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Noncryogenic Preparation of Functionalized Arylboronic Esters through a Magnesium-Iodine Exchange with in Situ Quench

2019-12-01 09:01:39


Emilien Demory, Veronique Blandin, Jacques Einhorn, and Pierre Y. Chavant
Departement de Chimie Moleculaire, UMR-5250, ICMG FR-2607, CNRS, Universite Joseph Fourier, BP 53, 38041 Grenoble Cedex 09, France.

 

INTRODUCTION
Arylboronic acids and esters have found a prominent place in the synthetic chemist’s toolbox, the latter being often preferred for convenience in their purification and characterization and for their ability to be observed via gas or liquid chromatography. Despite the recent developments in transition metal-catalyzed borylation,1-4 the cheapest and most common way of synthesizing arylboronic acids and esters remains the reaction of an organolithium or organomagnesium intermediate with a trialkylborate at low temperature, typically -78 C (Li) up to -10 C (Mg).1,5 An attractive method in this context is the generation of the aryl Grignard reagent by metal-halogen exchange using reagents such as i PrMgBr or i PrMgCl 3 LiCl.6 Compared to the historic Grignard synthesis from Mg0, this procedure, introduced by Knochel and Cahiez,7 allows the preparation of the reagent at milder temperatures (-40 C to room temperature), which broadly enlarges the functional group compatibility: for instance,
arylmagnesium halides bearing ester or nitrile substituents become accessible. The exchange reaction is generally completed within hours, and the organomagnesium species can then be reacted with an electrophile at temperatures below 0 C, typically -30 to -10 C in the case of a trialkylborate.

 

The functionalized Grignard reagents are intrinsically unstable, even if they can be kept for several hours at low temperature.6a Furthermore, with the expanding use of this magnesium-halogen method for the preparation of arylmagnesium reagents, some concerns have been raised regarding the stability of the reaction mixture. Process safety evaluation studies9 revealed that an exothermic decomposition of the solution is possible—even for phenylmagnesium chloride—and that onset temperatures as low as 55 C can be found. The structure of the aromatic ring and the concentration of the solution have a strong influence on the severity of the event, fluorine substituents and concentrated media being detrimental. A solution to avoid the prolonged coexistence of the aryl Grignard reagent, reactive functional
groups, and i PrX, the byproduct of the magnesium-halogen exchange, would be to directly trap the reactive species by the electrophile in situ. Such a procedure has proven efficient in some cases with organolithium species and triisopropyl borate, but yields are still inadequate for challenging substrates such as ethyl p-bromobenzoate.10 Regarding the magnesium-halogen exchange reaction, scarce examples of in situ trapping with trialkylborates can be found, with varying degrees of success.11

 

Among boronic acid derivatives, arylboronic hexylene glycol esters emerged as interesting compounds. Murata’s team12 and ours13 have shown that they exhibit excellent stability toward air, water, and chromatography,14 and undergo Suzuki-Miyaura reactions with aryl iodides, bromides, and triflates in excellent yields. Advantageously, hexylene glycol—a solvent—is much less expensive than pinacol.15 We thus wondered whether 2-isopropoxy-4,4,6-trimethyl-1,3,2-dioxaborinane16 (MPBOi Pr, 1) could be an efficient in situ trapping agent for arylmagnesium species issuing from a magnesium-halogen exchange.


RESULTS AND DISCUSSION
Reagent 1 was easily prepared from boric acid, hexylene glycol, and isopropanol by azeotropic removal of water (see Experimental Section),17 and methyl 4-iodobenzoate 2a was chosen as the first substrate. The magnesium-iodine exchange reaction was carried out with in situ quench, at 0 C, through gradual addition of a THF solution of i PrMgCl 3 LiCl to the mixture of 1 and 2a in THF (Scheme 1).18

 

Monitoring the reaction by GC analysis showed that the transformation of 2a into arylboronic ester 3a was complete by the end of the addition. Hydrolysis of the reaction mixture led to a dramatically clean crude product19 and to the corresponding boronic ester in 77% isolated yield after a simple filtration over silica gel. This first result was very promising, given the competitive reactions at stake (Scheme 2): magnesium-iodine exchange, nucleophilic addition of the organomagnesium species onto the electrophilic MPBOi Pr20 or onto the carboxylic ester.6b Once the exchange has occurred, the aryl Grignard reagent does not accumulate but instantaneously reacts with 1 to give the arylboronic ester. Indeed, we did not detect any methyl benzoate by GC analysis of hydrolyzed aliquots sampled during the addition of i PrMgCl 3 LiCl. The selectivity in the case of 2a can be partly explained by the presence of the electron-withdrawing substituent, known to strongly accelerate the magnesium-halogen exchange.21 However, the nature of the halogen is crucial.

