2-Propylidene

ANTIBIOTICS - BETA-LACTAMS - BETA-LACTAMASE INHIBITORS] (Vol 3) [2(S)-(2a,5a,6(Z))]-3,3-Dimethyl-7-o2o-6(2-oxo-propylidene)-4-thia-l-azabicydo [3.2.0]-heptane-2-carboxyhc acid... 

Trimeric acetone peroxide Trimeric propylidene peroxide... 

These substances differ structurally from niquidine (VI) by the substitution in the latter of a propylidene chain at C. Ainley and King having already found that d- and Z-dihydroquinicinols (VIII) which are y-substituted piperidine derivatives, were inactive, it appeared from these two sets of results that the strongly basic centre should not be separated by more than two carbon atoms frorn the point of attachment to the quinoline nucleus. King and Work therefore prepared a series of... 

Such methyenepyrans afford still another possibility for obtaining new pyrylium salts, namely, electrophilic alkylation or acylation at the exocyclio methylene carbon atom. Thus, 2,6-diphenyl-4-iso-propylidene-4/I-pyran is converted into 2,6-diphenyl-4-i-butyl-pyrylium iodide on refluxing with methyl iodide (see Scheme 3). Unlike the protonation of methylenepyrans, this reaction is no longer... 

Trans-2-chloro-9-(aj-dimethylamino-propylidene)-thioxanthene [MP 98°C, MP of the hydrochloride 225°C (corr.)], is a valuable medicinal agent, being used as a tranquilizer and antiemetic agent, whereas the corresponding cis isomer (MP 44°C, MP of the hydrochloride 209°C) is not useful for these indications, as described in U.S. Patent 3,115,502, which describes procedures for conversion of the cis to the trans form. 

The benzene layer is removed by decantation and the remaining mixture is rendered basic with 10% sodium hydroxide solution and is extracted with three 1,500 ml portions of benzene. The benzene extracts are washed, then dried with anhydrous sodium sulfate and concentrated in a vacuum leaving a residue of 1,530 grams, gas and thin layer chromatography analysis show this to be a cis/trans mixture (approx. 4 1) of 11-dimethylamino-propylidene-6,11-dihydrodibenz-(b,e)oxepin (90% yield). This mixture has substantially more activity pharmacologically than the cis/trans mixture obtained by the Grignard route disclosed in the Belgian Patent 641,498. This base is then converted to the hydrochloride with HCI. 

A mixture of 40 g of isonicotinyl hydrazine and 600 cc of acetone was heated on a steam bath until solution was complete. Upon cooling the reaction mixture, 1-isonicotinyl-2-iso-propylidene hydrazine precipitated in the form of white needles MP 161°Cto 161.5°C. 

Chemical Name 6-(3-Dimethylamino-1 -propylidene)-12H-benzofuro[26-e] benz[b] oxepin fumarate... 

Chemical Name (Z)-N,N-dimethyl-9-[3-(4-methyl-1-piperazinyl)propylidene] thioxanthene-2-sulfonamide... 

Figure 1. Part of NMR spectrum of 5-deoxy-l, 2-O-iso-propylidene-3-O-tosyl-p-L-threo-pent-4-enofuranose (32) at 60 Mc.p.s. in deuterochloroform.

The mass spectra of methyl 3-deoxy-p-v-tkreo-pentopyrano-side, methyl 4-deoxy-j3-T>-thieo-pentopyranoside, and 5-deoxy-fi-D-xylo-furanoside are discussed and compared fragmentation paths are sufficiently different to allow identification on the basis of their mass spectra. On the other hand, the mass spectra of methyl 2- and 3-deoxy-5-O-methyl-f3-i>-erythro-pentofuranosides do not exhibit fragmentation differences. The mass spectra of 3-deoxy-l,2 5,6-di-O-isopropylidene -d-xylo - hexofuranose, 5- deoxy -1,2-0-isopropylidene-D-xy o-hexofuranose, and 6-deoxy-l,2-0-iso-propylidene-D-glucofuranose show prominent differences, even between the 5- and 6-deoxy isomers. The interpretation of the spectra was aided by metastable-ion peaks, mass spectra of DzO-exchanged analogs, and the mass spectrum of an O-isopropylidene derivative prepared with acetone-d6. 

In ( )-[2-(l-propenyl)-l, 3-dithian-2-yl]lithium, no problem of EjZ selectivity arises. It is easily prepared by deprotonation of the allylic dithiane87,88 with butyllithium in THF, whereas deprotonation of the 2-propylidene-l, 3-dithiane requires the assistance of HMPA. The addition to saturated aldehydes proceeds with excellent y-regioseleetivity and anti selectivity88,89. As often observed in similar cases, aldehydes which bear an, p2-carbon atom adjacent to the carbonyl group give lower selectivities. The stereoselectivity decreases with ketones (2-bu-tanone y/a 84 16, antiisyn 77 23)88. The reaction with ethyl 2-oxopropanoate is merely nonstereoselective90, but addition of zinc chloride improved the syn/anti ratio to 96 4, leading to an efficient synthesis of ( )-crobarbatic acid. 

Cyclopropane, 1,1 -dibromo-2,2-diplienyl-[Benzene, l,l -(2,2-dibromocyclo-propylidene)bis-], 32 Cyclopropanecarboxyltc acid, 70 Cydopropanes, gem-dihalo, 32 CYCLOUNDECANONE, 107 Cycloundecanone, 2-hydroxy-, 110 Cycloundecene, 1-carboxy- [1-Cyclo-undecene-1-carboxylic acid], 111 Cycloundecene, 1-methoxy-, 111 1-Cycloundecene-l-carboxyhc acid, methyl ester, 108... 

