Nucleophilic fluoroalkylation of (bromomethyl)pinacolborane using silicon reagents

 

Vitalij V. Levin, Pavel K. Elkin, Marina I. Struchkova, Alexander D. Dilman *
N.D. Zelinsky Institute of Organic Chemistry, 119991 Moscow, Leninsky prosp. 47, Russian Federation

 

1. Introduction
Fluorinated organoboron compounds have emerged as valuable reagents with broad scope of applications [1–3]. While various structural types of fluoroboron compounds have been synthesized, boranes 1 bearing a methyl group substituted with a fluorinated fragment have been poorly studied (Scheme 1). Indeed, only compounds with pentafluorophenyl [4] of difluorovinyl [5] groups were described, which were prepared by nucleophilic substitution of halogen in halomethylboranes using fluorinated lithium or magnesium reagents [6]. At the same time, boranes 1 containing trifluoromethyl or fluorinated alkyl substituent at the a-carbon have not been reported. Herein we describe the application of fluorinated silanes as equivalents of fluorinated carbanions for the preparation of boranes 1.

Reactions of fluorinated silanes with sp2-centered electrophiles, such as C55O, C55N, and electron-deficient C55C bonds [7], as well as substitution of halogen at sp2-carbon [8], have been studied intensively, whereas reactions with sp3-centered electrophiles are notably less general. The displacement of halogen atthe sp3-carbon by fluorinated group can be performed by using fluorinated copper
species RfCu generated either from silane [9] or by other means[10]. Alternatively, direct SN2 type substitution can be realized when silane is activated by Lewis base without transition metal[11], though this process provides reasonable yields mainly with alkyl iodides or benzyl and alkyl bromides.

The major difference of halomethylboranes from conventional alkyl electrophiles is the ability of boron atom to interact with nucleophile to generate tetracoordinate borate salt [12]. Such a behavior was observed in reaction of alkylborates B(OR)3 and esters of boronic acids RB(OR)2 with TMSCF3 [13]. Therefore, it can be expected that the overall substitution of halogen in halomethylboranes can proceed in two steps: by formation of tetracoordinate borate salt followed by intramolecular SN2 substitution (Scheme 1).

 

2. Results and discussion
Bromomethyl pinacolborane 2 was reacted with CF3- and C2F5-substituted silanes (3a and 3b, respectively) in the presence of potassium fluoride in DMF at room temperature (Scheme 2). Trifluoromethylated borate salt 4a was formed cleanly and its structure was supported by 19F and 11B NMR spectroscopy. The yield of salt 4a was ca. 85% determined by 19F NMR spectroscopy with internal standard. To effect intramolecular substitution, the resulting solution of salt 4a was briefly heated at 70 8C to effect complete conversion. However, the desired product 5a was isolated in only 45% yield.

 

Analysis of reaction mixture by 19F NMR spectroscopy showed the formation of by-products which we could not identify. The reaction of borane 2 with TMSC2F5 (3b) proceeded similarly generating borate salt 4b, and its subsequent transformation was carried out at 50 8C affording product 5b in 80% yield after vacuum distillation. Functionalized silanes 3c–f were reacted with borane 2 under standard conditions (Table 1). In this case the formation of products 5 did not require heating, and proceeded at a rate comparable to that of the formation of the intermediate borate salts. These observations suggest that the rate of intramolecular SN2 substitution increases with increasing carbanion stability of migrating group. As a rule, products 5 were formed with the yields exceeding 50%, while their purification was accompanied by product losses.

 

The general problem for the preparation of 2,2,2-trifluoroethyl and related organometallic reagents is the facile b-elimination of metal fluoride from the fragment RCF2CH2M. Rewardingly, boranes 5 are thermally stable compounds showing no tendency for belimination under neutral conditions. However, borane 5c is prone to decomposition in CDCl3 solution, as well as neat upon storage at 5 8C, leading to unidentified mixture despite the fact that it can be distilled under vacuum.

3. Conclusions
In summary, a method for the synthesis of fluorine-substituted pinacolboranes by nucelophilic fluoroalkylation has been described. Taking into account the rich chemistry of organoboron compounds, the obtained boranes may find applications in transition metal catalyzed cross-couplings, as well as in other reactions involving transfer of a partially fluorinated group from boron.

 

4. Experimental
4.1. General experimental procedures
All reactions were performed under an argon atmosphere. DMF was distilled under vacuum from P2O5 and stored over MS 4 A˚ . NMR spectra were recorded on a Bruker AM-300 instrument. Microanalyses were performed on KarloErba 1106 instrument. Me3SiCF3 and Me3SiC2F5 were purchased from P&M. Silanes 3c [14], 3d,f [15] were obtained according to the literature procedures.

 

4.2. 2-(Bromomethyl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (2)

To a stirred solution of triisopropylborate (32.5 mL, 141 mmol) and dibromomethane (10.8 mL, 154 mmol) in anhydrous THF (150 mL) at 94 8C (acetone/liquid nitrogen), n-BuLi (54 mL of 2.4 M solution in hexane, 128 mmol) was added dropwise over 2 min at such a rate that the internal temperature did not rise above 80 8C. The resulting mixture was stirred for 15 min at 78 8C, the cooling bath was removed, and the mixture was stirred for 2 h at room temperature. The reaction mixture was cooled to 0 8C (ice/water bath) and a solution of concentrated sulfuric acid (3.8 mL, 70 mmol) in methanol (8.0 mL) was added dropwise over 2 min. The reaction was allowed to reach room temperature and was stirred for 1 h. Pinacol (12.1 g, 128 mmol) was added in one portion, and the mixture was stirred for 1 h at room temperature. The volatiles were removed under vacuum, and the residue was distilled (70 8C/12 Torr) to give 25.5 g (90% yield) of borane 2 as a colorless liquid.

4.3. Ethyl difluoro(trimethylsilyl)acetate (3e) [17]
Ethyl bromodifluoroacetate (3.2 mL, 25 mmol) was added dropwise to a suspension of magnesium turnings (1.21 mg, 50 mmol) and chlorotrimethylsilane (9.6 mL, 75 mmol) in anhydrous DMF (40 mL) at 0 8C. The reaction mixture was stirred for 90 min at room temperature and quenched with water (40 mL). The aqueous layer was extracted with pentane (3  15 mL), the combined organic phase was washed with water, dried over Na2SO4. The solvent was evaporated under vacuum, and the residue distilled (110–111 8C/90 Torr) furnishing product 3e as a pale yellow oil (2.71 g, 55%).

