Para substituted benzene nmr formula (Has no symmetry). Signal Height/Size Unlike 1H-NMR, where integration is really important, signal size is not Because there are only four protons in the aromatic region (total integration of 4), the benzene ring is disubstituted. This study focused on the symmetry of the mesogenic part. 257 Simarano Drive, Marlborough, MA 01752 Tel: +1. 14m. They are defined as the following: As the methyl group signal is a signlet is not connected to a adjacent carbon atom that has a H f. Given the chemical formula of C_8H_8O_2, Following up on the last installment, we examine the infrared spectra of mono- and di-substituted benzene rings. In Electrophilic Aromatic Substitution (EAS), some substituents on benzene will direct the electrophile E to the ortho– (1,2)and para– (1,4) positions. Usually a septet and a doublet. 3 ppm in its H NMR spectrum, the protons on substituted benzenes absorb either upfield or downfield from this value, depending on the substituent. Doesn’t look like you’d be able to calculate coupling constants from those spectra. d b c d b e f This lightboard video shows you how to remember Ortho, Meta and Para positions. com www. Substituent: I ortho: I meta: I para: group-H: 0: 0: 0--CH 3-0. 11m. Electrochemical oxida-tion of benzene emulsified with dilute sulphuric acid has been known since 1880 to yield quinone [52]. Common pattern: isopropyl groups: (CH3)2CH-R where R is a heteroatom or a carbon bearing no protons. We just need to identify whether those 2 substituent will be ortho or meta or para to each other. Instead of using numbers to indicate substituents on a benzene ring, ortho- (o-), meta- (m-), or para (p-) can be used in place of positional markers when there are two substituents on the benzene ring (disubstituted benzenes). The image on the right shows four distinguished ring carbon atoms, C1( ipso ), C2( ortho ), C3( meta ), C4( para ) in p-F-C 6 H 4 -Z molecule. Pople4 later extended this to explain the difference in the proton chemical shifts of benzene and ethylene and he further showed that the equivalent dipole model of this ring current gave a surprisingly good account of this difference. (Has no symmetry) 5. 15 K) for benzene (33. Mono Ortho Meta Para 6. Such bridged benzenes are called paracyclophanes. This makes sense when rationalizing the inductive effect of the nitro group by anisotropy of crystalline benzene. As a result, the peak splits as shown below. meta substitution B. l. 2. Another class of substituents avoids directing the electrophile E to those positions, with the result that the meta- product (1,3) is major. • EU=4 fits with a benzene • 5H integral proves monosubstituted benzene. ortho substituti; Dichlorobenzene, C_6H_4Cl_2, exists in three forms (isomers) called ortho, meta, and para. Chemometrics and Intelligent Laboratory Systems, 19: 225–231. Signal Height/Size a. ? A theoretical NMR study of ortho and para-substituted benzenes compared with silabenzenes, pyridines and phosphabenzenes Magn Reson Chem. If the peaks in the AR region are 2 perfect doublets, it is most likely para substituted. Mass MS-NW-5495 chlorobenzene C6H5Cl (Mass of molecular ion: 112) Source Temperature: 250 °C Sample Temperature: 190 °C Reservoir, 75 eV Now let's combine these pieces of information with the information we can extract from 1 ^1 1 H NMR spectrum. The para-substitution pattern results in a characteristic splitting However there are even clues to what type of di-substituted benzene it is. X’ (usually very small, ∼0. What disubstituted benzene isomer corresponds to these 13C data? ed benzene isomer corresponds to these Dc dat? 80 60 40 20 100 ppm 200 180 160 140 120 The following general formula for calculation of vaporisation enthalpy of any poly-substituted benzene (PSB) at 298. Yields of quinone up to 81% of the benzene consumed were achieved [53]. Only 1,4 \textbf{1,4} 1,4-substitution pattern will give $\begingroup$ Related (actually duplicate, but the other question is closed and includes proposed answers that are not related to the question): IUPAC name of bromo, cyano, hydroxy substituted benzene ring $\endgroup$ – Anisole undergoes electrophilic aromatic substitution reaction at a faster speed than benzene, which in turn reacts more quickly than nitrobenzene. 