OL,, -Trinitro-Propionaldehyde methyl imide ( 03,7,7-Trinitro-Propyliden]-methyl-amine). CH3.N CH.CH(N02).CH(N02)2 mw 206.14 N 27.19% white crysts. V sol in acet si sol in w insol in eth. Prepn is by reacting a,j3 J3-trinitro-propionaldehyde suspended in ammonia with an excess of methylammonium chloride. The imide is recovered by acidifying the mixt with HC1... 

Quentin may have been the first to sulfonate (arylene ether sulfone).168 In this patent, it was demonstrated that the bisphenol A polysulfone could be sulfonated by chlorosulfonic acid to produce a sulfonated polyfarylene ether sulfone), which was used for desalination via reverse osmosis. However, the chlorosulfonic acid may be capable of cleaving the bisphenol A polysulfone partially at the iso-propylidene link or it might induce branching and crosslinking reactions by... 

N-Diphenylmethylen- 374 N-Diphenylmethylen-O-aminocarbonyl- 612 N-[l,3-Diphenyl-propyl-(2) - 374 N-[l,3-Diphenyl-propyliden-(2)]- 374, 377, 380 N-(4-Halogen-phenyI)- 683 N-Heptyl- 375 N-Heptyl-N-acetyl- 376 N-Heptyliden- 375 N-Hcptyliden-O-acetyl- 376 0-(2-Hydroxy-athyl)-N-athoxycarbonyl- 133 N-(4-Hydroxy-phenyl)- 683 0-(2-Hydroxy-l-phenyl-athyI)-N-athoxycarbonyI-aus 0-(ci-AthoxycarbonyI-benzyl)-N-athoxycar-bonyl-hydroxylamin und Lithiumalanat 133 N-Isopropyl- 682 N-Isopropylidcn- 613 N-Methyl- 133, 682 O-Methyl-N-bcnzyliden- 377 O-Methyl-N-benzyliden- 375 0-Methyl-N-(4-chlor-benzyl)- 375 0-Methyl-N-(4-chlor-benzyliden)- 375 N-Methy -N,0-diacetyI- 682 N-(4-Methyl-phenyl)- 683 0-McthyI-N-( 1 -phenyl-athyliden)- 375 N-(4-Methylthio-phenyl)- 684 N-(4-Nitro-benzyl)- 374 N-[4-Nitro-benzyliden - 374, 377 N-(2-Nitro-phenyl)- 562 N-(4-Nitro-phenyl)- 682 N-Nitroso-N-cyclohexyl- 697 N-Octyl- 374 N-Octyl-(2)-N-acetyl- 376 N-Octyliden- 374 N-0ctyliden-(2)-0-acctyl- 376 N-(Pentafluor-phenyl)-0,N-diacetyl- 697 N-Phenyl- 474, 481, 682, 783 N-Phenylacetyl-O-benzoyl- 265 N-(l-Phenyl-athyl)- 374 N-(l-Phenyl-athyl)-N-acetyl- 376 N-(l-Phenyl-athyliden)-374, 613 N-( l-Phenyl-athyliden)-0-acetyl- 376 N-[ 1 -Phenyl-buten-( 1 )-yl-(3)-iden]- 582 N-f4-Phenyl-butyl-(2)-iden]- 581 N-Phcnyl-N,0-diacetyl- 682 N-(4-Phenylthio-phenyl)- 684 N-Propyl-N-cyclohexyl- 376 N-Propyl-N-isopropyl- 376 O-Sulfonyl- 481 N-(4-Sulfonyl-phenyI)- 683 N-(2-Vinyl-phenyl)- 698... 

Dimethyl-1-phenyl-propyl)- -dinitril 581 (2,2-Dimethyl-1-phenyl-propyliden)- -dinitril 581 -dinitril 112... 

Pcnten-(2)-yl-(4)- -diathylester 204 Pentyliden-(2)- -dinitril 666 1-Phenyl-athyliden- -dinitril 643 4-Phenylazo-benzoyl- -diathylester 195 (1-Phenyl-propyl)- -dinitril 559 (1-PhenyI-propyliden)- -dinitril 559 PropyI-(2-methyl-aIlyl)- -diathylester 202... 

Triphenyl-[2-oxo-hexyliden-(3)]- 637 Triphenyl-[3-oxo-5-phenyl-pentyliden-(2)]- 637 Triphenyl-(2-oxo-propyliden)- 637... 

Tris-[trifluormethyl]-l-(pentafluor-athyl)-3-[hcxafluor-propyliden-(2)]- 668... 

The ijo-Propylidene Derivatives of Hexahydric Alcohols. Part II. i.vo-Propylidene Derivatives of Sorbitol (D-Glucito )," E. J. Bourne, G. P. McSweeney, M. Stacey, and L. F. Wiggins, /. Chem. Soc.,... 

CN [ 1 -hydroxy-3-(methylpentylaniino)propylidene]bisphosphonic acid monosodium salt monohydrate anhydrous... 

Sugars having a difluoromethylene group were prepared by reaction of an aldehyde group in sugars with difluoromethylene tris(dimethyl-amino)phosphorane some of these were 554- 559. Similarly, (Z)- 560) and f ))-. tw-bromofluoroalkene 561 were prepared from l,2 3,4-di-0-iso-propylidene-a-D-gfl/ac/o-hexodialdo-l,5-pyranose (395) by treatment with Ph3P=CFBr. 

On the other hand, severe congestion and a lower temperature (20°C) prevent the hydrogenation of the propylidene double bond (tetrasubstituted but... 

---