 

4.4. Borate salt 4a
KF (145 mg, 2.5 mmol) was added to a solution of borane 2 (550 mg, 2.5 mmol) and silane 3a (443 mL, 3 mmol) in DMF (2.5 mL), and the resulting suspension was stirred for 18 h at room temperature. The stirring was discontinued, and the aliquot was analyzed by NMR spectroscopy. 19F NMR (282 MHz, DMF), d: 67.7 (br). 11B NMR (96 MHz, DMF), d: 1.2 (br).

 

4.5. Synthesis of boranes 5a,b
KF (291 mg, 5 mmol) was added to a solution of borane 2 (1.10 g, 5 mmol) and silane 3a or 3b (6 mmol) in DMF (5 mL), the resulting suspension was stirred for 18 h at room temperature, and then heated on water bath (for 5a, 1.5 h at 70 8C; for 5b, 1 h at 50 8C). The mixture was extracted with pentane (2  12 mL). More pentane (10 mL) was added to the DMF layer, the two-phase mixture was shaken, water (5 mL) was added,the mixture was again shaken, and the pentane layer was separated. The combined pentane phase was washed with water (3  3 mL), dried (Na2SO4), and pentane was evaporated at atmospheric pressure. The residue was distilled under vacuum.

Acknowledgments
This work was supported by Russian Foundation for Basic Research (Project 11-03-00362) and the Ministry of Science (Project MD-4750.2013.3).

Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the online version, at http://dx.doi.org/10.1016/j.jfluchem.2013. 06.007.

 

Angenechem offers custom synthesis of chemicals that are not commercially available:

