SU1318599A1 - Method for producing 1-alkyl-2-chlorine-2-alkoxyethenylalkyl (aryl)chlorphosphines - Google Patents

Abstract

This invention relates to the chemistry of organophosphorus compounds with a C-P bond, in particular, to 1-alkyl-2-chloro-2-alkoxyethenylalkyl (aryl) phenyl, p-methoxyphenyl, which can be used as intermediates in organophosphorus synthesis, for example for the synthesis optically active tertiary phosphines, phosphine oxides and thioxides of phosphines. The aim of the invention is to develop a new available method for producing compounds of HF. To obtain them, alkyl (aryl) - dichlorophosphine is reacted with alkyl alkoxy acetylene in a polar organic solvent at a temperature of 20-80 ° C under an inert gas atmosphere. Products are obtained in quantitative yield. 2 tab. S (L oo 00 ate: 0 co

Description

113

This invention relates to the chemistry of organophosphorus compounds with a phosphorus-carbon bond, and specifically to a method for producing 1-alkyl-2-chloro-2 alkoxy ethylenylalkyl (aryl) chlorophosphines of the general formula RjP (Cl) C (R) C (Cl) OR ,, where R and -R is C, is C-alkyl;

RJ - isopropyl, butyl, phenyl,

p-methoxyphenyl, which are not described in the literature, are new and can be used as intermediates in organophosphorus synthesis, for example, for the synthesis of optically active tertiary phosphines, oxides and phosphine thioxides.

The purpose of the invention is to develop a new available method for the preparation of 1-alkyl-2-chloro-2-alkoxy ethylene alkyl (aryl) chlorophosphines.

Example 1. To a solution of 1.79 g (1.37 ml, 0.01 mol) of phenyldichlorophosphine in 1.5 ml of absolute methylene chloride at room temperature with stirring for 5 minutes, a solution of 1.12 g is added dropwise (1.40 ml, 0.01 mol) of methylbutoxyacetylene in 1.5 ml of absolute methylene chloride. Stirring is continued for 4 hours. The solvent is distilled off, the residue is kept in vacuum (1 mm Hg) for 1.5 hours. 2.8 g of 1-methyl-2-chloro-2-butoxy ethylenylphenylchlorophosphine (IV) are obtained. .

Found,%: C 52.67; H 5.91; R 10.23.

C, jH ,,.

 Calculated,%: C 53.63; H 5.89; R 10.63.

Example 2. To a solution of 1.59 g (1.37 ml, 0.01 mol) of butyl chlorophosphine in 1.5 ml of absolute methylene chloride, a solution of 0.98 g is added dropwise at room temperature with stirring over 5 minutes. (1.21 ml, 0.01 mol) of ethylethoxy-acetylene in 1.5 ml of absolute methylene chloride. Mixing is continued for 60 hours. The solvent is distilled off in a water-jet pump vacuum (5 mm), the residue is kept in vacuum (1 mm Hg) for 1.5 hours. 2.45 g of 1-ethyl-2- are obtained. chloro-2-e. toxy-ethylenbutylchlorophosphate (II).

N-isdeno,%: With 47.45; H-7.43; 12.23.

5992

C, H, CljOP

Calculated,%: C, 46.73; H 7.41; R 12.05.

Example 3. To a solution of 1.45 g of 5 (1.19 ml, 0.01 mol) of isopropyl dichlorophosphine in 1.5 ml of absolute methylene chloride, a solution of W 0 is added dropwise at room temperature with stirring over 5 minutes 98 g (1.21 ml, 0.01 mol) of ethyl ethoxyacetylene in 1.5 ml of absolute methylene chloride. Stirring is continued for 140 hours. The solvent is distilled off, the residue is kept at 15 under vacuum (1 mm Hg) for

1.5 h. 2.35 g of I-ethyl-2-chloro--2-e | goxyethenyl isopropyl chlorofo-finone (IX) are obtained.

