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Regioselective methyloxygen bond cleavage at 2-position of monoaroyl-2,7- dimethoxynaphthalenes 1aa and 5aa apparently demonstrates the presence of the neighboring effect of the aroyl group. Contrarily, no methyl-oxygen bond cleavage proceeded for 1,8-diaroyl-2,7-dimethoxynaphthalene 7aa under the similar reaction conditions Table 3 , Entry 1. The ether cleavage reaction proceeded still scarcely even when ten equimolar amounts of AlCl3 were employed Entry 3. In refluxing toluene solution, 1,8-diaroyl-2,7-dimethoxynaphthalene 7aa gave unidentified compounds with trace amounts of halfly and dually methyl ether-cleaved products 8ba and 8bb Entry 4.

Table 2. Table 3. Ethereal Methyl-oxygen bond cleavagereaction of 1,8-diaroylnaphthalene 7aa by AlCl3[a]. The required conformation still remains indeterminable, however, the probable situation of AlCl3 between ketonic carbonyl oxygen atom and ether oxygen atom might promote the scission of methyl-oxygen bond. In the case of 1,8-diaroyl-2,7-dimethoxynaphthalene 7aa, the formation of the required conformation is presumably obstructed sterically compared to 1- and 3-monoaroylated naphthalene derivatives.

The ethyl-oxygen bond cleavage reactions carried out against the corresponding diethoxyna phthalene homologues Table 4 -6 manifest the essentially similar reaction behaviors to those of 2,7-dimethoxynaphthalene Table 4. Ethereal ethyl-oxygen bond cleavage reaction of 1-monoaroylated naphthalene 1cc by AlCl3[a]. Table 5. Ethyl-oxygen bonds in 1-mono, 3-mono, and 1,8-diaroylnaphthalenes were somewhat easily cleaved than the methyl-oxygen bonds in the corresponding homologous molecules.

According to the reaction conditions, halfly ether-cleaved products were obtained quantitatively or mixtures with dihydroxy derivatives were yielded. For example, 1-monoaroylated 2-hydroxyethoxynaphthalene 2bc was solely formed by use of a smaller amount of AlCl3 Table 4 , Entry 1 vs. However, half ethyl ether cleavage of 1,8-diaroylated 2,7-diethoxynaphthalene 7cc is rather difficult even under mild conditions Table 6 , Entries 2 and 6.

The results of the cleavage reaction of unsymmetrically dialkoxylated molecule of 1,8-diaroylethoxymethoxy naphthalene 7ca suggest that the methyl-oxygen bond cleavage is promoted after the cleavage of ethoxy group has completed Table 6. In refluxing CH2ClCH2Cl solution, the ethyl-oxygen bond of 1,8-diaroylethoxymethoxynaphthalene 7ca was cleaved in preference to the Table 6.

In refluxing toluene solution, the two kinds of alkyl-oxygen bonds were thoroughly cleaved Entry Figure 1 displays the crystal structures of aroylated 2,7-dimethoxynaphthalenes 1aa and 7aa [15,16] and aroylated 2-hydroxymethoxynaphthalenes 2ba and 8ba [17,18]. In 1-monoaroyl-2,7-dimethoxynaphthalene 1aa, the aroyl group non-coplanarly attaches to the naphthalene ring. On the other hand, the ketonic carbonyl moiety and hydroxy group in 1-monoaroylhydroxy methoxynaphthalene 2ba make a coplanar configuration with intramolecular hydrogen bond.

The same type of intramolecular hydrogen bond between ketonic carbonyl moiety and hydroxy group is observed in X-ray crystal structure of 1,8-diaroylhydroxymethoxynaphthalene 8ba. However, in contrast to anti-orientation of 1,8-diaroylnaphthalene 7aa, 1,8-diaroylhydroxymethoxy naphthalene 8ba has syn-orientation, i.

However, the steric hindrance around the ketonic carbonyl group might be meaningfully different to affect the rotational capability. The aroyl groups of 1,8-diaroylnaphthalene 7aa are deviated out of the naphthalene ring plane more largely than 1-monoaroylnaphthalene 1aa. The angles between C carbonyl -C naphthalene bond and naphthalene plane are The bond lengths between ketonic carbonyl group and a c d Figure 1.