CAS No. 1013-45-2 Benzene, 1,3,5-trichloro-2-[(trimethylsilyl)oxy]- Catalog No.:AG00046W MDL No.: MF:C9H11Cl3OSi MW:269.6275	CAS No. 1013-69-0 4H-1-Benzopyran-4-one, 5,7-dihydroxy-2-methyl- Catalog No.:AG00046V MDL No.:MFCD03001435 MF:C10H8O4 MW:192.1681	CAS No. 1013-75-8 Carbamic acid, N-ethyl-N-phenyl-, ethyl ester Catalog No.:AG00046U MDL No.: MF:C11H15NO2 MW:193.2423
CAS No. 1013031-65-6 Benzenemethanol, 2,6-dibromo- Catalog No.:AG000471 MDL No.:MFCD13185492 MF:C7H6Br2O MW:265.9299	CAS No. 101304-01-2 Benzamide, N-1-azabicyclo[2.2.2]oct-3-yl-2,4-dimethoxy-, sulfate (1:1) Catalog No.:AG00047G MDL No.: MF:C16H24N2O7S MW:388.4360	CAS No. 101305-44-6 3,4-Hexanedione, 2,5-bis(triphenylphosphoranylidene)- Catalog No.:AG00047F MDL No.: MF:C42H36O2P2 MW:634.6816
CAS No. 101306-10-9 Thiophene, 3,4-diethyl-2,5-diphenyl- Catalog No.:AG00047E MDL No.: MF:C20H20S MW:292.4378	CAS No. 101306-11-0 2,3':4',2''-Terthiophene Catalog No.:AG00047D MDL No.:MFCD01106341 MF:C12H8S3 MW:248.3869	CAS No. 101306-86-9 Acetamide, N-[4-[1-(hydroxyimino)-2-oxopropyl]phenyl]- Catalog No.:AG00047C MDL No.: MF:C11H12N2O3 MW:220.2246
CAS No. 1013071-74-3 2-Pyrrolidinone, 1-[3-(hydroxymethyl)-4-(4-morpholinyl)phenyl]- Catalog No.:AG000470 MDL No.: MF:C15H20N2O3 MW:276.3309	CAS No. 101308-47-8 Benzene, 1,1'-(1-methylethylidene)bis[4-(4-bromobutoxy)- Catalog No.:AG00047B MDL No.: MF:C23H30Br2O2 MW:498.2911	CAS No. 101308-54-7 Methanone, [4-(4-bromobutoxy)phenyl]phenyl- Catalog No.:AG00047A MDL No.: MF:C17H17BrO2 MW:333.2197
CAS No. 101308-61-6 Pyridine, 2-[2-(4-bromobutoxy)ethyl]- Catalog No.:AG000479 MDL No.: MF:C11H16BrNO MW:258.1548	CAS No. 101309-07-3 1,5-Naphthalenedisulfonic acid, 3-[2-(4-amino-3-sulfophenyl)diazenyl]- Catalog No.:AG000478 MDL No.: MF:C16H13N3O9S3 MW:487.4841	CAS No. 101309-22-2 3-Buten-2-one, 4-benzo[b]thien-3-yl- Catalog No.:AG000477 MDL No.: MF:C12H10OS MW:202.2722
CAS No. 101309-61-9 1H-Pyrazole-4-carbothioamide, 5-amino-1-(2-chlorophenyl)-3-methyl- Catalog No.:AG000476 MDL No.: MF:C11H11ClN4S MW:266.7498	CAS No. 101309-92-6 Benzoic acid, 2-(dodecyldithio)-, methyl ester Catalog No.:AG000475 MDL No.: MF:C20H32O2S2 MW:368.5969	CAS No. 10131-09-6 4H-Indol-4-one, 1,5,6,7-tetrahydro-6,6-dimethyl-3-phenyl- Catalog No.:AG00047K MDL No.: MF:C16H17NO MW:239.3123
CAS No. 10131-14-3 1H-Indole-2-carboxylic acid, 5,6-dihydroxy-, methyl ester Catalog No.:AG00047J MDL No.: MF:C10H9NO4 MW:207.1828	CAS No. 10131-47-2 Pyridine, 2-methyl-6-(phenylmethyl)-, compd. with 2,4,6-trinitrophenol (1:1) Catalog No.:AG00047I MDL No.: MF:C19H16N4O7 MW:412.3529	CAS No. 10131-61-0 3-Pyridinecarbonitrile, 2-methyl-6-(phenylmethyl)- Catalog No.:AG00047H MDL No.: MF:C14H12N2 MW:208.2585
CAS No. 101310-84-3 1H-Pyrrole-1-hexanoic acid, 3,4-dichloro-2,5-dihydro-2,5-dioxo- Catalog No.:AG000474 MDL No.: MF:C10H11Cl2NO4 MW:280.1046	CAS No. 1013101-73-9 1H-Pyrazole, 1-[2-(methoxymethoxy)ethyl]-4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)- Catalog No.:AG00046Z MDL No.:MFCD16659796 MF:C13H23BN2O4 MW:282.1437	CAS No. 101311-24-4 9,12-Octadecadienoic acid, hydroxy- Catalog No.:AG000473 MDL No.: MF:C18H32O3 MW:296.4449
CAS No. 1013112-48-5 Benzonitrile, 2-formyl-4,5-dimethoxy- Catalog No.:AG00046Y MDL No.:MFCD24678322 MF:C10H9NO3 MW:191.1834	CAS No. 1013117-42-4 3-Pyrrolidinecarboxylic acid, 4-(4-chlorophenyl)-1-(phenylmethyl)-, hydrochloride (1:1), (3R,4S)-rel- Catalog No.:AG00046X MDL No.: MF:C18H19Cl2NO2 MW:352.2550	CAS No. 101314-73-2 Thymidine, 5'-deoxy-5'-[(2-iodoacetyl)amino]- Catalog No.:AG000472 MDL No.: MF:C12H16IN3O5 MW:409.1770
CAS No. 101314-84-5 Propanoic acid, 3-bromo-, 2,5-dioxo-1-pyrrolidinyl ester Catalog No.:AG00047X MDL No.: MF:C7H8BrNO4 MW:250.0467	CAS No. 101315-21-3 4-Penten-2-yn-1-ol, 5-(2,6,6-trimethyl-1-cyclohexen-1-yl)-, (4E)- Catalog No.:AG00047W MDL No.: MF:C14H20O MW:204.3080	CAS No. 101317-85-5 BENZOTHIAZOLIUM, 3-METHYL-2-[(3-METHYL-2(3H)-BENZOTHIAZOLYLIDENE)AMINO]-, 4-METHYLBENZENESULFONATE (1:1) Catalog No.:AG00047U MDL No.: MF:C23H21N3O3S3 MW:483.6261