 

Indeed, in the case of aryl bromide 20 a, the exchange proved too slow22 compared to the nucleophilic addition onto 1, and methyl 4-bromobenzoate 20 a was recovered unchanged when submitted
to the protocol from Scheme 1. We then investigated the nature of the aryl iodides that could undergo the magnesium-iodine exchange in the presence of MPBOi Pr 1 (Scheme 3 and Table 1). The reaction proceeds smoothly with aryl iodides bearing electron-withdrawing reactive substituents such as ester and nitrile groups, leading to arylboronic hexylene glycol esters 3a-c in high yields (Table 1, entries 1-3).

 

The use of i PrMgCl 3 LiCl was not suitable for a nitro group and led to a complex mixture. PhMgCl is known to allow magnesiumiodine exchange in the presence of an o-nitro group, but to react on
a nitro group in meta- or para- position.23 In the present system, the only reaction that takes place is between PhMgCl and MPBOi Pr: a mixture of unreacted 1-iodo-3-nitrobenzene 2d and phenylboronic ester was obtained (Table 1, entry 4).

 

Starting from diiodobenzenes, the monoborylated products 3e-f are selectively obtained (Table 1, entries 5-6); traces (∼1%) of the diborylated compound were detected only in the case of the para disubstituted 2e, by 1 H NMR and GC analysis of the crude material.24 The borylation of o-halo iodobenzene occurs at the iodine position, and no product resulting from aryne formation25 could be detected (Table 1, entries 6-8).

 

Running the reaction at lower temperature slightly improved the yield in arylboronic ester 3f (Table 1, entry 6). The o-trifluoromethyl arylboronic ester 3i was prepared in quantitative yield up to a 100 mmol scale using only a slight excess (10 mol %) of reagents (Table 1, entry 9). This excellent result is particularly interesting as the corresponding aryl Grignard reagent is reported to be prone to a highly exothermic decomposition.9b The very clean crude product was engaged without further purification in a Suzuki-Miyaura coupling leading to biaryl 5 bearing electron-withdrawing substituents on both aryl rings in 80% unoptimised yield (Scheme 4).26 2-Pyridyl boronic acids are notoriously unstable, and ester derivatives are therefore attractive compounds;27 we were thus pleased to obtain 6 bromopyridin-2-yl boronic ester 3j in excellent yield (Table 1, entry 10).

 

Electron-donating substituents proved detrimental to the reaction: the slower rate of the magnesium-iodine exchange28 (constant k1 in Scheme 2) made the nucleophilic addition of the alkylmagnesium species onto 1 competitive. i PrMgCl 3 LiCl was consumed to give MPBi Pr and the conversion of aryl iodide 2 was therefore incomplete; no synthetically useful yield of arylboronic ester 3 could be obtained at 0 C (Table 1, entries 11-13).

 

As we can see from the above results, the electronic nature of the aryl iodide plays an important part in the outcome of the borylation, by modifying the rate constant k1 in Scheme 2. For a given aryl iodide, other parameters can favor the exchange reaction over the nucleophilic addition, by changing either the rate constants (k1, k2) or the reaction rates. To test the influence of the reaction conditions, we chose 2-iodoanisole as a borderline substrate for which k1 is close to k2; 29 some aryl iodide remained unreacted, and we used the conversion of 2m into arylboronic ester 3m as a measure of effectiveness (Scheme 5 and Table 2).


The conversion reached 25% when conditions from Table 1 were applied (Table 2, entry 1). Running the reaction at lower temperature was again beneficial (Table 2, entry 3). As stressed by Knochel, LiCl accelerates the magnesium-halogen exchange (higher k1);6b we observed in our case that i PrMgCl 3 LiCl significantly improved the conversion of 2m into 3m (compare Table 2, entries 1, 4, and 6).

 

Decreasing the amount of MPBOi Pr 1 (1.1 equiv vs 1.9 equiv) slows down the rate of the direct addition of i PrMgCl 3 LiCl onto 1. As a result, a better, albeit still low, conversion of the aryl iodide was achieved (compare Table 2, entries 2 vs 1 and 5 vs 4). More generally, decreasing the amount of MPBOi Pr 1 has a practical consequence: crude materials even cleaner than usual are obtained and can be directly engaged in further transformation (Scheme 4).30

 

Withthe rate constant k2 being directly correlated tothe structure of the trapping agent, we wondered whether our procedure for the preparation of functionalized arylboronic esters could be applied to the corresponding pinacol derivative 2-isopropoxy-4,4,5,5-tetramethyl[1,3,2]dioxaborolane (PinBOi Pr, 6).31 Indeed, pinacol esters are the best-known arylboronic esters for SuzukiMiyaura reactions.1 We chose o-iodo trifluoromethylbenzene 2i and o-iodo anisole 2m as representative substrates (Scheme 6 and Table 3). In the case of the aryl iodide bearing an electronwithdrawing substituent, an excellent 93% yield in the pinacol ester 7i was obtained (Table 3, entry 1). In the borderline case of substrate 2m, PinBOi Pr 6 gave better results than MPBOi Pr 1, whichever alkyl Grignard reagent was used (compare Table 3, entries 3 vs 2 and 5 vs 4). The extent of nucleophilic addition of the isopropylmagnesium species onto 6 is probably lessened by the increased steric hindrance around the boron atom compared to 1. Finally, as seen in Table 2, the effect of the borate ester stoichiometry proved significant (compare Table 3, entries 6 vs 5).