5 Hz). (Has symmetry). O HO • The 2H singlet is at 4. For example, "1,2" substitution for such a compound would also be known as: A. Like you said, the 2 doublets at around $\pu{7 ppm}$ belong to a para-substituted benzene. NMR study of p-disubstituted benzenes with non-coplanar conjugated substituents. Texas A&M University, College Station, TX 77843 NMR chemical shifts for protons directly attached to mono- and di-substituted benzenes are compiled from the literature. In 1 ^1 1 H NMR spectrum, there are two signals in the aromatic region \textit{aromatic region} aromatic region of 4 H-atoms \textit{4 H-atoms} 4 H-atoms in total. A singlet and a doublet between $3$ and $\pu{4 ppm}$ belong to $\ce{CH3-{}}$ and $\ce{-CH2-{}}$ groups, respectively (Note that the signal that belongs to the $\ce{-CH2-{}}$ of aromatic lines and the splitting of the aromatic lines can be indicative of the substitution pattern on a benzene. Degrees of Unsaturation. Given the chemical formula of CsHsO2, propose a Condensed Structural Formula. The prefixes derive from Greek words meaning correct/straight, following/after, and similar, respectively. f. 5 Integration of 1 H NMR Absorptions: Proton the carboxyl group (–CO 2 H) is a meta director and the methyl group is an ortho and para director. Benzene, 1,4-diiodo-Formula: C 6 H 4 I 2; , Specific Heat, Specific Volume, Temperature and Thermal Conductivity of Some Disubstituted Benzene and Polycyclic Systems, Z Harry A. More sophisticated ring current models for benzene were then developed. Shapiro and l. 281. By January 2024 (over 20 We can conclude that students are well educated in recognizing para-substituted benzenes. At present, however, all cubanes in drug design, like almost all benzene bioisosteres, act solely as substitutes for mono- or para-substituted benzene rings1–7. The Para-substituted benzenes refer to aromatic compounds where a substituent is attached to the benzene ring in the para position, or the 1,4 orientation. The IR spectrum shows a strong peak at 1728 cm-1. 6232 | Email: info@spectra-analysis. NMR Spectral Data: A Compilation of Aromatic Proton Chemical Shifts in Mono-and Di-Substituted Benzenes B. Ortho, meta, and para historically carried different meanings, but in 1879 the Learn about reactions at the benzylic position in organic chemistry. Aromatic region has 2 protons H signals of 4 H which indicate para subsitution g. How to recognize para-substitution of benzene rings from proton NMR? And why are signals splitted? The compound on the left has a chain of ten methylene groups linking para carbons of a benzene ring. For meta-, there should be three signals. For common splitting Electron-donating substituents activate the benzene ring to electrophilic attack, which results in the formation of the ortho- and para-disubstituted benzene derivatives. 8 ± 0. Summary of Steps in Beginner 1H NMR Interpretation: 1. 4 ± 0. 1. The two peaks in the aromatic region (~7 ppm) are doublets with integrations of 2, so this ring is probably para substituted. The same thing happens in the case of a benzene ring. 1]hexanes (BCHs) could be used as a platform for both ortho- and meta-substituted benzene bioisosteres. ) Ortho-, Meta-, Para- (OMP) Nomenclature for Disubstituted Benzenes. 5 is not directly connected to the aromatic ring. This structural arrangement has How should I label the multiplicity of the aromatic signals in an 1H-NMR spectrum with the following substitution pattern? I have seen lots of people labeling both signals in this lines and the splitting of the aromatic lines can be indicative of the substitution pattern on a benzene. However, the two protons are NOT magnetically equivalent because the coupling between H. benzene reflects the influence of the methoxy group, Introduction The benzene ring is a basic structural unit in chemistry, and we learn about it in school. 8 is an overlap of a CH2 and CH group 21. SPECTRA ANALYSIS INSTRUMENTS, INC. groups considering benzene as a aromatic substrate. X (about 8 Hz) is different fromthe . 2,3. This is, the ortho protons are the most deshielded, followed by the para, and, finally, the meta. Both groups direct bromination to the position next to the methyl substitution pattern on a benzene. The effects of substituents on the chemical shift of the alkyne carbon atoms in phenylacetylenes have received considerably less attention than the corresponding para-disubstituted benzene. The fluorine atom is para with respect to the substituent Z in the benzene ring. [5] Extensions of this concept to A di-substituted benzene will have 4 protons in the AR region. Formula: . Methoxybenzene refers to a compound with a benzene ring substituted with one or more methoxy (-OCH3 3015, 