CAS No. 101319-72-6 Arsine, diphenyl(tributylstannyl)- Catalog No.:AG00047T MDL No.: MF:C24H37AsSn MW:519.1732	CAS No. 101319-94-2 Phosphine, diphenyl(tributylstannyl)- Catalog No.:AG00047S MDL No.: MF:C24H37PSn MW:475.2253	CAS No. 10132-01-1 Phthalazine, 1-chloro-4-phenyl- Catalog No.:AG000489 MDL No.:MFCD00524786 MF:C14H9ClN2 MW:240.6877
CAS No. 10132-02-2 1-Phthalazinecarbonitrile, 4-phenyl- Catalog No.:AG000488 MDL No.: MF:C15H9N3 MW:231.2521	CAS No. 10132-05-5 Phthalazine, 1,4-diphenyl- Catalog No.:AG000487 MDL No.: MF:C20H14N2 MW:282.3386	CAS No. 10132-07-7 4-Pyrimidinamine, 2,6-dichloro- Catalog No.:AG000486 MDL No.:MFCD00038015 MF:C4H3Cl2N3 MW:163.9927
CAS No. 10132-14-6 Pyrimidine, 2-[(1-methylethyl)thio]- Catalog No.:AG000485 MDL No.: MF:C7H10N2S MW:154.2327	CAS No. 10132-28-2 2-Pyrimidinamine, N-butyl- Catalog No.:AG000484 MDL No.: MF:C8H13N3 MW:151.2089	CAS No. 10132-29-3 4-Pyrimidinamine, N-butyl- Catalog No.:AG000483 MDL No.: MF:C8H13N3 MW:151.2089
CAS No. 10132-44-2 Pyrazine, 2,5-dimethyl-3,6-bis(3-methylbutyl)- Catalog No.:AG000482 MDL No.: MF:C16H28N2 MW:248.4069	CAS No. 10132-50-0 Sulfonium, (carboxymethyl)dimethyl-, chloride (1:1) Catalog No.:AG000481 MDL No.: MF:C4H9ClO2S MW:156.6311	CAS No. 10132-71-5 Silane, ethylfluorodimethyl- Catalog No.:AG000480 MDL No.: MF:C4H11FSi MW:106.2140
CAS No. 10132-80-6 [2,6':2',6''-Terbenzothiazole]-7-sulfonic acid, 2''-(4-aminophenyl)-6-methyl-, sodium salt (1:1) Catalog No.:AG00047Z MDL No.: MF:C28H17N4NaO3S4 MW:608.7094	CAS No. 10132-99-7 Benzenesulfonic acid, 4-[4-[2-(3-chloro-2-hydroxy-5-nitrophenyl)diazenyl]-4,5-dihydro-3-methyl-5-oxo-1H-pyrazol-1-yl]-, sodium salt (1:1) Catalog No.:AG00047Y MDL No.: MF:C16H11ClN5NaO7S MW:475.7956	CAS No. 101320-56-3 Silanol, 1-ethenyl-, 1-acetate Catalog No.:AG00047R MDL No.: MF:C4H10O3Si MW:134.2059
CAS No. 101321-39-5 Acetaldehyde, 2-bromo-2-chloro-2-fluoro- Catalog No.:AG00047Q MDL No.: MF:C2HBrClFO MW:175.3841	CAS No. 101324-10-1 2-Heptenenitrile, 7-bromo-2-methoxy-, (Z)- (9CI) Catalog No.:AG00047P MDL No.: MF:C8H12BrNO MW:218.0910	CAS No. 101325-37-5 9H-Pyrrolo[2,3-f]quinoxaline Catalog No.:AG00047O MDL No.: MF:C10H7N3 MW:169.1827
CAS No. 101326-49-2 Urea, N-(2-cyanoethyl)-N-(2-hydroxyethyl)- Catalog No.:AG00047N MDL No.: MF:C6H11N3O2 MW:157.1704	CAS No. 101326-58-3 9H-Carbazole-9-acetamide, N,N-diethyl- Catalog No.:AG00047M MDL No.: MF:C18H20N2O MW:280.3642	CAS No. 101327-52-0 Propanoic acid, 2,2-dimethyl-, 2-buten-1-yl ester Catalog No.:AG00047L MDL No.: MF:C9H16O2 MW:156.2221
CAS No. 101327-84-8 2-Naphthalenecarboxaldehyde, 1-nitro- Catalog No.:AG00048N MDL No.:MFCD03427164 MF:C11H7NO3 MW:201.1782	CAS No. 101327-85-9 6-Quinolinecarboxaldehyde, 5-nitro- Catalog No.:AG00048M MDL No.: MF:C10H6N2O3 MW:202.1662	CAS No. 101327-87-1 7-Quinolinecarboxaldehyde, 8-nitro- Catalog No.:AG00048L MDL No.:MFCD08436438 MF:C10H6N2O3 MW:202.1662
CAS No. 101327-98-4 3-Piperidinecarboxylic acid, 1-methyl-2-oxo-, methyl ester Catalog No.:AG00048K MDL No.:MFCD28101622 MF:C8H13NO3 MW:171.1937	CAS No. 101328-75-0 Ergoline, 8,9-didehydro-6,8-dimethyl-1-pentyl- (9CI) Catalog No.:AG00048J MDL No.: MF:C21H28N2 MW:308.4604	CAS No. 101328-76-1 Ergoline, 8,9-didehydro-6,8-dimethyl-1-pentyl-, (2R,3R)-2,3-bis[(4-methylbenzoyl)oxy]butanedioate (1:1) (9CI) Catalog No.:AG00048I MDL No.: MF: MW:
CAS No. 101328-84-1 3(2H)-Pyridazinone, 6-(4-aminophenyl)-4,5-dihydro-5-methyl-, (5S)- Catalog No.:AG00048H MDL No.: MF:C11H13N3O MW:203.2404	CAS No. 101328-85-2 3(2H)-Pyridazinone, 6-(4-aminophenyl)-4,5-dihydro-5-methyl-, (5R)- Catalog No.:AG00048G MDL No.:MFCD09032921 MF:C11H13N3O MW:203.2404	CAS No. 101328-87-4 2-Propanol, 1-amino-3-[4-[2-(cyclopropylmethoxy)ethyl]phenoxy]-, (R)- (9CI) Catalog No.:AG00048F MDL No.: MF:C15H23NO3 MW:265.3480
CAS No. 101329-30-0 Oxirane, 2-[[2,6-dibromo-4-(1-methylethyl)phenoxy]methyl]- Catalog No.:AG00048E MDL No.: MF:C12H14Br2O2 MW:350.0464	CAS No. 101329-41-3 3-Thiophenecarboxylic acid, 2-(butylamino)-, methyl ester Catalog No.:AG00048D MDL No.: MF:C10H15NO2S MW:213.2966	CAS No. 101329-81-1 Benzenemethanol, 2-chloro-4-fluoro-5-nitro- Catalog No.:AG00048C MDL No.: MF:C7H5ClFNO3 MW:205.5709
