Bicyclo[3.2.0]hepta-1,4,6-triene: synthesis, thermal rearrangement, and anion formation

In order to determine the properties of the bicycloheptatrienyl anion (Ia) (predicted to be conjugatively stabilized by Hückel Molecular Orbital Theory) the neutral precursor, bicyclo[3. 2. 0] hepta-1, 4, 6-triene (I) was prepared by the following route.

Reaction of I with potassium-t-butoxide, potassium, or lithium dicyclohexylamide gave anion Ia in very low yield. Reprotonation of I was found to occur solely at the 1 or 5 position to give triene II, isolated as to its dimers.

A study of the acidity of I and of other conjugated hydrocarbons by means of ion cyclotron resonance spectroscopy resulted in determination of the following order of relative acidities:

H₂S ˃ C₅H₆ ˃ CH₃NO₂ ˃ 1, 4- C₅H₈ ˃ I ˃ C₂H₅OH ˃ H₂O; cyclo-C₇H₈ ˃ C₂ H₅OH; фCH₃ ˃ CH₃OH

In addition, limits for the proton affinities of the conjugate bases were determined:

350 kcal/mole ˂ PA(C₅ H₅^-) ˂ 360 kcal/mole

362 kcal/mole ˂ PA(C₅H₇^-, Ia, cyclo-C₇H₇^-) ˂ 377 kcal/mole PA(фCH₂^-) ˂ 385 kcal/mole

Gas phase kinetics of the trans-XVIII to I transformation gave the following activation parameters: E_a = 43.0 kcal/mole, log A = 15.53 and ∆S^ǂ (220°) = 9.6 cu. The results were interpreted as indicating initial 1,2 bond cleavage to give the 1,3-diradical which closed to I. Similar studies on cis-XVIII gave results consistent with a surface component to the reaction (E_a = 22.7 kcal/mole; log A = 9.23, ∆S^ǂ (119°) = -18.9 eu).

The low pressure (0.01 to 1 torr) pyrolysis of trans-XVIII gave in addition to I, fulvenallene (LV), ethynylcyclopentadiene (LVI) and heptafulvalene (LVII). The relative ratios of the C₇H₆ isomers were found to be dependent upon temperature and pressure, higher relative pressure and lower temperatures favoring formation of I. The results were found to be consistent with the intermediacy of vibrationally excited I and subsequent reaction to give LV and LVI.

Effects of magnetostriction and superlattice formation in ferromagnetic thin films

The contribution to the magnetic uniaxial perpendicular anisotropy which arises from substrate constraint through magnetostrictive effects has been measured in Ni-Fe and Ni-Co thin films evaporated on substrates at room temperature. This was accomplished by measuring the perpendicular anisotropy before and after removal of the film from the substrate. Data are given for the fcc crystal structure regions of both alloy systems, but data for Ni-Co include compositions with less than 60% Ni which have a small percentage of the hcp phase mixed with the fcc phase. The constraint contribution to the perpendicular anisotropy correlates well with the value of the bulk magnetostriction constant using the equation ∆K_˔=3/2λ_sσ. Measured values of isotropic stress for films thicker than 600 Å were 1.6 x 10¹⁰ dyn/cm². In films less than 600 Å thick the isotropic stress decreased with decreasing thickness. After removal of the films from the substrates, the measured perpendicular anisotropy deviated from the expected geometrical shape anisotropy near pure Ni in both alloys. This indicates that additional significant sources of anisotropy exist at these compositions.

The effect of substrate constraint on the crystalline anisotropy K₁ of Ni-Fe epitaxial films has been studied by use of a film removal technique, which involves the evaporation of an epitaxial layer of LiF on MgO, the epitaxial growth of the metallic film on the LiF, and the stripping of the film with water soluble tape. Films ranging in composition from 50% to 100% Ni have been studied. For compositions below 90% Ni the experimental values agree reasonably well with the first order theoretical prediction, ∆K₁=[-9/4(C₁₁-C₁₂)λ² 100+9/2C₄₄λ²111].

In order to compare the magnetic properties of epitaxial thin films more completely with the properties of bulk single crystals, Ni-Fe films ranging in composition from 60% to 90% Ni, which were evaporated epitaxially on (100) MgO substrates, have been subsequently annealed at 400°C in a vacuum of less than 10^-7 Torr to form the ordered Ni₃Fe structure near the 75% composition. This ordered structure has been confirmed by electron diffraction.

The saturation magnetization at Ni₃Fe increased about 6% with ordering which is in good agreement with previous bulk data. Measurements of the magnetocrystalline anisotropy energy K₁ for the epitaxial films show the same large changes with ordering as observed in bulk single crystal samples. In the (001) plane the magnetostriction constants ^λ100, ^λ111 are directly related to the induced anisotropy due to a uniform uniaxial strain in the [100] and [110] directions respectively. Assuming that the elastic constants of a film are the same as in bulk material and are unchanged by ordering, the changes in strain sensitivity with ordering for the epitaxial films are found to be in good agreement with values predicted from bulk data. The exchange constant A as measured by ferromagnetic resonance has been measured at the Ni₃Fe composition and found to increase 25% with ordering. This seems to indicate a significant increase in the Curie temperature which has only been inferred indirectly for bulk material.