 

CONCLUSION
Combining the generation, at 0 C, of the aryl Grignard reagent by magnesium-iodine exchange with its in situ trapping by a cyclic borate ester proved to be a very simple, safe, and selective procedure for the preparation, in excellent yields and crude purity, of functionalized arylboronic esters from electrondeficient aryl iodides. Regarding arylboronic hexylene glycol esters, the present procedure is complementary to the Pdcatalyzed borylation of electron-rich aryl halides with 4,4,6-trimethyl-1,3,2-dioxaborinane (methyl pentanediol borane).

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Catalog No.:AA00IU2J

CAS No.:1029987-67-4 MDL No.:MFCD04035636

MF:C17H20ClN4O2 MW:347.8193

89-55-4

(2Z)-3-{[4-(4-chlorophenyl)-1H-pyrazol-5-yl]amino}-2-(4-methylbenzenesulfonyl)prop-2-enenitrile

Catalog No.:AA00IUYD

CAS No.:1029989-13-6 MDL No.:MFCD03102626

MF:C19H15ClN4O2S MW:398.8660

89-55-4

N-({6-chloroimidazo[1,2-a]pyridin-3-yl}methyl)adamantan-1-amine hydrochloride

Catalog No.:AA00IQQ8

CAS No.:1029989-47-6 MDL No.:MFCD08281888

MF:C18H23Cl2N3 MW:352.3013

89-55-4

2-(morpholin-4-yl)-5-(1H-pyrazol-5-yl)aniline

Catalog No.:AA00IVVU

CAS No.:1029989-48-7 MDL No.:MFCD08281898

MF:C13H16N4O MW:244.2923

89-55-4

2-{[(furan-2-yl)methyl]amino}-4-(4-methylphenyl)-4-oxobutanoic acid hydrochloride