CAS No. 101329-82-2 Benzenemethanol, 5-amino-2-chloro-4-fluoro- Catalog No.:AG00048B MDL No.:MFCD17168711 MF:C7H7ClFNO MW:175.5880	CAS No. 101329-93-5 Cyclopentanecarboxylic acid, 1-(phenylthio)-, 2-(dimethylamino)ethyl ester, ethanedioate (1:1) Catalog No.:AG00048A MDL No.: MF:C18H25NO6S MW:383.4592	CAS No. 10133-07-0 2-Oxiranecarboxylic acid, 3-methyl-, methyl ester, (2S,3R)- Catalog No.:AG00048Y MDL No.: MF:C5H8O3 MW:116.1152
CAS No. 10133-20-7 Benzo[b]thiophene, 2-(bromomethyl)- Catalog No.:AG00048X MDL No.:MFCD09909594 MF:C9H7BrS MW:227.1209	CAS No. 10133-22-9 Benzo[b]thiophene, 5-(bromomethyl)- Catalog No.:AG00048W MDL No.: MF:C9H7BrS MW:227.1209	CAS No. 10133-24-1 Benzo[b]thiophene, 7-(bromomethyl)- Catalog No.:AG00048V MDL No.:MFCD08706224 MF:C9H7BrS MW:227.1209
CAS No. 10133-25-2 Benzo[b]thiophene-4-carboxaldehyde Catalog No.:AG00048U MDL No.:MFCD18432490 MF:C9H6OS MW:162.2083	CAS No. 10133-30-9 Benzo[b]thiophene-5-carbaldehyde Catalog No.:AG00048T MDL No.:MFCD05663673 MF:C9H6OS MW:162.2083	CAS No. 10133-33-2 Benzo[b]thiophene, 2-nitro- Catalog No.:AG00048S MDL No.:MFCD01151382 MF:C8H5NO2S MW:179.1958
CAS No. 10133-36-5 Benzo[b]thiophen-3-amine, 2-nitro- Catalog No.:AG00048R MDL No.: MF:C8H6N2O2S MW:194.2104	CAS No. 10133-38-7 Benzo[b]thiophen-3-amine, N,N-diethyl-2-nitro- Catalog No.:AG00048Q MDL No.: MF:C12H14N2O2S MW:250.3168	CAS No. 10133-53-6 2-Oxiranecarboxamide, N-(hydroxymethyl)- Catalog No.:AG00048P MDL No.: MF:C4H7NO3 MW:117.1033
CAS No. 10133-67-2 2-Furancarboxylic acid, tetrahydro-5-(phenylmethyl)- Catalog No.:AG00048O MDL No.:MFCD19302226 MF:C12H14O3 MW:206.2378	CAS No. 10133-76-3 Isoquinoline, 3,4-dihydro-6,7-dimethoxy-1-phenyl-, hydrochloride (1:1) Catalog No.:AG00049N MDL No.: MF:C17H18ClNO2 MW:303.7833	CAS No. 10133-81-0 9H-Thioxanthene, 10-oxide Catalog No.:AG00049M MDL No.: MF:C13H10OS MW:214.2829
CAS No. 10133-88-7 2H-Isoindole-2-acetic acid, 1,3-dihydro-5-nitro-1,3-dioxo- Catalog No.:AG00049L MDL No.:MFCD00435974 MF:C10H6N2O6 MW:250.1644	CAS No. 101330-11-4 3-Quinolinemethanol, 2-iodo- Catalog No.:AG00049I MDL No.: MF:C10H8INO MW:285.0811	CAS No. 101330-69-2 Phenol, 3-methoxy-5-[2-(3-methoxyphenyl)ethyl]- Catalog No.:AG00049H MDL No.: MF:C16H18O3 MW:258.3123
CAS No. 101330-74-9 9-Octadecynoic acid, 8-oxo-, methyl ester Catalog No.:AG00049G MDL No.: MF:C19H32O3 MW:308.4556	CAS No. 101333-98-6 2-Benzoxazolemethanamine Catalog No.:AG00049F MDL No.:MFCD03990563 MF:C8H8N2O MW:148.1619	CAS No. 1013333-20-4 4-Piperidinecarbonitrile, 3-hydroxy-1-(phenylmethyl)-, (3R,4R)-rel- Catalog No.:AG000493 MDL No.:MFCD23703764 MF:C13H16N2O MW:216.2789
CAS No. 1013333-23-7 3-Piperidinol, 4-(aminomethyl)-, hydrochloride (1:2), (3R,4R)-rel- Catalog No.:AG000492 MDL No.: MF:C6H16Cl2N2O MW:203.1100	CAS No. 1013333-61-3 Spiro[2H-1-benzopyran-2,4'-piperidine]-1'-carboxylic acid, 3,4-dihydro-6,7-dimethyl-4-oxo-, 1,1-dimethylethyl ester Catalog No.:AG000491 MDL No.: MF:C20H27NO4 MW:345.4327	CAS No. 101335-11-9 Benzene, 2-chloro-4-fluoro-1-iodo- Catalog No.:AG00049E MDL No.:MFCD00051774 MF:C6H3ClFI MW:256.4439
CAS No. 101335-18-6 Benzamide, 4-decyl-N-hydroxy-N-methyl- Catalog No.:AG00049D MDL No.: MF:C18H29NO2 MW:291.4284	CAS No. 101335-99-3 2-Thiophenepentanoic acid, 5-(3-phenylpropyl)- Catalog No.:AG00049C MDL No.: MF:C18H22O2S MW:302.4311	CAS No. 101336-13-4 2-Thiophenepentanoic acid, 5-(3-phenylpropyl)-, ethyl ester Catalog No.:AG00049B MDL No.: MF:C20H26O2S MW:330.4842
CAS No. 101336-63-4 Pyridine, 2-chloro-5-[[2-(nitromethylene)-1-imidazolidinyl]methyl]- Catalog No.:AG00049A MDL No.:MFCD05670547 MF:C10H11ClN4O2 MW:254.6729	CAS No. 101337-87-5 7H-Pyrido[1,2,3-de]-1,4-benzothiazine-6-carboxylic acid, 9-fluoro-2,3-dihydro-7-oxo-10-(1-piperazinyl)- Catalog No.:AG000499 MDL No.: MF:C16H16FN3O3S MW:349.3799	CAS No. 101337-95-5 2H-1,4-Benzothiazin-3(4H)-one, 8-chloro-7-fluoro- Catalog No.:AG000498 MDL No.: MF:C8H5ClFNOS MW:217.6478
CAS No. 101339-45-1 Benzonitrile, 2-chloro-6-[(4-methoxyphenyl)thio]- Catalog No.:AG000497 MDL No.: MF:C14H10ClNOS MW:275.7533	CAS No. 101339-72-4 Butane, 1-bromo-4-(2-propyn-1-yloxy)- Catalog No.:AG000496 MDL No.: MF:C7H11BrO MW:191.0656	CAS No. 101339-92-8 2,5,8-Undecatrien-1-ol, (E,E,E)- (9CI) Catalog No.:AG000495 MDL No.: MF:C11H18O MW:166.2600
