 1, wherein the stationary member extends from a lower portion of the mouth.