Catalog No.:AA00IZJQ

CAS No.:1029989-66-9 MDL No.:MFCD16074863

MF:C16H18ClNO4 MW:323.7714

89-55-4

1-(Cyclohexylamino)propan-2-ol

Catalog No.:AA009MTU

CAS No.:103-00-4 MDL No.:MFCD00021322

MF:C9H19NO MW:157.2533

89-55-4

N-Phenylglycine

Catalog No.:AA003T8H

CAS No.:103-01-5 MDL No.:MFCD00014009

MF:C8H9NO2 MW:151.1626

89-55-4

2-Phenylhydrazinecarboxamide

Catalog No.:AA003EK4

CAS No.:103-03-7 MDL No.:MFCD00007942

MF:C7H9N3O MW:151.1659

89-55-4

(Phenylthio)acetic acid

Catalog No.:AA003BZ4

CAS No.:103-04-8 MDL No.:MFCD00004355

MF:C8H8O2S MW:168.2129

89-55-4

2-Methyl-4-phenyl-2-butanol

Catalog No.:AA003HKK

CAS No.:103-05-9 MDL No.:MFCD00004472

MF:C11H16O MW:164.2441

89-55-4

2-Ethylhexyl acrylate

Catalog No.:AA003H51

CAS No.:103-11-7 MDL No.:MFCD00009495

MF:C11H20O2 MW:184.2753

89-55-4

Hydroquinone monobenzyl ether

Catalog No.:AA003KQZ

CAS No.:103-16-2 MDL No.:MFCD10687031

MF:C13H12O2 MW:200.2332

89-55-4

Chlorbensid

Catalog No.:AA01DZB8

CAS No.:103-17-3 MDL No.:MFCD00055267

MF:C13H10Cl2S MW:269.1895

89-55-4

P-Tolyl disulfide

Catalog No.:AA003TYL

CAS No.:103-19-5 MDL No.:MFCD00008547

MF:C14H14S2 MW:246.3910

89-55-4

Bis(2-ethylhexyl) adipate

Catalog No.:AA003O5S

CAS No.:103-23-1 MDL No.:MFCD00009496

MF:C22H42O4 MW:370.5665

89-55-4

AZELAIC ACID DI(2-ETHYLHEXYL) ESTER

Catalog No.:AA003NV2

CAS No.:103-24-2 MDL No.:MFCD00040496

MF:C25H48O4 MW:412.6462

89-55-4

Methyl 3-phenylpropionate

Catalog No.:AA003JT2

CAS No.:103-25-3 MDL No.:MFCD00017209

MF:C10H12O2 MW:164.2011

89-55-4

Methyl cinnamate

Catalog No.:AA00H9TU

CAS No.:103-26-4 MDL No.:MFCD00008458

MF:C10H10O2 MW:162.1852

89-55-4

Bibenzyl

Catalog No.:AA003DC4

CAS No.:103-29-7 MDL No.:MFCD00004796

MF:C14H14 MW:182.2610

89-55-4

Trans-stilbene

Catalog No.:AA003UWJ

CAS No.:103-30-0 MDL No.:MFCD00064300

MF:C14H12 MW:180.2451

89-55-4

4-Styrylpyridine

Catalog No.:AA003LY3

CAS No.:103-31-1 MDL No.:MFCD00137749

MF:C13H11N MW:181.2331

89-55-4

N-Phenylbenzylamine

Catalog No.:AA00359H

CAS No.:103-32-2 MDL No.:MFCD00003018

MF:C13H13N MW:183.2490

89-55-4

Azobenzene

Catalog No.:AA0038A5

CAS No.:103-33-3 MDL No.:MFCD00003022

MF:C12H10N2 MW:182.2212

89-55-4

4,4-Dithiodimorpholine

Catalog No.:AA003KDQ

CAS No.:103-34-4 MDL No.:MFCD00023319

MF:C8H16N2O2S2 MW:236.3548

89-55-4

Ethyl cinnamate

Catalog No.:AA003QBS

CAS No.:103-36-6 MDL No.:MFCD00009189

MF:C11H12O2 MW:176.2118

89-55-4

Benzyl butyrate

Catalog No.:AA003O18

CAS No.:103-37-7 MDL No.:MFCD00027133

MF:C11H14O2 MW:178.2277

89-55-4

2-((1-Phenoxypropan-2-yl)amino)ethanol

Catalog No.:AA003G4R

CAS No.:103-39-9 MDL No.:MFCD00713871

MF:C11H17NO2 MW:195.2582

89-55-4

Succinic acid monobenzyl ester

Catalog No.:AA003UDK

CAS No.:103-40-2 MDL No.:MFCD00447717

MF:C11H12O4 MW:208.2106

89-55-4

Benzyl cinnamate

Catalog No.:AA003O1A

CAS No.:103-41-3 MDL No.:MFCD00004789

MF:C16H14O2 MW:238.2812

89-55-4

2-ETHYLHEXYL VINYL ETHER

Catalog No.:AA003H57

CAS No.:103-44-6 MDL No.:MFCD00053800

MF:C10H20O MW:156.2652

89-55-4

Phenethyl acetate

Catalog No.:AA003TL7

CAS No.:103-45-7 MDL No.:MFCD00008720

MF:C10H12O2 MW:164.2011

89-55-4

(Benzylthio)acetic acid

Catalog No.:AA003BWT

CAS No.:103-46-8 MDL No.:MFCD00004358

MF:C9H10O2S MW:182.2395

89-55-4

N-Cyclohexyltaurine

Catalog No.:AA003SUI

CAS No.:103-47-9 MDL No.:MFCD00003835

MF:C8H17NO3S MW:207.2905

89-55-4

Dibenzylamine

Catalog No.:AA00H9TW

CAS No.:103-49-1 MDL No.:MFCD00004770

MF:C14H15N MW:197.2756

89-55-4

Benzyl ether

Catalog No.:AA003P92

CAS No.:103-50-4 MDL No.:MFCD00004780

MF:C14H14O MW:198.2604

89-55-4

Phenethyl cinnamate