CAS No. 101339-96-2 2,5,8-Undecatrien-1-ol, (2E,5Z,8Z)- Catalog No.:AG000494 MDL No.: MF:C11H18O MW:166.2600	CAS No. 1013398-57-6 1H-Indole, 5-fluoro-2,3-dihydro-, hydrochloride (1:1) Catalog No.:AG000490 MDL No.:MFCD12761537 MF:C8H9ClFN MW:173.6152	CAS No. 1013398-58-7 1H-Indole, 5-chloro-2,3-dihydro-, hydrochloride (1:1) Catalog No.:AG00048Z MDL No.:MFCD12761536 MF:C8H9Cl2N MW:190.0698
CAS No. 10134-01-7 Methanone, (3-bromo-4-methoxyphenyl)-1-isoquinolinyl- Catalog No.:AG00049K MDL No.: MF:C17H12BrNO2 MW:342.1867	CAS No. 10134-91-5 BENZO[B]THIOPHENE-7-CARBALDEHYDE Catalog No.:AG00049J MDL No.:MFCD08572207 MF:C9H6OS MW:162.2083	CAS No. 10134-95-9 Benzo[b]thiophene-4-carboxylic acid Catalog No.:AG0004AC MDL No.:MFCD01929340 MF:C9H6O2S MW:178.2077
CAS No. 10134-98-2 Benzo[b]thiophene-7-carboxylic acid Catalog No.:AG0004AB MDL No.:MFCD08572208 MF:C9H6O2S MW:178.2077	CAS No. 101340-38-9 Benzaldehyde, 3-nitro-2-(phenylmethoxy)- Catalog No.:AG0004A7 MDL No.: MF:C14H11NO4 MW:257.2414	CAS No. 1013405-24-7 9H-Carbazole, 9,9'-(2,6-pyridinediyldi-3,1-phenylene)bis- Catalog No.:AG00049R MDL No.:MFCD20275106 MF:C41H27N3 MW:561.6732
CAS No. 1013405-25-8 9H-Carbazole, 9,9'-(3,5-pyridinediyldi-3,1-phenylene)bis- Catalog No.:AG00049Q MDL No.:MFCD20275105 MF:C41H27N3 MW:561.6732	CAS No. 1013405-79-2 [1,1'-Biphenyl]-3-acetic acid, 3'-(phenylmethoxy)- Catalog No.:AG00049P MDL No.:MFCD20231507 MF:C21H18O3 MW:318.3658	CAS No. 101342-44-3 2-Butenedioic acid, 2,3-dicyano-, 1,4-dimethyl ester, (2Z)- Catalog No.:AG0004A6 MDL No.: MF:C8H6N2O4 MW:194.1442
CAS No. 101342-45-4 2-Naphthacenecarboxamide, 7-chloro-4-(dimethylamino)-1,4,4a,5,5a,6,11,12a-octahydro-3,6,10,12,12a-pentahydroxy-6-methyl-1,11-dioxo-, hydrochloride (1:1), (4R,4aS,5aS,6S,12aS)- Catalog No.:AG0004A5 MDL No.:MFCD09842537 MF:C22H24Cl2N2O8 MW:515.3406	CAS No. 101342-76-1 Pentanedioic acid, 1,1'-(1,10-decanediyl) 5,5'-bis(1-butylpentyl) ester Catalog No.:AG0004A4 MDL No.: MF:C38H68O8-- MW:652.9417	CAS No. 1013427-15-0 Pyrazolo[1,5-a]pyrimidine, 3-(5-bromo-3-chloro-2-thienyl)-2,5-dimethyl-7-(1-methylethyl)- Catalog No.:AG00049O MDL No.: MF:C15H15BrClN3S MW:384.7217
CAS No. 101346-02-5 Pyrimidine, 5-(chloromethyl)- Catalog No.:AG0004A3 MDL No.:MFCD10697061 MF:C5H5ClN2 MW:128.5596	CAS No. 101347-44-8 1,4,7,10-Tetraoxa-13-azacyclopentadecane, 13-[bis(1-aziridinyl)phosphinyl]- Catalog No.:AG0004A2 MDL No.: MF:C14H28N3O5P MW:349.3630	CAS No. 101347-53-9 Acetamide, N-(2-ethyl-4-penten-1-yl)- Catalog No.:AG0004A1 MDL No.: MF:C9H17NO MW:155.2374
CAS No. 101348-32-7 Pyrido[2,3-d]pyrimidine-2,4-diamine, 6-(bromomethyl)-5-methyl- Catalog No.:AG0004A0 MDL No.: MF:C9H10BrN5 MW:268.1132	CAS No. 101349-12-6 1H-Indole-3-ethanol, 5-fluoro- Catalog No.:AG00049Z MDL No.:MFCD09752697 MF:C10H10FNO MW:179.1909	CAS No. 101349-14-8 2H-Indol-2-one, 5,7-dichloro-1,3-dihydro-3-methyl- Catalog No.:AG00049Y MDL No.: MF:C9H7Cl2NO MW:216.0640
CAS No. 101349-61-5 Naphthalene, 1-(2-iodo-1-methylethyl)- Catalog No.:AG00049X MDL No.: MF:C13H13I MW:296.1468	CAS No. 101349-67-1 Benzene, 1,1'-[[(1Z)-1-butyl-1,2-ethenediyl]bis(seleno)]bis- Catalog No.:AG00049W MDL No.: MF:C18H20Se2 MW:394.2714	CAS No. 101349-71-7 Benzaldehyde, 4-chloro-3-methyl- Catalog No.:AG00049V MDL No.:MFCD02261736 MF:C8H7ClO MW:154.5936
CAS No. 101349-79-5 Benzene, (2-iodoethenyl)- Catalog No.:AG00049U MDL No.: MF:C8H7I MW:230.0457	CAS No. 101349-83-1 Benzaldehyde, 3-chloro-4-(methylsulfonyl)- Catalog No.:AG00049T MDL No.: MF:C8H7ClO3S MW:218.6574	CAS No. 101349-95-5 Benzaldehyde, 2-chloro-4-(methylsulfonyl)- Catalog No.:AG00049S MDL No.:MFCD04037960 MF:C8H7ClO3S MW:218.6574
CAS No. 10135-00-9 Benzo[b]thiophene-2-carboxaldehyde, 3-bromo- Catalog No.:AG0004AA MDL No.:MFCD00465001 MF:C9H5BrOS MW:241.1044	CAS No. 10135-17-8 2-Oxazolidinone, 3-(2-phenylethyl)- Catalog No.:AG0004A9 MDL No.: MF:C11H13NO2 MW:191.2264	CAS No. 10135-23-6 2-Pyrrolidinone, 1-(2-phenylethyl)- Catalog No.:AG0004B1 MDL No.:MFCD01605540 MF:C12H15NO MW:189.2536
