IL29294A - N-alkyl derivatives of alpha-thiolincos-aminide and process for preparing them - Google Patents

Description

DERIVATIVES PROCESS FOR PREPARING THEM derivatives of methyl 1 anos i which has been given the trivial name methyl ol ncosami i de to of ethyl 1 pyranoside to and processes for producing them exempl ified as fol condensation of MTL an aromatic aldehyde to form reduction of to give treatment of with a lower al iphatic aldehyde to give ysi s of 1 i to give and N i owe owera ky also is obtained by alkylating MTL or oweral The above compounds are useful for the resolution of racemic as to form urethanes and and as mothproofing Novel analogs of MTL and ETL are obtained by a chemical Using MTL as exemplary of the reactions which ETL also the process ceeds as fol MTL is condensed with an aromatic aldehyde to form idene MTL l is reduced using a platinum catalyst to give I I I is treated with a lower al iphatic aldehyde to give ryl 1 owe kyl i or and kyl or is hydrogenol yzed to give loweral and owera The above reactions can be ustrat y represented by the sequence of of 4 loweral kyl also can be formed by ating with one mole of alkylating ternati can be formed by ating MTL with at least two moles of kylati ng direct alkylation of MTL does not produce kyl wi th an aromatic al as shown is first ETL derivatives react in the same manner as MTL derivatives in the above reactions to give di These processes for the production of loweral or ETL can be i ustrati y sented by the fol ng sequence of A residue of alkylating ag and lowera can be an acyl reagent selected from acid and aci d hydrocarbon carboxyl c ds ni ng from 2 to 18 carbon to give lower pentaacylate and loweral kyl loweral kyl can be used to produce acylate and 1 oweral tetraacyl The above acylations can be represented by the lowing lower alkyl of from 1 to 4 carbon 3 a 1 i c aci d acyl radical of from 2 to l8 carbon X or The condensation of MTL with an aromatic aldehyde to form can be conducted y at room The aromatic aldehyde is added to a suspension of MTL in water has been made basic by an ine for sodium The solid material dissolves rapidly and crystals of are formed in a few The crystals can be recovered by filtering the washing the residue with and A variety of aromatic aldehydes can be used n the cess of the for furfural furfural dehyde sal i cylal dehyde orobenza 1 dehyde orobenzal dehyde dehyde dehyde mTmethoxybenzal dehyde d me t hox y nza de h yd e roxybenzal dehyde c piperonal tr imethoxybenzal dehyde orobenza 1 dehyde trobenzal dehyde phthal dehyde trobenzaldehyde va n i tereph dehyde met ha 1 dehyde dehyde The reduction of to is accomplished by subjecting in a methanol solution containing num oxi de catal yst stened ethanol tp about 20 pounds of hydrogen pressure for about 4 to 5 The catalyst can be removed by f trat and the vent distilled under The result i ng crystal ine residue cons st ng of I can be dissolved in methanol and diluted with The crystals of are col lected by f tration and I is converted to kyl MTL or by treating the former compound w i th at least 1 mole of a lower a kyl hat c a dehyde containing from one with 1 mole of formal in there is obtained ί ncosami de The reaction can be at room temperature for about 30 minutes to one Though the best analytical data cates that the idene bridges the i t ion of the this does negate the possibil that the group bridges the tion of the molecule the formula for i s shown as or A single structural formula represent i compounds shown in F wherein Ar is is hydrogen or lower of from 1 to carbon X is or y hydrogen attached to an and the remaining free bonds are Hydrogenol i of or affords and owera kyl The hydrogenol ys s can be at room using as a Acylation of and i owera is accompl shed by reacting these compounds wi th the hal or anhydride of a carboxyl acid of not more than l8 carbon or a and substituted carboxyl acid conta i ni ng from 2 to 18 carbon in the presence of an nd i ng for cyclic amines such as nol and soqu i nol nes such as tr ami tri ethyl ami and the and kylani 1 i nes suc dimethyl ani 1 i di ethyl i and the and kyl idines such as p per id and the The preferred base is The reaction is conducted by ng a suspension of kyl or loweral kyl depend on the end product in the tertiary amine the acid hal de or anhydride and heati ng the if for a short period at a temperature not greater o than about 100 to complete the The resulting acylated products can be isolated b conventional The term carboxylic acid acyl radical of from 2 to l8 carbon whenever used in the or claims is intended to mean