Catalog No.:AA003TL9

CAS No.:103-53-7 MDL No.:MFCD00022050

MF:C17H16O2 MW:252.3077

89-55-4

Cinnamyl acetate

Catalog No.:AA00H9TX

CAS No.:103-54-8 MDL No.:MFCD00008722

MF:C11H12O2 MW:176.2118

89-55-4

N1-Benzyl-N2,N2-dimethylethane-1,2-diamine

Catalog No.:AA003SPB

CAS No.:103-55-9 MDL No.:MFCD00008334

MF:C11H18N2 MW:178.2740

89-55-4

Cinnamyl propionate

Catalog No.:AA003OU5

CAS No.:103-56-0 MDL No.:MFCD00048610

MF:C12H14O2 MW:190.2384

89-55-4

2-Phenoxyethyl isobutyrate

Catalog No.:AA003TLS

CAS No.:103-60-6 MDL No.:MFCD00027363

MF:C12H16O3 MW:208.2536

89-55-4

butanoic acid 3-phenyl-2-propenyl ester

Catalog No.:AA003OIH

CAS No.:103-61-7 MDL No.:MFCD00027135

MF:C13H16O2 MW:204.2649

89-55-4

(2-Bromoethyl)benzene

Catalog No.:AA00H9TY

CAS No.:103-63-9 MDL No.:MFCD00000240

MF:C8H9Br MW:185.0611

89-55-4

2-Bromovinylbenzene

Catalog No.:AA003O37

CAS No.:103-64-0 MDL No.:MFCD00000185

MF:C8H7Br MW:183.0452

89-55-4

Propylbenzene

Catalog No.:AA003TX9

CAS No.:103-65-1 MDL No.:MFCD00009377

MF:C9H12 MW:120.1916

89-55-4

N-Methylbenzylamine

Catalog No.:AA00359K

CAS No.:103-67-3 MDL No.:MFCD00008289

MF:C8H11N MW:121.1796

89-55-4

N-Ethylaniline

Catalog No.:AA0035AX

CAS No.:103-69-5 MDL No.:MFCD00009025

MF:C8H11N MW:121.1796

89-55-4

N-Phenylformamide

Catalog No.:AA003QLX

CAS No.:103-70-8 MDL No.:MFCD00003276

MF:C7H7NO MW:121.1366

89-55-4

Phenyl isocyanate

Catalog No.:AA0085D6

CAS No.:103-71-9 MDL No.:MFCD00001994

MF:C7H5NO MW:119.1207

89-55-4

Isothiocyanatobenzene

Catalog No.:AA003R2W

CAS No.:103-72-0 MDL No.:MFCD00004798

MF:C7H5NS MW:135.1863

89-55-4

Phenetole

Catalog No.:AA003TLE

CAS No.:103-73-1 MDL No.:MFCD00009090

MF:C8H10O MW:122.1644

89-55-4

2-Pyridineethanol

Catalog No.:AA0037YI

CAS No.:103-74-2 MDL No.:MFCD00006364

MF:C7H9NO MW:123.1525

89-55-4

1-Piperazineethanol

Catalog No.:AA00357H

CAS No.:103-76-4 MDL No.:MFCD00005970

MF:C6H14N2O MW:130.1882

89-55-4

CYCLOHEXYLACETONE

Catalog No.:AA003P2K

CAS No.:103-78-6 MDL No.:MFCD00019396

MF:C9H16O MW:140.2227

89-55-4

Phenylacetyl chloride

Catalog No.:AA0035E9

CAS No.:103-80-0 MDL No.:MFCD00000729

MF:C8H7ClO MW:154.5936

89-55-4

2-Phenylacetamide

Catalog No.:AA00327C

CAS No.:103-81-1 MDL No.:MFCD18449377

MF:C8H9NO MW:135.1632

89-55-4

N,N-Dimethylbenzylamine

Catalog No.:AA003SI6

CAS No.:103-83-3 MDL No.:MFCD00008329

MF:C9H13N MW:135.2062

89-55-4

Acetanilide

Catalog No.:AA0034CM

CAS No.:103-84-4 MDL No.:MFCD00008674

MF:C8H9NO MW:135.1632

89-55-4

1-Phenylthiourea

Catalog No.:AA003EK5

CAS No.:103-85-5 MDL No.:MFCD00004933

MF:C7H8N2S MW:152.2168

89-55-4

Phenol,4-(2-aminopropyl)-

Catalog No.:AA00856U

CAS No.:103-86-6 MDL No.:MFCD00599960

MF:C9H13NO MW:151.2056

89-55-4

4'-Bromoacetanilide

Catalog No.:AA003KWJ

CAS No.:103-88-8 MDL No.:MFCD00000092

MF:C8H8BrNO MW:214.0592

89-55-4

4'-Methylacetanilide

Catalog No.:AA003410

CAS No.:103-89-9 MDL No.:MFCD00008677

MF:C9H11NO MW:149.1897

89-55-4

Acetaminophen

Catalog No.:AA0033T3

CAS No.:103-90-2 MDL No.:MFCD00002328

MF:C8H9NO2 MW:151.1626

89-55-4

Acetic acid, [(4-aminophenyl)amino]oxo-

Catalog No.:AA01CBND

CAS No.:103-92-4 MDL No.:MFCD00007852

MF:C8H8N2O3 MW:180.1607

89-55-4

4-Nitrophenyloxamic acid

Catalog No.:AA003LTL

CAS No.:103-94-6 MDL No.:MFCD00014709

MF:C8H6N2O5 MW:210.1436

89-55-4

N,N'-BIS(1-METHYLHEPTYL)-P-PHENYLENEDIAMINE

Catalog No.:AA008R44

CAS No.:103-96-8 MDL No.:MFCD00027305

MF:C22H40N2 MW:332.5664

89-55-4

N-(4-hydroxyphenyl)dodecanamide

Catalog No.:AA009QRX

CAS No.:103-98-0 MDL No.:MFCD00020147

MF:C18H29NO2 MW:291.4284

89-55-4

4-(Dimethylamino)chalcone