CAS No. 10135-38-3 2H-Pyrrole, 3,4-dihydro-2,2,4,4-tetramethyl-, 1-oxide Catalog No.:AG0004B0 MDL No.:MFCD00010542 MF:C8H15NO MW:141.2108	CAS No. 10135-43-0 Benzamide, N,N-bis[2-(benzoyloxy)ethyl]- Catalog No.:AG0004AZ MDL No.: MF:C25H23NO5 MW:417.4538	CAS No. 101350-03-2 1,2-Propanediol, 3-[(2-hydroxyethyl)methylamino]- Catalog No.:AG0004AU MDL No.: MF:C6H15NO3 MW:149.1882
CAS No. 101351-09-1 1H-Isoindole-1,3(2H)-dione, 2-[2-(4-aminophenoxy)ethyl]- Catalog No.:AG0004AT MDL No.:MFCD00418191 MF:C16H14N2O3 MW:282.2940	CAS No. 101353-61-1 8-Azabicyclo[3.2.1]octan-3-amine, 8-methyl-N-(phenylmethyl)- Catalog No.:AG0004AS MDL No.:MFCD09839704 MF:C15H22N2 MW:230.3486	CAS No. 101354-47-6 Benzamide, 4-nitro-N-(1,1,3,3-tetramethylbutyl)- Catalog No.:AG0004AR MDL No.:MFCD00831523 MF:C15H22N2O3 MW:278.3468
CAS No. 101355-80-0 Formamide, N-[2,4-bis(1,1-dimethylethyl)phenyl]- Catalog No.:AG0004AQ MDL No.: MF:C15H23NO MW:233.3492	CAS No. 101356-82-5 1-Propanone, 3-(diethylamino)-1-(4-ethoxyphenyl)-, hydrochloride (1:1) Catalog No.:AG0004AP MDL No.: MF:C15H24ClNO2 MW:285.8096	CAS No. 10136-52-4 9-Heptadecenoic acid Catalog No.:AG0004AY MDL No.: MF:C17H32O2 MW:268.4348
CAS No. 10136-57-9 8-Quinolinol, 5-(chloromethyl)- Catalog No.:AG0004AX MDL No.:MFCD06252469 MF:C10H8ClNO MW:193.6296	CAS No. 10136-64-8 Imidazo[2,1-b]-1,3,4-thiadiazol-2-amine, 6-phenyl- Catalog No.:AG0004AW MDL No.:MFCD03969504 MF:C10H8N4S MW:216.2623	CAS No. 10136-65-9 Bicyclo[3.1.1]heptan-3-one, 2-hydroxy-2,6,6-trimethyl- Catalog No.:AG0004AV MDL No.: MF:C10H16O2 MW:168.2328
CAS No. 101361-07-3 3-Pentanone, 1,1,2-trifluoro-1-(phenylthio)- Catalog No.:AG0004AO MDL No.: MF:C11H11F3OS MW:248.2646	CAS No. 1013621-67-4 Benzenepropanol, α-[3-[[(1,1-dimethylethyl)dimethylsilyl]oxy]phenyl]-3,4-dimethoxy-, (αR)- Catalog No.:AG0004AF MDL No.: MF:C23H34O4Si MW:402.5992	CAS No. 101363-10-4 7H-Pyrido[1,2,3-de]-1,4-benzothiazine-6-carboxylic acid, 9-fluoro-2,3-dihydro-10-(4-methyl-1-piperazinyl)-7-oxo- Catalog No.:AG0004AN MDL No.:MFCD00865073 MF:C17H18FN3O3S MW:363.4065
CAS No. 101363-28-4 Phosphonium, tributyl(1-pyrenylmethyl)-, bromide (1:1) Catalog No.:AG0004AM MDL No.: MF:C29H38BrP MW:497.4898	CAS No. 101364-80-1 2-Propenoic acid, 2-methyl-, 2,4,6-triiodophenyl ester Catalog No.:AG0004AL MDL No.: MF:C10H7I3O2 MW:539.8748	CAS No. 1013640-87-3 Borate(1-), trifluoro-1H-pyrazol-3-yl-, potassium (1:1), (T-4)- Catalog No.:AG0004AE MDL No.:MFCD11858601 MF:C3H3BF3KN2 MW:173.9738
CAS No. 1013648-04-8 3-Pyridinecarboxylic acid, 2,6-dichloro-4-methyl-, methyl ester Catalog No.:AG0004AD MDL No.:MFCD15144593 MF:C8H7Cl2NO2 MW:220.0527	CAS No. 101365-14-4 3-Pentenoic acid, 2,5-diamino-2-(fluoromethyl)-, methyl ester, (3E)- Catalog No.:AG0004AK MDL No.: MF:C7H13FN2O2 MW:176.1887	CAS No. 101365-44-0 Benzoic acid, 2-[[ethoxy[(1-methylethyl)amino]phosphinothioyl]oxy]-, methyl ester Catalog No.:AG0004AJ MDL No.: MF:C13H20NO4PS MW:317.3410
CAS No. 101365-91-7 Propanedinitrile, 2-[[4-(butylethylamino)phenyl]methylene]- Catalog No.:AG0004AI MDL No.: MF:C16H19N3 MW:253.3422	CAS No. 101366-34-1 Hydrazinecarboxamide, sulfate (2:1) Catalog No.:AG0004AH MDL No.: MF:C2H12N6O6S MW:248.2183	CAS No. 101366-35-2 Hydrazinecarboxamide, sulfate (1:1) Catalog No.:AG0004AG MDL No.: MF:CH7N3O5S MW:173.1484
CAS No. 101366-36-3 Hydrazinecarboxamide, phosphonate (2:1) Catalog No.:AG0004BJ MDL No.: MF:C2H13N6O5P MW:232.1356	CAS No. 101366-37-4 Hydrazinecarboxamide, phosphonate (1:1) Catalog No.:AG0004BI MDL No.: MF:CH8N3O4P MW:157.0657	CAS No. 101366-39-6 2-Butene, 1,4-dibutoxy-, (2E)- Catalog No.:AG0004BH MDL No.: MF:C12H24O2 MW:200.3178
CAS No. 101366-50-1 [1,1'-Biphenyl]-4-sulfonyl chloride, 3'-nitro- Catalog No.:AG0004BG MDL No.: MF:C12H8ClNO4S MW:297.7142	CAS No. 101366-51-2 [1,1'-Biphenyl]-4-sulfonyl chloride, 4'-methyl- Catalog No.:AG0004BF MDL No.:MFCD01631922 MF:C13H11ClO2S MW:266.7432	CAS No. 101366-61-4 Propanoic acid, 3-[4-(hydroxymethyl)phenoxy]- Catalog No.:AG0004BE MDL No.:MFCD00137851 MF:C10H12O4 MW:196.1999
CAS No. 101367-62-8 Thiazolo[4,5-f]quinoline-8-carbonitrile, 4,5,6,7-tetrahydro-7-oxo- Catalog No.:AG0004BD MDL No.: MF:C11H7N3OS MW:229.2578	CAS No. 10137-67-4 Propanoic acid, 3-cyano-, ethyl ester Catalog No.:AG0004BP MDL No.:MFCD01695650 MF:C6H9NO2 MW:127.1412	CAS No. 10137-73-2 Cyclopentane, 1,1'-oxybis- Catalog No.:AG0004BN MDL No.: MF:C10H18O MW:154.2493