an acyl corresponding to a carbon carboxy c acid of from 2 to carbon Suitable such acids include a saturated or straight or branched cha i phat c carboxyl c for ace i soval er i caproi capryl acryl octynoi c and the a saturated or unsaturated icyclic carboxyl for cyclobutanecarboxyl c opentanecarboxyl ί c cycl opentenecarboxyl i c methyl cycl open boxy 1 i c cycl ohexanecarboxyl c dimethyl cyclohexenecarboxyl c propyl cyclohexanecarboxyl c and the a saturated or unsaturated substituted aliphatic boxyl ic for cyclopentaneacetic cycl propionic c cyclohexanebutyri c methylcyclohexaneacetic and the an aromatic for benzoic toluic naphthoic 165 and the and an aromati i phati c carboxyl i c for phenylacetic c phenyl c cinnamic phenyl ol i c and naphthyl aceti c and the term and tuted hydrocarbon carboxyl ic acid acyl of from two to eighteen carbon is intended to mean hydrocarbon carboxyl ic acid acyl as hereinbefore defined which substi by one or more or Examples of substituted hydrocarbon carboxyl ic acids and and and and mevalonic and hexanecarboxyl i aci shikimic aci d t i c ac aci cyclohexanecarboxyl i c and and cyclohexanecarboxyl ic i cycl ohexane carboxyl ohexaneca rboxyl c bromo cyclohexanecarboxyl c meth c cycl ohexane carboxyl ic cyclohexanecarboxyl d ohexaneca 1 c aci cycl o hexanecarbpxyl i c i cycl ohexaneca rboxyl c ic cycl ohexanecarboxyl c homogentisic and orobenzoi c anisic aci ic c resorcyl c gallic veratric tr imethoxybenzoi c trimethoxycinnamic chlorobenzi 1 i c and trobenzoi c cyanoacetic and ni trobenzoic trobenzoic Compounds to i us i st in the protonated form or the form depending upon the of the These compounds form stable protonates addi tion by neutral ization of the free base with an acid by metathesi s between the ated form of the compound and the anion of an Suitable acids for this purpose include succi ni i mal fumar pamoi chol i glycol 1 sal I i cyl utari cyclohexanesul ohexanedi carboxyl octadecenyl octenyl succ i ni methanesui benzenesul benzenesul f octadecyl f ur i pi cr and 1 ike These acid addition salts are useful in upgrading th free The compounds of the i or and and the d on ts of these are useful for the lution of For reacts wi th racemi c ds to form as c add i tion salts which separate by fractional crystal 1 i nto diastereoi somers from which the 1 y acti ve aci ds are The above novel compounds of the invention are also useful as They react with isocyanates to form urethanes and ureas and can be used to fy polyurethane For the novel compounds of this invention react with an excess of toluene socyanate to form a prepol mer ch then reacts wi th the yol ethers and yol esters common y used to form The compounds of this invention also react to form pol ene compounds in react with toluene diisocyanate to form a The novel compounds of this invention are particularly useful for producing rigid polyurethane they condense with formaldehyde accord ing to Patents and especial 1 when the thiocyanic acid addition salt is to form polymers which are useful as pickling Their acid add t i on sal s are useful as mothproofing agents in accordance with Patents and he novel acylates pentaacylate and 1 can be used to upgrade owe ra and kyl by acylating compounds and pur ng the thereby separating it from e and other and deacyl at ng i t to pound and compound 1 these compounds are The deacylation is y accompl shed by reacting the acylates o with dilute aqueous base at or with ammonia in o at The ETL derivatives disclosed herein can be used for the same purposes as disclosed above for the MTL The examples are illustrative of the process and products of the present invention but are not to be construed as l All percentages are by weight and sol vent ture proportions are by volume unless otherwise PREPARATION OF METHYL I I DE Methyl nide can be in accordance with the set out in Patent PREPARATION OF ETHYL COSAMI IDE incosaminide can be prepared in accordance with the procedures set out in the ί cat on and at 2163 Argoudelis et in the operating conditions of The microorganism be used the tation procedure disclosed in pages EXAMPLE 1 NCOSAM DE and Ar X or I I DE Wi th vi of benzaldehyde was added to a suspension of of methyl i in 990 of water containing 99 drops of sod i urn The sol rapidly dissolved and crystals of ncosami i de formed in a few The solution was filtered and the residue washed with water and yield of de was point of for BENZYL 10L COSA DE By ng methyl nide i n Part A by ethyl i ncosami there is obtained By substi tuti ng the fol lowing aromati c aldehydes in Part A for there are obtained the