Catalog No.:AA007Y8B

CAS No.:1030-27-9 MDL No.:MFCD00168677

MF:C17H17NO MW:251.3230

89-55-4

Methyl 2-phenylimidazo[1,2-a]pyridine-7-carboxylate

Catalog No.:AA0095N8

CAS No.:1030-33-7 MDL No.:MFCD00022628

MF:C15H12N2O2 MW:252.2680

89-55-4

3'-O-Methyladenosine

Catalog No.:AA007Y8M

CAS No.:10300-22-8 MDL No.:MFCD00057003

MF:C11H15N5O4 MW:281.2679

89-55-4

3'-O-Methylguanosine

Catalog No.:AA008SLE

CAS No.:10300-27-3 MDL No.:MFCD00057057

MF:C11H15N5O5 MW:297.2673

89-55-4

Chloroacetamidine HCl

Catalog No.:AA003OQ9

CAS No.:10300-69-3 MDL No.:MFCD00053013

MF:C2H6Cl2N2 MW:128.9884

89-55-4

Methyl2-acetamido-4,6-O-benzylidene-2-deoxy-b-D-glucopyranoside

Catalog No.:AA008X0W

CAS No.:10300-76-2 MDL No.:MFCD04039590

MF:C16H21NO6 MW:323.3410

89-55-4

ethyl 5-(aminomethyl)-2-furoate hydrochloride

Catalog No.:AA00J3D8

CAS No.:1030012-30-6 MDL No.:MFCD02815367

MF:C8H12ClNO3 MW:205.6388

89-55-4

4-[5-(Aminomethyl)thien-2-yl]-2-methyl-1,3-thiazole diHCl

Catalog No.:AA00H9TZ

CAS No.:1030012-47-5 MDL No.:MFCD07704030

MF:C9H12Cl2N2S2 MW:283.2410

89-55-4

Ethyl 2-cyclopropyl-4-methyl-1,3-oxazole-5-carboxylate

Catalog No.:AA01A5L6

CAS No.:1030014-04-0 MDL No.:MFCD21291600

MF:C10H13NO3 MW:195.2151

89-55-4

Ethyl 1-(4-chlorobenzyl)-5-methyl-1H-1,2,3-triazole-4-carboxylate

Catalog No.:AA0090WM

CAS No.:1030014-82-4 MDL No.:MFCD10758099

MF:C13H14ClN3O2 MW:279.7222

89-55-4

Ethyl 5-methyl-1-(4-methylbenzyl)-1H-1,2,3-triazole-4-carboxylate

Catalog No.:AA0090WR

CAS No.:1030014-84-6 MDL No.:MFCD10758096

MF:C14H17N3O2 MW:259.3037

89-55-4

5-nitro-1H-pyrazol-3-amine hydrochloride

Catalog No.:AA01BTX2

CAS No.:1030018-90-6 MDL No.:MFCD28142358

MF:C3H5ClN4O2 MW:164.5504

89-55-4

CMP5

Catalog No.:AA01EQCW

CAS No.:1030021-40-9 MDL No.:

MF:C21H22ClN3 MW:351.8725

89-55-4

1-Methyl-3-((methylamino)methyl)quinolin-2(1H)-one hydrochloride

Catalog No.:AA01FM97

CAS No.:1030022-56-0 MDL No.:MFCD09792407

MF:C12H15ClN2O MW:238.7133

89-55-4

2-Hydroxymethylmorpholine

Catalog No.:AA007Y8L

CAS No.:103003-01-6 MDL No.:MFCD03426271

MF:C5H11NO2 MW:117.1463

89-55-4

2-(Trifluoromethoxy)benzenesulfonyl chloride

Catalog No.:AA003F2J

CAS No.:103008-51-1 MDL No.:MFCD00052316

MF:C7H4ClF3O3S MW:260.6181

89-55-4

2-(dimethylsulfamoyl)benzene-1-sulfonyl chloride

Catalog No.:AA01AFXQ

CAS No.:103008-52-2 MDL No.:MFCD09811998

MF:C8H10ClNO4S2 MW:283.7523

89-55-4

ethyl 2-(chlorosulfonyl)benzoate

Catalog No.:AA009KG8

CAS No.:103008-54-4 MDL No.:MFCD01961366

MF:C9H9ClO4S MW:248.6834

89-55-4

4-(5-amino-1,3,4-oxadiazol-2-yl)-1-phenylpyrrolidin-2-one

Catalog No.:AA00J9CJ

CAS No.:1030103-68-4 MDL No.:MFCD15119564

MF:C12H12N4O2 MW:244.2493

89-55-4

3-(1,3-Dioxolan-2-yl)thiophene-2-sulfonyl chloride

Catalog No.:AA007Y8G

CAS No.:103011-38-7 MDL No.:MFCD08271969

MF:C7H7ClO4S2 MW:254.7111

89-55-4

3-(1,3-dioxolan-2-yl)thiophene-2-sulfonamide

Catalog No.:AA01E809

CAS No.:103011-39-8 MDL No.:MFCD30750670

MF:C7H9NO4S2 MW:235.2807

89-55-4

2-Propenoic acid, 2-cyano-3-(3-pyridinyl)-, ethyl ester, (2E)-

Catalog No.:AA007I8M

CAS No.:103011-95-6 MDL No.:MFCD00564622

MF:C11H10N2O2 MW:202.2093

89-55-4

(E)-Ethyl2-cyano-5-methylhex-2-enoate

Catalog No.:AA01DZB9

CAS No.:103011-96-7 MDL No.:

MF:C18H14D4FNO2S MW:335.4291

89-55-4

3-Phenyl-9h-carbazole

Catalog No.:AA0091XR

CAS No.:103012-26-6 MDL No.:MFCD22052094

MF:C18H13N MW:243.3025

89-55-4

7-(2-methylphenyl)-3H,4H-thieno[3,2-d]pyrimidin-4-one

Catalog No.:AA00J0MD

CAS No.:1030120-83-2 MDL No.:MFCD16639688

MF:C13H10N2OS MW:242.2963

89-55-4

6-fluoro-1-methyl-4-oxo-7-(piperidin-1-yl)-1,4-dihydroquinoline-3-carboxylic acid