X-ray crystal structures of aroylnaphthalenes: a molecule 1aa; b molecule 2ba; c molecule 7aa; d molecule 8ba For clarity, an ethanol molecule is removed from the figure. About the 8-aroylgroup adjacent to methoxy group in 1,8-diaroylhydroxymethoxynaphthalene 8ba, the corresponding angle and bond length are 9. These data indicate that steric hindrance around ketonic carbonyl group increases in the order of monoaroyldimethoxy derivative 1aa 3. Methyl-oxygen bond cleavage of 1-monoaroyl- 2,7-dimethoxynaphthalene 1aa smoothly and regioselectively proceeds at the 2-position, however, that of 1,8-diaroylnaphthalene 7aa is apparently deactivated like the inertness of 2,7-dimethoxynaphthalene 3aa.

Replacement of one or two methoxy groups with ethoxy ones a little blunts the chemospecificity and the regioselectivity of aroylated naphthalenes. The observed specificity in the alkyl ether-cleavage reaction affords some hitherto-unknown aspects in structures and chemical properties relationship of these congested non-coplanarly aromatic-rings-accumulated molecules.

Experimental All reagents were of commercial quality and were used as received. Solvents were dried and purified using standard techniques. The combined extracts were washed with sat. NaCl aq. The solvent was removed under reduced pressure to give solid. Other ether cleavage reactions were undertaken by essentially the same procedure as above. Synthetic Procedure of Aroylnaphthalenes 1- 4-Chlorobenzoyl -2,7-dimethoxynaphthalene 1aa. To a solution of 2,7-dimethoxynaphthalene 0.

After the reaction mixture was stirred at r. The combined extracts were washed with 2 M NaOH aq. The solvent was removed under reduced pressure to give powdery product. The title compound was prepared by treatment of a mixture of 2,7-dimethoxynaphthalene 10 mmol; 1. The combined extracts were washed with 2 M aqueous NaOH followed by washing with brine. The organic layers thus obtained were dried over anhydrous MgSO4.

The solvent was removed under reduced pressure to give cake. To a solution of TiCl4 mmol, To a solution of 1- 4-chlorobenzoyl ethoxymethoxynaphthalene 0. Identification of the Products 1- 4-Chlorobenzoyl -2,7-dimethoxynaphthalene 1aa. Colorless needle hexane , Mp Use of the circuit of channel amplifiers in which frequency selectivity is carried out by the high-frequency SAW- filters included on an input and an output of the amplifier is analysed.

Introduction Now in Russia the rough growth of information technologies is observed. The important place in this process occupies the decision of a problem of multichannel television reception in cities, settlements and individual structures, there the qualitative reception and distribution in a collective network of ten - fifteen television programs probably at performance of the following conditions: Allocation of a spectrum of a signal of each received television channel; Equalization of a signal level before summation and supply in a distributive network.

The given work is devoted to the solution of a problem of a filtration and equalization of television channels TVC by means of the high-frequency channel SAW-filters being a the basic part of channel amplifiers CA. Main part In this work the selectivity of CA is achieved by high-frequency low-loss SAW-filters, which are established on an input and an output of each amplifier. The block-diagram of construction is shown on fig.

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The plan was simple: Wakeboard up a. Even they are also attracted towards to carbon dioxide. Pregnant women exhale large amount of carbon dioxide as compared to normal women and that is why they are also targeted by them. Jackass star Sean McInerney, also known as Poopies, was in tears as he recalled being bitten by a shark in a horrific attack. The accident happened ahead of Jackass 4 , with the crew filming a stunt called 'Jump The Shark' inspired by a Happy Days episode when The Fonz water-skis up a ramp and over a shark.

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Do you have caps locks on? Try it again. Uh-oh, login failed. Get him out! See Johnny Kno. I mean, I. Veneficus Witch : 2nd and 10th-level Hexes: Veneficus witches specialize in poisons—brewing both magical and traditional concoctions.

Dissociative identity disorder DID is a mental health condition. People with DID have two or more separate identities. These personalities control their behavior at different times. Each identity has its own personal history, traits, likes and dislikes.

