AU6115094A - Process for producing methanediphosphonate compound - Google Patents

Description

y Φ x * y ^■its®® JΞ. lό

* US H tt Jg 4- - h J * I tt SL jfc ffi *!l tr U -7 - SO _^ # ft

JSl lt 0 0

*iδi

fiέ*© 1 - T i + i - it & ι tt 1 - 71⁾ - ;i v⁵ * X

* & © -£ iδSK ^τii, tøl *. # & 4 - 29676 - & IβcEi έ tiτ i^ 0 c: : t έ ti T 1^ δ Λ 'J ^* S -s? tt ^■? y * 5fc B£ " h -57 l/ + l/ x Λ/ * 7K * -it i^~ h y ^Afoiiiλ

J^ t .£ ^#]£ £:£JSi§*ft{ £&L ^8^Λ 7 -f K £ ffl £-££ : έ 1: J; ^ g fø © 1 -7/l + ib έ δ !i 1 - 7 'J

- U - * ;? v> * X * > h 7 ll + l' λ f l/^ JS L T

§ 0 C © <y -7° u 7 K tt JR * * s < a s tε £ ^ tu lilllϊtt

© fife (- ^ i © * £ Jδ ^' x i ^" ^ K ft t> ^i: ^ ? Φ X * ϋ$ T Y

7 T ^} r J X -T ⁾l> t l£> K & 1 * -δ if > * § - - JI w λ L T fc t) :li cliι;ii ^* 'J ii ¥ Jl ft 7 Λ 0^•? h y =7 -J

-lcil Kn:ii^^i; 3λ h £ffifi»^*<^ST* o B Kl

^jfέδ v * x * s ft -^• fø Λ< H ^ ^ © ^ { & I TSΛT ffflt^ξ ά £ jf.^ £ ά , t^tt©λi«feiι^.^[ -rϋtJS©

£ tt ^ϋ < , _J: <9 ffiffiT-fS3 X h © fi at Si Λ< it t & 4 - 29676 -^&$βEfc© Λ ^>y 'J ^ s ιε K & tj- * * © M π •-.

ST 1 3tr|- e V vT' Mi V¹ π , a* 4 ft Si £S h- ri /~\ tt sr iffl π M, π H -fr - tt a § 1 >i i* sr ϊ

«f vS" §f Ά a» s^ ft (V V 531 sr sr 3- V Θ Θ H 4 y- Ϊ3- =Hr

# w -B- a 4 •- ft ≤ ..

ξ} -fr H ππ ^ & a ^ sr V l^ f ft

/

l # rl ft V. 1 3d >

V X 3 531 ^ι ^J- -fr W m Mm t w v..

V* s e~ X -a- H Si «_? ® \j' 7ϊ sr Si π π

H> " f π v..

c* ID -A V ST rt. t >i sr ri *l ft M s^ ~r iN ss ^ φ4 t — S Vi -fr c 13 Mi θ θ π ϋ- βr 4 Ml =Dr 04 SSI m St. ft ^ 4 V t

0 c s sr H e>« ^ 5ff θ<- π $ rv v> tf" E ^-s >i c i3- - -_^ rv M, rv sr θ rv

§ V la *ft H 4 4 4 / rt βl ft 1 ^1 ^= ft «_- -fr eH θ

Θ Vi j SI __^

V v. ft 0< C S ^ V 0-ι ft o

sr θ (fi

4* 4 rl J ^• •• ® ^ ϋ- ϋi 4 rl o

1 sr ^ •- 1» 4 _S- St.flf- <—

>J » rv V VJV π 1 aπj- -fr V 531 1 >J ft v>

H 4 rl )— _. π> Vi tt v_.

Jr _^_.

sr S sr ]- ^ s Si # f< V

V <J«" * & 4 0 Q « I ^ 1 r^ ^>= sr ^ 9 Vi

19 i^ σs Θ J £ rl sr 4 4 I ft §1 4

H Si ϊϋ 4 Θ * Φ ^ St. Θ S r fill 531 $ 4

SI -r Θ fπfF V ππ So iBr T' 4 ϊ π S^ y- c>f rv 4

Ml » 3 π ft 3- . V n ^ 4 ^- *l πη V

.'-s JtHR ft rv ft ππ i||ι

W e Vi n

« St. ft -fi- 3 m a sr n- at π> 3 cv r< V 4 cv r ϊ ~- π ^ Si

^-__^ -fr & & m § (V Vi >i s£ ?t V o JU Θ -r - ft _nl 94V gπ (V Vξ r^ 4 4 ft if Vi ?>i Φt Φ Ml