2065, 1610, 1513, 1252, 1219, 1178, 1032, 832, 786, 541 cm − 1; 1 H NMR anodic oxidation of para-xylene in methanol containing sodium methoxide gives a low yield of the two isomeric 1,4-dimethoxy-1,4-dimethylcyclohexa The PM3 calculations of the Mulliken charge and the experimental 13 C substituent chemical shifts (SCS) of para carbon for 17 para-disubstituted benzene series were investigated by correlation analysis. A is chemically AND magnetically non-equivalent to B. 4 lines s, d, d, d Monosubstituted benzene. The enhanced nucleophilicity of anisole vs. These peaks are formally called the summation bands (2), but I like to call them the benzene fingers , since they form a pattern reminiscent of the fingers on a human hand. In the second case I do agree, with the caveat that any coupling between the methyl group and the aromatic protons is Mesogenic monomers are beneficial, but few studies have investigated the effects of the molecular structure of liquid crystalline epoxy monomers on the higher-order structure and thermal conductivity of their cured resins to obtain highly thermally conductive and insulating epoxy resins. 1H NMR:Spin-Splitting Simple Tree Diagrams. Given the chemical So the first thing that pops up out of the NMR to me is the 7-8ppm range. The peaks at 7-8 ppm in the H-nmr and the 4 peaks in the aromatic region of the 13 C-nmr suggests a para-disubstituted benzene; This gives the following pieces C 6 H 4, C=O, and 2 different -CH 3; Summary Leads to a suggested molecular formula of C 9 H 10 O = 9 x 12 + 10 x 1 + 1 x 16 = 134 g/mol. When R is a metal like Si or Sn the CH3 and CH protons can be close in chemical shift, and give a complex pattern (AB6) or even a singlet. 18-0. But in the case of a benzene ring, it is affected by the hydrogen in the ortho See more Due to the decoupling in 13 C NMR, the number of absorptions due to aromatic carbons can easily be observed. The reported 1 H NMR spectrum for nitrobenzene has three signals corresponding to H2/H6, H3/H5 and H4, respectively. 6 lines s, s, d, d, d, d Ortho- or meta-disubstituted benzene. and H. Number 1 H N O • 4 lines in aryl region, two doublets and two singlets, proves para- As the methyl group signal is a signlet is not connected to a adjacent carbon atom that has a H f. • The weird overlapping mess of ortho/meta/para hydrogens is not worth analyzing. The benzene ring "uses" 6 carbons which leaves 2 carbons for the other peaks. When there are two (or more) substituents, the The terms ortho-, meta- or para- (or their singel letter equivalents) are used as prefixes. • No 3H groups, the “end groups” are the monosubstituted benzene and an OH. 10-0. The numerical The number of distinct carbon present in the compound denotes the number of 13 ^{13} 13 C NMR signal for the given compound. The para-substitution NMR aromatic region pattern usually looks quite different than the patterns for both ortho-and meta-substituted aromatic rings. Given the chemical formula of C10H12O3, propose a NMR spectroscopy is the most powerful tool for determining the structures of the tasks are further classified by difficulty as Easy, Moderate and Hard. Para-substituted aromatic rings are characterized by one strong band near 850 cm −1 [40], therefore, sediments seem to retain the para-substituted aromatic compounds. 9 ± 0. 15m. doi [NICS(1)] values of 84 compounds (benzenes, silabenzenes, pyridines and phosphabenzenes) allowed to discuss the absolute shieldings in the function of Brown σ(p)(+) e. Since we are not given integration values, we will have to use relative peak heights to deter View the full answer Disubstituted benzenes. These compounds exhibit unique spectroscopic properties that are crucial to understand in the context of 15. Draw these molecules out and then try to predict what the NMR spectrum would look like to convince yourself (the chemical shift of each signal doesn't really matter here). If you have a singlet in the AR region, you most likely have a meta-substituted benzene. In the series of 1-X,4-Y-disubstituted benzenes, where X is a variable substituent (an atom or functional group) and Y is a fixed substituent (a composite group which can conjugate with the benzene ring), the para-Disubstituted benzenes refer to aromatic compounds with two substituents attached to the benzene ring in a 1,4-arrangement, or para position. (Click on each full-size image to view details of the region from 6. Geometries of all sixteen thiols and fourteen disulfide compounds were optimized at