corresponding i thi i furfural furfural icylaldehyde tol 1 dehyde tol ual dehyde tol ual dehyde orobenzal orobenzal dehyde dehyde 1 dehyde dehyde thoxybe dehyde p be c pi peronal dehyd dehyde dehyde robenzaldehyde phthaldehyde dehyde i t robe dehyde 1 dehyde vani n chl orobenza dehyde terephthal dehyde me thai dehyde ci nnamal dehyde protocatechual ehyde By substituting the 1 aromat c aldehydes in Part B for benzal there are obtained the corresponding i ncosami furfural furfural sal cyl dehyde dehyde ual dehyde dehyde orobenzal dehyde dehyde dehyde p t hoxyberiza 1 dehyde Idehyde Idehyde imethoxybenza 2163 pi j tr imethoxybenzal dehyde orobenzal trobenzal dehyde trobenzal dehyde phthal dehyde naphtha dehyde trobervzal dehyde dehyde dehyde van i n chlorobenzal dehyde terephthal dehyde met 1 dehyde ci protocatechual dehyde EXAMPLE 2 OL and I OL I I Ar aryl I OL DE A solution of cosaminid as prepared in Example Part in 800 of methanol containing 8 of platinum oxide moistened with 100 of was shaken under 20 pounds of hydrogen pressure for The catalyst was removed by f i t rat i on and the solvent distilled under The crystal residue was d i ssol ved i n 100 of warm methanol and 1 uted wi th 400 of ethyl The crystals of which formed were col lected by 1 tration and for 7 BENZYL 1 By substituting i ni de in Part A by i ni as prepared in Example Part there is obtai ncosami By substituting i ni de ί n Part A by the incosaminides obtained in Example Part there obtained the corresponding methyl thiol ncosami ni By substituting the i inide in Part B by the i ncosami as prepared in Example Part there are obtained the ponding EXAMPLE 3 DENE NCOSAMI IDE or and I OL NCOSAMI N I DE or Hydrogen or lower of from 1 to 3 carbon X or OL DE solution of of h i inide as prepared in Example Part and of formalin in 200 of methanol was ma i nta ned at 26 for Evaporation of the ent gave a residue of which was chroma tographed over kilograms of silica gel using for A fraction of of oil was A portion of this was dissolved in clarified and evaporated to yield thiol i as a glassy sol id havi an optical rotation 25 o for N By substi ng ncosami ni de in Part A by ncosami as prepared in Example Part there is obtai By substituting incosaminide Part A by the obtained in Example Part there are the corresponding methyl i By substituting the i ni de in Part B by the ncosami nides ned n Example Part there are obtained the corresponding methyl hiol ncosami By substituting the n Part A by propi and butyral there are obtained i ncosami ni and i inco By substituting the formal in in Part B by prop ional and butyral there are obta i ned i ncosami and By substituting the forma n ί n Part C by aceta propi and there are obtained the respond i ng i dene thi o i ncosami ni By substituting the forma n Part D by aceta onal and there are obtained the ng i ethyl i ncosami EXAMPLE 4 NCOSAMI N O NCOS DE ί LOWERAL OL NCOS AM I and OL I COSA hydrogen or lower alkyl of from 1 to 3 carbon i R lower alkyl of from 1 to carbon COSA DE AND METHYL o TH NCOS AM A solution of 6 of ncosami ni de or as prepared in Example Part i l6o of methanol was aci di to give a red color with moistened pH with 6 hydrochloric Six grams of palladium on carbon stened wi th ml of was added to the acidified The resulting mixture was shaken for hours under of hydrogen A few drops of 6 hydrochlori c acid were added to tain the acidity of the sol ut on and hyd rogenat on was continued for 12 The catalyst was removed by f i 1 trat ion and the solvent disti led vacuo after making the mixture basic with ethyl was chromatographed over of silica Elution with methanol afforded of ncosami whi ch was recrystal from methanol to give 700 of crystals having melting o point of A portion of these crystals was recrystal from methanol to yield crystals having a melting point of o the crystals to be almost pure i i ncosami wi th a trace of thi The more polar fraction from the si ica gel column was recrystal 1 zed from to yield 900 o i ncosami ni de having a melting of Stripping of the column with methanol urn followed by recrystal lization gave addi 550 of ncosami nide having a melting point of o 188 A portion of these crystals was recrystal from o methanol to yield a preparation melting at and O i ng an optical rotation in The analysis for NCOSAMI N AND NCOSAMI NIDE By substituting the ncosami nide in Part A by as prepared in Example Part there are obtained ncosaminide and thiol ncosami By substituting the 1 ncosami in Part A by the ncosami as prepared in Example Part there are tained ncosami and methyl i By ng the i ncosami ni de