H φ d^ rt tv Θ -M m >i V ^ 7itm» 4 v 3 H 4 ^ (5÷- ft r~ Φ V EE 4 t_z_i_- /

» __ J Ϊ5- - e 5

Si Ϊ-Dτ Θ •- r § }^• ~ V Si * π 4 St. m -fr sr H ri 1 ϊ_5- i> rt T ?H Θ V m ^ π ^_«

Θ ST H &• 3t rv o

Si Ml r< ϋ- SI Hr V * H

-fr CN _. rλ J*. u t- -r H rv ≤ cv Wt Vi 3δ> J

R 2 S ^— S R 2

(^ψ^ R ₂ te 7 * Ji t tz .$ 7 ⁱ) - lM -b

ιz «fc V *> ft 5 V 7 J^] + u >> x 7 ^ K * /; tt s? 7 U - u x ^ KάSEέtδ i ^tlέtξ, TE^ ( I ) :

(ϊξt Ri .tmm . t tstizmjty, 7kmWs tz.im

£ tz .-i - T \.^X b £ < , f LTR i . M.zfe Lt m <O X h &

K&t mi nz 9 y * x * y M it & ® <D m &JΪ &. -f & <_ i-t-z-b*, , # 36 HJΪ © & & tt i -7 u + ^^- ^ * x * > e ft-^ftέδi i l - 7 u - i f 9 ^y ' * X * t ft tøi © Si it ; & tt . © £ J£ ϊξ (A) T έ iδo > γ^Sι feijδIit;jg

T T E © £ tt ft £ ^ft^f LΛCt Jl^

C ;tR' , tt£t^8. ι ~ 6 ©fi£*sιw*#ιtø&7 u* R te 7 Λ/ * Λ/ 36 * δ IWi 7 U - H^f *t§)

- tt^-ς,, ^Sfej;('^s^ft^© 4τ >' ^*>if h 57 i * ;u x -ψ J £ flu *. x tw f& L > m^x a x Ji7 ^ & Λn . α A φ sr vS" I θv 4 a-

CD cv 531 I v. 3S v ππ j' Si 0 rl 531 si. vj tt st ^ cr V -W Θ -7 Θ ϋ 3 3- -r rl fu ?}

Sv VI Q ' & w rv 9τ St. Si Θ eM Ml ζ O tt sr α 9fr -77, IS 53i Si voL c i_i- -fr < I W «Φ fr π; rt Θ l 5*1 "7- fr rl iH ^ V ft V Mi I f< sr rt o o

V sr ft iffl 53- 9τ US Mι rv π Vi H Θ -fr sr f I r< v sr -< ? J*ft l iStf I J' 11 4 ^ sr rv sr -fr

O α > 53- -fr θ* 1Ψ ft ^_

sr sr Tj- rl Θ ;θτ S3 >i -fr -fr ()»^■ H ..

sr * - >

vS-' λ Si sr Vi -fr ft Θ H 4 >i v ^ fig Θ v sr α s§ IS KΦ sr 531 I £5- to J V H v 531 Si 4

Sv sr 5*11 IS H Oi Si 4 5 v.

sr π fr GO -fr H -fr 531 •t

sr 9- >J *L sr τ# ° Si Si θt rt rv r< -fr I sr sr Si cv a- I 9fr v -r sr e _-_-. w- ^ rv

__ ^_

sr V SJ.. Θ (V Vi _-,- tm sr vT' M_ n Ml Θ i Hi- EE π π v S^ C sr >i a ft π T ff ^1 55- ft rv Θ

α Θ r\ sr ft ~t 9τ -fr v.

w- Θ sr Vi

> nl ft ft sj *4 Λ V cv -fr W- I rl r^ l

AH- -fr I vi <_N Vi ft cv 4 sr i s sr I Θ v

Φ v I St. π * Θ UK J »: ft V; r< H vl sr 4 ft S^ S3 θ •! ^ Hti ? T' as VJ;. - s^ sr W 0< ^ W- sJ 531 V ft fr Si sr cv -7 4 sr

V sr Ok sr ri rt V v rv St.

V H I ft θ*- & -T: t $ vTJ- & W- ft 4 ft Θ I e>ι α t

>. CD C Vi fr * Θ Φ ' Θ 9+ T' St. r V &^• 4 V Θ <?^■ S St. fr SI ^ Vi ^4 Θ Θ v S Θ ^>= rv V ^^< π Θ V 4 I

^.

sr I fr I V 9 Vi i3- Vi ft rv >i n

□ 9* ff sr IS i UK Vi I T H 4 4 rv

□ V rfr ft Vi 5*ft ^ Mi 4 fr a_ sr sr * rl V π rv v sr ft ^ 4 H vi 4

V Θ H r. Σ5- J* -= Φ ]^• CN iπ ^ ? π π Ml sr -fr vi' « 1 s- ft V

39 NJ n rt ^ /

Θ XT \Ξ1 H» S W ° vi' < Nl -fr _ V ? rt sr vl \%

Vi l SS Nζ - m ___: rt * π Vi J ^ ό sr sr r< ^ 7 s

St. -_.