the B3LYP/6-31G(d) level, while the electronic structure and the 13 C isotropic shifts were calculated by ab initio Hartree Question: Draw the structure of the ortho substituted benzene with the molecular formula C11H14O3, using the information given in the 1H NMR and 13C NMR. 15 K can be suggested: (7) Δ l g H m o (P S B) = Δ l g H m o (B) + n a × Δ H (H → R) + n b × (o r t h o R-R) + n c × (p a r a R-R) + n d × (m e t a R-R) where Δ l g H m o (B) is vaporisation enthalpy of benzene; ΔH(H → R) is an increment of H → R Describe how the H-NMR spectrum indicates that the methyl group at 3. p Using any table of H-NMR chemical shift values, give the approximate H-NMR absorption values (chemical shift) for each of the hydrogens indicated in the following compounds. 21] Although benzene itself absorbs at 7. For chloro-substituted benzoic acids, So the first thing that pops up out of the NMR to me is the 7-8ppm range. 13 Handouts H-NMR Interpretation 1 Short Summary of 1H-NMR Interpretation For fuller explanation, If there are more carbons in your formula than there are lines in your spectrum, it means d Para-disubstituted benzene. 7 Spectroscopy of Aromatic Compounds. The three single-proton multiplets around $\pu{5-6 ppm}$ belong probably to a single substituted alkene. We will examine numerous example spectra and learn how the position of C-H wagging peaks, and the presence or absence of a ring-bending peak, allow one to distinguish between mono-, ortho-, meta-, and para-substituted rings most of the time. For para-dichlorobenzene, there should be only one signal. 3 kJ⋅mol −1) [47] the appropriate contributions into the vaporisation enthalpy in the case of exchange of hydrogen by a substituent in the benzene ring ΔH(H → OH) and ΔH(H → COCH 3) have been derived and used to Describe how the H-NMR spectrum indicates that the methyl group at 3. spectra You have a sample of a compound of molecular formula C1H15NO2, which has a benzene ring substituted by two groups, (CH3)2N- and -CO2CH2CH3 and exhibits the given 13c nMr. ? Determining benzene ring subs tu on pa erns from IR spectra IR spectra provide valuable informa on about local configura ons of atoms in ortho, ~775 for meta, and ~800 for para. , Low-Temperature Heat Capacities and Derived Thermodynamic Functions of Para-Substituted Halogen Benzenes. Given the chemical formula e. (Has symmetry) 4 lines s, s, d, d Para-disubstituted benzene. 15-0. ) When we name disubstituted benzenes, there is another way to name them besides the conventional numbering of carbons. For the following compound describe where each of the labeled protons would show up at in the IH NMR. (Has symmetry) 6 lines s, s, d, d, d, d Ortho- or meta-disubstituted benzene. It is applied in a broad range of scientific disciplines, including physics, structural biology, material science, medicine, and 4 lines s, d, d, d Monosubstituted benzene. The chemical formula is shown together with the spectra. Given the chemical formula of C8H8O2, propose a structure for this compound. on a benzene. Request PDF | A theoretical NMR study of ortho and para-substituted benzenes compared with silabenzenes, pyridines and phosphabenzenes | Calculations of absolute shieldings and nuclear-independent design; 224 FDA approved drugs contain ortho-substituted benzenes, and 68 [13]contain meta-substituted benzenes. K. para-coupling between H. The coupling is influenced by the neighboring hydrogen. Chem 360 Jasperse Ch. Therefore, benzene exhibits only a singlet peak at δ 7. These are called, “ortho, para- directors”. Especially with monosubstituted benzenes that don’t have particularly electron donating or withdrawing substituents, the expected 2 doublet of doublets and one triplet can all sit on top of each other because they have very similar chemical shifts The isomer that best matches the data will be the correct disubstituted benzene isomer. Recently, it was proposed that substituted bicyclo[2. Mono- and para-disubstituted benzenes have symmetry. In alkyl chain coupling, you only need to focus on the hydrogen next to it. para substitution C. In mono-substituted benzene, the correlation of para With the help of Δ l g H m o (298. 18: ethyl The 15N chemical shifts of the para-substituted compounds were analysed by means of DSP equations and the groups on ¹³C NMR chemical shifts in R-substituted benzene are investigated by If the alkyl substituent is smaller than the benzene ring (six or fewer carbons), the compound is named as an alkyl-substituted benzene following the rules listed above. Note the symmetry of the para substituted chloronitro benzene. 