in Part B by the as prepared in Example Part there are obtained thi ncosami de and ethyl i ncosami By substi tuting the i ncosami nide jn Part A by the oweral ky i in Example Part there are obtained the cor i ng oweral kyl thiol i inides and o thiol ncosami By substituting 1 ncosami des in Part B by the kyl obtained the ng oweralkyl 1 hi ol i ncosami ides and By substituting the aminides in Part C by the kyl i ncosami obtained in Example Part there are obtained the cor respond i ng kyl i ncosami ni des and By substituting the thiol saminides in Part D by the i ncosami in Example Part there are obtained the corresponding thi ncosami des and ni EXAMPLE 5 LOWERAL NCOSAMI IDE NCOSAMI of i ncosami de or as prepared in Example Part is hydrogenol yzed over 100 of pal 1 ad 1 urn on charcoal for hours under of hydrogen The catalyst is removed by f i trat ion and the solvent ed n vacuo to give a crystall ine residue of which is then recrystalli from methanol to yield o methyl ide t ng at The elemental analysis for i ncosami as for B the 2165 as prepared in Example Part there is obtained By substituting the i in Part A by ncosami as prepared in Example Part there is obtained ncosami By substituting the l i ncosami nide Part B by the i as prepared in Part there is obta i ned methyl thiol i By the sami nide in Part C by the as prepared Example Part there is obtained the correspondi ng kyl By substituting the saminide in D by the ncosami as prepared in Example Part there is tained the corresponding sami EXAMPLE 6 COS AMi PENTAACETATE A sol ut ion of 5Q0 of as prepared in Example Part in 2 of pyridine and 2 of acetic is kept at ambient temperature for Two of water and after 10 mi an additional 15 of is pentaacetate is recovered by extract on wi th methylene After drying the product and evaporating the a residue of ncosami nide pentaacetate I NCOSAMI DE TETRAACETATE By subs the thi ol ncosami de in Part A by as pared in Example Part there is obta methyl thi ncosami n i de By substituting the ncosami nide in Part A by as prepared in Example Part there s obtai ned saminide By substitu the in Part B by ncosami i as prepared in Example there is obtained ethyl i ncosami de By substituting the acetic in Parts and D by propionyl isobutyryl valeryl isovaleryl neopentyl acetyl hexanoyl heptanoyl phenylacetyl toluoyl cyclopentanepropionyl propionyl acrylyl crotonyj chloroacetyl anisoyl lcyloyl trobenzoyl cyanoacetyl caprylyl palmitoyl and stearyl there are obtained the tetraacylates and insufficientOCRQuality

Claims (1)

1. IS CLAIMED IS i A compound of and the salts thereof wherein Y is wherein R is lower from to carbon acyl carbox said acyl advantageousl being acyl of a hydrocarbon carboxylic acid containing not more than 18 carbon or a and carboxylic acid acyl adical of not than 18 carbon and X or r 1 A compound of 9 and the salts wherein Rg i s ower kyl of from 1 to 4 carboxylic carbon R3 is hydrogen or said acyl 11 advantageous 1 y being the acyl of a hydrocarbon i c acid containing not more than l8 carbon or a 13 hydroxy and tuted hydrocarbon 1 carboxylic acid acyl radical of not more than l8 carbon 15 and X is or 1 A compound accord ng to claim salts wherein R2 and X are and s 1 A compound according to claim and salts 2 wherein is X is and R3 is 1 A compound of the formulas and the wherein is lower of from 1 to carbon is as defined in Claim and X is or A compound according to Claim and salts wherein and X are and is A compound according to Claim salts wherein is X is and is 2l6j A process for producing a compound of the wherein both are lower of from 1 to carbon or wherein one is hydrogen and the other R2 is lower alkyl of from 1 to carbon and wherein X is which condensing methyl i ncosami de with an aromatic aldehyde to form i dene methyl i ncosami reducing thiol de using platinum catalyst to give thi ncosami treating with a lower aliphatic aldehyde to give loweral i i and ating ncosami de to give incosaminide and oweral methyl i ncosami 10 and X is or ch ses kyl ati ng a 11 pound of the 19 wherein and X are as defined with mole of 20 the A is of the alkylating 1 A process for a compound of the 2 9 wherein both are lowe alkyl of from 1 to carbon 0 or wherein one is hydrogen and the other is 1 lower alkyl of from 1 to carbon ncl us and wherein 2 X is which comprises condensing ethyl 3 sami nide with an aromatic aldehyde to form ncosami n i reducing thi ol i 5 saminide using a pi yst to g ve 6 i ncosami treating i cosami 7 th a ower i phat c aldehyde to give 1 oweral 8 ethyl ncosami and hydrogenat ng 9 thi de to give insufficientOCRQuality