V I Λ vT< Sffl Nl tt r >r > rl ^. rl -fr H Ϊ3- ^5^" λ sr m sr

^'rH ^ 4 3^" sr ⁽^ a» Vi 0 sr 3i ft 4& sr J ri sr \i' V rv U sr H V φ» B S -fr Wt s 4 rl V] o< H vi' H Si 4π -fr ft Θ , "fr c^~ -fr o

NJ in <?- ϋl ^. sr c^* Θ X » - r< X 3- 4 sr vi' sr Nl S V. rl V

\> V tt c w* s» 4 am -T_; (V Si <_N Si θt ^ w* Nl l AJ" /

o

V ri * § >= ri rt tø V π Θ sr sr e 4 rv 1 „ V v_oL θt ll -S r~ . S* & t- « Vi S- l r< ϊ_J- — <r .

sr 1 fr

-T fr φ E£ ft. v-J- d>» c * ft 4 π Ofr 13$ js- s* ft 1 lι rl ft sr Λ V

o _H> Θ fr^* w fr ^■ X S «>. » ft - Nl -r ff Θ "7"

St. π / / o

9fr B> ζ ft 13 Q 4 ι^ nl I 1 sr π λ -fr cS*- α * 3^" V ? -M- s- Λ iHr V 3 π &j & -fr α V v. DJ> sr vT' d-i V -r π 3* 4 Q UP Θ an) 3 fr ^ sr N] ^ Q ^ WV Nl rv o

NJ HI § j >= 9tV V rv ft ft Vi I v in V & 4 V ts- in in c φ l ^« !> vQ- HV rt rv Φ ^_-

&- w- W fr 4 sr 4 V. Θ -fr >»

V rl ] V ft ^ C ft ft Tl ^ H la S >J M St. ft Nl o

4 Sv

/

ft rH Nl J* 5ϋ fr> ri J « .- Θ 4 4 v> rv sr w v; 4 Nl H

H H V 1« sr sr id- *m ffi s ow- Φ St i' t V St. V r*v -fr 1 V] *= >J s* V Θ V in V » B Θ >« « sr 5ff « ^ Vi BJ> sr Ok sr H 1 Si ϋ t C3

sr ^■w S lι vTJ- vTJ- » ff 3 π 53- V 4 cj- 3^" ft V sr sr

NJ H V (V 3- t- t- A J Λ 5ff 9fr rf ^r £=t- Vi >i Nl rl r rv /

// H rH c S> ft ft 4 — - 4 Ti t a FΆ ri ϋ ^^« 4 4 - sr - 55- rr₀ c λ

/

V H rl fV rv. V Θ V <fr r< EE Θ ^ rl φ >i V U H rl V

St. 3- ft lit Θ ft ft W 3- Θ 5^ 531 lira ≤l S5 4 « -fr ⁽J⁴- . Vi ft ft.

/

Vi Sv !> $ S i - Nl 3t -^ 4 _-_S- πtr V Si V Θ i' V V] V

H sr ft Nl A NJ NV V cv π 9fr ri fr ri e>« \M T a- ?*^■ H ^ ^_-

H ?τ V SS 4 Nl sr rt ηH Ok c~ rt Φ π θV r< Si Ml V tø M π; |ι ft sr in Q. riH ft V sr ϋ- ft U r rl ft Vj' (V ?>i rv T Nl α o α sr (V.

s^ oo

sr <____> Vi w VJltt rl Θ (DFF -fr Nl v-j- ^_.

rH sr S^ A Nl v] Φ rt. 4 v S §£ Si ant sr ^z sr SN |l Nl sr /// r< J vj sr ft Q S_t & « W Sv hr -fr ft ^■ Nl v; V sr Θ c 4 U„ rl S# ft 4 Θ sr rv J> V in / α ft co

rt rl V V ~ia\ 55- θv < N] Σ- tit V π; -7- oo r < » OO > (V ^ S v φ. < * 9τ ✓

Vi sr ft ~r Si OQ C I fr ft ri v_S" X <- π V i . H Λ Nl H

W Θ 3. ~r Θ -A rl St. <s- ' & 3$ Θ ff Θ l' Si S

Ml Sv Θ tt CH H .