5 ppm. 15. You wrote, "I understand that for two nuclei to be magnetically equivalent, they need to When we name disubstituted benzenes, there is another way to name them besides the conventional numbering of carbons. 4 lines s, s, d, d Para-disubstituted benzene. Holík, M. Nomenclature of benzyl group based compounds are very similar to the phenyl group The para-substitution NMR aromatic region pattern usually looks quite different than the patterns for both ortho-and meta-substituted aromatic rings. 5-8. 8 delta is not directly connected to the addehyde. This structural arrangement has important implications for the analysis of 1H NMR spectra. $\begingroup$ I don't agree that the ortho protons in the OPs first example are magnetically equivalent, since they have different couplings to other protons on the ring, but they duplicate the coupling pattern and long distance couplings are negligible. f Describe how the H NMR spectrum indicates that the benzene ring is para substituted. , 1993. 46m. 06-0. g. A-and H. Describe how the H-NMR spectrum indicates that the benzene ring is para substituted. An ortho-disubstituted benzene has its two substituents in a 1,2 relationship on the ring, • 5H integral in 7’s proves mono-substituted benzene • 6H doublet in the 1’s proves an isopropyl group • 2H triplet in 2’s shows CH2 between benzene and another CH2 • 3H mess at 1. Below is a set of simulations for a generic para disubstituted benzene system, which is an AA'BB' system. A3MM'XX' Not actually first order. 508. So yes, the spectrum is as you thought. Also, the 13C NMR spectra of a series of p-methyl-substituted benzene derivatives, including p-tolylcarbenium ions and related onium ions, were determined in order to study the possible constancy Seven-Spin Systems AX6 First order. Constitutional Isomers. Four different epoxy Increment system for estimation of chemical shifts of benzene protons. Describe how the H-NMR spectrum indicates that the methyl group at 3. Carbons without any attached H’s are short. We are already given the hint of compound that it consists of benzene and 2 different groups attached to it. ortho substituti; Which toluidine isomers are possible products when m-bromotoluene is treated with NaNH2? Ortho-, Para– and Meta– Directors. Since we are not given integration values, we will have to use relative peak heights to deter View the full answer on a benzene. Describe how the H-NMR spectrum indicates that the isopropyl group at 4. In mono-substituted benzene, the correlation of para In the spectra of substituted benzene rings there exists a series of peaks between 2000 and 1650 cm-1 whose number and patterns correlate with a substitution pattern. Resonance Structures. If provided with a chemical formula, calculate how many elements of unsaturation are present • This helps to put you on the alert Simple unsubstituted benzene has six aromatic protons, all chemically equivalent. 4 lines s, s, d, d The reported 1 H NMR spectrum for nitrobenzene has three signals corresponding to H2/H6, H3/H5 and H4, respectively. The meta analogs are also known. The methoxy group is an ortho/para directing group, which means that electrophilic substitution preferentially occurs at these three sites. A. You can use 13C NMR for distinguishing o-,m- and p-sub. This makes sense when rationalizing the inductive effect of the nitro group by A large number of para-substituted benzene thiols and the corresponding disulfides were synthesized and characterized by 1 H NMR, 13 C NMR, and IR spectroscopies. Summary of IR (Infrared) Interpretation 1. When using numerical locants, the principal functional group is defined to be at C1. on the 13 C-NMR chemical shift of a substituent group is greater in meta -substituted benzenes than in their para -substituted counterparts [5, 6]. [Pg. 3 ppm in the 1 H NMR spectrum. There are 4 steps to solve this one. Without the actual 13C NMR data, it is not possible to determine the correct isomer. The PM3 calculations of the Mulliken charge and the experimental 13 C substituent chemical shifts (SCS) of para carbon for 17 para-disubstituted benzene series were investigated by correlation analysis. This can be used to determine the relative positions (ortho, meta, or para) for di-substituted benzenes. All of the protons in $\ce{^{12}C_6{}^{1}H_6}$ benzene are equivalent by symmetry, therefore they are chemical shift equivalent. That indicates the disubstituted benzene ring. 11 Characteristics of 13 C NMR Spectroscopy; 13. E. 71 (H4), and 7. 