Found,%: P 11.83. 0

Calculated,%: P 12,74. Example 4. A solution of 1.45 g (1.19 ml, 0.01 mol) of isopropyl dichlorophosphine and 1.12 g (1.40 ml, 0.01 mol) of 5 isopropylLethoxyacetylene in 3 ml of absolute acetonitrile is heated

Q

at 70-80 ° C for 16 hours. The solvent and unreacted starting compounds are distilled off in a vacuum of 30 (1 mm Hg) to obtain 1.3 g (50%) of 1-isopropyl-2-chloro-2-ethoxythenyl zopropylchlorophosphine (X).

Found,%: P 1.88,

35

Calculated,%: R 12.05.

Example J5. To a solution of 2.09 g (1.57 ml, 0.01 mol) of p-methoxyphenyldichlorophosphine in 5 ml of absolute methylene chloride at room temperature, a solution of 0.70 g (0.90 g) is added dropwise during 5 min. MP, 0.01 mol) of methylmethoxyacetylene in 1 ml of absolute methylene chloride. Stirring is continued for 34 hours. The solvent is distilled off, the residue is held under vacuum (1 mm Hg). Get

2.7 g of 1-methyl-2-chloro-2-methoxyiste-, nyl-p-methoxyphenylchlorophosphine (XI). Found,%: P 11.15. Ci, H, C1.0, P Calculated,%: P .1 1, 10 ..

Thus, the proposed method allows to obtain previously undescribed compounds with high yields under mild conditions and does not require complex instrumentation.

The data of elemental analysis, NMR H, and IR spectra of 1-alkyl-2-chloro-2-alkoxy ethylene alkyl (aryl) -chlorophosphines are presented in Table.

1 and 2.

The method of obtaining 1-alkyl-2-chloro-2-alkoxyethenylalkyl (aryl) chlorophosphines of the general formula

C1 RoPv / C1

XII n-CH, OCjH, (Cl) PC (CjHj) -C (Cl) OC, K, Coli 78

comic

Xlir it-CH, OCjH4 (Cl) PC С, Н, -иэо) С (С1) 0 30 52.70 5.85 9.23, P 52.35 5.96 9.02

day

 Reahtsch in sh etyitrnle,

where R and R, - With, -C-alkyl;

R. - isopropyl, butyl, phenyl, p-methoxyfekyl,

that is, alkyl (aryl dichlorophosphine of the general formula

RjPCPj

where R, has the indicated meanings, is reacted with alkyl alkoxy acetylene in a polar organic solvent at 20-80 ° C in an inert gas atmosphere.

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10.07. „S1,0, R Yu. OI

about

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Yu

ABOUT

3

oh oh

Claims (3)