U3 ^ -r v. vi V sr sr rt V I Λ sr a- v sr rl ft Fff 1 A CH Ml 1 N] H v: H 4 Sv 94- in. <$*- π Nl o

1% 4 St. sr sr Vi /< iA- V fa* , v » 4 ft ft Θ fv >= CV V -e- Sv NJ Nl A V o α — *

o vl FT r 1 ^ Ϊ.5- rl sr in

rt-. e I π; Θ I V H ft ri _^_.

sr r^ $i cJ*- Nl V V M. vl r< sr sr US 3- ffl |ι vol. V3- s /

^ W S- V π π rv ff H !> sr Kf 4 C^" ~r rH -r r+ π π; π Φ 4 I ft w Sv rt S <_— = ll - 1 sr sr

Vi * Si vl. m 4 & m r fr o

vl- vT H vl Nl Nl

St. 0 m fa* <- St. π 3 c V r< t^* 1> v> Sv in in rl pfe r -fr fr > 6Jr / Vi rv v. sr V V vnL ° sr 531 oo

t v V Mi !^ s 4 r^ J* Si 1 Nl

fr _£H Sv B Vi fr b- 4 Φ ^ ~r sr In vl. Vi

4 Hf ι^ 4 H c 4 » j Vjl H V S vl

y CD /

Vi fa _-_*! CD >i Θ * V rv IN H r α Θ W- vl ft r* Oq 4 3 r^ m nL Sv V rH N] rr.

H I fr π ' IΦ V θ<- $1 ^ cv i\ N] sr ft in sr π_ |ι π w fr π π V Nj v H V NJ

531 ^ sr r« rt r< π Φ ^ 1 rH V Θ /'/ \ I Vi Θ v # c Θ Nl lι rH Nl Vi V vl„ 0 ^ rv V ς tt <r- « m sr Nl l^l V I SJ, /

ζ>ft c#$E£, 1.5mHZMWl50m\toZ.m L < δfftδo fii^ ^IL, TRSfrζ, h l l0ml- 3 llttffi -δβ ^ *I jf - . Sft ϊfc T' * - tf Λ"r-g«Lfc©-£Jgfi&®*-r* έilβ^Φx^ ift © - h 7 v π h° 7 x x l ft fr S? x Λ/ 7 ^ έoi^ έ L T ζ> ft S„ C-©ffi j&$j£20ml© JM®?ψ-i? 5 B# H in !& 38fe L fcgK SJSTf Sffi* 1.5S^i»t 2 fg ^^-T So £©*&«£ h x 8 m\X 3 ® & Z t IZ _t. - Xmft % ϊ X 7174 K £ It * , *§***it&«li'tδ <i:ήfi,liftΛ< bftδo ft £ 7 -t? h - ^^ π o ^ t? ΪW HH -r δ t ©ft tø 1.23 frff ζ» ft δ (IR$93%, m. p.215-216 °C (dec))₀ * % tt K ζ, ft / ή ft@«:^ f ψ-i?K»^ h U iα ^) 2 h ιj 7 A ft L , ^ttj^tø S tt jfi . ^ fit L / , x-9 J - 7 -τ .z rm Q π & & ft . 1 Its -t δ - φ ψ l® 2 t h H λi|Ϋiit^ ( IR $ 93% _^ m. p. 300 °C^ ) o

2 Na 'HNMR(D₂0. ppm)

2.49 ( s . 3 H ) -. 3.23 ( t , J = 20Hz, 1 H ) -. 7.25-7.32 (m, 2 H ) . 7.51-7.58 (m, 2 H )

2 Na^ IRCKBr. cm^"1)

1479, 1197. 1158. 1110. 1071. 928

2 Na^MASSCFAB) m/ z 375CM + H) ⁺

C₈Hι o0₆S2P₂Na2 t X

C 25.68% H 2.70%

um . C 25.71% H 2.73% 2$ aι ^ V! ifl. SD 3- null *n A la *S W fr ' VJltt

rv cv 5? Ss tt Φ CD

CO -K. % Θ ^ ^θ I-] ^

4 Pf Pf ^ £ ft Θ 56 ^

^"Vζ Θ -ffl Vi Θ

m Θ I o o r_. S _——• ft π rv 56 π rv ^ 4^

Q V Sc -tø sr It ft I 3? όV c^~ I

O

vl- t

rv Sv to ro ri vilt V] v 4 ¹ rl V. 1 + r\ v.