Catalog No.:AA00J0HW

CAS No.:1030120-88-7 MDL No.:MFCD14729054

MF:C16H17FN2O3 MW:304.3162

89-55-4

1-(2H-1,3-benzodioxol-5-yl)-N-[5-(4-fluorophenyl)-1H,4H-thieno[2,3-d]pyrimidin-4-ylidene]methanamine

Catalog No.:AA01C13I

CAS No.:1030123-90-0 MDL No.:MFCD15017488

MF:C20H14FN3O2S MW:379.4075

89-55-4

tert-Butyl 4-(prop-2-yn-1-ylcarbamoyl)piperidine-1-carboxylate

Catalog No.:AA01B909

CAS No.:1030181-52-2 MDL No.:MFCD10605357

MF:C14H22N2O3 MW:266.3361

89-55-4

6-Chloro-N-(4-methylphenyl)-2-pyrazinamine

Catalog No.:AA01FOCP

CAS No.:1030187-29-1 MDL No.:

MF:C11H10ClN3 MW:219.6702

89-55-4

4-Amino-1-(2,3,5-tri-o-acetyl-beta-d-ribofuranosyl)-1,3,5-triazin-2(1h)-one

Catalog No.:AA007I8E

CAS No.:10302-78-0 MDL No.:MFCD11113159

MF:C14H18N4O8 MW:370.3147

89-55-4

3',5'-di-o-toluoyl-2-deoxy-5-azacytosine

Catalog No.:AA008X4R

CAS No.:10302-79-1 MDL No.:MFCD09750854

MF:C24H24N4O6 MW:464.4706

89-55-4

1.2-dibromoethane-1-sulfonyl fluoride

Catalog No.:AA01EIVS

CAS No.:103020-97-9 MDL No.:MFCD31615713

MF:C2H3Br2FO2S MW:269.9154

89-55-4

Ethenesulfonyl fluoride, 1-bromo-

Catalog No.:AA007Y8E

CAS No.:103020-98-0 MDL No.:MFCD29054906

MF:C2H2BrFO2S MW:189.0035

89-55-4

HS38

Catalog No.:AA01DZBA

CAS No.:1030203-81-6 MDL No.:MFCD10610687

MF:C14H12ClN5O2S MW:349.7954

89-55-4

trans-4-(Dimethylamino)cyclohexanol

Catalog No.:AA008SR1

CAS No.:103023-51-4 MDL No.:MFCD09258736

MF:C8H17NO MW:143.2267

89-55-4

1,4-Dioxa-9-thia-12-azadispiro[4.2.4.2]tetradecane-11-carboxylic acid

Catalog No.:AA0090V1

CAS No.:1030253-98-5 MDL No.:MFCD06411612

MF:C11H17NO4S MW:259.3220

89-55-4

4-Acetyl-8-benzyl-1-thia-4,8-diazaspiro[4,5]decane-3-carboxylic acid, HCl

Catalog No.:AA0090W4

CAS No.:1030253-99-6 MDL No.:MFCD06795478

MF:C17H23ClN2O3S MW:370.8941

89-55-4

2-Amino-1-(furan-2-ylmethyl)-4,5-dimethyl-1H-pyrrole-3-carbonitrile

Catalog No.:AA008631

CAS No.:103026-02-4 MDL No.:MFCD06655398

MF:C12H13N3O MW:215.2511

89-55-4

2-Amino-1-cyclopentyl-4,5-dimethyl-1h-pyrrole-3-carbonitrile

Catalog No.:AA01C4ZB

CAS No.:103026-11-5 MDL No.:MFCD08898941

MF:C12H17N3 MW:203.2835

89-55-4

7-(furan-2-ylmethyl)-5,6-dimethyl-7H-pyrrolo[2,3-d]pyrimidin-4-amine

Catalog No.:AA007I8G

CAS No.:103026-12-6 MDL No.:MFCD06655548

MF:C13H14N4O MW:242.2765

89-55-4

4-Chloro-7-(2-furylmethyl)-5,6-dimethyl-7h-pyrrolo[2,3-d]pyrimidine

Catalog No.:AA007Y8C

CAS No.:103026-14-8 MDL No.:MFCD09040565

MF:C13H12ClN3O MW:261.7069

89-55-4

7-cyclohexyl-5,6-dimethyl-7H-pyrrolo[2,3-d]pyrimidin-4-ol

Catalog No.:AA01BA8T

CAS No.:103026-47-7 MDL No.:MFCD28397592

MF:C14H19N3O MW:245.3202

89-55-4

7-cyclopentyl-5,6-dimethyl-7H-pyrrolo[2,3-d]pyrimidin-4-ol

Catalog No.:AA01C59S

CAS No.:103026-49-9 MDL No.:MFCD29907070

MF:C13H17N3O MW:231.2936

89-55-4

Dehydro Nisoldipine

Catalog No.:AA008630

CAS No.:103026-83-1 MDL No.:MFCD10565997

MF:C20H22N2O6 MW:386.3985

89-55-4

3-Succinamidophenylboronic acid, pinacol ester