CAS No. 10137-87-8 Benzenemethanamine, N-ethyl-α-methyl- Catalog No.:AG0004BL MDL No.:MFCD00463430 MF:C10H15N MW:149.2328	CAS No. 10137-90-3 3-Nonen-2-one, 5-ethyl- Catalog No.:AG0004BK MDL No.: MF:C11H20O MW:168.2759	CAS No. 101370-75-6 1H-Tetrazole, 4,5-dihydro-1-methyl-5,5-diphenyl-4-(phenylmethyl)- Catalog No.:AG0004BC MDL No.: MF:C21H20N4 MW:328.4103
CAS No. 101370-77-8 1H-Tetrazole, 4,5-dihydro-1,5,5-triphenyl-4-(phenylmethyl)- Catalog No.:AG0004BB MDL No.: MF:C26H22N4 MW:390.4797	CAS No. 101371-00-0 2-Butanone, 2,2',2''-[O,O',O''-(ethoxysilylidyne)trioxime] Catalog No.:AG0004BA MDL No.: MF: MW:	CAS No. 101371-01-1 2-Butanone,O-(triethoxysilyl)oxime Catalog No.:AG0004B9 MDL No.: MF:C10H23NO4Si MW:249.3794
CAS No. 101371-20-4 Benzene, 1-(1-ethylpropyl)-4-(1-methylbutyl)- Catalog No.:AG0004B8 MDL No.: MF:C16H26 MW:218.3776	CAS No. 101372-99-0 4,6,10-Hexadecatrien-1-ol, 1-acetate, (4E,6E,10Z)- Catalog No.:AG0004B7 MDL No.: MF:C18H30O2 MW:278.4296	CAS No. 101373-01-7 4,6,10-Hexadecatrien-1-ol, (4E,6E,10Z)- Catalog No.:AG0004B6 MDL No.: MF:C16H28O MW:236.3929
CAS No. 101373-20-0 Ethanol, 2,2'-[(dioctylstannylene)bis(oxy)]bis[2-oxo- (9CI) Catalog No.:AG0004B5 MDL No.: MF:C20H40O6Sn MW:495.2290	CAS No. 101373-23-3 Hexadecanoic acid, 16-(iodo-123I)-3-methyl- (9CI) Catalog No.:AG0004B4 MDL No.: MF:C17H33IO2 MW:392.3483	CAS No. 101373-58-4 Pyrrolidinium, 1-(chloro-1-pyrrolidinylmethylene)-, chloride (1:1) Catalog No.:AG0004B3 MDL No.: MF:C9H16Cl2N2 MW:223.1427
CAS No. 101374-15-6 Acetamide, N-[2-[methyl(3-methylphenyl)amino]ethyl]- Catalog No.:AG0004B2 MDL No.: MF:C12H18N2O MW:206.2841	CAS No. 101375-73-9 Cyclopropanemethanol, 2-butyl-, (1R,2R)-rel- Catalog No.:AG0004C0 MDL No.: MF:C8H16O MW:128.2120	CAS No. 101375-82-0 Octadecanoic acid, 6-hydroxy-6-methyl- Catalog No.:AG0004BZ MDL No.: MF:C19H38O3 MW:314.5032
CAS No. 1013753-99-5 4-Piperidinecarboxamide, N-[(1S)-2-[[(2-methoxyphenyl)methyl]amino]-1-methyl-2-oxoethyl]-1-(phenylsulfonyl)- Catalog No.:AG0004BQ MDL No.:MFCD08290616 MF:C23H29N3O5S MW:459.5585	CAS No. 101376-25-4 3-Morpholinemethanol, 4-(phenylmethyl)-, (3S)- Catalog No.:AG0004BY MDL No.:MFCD06799482 MF:C12H17NO2 MW:207.2689	CAS No. 101376-26-5 3-Morpholinemethanol, 4-(phenylmethyl)-, (3R)- Catalog No.:AG0004BX MDL No.:MFCD06799481 MF:C12H17NO2 MW:207.2689
CAS No. 101376-27-6 Morpholine, 3-[(phenylmethoxy)methyl]-, (S)- (9CI) Catalog No.:AG0004BW MDL No.: MF:C12H17NO2 MW:207.2689	CAS No. 101376-73-2 2-Butenoic acid, 2-methyl-4-(phenylmethoxy)-, methyl ester, (E)- (9CI) Catalog No.:AG0004BV MDL No.:MFCD21272776 MF:C13H16O3 MW:220.2643	CAS No. 101376-74-3 2-Butenal, 2-methyl-4-(phenylmethoxy)-, (2E)- Catalog No.:AG0004BU MDL No.: MF:C12H14O2 MW:190.2384
CAS No. 101377-33-7 2,6,10,14,18,22,26-Heptaoxaheptacosane-4,12,20-triol, 1,27-bis(2-oxiranyl)-8,16,24-tris(2-oxiranylmethoxy)- Catalog No.:AG0004BT MDL No.: MF:C33H58O18 MW:742.8028	CAS No. 101377-34-8 2,6,10,14,18-Pentaoxanonadecane-4,12-diol, 1,19-bis(2-oxiranyl)-8,16-bis(2-oxiranylmethoxy)- Catalog No.:AG0004BS MDL No.: MF:C24H42O13 MW:538.5825	CAS No. 101377-46-2 Benzoic acid, 4-chloro-2-(isocyanatosulfonyl)-, 1-methylethyl ester Catalog No.:AG0004BR MDL No.: MF:C11H10ClNO5S MW:303.7188
CAS No. 10138-36-0 7-Oxabicyclo[4.1.0]heptane-3,4-dicarboxylic acid, 3,4-bis(2-ethylhexyl) ester Catalog No.:AG0004C9 MDL No.: MF:C24H42O5 MW:410.5873	CAS No. 10138-46-2 Butanamide, N-ethyl-3-oxo- Catalog No.:AG0004C7 MDL No.: MF:C6H11NO2 MW:129.1570	CAS No. 10138-59-7 1,2-Cyclohexanedicarboxylic acid, 1,2-diethyl ester Catalog No.:AG0004C5 MDL No.:MFCD00029449 MF:C12H20O4 MW:228.2848
CAS No. 10138-62-2 Holmium chloride (HoCl3) Catalog No.:AG0004C3 MDL No.:MFCD00011051 MF:Cl3Ho MW:271.2893	CAS No. 10138-71-3 Ethanol, 2,2'-[[2-[(2-aminoethyl)amino]ethyl]imino]bis- (9CI) Catalog No.:AG0004C2 MDL No.: MF:C8H21N3O2 MW:191.2712	CAS No. 10138-79-1 Silane, tris(2-chloroethoxy)- Catalog No.:AG0004C1 MDL No.: MF:C6H13Cl3O3Si MW:267.6101