SUMMARY OF THE INVENTION Method for the preparation of 1-alkyl-2-chloro 2-alkoxyethenylapkyl (aryl) chlorophosphines of the general formula П Н ₂ Р \ where R and R are - -C ^-alkyl; R _t is isopropyl, butyl, phenyl, p-methoxyphenyl, which consists in the fact that alkyl (aryl) dichlorophosphine of the general formula RjPCP _z , where Rg has the indicated meanings, is reacted with alkylalkoxyacetylene in a polar organic solvent at. 20-80¾ in an inert gas atmosphere. Table I q a 1 - No. p / p Compound Exit Reaction time in methylene chloride _{• t} h Found, Z Formula Calculated, X FROM n F FROM n g I ^ n, pc1 (cn _} ) ss <s1) Quantitative 4 47.94 4.39 12.52 S "N, S1.0R 48.22 4.45. 12.44 II С, Н, (С1) RS <С ₂ Н,) - С (С1> 0С ₁ Н, 6 52.18 5.49 11.15 C „B“ S1,0P 52.01 5.46 11.18 ΙΙζ0 ₄ Η _Ι (01) Ρ0 (0, Β, -Η »ο) - € (<: 1) 00 _ι Η ₅ - * · - 25 53.97 6.09 11.23 C, ₄ V „C1 ₂ 0P 53.63 5.89 10.64 IV C ₄ N, (C1) RS (CH,) - C (C1) OS ₄ H ₉ 4 52, ¢ 7 5.91 10.23 C "B" C1 ₂ 0P 53.63 5.89 10.64 v s ₄ n, (s1) pc (sv.) - s (s1) 20 - 11.14 With "In ₂ .S1,0R - - 11.42 VI C ₄ H, (Cl) PC (C ₂ B _f ) -C (Cl) 0C ₂ H _f 60 47.45 7.43 12.23 C „B“ S1,0P 46.73 7.41 12.05 VII C ₄ V, (C1) RS (C, H ₇ IEO) -C (C1) 0C ₁ V, - 40 - 11.44 ^ Β ,, Ο ^ ΟΡ - - 11.42 VIII I "о-С, Н, (С1) RS (CH,) - С (С1) OCH, 96 - 14.23 ο, Η ,, ει ^ ορ - - 14.40 IX MO-CjH / CDPCCCjHjKCiCDOCjH, 140 - - 11.83 С, В „С1,0Р - - 12.74 X iso-C, H, (C1) RS (C, H, -and "o) -C (C1) OS ₁ H, fifty 30 li (80¾) - - 11.88 ο ,, μ ,, οι, ορ • 6 - 12.05 XI p-CH, 0C ₄ H ₄ (C1) RS (CH,) “C (C1) 0CH, Amount explicit 34 1 11.15 c „h, ₄ ci ₂ o, p 11.10 XII p-CH, 0C ₄ n ₄ (C1) RS (C, H _{ ) -C (C1) OS, K, Kolimest — vein 78 - 10.07 c „ii„ ci ₂ o ₂ p - - 10.08 XIII p-CH, 0C ₄ H ₄ (C1) RS C _e B, -ioo) -C (C1) 0 <^ H, "··". 30 52.70 day 5.85 9.23 ^ m ^^ SC OjP 52.35 5.96 9.02 * Reahcim time in acetonitrile. Compound </ ( ³¹ P), Chemical shifts ¹ N, /, m, d. (J, Hz) IR sector ppm ------------— I -----— η --—- g - ”- (C = s), HC-C = C C = C-O-CH | НС-С-С = С С = С-ОССН Н— cm '' кО X about MO And "I X l o io l g * · f X ff cm <34 ♦ »about so about and to MO SO g. with X m IO O About 00 * With About h <g * l CO CM X g. • h cm I " Ff mo SO • And my Oh 40 ** l CO about <g With Ct * / -> o <r G4 * * CM Pts cm ₽ * * o <t with oo About <g • h O / \ r? £ £ with and about w about. ABOUT about about * “· cho 40 cho 40 About 40 I X es | I b O4 cn υ I Q S ¢ 4 * »r (b Σ I • · X 4h m * cn * <r ** O "V 4h SCH <G X Joint venture CN I n l Joint venture joint venture 4h X 4h mid 4 hours and "I sh about l <r X 4 hours Joint venture I and h0 cn ti w cf 00 * * cf »1 o o> g * 4 < SP σ < g * σ> σ 'm σ \ och I b < mid SP h 04 About 4h AND Oh oh X About joint venture Joint venture 44 <r o ο <τ I • ί- g *. S-Z • “η υ Λ Λ ο ο CM Γ ⁴ * * l * - ΟΠ о σ> <h O e F ι / Ί cg> "I SP" "• Ci * 1 hO CM l cm s o <g XIIIP - СНЧОС _b НкРС1 ^ С = С (С1ЮСН ₂ СН ₃ CH3CH2 86.75 2.86, M. 3.93, K. 1.05, M. 1.15, T. 7.40, M. 1600 3.66, p. (CH, oqiy I