Conditioned responses in the reticular formation

Unit activity was recorded from the midbrain and pons of 40 freely moving rats in an appetitive classical conditioning situation. Responses to auditory stimuli were observed from 100 units before and during a conditioning procedure in which presentation of food occurred 1 sec after the onset of the auditory stimulus. Conditioned unit responses (i.e., spike rate accelerations or decelerations) were considered to be positive when 1) no similar responses appeared prior to conditioning, and 2) latencies were equal to or less than those of sensory responses derived from the inferior colliculus. Such short latency conditioned unit responses were recorded from 11 probes located in the mid-lateral pert of the ventral region of the brain stem. This region was differentiated from paramedian, far lateral and dorsal parts of the brain stem reticular formation. Conditioned unit responses of considerably longer latencies were recorded from 76 probe located in these other regions. Among the longer latency responses interesting differences appeared in experiments conducted after the first conditioning series was completed. With additional training, units in the "reticular activating system" of midbrain and pons tended to yield stabilized responses in the early portion of the CS-US interval closely related in time to the orientation responses evoked by the CS. In contrast, the responses of units in the limbic midbrain tended to stabilize in the later part of the CS-US interval closely related in time to preparatory responses tied to the US. During extinction when the auditory stimulus was no longer followed by presentation of food, many of the responses were reduced to their pre-conditioning levels. However, there was a tendency for units which had displayed short latency responses on the first conditioning day to be more resistant to extinction than units which had displayed longer latency conditioned responses. The data were interpreted as indicating a local correlate of learning in the reticular formation of midbrain end pons and a separation of the midbrain system into at least two areas: 1) the classical "reticular activating system" related to orienting reactions, and 2) the limbic midbrain areas related to drives and rewards. Because the ventral and mid-lateral area with very short latency conditioned responses was not clearly tied to either of these; it was considered as possibly representing a third division.

Report of the Inter-American Tropical Tuna Commission for the year 1992

ENGLISH: The Inter-American Tropical Tuna Commission operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which carne into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas in the eastern Pacific Ocean. Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, and France and Nicaragua in 1973. Ecuador withdrew from the Commission in 1968, Mexico in 1978, Costa Rica in 1979, and Canada in 1984. Costa Rica re-adhered to the convention in 1989, and Vanuatu and Venezuela joined the Commission in 1990 and 1992, respectively. The Commission held its 50th meeting in La Jolla, California, USA, on June 16-18, 1992. SPANISH: La Comisión Interamericana del Atún Tropical funciona bajo la autoridad y dirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto a la afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales en el Océano Pacífico oriental. Bajo esta estipulación, la República de Panamá se afilió en 1953, Ecuador en 1961, México en 1964, Canadá en 1968, Japón en 1970, y Francia y Nicaragua en 1973. Ecuador se retiró de la Comisión en 1968, México en 1978, Costa Rica en 1979, y Canadá en 1984. Costa Rica se adhirió de nuevo al Convenio en 1989; y Vanuatu y Venezuela se hicieron miembros de la Comisión en 1990 y 1992, respectivamente. La Comisión celebró su quincuagésima reunión en La Jolla, California, EE.UU., del 16 al 18 de junio de 1992. (PDF contains 316 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1993

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which carne into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean. Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, and Venezuela in 1992. Ecuador withdrew from the IATTC in 1968, Mexico in 1978, Costa Rica in 1979, and Canada in 1984. Costa Rica readhered to the convention in 1989. The Commission held its 51st meeting in Port Vila, Vanuatu, on June 8-10, 1993. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad y dirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto a la afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacífico oriental. Bajo esta estipulación, la República de Panamá se afilió en 1953, Ecuador en 1961, México en 1964, Canadá en 1968, Japón en 1970, Francia y Nicaragua en 1973, Vanuatu en 1990, y Venezuela en 1992. Ecuador se retiró de la CIAT en 1968, México en 1978, Costa Rica en 1979, y Canadá en 1984. Costa Rica se adhirió de nuevo al Convenio en 1989. La Comisión celebró su 51ª reunión en Port Vila (Vanuatu) del 8 al 10 de junio de 1993. (PDF contains 316 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1994

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean. Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, and Venezuela in 1992. Ecuador withdrew from the IATTC in 1968, Mexico in 1978, and Canada in 1984. The Commission held its 53rd meeting in Cumaná, Venezuela, on June 7-8, 1994. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad ydirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto a la afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacífico oriental. Bajo esta estipulación, la República de Panamá seafilióen 1953, Ecuadoren 1961, México en 1964, Canadáen 1968,Japónen 1970, FranciayNicaragua en 1973, Vanuatu en 1990, y Venezuela en 1992. Ecuador se retiró de la CIAT en 1968, México en 1978, y Canadá en 1984. La Comisión celebró su 53a reunión en Cumaná (Venezuela) el 7 y 8 de junio de 1994. (PDF contains 296 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1995