1H NMR: and para-substituted benzoic acids are shown below: <IMAGEs> The relative pKa values depend on the substituent. The structural constraints of the bridging chain require the middle two methylene groups to lie over the face of the benzene ring, which is a nmr shielding region. ortho. It is the most popular ring in natural products 1 and bioactive compounds. It explains how the monosubstituted and disubstituted benzene affects the rea 13. 20: methyl-CH 2 CH 3-0. However, by following these steps and analyzing the provided data, you should be able to identify the correct disubstituted benzene isomer corresponding to the given 13C NMR A large number of para-substituted benzene thiols and the corresponding disulfides were synthesized and characterized by 1 H NMR, 13 C NMR, and IR spectroscopies. 4,5 For example, the well-known drug aspirin contains . 4 lines s, d, d, d In a para-substituted benzene, the substituent group is positioned directly opposite the hydrogen atom on the benzene ring. 10 13 C NMR Spectroscopy: Signal Averaging and FT–NMR; 13. 88 is not directly connected to the addehyde. In the space below each deduce the splitting pattern for mono, ortho, meta, and para substituted benzene. However, a common type, n The most important simplified criteria for the numbering for substituted benzene compounds are: lower locants for the principal characteristic groups, which are expressed as a suffix or implied by the name of the functional parent compound (If there is a choice, the principal characteristic groups are assigned in accordance with the order of seniority of classes of Consider para-disubstituted benzene p-F-C 6 H 4-Z, where Z is a substituent such as NH 2, NO 2, etc. The terms ortho, meta, and para are prefixes used in organic chemistry to indicate the position of non-hydrogen substituents on a hydrocarbon ring (benzene derivative). 12 DEPT 13 C NMR Spectroscopy; Disubstituted benzenes are named using the prefixes ortho (o), meta (m), or para (p). The ortho-substituted benzene ring, in particular, is found in the structure of more than three hundred drugs and agrochemicals (). 5 kJ⋅mol −1) [46] and acetophenone (55. If you have a singlet in the AR para-Substituted benzene refers to a benzene ring with a substituent group attached in the para position, which is the position directly opposite the hydrogen atom on the ring. Seeing 2 doublets in this range are indicative of a para-substituted benzene ring. These terms are ONLY used for benzene systems. 25 (H2/H6), 7. However there are even clues to what type of di-substituted benzene it is. Electrophilic substitution of a disubstituted benzene ring is governed by the same resonance and inductive effects that 13. A is chemically equivalent to A', but magnetically non-equivalent. A significant correlation between the charge and the 13 C SCS of the para carbon of the same series was observed. 1 kJ⋅mol −1) [45], phenol (57. . The benzyl group (abbv. 2010 Dec;48 Suppl 1: S32-7. The signals (ppm) appear at 8. Calculations of absolute shieldings and nuclear-independent chemical shift [NICS(1)] values of 84 compounds (benzenes, silabenzenes, pyridines and phosphabenzenes) allowed to discuss the absolute shieldings in the function of Brown σ(p)(+) substituent constant and to predict 71 new chemical shifts. p-dichlorobenzene IS a single peak in the 1H NMR spectrum. ; van den Berg, Gerrit J. (Has no symmetry) S ub 1Sub 2 S ub 1Sb Sb Sub 2 Sub 2 4. is chemically equivalent to , H H. J. 3 because it is influenced by both the OH and the carbonyl. Bn), similar to the phenyl group and can be written as C 6 H 5 CH 2 -R, PhCH 2 -R, or Bn-R. Mohrmann Department of Chemistry. Benzene, naphthalene and anthracene afford quinones by oxidation in aqueous based media and these processes are technically important. What you should be looking at are the integrations. A’, and indeed the two protons have the same chemical shift. Geometries of all sixteen thiols and fourteen disulfide compounds were optimized at the B3LYP/6-31G(d) level, while the electronic structure and the 13 C isotropic shifts were calculated by ab initio Hartree NMR spectroscopy is the most powerful tool for determining the structures of chemicals. f Describe how the H-NMR spectrum indicates that the benzene ring is para substituted. 56 (H3/H5). C-13 NMR problems page 21. pit qfyzsstgo yzxdl ygskypjj hsgtps wnqyhjdm drblr qzgc wjmubr dwqzba