Catalog No.:AA003LVA

CAS No.:1030269-28-3 MDL No.:MFCD06795662

MF:C16H22BNO5 MW:319.1606

89-55-4

3,5-BIS(PERFLUOROPROPYL)PYRAZOLE

Catalog No.:AA009LIE

CAS No.:1030269-34-1 MDL No.:MFCD06246012

MF:C9H2F14N2 MW:404.1032

89-55-4

6-chloronaphthalene-2-sulfonamide

Catalog No.:AA01EIX9

CAS No.:103027-67-4 MDL No.:MFCD27941009

MF:C10H8ClNO2S MW:241.6940

89-55-4

1H-Indole-2,6-dicarboxylic acid

Catalog No.:AA008RNG

CAS No.:103027-97-0 MDL No.:MFCD03095180

MF:C10H7NO4 MW:205.1669

89-55-4

4-Bromo-8-methoxyquinoline

Catalog No.:AA003KWI

CAS No.:103028-31-5 MDL No.:MFCD08063209

MF:C10H8BrNO MW:238.0806

89-55-4

6-Bromo-8-methoxyquinoline

Catalog No.:AA0095S8

CAS No.:103028-32-6 MDL No.:MFCD11878494

MF:C10H8BrNO MW:238.0806

89-55-4

1-(4-methylpyridin-2-yl)butan-1-one

Catalog No.:AA01C023

CAS No.:103028-75-7 MDL No.:MFCD18897781

MF:C10H13NO MW:163.2163

89-55-4

6-Methoxy-2,3-dihydro-1H-inden-1-amine

Catalog No.:AA007I8A

CAS No.:103028-81-5 MDL No.:MFCD04972430

MF:C10H13NO MW:163.2163

89-55-4

1-Amino-1,2,3,4-tetrahydronaphthalen-2-ol hydrochloride

Catalog No.:AA00H9U5

CAS No.:103028-83-7 MDL No.:MFCD07792554

MF:C10H14ClNO MW:199.6773

89-55-4

3-Amino-1,2,3,4-tetrahydronaphthalen-2-ol hydrochloride

Catalog No.:AA01FM9Z

CAS No.:103028-84-8 MDL No.:MFCD28388520

MF:C10H14ClNO MW:199.6773

89-55-4

5-(Anilinocarbonothioyl)-4,5,6,7-tetrahydro-3h-imidazo[4,5-c]pyridine-6-carboxylic acid hydrochloride

Catalog No.:AA01AQWA

CAS No.:1030285-50-7 MDL No.:MFCD04448843

MF:C14H15ClN4O2S MW:338.8125

89-55-4

(4-(2,5-Dioxoimidazolidin-4-yl)phenyl)boronic acid

Catalog No.:AA01FLY8

CAS No.:1030287-04-7 MDL No.:MFCD03541055

MF:C9H9BN2O4 MW:219.9898

89-55-4

2-Hydrazinylbenzonitrile hydrochloride

Catalog No.:AA003A8D

CAS No.:1030287-80-9 MDL No.:MFCD03094641

MF:C7H8ClN3 MW:169.6115

89-55-4

1-(4-methoxybenzoyl)piperazine hydrochloride

Catalog No.:AA019L6N

CAS No.:1030288-85-7 MDL No.:MFCD09863359

MF:C12H17ClN2O2 MW:256.7286

89-55-4

5-(2-chlorophenyl)imidazolidine-2,4-dione

Catalog No.:AA01DX4L

CAS No.:103029-09-0 MDL No.:MFCD17237684

MF:C9H7ClN2O2 MW:210.6171

89-55-4

3-((2-(Pyridin-4-yl)ethyl)thio)propanoic acid

Catalog No.:AA01CB1U

CAS No.:103029-28-3 MDL No.:MFCD06795662

MF:C10H13NO2S MW:211.2807

89-55-4

2-Cyano-3-(pyridin-3-yl)acrylic acid

Catalog No.:AA007I88

CAS No.:103029-74-9 MDL No.:MFCD02668152

MF:C9H6N2O2 MW:174.1561

89-55-4

3-Nitroquinolin-2-ol

Catalog No.:AA007I87

CAS No.:103029-75-0 MDL No.:MFCD09754181

MF:C9H6N2O3 MW:190.1555

89-55-4

2-(2-hydroxy-4-methoxyphenyl)-5,5-dimethyl-1,3-thiazolidine-4-carboxylic acid

Catalog No.:AA00IT42

CAS No.:1030291-57-6 MDL No.:MFCD00955337

MF:C13H17NO4S MW:283.3434

89-55-4

(S)-Methyl 2,3-dihydroxypropanoate

Catalog No.:AA007I82

CAS No.:10303-88-5 MDL No.:MFCD14636488

MF:C4H8O4 MW:120.1039

89-55-4

Adamantane-1,3-diamine

Catalog No.:AA00862Q

CAS No.:10303-95-4 MDL No.:MFCD01831403

MF:C10H18N2 MW:166.2633