CO CO

\> sr 4S §t -e- α π 0* SI Sv It ό< i Sv g ft ζ t O

» CO co -a l' ^ -7 α rv rv sr vo rv sr rv in 4 « X _Z_ t* rv S3 vl r . rv ϋ Sv r< rv m S

§51 V vl C (V c~ H 9τ >d 4 rv ^ & ? 4 vTJ- H rv o

13 rl l« VS- VJ; l π ^ ft j r ^<: |ι c *>. EC sr H ^1- H

ft w sr DC X rl 3 v V fr EC |ι s V EC lι

CM $E r S 4 Θ rj. i sr 3- fr sr

V. 94- 4 ^ = ^ v. rv a* *J Sv SN W 4 * vjlfl. C CD CD

CO αi tf 1 Θ 4 Θ Θ tff 4

V V -S £ St Vi V v. rv ^ v.

Vi V v Vi π V3- ϊ 4 Vi r< π 4 oo

cπ π v π I V J rv π 4 rv α >i ro Vi « ro Vi π Vi -a CD o

4 Θ rv o

4 J 4 < rv -α 4

EX

V ^ $ 1 4 ih- vl V J « m >4

Si ID V -S- H 4 Θ ® 4 Si *l IS H ri αi H> C~3

V ≠a V Θ £_h CD

T -___. m sr ^■ OO

vii $ - _. Θ Vi \J* ft ri Oq

rv rv ^ cv t≤ P? rv

\Α ^-,

sr cn s ' S

- π fc? )\ x X 7- Λ/ώ 3P © Λ v 7° U / ft ( ) a ©I^ * #

# ζ ft Λ: ffi ^ΦλΦ >H^IJI« 1 © ^ i£ i Jέ ^ > 2 *^■ h 'J sHSi_B ^B _at i ^ ( > ϋ^ ι©^ ^ mcD4t&ⁱfat# ti v 7°■) y 9^* W <D ZLJ&VGZ Mfe tz ₀ te ffi fi« © ' HNMR X ^ h H: fc ιtδ*xΦ © α ft© π h ^{y (}D frit ( ft ,Δ. tøl : 3.23ppm t , J = 20Hz, 1 H tl 7° T' ft : 2.12ppm , t , J =2OHZ, 2 H) lα^iiii Lfco ^ © *§ n , m m. <t -\ t

Λ >y <J ^' ft © J te fc «£ 2 : 5 ( * Λ/ Jfc ) ά tt *9 , & M Wt ft tø * & T fc fc tt δ S JS ft tøl © JR * tt fa 30% ά tt fc o

*i^© li{t ^ttt^ v i^#l(_:t 1 - 77\ ^r )\y

* * ^y v *x ^ym\ ^ & ^.t \ -7 v - 7\^; i3- 19 y * x * y mit^ < .& \ , *(Diϊ&ιz} iχw. ϊ) i < ft

Claims (1)

«ϊE$*i .__f#<7)«Sϊ [1994^7fl270(27.07.94)SIS*»©δSI;ffi ^tøΛ- ^W«Bffllli εM;&:t;fft -«*<?) tab^ (2K)]

1. TISϊζ (E)

liifr^ lllkftøSftT , TIΞϊζ (DI) :

R₂ S S— R₂

(ϊζφ_^ R₂ .t7 J ^ M tz. 'J -J M -b

m «9 t> £ tl ' 7 )\ ' X )\ 74 K tz .t ' 7 U - J ' X 74 Vt itξ, tl tZ .t , TIBϊζ ( I ) :

(ϊζψ. R, . mm^wi jfrn nzi J * >, Tkm -T-ttz.t i-T- . i ~ β m® .m£tz. tti$m7i iMτ*&) _^ m-x m tl^U(, ^<£LTR₂ .t i-~ ^LtzM -C-b ) (ϋfiπ) TISϊζ ( I ⁾

iα^t^έ iδ 9 > ^ * x * > SHfc tøi o

s co oft to rv

££ Θ •

» * 1$ Φ > Ml

Sffi Si » 3ff \_/ ^

null tø φ

F r» c & αnfr 9+ ; , spf

^ fitø r» d- -H a IS

^QA & ^ Θ Θ Fϊϋ IR ϊd- iSp c tt * Θ Ti ^

nun

^* rt 3^" a a &^' ru

πiiu a?

{ rt CD vS an tfv m o ft 5 <r CO zώf- Θ - ) Q t ft* v a- £f 0* null

,— \ ϋn B§ v__ o

(πά EδjF

o fc

$ Θ _____ fr Θ

Q, £_π Ok φ Θ

SR frfr r vo 11

r*- π rt (V

o

r< UK m r rϊxr vX S to

/

3=1 π ϋ. c 3lJ7 ss r ft Efl IS null

-Wr 94- c S

rt ml

Θ H milt

If

~~~ is Θ

Θ