DID can lead to gaps in memory and hallucinations believing something is real when it isn. Start studying poopies. Learn vocabulary, terms and more with flashcards, games and other study How much energy does each organism producer, concumer, decomposer get in a food chain? Renewable- can be used over and over again-water, air nonrenreable-cannot be used again-fossil. While initially reluctant to stay there, she falls in love with the people and the place.

Jackass 4 new member Sean "Poopies" McInerney gets attacked by a shark, bit really bad on his wrist on this past week's episode of Shark Week! In an interview taped after his injury, Poopies was shown kicking back with a drink, his arm wrapped up in a cast.

Puppies spend a great deal of time playing, chewing and investigating objects. All of these normal activities involve puppies using their mouths and their needle-sharp teeth. When puppies play with people, they often bite, chew and mouth on people's hands, limbs and clothing. This kind of behavior may seem cute when your puppy is seven weeks. When you are describing the pictures, use these. Until you get your first pull-up done, focus on the back exercises detailed in the levels and workouts Make sure you give yourself at least 48 hours until you do the Level 1 Dumbbell Rows again, so you We'll then work to transfer more weight - bit by bit over several workouts - off our feet and onto our.

The sewers are easily accessible in town. Get Bit! The order of the swimmers is determined by simultaneously playing cards face-down then revealing the values. The number on each player's card determines position in line higher numbers in front, lower numbers in back , however ties don.

When Poopies performed one of his first stunts with the "Jackass" crew for Discovery's "Shark Week," it ended in absolute disaster. Poopies almost lost a hand like his father. Again, he does kind of stalk me as well because he, he's very paranoid about Facebook After years of bad traveling luck, she always gets a bit paranoid before she goes on trips. When people start talking about something that makes you uncomfortable, you.

Sean McInerey, aka Poopies, appeared in a Sunday special but things went awry when the stuntman performed a wakeboard jump. Patrick, enraged that his best friend SpongeBob got him absolutely nothing for the holiday while giving complete strangers exorbitant gifts, goes on a rampage at the Valentine's Day Fair. SpongeBob did get Patrick something, but by the time the gift shows up, Patrick is too far along in his Hulk-like fury.

What exactly does this mean to your network? Does higher ethernet cable MHz speed matter when it comes to ethernet cable and its category? Does this equate to higher bandwidth? The answer is not a simple yes or no, as you likely have guessed by now. Then we will put this in a real-world situation so that everyone can make sense of it.

MHz or Megahertz Defined Megahertz is abbreviated as MHz Megahertz is a clock speed measurement of how fast something can go Megahertz, for the curious, is an electrical frequency take note on the electrical part How do you visualize this? Think of MHz as the width of a water pipe. The wider the pipe, the more water it can handle.

Category Defined Ethernet Category referred to as Cat is the specific standard used by manufacturers when constructing Ethernet cable. It defines how a category of cable should perform over a defined maximum distance. Application protocols are strictly defined, and literally define how fast your network is capable of running, this is application bandwidth. Sometimes, even the software you use can hold you back. There is a direct correlation between application bandwidth and how much money you need to spend to achieve it.

For a more advanced discussion about what this translates to for your ethernet cable MHz speed, see The Need for Speed. To support higher application protocols like 10 Gigabit 10GBASE-T , the Ethernet cable in question must support higher operating frequencies Megahertz The higher the ethernet MHz, the more bandwidth the cable can support over distance The physical construction of Ethernet cable plays a crucial role in this… Thinner copper conductors, like what is found in Cat5e cable 24AWG , can only operate up to a certain Megahertz at a certain distance.

Thicker copper conductors, like what is found in Cat6 cable 23AWG can operate at a higher Megahertz frequency over the same distance Thicker copper can accommodate more electrons. Conductors are not the only criteria for supporting higher Megahertz. The following are also factors: The thickness of the outer cable jacket The thickness of the plastic insulation around the copper conductors The number of twists per inch found inside an Ethernet cable on anyone wire pair.

What are the lowest frequencies needed to achieve a certain bandwidth at a certain distance? Cat6 can support 10GBASE-T, as long as the length is kept to less than or equal to feet under ideal conditions mind you.