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean. Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, and Venezuela in 1992. Ecuador withdrew from the IATTC in 1968, Mexico in 1978, and Canada in 1984. The IATTC held its 55th meeting in La Jolla, California, USA, on June 13-15, 1995. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad ydirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto a la afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacífico oriental. Bajo esta estipulación, la República de Panamá seafilióen 1953, Ecuadoren 1961, México en 1964, Canadáen 1968,Japónen 1970, FranciayNicaragua en 1973, Vanuatu en 1990, y Venezuela en 1992. Ecuador se retiró de la CIAT en 1968, México en 1978, y Canadá en 1984. La CIAT celebró su 55a reunión en La Jolla, California (EE.DU.) del 13 al15 de junio de 1995. (PDF contains 336 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1996

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean. Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, and Venezuela in 1992. Ecuador withdrew from the IATTC in 1968, Mexico in 1978, and Canada in 1984. The IATTC held its 57th meeting in La Jolla, California, USA, on October 21-23, 1996. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad y dirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto a la afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacífico oriental. Bajo esta estipulación, la República de Panamá seafilióen 1953, Ecuador en 1961, México en 1964, Canadá en 1968, Japón en 1970, Francia y Nicaragua en 1973, Vanuatu en 1990, y Venezuela en 1992. Ecuador se retiró de la CIAT en 1968, México en 1978, y Canadá en 1984. La CIAT celebró su 57a reunión en La Jolla, California (EE.DU.) del 21 a123 de octubre de 1996. (PDF contains 360 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1997

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean (EPO). Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, Venezuela in 1992, and EI Salvador in 1997. Mexico withdrew from the IATTC in 1978 and Canada in 1984. The 58th meeting of the IATTC was held in San Jose, Costa Rica, on June 3-4, 1997. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad y dirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto ala afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacifico oriental (OPO). Bajo esta estipulación, la República de Panamá seafilió en 1953, Ecuador en 1961, México en 1964, Canadá en 1968, Japón en 1970, Francia y Nicaragua en 1973, Vanuatu en 1990, Venezuela en 1992, y El Salvador en 1997. México se retiro de la CIAT en 1978, y Canadá en 1984. La CIAT celebró su 58' reunión en San Jose de Costa Rica el 3 y 4 de junio de 1997. (PDF contains 310 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1998

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean (EPO). Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, Venezuela in 1992, and El Salvador in 1997. Canada withdrew from the IATTC in 1984. The 60th meeting of the IATTC was held in La Jolla, California, USA, on February 7, 1998. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad y dirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto ala afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacifico oriental (OPO). Bajo esta estipulación, la República de Panamá seafilió en 1953, Ecuador en 1961, México en 1964, Canadá en 1968, Japón en 1970, Francia y Nicaragua en 1973, Vanuatu en 1990, Venezuela en 1992, y El Salvador en 1997. México se retiro de la CIAT en 1978, y Canadá en 1984. La 60a reunión de la CIAT tuvo lugar el 7 de febrero de 1998. (PDF contains 358 pages.)

Report of the Inter-American Tropical Tuna Commission for the year 1999

ENGLISH: The Inter-American Tropical Tuna Commission (IATTC) operates under the authority and direction of a convention originally entered into by Costa Rica and the United States. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas and tuna-like species in the eastern Pacific Ocean (EPO). Under this provision Panama adhered in 1953, Ecuador in 1961, Mexico in 1964, Canada in 1968, Japan in 1970, France and Nicaragua in 1973, Vanuatu in 1990, Venezuela in 1992, and El Salvador in 1997. Canada withdrew from the IATTC in 1984. The 63rd meeting of the IATTC was held in Guayaquil, Ecuador, on June 8-10,1999. SPANISH: La Comisión Interamericana del Atún Tropical (CIAT) funciona bajo la autoridad y dirección de un convenio suscrito originalmente por Costa Rica y los Estados Unidos de América. El convenio, vigente desde 1950, está abierto ala afiliación de cualquier país cuyos ciudadanos pesquen atunes tropicales y especies afines en el Océano Pacifico oriental (OPO). Bajo esta estipulación, la República de Panamá seafilió en 1953, Ecuador en 1961, México en 1964, Canadá en 1968, Japón en 1970, Francia y Nicaragua en 1973, Vanuatu en 1990, Venezuela en 1992, y El Salvador en 1997. México se retiro de la CIAT en 1978, y Canadá en 1984. La 63a reunión de la CIAT tuvo lugar del 8 al 10 de junio de 1999 en Guayaquil (Ecuador). (PDF contains 184 pages.)