Phosphine (PH3) is a colorless, flammable gas with a strong odor. It is commonly used in organic synthesis and as a reducing agent. Phosphine can be obtained through various methods, but in this question, we are asked to identify the reaction that does not produce phosphine.

- White P is heated with NaOH: This reaction involves heating white phosphorus (P4) with sodium hydroxide (NaOH). The reaction produces phosphine gas (PH3) along with sodium phosphite (Na3PO3). The balanced equation for this reaction is:
P4 + 3NaOH → PH3 + 3Na3PO3
Since this reaction produces phosphine, it cannot be the correct answer.

- Red P is heated with NaOH: Red phosphorus is a less reactive form of phosphorus compared to white phosphorus. However, when red phosphorus is heated with sodium hydroxide, it can still react to produce phosphine gas. The balanced equation for this reaction is:
2P4 + 3NaOH → 6PH3 + 3Na3PO4
As the reaction produces phosphine, this cannot be the correct answer.

- CaP reacts with water: Calcium phosphide (CaP) is a compound that reacts vigorously with water to produce phosphine gas. The balanced equation for this reaction is:
CaP + 6H2O → 3Ca(OH)2 + 2PH3
Since this reaction produces phosphine, it cannot be the correct answer.

- PH3 is boiled with water: This reaction involves boiling phosphine gas with water. However, phosphine is not stable in the presence of water and decomposes into phosphoric acid (H3PO4). The balanced equation for this reaction is:
4PH3 + 8H2O → 3H3PO4 + 5H2
As the reaction does not produce phosphine, this is the correct answer.

Therefore, the correct answer is option B, which states that phosphine is not obtained when red phosphorus is heated with NaOH.